KR101170930B1 - Preparation method for synthetic leather with pattern - Google Patents
Preparation method for synthetic leather with pattern Download PDFInfo
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- KR101170930B1 KR101170930B1 KR1020110011584A KR20110011584A KR101170930B1 KR 101170930 B1 KR101170930 B1 KR 101170930B1 KR 1020110011584 A KR1020110011584 A KR 1020110011584A KR 20110011584 A KR20110011584 A KR 20110011584A KR 101170930 B1 KR101170930 B1 KR 101170930B1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/128—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 silicon polymers
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C23/00—Making patterns or designs on fabrics
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06H—MARKING, INSPECTING, SEAMING OR SEVERING TEXTILE MATERIALS
- D06H5/00—Seaming textile materials
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—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
- D06M11/78—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; with halides or oxyhalides of silicon; with fluorosilicates
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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
- 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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- 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
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/04—Properties of the materials having electrical or magnetic properties
- D06N2209/043—Insulating
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/142—Hydrophobic
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- Dispersion Chemistry (AREA)
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Abstract
Description
본 발명은 합성피혁의 제조방법에 관한 것으로, 더욱 상세하게는 무늬가 형성된 원단을 이용한 합성피혁의 제조방법에 관한 것이다.
The present invention relates to a method for manufacturing synthetic leather, and more particularly, to a method for manufacturing synthetic leather using a patterned fabric.
종래 합성피혁 제조시 코팅재 또는 함침재로는 폴리우레탄이 주로 사용되어 왔다. 이는 폴리우레탄의 우수한 탄성과 물성이 합성피혁의 소재로 적합하였기 때문이다. 일반적인 폴리우레탄 합성피혁의 제조는 디메틸포름아미드나 메틸에틸케톤등의 유기용매하에 우레탄 원료인 폴리올, 사슬연장제, 이소시아네이트를 중합하여 만든 고형분이 20 내지 80중량부이고 점도가 50,000 내지 150,000cps/25℃인 폴리우레탄을 함침재와 코팅재로 이용하여 합성피혁을 제조하는 데, 그 제조 방법에는 건식법과 습식법이 있다.Conventionally, polyurethane has been mainly used as a coating material or impregnating material in the production of synthetic leather. This is because the excellent elasticity and physical properties of polyurethane were suitable as a material for synthetic leather. General polyurethane synthetic leather is 20 to 80 parts by weight of a solid made by polymerizing a urethane raw material polyol, a chain extender, and an isocyanate under an organic solvent such as dimethylformamide or methyl ethyl ketone, and has a viscosity of 50,000 to 150,000 cps / 25. Synthetic leather is manufactured by using polyurethane, which is ℃, as an impregnating material and a coating material. There are a dry method and a wet method.
건식법에서는 폴리우레탄을 코팅층과 접착층으로 사용하는 데, 폴리우레탄, 디메틸포름아미드, 메틸에틸케톤 및 안료를 적정비로 배합한 코팅액을 적어도 1회이상 이형지 위에 코팅을 한 후, 상기 이형지를 건조기를 통과하여 용매를 휘발시켜 필름을 형성시키고, 그 위에 다시 폴리우레탄 접착제와 경화제, 경화촉진제 및 디메틸포름아미드, 메틸에틸케톤을 적정비로 배합한 코팅액으로 코팅한 후, 원단(직물, 부직포, 기타원단)을 접착하여 접착제가 충분히 경화되도록 한 후, 이형지를 박리하여 합성피혁을 제조한다.In the dry method, polyurethane is used as a coating layer and an adhesive layer. A coating solution containing polyurethane, dimethylformamide, methyl ethyl ketone, and a pigment in an appropriate ratio is coated on at least one time on a release paper, and then the release paper is passed through a dryer to obtain a solvent. Volatilized to form a film, coated on top of it with a coating solution containing a polyurethane adhesive, a curing agent, a curing accelerator, dimethylformamide, and methyl ethyl ketone at an appropriate ratio, and then a fabric (woven fabric, nonwoven fabric, or other fabric) was adhered to After the adhesive is sufficiently cured, release paper is peeled to prepare synthetic leather.
습식법에서는 원단(부직포, 직물)을 폴리우레탄, 디메틸포름아미드 및 안료를 적정비로 배합한 함침액에 함침한 후, 상기 함침된 원단을 물 및 디메틸포름아미드가 혼합된 응고조에서 응고시킨 다음, 폴리우레탄, 디메틸포름아미드 및 안료를 적정비로 배합한 코팅액을 폴리우레탄이 함침된 원단에 코팅을 하고, 물 및 디메틸포름아미드가 혼합된 응고조에서 응고시키고, 수세조와 건조기를 통해 건조시킨 후, 여러가지 후가공(엠보싱, 버핑, 열처리, 처리 등)을 거쳐 합성피혁을 제조한다.In the wet method, the fabric (nonwoven fabric, fabric) is impregnated with an impregnation solution containing a mixture of polyurethane, dimethylformamide and pigment in an appropriate ratio, and then the impregnated fabric is solidified in a coagulation bath mixed with water and dimethylformamide, and then After coating the coating liquid containing urethane, dimethylformamide and pigment at an appropriate ratio, it is coated on the fabric impregnated with polyurethane, coagulated in a coagulation bath mixed with water and dimethylformamide, dried through a washing tank and a dryer, and then Synthetic leather is manufactured through post-processing (embossing, buffing, heat treatment, treatment, etc.).
그러나, 폴리우레탄을 이용하여 합성피혁을 제조하는 방법은 디메틸포름아미드나 메틸에틸케톤과 같은 유기용매가 사용되고, 온도에 따른 유연성의 변화로 저온 지방에서 사용될 때 합성피혁이 단단해지고 고온 지방에서 사용될 때는 너무 유연해져 온도에 따른 형태 안정성이 떨어지며, 120℃ 이상에서도 폴리우레탄은 열분해가 일어날 수 있어 고온에서 사용되는 분야에서 제약을 받게 되고, 물에 대한 내가수분해성이 약하며, 내오염성이 좋지 않아 특히 밝은 색깔의 경우 쉽게 오염되어 세탁을 자주 필요로 하는 단점이 있었다.
However, the method for producing synthetic leather using polyurethane is when organic solvents such as dimethylformamide and methyl ethyl ketone are used, and the synthetic leather becomes hard when used in low temperature fat due to the change of flexibility with temperature, and when used in high temperature fat. It is so flexible that its shape stability decreases with temperature. Polyurethane can be thermally decomposed at temperatures above 120 ° C, which is restricted in the fields used at high temperatures, and it is particularly bright due to its poor hydrolysis resistance to water and poor pollution resistance. Color was easily contaminated and had a disadvantage of requiring frequent washing.
본 발명의 목적은 폴리우레탄을 이용한 합성피혁의 단점을 극복하기 위하여 제조시 유해성이 없고 고온 및 저온에서 안정적이며, 방수성, 내열성, 절연성, 내가수분해성, 신율 및 항균성이 뛰어난 실리콘을 이용한 합성피혁의 제조방법을 제공하면서, 더불어 실리콘 코팅 표면에 다양한 무늬가 형성된 합성피혁의 제조방법을 제공하는데 있다.
The purpose of the present invention is to avoid the disadvantages of synthetic leather using polyurethane, it is not harmful during manufacture and is stable at high and low temperatures, the synthetic leather using a silicone having excellent waterproof, heat resistance, insulation, hydrolysis resistance, elongation and antibacterial properties In addition, while providing a manufacturing method, to provide a method of manufacturing a synthetic leather with a variety of patterns formed on the surface of the silicon coating.
본 발명의 무늬가 형성된 합성피혁의 제조방법은, 제1 원단에 부가형 액상 실리콘 고무의 코팅액을 1차로 코팅하여 가온 건조하여 경화시키는 단계; 상기 1차 경화된 제1 원단을 부가형 액상 실리콘 고무의 코팅액으로 2차 코팅하는 단계; 상기 2차 코팅된 제1 원단의 2차 코팅면과 제2 원단을 서로 합포시킨 다음, 가온 건조하여 경화시키는 단계; 및 상기 2차 코팅된 제1 원단과 합포된 제2 원단으로부터 제1 원단을 박리시키는 단계; 를 포함한다.The method of manufacturing a patterned synthetic leather of the present invention comprises the steps of first coating the coating liquid of the additive-type liquid silicone rubber on the first fabric by heating and drying; Second coating the first cured first fabric with a coating liquid of an additive liquid silicone rubber; Combining the secondary coated surface and the second fabric of the second coated first fabric with each other, and then curing by heating and drying; And peeling a first fabric from a second fabric overlapped with the second coated first fabric. It includes.
본 발명의 무늬가 형성된 합성피혁의 제조방법에서, 상기 제1 원단은 직물원단에 실리콘이 코팅된 이형원단인 것을 특징인 것을 특징으로 한다.In the method for manufacturing a patterned synthetic leather of the present invention, the first fabric is characterized in that the release fabric coated with silicon on the fabric fabric.
본 발명의 무늬가 형성된 합성피혁의 제조방법에서, 상기 직물원단에 실리콘이 코팅된 이형원단은 상기 실리콘 코팅과 직물원단 사이에 다수의 기공이 형성되어 있는 것을 특징으로 한다.In the method of manufacturing a patterned synthetic leather of the present invention, the release fabric coated with silicon on the fabric fabric is characterized in that a plurality of pores are formed between the silicon coating and the fabric fabric.
본 발명의 무늬가 형성된 합성피혁의 제조방법에서, 상기 제1 원단의 실리콘 코팅면에 그림 또는 무늬를 도트 프린트 하는 단계를 더 포함하는 것을 특징으로 한다.In the method of manufacturing a patterned synthetic leather of the present invention, it characterized in that it further comprises the step of printing a picture or pattern on the silicon coated surface of the first fabric.
본 발명의 무늬가 형성된 합성피혁의 제조방법은, 상기 제2 원단의 1차 코팅층에 그림 또는 무늬를 실리콘으로 도트 프린트 하는 단계를 더 포함하는 것을 특징으로 한다.The method of manufacturing a patterned synthetic leather of the present invention, characterized in that it further comprises the step of dot-printing a picture or pattern in silicon on the primary coating layer of the second fabric.
본 발명의 무늬가 형성된 합성피혁의 제조방법은, 상기 제2 원단의 1차 및 2차 코팅층이 형성된 반대면에 그림 또는 무늬를 실리콘으로 도트 프린트 하는 단계를 더 포함하는 것을 특징으로 한다.
The method of manufacturing a patterned synthetic leather of the present invention, characterized in that it further comprises the step of dot-printing the picture or pattern with silicon on the opposite side on which the primary and secondary coating layers of the second fabric is formed.
본 발명은 제조시 유해성이 없고 고온 및 저온에서 안정적이며, 방수성, 내열성, 절연성, 내가수분해성, 신율 및 항균성이 뛰어나면서 표면에 다양한 무늬가 형성된 합성피혁의 제조방법을 제공한다.
The present invention provides a manufacturing method of synthetic leather having various patterns formed on the surface while having no harmful effects in manufacturing and stable at high and low temperatures, and having excellent waterproofness, heat resistance, insulation, hydrolysis resistance, elongation and antibacterial properties.
도 1은 본 발명의 합성피혁의 제조방법의 하나의 실시예를 나타낸 개략적인 제조공정도이다.
도 2는 본 발명의 합성피혁의 제조방법의 하나의 실시예에서 제1 원단을 박리하기 전의 합성피혁의 구조를 나타낸 단면도이다.
도 3은 본 발명의 합성피혁의 제조방법의 하나의 실시예에서 제1 원단을 박리한 후의 합성피혁의 구조를 나타낸 단면도이다.
도 4는 본 발명의 합성피혁의 제조방법의 다른 하나의 실시예에서 1차 및 2차 코팅된 제1 원단과 제2 원단의 합포하기 전의 구조를 나타낸 단면도이다.
도 5는 본 발명의 합성피혁의 제조방법의 다른 하나의 실시예에서 1차 및 2차 코팅된 제1 원단과 제2 원단의 합포한 후의 구조를 나타낸 단면도이다.
도 6는 본 발명의 실시예1에 사용된 직물과 섬유의 전자주사현미경 사진이다.
도 7의 (a)는 본 발명의 실시예1에 사용된 실리콘 코팅층과 직물 사이에 기공이 형성된 이형원단의 전자주사현미경 사진, (b)는 (a)에서 직물 고유 무늬에서 표면으로 솟은 부분과 실리콘 코팅층의 접합면을 확대한 전자주사현미경 사진, (c)는 실시예 1보다 굵은 섬유로 직조된 직물에 실리콘 코팅층을 형성한 이형원단의 전자주사현미경 사진이다.
도 8은 본 발명의 실시예1에서 제조한 합성피혁의 표면 사진이다.
도 9는 본 발명의에서 제조한 합성피혁의 표면 사진이다.1 is a schematic manufacturing process diagram showing one embodiment of a method for manufacturing synthetic leather of the present invention.
Figure 2 is a cross-sectional view showing the structure of the synthetic leather before peeling the first fabric in one embodiment of the method for producing a synthetic leather of the present invention.
Figure 3 is a cross-sectional view showing the structure of the synthetic leather after peeling the first fabric in one embodiment of the method for producing a synthetic leather of the present invention.
Figure 4 is a cross-sectional view showing the structure before combining the primary and secondary coated first fabric and the second fabric in another embodiment of the manufacturing method of synthetic leather of the present invention.
Figure 5 is a cross-sectional view showing the structure after the combination of the first and second coated first fabric and the second fabric in another embodiment of the method for producing a synthetic leather of the present invention.
6 is an electron scanning micrograph of the fabric and fibers used in Example 1 of the present invention.
7 (a) is an electron scanning micrograph of a release fabric in which pores are formed between the silicon coating layer and the fabric used in Example 1 of the present invention, (b) is a portion that rises to the surface from the original pattern of the fabric in (a) and The electron scanning microscope photograph which enlarged the bonding surface of a silicone coating layer, (c) is the electron scanning microscope photograph of the release fabric which formed the silicone coating layer in the fabric woven with coarse fiber than Example 1.
8 is a surface photograph of the synthetic leather prepared in Example 1 of the present invention.
9 is a photograph of the surface of the synthetic leather produced in the present invention.
이하, 도면을 참조하여 본 발명의 무늬가 형성된 합성피혁의 제조방법을 상세하게 설명한다.Hereinafter, with reference to the drawings will be described in detail a method of manufacturing a patterned synthetic leather of the present invention.
본 발명의 무늬가 형성된 합성피혁의 제조방법은 도 1에 나타낸 바와 같이, 제1 원단(1)에 부가형 액상 실리콘 고무의 코팅액을 1차로 코팅(2)하여 가온 건조(3)하여 경화시키는 단계; 상기 1차 경화된 제1 원단을 부가형 액상 실리콘 고무의 코팅액으로 2차 코팅(4)하는 단계; 상기 2차 코팅된 제1 원단의 2차 코팅면과 제2 원단(5)을 서로 합포(6)시킨 다음, 가온 건조(7)하여 경화시키는 단계; 및 상기 2차 코팅된 제1 원단과 합포된 제2 원단으로부터 제1 원단(1)을 박리시키는 단계; 를 포함한다.The method of manufacturing a patterned synthetic leather of the present invention, as shown in Figure 1, the first coating (1) of the coating liquid of the additional type liquid silicone rubber on the first fabric (1) by heating and drying (3) to cure; Second coating (4) the first cured first fabric with a coating liquid of an additive liquid silicone rubber; Combining the secondary coated surface of the secondary coated first fabric and the second fabric (5) with each other (6), and then heating and drying (7) to cure; And peeling the first fabric (1) from the second fabric blended with the second coated first fabric; It includes.
본 발명의 합성피혁의 제조방법에서 제1 원단은 직물을 사용하는 것이 바람직하다. 부직포는 표면에 형성된 무늬에 요철이 거의 없고 또한 무늬를 일정하게 조절하는 것이 불가능하고, 편물의 경우에는 공극이 너무 커서 실리콘을 일정 두께로 코팅하는 것이 거의 불가능하거나 손실이 너무 많다. In the method of manufacturing synthetic leather of the present invention, it is preferable to use a fabric as the first fabric. The nonwoven fabric has little irregularities in the pattern formed on the surface and it is impossible to adjust the pattern uniformly, and in the case of the knitted fabric, the voids are so large that it is almost impossible to coat the silicon to a certain thickness or there is too much loss.
본 발명에 사용되는 제1 원단의 직물은 실리콘 코팅이 누수되지 않을 정도로 촘촘하게 짜여 있는 것으로 합성피혁의 1차 코팅층에 반영하려는 무늬를 고려하여 평직, 능직, 단직, 주자직 이나 이중직과 같은 어느 형태의 직물을 사용하는 것도 가능하다. 본 발명에서 무늬는 상기 직물 자체가 가지는 경사와 위사가 교차하는 고유의 무늬뿐만 아니라, 이러한 직물에 별도의 문양이나 그림이 양각 또는 음각으로 입체적으로 형성된 자카드 직물 등을 사용하는 것도 가능하다. The fabric of the first fabric used in the present invention is tightly woven so that the silicone coating does not leak, and in consideration of the pattern to be reflected in the primary coating layer of synthetic leather, any type such as plain weave, twill weave, single weave, runner weave or double weave It is also possible to use fabrics. In the present invention, the pattern is not only a unique pattern intersecting the warp and weft yarns of the fabric itself, it is also possible to use a jacquard fabric, such as a separate pattern or figure is three-dimensionally embossed or engraved on the fabric.
본 발명의 제1 원단의 직물에 사용되는 섬유로는 식물성과 동물성의 천연섬유, 합성섬유 및 이들을 혼합한 혼합섬유 어느 것이나 사용할 수 있다. 예를 들어 식물성 섬유로는 면, 아마, 대마 등을 사용할 수 있고, 동물성 섬유로는 양모, 알골라, 실크 등을 사용할 수 있으며, 합성섬유로는 아세테이트 섬유, 폴리아미드 섬유, 폴리에스테르섬유, 폴리아크릴로니트릴 섬유, 폴리우레탄 섬유, 폴리프로필렌 섬유, 폴리에틸렌 섬유, 폴리비닐알코올 섬유, 폴리플루오로에틸렌 섬유 등을 사용할 수 있다. 바람직하게는 내열성과 방염성이 뛰어난 폴리아미드 계열의 아라미드 섬유이고, 특히 페닐기가 메타 형태로 결합된 아라미드 섬유가 바람직하다. 상업적으로 활용가능한 페닐기가 메타 형태로 결합된 아라미드 섬유는 듀폰사의 Nomex 섬유가 있다.As the fiber used for the woven fabric of the first fabric of the present invention, any of vegetable and animal natural fibers, synthetic fibers, and mixed fibers thereof may be used. For example, cotton, flax, hemp, etc. may be used as the vegetable fiber, and wool, algola, silk, etc. may be used as the animal fiber, and acetate fiber, polyamide fiber, polyester fiber, poly may be used as the synthetic fiber. Acrylonitrile fiber, polyurethane fiber, polypropylene fiber, polyethylene fiber, polyvinyl alcohol fiber, polyfluoroethylene fiber and the like can be used. Preferably, it is a polyamide-based aramid fiber having excellent heat resistance and flame resistance, and particularly preferred is aramid fiber in which a phenyl group is bonded in a meta form. Aramid fibers in which a commercially available phenyl group is bound in a meta form is Dume's Nomex fiber.
본 발명의 제1 원단에 사용하는 직물에 사용되는 섬유의 두께는 120 ~ 3000 데니아, 바람직하게는 200 ~ 1800 데니아, 더욱 바람직하게는 300 ~ 1200 데이아인 것이다. 두께가 상기 상한치를 초과하면 섬유가 너무 가늘고, 또 이를 가지고 제직하면 경사나 위사의 피치(단위 길이당 실 수)가 높은 경우가 많아서 직물 자체의 고유 무늬의 표면으로 솟은 부분과 가라앉은 부분의 높이의 차가 적어 1차 코팅층으로 무늬의 전달이 어렵고, 상기 하한치 미만이면 섬유가 너무 두껍고, 이에 따라 섬유 사이의 공극이 너무 커져 제1 원단에 실리콘 코팅을 할 때 실리콘 코팅이 섬유 사이로 누수되는 양이 많고 직물 자체의 고유 무늬의 표면에서 가라앉은 부분까지 실리콘 코팅액으로 모두 채워지는 경우가 많아 무늬의 형성 및 전달에 불리하다. The thickness of the fiber used in the fabric used for the first fabric of the present invention is 120 to 3000 denier, preferably 200 to 1800 denier, more preferably 300 to 1200 deia. If the thickness exceeds the upper limit, the fibers are too thin, and if weaving with them, the pitch (weft per unit length) of the warp yarn or weft yarn is often high, so that the height of the raised part and the sinking part of the unique pattern surface of the fabric itself is high. It is difficult to transfer the pattern to the primary coating layer due to the small difference between the fibers. If the lower limit is less than the lower limit, the fibers are too thick, and thus the voids between the fibers become too large, so that the silicone coating leaks through the fibers when the first coating is coated with silicone. It is often disadvantageous for the formation and delivery of a pattern because the entire surface of the fabric itself is filled with the silicon coating liquid from the sunk surface.
본 발명의 제1 원단은 이형성을 가지도록 실리콘 코팅 처리된 것이 바람직하다. 실리콘 코팅 처리시 코팅에 의해 직물원단이 가지는 무늬가 본 발명의 1차 코팅에 직물 자체의 격자 무늬 또는 직물 위에 형성된 별도의 무늬가 전이될 수 있도록 실리콘 코팅은 20 ~ 200 ㎛ 두께인 것이 바람직하다. The first fabric of the present invention is preferably a silicone coating treatment to have a release property. The silicon coating is preferably 20 to 200 μm thick so that the pattern of the fabric fabric by the coating during the silicone coating process can be transferred to the primary coating of the present invention or a separate pattern formed on the fabric itself.
또한 본 발명의 제1 원단은 직물 조직을 단면에서 볼 때 아래로 가라않은 부분에 실리콘 코팅이 충진되지 않는 기공층(도 4의 13)이 형성되고, 직물 조직의 단면에서 위로 솟은 부분은 실리콘 코팅층과 연결되어 실리콘 코팅층 아래에 직물 자체 또는 직물에 형성된 별도의 무늬에 따른 촘촘한 기공이 형성되어 있는 실리콘이 코팅된 이형원단이 바람직하다. 이와 같은 형태의 실리콘 코팅된 이형원단은 이형원단 자체에 무늬는 선명하지 않지만 실리콘 코팅층 아래에 무늬에 따라 촘촘하게 형성된 기공층에 의해서, 이형원단 위의 1차 코팅층과 합포 공정에서 압착되어 직물 자체 또는 직물에 형성된 별도의 무늬가 1차 코팅층으로 선명하게 이행될 수 있다.In addition, the first fabric of the present invention is a pore layer (13 of FIG. 4) is not filled with the silicone coating is formed in the portion not cut down when viewed from the cross section of the fabric tissue, the portion of the top surface of the cross section of the fabric tissue is a silicone coating layer It is preferable that the release fabric coated with silicon in which the fine pores according to the separate pattern formed on the fabric itself or the fabric is connected under the silicon coating layer. This type of silicone-coated release fabric has a clear pattern on the release fabric itself, but is formed by a pore layer formed densely according to the pattern under the silicone coating layer, and is compressed in the laminating process with the primary coating layer on the release fabric. A separate pattern formed in the may be clearly transferred to the primary coating layer.
또한 상기 실리콘 코팅된 이형원단에 별도의 그림이나 무늬를 추가적으로 부여하기 위하여 그림이나 무늬를 도트 프린트 할 수 있다.In addition, it is possible to dot print the picture or pattern in order to add a separate picture or pattern to the silicone coated release fabric.
한편 상기 제1 원단과 달리 제2 원단은 합성피혁의 기재가 되는 것으로 부직포나 직포 어느 형태의 것이나 사용될 수 있으나, 합성피혁의 탄성과 신율을 높이기 위해서는 직물이 바람직하고, 직물로는 제1 원단에 사용되는 직물을 제한없이 사용할 수 있으며, 다만 제2 원단의 경우 별도로 실리콘 코팅 처리된 것을 사용하지 않는다.
On the other hand, unlike the first fabric, the second fabric is a base of the synthetic leather can be used in any form of non-woven fabric or woven fabric, but in order to increase the elasticity and elongation of the synthetic leather, the fabric is preferred, the fabric as the first fabric The fabric used can be used without limitation, but in case of the second fabric, a silicone coating is not used separately.
또한 본 발명의 합성피혁의 제조방법에서 1차 코팅 경화된 실리콘수지는 합성피혁의 외피가 되고, 2차 코팅은 상기 합성피혁의 외피와 제2 원단을 접착시킨다.In addition, in the manufacturing method of the synthetic leather of the present invention, the primary coating cured silicone resin becomes the outer skin of the synthetic leather, and the secondary coating bonds the outer skin of the synthetic leather and the second fabric.
상기 1차 코팅액의 코팅재로는 제반 물성에서 우수하고, 부산물이 발생하지 않는 부가형 액상 실리콘 고무를 사용하는 데, 이는 디메틸비닐 말단기를 갖는 실리콘 고무와 디메틸 말단기를 갖는 실리콘 고무를 포함하는 유동성 액체 실리콘으로서, 고온에서 백금 등의 촉매에 의하여 상기 디메틸비닐 말단의 이중결합이 라디칼로 생성되고, 디메틸 말단기와 부가반응하여 경화되어 실리콘수지가 형성된다.As the coating material of the primary coating solution, an additional liquid silicone rubber having excellent physical properties and no by-products is used, which is a fluid liquid including a silicone rubber having dimethylvinyl end groups and a silicone rubber having dimethyl end groups. As silicon, a double bond of the dimethylvinyl end is generated as a radical by a catalyst such as platinum at a high temperature, and is cured by addition reaction with a dimethyl end group to form a silicone resin.
상기 1차 코팅액에는 코팅액의 점도를 낮추어 코팅가공성을 증가시키고, 실리콘을 코팅재로 하여 합성피혁을 제조하는 경우 발생할 수 있는 합성피혁의 끈적거림을 감소시키기 위하여 실리콘 오일을 첨가할 수 있다. 이러한 실리콘 오일로는 일반적으로 헥사메틸디실록산, 옥타메틸트리실록산, 데카메틸테트라실록산, 옥타메틸시크로테트라실록산 등의 폴리디메틸실록산을 사용하며, 바람직하게는 상기 부가형 액상 실리콘 고무 100중량부에 대해 30중량부 이하를 첨가한다.The first coating liquid may be added to the silicone oil to reduce the viscosity of the coating liquid to increase the coating processability, and to reduce the stickiness of the synthetic leather that may occur when manufacturing the synthetic leather using the silicone as a coating material. As such silicone oils, polydimethylsiloxanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and octamethylcyclotetrasiloxane are generally used, and preferably 100 parts by weight of the addition liquid silicone rubber. 30 parts by weight or less are added.
또한 상기 1차 코팅액에는 상기 코팅액의 점도를 낮추어 코팅가공성을 증가시키기 위하여 실리콘용제를 첨가할 수 있는 데, 바람직하게는 상기 부가형 액상 실리콘 고무 100중량부에 대해 200중량부 이하의 실리콘용제를 첨가한다.In addition, a silicone solvent may be added to the primary coating liquid in order to lower the viscosity of the coating liquid to increase coating processability. Preferably, a silicon solvent of 200 parts by weight or less is added to 100 parts by weight of the additional liquid silicone rubber. .
또한 상기 1차 코팅액에는 합성피혁의 색상을 구현하기 위한 착색제로서 실리콘 안료를 첨가할 수 있는 데, 바람직하게는 상기 부가형 액상 실리콘 고무 100중량부에 대해 20중량부 이하의 실리콘 안료를 첨가한다.In addition, the first coating liquid may be added to the silicone pigment as a colorant for realizing the color of the synthetic leather, preferably 20 parts by weight or less of the silicone pigment is added to 100 parts by weight of the additional liquid silicone rubber.
상기 2차 코팅과정은 합성피혁의 외피가 되는 상기 1차 경화된 실리콘수지와 상기 제2 원단을 접착시키기 위하여 필요한 공정이다.The secondary coating process is a process necessary for bonding the primary cured silicone resin and the second fabric to be the outer skin of the synthetic leather.
상기 2차 코팅액은 상기 1차 코팅액과 마찬가지로 부가형 액상 실리콘 고무를 코팅재로 사용한다. 다만, 1차 코팅액과 다른 점은 상기 2차 코팅은 1차 경화된 실리콘수지와 제2 원단을 접착시키는 역할을 하므로 실리콘 용제 및 실리콘 오일을 첨가하지 않는다는 것이다. 실리콘 용제 또는 실리콘 오일이 첨가되게 되면 접착력이 감소되어 상기 1차 경화된 실리콘수지와 원단을 결합시키는 데 어려움이 발생한다.The secondary coating solution is an additional liquid silicone rubber as a coating material, similar to the primary coating solution. However, the difference from the primary coating solution is that the secondary coating serves to bond the first cured silicone resin and the second fabric so that the silicone solvent and the silicone oil are not added. When the silicone solvent or the silicone oil is added, the adhesive force is reduced, which causes difficulty in bonding the primary cured silicone resin and the fabric.
또한 상기 2차 코팅액에는 합성피혁의 색상을 구현하기 위한 착색제로서 실리콘 안료를 사용할 수 있는 데, 바람직하게는 30중량부 이하의 실리콘 안료를 첨가한다.In addition, the secondary coating solution may use a silicone pigment as a colorant for realizing the color of synthetic leather, preferably 30 parts by weight or less of the silicone pigment is added.
상기 도 1에 도시된 것과 같이 제1 원단(1)에 부가형 액상 실리콘 고무의 코팅액을 1차로 코팅(2)하여 건조기(3)로 이동시켜 80 내지 180℃에서 가온하게 되면, 메틸비닐기의 이중결합은 라디칼화되고 메틸 말단기와 라디칼 부가반응하여 반경화되어 실리콘수지가 생성되며, 상기 온도에 의해 실리콘 용제는 증발하게 된다. 상기 1차 경화된 제1 원단(1) 위에 다시 상기 부가형 액상 실리콘 고무를 코팅재로 하는 2차 코팅액(4)을 코팅하게 된다.As shown in FIG. 1, the coating solution of the additional liquid silicone rubber on the
상기 1차 및 2차 코팅을 위한 코팅법으로는 그라비아 코트법, 스프레이법, 에어 나이프법, 롤 코트법을 사용할 수 있고, 바람직하게는 대량생산의 연속공정에서 균일한 두께의 코팅을 형성할 수 있는 롤 코트법을 사용한다.As the coating method for the primary and secondary coatings, a gravure coating method, a spray method, an air knife method, a roll coating method may be used, and preferably, a coating having a uniform thickness may be formed in a continuous process of mass production. Roll coat method is used.
상기 1차 건조 온도가 80℃ 미만인 경우에는 건조가 불충분하며 건조 온도가 180℃ 초과인 경우에는 제1 원단에 변형이 생길 수 있으며 180℃ 이하에서 건조 및 경화시킬 때와 비교하여 성능면에서 유리한 점이 없을 뿐만 아니라, 에너지적인 면에서 비경제적이다.If the primary drying temperature is less than 80 ℃ drying is insufficient, if the drying temperature is more than 180 ℃ may cause deformation of the first fabric and has an advantage in terms of performance compared to when drying and curing below 180 ℃ Not only is it non-economical?
상기 2차 코팅된 제1 원단은 상기 합포공정(6)에서 제2 원단(5)와 합포된 후 건조기(7)로 이동하여 120 내지 160℃에서 부가반응하여 2차 경화되어 1차 경화된 실리콘수지와 상기 제2 원단은 접착된다. 이때 도 2 또는 4와 같은 제1 원단이 분리되기 전의 합성피혁이 제조되고, 이로부터 제1 원단을 박리시켜 도 3 또는 5와 같은 실리콘이 적용된 합성피혁이 제조된다. The second coated first fabric is combined with the second fabric (5) in the mixing process (6) and then moved to a dryer (7) to secondary reaction by secondary reaction at 120 to 160 ℃ the first cured silicone The resin and the second fabric are bonded. At this time, the synthetic leather before the first fabric is separated as shown in FIG. 2 or 4 is manufactured, and the synthetic leather is applied to the silicon as shown in FIG.
상기 2차 건조 온도가 120℃ 미만인 경우에는 1차 경화된 코팅층과 제2 원단의 접착이 불충분하며 건조 온도가 160℃ 초과인 경우에는 1차 경화된 코팅층 및 제2 원단에 변형이 생길 수 있다.If the secondary drying temperature is less than 120 ℃ the adhesion of the first cured coating layer and the second fabric is insufficient, if the drying temperature is more than 160 ℃ may cause deformation of the primary cured coating layer and the second fabric.
상기 제2 원단의 1차 코팅층에 별도의 그림 또는 무늬를 실리콘으로 도트 프린트 하여 다양한 형상과 무늬를 가지는 슬립(slip)성이 우수한 합성피혁을 제조할 수 있다.By printing a separate picture or pattern on the primary coating layer of the second fabric with silicon, a synthetic leather having excellent slip property having various shapes and patterns can be manufactured.
또한 상기 제2 원단의 1차 및 2차 코팅층이 형성된 반대면에 그림 또는 무늬를 실리콘으로 도트 프린트 하여 원단의 밀림을 방지할 수 있다.
In addition, it is possible to prevent the rolling of the fabric by dot-printing the picture or pattern with silicon on the opposite side on which the first and second coating layers of the second fabric are formed.
본 발명을 실시예를 통하여 본 발명을 보다 상세히 설명한다. 하기 실시예는 본 발명을 설명하기 위한 예시적인 것일 뿐 이에 의해 본 발명의 기술적 사상의 범위가 한정되는 것은 아니다.
The present invention will be described in more detail with reference to the following examples. The following examples are merely illustrative for the purpose of illustrating the present invention, and the scope of the technical spirit of the present invention is not limited thereto.
[실시예 1]Example 1
듀폰사의 아라미드 섬유(Nomex)로 직조한 직물(경사와 위사는 380 데니아)에 실리콘 코팅층을 형성한 실리콘 코팅 이형원단을 제조하였다. 주사전자현미경[Scanning Electron Microscope(SEM) ; JSM-5410, JEOL, Japan]을 이용하여 섬유의 표면을 관찰한 결과 섬유사의 굵기는 약 10 ㎛로 일정하고 조직은 치밀하였고(도 6), 코팅 단면을 관찰한 결과 일반 섬유에 비해 조직이 치밀하여 실리콘 코팅의 침투 깊이가 현저히 낮고, 실리콘 코팅층과 직물 사이에 기공이 형성되어 있음을 확인할 수 있었다(도 7의 (a)).A silicone coated release fabric was prepared in which a silicon coating layer was formed on a fabric woven with aramid fibers (Nomex) manufactured by DuPont. Scanning Electron Microscope (SEM); JSM-5410, JEOL, Japan] was used to observe the surface of the fiber, the thickness of the fiber yarn is constant to about 10 ㎛ and the structure is dense (Fig. 6), the coating cross section observed the tissue was dense compared to the general fiber As a result, the penetration depth of the silicone coating was remarkably low, and pores were formed between the silicone coating layer and the fabric (FIG. 7 (a)).
경도 60 Shore A, 인장강도 1740 psi, 인열강도 380 lbs/in, 신율 500 %인 부가형 액상 실리콘 100 중량부에 실리콘 안료 5 중량부를 첨가한 후 진공믹서기로 기포를 제거하여 제조한 코팅액을 상기 직물과 실리콘 코팅층 사이에 기공층이 형성된 실리콘 코팅 이형원단에 100g/㎡로 1차 코팅하고 130℃의 건조기에서 반경화시킨 후 다시 코팅액을 300g/㎡로 2차 코팅하고, 상기 2차 코팅면과 290g/㎡ 인 니들펀칭용 부직포를 합포시킨 후 120 내지 150℃의 건조기로 통과시켜 경화시켰다. 건조기를 빠져 나온 부직포로부터 상기 직물과 실리콘 코팅층 사이에 기공층이 형성된 실리콘 코팅 이형원단를 박리시켜 합성피혁을 제조하였다.The coating solution was prepared by adding 5 parts by weight of a silicone pigment to 100 parts by weight of an added liquid silicone having a hardness of 60 Shore A, a tensile strength of 1740 psi, a tear strength of 380 lbs / in, and an elongation of 500%. 100 g /
제조된 합성피혁의 표면(1차 코팅층)은 Nomex 섬유로 직조한 직물의 무늬가 그대로 형성되었음을 확인하였다(도 8).
The surface of the prepared synthetic leather (primary coating layer) was confirmed that the pattern of the fabric woven with Nomex fibers were formed as it is (Fig. 8).
[실시예 2][Example 2]
실시예 1의 합성피혁의 1차 코팅층과 제2 원단에 실리콘 코팅액을 도트 프린트한 합성피혁을 제조하였다.
Synthetic leather obtained by dot-printing a silicone coating solution on the first coating layer and the second fabric of the synthetic leather of Example 1 was prepared.
[비교예 1]Comparative Example 1
경사와 위사로 3500 데니아인 섬유로 직조한 직물에 실리콘 코팅층을 형성한 실리콘 코팅 이형원단을 제조한 것을 제외하고는 실시예1과 동일하게 합성피혁을 제조하였다. 제조된 합성피혁의 표면(1차 코팅층)은 무늬가 형성되지 않았음을 확인하였다(도 9).
Synthetic leather was prepared in the same manner as in Example 1 except that a silicone coated release fabric was formed on a fabric woven with 3500 denier fibers with warp and weft. The surface (primary coating layer) of the prepared synthetic leather was confirmed that no pattern is formed (Fig. 9).
[실험예 1][Experimental Example 1]
상기와 같이 제조된 실리콘 고무 합성피혁과 폴리우레탄 합성피혁(대조군)의 물성을 비교하여 다음 표 1에 나타내었다. 투습도는 ASTM E96-95 CaCl2, 38℃, 90% RH 조건에서 24시간 측정한 것이고, 마모도는 H-32 M/C방법으로, 내수도는 ISO 811법으로 측정하였다.Table 1 compares the physical properties of the silicone rubber synthetic leather and polyurethane synthetic leather (control) prepared as described above. Moisture permeability was measured in ASTM E96-95 CaCl2, 38 ℃, 90% RH conditions for 24 hours, wear was measured by the H-32 M / C method, water resistance was measured by the ISO 811 method.
상기 표 1에 보이는 바와 같이, 본 실시예에 따라 제조된 합성피혁은 투습도, 마모도, 내가수분해, 내황변, 굴곡성 등에서 합성피혁에 요구되는 물성을 가지는 것으로 나타났고, 대조군의 폴리우레탄 합성피혁과 비교하여서도 동등한 물성을 가지는 것으로 나타났다.
As shown in Table 1, the synthetic leather prepared according to the present embodiment was found to have the physical properties required for synthetic leather in moisture permeability, wear, hydrolysis, yellowing resistance, flexibility, etc., and the polyurethane synthetic leather of the control It was shown to have the same physical properties in comparison.
1: 제1 원단 2: 1차 코팅
3: 1차 건조 4: 2차 코팅
5: 제2 원단 6: 합포
7: 2차 건조 8: 박리
9: 합성피혁
11: 제1 원단의 실리콘 코팅층 12: 제1 원단의 직물
13: 제1 원단의 기공1: first fabric 2: primary coating
3: primary drying 4: secondary coating
5: second fabric 6: fabric
7: secondary drying 8: peeling
9: synthetic leather
11: silicone coating layer of first fabric 12: fabric of first fabric
13: pore of the first fabric
Claims (6)
First coating the coating liquid of the additional liquid silicone rubber on the first fabric and curing by heating and drying; Second coating the first cured first fabric with a coating liquid of an additive liquid silicone rubber; Combining the secondary coated surface and the second fabric of the second coated first fabric with each other, and then curing by heating and drying; And peeling a first fabric from a second fabric overlapped with the second coated first fabric. Method of producing a patterned synthetic leather comprising a.
The method of claim 1, wherein the first fabric is a release fabric coated with silicon on a fabric fabric.
The method of claim 2, wherein the release fabric coated with silicon on the fabric fabric is a plurality of pores are formed between the silicon coating and the fabric fabric.
The method of claim 2, further comprising dot printing a picture or a pattern on the silicon coated surface of the first fabric.
The method of claim 1, further comprising the step of dot-printing a picture or pattern in silicon on the primary coating layer of the second fabric.
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| KR101381027B1 (en) | 2013-05-16 | 2014-04-10 | 이영애 | Flame-retardant artificial leather material |
| KR101573630B1 (en) | 2014-09-23 | 2015-12-01 | 김미숙 | Apparatus and method for painting leather haviing hybrid painting type |
| KR20160140136A (en) | 2015-05-29 | 2016-12-07 | 주식회사 노비아레텍 | Method of manufacturing the excellent leather stain resistance |
| KR101823758B1 (en) | 2016-05-04 | 2018-02-09 | 주식회사 비에스테크놀러지 | Synthetic leather having stain resistance and the preparation method thereof |
| KR101955243B1 (en) * | 2018-08-16 | 2019-03-08 | 윤주섭 | Mehtod for manufacturing silicon synthetic leather and silicon synthetic leather manufactured by the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101381027B1 (en) | 2013-05-16 | 2014-04-10 | 이영애 | Flame-retardant artificial leather material |
| KR101573630B1 (en) | 2014-09-23 | 2015-12-01 | 김미숙 | Apparatus and method for painting leather haviing hybrid painting type |
| KR20160140136A (en) | 2015-05-29 | 2016-12-07 | 주식회사 노비아레텍 | Method of manufacturing the excellent leather stain resistance |
| KR101823758B1 (en) | 2016-05-04 | 2018-02-09 | 주식회사 비에스테크놀러지 | Synthetic leather having stain resistance and the preparation method thereof |
| KR101955243B1 (en) * | 2018-08-16 | 2019-03-08 | 윤주섭 | Mehtod for manufacturing silicon synthetic leather and silicon synthetic leather manufactured by the same |
| KR102083631B1 (en) * | 2018-08-22 | 2020-03-02 | 주식회사 제일화성 | The laminated vinyl film made of synthetic leather and manufacturing method thereof |
| KR20210134451A (en) * | 2020-05-01 | 2021-11-10 | 주식회사 케이엘투 | Sunroof blinds with excellent low temperature stability, heat aging resistance and light resistance using silicone rubber |
| KR102324355B1 (en) | 2020-05-01 | 2021-11-11 | 주식회사 케이엘투 | Sunroof blinds with excellent low temperature stability, heat aging resistance and light resistance using silicone rubber and method for producing the same |
| KR102274694B1 (en) | 2020-10-08 | 2021-07-09 | 주식회사 서연이화 | Multi-layer composite material for covering variable protruding switch and its manufacturing method |
| KR102290449B1 (en) * | 2021-05-06 | 2021-08-19 | 주식회사 케이엘투 | Fabrics having excellent wear resistance keeping concave and convex pattern and method for producing the same |
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