WO2017119798A2 - Method for manufacturing artificial leather - Google Patents
Method for manufacturing artificial leather Download PDFInfo
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- WO2017119798A2 WO2017119798A2 PCT/KR2017/000284 KR2017000284W WO2017119798A2 WO 2017119798 A2 WO2017119798 A2 WO 2017119798A2 KR 2017000284 W KR2017000284 W KR 2017000284W WO 2017119798 A2 WO2017119798 A2 WO 2017119798A2
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- WIPO (PCT)
- Prior art keywords
- artificial leather
- solvent
- based resin
- manufacturing
- urethane
- Prior art date
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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
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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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
- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Definitions
- the present invention relates to a method of manufacturing artificial leather.
- Artificial leather is widely used as a material that can replace natural leather with the development of technology related to fibers and polymers. Artificial leather has been adopted in various fields because it can provide flexibility and extensibility not expected from natural leather.
- An object of the present invention is to provide a method for producing artificial leather having excellent physical properties through an environmentally friendly manner.
- the present invention can adopt one of the group consisting of a solventless urethane resin, a latex material, an aqueous urethane resin, and a mixture thereof as the polymer elastic body.
- Solvent-free urethane-based resin is impregnated in a nonwoven felt (S210), it is heat-cured for 72 to 96 hours at room temperature or 20 ⁇ 80 °C can be produced as a post-dissolution artificial leather.
- the impregnating cloth is a step of impregnating the impregnated cloth in a mixed liquid of silica aerosol and water; Drying and washing; And removing the silica powder.
- the impregnation cloth may further include a step (S220) of impregnating a latex or an aqueous urethane-based resin.
- the solvent contains an aqueous alkali solution, wherein the aqueous alkali solution preferably consists of a dilute sodium hydroxide aqueous solution, and particularly consists of a 10% aqueous sodium hydroxide solution.
- the post-elute foam of the present invention further comprises the step (S400) of applying an adhesive layer on its surface.
- nubuck-type artificial leather After elution can be produced nubuck-type artificial leather through the curing step (S410) and surface treatment step (S420) of the adhesive layer.
- the present invention comprises the steps of preparing a release paper formed a variety of embossed pattern and applying a skin-based urethane resin on the release paper (S500); After applying the adhesive layer and the step of combining the release paper coated with the urethane-based resin for the skin (S600); and can further include artificial leather formed a variety of patterns and patterns on the skin layer.
- the back side of the post-containing cloth may further include a step (S800) of applying a solvent-free urethane-based resin.
- the artificial leather may further include the step (S900) of applying a flame retardant on the surface or the back.
- the present invention can be produced in an environmentally friendly leather by excluding the use of volatile organic solvents.
- the present invention will be able to obtain an artificial leather that provides excellent elasticity, compressibility, volume, and durability than natural leather through the artificial leather formed with a microporous layer.
- the present invention can produce a post-dissolution artificial leather, nubuck artificial leather, and skin type artificial leather with various pattern patterns according to the user's purpose and taste through a series of manufacturing methods.
- FIG. 1 is a process flow chart according to the manufacturing method of artificial leather according to a preferred embodiment of the present invention.
- FIG. 1 is a process flow chart according to the manufacturing method of artificial leather according to a preferred embodiment of the present invention.
- the present invention is to produce an artificial leather using a microfiber nonwoven fabric, not only can provide a surface granularity and texture similar to natural leather, but also provide an environmentally friendly artificial leather without using a volatile organic solvent during the manufacturing process.
- the present invention includes the step (S100) of supplying the nonwoven felt.
- the supplying step (S100) of the nonwoven fabric felt includes preparing a island-in-the-sea fiber (S110), and preparing a nonwoven fabric felt (S120) using the island-in-the-sea fiber.
- the manufacturing step (S110) of the island-in-the-sea fiber described above is a composite spinning of the first polymer of island component remaining in the solvent and the second polymer of sea component dissolved in the solvent and eluted. Through it can provide a thin island.
- the island-in-the-sea yarn is a kind of composite yarn composed of two polymers having different solubility in solvent as described above.
- the first polymer may be made of polyester or nylon that is not soluble in an alkaline solvent, and is not limited thereto, and may be sufficiently substituted with a polymer elastomer that is not soluble in an alkali solvent.
- the second polymer prevents breakage or detachment of the first polymer during the island-in-the-sea yarn manufacturing process, it is possible to employ a polyester which is easily decomposed in an aqueous alkali solution.
- the island-in-the-sea fibers can be composed of 70 wt% of the first polymer and 30 wt% of the second polymer.
- the island-in-the-sea yarn in the staple state may form a web through a carding process or the like, and stack the web to manufacture a nonwoven felt (also known as nonwoven fabric) through a needle punch (S120).
- a nonwoven felt also known as nonwoven fabric
- S120 needle punch
- the present invention produces the impregnated fabric through the step (S200) of impregnating the polymer elastic body in the prefabricated nonwoven felt.
- the polymer elastomer is able to provide a dense and uniform porous shape while being filled in the three-dimensional fall-out nonwoven fabric.
- the polymer elastomer may be selected from the group consisting of solvent-free urethane resins, latex materials, aqueous urethane resins, and mixtures thereof, depending on the intended use.
- the nonwoven felt is impregnated with a solvent-free urethane-based resin (S210) and cured for about 72 hours to 96 hours (about 3 days) at room temperature or 20 to 80 ° C.
- Solvent-free urethane-based resin not only strengthens the binding force between nonwoven fabric felts while crosslinking nonwoven fabrics in three dimensions, but also voids where polymer elastomers do not penetrate remain after artificial leather to form a better texture and elasticity of urethane's inherent properties. And durability such as flexibility can be provided to the impregnated fabric.
- the impregnated fabric hardened not only provides a texture of tackyness (stickiness) but also helps to form a coating layer in a later step (S400). Impregnation of the urethane-based resin and the impregnated cloth provides a peeling phenomenon and cannot be marketed as the impregnated cloth itself without further processing.
- the present invention further performs the following process to complement the tackiness to the impregnated cloth cured through the solvent-free urethane-based resin impregnation step (S210). First, the impregnated cloth is impregnated with a mixed solution of silica aerosol and water and dried. After drying, the impregnated cloth is washed with water to remove silica powder.
- the present invention may be impregnated with SBR-based latex, NBR-based latex, CR-based latex in the nonwoven felt of step (S120) or impregnated fabric of step (S210) (S220).
- the latex provides the elasticity of the impregnated cloth and at the same time provides the advantage of maintaining the manufacturing cost.
- Step S220 may be impregnated with an aqueous urethane-based resin (aka 73) in addition to the above-described latex according to the quality of the finished product.
- an aqueous urethane-based resin aka 73
- the tackiness may be completely removed by impregnating the latex or aqueous urethane-based resin of step (S220).
- the impregnated cloth passed through step (S220) allows the water component contained in the aqueous urethane-based resin and the slippery oil component contained in the solvent-free urethane-based resin to be mixed without a surfactant to ensure a reliable adhesion state. This can maintain a firm bond between the nonwoven felt and the impregnated aqueous urethane-based resin of step (S220) and the film-forming aqueous urethane-based resin of step (S400).
- the present invention can provide a property that is not easily torn with a soft texture, such as natural leather by the water component and the oil component through the impregnation step (S200) of the polymer elastomer.
- the present invention can be provided with excellent moisture permeability and breathability than natural leather by forming a fine hole through the drying process of the aqueous component through the aqueous chemical impregnation method rather than the conventional laminating method.
- the present invention includes an elution step (S300) for removing soluble components with a solvent, especially an aqueous alkali solution.
- the impregnated fabric may be reacted with a solvent to elute or decompose and remove the second polymer as a soluble component to produce a post-eluted foam.
- a void is formed between the nonwoven felt and the polymer elastomer by using a volatile organic solvent such as dimethylformamide.
- a volatile organic solvent such as dimethylformamide.
- the present invention can produce artificial leather in an environmentally friendly process that can significantly reduce wastewater and air pollution by using an aqueous alkali solution as a solvent without using dimethylformamide.
- the present invention employs, for example, about 10% aqueous sodium hydroxide solution as a solvent, and the impregnated cloth is immersed in the aqueous sodium hydroxide solution to remove the second polymer.
- a dilute solution of sodium hydroxide provides the advantage of not damaging the polymeric elastomer and voids while eluting the second polymer.
- the solvent elutes only the second polymer, leaving only polyester or nylon and a polymer elastomer (solvent-free urethane resin and / or latex).
- the present invention is to produce the eluent after eluting the sea component and forming a microporous layer by micronized the nonwoven felt felt.
- the present invention is dried after removing the component to be eluted. Then, the post-exposure blister can be marketed as an artificial leather by a series of surface treatments such as dyeing, smoothing, polishing, buffing, sanding, and the like.
- the present invention includes a step (S400) of applying an adhesive layer to the post-elut foam obtained in step (S300).
- the adhesive layer may be laminated or impregnated by applying an adhesive synthetic resin, such as an aqueous urethane-based resin, on the cured surface of the post elution cloth.
- the adhesive layer may be evenly applied to the entire surface of the post-treatment foam or may be partially patterned and applied as necessary.
- the portion where the adhesive layer is not applied may form an napped portion made of ultrafine fibers.
- the present invention completely cures the adhesive layer applied to the surface of the post-dissolution foam through a process such as drying (S410).
- the surface of the post-exposure foam forms a coating layer formed by curing the adhesive layer.
- the coating layer forms a soft and soft surface touch, surface abrasion resistance, and three-dimensional feeling on the surface to produce nubuck artificial leather. do.
- the artificial leather drying the adhesive layer of the post-exposure foam can provide a nubuck-type artificial leather expressing a different unevenness and differentiation from the post-dissolution type artificial leather through the surface treatment step (S420) such as sanding.
- the present invention is characterized in that it is possible to produce artificial leather with a pattern such as embossing on the surface of the post-treatment bubble.
- the present invention includes a step (S500) to prepare a release paper on which the embossed pattern is formed.
- Release paper forms a variety of patterned patterns as described above, on which the urethane-based resin for skin (skin) is applied and cured.
- the urethane-based resin for skin forms a skin layer that matches the embossed shape of the release paper.
- the urethane-based resin for skin may be an aqueous urethane-based resin.
- the present invention includes the step (S600) of laminating the pattern transfer paper (S500) on the elution foam (S400) after applying the adhesive layer.
- the skin-based urethane-based resin applied to the release paper is placed on the adhesive layer applied on the surface of the post-expanded foam, and then laminated.
- the release paper is peeled off (S700) and the skin layer cured to the embossed shape of the release paper is combined with the post-treatment bubble to laminate the skin layer on the surface of the post-treatment bubble.
- the skin layer is fixed in a stacked state by means of an adhesive layer applied / impregnated on the surface of the post-treatment bubble.
- the skin layer and the post-explosion bubble may be pressed through a roller to simultaneously strengthen the cohesion of the adhesive layer and planarize the artificial leather.
- Artificial leather coated with a skin layer can provide fine and sophisticated patterns and patterns on the surface of artificial skin by release paper.
- the present invention may be applied and / or impregnated with the solvent-free urethane resin on the back surface of the post-expanded foam according to the use purpose (S800). Since the surface of the post-exposure bubble is coated and / or impregnated with an adhesive layer through step S400, impregnating a solvent-free urethane resin on the back surface may impart surface wear resistance and elasticity.
- the present invention may further include the step (S900) of applying a flame retardant to the surface and / or back of the post-dissolution artificial leather or nubuck artificial leather.
- the flame retardant is to be fixed on the surface of the skin layer of the artificial leather or on the opposite back thereof, it should be able to retain the volume and soft touch of the artificial leather even when the flame retardant is fixed.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Description
본 발명은 인공피혁의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing artificial leather.
인공피혁은 섬유와 고분자에 관한 기술이 발전하면서 천연피혁을 대체할 수 있는 소재로 널리 사용되고 있다. 인공피혁은 천연피혁에서 기대할 수 없는 유연성과 신장성을 제공할 수 있기에 다양한 분야에서 채택되고 있다.Artificial leather is widely used as a material that can replace natural leather with the development of technology related to fibers and polymers. Artificial leather has been adopted in various fields because it can provide flexibility and extensibility not expected from natural leather.
인공피혁은 저렴한 가격의 재질로 만들어진 부직포를 통해 안정화되고 고밀도 구조를 갖도록 제작되어야 하는데, 특허문헌 1(대한민국 특허등록번호 제10-0963147호)에서는 유기용제에 부직포를 함침하여 유기용제 함유 부직포를 제작하고 이를 유연제 수용액의 전처리를 통해 섬유 거동을 용이하게 완화시켜 유기 용제를 휘발시켜 제작하는 방법을 제안하고 있다.Artificial leather should be manufactured to have a stable and high-density structure through a non-woven fabric made of a low-cost material, Patent Document 1 (Korean Patent Registration No. 10-0963147) impregnated the organic solvent with a non-woven fabric to produce an organic solvent-containing nonwoven fabric And it is proposed a method to volatilize the organic solvent by easily alleviating the fiber behavior through the pretreatment of the aqueous solution of the softener.
종래기술에 따른 인공피혁은 휘발성 유기 용제를 사용하고 있어 배출된 유기 용제는 대기오염원으로서 확실한 포획과정을 수반해야 할 것이다.Artificial leather according to the prior art uses a volatile organic solvent, so the organic solvent discharged must be accompanied by a certain capture process as an air pollution source.
본 발명은 친환경적 방식을 통해 우수한 물성을 갖는 인공피혁을 제조하는 방법을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a method for producing artificial leather having excellent physical properties through an environmentally friendly manner.
상기 목적을 달성하기 위해서, 본 발명의 바람직한 실시예에 따른 인공피혁의 제조방법은, In order to achieve the above object, the manufacturing method of artificial leather according to a preferred embodiment of the present invention,
용제에 용해되지 않는 제1 폴리머와 용제에 용해되어 용출되는 제2 폴리머로 구성된 복합사를 통해 부직포 펠트를 공급하는 단계(S100)와;Supplying a nonwoven felt through a composite yarn composed of a first polymer not dissolved in the solvent and a second polymer dissolved and dissolved in the solvent (S100);
부직포 펠트에 고분자 탄성체를 함침하여 함침포를 제조하는 단계(S200); 및Preparing an impregnated fabric by impregnating a polymer elastic body in a nonwoven fabric felt (S200); And
함침포에서 제2 폴리머를 후용출하는 단계(S300);를 통해 후용출포를 생산할 수 있다.After elution of the second polymer in the impregnated cloth (S300); through the eluted foam can be produced.
특별하기로, 본 발명은 무용제 우레탄계 수지, 라텍스 소재, 수성 우레탄계 수지 및 이들의 혼합물로 구성되는 그룹 중 하나를 고분자 탄성체로서 채택할 수 있다. Specifically, the present invention can adopt one of the group consisting of a solventless urethane resin, a latex material, an aqueous urethane resin, and a mixture thereof as the polymer elastic body.
무용제 우레탄계 수지는 부직포 펠트에 함침(S210)되고, 상온 혹은 20~80℃ 하에서 72시간 내지 96시간 동안 열경화되어 후용출 인공피혁으로 제작될 수 있다.Solvent-free urethane-based resin is impregnated in a nonwoven felt (S210), it is heat-cured for 72 to 96 hours at room temperature or 20 ~ 80 ℃ can be produced as a post-dissolution artificial leather.
무용제 우레탄계 수지를 함침하는 단계(S210) 이후에, 함침포는 함침포를 실리카 에어로졸과 물을 교반한 혼합액에 함침하는 단계와; 건조 및 세수하는 단계; 및 실리카 분말을 제거하는 단계;를 추가로 포함할 수 있다. After impregnating the solvent-free urethane-based resin (S210), the impregnating cloth is a step of impregnating the impregnated cloth in a mixed liquid of silica aerosol and water; Drying and washing; And removing the silica powder.
무용제 우레탄계 수지를 함침하는 단계(S210) 이후에, 함침포는 라텍스 또는 수성 우레탄계 수지를 함침하는 단계(S220)를 추가로 포함할 수 있다. After impregnating the solvent-free urethane-based resin (S210), the impregnation cloth may further include a step (S220) of impregnating a latex or an aqueous urethane-based resin.
용제는 알칼리 수용액을 포함하고, 여기서 알칼리 수용액은 묽은 수산화나트륨 수용액으로 이루어지는 것이 바람직하며, 특히 10% 수산화나트륨 수용액으로 이루어져 있다.The solvent contains an aqueous alkali solution, wherein the aqueous alkali solution preferably consists of a dilute sodium hydroxide aqueous solution, and particularly consists of a 10% aqueous sodium hydroxide solution.
후용출 단계(S300) 이후에, 본 발명의 후용출포는 이의 표면상에 접착층을 도포하는 단계(S400)를 추가로 포함한다. After the post-dissolution step (S300), the post-elute foam of the present invention further comprises the step (S400) of applying an adhesive layer on its surface.
후용출포는 접착층의 경화 단계(S410)와 표면 처리 단계(S420)를 통해 누벅형 인공피혁을 제작할 수 있다.After elution can be produced nubuck-type artificial leather through the curing step (S410) and surface treatment step (S420) of the adhesive layer.
이와 달리, 본 발명은 다양한 엠보싱 무늬를 형성한 이형지를 준비하고 이형지 상에 스킨용 우레탄계 수지를 도포하는 단계(S500)와; 접착층을 도포한 후용출포와 스킨용 우레탄계 수지를 도포한 이형지를 합포하는 단계(S600);를 추가로 포함하여 스킨층에 다양한 무늬와 패턴을 형성한 인공피혁을 제조할 수 있다.On the contrary, the present invention comprises the steps of preparing a release paper formed a variety of embossed pattern and applying a skin-based urethane resin on the release paper (S500); After applying the adhesive layer and the step of combining the release paper coated with the urethane-based resin for the skin (S600); and can further include artificial leather formed a variety of patterns and patterns on the skin layer.
선택가능하기로, 후출용포의 이면에는 무용제 우레탄계 수지를 도포하는 단계(S800)를 추가로 포함할 수 있다.Optionally, the back side of the post-containing cloth may further include a step (S800) of applying a solvent-free urethane-based resin.
또한, 인공피혁은 표면 또는 이면에 난연제를 도포하는 단계(S900)를 추가로 포함할 수도 있다.In addition, the artificial leather may further include the step (S900) of applying a flame retardant on the surface or the back.
본 발명의 특징 및 이점들은 첨부도면에 의거한 다음의 상세한 설명으로 더욱 명백해질 것이다.The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.
이에 앞서 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이고 사전적인 의미로 해석되어서는 아니 되며, 발명자가 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합되는 의미와 개념으로 해석되어야만 한다. Prior to this, the terms or words used in this specification and claims are not to be interpreted in a conventional and dictionary sense, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
이상 본 발명의 설명에 의하면, 본 발명은 휘발성 유기 용제의 사용을 배제하여 친환경적으로 인공피혁을 제조할 수 있다.According to the description of the present invention, the present invention can be produced in an environmentally friendly leather by excluding the use of volatile organic solvents.
또한, 본 발명은 미세다공층을 형성한 인공피혁을 통해 천연피혁보다 우수한 신축성과, 압축성, 볼륨감, 및 내구성을 제공하는 인공피혁을 획득할 수 있을 것이다. In addition, the present invention will be able to obtain an artificial leather that provides excellent elasticity, compressibility, volume, and durability than natural leather through the artificial leather formed with a microporous layer.
특별하기로, 본 발명은 사용자의 사용 목적과 취향에 따라 후용출 인공피혁, 누벅형 인공피혁, 및 다양한 무늬패턴을 갖춘 스킨형 인공피혁을 일련의 제조방법을 통해 생산해 낼 수 있다.In particular, the present invention can produce a post-dissolution artificial leather, nubuck artificial leather, and skin type artificial leather with various pattern patterns according to the user's purpose and taste through a series of manufacturing methods.
도 1은 본 발명의 바람직한 실시예에 따른 인공피혁의 제조방법에 따른 공정 순서도이다.1 is a process flow chart according to the manufacturing method of artificial leather according to a preferred embodiment of the present invention.
본 발명의 목적, 특정한 장점들 및 신규한 특징들은 첨부된 도면들과 연관되어지는 이하의 상세한 설명과 실시예들로부터 더욱 명백해질 것이다. 본 명세서에서 각 도면의 구성요소들에 참조번호를 부가함에 있어서, 동일한 구성 요소들에 한해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 번호를 가지도록 하고 있음에 유의하여야 한다. 또한, 본 발명을 설명함에 있어서, 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우 그 상세한 설명은 생략한다. 본 명세서에서, 제1, 제2 등의 용어는 하나의 구성요소를 다른 구성요소로부터 구별하기 위해 사용되는 것으로, 구성요소가 상기 용어들에 의해 제한되는 것은 아니다. 첨부 도면에 있어서, 일부 구성요소는 과장되거나 생략되거나 또는 개략적으로 도시되었으며, 각 구성요소의 크기는 실제 크기를 전적으로 반영하는 것은 아니다.The objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and embodiments associated with the accompanying drawings. In the present specification, in adding reference numerals to the components of each drawing, it should be noted that the same components as possible, even if displayed on different drawings have the same number as possible. In addition, in describing the present invention, if it is determined that the detailed description of the related known technology may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. In this specification, terms such as first and second are used to distinguish one component from another component, and a component is not limited by the terms. In the accompanying drawings, some components are exaggerated, omitted, or schematically illustrated, and the size of each component does not fully reflect the actual size.
이하, 첨부된 도면을 참조하여 본 발명의 실시예를 상세히 설명하기로 한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명의 바람직한 실시예에 따른 인공피혁의 제조방법에 따른 공정순서도이다. 1 is a process flow chart according to the manufacturing method of artificial leather according to a preferred embodiment of the present invention.
본 발명은 초극세사 부직포를 이용한 인공피혁을 제조하는 것으로, 천연가죽과 유사한 표면 입도와 감촉을 제공할 수 있을 뿐만 아니라 제조과정중 휘발성 유기 용제를 사용하지 않아 친환경적 인공피혁을 제공할 수 있다.The present invention is to produce an artificial leather using a microfiber nonwoven fabric, not only can provide a surface granularity and texture similar to natural leather, but also provide an environmentally friendly artificial leather without using a volatile organic solvent during the manufacturing process.
우선적으로, 본 발명은 부직포 펠트를 공급하는 단계(S100)를 포함한다. 부직포 펠트의 공급 단계(S100)는 해도형 섬유를 제조하는 단계(S110)와, 해도형 섬유를 이용하여 부직포 펠트의 제조 단계(S120)를 포함한다.Firstly, the present invention includes the step (S100) of supplying the nonwoven felt. The supplying step (S100) of the nonwoven fabric felt includes preparing a island-in-the-sea fiber (S110), and preparing a nonwoven fabric felt (S120) using the island-in-the-sea fiber.
기술된 해도(海島)형 섬유의 제조단계(S110)는 용제에 용해되지 않고 남아 있는 도(島)성분의 제1 폴리머와 용제에 용해되어 용출되는 해(海)성분의 제2 폴리머를 복합방사를 통해 얇은 해도사를 제공할 수 있다. 해도사는 전술된 바와 같이 용매에 대한 용해성이 다른 2종의 폴리머로 구성된 복합사의 일종이다.The manufacturing step (S110) of the island-in-the-sea fiber described above is a composite spinning of the first polymer of island component remaining in the solvent and the second polymer of sea component dissolved in the solvent and eluted. Through it can provide a thin island. The island-in-the-sea yarn is a kind of composite yarn composed of two polymers having different solubility in solvent as described above.
구체적으로, 제1 폴리머는 알칼리 용제에 용해되지 않는 폴리에스테르 또는 나일론 등으로 이루어질 수 있으며, 이에 국한되지 않고 알칼리 용제에 용해되지 않는 고분자 탄성체로도 충분히 대체가능하다. Specifically, the first polymer may be made of polyester or nylon that is not soluble in an alkaline solvent, and is not limited thereto, and may be sufficiently substituted with a polymer elastomer that is not soluble in an alkali solvent.
제2 폴리머는 해도사 제조공정 도중에 제1 폴리머의 파손이나 이탈을 방지하는데, 알칼리 수용액에 쉽게 분해되는 폴리에스테르를 채용할 수 있다.Although the second polymer prevents breakage or detachment of the first polymer during the island-in-the-sea yarn manufacturing process, it is possible to employ a polyester which is easily decomposed in an aqueous alkali solution.
선택가능하기로, 해도형 섬유는 70 wt%의 제1 폴리머와 30 wt%의 제2 폴리머로 조성될 수 있다.Optionally, the island-in-the-sea fibers can be composed of 70 wt% of the first polymer and 30 wt% of the second polymer.
스테이플 상태의 해도사는 카딩 공정 등을 통해 웹(web)을 형성하고서 웹을 적층시켜 니들 펀치를 통해 부직포 펠트(일명 부직포 생지)를 제조할 수 있다(S120).The island-in-the-sea yarn in the staple state may form a web through a carding process or the like, and stack the web to manufacture a nonwoven felt (also known as nonwoven fabric) through a needle punch (S120).
전술되었듯이, 본 발명은 기 제작된 부직포 펠트에 고분자 탄성체를 함침하는 단계(S200)를 거쳐 함침포를 제작한다. 고분자 탄성체는 3차원 낙합 부직포의 내부에 충전되면서 치밀하고 균일한 다공질 형상을 제공할 수 있게 된다. As described above, the present invention produces the impregnated fabric through the step (S200) of impregnating the polymer elastic body in the prefabricated nonwoven felt. The polymer elastomer is able to provide a dense and uniform porous shape while being filled in the three-dimensional fall-out nonwoven fabric.
고분자 탄성체는 목적 용도에 따라 무용제 우레탄계 수지, 라텍스(latex) 소재, 수성 우레탄계 수지 및 이들의 혼합물로 구성된 그룹 중 하나를 선택할 수 있다. The polymer elastomer may be selected from the group consisting of solvent-free urethane resins, latex materials, aqueous urethane resins, and mixtures thereof, depending on the intended use.
부직포 펠트가 무용제 우레탄계 수지에 함침되고서(S210), 상온 혹은 20~80℃ 하에서 대략 72시간 내지 96시간(대략 3일) 동안 경화시킨다. 무용제 우레탄계 수지는 부직포 섬유를 상호 3차원적으로 가교시키면서 부직포 펠트 간의 결속력 강화 뿐만 아니라 고분자 탄성체가 침투하지 않은 공극 부위는 인공피혁 제조 이후에도 잔존해 있어 더욱 우수한 질감을 형성하고, 우레탄의 고유 특성의 탄성과 유연성 등의 내구성을 함침포에 제공할 수 있다. The nonwoven felt is impregnated with a solvent-free urethane-based resin (S210) and cured for about 72 hours to 96 hours (about 3 days) at room temperature or 20 to 80 ° C. Solvent-free urethane-based resin not only strengthens the binding force between nonwoven fabric felts while crosslinking nonwoven fabrics in three dimensions, but also voids where polymer elastomers do not penetrate remain after artificial leather to form a better texture and elasticity of urethane's inherent properties. And durability such as flexibility can be provided to the impregnated fabric.
단계(S210)를 통해 부직포 상에 무용제 우레탄계 수지(일명 NS)를 함친한 후 경화된 함침포는 택기성(끈적거림)의 질감을 제공할 뿐만 아니라 추후의 단계(S400)에서 피막층 형성을 돕는 수성 우레탄계 수지와 함침포의 접착성을 저감시키는 박리 현상을 제공하여 별도의 가공 없이는 함침포 자체로는 시판할 수 없다. 이에 본 발명은 무용제 우레탄계 수지 함침 단계(S210)를 거쳐 경화된 함침포에 택기성을 보완하기 위해 다음과 같은 공정을 추가로 실시한다. 우선, 함침포는 실리카 에어로졸과 물을 교반한 혼합액으로 함침하고 이를 건조한다. 건조 후에, 함침포는 세수과정을 거쳐 실리카 분말을 제거하게 된다. After impregnating the solvent-free urethane-based resin (aka NS) onto the nonwoven fabric through step S210, the impregnated fabric hardened not only provides a texture of tackyness (stickiness) but also helps to form a coating layer in a later step (S400). Impregnation of the urethane-based resin and the impregnated cloth provides a peeling phenomenon and cannot be marketed as the impregnated cloth itself without further processing. In this regard, the present invention further performs the following process to complement the tackiness to the impregnated cloth cured through the solvent-free urethane-based resin impregnation step (S210). First, the impregnated cloth is impregnated with a mixed solution of silica aerosol and water and dried. After drying, the impregnated cloth is washed with water to remove silica powder.
덧붙여서, 본 발명은 단계(S120)의 부직포 펠트 또는 단계(S210)의 함침포에 SBR계 라텍스, NBR계 라텍스, CR계 라텍스로 함침될 수 있다(S220). 라텍스는 함침포의 탄성을 부여하는 동시에 제작 단가를 유지할 수 있는 장점을 제공하게 된다.In addition, the present invention may be impregnated with SBR-based latex, NBR-based latex, CR-based latex in the nonwoven felt of step (S120) or impregnated fabric of step (S210) (S220). The latex provides the elasticity of the impregnated cloth and at the same time provides the advantage of maintaining the manufacturing cost.
단계(S220)는 전술된 라텍스 이외에 완제품의 품질에 따라 수성 우레탄계 수지(일명 73)로도 함침할 수 있다. 예컨대, 무용제 우레탄계 수지(NS)의 택기성을 실리카와 물의 혼합액에 함침하여 택기성을 제거한 후에, 단계(S220)의 라텍스 또는 수성 우레탄계 수지를 함침하여 택기성을 완전히 제거할 수 있을 것이다. 단계(S220)를 거친 함침포는 계면활성제 없이도 수성 우레탄계 수지에 함유된 물 성분과 무용제 우레탄계 수지에 함유된 미끄러운 기름 성분을 섞이게 하여 신뢰할 수 있는 접착 상태를 보장할 수 있게 한다. 이는 부직포 펠트와 단계(S220)의 함침 수성 우레탄계 수지 및 단계(S400)의 피막형성 수성 우레탄계 수지의 견고한 결합을 유지할 수 있다. Step S220 may be impregnated with an aqueous urethane-based resin (aka 73) in addition to the above-described latex according to the quality of the finished product. For example, after removing the tackiness by impregnating the tackiness of the solvent-free urethane-based resin (NS) in a mixture of silica and water, the tackiness may be completely removed by impregnating the latex or aqueous urethane-based resin of step (S220). The impregnated cloth passed through step (S220) allows the water component contained in the aqueous urethane-based resin and the slippery oil component contained in the solvent-free urethane-based resin to be mixed without a surfactant to ensure a reliable adhesion state. This can maintain a firm bond between the nonwoven felt and the impregnated aqueous urethane-based resin of step (S220) and the film-forming aqueous urethane-based resin of step (S400).
일반적으로, 당해 분야의 숙련자들은 부직포 펠트에 수성 우레탄계 수지를 함침하여 인공피혁을 제조하는데, 수성 우레탄계 수지만을 부직포 펠트에 함침하게 될 경우에 매우 딱딱해지고 아주 쉽게 찢어지는 단점을 갖는다. 그러나, 본 발명은 전술된 고분자 탄성체의 함침 단계(S200)를 통해 물 성분과 기름 성분을 융화시켜 천연피혁과 같이 부드러운 질감과 함께 쉽게 찢어지지 않는 특성을 제공할 수 있다. 또한, 본 발명은 종래의 라미네이팅 방식이 아닌 수성 케미컬 함침 방식을 통해 수성 성분의 건조과정을 통해 미세한 구멍을 형성하여 천연피혁보다 탁월한 투습성과 통풍성도 갖출 수 있다.In general, those skilled in the art produce artificial leather by impregnating a nonwoven felt with an aqueous urethane-based resin, which has the disadvantage of being very hard and very easily torn when only the aqueous urethane-based resin is impregnated into the nonwoven felt. However, the present invention can provide a property that is not easily torn with a soft texture, such as natural leather by the water component and the oil component through the impregnation step (S200) of the polymer elastomer. In addition, the present invention can be provided with excellent moisture permeability and breathability than natural leather by forming a fine hole through the drying process of the aqueous component through the aqueous chemical impregnation method rather than the conventional laminating method.
본 발명은 용제, 특히 알칼리 수용액으로 가용성 성분을 제거하는 용출 단계(S300)를 포함한다.The present invention includes an elution step (S300) for removing soluble components with a solvent, especially an aqueous alkali solution.
즉 부직포 펠트를 고분자 탄성체에 함침시켜 함침포를 제작하고 난 다음에, 함침포에 용제와 반응시켜 가용성 성분인 제2 폴리머를 용출 또는 분해제거하여 후용출포를 제작할 수 있다. That is, after impregnating the nonwoven fabric felt with a polymer elastomer to produce an impregnated fabric, the impregnated fabric may be reacted with a solvent to elute or decompose and remove the second polymer as a soluble component to produce a post-eluted foam.
종래기술에 따른 인공피혁 제조시에는, 디메틸포름아마이드(dimethylformamide)와 같은 휘발성 유기용제를 사용하여 부직포 펠트와 고분자 탄성체 사이에 공극을 형성하게 되어 있다. 하지만, 본 발명은 디메틸포름아마이드를 사용하지 않고 알칼리 수용액을 용제로 사용하여 폐수와 대기오염을 현저하게 저감시킬 수 있는 친환경 공정으로 인공피혁을 생산해 낼 수 있다. In the manufacture of artificial leather according to the prior art, a void is formed between the nonwoven felt and the polymer elastomer by using a volatile organic solvent such as dimethylformamide. However, the present invention can produce artificial leather in an environmentally friendly process that can significantly reduce wastewater and air pollution by using an aqueous alkali solution as a solvent without using dimethylformamide.
본 발명은 예컨대 약 10% 수산화나트륨 수용액을 용제로 채택하는바, 함침포를 수산화나트륨 수용액에 침지시켜 제2 폴리머를 제거한다. 묽은 농도의 수산화나트륨 수용액은 제2 폴리머를 용출하는 동안에 고분자 탄성체와 공극을 손상시키지 않는 장점을 제공하게 된다. 따라서, 용제는 제2 폴리머 만을 용출하게 되어 폴리에스테르 혹은 나일론과 고분자 탄성체(무용제 우레탄계 수지 및/또는 라텍스)만을 남기게 된다. 결과적으로, 본 발명은 해성분을 용출하고 부직포 펠트를 극세섬유화하여 미세다공층을 형성한 후용출포를 제작하게 된다. The present invention employs, for example, about 10% aqueous sodium hydroxide solution as a solvent, and the impregnated cloth is immersed in the aqueous sodium hydroxide solution to remove the second polymer. A dilute solution of sodium hydroxide provides the advantage of not damaging the polymeric elastomer and voids while eluting the second polymer. Thus, the solvent elutes only the second polymer, leaving only polyester or nylon and a polymer elastomer (solvent-free urethane resin and / or latex). As a result, the present invention is to produce the eluent after eluting the sea component and forming a microporous layer by micronized the nonwoven felt felt.
덧붙여서, 본 발명은 피용출성분을 제거한 이후에 건조한다. 그런 다음에, 후용출포는 염색, 평활, 연마, 버핑, 샌딩 등의 일련의 표면 처리를 하여 인공피혁으로 시판할 수 있다.Incidentally, the present invention is dried after removing the component to be eluted. Then, the post-exposure blister can be marketed as an artificial leather by a series of surface treatments such as dyeing, smoothing, polishing, buffing, sanding, and the like.
덧붙여서, 본 발명은 단계(S300)에서 수득된 후용출포에 접착층을 도포하는 단계(S400)를 포함한다. 접착층은 후용출포의 경화된 표면 상에 접착용 합성수지, 예컨대 수성 우레탄계 수지를 도포하여 적층되거나 함침될 수도 있다. In addition, the present invention includes a step (S400) of applying an adhesive layer to the post-elut foam obtained in step (S300). The adhesive layer may be laminated or impregnated by applying an adhesive synthetic resin, such as an aqueous urethane-based resin, on the cured surface of the post elution cloth.
여기서, 접착층은 후용출포의 표면 전면에 골고루 도포할 수도 있고 필요에 따라 부분적으로 패턴화되어 도포할 수도 있다. 접착층이 도포되지 않은 부분은 극세섬유로 이루어진 입모부를 형성할 수도 있을 것이다.Here, the adhesive layer may be evenly applied to the entire surface of the post-treatment foam or may be partially patterned and applied as necessary. The portion where the adhesive layer is not applied may form an napped portion made of ultrafine fibers.
접착층 도포 단계(S400) 이후에, 본 발명은 후용출포의 표면에 도포된 접착층을 건조 등의 공정을 통해 완전 경화시킨다(S410). 후용출포의 표면은 접착층의 경화로 형성된 피막층을 형성하게 되는데, 피막층은 유연하고 부드러운 표면 터치감, 내표면 마모성, 및 입체감을 표면에 형성하여 누벅(nubuck)형의 인공피혁을 제조할 수 있게 된다. 다시 말하자면, 후용출포의 접착층을 건조한 인공피혁은 샌딩 등의 표면 처리 단계(S420)를 통해 후용출형 인공피혁과는 다른 요철감과 이색감을 표현한 누벅형 인공피혁을 제공할 수 있게 된다.After the adhesive layer application step (S400), the present invention completely cures the adhesive layer applied to the surface of the post-dissolution foam through a process such as drying (S410). The surface of the post-exposure foam forms a coating layer formed by curing the adhesive layer. The coating layer forms a soft and soft surface touch, surface abrasion resistance, and three-dimensional feeling on the surface to produce nubuck artificial leather. do. In other words, the artificial leather drying the adhesive layer of the post-exposure foam can provide a nubuck-type artificial leather expressing a different unevenness and differentiation from the post-dissolution type artificial leather through the surface treatment step (S420) such as sanding.
본 발명은 후용출포의 표면에 엠보싱 등의 무늬를 형성한 인공피혁을 제작할 수 있는 것을 특징으로 한다. 이를 위해서, 본 발명은 엠보싱 무늬를 형성한 이형지를 준비하는 단계(S500)를 포함한다. 이형지(release paper)는 전술된 바와 같이 다양한 무늬패턴을 형성하고, 그 위에 스킨(skin)용 우레탄계 수지를 도포하고 경화시킨다. 스킨용 우레탄계 수지는 이형지의 엠보싱 형상과 일치되는 스킨층을 형성하게 된다. 스킨용 우레탄계 수지는 수성 우레탄계 수지일 수 있다.The present invention is characterized in that it is possible to produce artificial leather with a pattern such as embossing on the surface of the post-treatment bubble. To this end, the present invention includes a step (S500) to prepare a release paper on which the embossed pattern is formed. Release paper forms a variety of patterned patterns as described above, on which the urethane-based resin for skin (skin) is applied and cured. The urethane-based resin for skin forms a skin layer that matches the embossed shape of the release paper. The urethane-based resin for skin may be an aqueous urethane-based resin.
그런 다음에, 본 발명은 접착층을 도포한 후용출포(S400) 상에 무늬전이용 이형지(S500)를 합포하는 단계(S600)를 포함한다. 접착층이 경화되기 전에, 이형지에 도포된 스킨용 우레탄계 수지가 후용출포의 표면 상에 도포된 접착층 상에 배치되도록 하여 합포된다. 건조/경화한 이후에, 이형지는 박리(S700)되고 이형지의 엠보싱 형상으로 경화된 스킨층이 후용출포와 합포되어 후용출포의 표면 상에 스킨층을 적층배치된다. 이때, 스킨층은 후용출포의 표면에 도포/함침된 접착층을 수단으로 하여 스택상태로 위치고정된다. 스킨층과 후용출포는 롤러를 통해 가압되어 접착층의 결속력 강화와 함께 인공피혁의 평탄화 작업도 동시에 수행할 수 있을 것이다.Then, the present invention includes the step (S600) of laminating the pattern transfer paper (S500) on the elution foam (S400) after applying the adhesive layer. Before the adhesive layer is cured, the skin-based urethane-based resin applied to the release paper is placed on the adhesive layer applied on the surface of the post-expanded foam, and then laminated. After drying / curing, the release paper is peeled off (S700) and the skin layer cured to the embossed shape of the release paper is combined with the post-treatment bubble to laminate the skin layer on the surface of the post-treatment bubble. At this time, the skin layer is fixed in a stacked state by means of an adhesive layer applied / impregnated on the surface of the post-treatment bubble. The skin layer and the post-explosion bubble may be pressed through a roller to simultaneously strengthen the cohesion of the adhesive layer and planarize the artificial leather.
스킨층으로 코팅된 인공피혁은 이형지에 의해 미세하고 정교한 무늬와 패턴을 인공피역의 표면에 제공할 수 있다.Artificial leather coated with a skin layer can provide fine and sophisticated patterns and patterns on the surface of artificial skin by release paper.
덧붙여서, 본 발명은 사용 용도에 맞춰 후용출포의 이면을 무용제 우레탄계 수지에 도포 및/또는 함침할 수도 있다(S800). 후용출포의 표면은 단계(S400)를 통해 접착층으로 도포 및/또는 함침되어 있기 때문에, 이면에 무용제 우레탄계 수지를 함침하여 내표면마모성과 탄성을 부여할 수 있을 것이다.Incidentally, the present invention may be applied and / or impregnated with the solvent-free urethane resin on the back surface of the post-expanded foam according to the use purpose (S800). Since the surface of the post-exposure bubble is coated and / or impregnated with an adhesive layer through step S400, impregnating a solvent-free urethane resin on the back surface may impart surface wear resistance and elasticity.
본 발명은 후용출 인공피혁 혹은 누벅형 인공피혁의 표면 및/또는 이면에 난연제를 도포하는 단계(S900)를 추가로 포함할 수 있다. 난연제는 인공피혁의 스킨층을 도포한 표면 혹은 이의 대향되는 이면 상에 고착되도록 하는데, 난연제의 고착에도 인공피혁의 볼륨감과 부드러운 촉감을 보유할 수 있어야 할 것이다.The present invention may further include the step (S900) of applying a flame retardant to the surface and / or back of the post-dissolution artificial leather or nubuck artificial leather. The flame retardant is to be fixed on the surface of the skin layer of the artificial leather or on the opposite back thereof, it should be able to retain the volume and soft touch of the artificial leather even when the flame retardant is fixed.
이상 본 발명은 실시예를 통하여 상세히 설명하였으나, 이는 본 발명을 구체적으로 설명하기 위한 것으로, 본 발명에 따른 인공피혁의 제조방법은 이에 한정되지 않으며, 본 발명의 기술적 사상 내에서 당해 분야의 통상의 지식을 가진 자에 의해 그 변형이나 개량이 가능함은 명백하다고 할 것이다.Although the present invention has been described in detail by way of examples, it is intended to explain the present invention in detail, and the manufacturing method of artificial leather according to the present invention is not limited thereto, and the technical features of the present invention are those of ordinary skill in the art. It is clear that modifications and improvements are possible by the knowledgeable.
본 발명의 단순한 변형 내지 변경은 모두 본 발명의 영역에 속하는 것으로 본 발명의 구체적인 보호범위는 첨부된 특허청구범위에 의하여 명확해질 것이다.All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of the present invention will be apparent from the appended claims.
Claims (11)
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| KR10-2016-0002366 | 2016-01-08 | ||
| KR1020160002366A KR101811584B1 (en) | 2016-01-08 | 2016-01-08 | Method for manufacturing an artificial leather |
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| WO2017119798A2 true WO2017119798A2 (en) | 2017-07-13 |
| WO2017119798A3 WO2017119798A3 (en) | 2018-08-02 |
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| PCT/KR2017/000284 Ceased WO2017119798A2 (en) | 2016-01-08 | 2017-01-09 | Method for manufacturing artificial leather |
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| KR101969325B1 (en) * | 2018-08-21 | 2019-04-17 | 주식회사 코더 | Manufacturing Method of Artificial Upper Leather |
| KR101969324B1 (en) * | 2018-08-21 | 2019-04-17 | 주식회사 코더 | Manufacturing Method of Artificial Upper Leather |
| KR102674675B1 (en) * | 2021-10-27 | 2024-06-12 | (주)타스지혁 | Eco friendly synthetic leather and a method of manufacturing the same |
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| KR100530570B1 (en) * | 1997-12-12 | 2006-01-27 | 주식회사 코오롱 | Release label for wet laminating, method for manufacturing the same, and method for manufacturing laminated moisture-permeable waterproof cloth using the same. |
| JP3767826B2 (en) * | 2004-02-26 | 2006-04-19 | 大日本インキ化学工業株式会社 | Leather-like sheet manufacturing method |
| JP4633606B2 (en) * | 2005-11-15 | 2011-02-16 | 株式会社クラレ | Flame-retardant leather-like sheet and method for flame-retardant processing of leather-like sheet |
| KR101310119B1 (en) * | 2007-12-13 | 2013-10-14 | 현대자동차주식회사 | Artificial leather and method of manufacturing the same |
| KR20150112355A (en) * | 2014-03-27 | 2015-10-07 | 코오롱인더스트리 주식회사 | Manufacturing method of artificial leather |
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| KR101811584B1 (en) | 2017-12-26 |
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