KR101492728B1 - polyurethane resin composition for artificial leather impregnation - Google Patents
polyurethane resin composition for artificial leather impregnation Download PDFInfo
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- KR101492728B1 KR101492728B1 KR20130101891A KR20130101891A KR101492728B1 KR 101492728 B1 KR101492728 B1 KR 101492728B1 KR 20130101891 A KR20130101891 A KR 20130101891A KR 20130101891 A KR20130101891 A KR 20130101891A KR 101492728 B1 KR101492728 B1 KR 101492728B1
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/14—Dyeability
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/904—Artificial leather
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Abstract
본 발명은 합성피혁 함침용 폴리우레탄 수지 조성물에 관한 것으로, 더욱 상세하게는 폴리에스테르 폴리올과 폴리에테르 폴리올의 적합한 조합과 폴리우레탄의 구조 중 경성 세크먼트(Hard segment)에 해당하는 쇄연장제(Chain Extender)의 종류 및 양을 달리하여 기존의 함침용 수지보다 탈(脫) 디엠프(DMF, Dimethyl formamide)성 및 볼륨감이 우수하면서 발색성이 우수한 합성피혁 용 폴리 우레탄 수지 조성물에 관한 것이다.The present invention relates to a polyurethane resin composition for impregnating synthetic leather, and more particularly, to a polyurethane resin composition for impregnating synthetic leather, and more particularly to a polyurethane resin composition for polyurethane resin impregnation for synthetic leather impregnation, (DMF) and a high volume feeling and excellent coloring property by using different kinds and amounts of polyurethane resins and extender. The present invention relates to a polyurethane resin composition for synthetic leather for synthetic leather.
Description
본 발명은 합성피혁 함침용 폴리우레탄 수지 조성물에 관한 것으로, 더욱 상세하게는 폴리에스테르 폴리올과 폴리에테르 폴리올의 적합한 조합과 폴리우레탄의 구조 중 경성 세크먼트(Hard segment)에 해당하는 쇄연장제(Chain Extender)의 종류 및 양을 달리하여 기존의 함침용 수지보다 탈(脫) 디엠프(DMF, Dimethyl formamide)성 및 볼륨감이 우수하면서 발색성이 우수한 합성피혁용 폴리 우레탄 수지 조성물에 관한 것이다.
The present invention relates to a polyurethane resin composition for impregnating synthetic leather, and more particularly, to a polyurethane resin composition for impregnating synthetic leather, and more particularly to a polyurethane resin composition for polyurethane resin impregnation for synthetic leather impregnation, (DMF) and a high volume feeling and excellent coloring property by using different kinds and amounts of polyurethane resins and extender. The present invention relates to a polyurethane resin composition for synthetic leather for synthetic leather.
합성피혁이란 폴리우레탄 수지 조성물과 부직포, 직물 , 편직물 등을 조합시킨 형태의 시트상 물질을 말한다.Synthetic leather means a sheet-like material in the form of a combination of a polyurethane resin composition and a nonwoven fabric, a woven fabric, a knitted fabric, or the like.
합성피혁의 구조는 각종 짧은 섬유에 3차원적으로 얼기설기 엮은 구조를 폴리우레탄 수지를 바인더로 하는 부직포를 바탕천으로 하고 폴리우레탄 수지를 표면층으로 하는 2층 구조로서, 전체에 연속적으로 미세한 다공 구조를 갖는다.The structure of the synthetic leather is a two-layer structure in which a nonwoven fabric made of a polyurethane resin as a base cloth and a polyurethane resin as a surface layer are three-dimensionally loosely bonded to various short fibers, and a fine porous structure .
그 중에는 두 층 사이에 직편포가 들어간 3층 구조나, 바탕천 또는 표면층만의 1층 구조인 것도 있다.Among them, there is a three-layer structure in which a direct bobbin is inserted between two layers, and a one-layer structure in only a base cloth or a surface layer.
합성피혁은 천연피혁의 장점을 유지하면서도 천연피혁의 문제점인 공급량의 한정, 물세탁의 어려움, 통기성, 염색, 방부성 등을 보완한 것으로, 가공 기술의 발달에 따라 품질이 우수하여 천연피혁보다 가볍고 표면 강도가 크며 내마모성이 우수하고 투습, 방수성이 좋으며 색상이 다양할 뿐 아니라, 재단 봉제 접착 등 작업의 용이성, 제품의 균일성, 대량 생산이 가능한 특징들을 가지고 있다.Synthetic leather complements the limitation of supply, difficulty of water washing, ventilation, dyeing, anticorrosion, etc., which is the problem of natural leather while maintaining the advantages of natural leather. It is superior in quality due to development of processing technology, It has high strength, high abrasion resistance, good moisture permeability, good water resistance, and various colors, as well as ease of work such as cutting and sewing, uniformity of product, and mass production.
최근에는 원단, 합성수지 및 가공방법의 개발로 천연가죽과 비슷한 촉감 및 물성을 가진 합성피혁이 개발되어 신발, 가방, Ball, 골프장갑, 점퍼 등 생활용품에서 인테리어 제품에 이르기까지 다양하게 적용되고 있다.In recent years, synthetic leather having a touch and physical properties similar to those of natural leather has been developed due to the development of fabrics, synthetic resins and processing methods, and has been applied to a variety of products ranging from household goods such as shoes, bags, balls, golf gloves and jumpers to interior products.
합성피혁을 가공하는 방법은 건식법과 습식법으로 나뉜다. The methods of processing synthetic leather are divided into a dry method and a wet method.
건식법은 80~120℃의 열풍에 의하여 코팅된 수지의 휘발성분을 증발시켜 분자간의 강력한 상호작용에 의하여 탄성이 풍부하고 강인한 피막을 형성하는 공정을 말한다. 습식법은 습식용 폴리우레탄수지용액에 존재하는 폴리머간의 강력한 분자 간 응집력과 용매로 사용된 DMF의 수용해성을 이용하여, 우레탄 수지용액을 물속에 침적시킨 후 삼투압의 원리에 의해 DMF를 추출(탈DMF)시키면서 폴리머의 강한 분자 간의 응집력에 의해 피막을 형성시키며, DMF가 물로 치환된 부분에 연속기공이 형성되어 미세다공질의 투습성이 있는 피막을 제조하는 공정이다.The dry method refers to a process in which a volatile component of a resin coated by hot air at 80 to 120 ° C is evaporated to form a strong and elastic film by strong interaction between molecules. The wet method utilizes the strong intermolecular cohesive force between the polymers present in the wet polyurethane resin solution and the water solubility of the DMF used as the solvent. After the urethane resin solution is immersed in water, the DMF is extracted (DMF ) To form a coating film by the strong intermolecular force of the polymer, and forming continuous pores in the portion where DMF is substituted with water to produce a microporous moisture permeable film.
습식가공에 있어 탈DMF성은 최종 제품의 볼륨감, 터치감 및 물성에 중요한 인자로 작용하게 된다. 또한, 폴리올과 쇄연장제(Chain Extender)의 종류 및 양을 달리함으로써 탈DMF 속도에 차이가 발생하게 되고 최종 제품에 있어 볼륨감, 터치감 및 발색성에 차이가 발생하게 된다.
In the wet process, the DMF removal is an important factor for volume, touch, and physical properties of the final product. Also, by varying kinds and amounts of the polyol and the chain extender, there is a difference in the DMF removal rate, and there is a difference in the volume, touch, and color of the final product.
본 발명은 합성피혁 함침용 폴리우레탄 수지 조성물에 관한 것으로, 더욱 상세하게는 폴리에스테르 폴리올과 폴리에테르 폴리올의 적합한 조합과 폴리우레탄의 구조중 경성 세그먼트(Hard Segment)에 해당하는 쇄연장제(Chain Extender)의 종류 및 양을 달리하여 우수한 탈DMF과 볼륨감이 우수하면서 기존 함침용 수지보다 발색성이 뛰어난 합성피혁용 폴리우레탄 수지조성물에 관한 것이다.The present invention relates to a polyurethane resin composition for impregnating synthetic leather, and more particularly, to a polyurethane resin composition for impregnating synthetic leather, and more particularly to a polyurethane resin composition for polyurethane resin impregnation for synthetic leather impregnation, ), Which is excellent in DMF removal and volume feeling, and is superior in coloring property to the existing impregnating resin, with respect to the polyurethane resin composition for synthetic leather.
즉, 폴리우레탄 수지 조성물의 디메틸포름아미드(DMF) 용액을 스웨이드(Suede), 부직포 원단에 함침시키거나 코팅시키고 이것을 수응고욕 또는 DMF-물의 혼합 용액으로 이루어진 응고욕 속에서 폴리우레탄 수지를 다공질상으로 응고시킨 다음 세정 및 건조공정을 경유시켜 수행하는 이른바 습식가공을 채용함에 있어서, 빠른 탈DMF 추출속도와 풍부한 볼륨감, 부드러운 터치감, 우수한 발색성을 갖는 함침용 습식 폴리우레탄 수지를 합성하는 조성물 및 제조방법을 제공하고자 한다.
That is, a dimethylformamide (DMF) solution of a polyurethane resin composition is impregnated or coated on a suede and nonwoven fabrics and the resultant polyurethane resin is allowed to stand in a coagulating bath comprising a coagulating bath or a mixed solution of DMF and water, , A composition for synthesizing a wet polyurethane resin for impregnation having a rapid DMF removal rate, a rich volume feeling, a smooth touch feeling, and an excellent coloring property in a so-called wet processing which is carried out by a washing and drying process, And to provide a manufacturing method thereof.
본 발명에 의한 발색성이 우수한 합성피혁 함침용 폴리우레탄 수지 조성물의 일 실시예는 폴리테트라 메틸렌 에테르 글리콜계 폴리올 70 내지 120중량부와, 부틸렌글리콜계 폴리에스테르 폴리올 70 내지 120중량부와, 부틸렌글리콜 10 내지 15중량부와, 네오펜틸글리콜 13 내지 18중량부와, 산화방지제 0.1 내지 0.4중량부 및 디메틸포름아미드가 혼합되어 불휘발분이 28~33wt%인 것을 특징으로 한다.One embodiment of the polyurethane resin composition for synthetic leather impregnation according to the present invention is a polyurethane resin composition for polyurethane resin impregnation which comprises 70 to 120 parts by weight of a polytetramethylene ether glycol polyol, 70 to 120 parts by weight of a butylene glycol-based polyester polyol, 10 to 15 parts by weight of glycol, 13 to 18 parts by weight of neopentyl glycol, 0.1 to 0.4 part by weight of an antioxidant, and dimethylformamide, and 28 to 33% by weight of nonvolatile matter.
그리고 본 발명의 다른 실시예는 폴리테트라 메틸렌 에테르 글리콜계 폴리올 70 내지 120중량부와, 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 70 내지 120중량부와, 부틸렌글리콜 10 내지 15중량부와, 네오펜틸글리콜 13 내지 18중량부와, 산화방지제 0.1 내지 0.4중량부 및 디메틸포름아미드가 혼합되어 불휘발분이 28~33wt%인 것을 특징으로 한다.Another embodiment of the present invention is a polytetramethylene ether glycol polyol composition comprising 70 to 120 parts by weight of a polytetramethylene ether glycol polyol, 70 to 120 parts by weight of an ethylene glycol-butylene glycol-based polyester polyol, 10 to 15 parts by weight of butylene glycol, 13 to 18 parts by weight of pentyl glycol, 0.1 to 0.4 parts by weight of an antioxidant, and dimethylformamide, and a non-volatile content of 28 to 33% by weight.
또한, 상기 폴리테트라 메틸렌 에테르 글리콜계 폴리올은 수산기값이 56±3이고, 산값이 0.05 이하인 것을 특징으로 한다.The polytetramethylene ether glycol-based polyol has a hydroxyl value of 56 + 3 and an acid value of 0.05 or less.
또한, 상기 폴리테트라 메틸렌 에테르 글리콜계 폴리올, 부틸렌글리콜계 폴리에스테르 폴리올 및 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올은 수평균분자량이 2000인 것을 특징으로 한다.
The polytetramethylene ether glycol-based polyol, butylene glycol-based polyesterpolyol and ethylene glycol-butylene glycol-based polyesterpolyol have a number average molecular weight of 2000.
본 발명은 합성피혁 함침용 폴리우레탄 수지 조성물에 관한 것으로, 폴리에스테르 폴리올과 폴리에테르 폴리올의 적합한 조합과 폴리우레탄의 구조 중 경성 세그먼트(Hard Segment)에 해당하는 쇄연장제(Chain Extender)의 종류 및 양을 달리함으로써 기존의 일반 폴리에스테르-에테르 폴리우레탄 수지 조성물과 비교하여 우수한 탈DMF, 볼륨감을 가지면서 특히, 발색성이 우수한 함침용 습식 폴리우레탄 수지 조성물을 얻을 수 있다.The present invention relates to a polyurethane resin composition for impregnation of synthetic leather, which comprises a suitable combination of a polyester polyol and a polyether polyol, a kind of a chain extender corresponding to a hard segment of the polyurethane structure, By varying the amount, it is possible to obtain a wet polyurethane resin composition for impregnation having excellent DMF and volume feeling, particularly excellent in color development, as compared with the conventional general polyester-ether polyurethane resin composition.
즉, 폴리우레탄 수지 조성물의 디메틸포름아미드(DMF) 용액을 스웨이드(Suede), 부직포 원단에 함침시키거나 코팅시키고 이것을 수응고욕 또는 DMF-물의 혼합 용액으로 이루어진 응고욕 속에서 폴리우레탄 수지를 다공질상으로 응고시킨 다음 세정 및 건조공정을 경유시켜 수행하는 이른바 습식가공을 채용함에 있어서, 빠른 탈DMF 추출속도와 풍부한 볼륨감, 부드러운 터치감, 우수한 발색성을 갖는 함침용 습식 폴리우레탄 수지이다. That is, a dimethylformamide (DMF) solution of a polyurethane resin composition is impregnated or coated on a suede and nonwoven fabrics and the resultant polyurethane resin is allowed to stand in a coagulating bath comprising a coagulating bath or a mixed solution of DMF and water, , Followed by a washing and drying process. The wet polyurethane resin for impregnation has a rapid DMF removal rate, rich volume feeling, smooth touch feeling, and excellent coloring property.
본 발명은 기존의 일반 폴리에스테르-에테르 폴리우레탄 수지 조성물보다 빠른 탈 DMF 속도로 다공성의 형상(Cell 구조)을 부여하여 부드러운 터치감과 볼륨감이 우수하며 특히, 쇄연장제(Chain Extender)의 적절한 조합으로 기존 폴리에스테르-에테르 폴리우레탄 수지 조성물보다 발색성이 우수하다.
The present invention relates to a novel polyester-ether polyurethane resin composition which imparts a porous shape (cell structure) at a higher DMF rate than a conventional general polyester-ether polyurethane resin composition, Is superior in color development to the conventional polyester-ether polyurethane resin composition.
폴리우레탄 또는 우레탄 폴리머라고 총칭되는 폴리머는 우레탄(-NH-COO-) 그룹을 포함하고 있는 고분자를 이른다. Polymers generally referred to as polyurethanes or urethane polymers are referred to as polymers containing urethane (-NH-COO-) groups.
대부분의 경우 폴리우레탄은 우레탄 그룹 이외에도 ether, ester, amide, urea 등의 극성그룹은 물론 선상 또는 환상 aliphatics 또는 aromatics 탄화수소의 비극성 구조를 갖는 화합물로부터 제조되기 때문에 이들 그룹의 종류 및 함량비에 따라 물성의 변화가 다양해지는 특성을 갖고 있다.In most cases, polyurethanes are produced from compounds having nonpolar structures of linear or cyclic aliphatics or aromatics hydrocarbons, as well as polar groups such as ether, ester, amide and urea, as well as urethane groups. And has a characteristic that the variation is varied.
일반적으로 우레탄기는 다른 구조 단위에 비해 오히려 소량이고 우레탄기 이외 부분의 구조가 다양하다. 이 구조의 다양성 때문에 우레탄 폴리머의 성질도 다양하며, 이것이 광범위한 응용을 가능하게 하며 또 폴리우레탄의 구조물성 관계를 복잡하게 하고 있다.Generally, the urethane groups are rather small in amount compared with other structural units and the structures other than the urethane groups are various. Due to the diversity of this structure, the properties of the urethane polymer are also varied, which makes it possible for a wide range of applications and complicates the structural properties of the polyurethane.
폴리우레탄은 이소시아네이트(-NCO)와 하이드록시(-OH) 그룹의 반응으로 만들어지나, -OH 이외에 활성수소를 갖고 있는 화합물 즉, -COOH, -NH2, -CO-NH-, -NH-CO-NH- 등도 NCO와 반응성이 크며 반응생성물이 매우 다양하므로, 그 물성의 조절이 까다로우며 대부분의 경우 가교구조를 갖기 때문에 분석이 어려운 특성을 갖고 있다.Polyurethane is isocyanate (-NCO) and hydroxyl (-OH) made through the reaction of the group, -OH having the active hydrogen compound that is, -COOH, in addition to -NH 2, -CO-NH-, -NH -CO -NH- and the like are highly reactive with NCO and their reaction products are very diverse, so that their physical properties are difficult to control, and in most cases, they have a crosslinking structure and thus are difficult to analyze.
폴리우레탄의 구조는 폴리올 성분으로 이루어지는 연성 세그먼트(Soft Segment)와 이소시아네이트, 쇄연장제(Chain Extender), 우레탄 결합, 우레아 결합으로 이루어지는 경성 세그먼트(Hard Segment)로 이루어진다.The structure of the polyurethane is composed of a soft segment made of a polyol component and a hard segment made of isocyanate, a chain extender, a urethane bond, and a urea bond.
연성 세그먼트(Soft Segment) 부분은 약한 분자간력(Van der waals Force)으로 우레탄 수지의 가소성, 유연성, 굴곡성, 내한성 등의 특징을 나타내며, 경성 세그먼트(Hard Segment) 부분은 수소결합을 이루는 강한 분자간력으로 우레탄 수지의 강인성, 내용제성, 내열성, 내마모성 등의 특징을 나타낸다.The Soft Segment is characterized by a weak molecular force (Van der Waals Force), which is characterized by plasticity, flexibility, flexibility and cold resistance of the urethane resin. The hard segment is a strong intermolecular force And exhibits characteristics such as toughness, solvent resistance, heat resistance and abrasion resistance of the urethane resin.
우레탄 수지의 특징은 위와 같은 연성 세그먼트(Soft Segment)와 경성 세그먼트(Hard Segment)의 다양한 조합에 따라 다양한 물성을 나타낼 수 있다는 점이다.The characteristic of the urethane resin is that it can exhibit various physical properties according to various combinations of the above soft segment and hard segment.
연성 세그먼트(Soft Segment)를 이루는 폴리올에는 폴리에스테르 폴리올과 폴리에테르 폴리올이 있으며 이 밖에 폴리카보네이트 폴리올 등이 사용된다.Polyols forming a soft segment include polyester polyols and polyether polyols, and polycarbonate polyols are also used.
폴리에스테르 폴리올은 에틸렌 글리콜, 프로필렌 글리콘, 부틸렌 글리콜, 디에틸렌글리콜, 네오펜틸 글리콜, 헥실렌 글리콘등의 글리콜류와 아디핀산, 프탈산등의 디카르복실산의 축합반응에 의한 선상구조의 폴리에스테르 폴리올이 있다. 합성피혁용 폴리에스테르 폴리올은 유연성 때문에 아디핀산을 주로 사용하게 된다. 이 밖에 카프로락톤을 개환중합한 폴리 카프로락톤 폴리올이 사용된다.The polyester polyol is a polyester polyol obtained by condensation reaction of a glycol such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol or hexylene glycol with a dicarboxylic acid such as adipic acid or phthalic acid, There are polyester polyols. Adipic acid is mainly used for synthetic polyester polyol because of flexibility. In addition, polycaprolactone polyol obtained by ring-opening polymerization of caprolactone is used.
폴리에테르 폴리올은 에틸렌 옥사이드, 프로필렌 옥사이드, 테트라 하이드로퓨란의 개환중합에 의한 폴리에틸렌 글리콜, 폴리프로필렌 글리콜, 폴리테트라 메틸렌 에테르 글리콜이 있다.Polyether polyols include ethylene oxide, propylene oxide, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol by ring-opening polymerization of tetrahydrofuran.
쇄연장제에는 분자량 500 이하의 저분자량체로 에틸렌 글리콜, 프로필렌 글리콘, 부틸렌 글리콜, 디에틸렌글리콜, 네오펜틸 글리콜, 헥실렌 글리콜등의 글리콜류가 주로 사용되며 용도에 따라 이소포론 디아민, 에틸렌 디아민 등의 디아민이 사용된다.As the chain extender, low molecular weight compounds having a molecular weight of 500 or less are mainly used as glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol and hexylene glycol. Depending on the application, isophoronediamine, And the like.
이소시아네이트의 종류에는 4,4'-디페닐메탄디이소시아네이트, 톨루엔디이소시아네이트, 1,5-나프탈렌디이소시아테이트, 자일렌디이소시아네이트 등 aromatic계와 헥사메틸렌디이소시아네이트, 이소프론디이소시아네이트, 하이드로진네이티드 MDI 등과 같은 aliphatic 계가 있으며 aromatic계가 황변현상이 발생하는 단점이 있지만 반응성이 우수하고 경제성이 뛰어나므로 일반적으로 많이 사용되고 있다. Aromatic계 중에도 가격이 저렴하고 일반적 물성이 뛰어난 4,4'-디페닐메탄 디이소시아네이트, 톨루엔디이소시아네이트가 많이 사용된다.Examples of the isocyanate include aromatic compounds such as 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, and xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydroxyned MDI And the aromatic system has a disadvantage of causing yellowing, but it is generally used because of its excellent reactivity and economical efficiency. Among aromatic compounds, 4,4'-diphenylmethane diisocyanate and toluene diisocyanate, which are inexpensive and have excellent general properties, are widely used.
위의 원료들로 합성된 수지조성물을 이용하여 합성피혁을 습식 가공에 있어 탈DMF성은 최종 제품의 볼륨감, 터치감 및 물성에 중요한 인자로 작용하게 된다. 또한, 폴리올과 쇄연장제(Chain Extender)의 종류 및 양을 달리함으로써 탈DMF 속도에 차이가 발생하게 되고 최종 제품에 있어 볼륨감, 터치감 및 발색성에 차이가 발생하게 되는데, 본 발명은 합성피혁 함침용 폴리우레탄 수지 조성물은 폴리에스테르 폴리올과 폴리에테르 폴리올의 적합한 조합과 폴리우레탄의 구조 중 경성 세그먼트(Hard Segment)에 해당하는 쇄연장제(Chain Extender)의 종류 및 양을 달리함으로써 기존의 일반 폴리에스테르-에테르 폴리우레탄 수지 조성물과 비교하여 우수한 탈DMF, 볼륨감을 가지면서 특히, 발색성이 우수하다.In the wet processing of synthetic leather using the resin composition synthesized from the above raw materials, DMF is an important factor for volume, touch, and physical properties of the final product. In addition, differences in the type and amount of the polyol and the chain extender cause a difference in DMF removal rate, resulting in differences in volume, touch, and color of the final product. The impregnation polyurethane resin composition can be prepared by appropriately combining a polyester polyol and a polyether polyol and a kind and an amount of a chain extender corresponding to a hard segment in the structure of a polyurethane, Compared with the ester-ether polyurethane resin composition, it has excellent DMF and volume, and is particularly excellent in color development.
본 발명의 일 실시예는 수산기값 56±3, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 70~120중량부, 수산기값 56±3, 산값 1이하인 수평균분자량이 2000인 부틸렌글리콜계 폴리에스테르 폴리올 70~120중량부, 부틸렌글리콜 10~15중량부, 네오펜틸글리콜 13~18중량부, 산화방지제 0.1~0.4중량부, 초기 디메틸포름아미드 300-400중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.An embodiment of the present invention is a polytetramethylene ether glycol-based polyol having a hydroxyl value of 56 + 3 and a number average molecular weight of 2000: 70 to 120 parts by weight, a hydroxyl value of 56 3, a butylene glycol having a number average molecular weight of 2,000 70 to 120 parts by weight of a polyester polyol, 10 to 15 parts by weight of butylene glycol, 13 to 18 parts by weight of neopentyl glycol, 0.1 to 0.4 part by weight of an antioxidant and 300 to 400 parts by weight of an initial dimethylformamide, Place the device in the attached reactor and dissolve uniformly.
이어서 우레탄 반응을 위해 40~45℃에서 4,4’-디페닐메탄디이소시아네이트 60~110중량부를 투입하고, 65~70℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 200~300중량부를 3회 분할하여 투입하며 반응을 진행한다. Subsequently, 60 to 110 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 to 45 ° C for the urethane reaction, and the reaction was carried out at 65 to 70 ° C. The viscosity was measured, and the viscosity of the dimethyl form And 200-300 parts by weight of an amide is divided into three portions, and the reaction proceeds.
반응 중에 조성물의 점도가 급격하게 상승하면 제어가 힘들기 때문에 제어 안정성을 위해 디메틸포름아미드 200~300중량부를 3회 분할하여 투입한다.When the viscosity of the composition rises sharply during the reaction, it is difficult to control. Therefore, 200-300 parts by weight of dimethylformamide is divided into three portions for control stability.
Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 120~170중량부와 함께 반응 종료제인 MeOH를 0.1~0.4 중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물이 수득된다.When the cut viscosity is reached, the reaction is terminated by adding 0.1 to 0.4 part by weight of MeOH as a reaction terminator together with 120 to 170 parts by weight of dimethylformamide as a cut solvent. The nonvolatile matter content is 28 to 33 wt% and the Brookfield viscosity at 25 DEG C Lt; RTI ID = 0.0 > 800 + 100 < / RTI > poise.
그리고 본 발명의 다른 실시예는 수산기값 56±3, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 70~120중량부, 수산기값 56±3, 산값 1이하, 수평균분자량이 2000인 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 70~120중량부, 부틸렌글리콜 10~15중량부, 네오펜틸글리콜 13~18중량부, 산화방지제 0.1~0.4중량부, 초기 디메틸포름아미드 300-400중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.Another embodiment of the present invention is a polytetramethylene ether glycol-based polyol having a hydroxyl value of 56 + 3 and a number average molecular weight of 2000: 70 to 120 parts by weight, an ethylene value of 56 + 3, an acid value of 1 or less, 70 to 120 parts by weight of a glycol-butylene glycol-based polyester polyol, 10 to 15 parts by weight of butylene glycol, 13 to 18 parts by weight of neopentyl glycol, 0.1 to 0.4 parts by weight of an antioxidant and 300 to 400 parts by weight of an initial dimethylformamide Put in a reactor equipped with a thermometer, a stirrer, and a temperature raising device and dissolve uniformly.
이어서 40~45℃에서 4,4’-디페닐메탄디이소시아네이트 60~110중량부를 투입하고 65~70℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 200~300중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 120~170중량부와 함께 반응 종료제인 MeOH를 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 60 to 110 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 to 45 ° C and the reaction was carried out at 65 to 70 ° C. The viscosity was measured to find that 200-300 parts by weight of dimethylformamide And the reaction is carried out by dividing the part three times. When the cut viscosity is reached, the reaction is terminated by adding MeOH as a reaction terminator together with 120 to 170 parts by weight of dimethylformamide as a cut solvent. The nonvolatile matter content is 28 to 33 wt% and the Brookfield viscosity at 25 DEG C is 800 +/- 100 poise To obtain a polyester-ether polyurethane resin composition.
실시예 1Example 1
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 부틸렌글리콜 13중량부, 네오펜틸글리콜 15중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of a butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5, a number average molecular weight of 2000, 15 parts by weight of neopentyl glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of an initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device, and dissolved uniformly.
이어서 우레탄 반응을 위해 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고, 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 DEG C for the urethane reaction. The reaction was carried out at 65 DEG C and the viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, And the reaction is carried out.
Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3 중량부 투입하여 반응을 종료하여, 불휘발분 30wt%인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to terminate the reaction to obtain a polyester-ether polyurethane resin composition having a nonvolatile content of 30 wt%.
실시예 2Example 2
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수간기값 56, 산값 0.5, 수평균분자량이 2000인 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 부틸렌글리콜 13중량부, 네오펜틸글리콜 15중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of an ethylene glycol-butylene glycol-based polyester polyol having an average value of 56, an acid value of 0.5 and a number average molecular weight of 2000, 13 parts by weight of phenol, 15 parts by weight of neopentyl glycol, 0.3 part by weight of antioxidant and 350 parts by weight of initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device, and dissolved uniformly.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, .
Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 30wt%인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to terminate the reaction to obtain a polyester-ether polyurethane resin composition having a nonvolatile content of 30 wt%.
비교예 1Comparative Example 1
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 에틸렌글리콜 10중량부, 네오펜틸글리콜 14중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of a butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5 and a number average molecular weight of 2000, 10 parts by weight of ethylene glycol , 14 parts by weight of neopentyl glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device, and dissolved uniformly.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, . After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to complete the reaction. The nonvolatile matter content was 28 to 33 wt% and the Brookfield viscosity at 25 DEG C was 800 +/- 100 ether-polyurethane resin composition is obtained.
비교예 2Comparative Example 2
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 에틸렌글리콜 10중량부, 헥실렌글리콜 14중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of a butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5 and a number average molecular weight of 2000, 10 parts by weight of ethylene glycol , 14 parts by weight of hexylene glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of an initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device to dissolve uniformly.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, . After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to complete the reaction. The nonvolatile matter content was 28 to 33 wt% and the Brookfield viscosity at 25 DEG C was 800 +/- 100 ether-polyurethane resin composition is obtained.
비교예 3Comparative Example 3
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 부틸렌글리콜 13중량부, 헥실렌글리콜 16중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of a butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5, a number average molecular weight of 2000, 16 parts by weight of hexylene glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of an initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device, and dissolved uniformly.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, . After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to complete the reaction. The nonvolatile matter content was 28 to 33 wt% and the Brookfield viscosity at 25 DEG C was 800 +/- 100 ether-polyurethane resin composition is obtained.
비교예 4Comparative Example 4
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 에틸렌글리콜 10중량부, 부틸렌글리콜 14중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of an ethylene glycol-butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5 and a number average molecular weight of 2000, , 14 parts by weight of butylene glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of an initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device to dissolve uniformly.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, . After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to complete the reaction. The nonvolatile matter content was 28 to 33 wt% and the Brookfield viscosity at 25 DEG C was 800 +/- 100 ether-polyurethane resin composition is obtained.
비교예 5Comparative Example 5
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 에틸렌글리콜 10중량부, 네오펜틸글리콜 14중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of an ethylene glycol-butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5 and a number average molecular weight of 2000, 10 parts by weight of neopentyl glycol, 14 parts by weight of neopentyl glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, . After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to complete the reaction. The nonvolatile matter content was 28 to 33 wt% and the Brookfield viscosity at 25 DEG C was 800 +/- 100 ether-polyurethane resin composition is obtained.
비교예 6Comparative Example 6
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 에틸렌글리콜 10중량부, 헥실렌글리콜 14중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of an ethylene glycol-butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5 and a number average molecular weight of 2000, 10 parts by weight of hexylene glycol, 14 parts by weight of hexylene glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of an initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, . After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to complete the reaction. The nonvolatile matter content was 28 to 33 wt% and the Brookfield viscosity at 25 DEG C was 800 +/- 100 ether-polyurethane resin composition is obtained.
비교예 7Comparative Example 7
수산기값 56, 수평균분자량이 2000인 폴리테트라 메틸렌 에테르 글리콜계 폴리올 100중량부, 수산기값 56, 산값 0.5, 수평균분자량이 2000인 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 100중량부, 부틸렌글리콜 13중량부, 헥실렌글리콜 16중량부, 산화방지제 0.3중량부, 초기 디메틸포름아미드 350중량부를 온도계, 교반기, 승온 장치가 부착된 반응기에 넣고 균일하게 용해시킨다.100 parts by weight of a polytetramethylene ether glycol polyol having a hydroxyl value of 56 and a number average molecular weight of 2000, 100 parts by weight of an ethylene glycol-butylene glycol-based polyester polyol having a hydroxyl value of 56, an acid value of 0.5 and a number average molecular weight of 2000, 13 parts by weight of glycol, 16 parts by weight of hexylene glycol, 0.3 part by weight of an antioxidant and 350 parts by weight of an initial dimethylformamide were placed in a reactor equipped with a thermometer, a stirrer and a temperature raising device to dissolve uniformly.
이어서 40℃에서 4,4’-디페닐메탄디이소시아네이트 85중량부를 투입하고 65℃에서 반응을 실시한 후 점도를 측정하여 Cut점도 부근에서 중간용제인 디메틸포름아미드 240중량부를 3회 분할하여 투입하며 반응을 진행한다. Cut 점도에 도달하면 Cut용제인 디메틸포름아미드 140중량부와 함께 반응 종료제인 MeOH를 0.3중량부 투입하여 반응을 종료하여, 불휘발분 28~33wt%이며 또한 25℃에서의 부룩필드 점도가 800±100 poise인 폴리에스테르-에테르 폴리우레탄 수지 조성물을 수득한다.
Subsequently, 85 parts by weight of 4,4'-diphenylmethane diisocyanate was added at 40 ° C., and the reaction was carried out at 65 ° C. The viscosity was measured. 240 parts by weight of dimethylformamide, which is an intermediate solvent, . After reaching the cut viscosity, 140 parts by weight of dimethylformamide as a cut solvent and 0.3 part by weight of MeOH as a reaction terminator were added to complete the reaction. The nonvolatile matter content was 28 to 33 wt% and the Brookfield viscosity at 25 DEG C was 800 +/- 100 ether-polyurethane resin composition is obtained.
<시험방법 및 평가방법><Test Method and Evaluation Method>
1) 탈DMF 속도 가공시험1) De-DMF rate processing test
- 배합액 제조- Preparation of compounding liquid
합성된 수지 조성물 100중량부에 우레탄수지와 상용성이 우수한 계면활성제 2중량부, Cell의 크기를 조절하는 계면활성제 1중량부, 디메틸포름아미드 40중량부로 균일하게 혼합하고 원심분리기로 1000rpm으로 15분간 탈포하여 배합액을 제조한다.2 parts by weight of a surfactant excellent in compatibility with a urethane resin, 1 part by weight of a surfactant for controlling the size of a cell, and 40 parts by weight of dimethylformamide were uniformly mixed in 100 parts by weight of the synthesized resin composition and centrifuged at 1000 rpm for 15 minutes Followed by defoaming to prepare a compounding liquid.
- 탈DMF속도 측정방법- How to measure DMF removal rate
위의 배합액의 온도를 25℃로 맞춘 다음 30×30cm의 유리판에 m2 당 1,200g을 도포한다. 도포 30초 후 18% 디메틸포름아미드 수용액의 응고조에 입수시켜 응고를 실시한다.The temperature of the above compounding liquid is adjusted to 25 ° C, and 1,200 g is applied per m 2 on a 30 × 30 cm glass plate. After 30 seconds of application, it is supplied to a coagulation tank of an aqueous solution of 18% dimethylformamide and coagulated.
응고 후 6분부터 100g 분동을 수지 은면부에 올려 60초 간격으로 옮겨 10분까지 측정한다.After the solidification, weigh 100 g from 6 minutes to the surface of the resin, transfer it at intervals of 60 seconds, and measure it for 10 minutes.
- 탈DMF속도 평가방법- Method for Evaluating DMF Rate
상기 방법대로 측정하여 50℃의 수세조에서 15분간 수세를 해준 뒤 완전한 탈DMF를 위해 5회 squeezing 후 120℃ 오븐에서 20분간 완전 건조하여 추를 옮긴 자국이 없어지기 전까지 시간을 측정하여 이를 표기한다.After washing in a water bath at 50 ° C for 15 minutes, squeeze 5 times for complete DMF removal, and then completely dry in an oven at 120 ° C for 20 minutes to measure the time until the marks disappear. .
평가예) 만약 추 자국이 8분 30초에 희미하게 나타나고 9분에 나타나지 않는다면 응고속도를 9분으로 기록한다.
Evaluation example) If the marker appears dimmed at 8 minutes 30 seconds and does not appear at 9 minutes, record the coagulation rate as 9 minutes.
2) 은면 가공시험2) Silver surface test
- 배합액제조- Preparation of compounding liquid
합성된 수지 조성물 100중량부에 우레탄수지와 상용성이 우수한 계면활성제 2중량부, Cell의 크기를 조절하는 계면활성제 1중량부, 디메틸포름아미드 40중량부를 균일하게 혼합하고 원심분리기로 1000rpm으로 15분간 탈포하여 배합액을 제조한다.2 parts by weight of a surfactant excellent in compatibility with a urethane resin, 1 part by weight of a surfactant for controlling the size of a cell, and 40 parts by weight of dimethylformamide were uniformly mixed in 100 parts by weight of the synthesized resin composition and centrifuged at 1000 rpm for 15 minutes Followed by defoaming to prepare a compounding liquid.
- 은면가공 및 측정방법- silver surface processing and measurement method
위의 배합액의 온도를 25℃로 맞춘 다음 30×30cm의 유리판에 m2 당 1200g을 도포한다. 도포 30초 후 18% 디메틸포름아미드 수용액의 응고조에 입수시켜 10분간 응고를 실시한다. 50℃의 수세조에서 15분간 수세를 해준 뒤 완전한 탈DMF를 위해 5회 squeezing 후 120℃ 오븐에서 20분간 완전 건조 후 시편의 두께를 후도계로 측정한다.
The temperature of the above compounding liquid is adjusted to 25 占 폚, and 1200 g per m < 2 > is applied to a 30 x 30 cm glass plate. After 30 seconds of application, the solution was taken in a coagulation bath of 18% dimethylformamide aqueous solution and coagulated for 10 minutes. After washing for 15 minutes in a water bath at 50 ° C, squeeze 5 times for complete denitrification and then completely dry in an oven at 120 ° C for 20 minutes.
3) 함침 가공시험3) Impregnation test
- 배합액제조- Preparation of compounding liquid
합성된 수지 조성물 100중량부에 우레탄수지와 상용성이 우수한 계면활성제 2중량부, Cell의 크기를 조절하는 계면활성제 1중량부, 블랙토너 10중량부, 디메틸포름아미드 250중량부를 균일하게 혼합하여 배합액을 제조한다.2 parts by weight of a surfactant excellent in compatibility with a urethane resin, 1 part by weight of a surfactant for controlling the size of a cell, 10 parts by weight of a black toner and 250 parts by weight of dimethylformamide were mixed uniformly in 100 parts by weight of the synthesized resin composition, Solution.
-함침가공 - - Impregnation processing -
위의 배합액을 스웨이드(Suede)원단에 골고루 침투시켜 squeezing하여 원단속의 함침액의 양을 조절한 후 25% 디메틸포름아미드 수용액의 응고조에 입수시켜 10분간 응고를 실시한다.The amount of the impregnation solution in the fabric is adjusted by squeezing the solution in a uniform manner onto the Suede fabric, and then the solution is supplied to a coagulation bath of 25% dimethylformamide aqueous solution and coagulated for 10 minutes.
50℃의 수세조에서 15분간 수세를 해준 뒤 완전한 탈DMF를 위해 5회 squeezing 후 120℃ OVEN에서 20분간 완전 건조한다. After washing for 15 minutes in a water bath at 50 ° C, squeeze 5 times for complete DMF removal and then completely dry at 120 ° C for 20 minutes.
- 평가방법 - - Assessment Methods -
터치감 : 위의 함침 가공된 스웨이드(Suede) 원단의 터치감을 손으로 만져 우수(○), 보통(△), 불량(×)의 3단계로 나눈다. Touch feeling: The touch feeling of the impregnated suede fabric is divided into three stages of excellent (○), normal (△), and poor (×).
발색성 : 위의 함침 가공된 스웨이드(Suede) 원단을 육안으로 확인해 우수(○), 보통(△), 불량(×)의 3단계로 나눈다.
Color development: The impregnated suede fabric is visually inspected and divided into three stages: excellent (◯), normal (△), and poor (×).
[표 1] 시험 결과표[Table 1] Test result table
상기 비교예1 내지 비교예7의 경우는 표 1에서와 같이 터치감이 좋으면 발색성이 부족하고, 발색성이 좋으면 터치감이 떨어지는 결과를 보였다. 그리고 본 발명에 의한 실시예1 및 실시예2는 모두 터치감과 발색성이 좋은 결과를 보였다.In the case of Comparative Examples 1 to 7, as shown in Table 1, color fastness was poor when the touch feeling was good, and touch feeling was poor when color fastness was good. Both Example 1 and Example 2 according to the present invention showed good touch feeling and good color development.
그리고 본 발명의 실시예1 및 실시예2는 비교예1 내지 비교예7에 비해 탈DMF속도가 같거나 더 빠르고, 후도도 같거나 우수하게 나타났다.In Examples 1 and 2 of the present invention, the DMF removal rate was equal to or faster than that of Comparative Examples 1 to 7, and was equal to or better than that of Comparative Example 1.
본 발명은 일반 폴리에스테르-에테르 폴리우레탄 수지 조성물보다 빠른 탈 DMF 속도로 다공성의 형상(Cell 구조)을 부여하여 부드러운 터치감과 볼륨감이 우수하며 특히, 쇄연장제(Chain Extender)의 적절한 조합으로 기존 폴리에스테르-에테르 폴리우레탄 수지 조성물보다 발색성이 우수하다.The present invention provides a porous structure (cell structure) at a higher DMF rate than a general polyester-ether polyurethane resin composition, thereby providing a smooth touch feeling and a good volume feeling. Especially, a proper combination of a chain extender It is more excellent in color development than the polyester-ether polyurethane resin composition.
이상, 본 발명에 의한 발색성이 우수한 합성피혁 함침용 폴리우레탄 수지 조성물에 대해 설명하였다.The polyurethane resin composition for impregnating synthetic leather according to the present invention having excellent color development has been described above.
상기 본 발명의 기술적 구성은 본 발명이 속하는 기술분야의 당업자가 그 기술적 사상이나 필수적 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다.It will be understood by those skilled in the art that the technical features of the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof.
그러므로, 이상에서 기술한 실시 예들은 모든 면에서 예시적인 것이며 한정적인 것이 아닌 것으로서 이해되어야 하고, 본 발명의 범위는 전술한 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 할 것이다.
Therefore, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than the foregoing description, Ranges and equivalents thereof are to be construed as being included within the scope of the present invention.
Claims (4)
부틸렌글리콜계 폴리에스테르 폴리올 70 내지 120중량부와,
부틸렌글리콜 10 내지 15중량부와,
네오펜틸글리콜 13 내지 18중량부와,
산화방지제 0.1 내지 0.4중량부 및 디메틸포름아미드가 혼합되어 불휘발분이 28~33wt%인 것을 특징으로 하는 발색성이 우수한 합성피혁 함침용 폴리우레탄 수지 조성물.
70 to 120 parts by weight of a polytetramethylene ether glycol-based polyol,
70 to 120 parts by weight of a butylene glycol-based polyester polyol,
10 to 15 parts by weight of butylene glycol,
13 to 18 parts by weight of neopentyl glycol,
0.1 to 0.4 parts by weight of an antioxidant, and dimethylformamide are mixed to have a nonvolatile content of 28 to 33% by weight, wherein the polyurethane resin composition is excellent in color development.
에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올 70 내지 120중량부와,
부틸렌글리콜 10 내지 15중량부와,
네오펜틸글리콜 13 내지 18중량부와,
산화방지제 0.1 내지 0.4중량부 및 디메틸포름아미드가 혼합되어 불휘발분이 28~33wt%인 것을 특징으로 하는 발색성이 우수한 합성피혁 함침용 폴리우레탄 수지 조성물.
70 to 120 parts by weight of a polytetramethylene ether glycol-based polyol,
70 to 120 parts by weight of an ethylene glycol-butylene glycol-based polyester polyol,
10 to 15 parts by weight of butylene glycol,
13 to 18 parts by weight of neopentyl glycol,
0.1 to 0.4 parts by weight of an antioxidant, and dimethylformamide are mixed to have a nonvolatile content of 28 to 33% by weight, wherein the polyurethane resin composition is excellent in color development.
상기 폴리테트라 메틸렌 에테르 글리콜계 폴리올은 수산기값이 56±3이고, 산값이 0.05 이하인 것을 특징으로 하는 발색성이 우수한 합성피혁 함침용 폴리우레탄수지 조성물.
3. The method according to claim 1 or 2,
Wherein the polytetramethylene ether glycol polyol has a hydroxyl value of 56 3 and an acid value of 0.05 or less.
상기 폴리테트라 메틸렌 에테르 글리콜계 폴리올, 부틸렌글리콜계 폴리에스테르 폴리올 및 에틸렌글리콜-부틸렌글리콜계 폴리에스테르 폴리올은 수평균분자량이 2000인 것을 특징으로 하는 발색성이 우수한 합성피혁 함침용 폴리우레탄수지 조성물.
3. The method according to claim 1 or 2,
Wherein said polytetramethylene ether glycol-based polyol, butylene glycol-based polyester polyol, and ethylene glycol-butylene glycol-based polyester polyol have a number average molecular weight of 2000.
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| CN110498900A (en) * | 2019-09-10 | 2019-11-26 | 浙江华峰合成树脂有限公司 | High black color developing leather polyurethane resin and preparation method thereof |
| KR20220165580A (en) * | 2021-06-08 | 2022-12-15 | 강남제비스코 주식회사 | A polyurethane skin resin composition for pet film and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101739689B1 (en) | 2016-04-19 | 2017-05-24 | 강남제비스코 주식회사 | polyurethane resin composition for artificial leather impregnation |
| CN110498900A (en) * | 2019-09-10 | 2019-11-26 | 浙江华峰合成树脂有限公司 | High black color developing leather polyurethane resin and preparation method thereof |
| KR20220165580A (en) * | 2021-06-08 | 2022-12-15 | 강남제비스코 주식회사 | A polyurethane skin resin composition for pet film and its manufacturing method |
| KR102641079B1 (en) * | 2021-06-08 | 2024-02-27 | 강남제비스코 주식회사 | A polyurethane skin resin composition for pet film and its manufacturing method |
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