JPH02191778A - Production of synthetic leather - Google Patents
Production of synthetic leatherInfo
- Publication number
- JPH02191778A JPH02191778A JP1108489A JP1108489A JPH02191778A JP H02191778 A JPH02191778 A JP H02191778A JP 1108489 A JP1108489 A JP 1108489A JP 1108489 A JP1108489 A JP 1108489A JP H02191778 A JPH02191778 A JP H02191778A
- Authority
- JP
- Japan
- Prior art keywords
- water
- polyurethane resin
- synthetic leather
- soluble natural
- polymer substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 59
- 239000000126 substance Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229920005615 natural polymer Polymers 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 21
- 102000004190 Enzymes Human genes 0.000 claims description 11
- 108090000790 Enzymes Proteins 0.000 claims description 11
- 238000009981 jet dyeing Methods 0.000 claims description 11
- 230000000593 degrading effect Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 20
- 239000010985 leather Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 9
- 229920000728 polyester Polymers 0.000 abstract description 9
- 229920002472 Starch Polymers 0.000 abstract description 6
- 235000019698 starch Nutrition 0.000 abstract description 5
- 239000008107 starch Substances 0.000 abstract description 4
- 239000004677 Nylon Substances 0.000 abstract description 3
- 229920001778 nylon Polymers 0.000 abstract description 3
- 239000003292 glue Substances 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 54
- 210000003491 skin Anatomy 0.000 description 19
- 229920001592 potato starch Polymers 0.000 description 11
- 210000002615 epidermis Anatomy 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000005018 casein Substances 0.000 description 6
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 6
- 235000021240 caseins Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- -1 ester salts Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002335 surface treatment layer Substances 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- 239000004382 Amylase Substances 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 239000004808 2-ethylhexylester Substances 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は合成皮革の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing synthetic leather.
近年、天然皮革にかわって織布、不織布等の基材にポリ
ウレタン等の合成樹脂弾性体を積層して形成した人工皮
革、合成皮革が広（利用されるようになっているが、こ
れら人工皮革、合成皮革の外観、風合、感触をより天然
皮革に近いものとするために種々の改良が加えられてい
る。In recent years, instead of natural leather, artificial leather and synthetic leather, which are formed by laminating a synthetic resin elastic material such as polyurethane on a base material such as woven fabric or non-woven fabric, have become widely used. Various improvements have been made to make the appearance, texture, and feel of synthetic leather more similar to natural leather.
人工皮革、合成皮革の風合、触感等を天然皮革に近づけ
るための方法として、合成樹脂中に天然皮革＄５）末を
添加する方法が提案されており、例えば５０〜２５０メ
ツシユ（約３００〜６０μ）の天然皮革粉末を、該皮革
粉末に対して重量比で７０〜３０重量％の熱可塑性樹脂
コンパウンドに添加し、更にこれに発泡剤を添加してこ
れらを混合した後、加熱圧延して発泡シートとした人工
皮革（特開昭６３−１０６４１号公報）等が知られてい
る。As a method for bringing the texture, touch, etc. of artificial leather and synthetic leather closer to those of natural leather, a method has been proposed in which natural leather powder ($5) is added to synthetic resin. 60μ) of natural leather powder is added to a thermoplastic resin compound with a weight ratio of 70 to 30% based on the leather powder, and a blowing agent is added to this and mixed, followed by hot rolling. Artificial leather made into a foam sheet (Japanese Unexamined Patent Publication No. 10641/1983) is known.
しかしながら上記特開昭６３−１０６４１号公報に記載
された人工皮革は加熱圧延して発泡してシート状に形成
しているため、表皮部分に所謂スキン層が形成され、こ
のスキン層によって天然皮革粉末を添加したことにより
得られる天然皮革様の触感が阻害されるとともに、透湿
性、通気性にも劣ったものとなる。このためスキン層部
分をスライスして除去する必要があり、製造作業が煩雑
になるとともに、樹脂中に天然皮革粉末を添加して発泡
しているために、天然皮革粉末が人工皮革全体に分散し
ており、このため天然皮革粉末を多量に添加しないと表
面感触の充分な向上が得られず、また天然皮革粉末を多
量に添加すると、表面感触の向上は得られるものの皮革
全体の強度が低下して実用に耐え得ないものとなるとい
う相矛盾する欠点があった。However, since the artificial leather described in JP-A No. 63-10641 is heat-rolled and foamed to form a sheet, a so-called skin layer is formed on the epidermis, and this skin layer allows natural leather powder to be The addition of this material impairs the natural leather-like feel, and also results in poor moisture permeability and air permeability. For this reason, it is necessary to slice and remove the skin layer, which complicates the manufacturing process, and because natural leather powder is added to the resin and foamed, the natural leather powder is dispersed throughout the artificial leather. Therefore, unless a large amount of natural leather powder is added, the surface feel cannot be sufficiently improved, and if a large amount of natural leather powder is added, although the surface feel can be improved, the strength of the entire leather decreases. However, it had contradictory drawbacks, such as making it impractical for practical use.
本発明は上記の従来技術の欠点を解決し、外観、風合、
感触等に優れるとともに透湿性、通気性等の物性にもば
れた合成皮革の製造方法を提供することを目的とする。The present invention solves the above-mentioned drawbacks of the prior art, improves appearance, texture,
The purpose of the present invention is to provide a method for producing synthetic leather that is excellent in feel, etc., and also exhibits physical properties such as moisture permeability and air permeability.
即ち本発明は、
（１） 基材の少なくとも片面に水溶性天然高分子物
質を含有するポリウレタン樹脂層を形成した後、該積層
体を浸透剤を添加した水中に浸漬して水溶性天然高分子
物質を溶解除去して多孔性の表皮層を形成することを特
徴とする合成皮革の製造方法。That is, the present invention provides the following steps: (1) After forming a polyurethane resin layer containing a water-soluble natural polymer substance on at least one side of a base material, the laminate is immersed in water to which a penetrating agent is added to form a water-soluble natural polymer substance. A method for producing synthetic leather, which comprises dissolving and removing a substance to form a porous skin layer.
（２）基材の少なくとも片面にポリウレタン樹脂の親水
性有機溶媒溶液を塗布した後、水中に浸漬して溶媒を除
去するとともにポリウレタンを凝固させてポリウレタン
樹脂の微多孔層を形成し、次いでその表面に水溶性天然
高分子物質を含有するポリウレタン樹脂層を形成した後
、該積層体を浸透剤を添加した水中に浸漬して水溶性天
然高分子物質を溶解除去して多孔性の表皮層を形成する
ことを特徴とする合成皮革の製造方法。(2) After coating a hydrophilic organic solvent solution of polyurethane resin on at least one side of the substrate, immerse it in water to remove the solvent and coagulate the polyurethane to form a microporous layer of polyurethane resin, and then form a microporous layer of polyurethane resin on the surface. After forming a polyurethane resin layer containing a water-soluble natural polymer substance, the laminate is immersed in water containing a penetrant to dissolve and remove the water-soluble natural polymer substance to form a porous skin layer. A method for producing synthetic leather characterized by:
（３）請求項１または２記載の合成皮革の製造方法にお
いて、浸透剤及び水溶性高分子物質の分解酵素を含む水
中で水溶性天然高分子物質を溶解除去することを特徴と
する合成皮革の製造方法。(3) The method for producing synthetic leather according to claim 1 or 2, characterized in that the water-soluble natural polymer substance is dissolved and removed in water containing a penetrant and a water-soluble polymer substance degrading enzyme. Production method.
（４）請求項１〜３のいずれかに記載の合成皮革の製造
方法において、液流染色機にて水溶性天然高分子物質を
溶解除去することを特徴とする合成皮革の製造方法。(4) The method for producing synthetic leather according to any one of claims 1 to 3, characterized in that the water-soluble natural polymer substance is dissolved and removed using a jet dyeing machine.
を要旨とするものである。The main points are as follows.
（実施例） 以下、本発明の一実施例を図面に基き説明する。(Example) Hereinafter, one embodiment of the present invention will be described based on the drawings.
第１図は本発明の合成皮革の製造方法の一例を示し、ま
ず例えばシボ付き離型紙１のシボ而に、水溶性天然高分
子物質２（第２図）を含有する表皮層形成用ポリウレタ
ン樹脂の溶液をドクターナイフ３等によって塗布して均
一厚さとした後、加熱オーブン４中で乾燥させて水溶性
天然高分子物質２を含有するポリウレタン樹脂層５を形
成し、次いで基材６と重ね合わせて加熱ロール７によっ
て加熱して両者を熱圧着し更に加熱オーブンＢ中を通過
させて残存する溶剤を完全に揮散させた後に離型紙ｌを
剥離することにより水溶性天然高分子物質２を含有する
ポリウレタン樹脂層５を基材６に転写積層した積層体９
を得る。FIG. 1 shows an example of the method for producing synthetic leather of the present invention. First, for example, a polyurethane resin for forming a skin layer containing a water-soluble natural polymer substance 2 (FIG. 2) is applied to the wrinkles of a textured release paper 1. The solution is applied with a doctor knife 3 or the like to have a uniform thickness, and then dried in a heating oven 4 to form a polyurethane resin layer 5 containing a water-soluble natural polymer substance 2, which is then overlapped with a base material 6. The mixture is heated by a heating roll 7 to bond them together by thermocompression, and then passed through a heating oven B to completely volatilize the remaining solvent, and then the release paper 1 is peeled off to contain the water-soluble natural polymer substance 2. A laminate 9 in which a polyurethane resin layer 5 is transferred and laminated onto a base material 6
get.
上記基材６としてはナイロン、ポリエステル、綿、レー
ヨン等の繊維単独又はこれらの混紡繊維よりなる織布、
不織布、編布等が用いられる。The base material 6 may be a woven fabric made of fibers such as nylon, polyester, cotton, or rayon alone or a blend of these fibers;
Nonwoven fabrics, knitted fabrics, etc. are used.
水溶性天然高分子物質２としては甘苦デンプン、馬鈴薯
デンプン、小麦デンプン、クビオカデンプン、コーンス
ターチ等のデンプン質、にかわ、ゼラチン、カゼイン、
コラーゲン等の蛋白質等が挙げられる。これら水溶性天
然高分子物ｆａ２は粒径３０μ以下、特に２０μ以下の
ものを用いることが好ましく、粒径が大きすぎるとこれ
らの水溶性天然高分子物質２を含むポリウレタン樹脂を
塗布した際に均一な塗布ができ難くなり、表面にスジ等
が生じ易くなる。上記水溶性天然高分子物質２のポリウ
レタン樹脂中への添加量は、樹脂に対して１００〜２０
重量％、特に７０〜３０重量％が好ましい、水溶性天然
高分子物質２の添加量が少なずぎると透湿性、通気性の
向上が望めず、また多すぎると透湿性、通気性は良好と
なるが、膜強度が著しく低下する。Examples of water-soluble natural polymer substances 2 include starches such as sweet and bitter starch, potato starch, wheat starch, kubioka starch, cornstarch, glue, gelatin, casein,
Examples include proteins such as collagen. It is preferable to use these water-soluble natural polymer substances fa2 with a particle size of 30μ or less, particularly 20μ or less.If the particle size is too large, the polyurethane resin containing these water-soluble natural polymer substances 2 may not be uniform when applied. It becomes difficult to apply the product in a consistent manner, and streaks are more likely to occur on the surface. The amount of the water-soluble natural polymer substance 2 added to the polyurethane resin is 100 to 20% based on the resin.
Weight%, preferably 70 to 30% by weight. If the amount of water-soluble natural polymer substance 2 added is too small, no improvement in moisture permeability and air permeability can be expected, and if it is too large, moisture permeability and air permeability will be poor. However, the film strength decreases significantly.
上記水溶性天然高分子物￥ｔ２が添加されるポリウレタ
ン樹脂としてはポリエステル系ポリウレタン、ポリエー
テル系ポリウレタン、ポリカプロラクトン系ポリウレタ
ン、ポリカーボネート系ポリウレタン等のいずれでも使
用可能である。As the polyurethane resin to which the water-soluble natural polymer t2 is added, any of polyester polyurethane, polyether polyurethane, polycaprolactone polyurethane, polycarbonate polyurethane, etc. can be used.
次いで上記積層体９を、浸透剤を添加した水中に浸漬し
て水溶性天然高分子物質２を溶解除去することにより、
第３図に示す如き微細孔１０を有する表皮［１１を形成
した合成皮革１２が得られる。上記浸透剤とＬ７てはス
ルホこはく酸ジー２−エチルへキシルエステルナトリウ
ム塩等のスルホこはく酸ジアルキルエステル塩（エアロ
ゾルＯＴ型）、ドデシルベンゼンスルホン酸ナトリウム
等のアルキルベンゼンスルホン酸塩、ラウリル硫酸エス
テルナトリウム等のアルキル硫酸エステル塩、ブチルナ
フタレンスルホン酸ナトリウム等のアルキルナフタレン
スルホン酸塩（ネカールＢＸ型）、オレイン酸ブチルス
ルホン酸ナトリウム等のオレイン酸アルキル硫酸化物等
のアニオン系浸透剤；ノニルフェノールのエチレンオキ
サイド（ＥＯ）付加物、オクチルフェノールのエチレン
オキサイド（７〜１０モル）付加物等のアルキルフェノ
ールのエチレンオキサイド（７〜１０モル）付加物、ラ
ウリルアルコールのエチレンオキサイド（５〜１０モル
）付加物等の中級〜高級アルコールのエチレンオキサイ
ド（ＥＯ）付加物等の非イオン系浸透剤等が好ましく使
用できる。これら浸透剤は単独で又は２種以上混合して
使用でき、その使用量は水１０００ｃｃに対して浸透剤
０．１〜ｌＯｇ、好ましくは０．５〜５ｇの範囲で添加
使用するのが良い。Next, the laminate 9 is immersed in water containing a penetrating agent to dissolve and remove the water-soluble natural polymer substance 2.
A synthetic leather 12 having a skin [11] having micropores 10 as shown in FIG. 3 is obtained. The above penetrants and L7 include sulfosuccinic acid dialkyl ester salts (aerosol OT type) such as sulfosuccinic acid di-2-ethylhexyl ester sodium salt, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, etc. anionic penetrants such as alkyl sulfate salts of , alkylnaphthalene sulfonates (Necal BX type) such as sodium butylnaphthalene sulfonate, alkyl oleate sulfates such as sodium butyl oleate; ethylene oxide (EO) of nonylphenol; ) adducts, ethylene oxide (7 to 10 moles) adducts of alkylphenols such as ethylene oxide (7 to 10 moles) adducts of octylphenol, and intermediate to higher alcohols such as ethylene oxide (5 to 10 moles) adducts of lauryl alcohol. Nonionic penetrants such as ethylene oxide (EO) adducts can be preferably used. These penetrants can be used alone or in combination of two or more, and the amount used is preferably 0.1 to 10 g, preferably 0.5 to 5 g, of the penetrant per 1000 cc of water.
本発明においては上記浸透剤を添加した水中、好ましく
は温水中に、ポリウレタン樹脂層５中に含まれる水溶性
天然高分子物質２０分解酵素を添加しても良く、この場
合の分解酵素としてはポリウレタン樹脂層５中に含まれ
る水溶性天然高分子物質２がデンプン質である場合には
アミラーゼが、水溶性天然高分子物質２が蛋白質である
場合にはプロテアーゼが使用される。これらの分解酵素
が水溶性高分子物質を溶解処理するための温水中に含ま
れていることにより、分解酵素を含まない場合に比べて
低温で効率よく水溶性天然高分子物質の溶解処理を行う
ことができ、ポリウレタン樹脂の劣化を防止できるとも
に、水溶性天然高分子物質の溶解除去時間の更なる短縮
、除去率の向上を図ることができる。これらの分解酵素
の添加量は浸漬処理するシートのポリウレタン樹脂中に
含まれる水溶性天然高分子物質の重量の０．０１〜５重
景％が好ましい、水溶性天然高分子物質２の溶解除去に
際し、処理液のｐｉ＋を分解酵素の活性が高くなる範囲
に調整することが好ましく、酵素がアミラーゼの場合に
はｐＨ−５〜７が、プロテアーゼの場合にはｐｌ＋＝７
〜１１とすることが好ましい。水溶性天然高分子物質２
の溶解除去は５０〜７０″Ｃ程度の温水中に積層体９を
０．５〜２時間程度浸漬して行うことが好ましい。水溶
性天然高分子物質２の溶解除去を揉み処理を施しながら
行うと、溶解除去率が向上するとともに、柔軟処理を同
時に行うことができる。この揉み処理は液流染色機によ
り行うと良好に行うことができ好ましい。In the present invention, an enzyme that decomposes the water-soluble natural polymer substance 20 contained in the polyurethane resin layer 5 may be added to water to which the above-mentioned penetrating agent has been added, preferably hot water. When the water-soluble natural polymer substance 2 contained in the resin layer 5 is starch, amylase is used, and when the water-soluble natural polymer substance 2 is protein, protease is used. By containing these degrading enzymes in the hot water for dissolving water-soluble polymeric substances, the dissolution process of water-soluble natural polymeric substances can be carried out more efficiently at lower temperatures than when no degrading enzymes are included. This makes it possible to prevent deterioration of the polyurethane resin, further shorten the time required to dissolve and remove the water-soluble natural polymer substance, and improve the removal rate. The amount of these degrading enzymes added is preferably 0.01 to 5% by weight of the water-soluble natural polymer substance contained in the polyurethane resin of the sheet to be immersed. It is preferable to adjust the pi+ of the treatment solution to a range where the activity of the degrading enzyme is high, and when the enzyme is amylase, the pH is -5 to 7, and when the enzyme is protease, the pH is pl+ = 7.
It is preferable to set it as 11. Water-soluble natural polymer substance 2
It is preferable to dissolve and remove the laminate 9 by immersing it in hot water of about 50 to 70''C for about 0.5 to 2 hours.The dissolution and removal of the water-soluble natural polymer substance 2 is carried out while performing a rubbing treatment. This improves the dissolution/removal rate and allows softening treatment to be carried out at the same time.This rolling treatment is preferably carried out using a jet dyeing machine because it can be carried out well.
尚、揉み処理は水溶性天然高分子物質の溶解除去後に別
工程で行ってもよい。Note that the rubbing treatment may be performed in a separate step after the water-soluble natural polymer substance is dissolved and removed.
上記の例では水溶性天然高分子物質２を含有するポリウ
レタン樹脂層５を加熱ラミネートにより基材ｌに積層一
体化する場合について示したが、接着剤により基材ｌに
接着してもよく、この場合、接着剤中にも水溶性天然高
分子物質２を含有させておく。これは表皮層を形成する
ためのポリウレタン樹脂層中に含有される水溶性天然高
分子物質２が積層体９０表面側からも裏面側からも効率
良く溶解除去されるようにするためである。接着剤とし
てはポリエステル系ポリウレタン、ポリエーチル系ポリ
ウレタン、ポリカプロラクトン系ポリウレタン、ポリカ
ーボネート系ポリウレタン等の２液型ポリウレタン樹脂
等を用いることができる。The above example shows the case where the polyurethane resin layer 5 containing the water-soluble natural polymer substance 2 is laminated and integrated with the base material l by heating lamination, but it may also be adhered to the base material l with an adhesive. In this case, the water-soluble natural polymer substance 2 is also contained in the adhesive. This is to ensure that the water-soluble natural polymer substance 2 contained in the polyurethane resin layer for forming the skin layer is efficiently dissolved and removed from both the front side and the back side of the laminate 90. As the adhesive, two-component polyurethane resins such as polyester polyurethane, polyethyl polyurethane, polycaprolactone polyurethane, and polycarbonate polyurethane can be used.
本発明においては基材１の少なくとも片面にポリウレタ
ン樹脂の親水性有機溶媒溶液（例えばＤＭＦ等）を塗布
した後、水中に浸漬して溶媒を除去してポリウレタンを
凝固させるとともに、脱溶媒による孔１３を有する微多
孔Ｍ１４を形成し、しかる後、この表面に前記と同様に
して水溶性天然高分子物質２を含有するポリウレタン樹
脂層５を形成し、次いでこのポリウレタン樹脂層５中の
水溶性天然高分子物質２を同様にして溶解除去して微細
孔１０を有する表皮層１１を設けた第４図に示す如き合
成皮革とすることもできる。このような微多孔層１４を
設けると柔軟性がより向２トシ更に天然皮革にＭ（ｌ！
シた感触を有する合成皮革となる。In the present invention, a hydrophilic organic solvent solution (for example, DMF, etc.) of a polyurethane resin is applied to at least one side of the base material 1, and then the polyurethane is solidified by removing the solvent by immersing it in water. After that, a polyurethane resin layer 5 containing a water-soluble natural polymer substance 2 is formed on this surface in the same manner as described above. It is also possible to dissolve and remove the molecular substance 2 in the same manner to obtain a synthetic leather as shown in FIG. 4, in which a skin layer 11 having micropores 10 is provided. Providing such a microporous layer 14 increases the flexibility of the natural leather.
The result is synthetic leather with a soft feel.
更に表皮層１１の表面又は表皮層１１を形成するための
ポリウレタン樹脂層５０表面に水溶性天然高分子物質を
含有するポリウレタン樹脂層をグラビアコート法等によ
って塗布し、次いで水溶性天然高分子物質を溶解除去し
て微細孔１０を有する表面処理層１５を設けた第５図に
示す如き合成皮革とすることもできる。表面処理層Ｉ５
を形成するためのポリウレタン樹脂は、乾燥時の塗布量
が１〜５ ｇ／ｒｒｒ程度となるように塗布することが
好ましい。この表面処理層Ｉ５を形成するために用いる
ポリウレタン樹脂溶液としては通常のポリウレタン樹脂
の他にシリコン変性ポリウレタン樹脂、アミノ酸変性ポ
リウレタン樹脂、ポリアミド変性ポリウレタン樹脂等が
用いられる。表皮層１１の表面に更に微細孔１０を有す
る表面処理層１５を設けると、表面の感触を更に天然皮
革の感触に類似させることができる。Further, a polyurethane resin layer containing a water-soluble natural polymer substance is coated on the surface of the skin layer 11 or the surface of the polyurethane resin layer 50 for forming the skin layer 11 by a gravure coating method, and then a water-soluble natural polymer substance is applied. It is also possible to obtain a synthetic leather as shown in FIG. 5 in which a surface treatment layer 15 having micropores 10 is provided by dissolving and removing it. Surface treatment layer I5
It is preferable to apply the polyurethane resin for forming the film so that the dry coating amount is about 1 to 5 g/rrr. As the polyurethane resin solution used to form this surface treatment layer I5, in addition to ordinary polyurethane resins, silicon-modified polyurethane resins, amino acid-modified polyurethane resins, polyamide-modified polyurethane resins, etc. are used. If a surface treatment layer 15 having micropores 10 is further provided on the surface of the skin layer 11, the feel of the surface can be made more similar to that of natural leather.
尚、本発明において表皮層１１の着色の目的で表皮層１
１を形成するポリウレタン樹脂層５中又は必要により上
記ポリウレタン樹脂層５の接着の目的で設けられる接着
剤層中に顔料、染料等の着色剤を添加することができる
。また表皮層１１中には更に必要により各種安定剤、充
＠剤等、その他の添加剤を添加することもできる。In addition, in the present invention, for the purpose of coloring the epidermal layer 11, the epidermal layer 1
A coloring agent such as a pigment or dye can be added to the polyurethane resin layer 5 forming the polyurethane resin layer 1 or, if necessary, to an adhesive layer provided for the purpose of adhering the polyurethane resin layer 5. Furthermore, other additives such as various stabilizers and fillers may be added to the skin layer 11 if necessary.
以下、具体的実施例を挙げて本発明を更に詳細に説明す
る。Hereinafter, the present invention will be explained in more detail by giving specific examples.
実施例１
シボ付き離型紙の表面に、平均粒径１７μの馬鈴薯デン
プンを５０重量％含有する１００％モジュラスが７０ｋ
ｇ／ｃｄのポリエステル系ポリウレタン樹脂（大目本イ
ンキ製：クリスボンＮＢ−６３ｉｓ）の２０％ＤＭＦ−
ＭＥＫ溶液（着色剤をポリウレタン樹脂１００重量部当
たりに対して１５重量部含有）を乾燥時のｊγさが２０
μとなるようにナイフコーターにて塗布して１００ ’
Ｃで１．５分間熱風乾燥させ、ポリウレタン樹脂層を形
成した。Example 1 The surface of the textured release paper contained 50% by weight of potato starch with an average particle size of 17μ, and the 100% modulus was 70k.
20% DMF of g/cd polyester polyurethane resin (manufactured by Ohmemoto Ink: Crisbon NB-63is)
MEK solution (contains 15 parts by weight of colorant per 100 parts by weight of polyurethane resin) has a jγ value of 20 when dried.
Coat with a knife coater so that μ is 100'
It was dried with hot air at C for 1.5 minutes to form a polyurethane resin layer.
次いでこのポリウレタン樹脂層表面に平均位径が１７μ
の馬鈴薯デンプンを５０重蟹％含有する１００％モジュ
ラスが２０ｋｇ／ｃ・Ｊの２液型ボ゛・Ｊウレタン接着
剤（大ト１本インキ製：クリスボンＴＡ４６５）の４０
％ＭＥＫ−トルエン溶液を１１付量が９０ ｇ／ｒｒｆ
となるように塗布し、これを９０°Ｃで１．５分間熱風
乾燥させた後、厚さ０．５ｍのウーリーナイロントリコ
ット編布（基材）と貼合わせ、更に加熱乾燥して接着剤
を硬化させ、しかる後、離型紙を剥離して積層体を形成
した。この積層体を液流染色機により処理するにあたり
、スルホこはく酸ジー２−エチルヘキシルエステルナト
リウム塩（三洋化成社製：サンモリン０Ｔ−７０）を０
．３％含む９０゛Ｃの温水に６０分間浸漬して揉み処理
しながら馬鈴薯デンプンを溶解除去し、微細孔を有する
表皮層１１中して合成皮革とした（液流染色機処理条件
：布速２５０ｒｎ／分、圧力２．１ｋｇ ／ ｃｄ、浴
比１：２０）。Next, the surface of this polyurethane resin layer was coated with an average diameter of 17 μm.
40 of a two-component type Vo/J urethane adhesive (manufactured by large size one ink: Crisbon TA465) with a 100% modulus of 20 kg/c/J containing 50% potato starch.
%MEK-toluene solution 11 loading amount is 90 g/rrf
After drying this with hot air at 90°C for 1.5 minutes, it was bonded to a woolly nylon tricot knitted fabric (base material) with a thickness of 0.5 m, and further heat-dried to remove the adhesive. After curing, the release paper was peeled off to form a laminate. When processing this laminate using a jet dyeing machine, sulfosuccinic acid di-2-ethylhexyl ester sodium salt (manufactured by Sanyo Chemical Co., Ltd.: Sanmorin 0T-70) was added to
．． The potato starch was dissolved and removed by immersion in warm water at 90°C containing 3% for 60 minutes while being rubbed, and the skin layer 11 having micropores was made into synthetic leather (jet dyeing machine processing conditions: cloth speed 250rn). /min, pressure 2.1 kg/cd, bath ratio 1:20).
得られた合成皮革は風合がソフトでドレープ性があり、
かつ揉み皺が長期間に亘って保持され、きわめて柔軟性
に富み、外観、風合ともに天然皮革に酷似し、衣料用素
材として好適なものであった。この合成皮革の透湿度（
ＪＩＳ Ｚ−０２０８による）は２６５０ ｇ ／ ｎ
（・２４時間であった。また表皮層中の馬鈴薯デンプン
の除去率は９４％であった。The resulting synthetic leather has a soft texture and drapability.
Moreover, it retained its wrinkles after being rubbed for a long period of time, was extremely flexible, and had an appearance and feel very similar to natural leather, making it suitable as a material for clothing. The moisture permeability of this synthetic leather (
According to JIS Z-0208) is 2650 g/n
(・24 hours. Also, the removal rate of potato starch in the epidermal layer was 94%.
実施例２
厚さ０．４５ｍｍのポリノジック織布の起毛面にｌ００
％モジュラスが２０ｋｇ／ｃｉｉｌのポリエステル系ポ
リウレタン樹脂（大日本インキ製：クリスボンＭｌ’８
１２ＮＢ）の１１％ＤＭＦ溶液を目付量が６５０ｇ／ｎ
（となるように塗布した後、２０℃の水中で脱溶媒して
凝固し、次いで脱水後１２０℃の熱風下で乾燥して厚さ
０．５７＋ｗの微多孔層を有する基材を得た。Example 2 100 on the raised surface of a polynosic woven fabric with a thickness of 0.45 mm
Polyester polyurethane resin with a % modulus of 20 kg/ciil (manufactured by Dainippon Ink: Crisbon Ml'8
12NB) 11% DMF solution with a basis weight of 650g/n
(After coating, it was coagulated by desolvation in water at 20°C, and then dried under hot air at 120°C after dehydration to obtain a base material having a microporous layer with a thickness of 0.57+w.
一方、シボ付き離型紙の表面に、平均粒径１５μのカゼ
インを５０重量％含有する１００％モジュラスが５５ｋ
ｇ／ｃｄのポリエステル系ポリウレタン樹脂（大日精化
製：レザミンＭＥ３６１２ＬＰ）の２０％ＤＭＦ−ＭＥ
Ｋ溶液（着色剤をポリウレタン樹脂１００重量部に対し
て２０重量部含有）を乾燥時の厚さが２５μとなるよう
にナイフコーターにて塗布して１００″Ｃにて２分間熱
風乾燥させ、ポリウレタン樹脂層を形成し、このポリウ
レタン樹脂層の表面に前記微多孔層を形成した基材の微
多孔層面を加熱しなから１４０ ’Ｃにて熱圧着した後
、離型紙を剥離して微多孔層表面にカゼインを含有する
ポリウレタン樹脂層を転写した積層体を得た。この積層
体を液流染色機により処理するにあたり、ポリオキシエ
チレンノニルフェニルエーテル（日本油脂社製：ニラサ
ンノニオンＮＳ）を０．４％含む１００″Ｃの温水に５
０分間浸漬して揉み処理しながらカゼインを溶解除去し
、微細孔を有する表皮層を形成して合成皮革とした（液
流染色機処理条件：布速２７０ｍ／分、圧力２．３ｋｇ
／ｃｄ、浴比１８２０）。On the other hand, the surface of the textured release paper contains 50% by weight of casein with an average particle size of 15μ, and the 100% modulus is 55k.
20% DMF-ME of polyester polyurethane resin (Rezamin ME3612LP, manufactured by Dainichiseika Chemical Co., Ltd.) of g/cd
K solution (containing 20 parts by weight of coloring agent per 100 parts by weight of polyurethane resin) was applied with a knife coater to a dry thickness of 25μ, and dried with hot air at 100"C for 2 minutes to coat the polyurethane resin. A resin layer is formed, and the surface of the microporous layer of the base material on which the microporous layer is formed on the surface of the polyurethane resin layer is thermocompressed at 140'C without heating, and then the release paper is peeled off to form the microporous layer. A laminate was obtained with a polyurethane resin layer containing casein transferred to the surface. When this laminate was processed using a jet dyeing machine, 0% of polyoxyethylene nonylphenyl ether (Nirasan Nonion NS, manufactured by NOF Corporation) was added. 5 in 100″C hot water containing .4%
The casein was dissolved and removed while immersed for 0 minutes and rubbed, forming a skin layer with micropores to obtain synthetic leather (jet dyeing machine processing conditions: cloth speed 270 m/min, pressure 2.3 kg
/cd, bath ratio 1820).
得られた合成皮革は風合がソフトでドレープ性があり、
かつ揉み皺が長期間に亘って保持され、きわめて柔軟性
に富み、外観、風合ともに天然皮革に酷似し、衣料用素
材として好適なものであった。この合成皮革の透湿度は
３５５０ｇ１０ｆ・２４時間であった。また表皮層中の
カゼインの除去率は９６％であった。The resulting synthetic leather has a soft texture and drapability.
Moreover, it retained its wrinkles after being rubbed for a long period of time, was extremely flexible, and had an appearance and feel very similar to natural leather, making it suitable as a material for clothing. The moisture permeability of this synthetic leather was 3550 g 10 f/24 hours. Furthermore, the removal rate of casein in the epidermal layer was 96%.
実施例３
厚さ０．４５ｍｍのポリノジック織布（基材）の起毛面
に１００％モジュラスが２５ｋｇ／ｃｉｉのポリエステ
ル系ポリウレタン樹脂（大日精化製：レザミンＣＵＳ−
１００）の１０％Ｄ Ｍ Ｆ溶液を目付量が６ｏｏｇ／
ｒイとなるように塗布した後、２０°Ｃの水中で脱溶媒
して凝固し、次いで脱水後１３０℃の熱風下で乾燥して
厚さ０．６０閤の微多孔層を有する基材を得た。Example 3 A 100% polyester polyurethane resin with a modulus of 25 kg/cii (manufactured by Dainichiseika: Rezamin CUS-
100) 10% DMF solution with a basis weight of 6oog/
After applying the material so as to give the desired temperature, the solvent is removed and solidified in water at 20°C, and then dehydrated and dried under hot air at 130°C to form a base material having a microporous layer with a thickness of 0.60°C. Obtained.
一方、シボ付き離型紙の表面に、平均粒径」７μの馬鈴
薯デンプンを６０重量％含有する１００％モジュラスが
４０ｋｇ／ｃ−のポリエステル系ポリウレタン樹脂（大
日精化製：レザミンＭＥ３４１２ Ｌ Ｐ ）の１８％
ＤＭＦ−ＭＥＫ溶１（着色剤をポリウレタン樹脂１００
重量部に対して２０重量部含有）を乾燥時の厚さが２０
μとなるようにナイフコーターにて塗布して９０℃にて
２分間熱風乾燥させ、ポリウレタン樹脂層を形成し、こ
のポリウレタン樹脂層の表面に前記微多孔層を形成した
基材の微多孔層面を加熱しながら１４５℃にて熱圧着し
た後、離型紙を剥離して微多孔層表面にに馬鈴薯デンプ
ンを含有するポリウレタン樹脂層を転写した積層体を得
た。この積層体を液流染色機により、馬鈴薯デンプンの
分解酵素であるエンチロンＦＡ（洛東化成製：アスベル
ギルス属の細菌アミラーゼ）を２重量％及びドデシルベ
ンゼンスルホン酸ナトリウム（松本油脂製薬社製：ラバ
ジョン）を０．４％含有するｐＨ＝５．５の６０°Ｃの
温水に６０分間浸漬して揉み処理しながら馬鈴薯デンプ
ンを溶解除去し、微細孔を有する表皮層を形成して合成
皮革とした。On the other hand, on the surface of the textured release paper, a polyester polyurethane resin (Rezamin ME3412 LP manufactured by Dainichiseika Chemical Co., Ltd.) containing 60% by weight of potato starch with an average particle size of 7 μm and a 100% modulus of 40 kg/c- was applied. %
DMF-MEK solution 1 (coloring agent polyurethane resin 100%)
Contains 20 parts by weight) to a dry thickness of 20 parts by weight
μ using a knife coater and drying with hot air at 90°C for 2 minutes to form a polyurethane resin layer. After thermocompression bonding at 145° C. while heating, the release paper was peeled off to obtain a laminate in which a polyurethane resin layer containing potato starch was transferred to the surface of the microporous layer. This laminate was dyed using a jet dyeing machine with 2% by weight of Enthilon FA (manufactured by Rakuto Kasei, Asbergillus bacterial amylase), which is a degrading enzyme for potato starch, and sodium dodecylbenzenesulfonate (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., Ravajon). ) in 60°C warm water with a pH of 5.5 containing 0.4% for 60 minutes, the potato starch was dissolved and removed while being rubbed, and a skin layer with micropores was formed to form synthetic leather. .
得られた合成皮革は風合がソフトでドレープ性があり、
かつ揉み皺が長期間に亘って保持され、きわめて柔軟性
に富み、外観、風合ともに天然皮革に酷似し、衣料用素
材として好適なものであった。この合成皮革の透湿度は
３２４０ｇ／ｒ［・２４時間であった。また表皮層中の
馬鈴薯デンプンの除去率は９２％であった。The resulting synthetic leather has a soft texture and drapability.
Moreover, it retained its wrinkles after being rubbed for a long period of time, was extremely flexible, and had an appearance and feel very similar to natural leather, making it suitable as a material for clothing. The moisture permeability of this synthetic leather was 3240 g/r[·24 hours. The removal rate of potato starch in the epidermal layer was 92%.
比較例１
水中に浸透剤を添加しない他は実施例１と同様にして合
成皮革を得た（液流染色機による揉み処理も同様に施し
た。）、得られた合成皮革の透湿度は１５３０ｇ／ｎｆ
・２４時間であった。また表皮層中の馬鈴薯デンプンの
除去率は６３％であった。Comparative Example 1 Synthetic leather was obtained in the same manner as in Example 1 except that no penetrant was added to the water (rubbing treatment using a jet dyeing machine was also performed in the same manner). The moisture permeability of the obtained synthetic leather was 1530 g. /nf
・It was 24 hours. The removal rate of potato starch in the epidermal layer was 63%.
比較例２
水中に浸透剤を添加しない他は実施例２と同様にして合
成皮革を得た（液流染色機による揉み処理も同様に施し
た。）、得られた合成皮革の透湿度は２１１０ｇ／ｒｒ
ｆ・２４時間であった。また表皮層中のカゼインの除去
率は５９％であった。Comparative Example 2 Synthetic leather was obtained in the same manner as in Example 2 except that no penetrant was added to the water (rubbing treatment using a jet dyeing machine was also performed in the same manner). The moisture permeability of the obtained synthetic leather was 2110 g. /rr
f・24 hours. Furthermore, the removal rate of casein in the epidermal layer was 59%.
以上説明したように本発明方法は基材の表面に水溶性天
然高分子物質を含有するポリウレタン樹脂層を設けた後
、該ポリウレタン樹脂層中の水溶性天然高分子物質を、
浸透剤を含有する水中で溶解除去して多孔性とした表皮
層を形成する方法を採用したことにより、透湿性、通気
性に優れ、しかも感触がソフトでドレープ性を有するき
わめて柔軟性に優れ、外観、風合もきわめて天然皮革に
Ｗｉ偵した合成皮革を得ることができる。また表皮層と
基材との間に湿式法によって形成した微多孔層を設ける
と柔軟性を更に向上することができる。As explained above, in the method of the present invention, after providing a polyurethane resin layer containing a water-soluble natural polymer substance on the surface of a base material, the water-soluble natural polymer substance in the polyurethane resin layer is
By adopting a method that dissolves and removes penetrants in water to form a porous skin layer, it has excellent moisture permeability and air permeability, and is extremely flexible with a soft feel and drapability. It is possible to obtain synthetic leather that is very similar in appearance and texture to natural leather. Further, the flexibility can be further improved by providing a microporous layer formed by a wet method between the skin layer and the base material.
また本発明の方法によれば、浸透剤の水中への添加によ
り、ポリウレタン樹脂と水との界面における界面張力を
著しく低下させ、濡れ効果により水がポリウレタン樹脂
中に浸透し易くなるため、表皮層形成用ポリウレタン樹
脂層中の水溶性天然高分子物質を効率良く溶解除去でき
る。また浸透剤とともに、水溶性天然高分子物質の分解
酵素を併用すると、より低温で効率良（水溶性天然高分
子物質の溶解除去を行うことができ、ポリウレタン樹脂
の劣化を防止できるとともに、水溶性天然高分子物質の
溶解除去時間の更なる短縮、除去率の向上を図ることが
できる。更に水溶性天然高分子物質の溶解除去に液流染
色機を用いると水溶性天然高分子物質の除去と柔軟化処
理とを同時に施すことができる等の効果を有する。Furthermore, according to the method of the present invention, by adding a penetrant to water, the interfacial tension at the interface between the polyurethane resin and water is significantly lowered, and the wetting effect makes it easier for water to penetrate into the polyurethane resin. Water-soluble natural polymer substances in the forming polyurethane resin layer can be efficiently dissolved and removed. In addition, if a water-soluble natural polymer degrading enzyme is used in combination with a penetrant, the water-soluble natural polymer can be dissolved and removed more efficiently at lower temperatures, preventing deterioration of the polyurethane resin, and It is possible to further shorten the dissolution and removal time of natural polymeric substances and improve the removal rate.Furthermore, if a jet dyeing machine is used to dissolve and remove water-soluble natural polymeric substances, the removal of water-soluble natural polymeric substances and It has the advantage of being able to perform softening treatment at the same time.
図面は本発明の一実施例を示し、第１図は本発明の製造
方法の一例を示す説明図、第２図は第１図のＩＩ−■線
縦断面図、第３図は本発明により得られる合成皮革の一
例を示す縦断面図、第４図、第５図は各々本発明により
得られる合成皮革の異なる態様を示す縦断面図である。
２・・・水溶性天然高分子物質 ５・・・ポリレタン樹
脂層 ６・・・基材 １０・・・微細孔 １１・・・表
皮層１２・・・合成皮革 １３・・・孔 １４・・・微
多孔層第３図
第４図The drawings show one embodiment of the present invention, FIG. 1 is an explanatory view showing an example of the manufacturing method of the present invention, FIG. 2 is a vertical cross-sectional view taken along line II-■ of FIG. 1, and FIG. A vertical cross-sectional view showing an example of the synthetic leather obtained, and FIGS. 4 and 5 are longitudinal cross-sectional views showing different aspects of the synthetic leather obtained by the present invention, respectively. 2... Water-soluble natural polymer substance 5... Polyurethane resin layer 6... Base material 10... Fine pores 11... Skin layer 12... Synthetic leather 13... Holes 14... Microporous layer Fig. 3 Fig. 4
Claims (4)
含有するポリウレタン樹脂層を形成した後、該積層体を
浸透剤を添加した水中に浸漬して水溶性天然高分子物質
を溶解除去して多孔性の表皮層を形成することを特徴と
する合成皮革の製造方法。(1) After forming a polyurethane resin layer containing a water-soluble natural polymer substance on at least one side of the base material, the laminate is immersed in water containing a penetrant to dissolve and remove the water-soluble natural polymer substance. A method for producing synthetic leather, characterized by forming a porous skin layer.
性有機溶媒溶液を塗布した後、水中に浸漬して溶媒を除
去するとともにポリウレタンを凝固させてポリウレタン
樹脂の微多孔層を形成し、次いでその表面に水溶性天然
高分子物質を含有するポリウレタン樹脂層を形成した後
、該積層体を浸透剤を添加した水中に浸漬して水溶性天
然高分子物質を溶解除去して多孔性の表皮層を形成する
ことを特徴とする合成皮革の製造方法。(2) After coating a hydrophilic organic solvent solution of polyurethane resin on at least one side of the substrate, immerse it in water to remove the solvent and coagulate the polyurethane to form a microporous layer of polyurethane resin, and then form a microporous layer of polyurethane resin on the surface. After forming a polyurethane resin layer containing a water-soluble natural polymer substance, the laminate is immersed in water containing a penetrant to dissolve and remove the water-soluble natural polymer substance to form a porous skin layer. A method for producing synthetic leather characterized by:
いて、浸透剤及び水溶性高分子物質の分解酵素を含む水
中で水溶性天然高分子物質を溶解除去することを特徴と
する合成皮革の製造方法。(3) The method for producing synthetic leather according to claim 1 or 2, characterized in that the water-soluble natural polymer substance is dissolved and removed in water containing a penetrant and a water-soluble polymer substance degrading enzyme. Production method.
方法において、液流染色機にて水溶性天然高分子物質を
溶解除去することを特徴とする合成皮革の製造方法。(4) The method for producing synthetic leather according to any one of claims 1 to 3, characterized in that the water-soluble natural polymer substance is dissolved and removed using a jet dyeing machine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1108489A JPH02191778A (en) | 1989-01-20 | 1989-01-20 | Production of synthetic leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1108489A JPH02191778A (en) | 1989-01-20 | 1989-01-20 | Production of synthetic leather |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02191778A true JPH02191778A (en) | 1990-07-27 |
Family
ID=11768108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1108489A Pending JPH02191778A (en) | 1989-01-20 | 1989-01-20 | Production of synthetic leather |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02191778A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150055406A (en) * | 2013-11-13 | 2015-05-21 | 코오롱글로텍주식회사 | Artificial leather fabric having improved nappy property and manufacturing method thereof |
| CN104894882A (en) * | 2014-03-07 | 2015-09-09 | 安踏（中国）有限公司 | Preparation method of synthetic leather and polyurethane composition used for synthetic leather |
| CN106702760A (en) * | 2016-12-14 | 2017-05-24 | 上海华峰超纤材料股份有限公司 | Waterborne polyurethane superfine fiber synthetic leather original base fabric and preparation method thereof |
-
1989
- 1989-01-20 JP JP1108489A patent/JPH02191778A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150055406A (en) * | 2013-11-13 | 2015-05-21 | 코오롱글로텍주식회사 | Artificial leather fabric having improved nappy property and manufacturing method thereof |
| CN104894882A (en) * | 2014-03-07 | 2015-09-09 | 安踏（中国）有限公司 | Preparation method of synthetic leather and polyurethane composition used for synthetic leather |
| CN106702760A (en) * | 2016-12-14 | 2017-05-24 | 上海华峰超纤材料股份有限公司 | Waterborne polyurethane superfine fiber synthetic leather original base fabric and preparation method thereof |
| CN106702760B (en) * | 2016-12-14 | 2019-06-21 | 上海华峰超纤材料股份有限公司 | Primary base fabric of aqueous polyurethane superfine fiber synthetic leather and preparation method thereof |
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