US3607481A - Process for production of synthetic leather - Google Patents
Process for production of synthetic leather Download PDFInfo
- Publication number
- US3607481A US3607481A US667976A US3607481DA US3607481A US 3607481 A US3607481 A US 3607481A US 667976 A US667976 A US 667976A US 3607481D A US3607481D A US 3607481DA US 3607481 A US3607481 A US 3607481A
- Authority
- US
- United States
- Prior art keywords
- binder
- solution
- web
- synthetic resin
- viscosity
- 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.)
- Expired - Lifetime
Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 127
- 239000000835 fiber Substances 0.000 claims abstract description 55
- 239000000057 synthetic resin Substances 0.000 claims abstract description 53
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 53
- 230000001112 coagulating effect Effects 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims description 25
- 238000005345 coagulation Methods 0.000 claims description 18
- 230000015271 coagulation Effects 0.000 claims description 18
- 230000035515 penetration Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 10
- 238000004080 punching Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 45
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 239000002344 surface layer Substances 0.000 description 27
- 229920002635 polyurethane Polymers 0.000 description 21
- 239000004814 polyurethane Substances 0.000 description 21
- 239000010985 leather Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 11
- 239000004745 nonwoven fabric Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- -1 poly(vinyl chloride) Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 101150106671 COMT gene Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920000616 Poly(1,4-butylene adipate) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Definitions
- Solyst AttarneyWenderoth, Lind & Ponaek ABSTRACT A synthetic leather is produced by impregnating a fiber web with a binder solution, coating one surface of the said web with a solution of a synthetic resin having a viscosity higher than that of the said binder solution before the said binder is coagulated, and thereafter coagulating the said binder and the synthetic resin simultaneously.
- it is produced by impregnating a fiber web with a binder solution, applying to one surface of the said web at least one kind of binder solution having a viscosity higher than that of the first-mentioned binder solution in the order of a lower viscosity before the already applied binders are coagulated, applying to the said surface a solution of a synthetic resin having a viscosity of 5010,000 poises, and thereafter coagulating the said binders and the synthetic resin simultaneously.
- This invention relates to a process for the production of a synthetic leather comprising a fiber web as a substrate and a synthetic resin as a surface layer.
- the invention relates to a process for theproduction of a synthetic leather by impregnating a fiber web with a binder solution, coating the web with a solution of a synthetic resin having a viscosity higher than that of the said binder solution before the binder is coagulated, and thereafter coagulating the said binder and synthetic resin simultaneously.
- a synthetic resin is coated on a dried nonwoven fabric as a surface layer. It is impossible therefore for this method to obtain an integrated area consisting of the resinous surface layer and the binder, and to give a synthetic leather satisfactory in respect of density gradient and cohesion between layers.
- Some of the known methods of giving a density gradient to a nonwoven fabric are as follows; that is, a method by which a binder is applied to a laminate consisting of a plurality of fiber webs each having a different denier or the laminate is punched; a method by which a laminate consisting of a plurality of fiber webs each having a different shrinkage is punched, and then subjected to a shrinkage treatment; a method by which the depth of a needle penetration into the laminate is controlled; and a method of imparting a density gradient by applying a binder or paste to a nonwoven fabric, and pressing it thereinto from the side on which it is applied or sucking it from the opposite side. But all of these methods are complicated in respect of operation and apparatus.
- An object of this invention is to remove the abovementioned defects, and to provide a synthetic leather having a structure and an outer appearance like those of a natural leather in which an interface of a binder for a nonwoven fabric and that of a resin in a surface layer are integrated whereby a high strength is retained against the separation of the surface resinous layer from the nonwoven fabric.
- Another object of this invention is to provide a synthetic leather having an interior structure with a density gradient.
- a synthetic leather which conforms to these objects of the invention can be obtained by impregnating a fiber web with a binder solution, coating one surface of the said web with a solution of a synthetic resin having a viscosity higher than that of the said binder solution before the binder is coagulated, and thereafter simultaneously coagulating the binder impregnated among the fibers of the web and the resin coated on the surface of the web thereby to integrate them.
- FIG. 1 is a cross-sectional view of the synthetic leather according to this invention.
- FIGS. 2 and 3 are graphs showing a density gradient.
- a natural fiber such as cotton, flax, silk and wool
- a regenerated fiber such as rayon
- a synthetic fiber such as polyamide, polyester, polyacrylonitrile and polyolefine
- These fibers may be modified by an ordinarily known method such as composite-spinning, copolymerization and grafting.
- these fibers may have a denier of 0.5 to l0,but from the standpoint of tactile hand as synthetic leather, the denier of 1.5 to 4 is most preferable.
- the fiber length is preferably in the range of 10 mm. to mm., especially preferred being a length of 38 mm. to 76 mm. in view of the tactile hand and operability as synthetic leather.
- the fiber web as a substrate of the synthetic leather of this invention is prepared from such fiber by a customary method and apparatus such as card, gamett and random webber.
- a preferable fiber web has a weight per unit area of l00-l ,000 g./m. especially 200-300 g./m. lf necessary, the intertwining of the individual fibers with each other can be enhanced by needle-punching such web.
- the conditions for punching may be determined depending on the denier of the fiber to be used, the fiber length, the type of the fiber to be used, the weight of the web per unit area and the properties required of a final product. Under the ordinarily used conditions, punching is carried out by using needles (No.
- the web can also be set by compression with a hot roll instead of punching.
- the binder to be impregnated into the fiber web and the synthetic resin to be applied on its surface preferably have a chemical composition of the same series as they are coagulated simultaneously.
- Preferable resins to be used as the binder and the surface layer-forming synthetic resin are thermoplastic resins such as polyamides, polyesters, poly(vinyl chloride), polyacrylonitrile and polyurethane. They may be used in combinations of two or more. These resins are applied to the fiber web in the form of a solution in a solvent which is nonsolvent for the fibers that make up the fiber web.
- the solution of the synthetic resin for forming a surface layer should have a viscosity higher than the binder solution does.
- the viscosity of the solution of the surface layer resin is in the range of 20 to 10,000 poises, and that of the binder solution is chosen within the range of 0.] to 100 poises.
- a filler I such as wood powder and calcium carbonate, a pigment such as carbon black, an antifoaming agent. or an antioxidant can be incorporated into a solution of the synthetic resin.
- the binder uniformly into the interior layer of the web by using a squeezing device such as screen and mangle.
- a squeezing device such as screen and mangle.
- the synthetic resin for the surface layer is coated all over one surface of the web by means of a reverse roll coater or knife coater before the binder is coagulated. in this manner, the surface layer-forming resin is applied before the binder is coagulated and a liquidliquid mixing is effected at the interfaces. Consequently, when the surface layer of the synthetic resin and the binder are simultaneously coagulated, the web an surface layer are integrated to an extent such that they may not be separated from each other.
- the coagulation of the binder and the surface layer-forming resin is carried out by two ways, one of which is a wet method wherein the solvent is extracted in a liquid such as water which is compatible with the solvent, and the other of which is a dry method wherein the solvent extraction: is carried out by such operation as heating.
- the wet method is desirable to get a synthetic leather.
- the intended synthetic leather akin to a natural leather can be obtained by water-washing and drying after the coagulating step.
- the resulting leather is pressed while heating at a temperature below the melting point of the fiber of the web and above the softening point of the resin.
- the synthetic leather obtained in this manner may be subjected to an embossing apparatus.
- a paint such as nitrocellulose lacquer may be applied to the leather by spraying, coating or printing.
- the density gradient of the structure can be made more resembling to that of a natural leather by changing the method of applying a binder solution to a fiber web.
- a synthetic leather having such density gradient can be obtained by impregnating a fiber web with a binder solution, applying at least one kind of binder solution having a viscosity higher than that of the firstmentioned binder solution to one surface of the said web in the order of a lower viscosity before the already applied binders are coagulated, coating the said surface with a solution of a synthetic resin having a viscosity preferably higher than that of the last-applied binder solution before these binders are coagulated, and thereafter coagulating the said binders and the synthetic resin simultaneously.
- the binder is present in the web in concentration higher towards the surface owing to the difference in the amount of the binder to be penetrated into the web which is caused by the difference in viscosity of the binder solutions applied in sequence.
- the structure of the synthetic leather obtained according to this embodiment of the invention is not a simple laminated structure as seen in the conventional synthetic leather, but looks almost like that of a natural leather.
- the behavior of this synthetic leather towards bending deformation is almost the same as that of a natural leather, too.
- the same kind of a substrate web, binder and synthetic resin of the surface layer can be used in this embodiment, and the same method is also used in coagulation.
- the difference in viscosity of the binder solutions gives a density gradient changing continuously from the surface layer to the back layer of the web, the density gradient is more gentle as more kinds of binder solution of different viscosity are used, with the result that the structure is more like that of a natural leather. It is however desirable to restrict the number of binder applying procedures to two to three times because of disadvantages in productivity and cost of production.
- a synthetic leather satisfactory for practical purposes can be obtained by impregnating a web with a binder solution, applying a binder solution having a viscosity higher than that of the first-mentioned binder solution to one surface of the web, further coating the said surface with a solution of a synthetic resin for a surface layer having a viscosity preferably higher than that of the said binder solution, and thereafter coagulating the said binders and the synthetic resin.
- the binder solution to be impregnated into the web has a viscosity of 01-100 poises
- the second-applied binder solution and the finally coated synthetic resin solution both have a viscosity in the range of 50 to 10,000 poises.
- The, binder first impregnated into the web is primarily intended to bond individual fibers of the web at intersecting points, and the next-applied binder is intended to bring about a density gradient by utilizing its smaller amount of penetration (distance of penetration from the surface on which the binder is applied) than the first-applied binder which is penetrated throughout the section of the web, and also to set the individual fibers of the web at the surface layer.
- synthetic resin finally coated on the web surface is for the purpose of enhancing the outer appearance of the product as a leather, and to improve such mechanical properties as resistance to scuffing and to flexural fatigue.
- FIG. 1 of the accompanying drawings is an enlarged sectional view of the synthetic leather obtained bythe abovementioned embodiment of this invention.
- the reference numeral 1 represents a microcell structure, 2 a macrocell structure, 3 and 4, a nylon 6 fiber that makes up the web, 5, a binder impregnated into the web at the outset and a filler, 6, a microporous film composed of a filler and a synthetic resin for forming a surface layer which is coated in the last place, and 7, a structure having a density gradient formed of the first-impregnated binder solution and the next-applied binder solution having a higher viscosity.
- the binders in the web and the surface layer-forming resin are simultaneously coagulated and integrated at their interface, and so it has a high cohesion between layers. Also, because of the penetration of the surface resin into the interior of the web, a density gradient is provided from the surface to the back surface by the surface layer resin and the binders. It is therefore possible for the method of this invention to provide a structure having a density gradient continuous from the flesh side to the grain surface side and a structure wherein the flesh side and the grain side are integrated.
- the traces of punching do not appear on the surface of the synthetic leather of this invention in a processing procedure in which the leather is processed in an elongated state, for instance in toe-lasting step of shoemaking.
- the surface of the synthetic leather is not roughened.
- EXAMPLE 1 A web having a weight per unit area of 300 g./m. was produced by means of a random webber from nylon 6 staples having a denier of 4, a fiber length of 51 mm., a titanium oxide content of 0.2 percent, and a number of crimps of i5 turns/25 This web was needle punched by means of a needle-loom (James Hunter Co., U.S.A.). The needles used were regular barbs (standard No. 42 of The Torrington Co., U.S.A.). The number of needle penetration per square centimeter was 500, and the needle penetration depth was 8 mm.
- the resulting punched web was immersed in a 15 percent solution (with a viscosity of 20 poises) in dimethylformamide of a polyester polyurethane prepared by chain-extending with butanediol a prepolymer form polyethylene adipate having a molecular weight of about 2,000 and diphenylmethane-4,4'-diisocyanate (MDl), compressed until the takeup reached 20 parts by weight as against l00 parts of the fiber, and then immediately coated on its one surface with a 20 percent solution (with a viscosity of 128 poises) in dimethylformamide of the same polyester polyurethane as mentioned above by using a blade with a clearance of 2.0 mm.
- MDl diphenylmethane-4,4'-diisocyanate
- control synthetic leather (corresponding to the conventional article obtained by method 2 mentioned at the outset of this specification).
- a comparison of this control leather with the synthetic leather obtained by this example reveals, as shown in table 1, that the synthetic leather according to the method of this invention is remarkably superior to the control product in respect of pliability and water permeability, and no separation between the surface resin layer and the nonwoven fabric is seen.
- Synthetic leather of this invention 1. 50 0.56 18.0 120 2, 350 1, 750 Inseparable Control synthetic leather 1. 50 0.55 15. 1 90 3, 500 1, 003 2.0
- One mole of poly (e-caprolactone) having a molecular weight of 1850 and an acid value of 0.1 l was reacted with 2 moles of diphenylmethane-4,4'-diisocyanate to form a prepolymer having a molecular weight of 2530.
- One mole of the resulting prepolymer and 0.985 mole of ethylene diamine are chain-extended in dimethylformamide to give a 25 percent polyurethane solution having a viscosity of l,250 poises.
- a polyurethane prepolymer was prepared by reacting 2 moles of polytetrahydrofuran having a molecular weight of 2,080 with 3.2 moles of a mixture of 2,4-tolylenediisocyanate with 2,6-tolylenediisocyanate. This prepolymer was reacted with an equimolar amount of hydraxine hydrate in dimethylformamide to form a polyurethane solution.
- a copolymer of 65 mole butadiene and 35 mole acrylonitrile in an amount same as that of the polyurethane solid content was dissolved into the resulting polyurethane solution, and diluted with dimethylformamide to give a solution having a viscosity of 5 poises and a solid concentration of percent.
- the same procedure as that of example 2 was followed except that a knife coater was used instead of the reverse roll coater.
- the obtained product was serviceable as a synthetic leather as it had a strong cohesion between layers and a density gradient owing to the penetration of the surface layer resin solution into the interior of the web.
- EXAMPLE 4 A prepolymer was prepared by reacting poly (1,4-butylene adipate) having a molecular weight of 2,000 and an acid value of 4.6 with diphenylmethane-4,4'-diis0cyanate. The resulting prepolymer was reacted with butanediol in dimethylformamide to effect chain extension to form a polyurethane solution having a viscosity of 520 poises and a concentration of 35 percent. This polyurethane solution was diluted to percent 520 poises, and adjusting the concentration and the viscosity to 36.7 percent and 560 poises respectively.
- EXAMPLE 5 A web having a weight per unit area of 200 g./m. was produced from nylon 6 staples having a denier of 1.5, a fiber length of 38 mm., a number of crimps of 15 turns/inch, and a titanium oxide content of 0.2 percent by means of a random webber. The web was passed through a pair of hot rolls heated to 160 C., compressed and set. The same treatment as that of example I gave a synthetic leather having a good tactile hand.
- a web having a weight per unit area of 250 g./m.. was produced from a polyester fiber having a denier of 1.5, a fiber length of 38 mm., and a number of crimps of i5 turns/inch by means of a cross lappcr.
- the web was punched by a needle loom (James-Hunter C0,, U.S.A.) with the number of needle penetration of LOGO/cm, and the needle penetration depth of 6 mm.
- the so treated web was passed through a pair of hot rolls heated to 160 C., and the thickness after hot-pressing was adjusted to 1.0 mm.
- a copolymer of 65 mole butadiene and 35 mole acrylonitrile was dissolved in dimethylformamide to a concentration of l5 percent to make a solution having a viscosity of6 poises.
- the web was immersed in this solution, and squeezed by a mangle until the takeup of the solid copolymer content reached 50 parts as against parts of the fiber of the web.
- a resin solution for forming a surface layer was applied to one surface of the web by means of a reverse roll coater.
- This resin solution had been prepared by adding to the said copolymer solution 20 parts of cellulose powder having an average particle size of 20 microns and 5 parts of carbon black, all amounts being based on 100 parts of the copolymer and adjusting the concentration and the viscosity of the solution to 30 percent and 230 poises respectively with the use ofdimethylformamide.
- EXAMPLE 7 One hundred parts of a copolymer composed of 35 moles of vinyl acetate and 65 moles of vinyl chloride, 20 parts of carbon black, 50 parts of a plasticizer (DOP) and 35 parts of calcium carbonate were dissolved in dimethylformamide to make a solution having a concentration of 30 percent and a viscosity of 100 poises. With the use of the resulting solution as a resin solution for forming a surface layer, the same procedure as that of example 6 was followed, and a synthetic leather conforming to the objects of this invention was obtained.
- DOP plasticizer
- solution III was applied to the same surface by means of a knife coater until the takeup of the solid content reached 48 parts by weight as against 100 parts by weight of the fiber of the web.
- the so treated web was immersed in water at 20 C. for 15 minutes to coagulate the solution, immersed in an open soaping at 80 C. for 20 minutes, washed with water, and dried.
- Sample B was obtained by impregnating the needlepunched web with the said solution I, coagulating it, applying solution I] to one surface of it, coagulating it in water in the like manner, and drying it.
- sample A is a synthetic leather wherein a woven fabric is disposed between the substrate and the surface coat
- sample B is a synthetic leather wherein a woven fabric is not disposed between them.
- a web having a weight per unit area of 250 g./m. was produced from nylon 6 staples having a denier of 3.5, a fiber length of 51 mm., a titanium oxide content of 0.2 percent and a number of crimps of i5 turns/25 mm. by means of a random webber.
- the web was punched by means of a needle loom (James-Hunter Co., U.S.A.).
- the used needles were standard No. 42 regular barbs of The Torrington Co., U.S.A.
- the number of needle penetration was 500/cm, and the needle 10 penetration depth was 10 mm.
- a prepolymer was prepared from polyethylene adipate having a molecular weight of about 2,000 and MD], and chain extended with butanediol to form polyester polyurethane.
- a mixture composed of 80 parts of this polyurethane, 20 parts of carbon black and 60 parts of pulp was dissolved into dimethylformamide to form three solutions having a solid content concentration of 15 percent (solution I), 30 percent (solution ii),
- Synthetic leather was g in these three kinds of solution having a different viscosity and tactile hand, and consisted of about 1.1 mm. of a thick sub- 40 lmpreg-natmg coatmg coagulatmg watqr washmgl ER strate layer and about 0.4 mm.
- curve 3 is a plot of thickness against apparent density for solution were prepared. Namely, we provided a solution havthree leathers, of which curve I is for the synthetic leather of i a i it f 1 oi e re ared b di olving a copolymcr the Present invention: curve is for comparison Sample A and of 35 mole acrylonitrile and 65 mole butadiene in dimethylforcurve ill is for comparison sample B. mamide to a concentration of 10 percent, and two solutions Sample A was obtained by the following procedure. The having a viscosity of 200 poises and 850 poises respectively punched web was dip coated with the said solution I under the prepared by adding to the said solution 5 parts by weight of same conditions, immersed in water at 20 C.
- the "like natural leather” means that in a bending test of a synthetic leather at the radius of curvature of 0.5-1.0 cm., a bending resistance Bi measured when the leather is bent with the surface (grain side) directed outwardly and a bonding resistance Bi, measured when the leather is bent with the said surface directed inwardly satisfy the following relation: Bt B
- the needle-punched web of example 8 was coated with the three solutions in the order of a lower viscosity to give a synthetic leather excellent in cohesion between layers and smoothness which had a continuous density gradient.
- EXAMPLE 1 1 One surface of the web of example 8 containing solution I was coated with a resin solution having a concentration of 30 percent and a viscosity of 2,000 poises obtained by adding 20 parts of poly(vinyl chloride), 10 parts of plasticizer (DO?) and 50 parts of cellulose powder having an average particle size of microns, all amounts being based on 100 parts of the solid polyurethane content, to the polyurethane solution used in example 8 and diluting the solution with dimethylformamide, and further with a resin solution having a concentration of 36 percent and a viscosity of 1,300 poises prepared by adding 10 parts of a plasticizer (DOP) and 30 parts of calcium carbonate, all amounts based on 100 parts of the solid polyu rethane content, to the said polyurethane solution, and diluting it with dimethylformamide.
- DOP plasticizer
- the subsequent treatment in the same manner as in example 8 gave a synthetic leather excellent in smoothness and cohesion between layers having a continuous density gradient.
- EXAMPLE 12 A web having a weight per unit area of 250 g/m was produced by means of a random webber from nylon 6 staples having a denier of 3, a fiber length of 51 mm., a number of crimps of turns/inch, and a titanium oxide content of 0.2 percent. The resulting web was passed through a pair of hot rolls heated to 160 C., and set to a thickness of 1.0 mm. The same treatment as in example 9 of this web gave a similar synthetic leather.
- a process for manufacturing synthetic leather which comprises impregnating a fiber web with a solution ofa binder and solvent, coating one surface of the web prior to coagulation of the binder, with a solution of a synthetic resin and sol' vent having a viscosity higher than that of the binder solution, and simultaneously coagulating the binder and synthetic resin by a wet method wherein the solvents are extracted in a liquid which is compatible with the solvents.
- a process for manufacturing synthetic leather which comprises impregnating a fiber web with a solution ofa binder and solvent, applying to one surface of the web prior to coagulation of the said binder, and in the order of increasing viscosities, a plurality of binder solutions exhibiting viscosities differing each from the others, each binder solution having a viscosity higher than the binder solution initially impregnated into the web, coating this same surface of the web prior to coagulation of the binder solutions, with a solution of a synthetic resin and solvent having a viscosity higher than the last-applied binder solution and within the range of 50-l0,000 poises, and simultaneously coagulating the binders and synthetic resin by a wet method wherein the solvents are extracted in a liquid which is compatible with the solvents.
- a process for manufacturing synthetic leather which comprises a. forming a fiber web of a weight per unit area of -1 ,000 g,/cm.,
- a process for manufacturing synthetic leather which comprises a. forming a fiber web of a weight per unit area of l001,000 g./cm.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6148266 | 1966-09-19 | ||
JP1346867 | 1967-03-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3607481A true US3607481A (en) | 1971-09-21 |
Family
ID=26349274
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US667976A Expired - Lifetime US3607481A (en) | 1966-09-19 | 1967-09-15 | Process for production of synthetic leather |
Country Status (3)
Country | Link |
---|---|
US (1) | US3607481A (enrdf_load_stackoverflow) |
DE (1) | DE1619303C3 (enrdf_load_stackoverflow) |
GB (1) | GB1165228A (enrdf_load_stackoverflow) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3956560A (en) * | 1972-01-28 | 1976-05-11 | The Fiberwoven Corporation | Smooth surfaced textile fabric |
US20030019089A1 (en) * | 2001-07-03 | 2003-01-30 | Filzfabrik Fulda Gmbh & Co. | Method for the production of a patterned textile surface |
EP1377444A4 (en) * | 2001-03-02 | 2006-05-10 | Polymer Group Inc | Stretchable laminate |
EP2251473A1 (en) * | 2009-04-29 | 2010-11-17 | Fiscagomma S.p.A. | Label |
US20180044825A1 (en) * | 2015-03-24 | 2018-02-15 | Really Aps | Reuse of used woven or knitted textile |
WO2019076999A1 (de) * | 2017-10-18 | 2019-04-25 | Frumat Srl | Zusammensetzung bestehend aus pflanzenmaterial mit zellulose insbesondere aus abfallprodukten von äpfeln zur erzeugung eines laminats und ein verfahren zur herstellung eines laminat aus pflanzenmaterial mit zellulose, insbesondere aus abfallprodukten von äpfeln und laminat hergestellt durch das genannte verfahren wird |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA756053B (en) * | 1974-10-04 | 1976-09-29 | Inmont Corp | Sheet material |
-
1967
- 1967-09-15 US US667976A patent/US3607481A/en not_active Expired - Lifetime
- 1967-09-18 DE DE1619303A patent/DE1619303C3/de not_active Expired
- 1967-09-19 GB GB42678/67A patent/GB1165228A/en not_active Expired
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3956560A (en) * | 1972-01-28 | 1976-05-11 | The Fiberwoven Corporation | Smooth surfaced textile fabric |
EP1377444A4 (en) * | 2001-03-02 | 2006-05-10 | Polymer Group Inc | Stretchable laminate |
US20030019089A1 (en) * | 2001-07-03 | 2003-01-30 | Filzfabrik Fulda Gmbh & Co. | Method for the production of a patterned textile surface |
EP2251473A1 (en) * | 2009-04-29 | 2010-11-17 | Fiscagomma S.p.A. | Label |
US20180044825A1 (en) * | 2015-03-24 | 2018-02-15 | Really Aps | Reuse of used woven or knitted textile |
US10988874B2 (en) * | 2015-03-24 | 2021-04-27 | Really Aps | Reuse of used woven or knitted textile |
WO2019076999A1 (de) * | 2017-10-18 | 2019-04-25 | Frumat Srl | Zusammensetzung bestehend aus pflanzenmaterial mit zellulose insbesondere aus abfallprodukten von äpfeln zur erzeugung eines laminats und ein verfahren zur herstellung eines laminat aus pflanzenmaterial mit zellulose, insbesondere aus abfallprodukten von äpfeln und laminat hergestellt durch das genannte verfahren wird |
CN111344451A (zh) * | 2017-10-18 | 2020-06-26 | 福马特有限责任公司 | 用于制备层合体的由具有纤维素的植物材料、特别是来自苹果的废品构成的组合物,和用于从具有纤维素的植物材料、特别是来自苹果的废品制备层合体的方法,和由所述方法制备的层合体 |
Also Published As
Publication number | Publication date |
---|---|
DE1619303B2 (enrdf_load_stackoverflow) | 1974-09-12 |
GB1165228A (en) | 1969-09-24 |
DE1619303C3 (de) | 1975-05-07 |
DE1619303A1 (de) | 1970-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3067482A (en) | Sheet material and process of making same | |
EP2261382B1 (en) | Split leather product and manufacturing method therefor | |
US4515854A (en) | Entangled fibrous mat having good elasticity and methods for the production thereof | |
US4028161A (en) | Method of making sheet material | |
US3067483A (en) | Sheet material and process of making same | |
GB2065732A (en) | Suede-like sheet-form material | |
US2994617A (en) | Leather substitute | |
US6274203B1 (en) | Process for the production of artificial leather | |
KR102664474B1 (ko) | 탄력 특성이 향상된 인공피혁 및 이의 제조방법 | |
US3238055A (en) | Poromeric material and method of making same | |
US3607481A (en) | Process for production of synthetic leather | |
US3597307A (en) | Supple sheet material and method of producing same | |
US4053546A (en) | Method of making a leather-like sheet material by coagulating two polymers | |
US3565670A (en) | Process for manufacture of artificial leather | |
JP3742215B2 (ja) | 人工皮革基体 | |
JPH0881886A (ja) | ヌバック調人工皮革の製造方法 | |
JP2944780B2 (ja) | 成形用シート材の製造方法 | |
JP2002249986A (ja) | 人工皮革の製造方法 | |
JP2786866B2 (ja) | 皮革様シートの製造法 | |
JPH0138917B2 (enrdf_load_stackoverflow) | ||
DE2056542A1 (en) | Bonded fibre fleece prodn useful as a - substitute leather | |
JPH09188975A (ja) | 皮革様シート状物およびその製造方法 | |
JPS6017872B2 (ja) | 皮革様シ−ト物質の製造法 | |
CA1069425A (en) | Artificial leather and method of manufacture | |
JP2002242081A (ja) | 人工皮革の製造方法 |