CN116377141B - Preparation method of transparent leather - Google Patents
Preparation method of transparent leather Download PDFInfo
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- CN116377141B CN116377141B CN202310426003.0A CN202310426003A CN116377141B CN 116377141 B CN116377141 B CN 116377141B CN 202310426003 A CN202310426003 A CN 202310426003A CN 116377141 B CN116377141 B CN 116377141B
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- transparent leather
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- 239000010985 leather Substances 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 23
- 125000004386 diacrylate group Chemical group 0.000 claims description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 11
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- 229960004063 propylene glycol Drugs 0.000 claims description 6
- 241000283707 Capra Species 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- 241001494479 Pecora Species 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 2
- 102000008186 Collagen Human genes 0.000 abstract description 42
- 108010035532 Collagen Proteins 0.000 abstract description 42
- 229920001436 collagen Polymers 0.000 abstract description 42
- 239000000835 fiber Substances 0.000 abstract description 33
- 239000000126 substance Substances 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 57
- 238000003892 spreading Methods 0.000 description 15
- 230000007480 spreading Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 241001465754 Metazoa Species 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 9
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 6
- 229940035437 1,3-propanediol Drugs 0.000 description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102000016942 Elastin Human genes 0.000 description 1
- 108010014258 Elastin Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 229920002549 elastin Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a preparation method of transparent leather. Taking the de-ashed and softened pelts as raw materials, soaking the pelts in an impregnating solution consisting of vinyl monomers, an initiator, a cross-linking agent, polyalcohol and water for 4-48 hours at 20-35 ℃, then heating and curing the pelts for 2-24 hours at 40-90 ℃, and airing the pelts to obtain transparent leather. In the method, vinyl monomers are polymerized in situ in the gaps of the collagen fibers to form a polymer cross-linked network, and form a network interpenetrating structure with the collagen fiber framework, so that the physical and mechanical properties of the transparent leather are improved, and the polyol is fixed in the leather, thereby thoroughly solving the problems of dissolution and loss of the polyol when the polyol is dissolved in water. The gaps between the collagen fibers of the leather are fully filled by the polymer, so that the refraction, scattering and reflection of light in the leather are reduced, and the transparency of the leather is greatly enhanced. The method has simple process, few types of chemical materials, low price and easy industrialization.
Description
Technical Field
The invention relates to the technical field of transparent leather, in particular to a method for preparing transparent leather by impregnating bare leather with a mixed solution containing polyol and vinyl monomer and then carrying out in-situ polymerization.
Background
The natural animal skin and the traditional leather prepared by taking the animal skin as raw materials have no transparency. However, in the conventional shadow play, the leather is required to have a certain transparency, and with the gradual change of consumer consumption concepts, such as individuation, differentiation, novel consumption, and the like, and some special leather application scenes (such as a mobile phone shell), the leather is also required to have a transparent feature. Therefore, the transparent leather has an increasingly large application prospect and market demand.
At present, the performance and the preparation method of the transparent leather have some defects. For example. The shadow puppet for shadow puppet play prepared by the traditional method has certain transparency, but has low light transmittance, and has the biggest defects of very hard and brittle texture, intolerance to bending and very limited application range. Chinese patent CN108998600a discloses a transparent leather and a method for manufacturing the same. The method adopts deashed softened leather as a raw material, firstly carries out alkali expansion treatment, then carries out soaking treatment in transparent liquid composed of polyalcohol, nano silver, curing agent and the like, and finally obtains transparent leather after airing. The method uses alkali expansion to destroy part of the leather fiber structure, resulting in lower strength of the transparent leather. In addition, the method uses n-butyraldehyde, furfural, tetrakis (hydroxymethyl) phosphonium sulfate, crotonaldehyde or glutaraldehyde and other substances as curing agents, and the curing effect on the polyalcohol in the transparent leather is not ideal, so that the risk of dissolution and loss in water exists, and the problem of reduced transparency of the leather is caused. Chinese patent CN111455118A adopts multifunctional active substances such as fatliquoring agent for leather, special surfactant and the like, and can also prepare transparent leather with good softness, but the leather is not tanned, and the durability is poor. Chinese patent CN112322807a discloses a method for preparing transparent leather based on solution refractive index, wherein the transparent leather is prepared by treating bare leather with polyalcohol with refractive index of 1.31-1.59, and the polyalcohol is dissolved out and lost when meeting water. Chinese patent CN112322806a discloses a method for producing transparent leather based on organic tanning agent, which uses polyurethane tanning agent, cyanuric chloride active tanning agent, tetra-methylol phosphate sulfate or tetra-methylol phosphate to pretanning de-ash softened leather, then uses polyalcohol to soak to produce transparent leather. The problems of the dissolution and the loss of the polyol in the transparent leather produced by the method in water are not solved effectively. Chinese patent CN110184398a discloses a transparent leather prepared from tanned leather and a preparation method thereof, wherein the transparent leather is obtained by immersing in an ionic liquid, washing, drying, and calendaring. The ionic liquid used by the method is relatively expensive, and the problems of dissolution and loss of the ionic liquid when meeting water also exist. Chinese patent CN114574636a discloses an ecological colour transparent soft leather and its processing method. The method adopts de-ashed softened leather or acid leather as raw material, and the color transparent soft leather without free formaldehyde and heavy metal is obtained after neutralization, fat-liquoring, dyeing, fat-liquoring filling, tanning and drying treatment. However, the process of the method is too complex, and the refractive index of the chemical materials such as tanning agent, dye, fatliquoring agent and the like is not matched with that of the collagen fibers of the leather, so that the transparency of the obtained transparent leather is not ideal.
From the above analysis, the currently reported transparent leather and the preparation method thereof have a plurality of defects and drawbacks, and it is necessary to develop a simple, low-cost and easy-to-industrialize preparation method of transparent leather, so as to promote the wide application of transparent leather in the leather product field and other emerging fields (such as intelligent wearing equipment, electronic skin, flexible display, etc.).
Disclosure of Invention
Animal skin is a natural composite material with chemical components of protein (including collagen, elastin, keratin, etc.), lipid and polysaccharide and their composite, wherein the collagen is skeleton substance of animal skin. Collagen undergoes a series of steps such as biosynthesis, modification, self-assembly and the like in an animal body, various physical (such as hydrogen bond, hydrophobic effect, electrostatic effect and the like) and chemical (such as Schiff base generated by enzyme catalytic oxidation) effects are generated among collagen molecules, the evolution process from collagen molecules, collagen microfibers, collagen fibers and collagen fiber bundles is carried out, the collagen fiber bundles are further woven to form a three-dimensional network structure, so that a basic skeleton of the animal skin is formed, and other substances are respectively distributed in the collagen fiber skeleton in a specific mode. The leather making process is based on animal skin collagen fiber skeleton, and includes the combination of tanning agent and collagen fiber active group to maintain the animal skin collagen fiber skeleton structure, excellent physical, mechanical and chemical performance, retanning, dyeing, fatliquoring, etc. the leather collagen fiber skeleton is filled with various functional matters, and the subsequent drying, finishing, surface finishing, etc. to form the final leather product.
From the above composition and structural analysis, it can be seen that natural animal hides and traditional leather are opaque for the reason of: on one hand, because the refractive index of collagen, which is a main component of animal skin and conventional leather, is not matched with that of other substances contained in the collagen and air in pores of collagen fibers, light rays are refracted, scattered and reflected at all interfaces when the light rays are transmitted, so that the light cannot pass through the animal skin and the conventional leather; on the other hand, due to the existence of some substances (such as pigments, polyphenol retanning agents and the like) containing chromophoric groups in the natural animal skin and the traditional leather, the leather has certain light absorption property and can absorb light with the wavelength of 380-780 nm in the visible light region. The basic principle of leather transparentization is therefore to first remove the chromonic material, refill the material matching the refractive index of the collagen fibers of the leather and cure. Based on this, the basic process for preparing transparent leather can be summarized in the following three steps: ① Removing non-collagenous components in animal skin to obtain skin collagen fiber skeleton composed of collagen only. This process can be accomplished by processes of conventional tanning preparation stations, such as soaking, degreasing, fleshing, dehairing, liming, deliming, softening, pickling, etc. By these treatments, the resulting de-ash softened pelt or pickled pelt is then a pelt collagen fibrillar skeleton containing only collagen components. ② A substance (e.g., a polyol) having a refractive index similar to that of the collagen fibers is selected for impregnation to drive out most of the moisture and air in the collagen fiber skeleton and to fill up the pores in the collagen fiber skeleton as much as possible. ③ And (3) through curing treatment, the mutual contact surface of the substance with the matched refractive index and the collagen fiber skeleton of the leather is stable, so that a fixed interface layer is formed, and finally, the transparent leather is formed. The main defect of the currently reported transparent leather preparation method is that the third step of curing treatment is improper, so that the filled substances (such as polyalcohol) which are matched with the refractive index of the collagen fibers of the leather are dissolved out and lost when meeting water, and the problem of reduced transparency of the leather is caused.
In order to solve the solidification problem, the invention provides a novel method for preparing transparent leather on the basis of a large number of experiments. Taking de-ashed and softened pelts with retained pelt collagen fiber skeletons as raw materials, and preparing an impregnating solution by adopting vinyl monomers, an initiator, a cross-linking agent, polyalcohol and water. Firstly, putting the bare skin into impregnating solution, penetrating and uniformly distributing each component in the impregnating solution into the gaps of collagen fibers of the bare skin through proper mechanical treatment, then, in a flat state of the bare skin, carrying out heating and curing treatment to enable monomers to be polymerized in situ to form a polymer cross-linked network, and forming a network interpenetrating structure with a collagen fiber skeleton of the bare skin, thereby fixing polyalcohol matched with the refractive index of the collagen fibers in the leather, and simultaneously, the refractive index of the polymer network formed by the selected monomers is matched with the refractive index of the collagen fibers, so that the prepared leather has good transparency.
Specifically, the invention aims to provide a preparation method of transparent leather, which is characterized by comprising the following steps: 1) Weighing the de-ashed and softened pelts, placing the pelts in a rotary drum, adding an impregnating solution with the weight of 50% -200% of the pelts, and rotating the pelts at 20-35 ℃ for 4-48 hours; 2) Taking out the immersed bare leather, heating and curing for 2-24 hours at 40-90 ℃ under the state of keeping the bare leather flat, and naturally airing to obtain the transparent leather. The de-ashed and softened pelts used in the method are any one of cowhide, pigskin, goat skin or sheep skin, and the pelt thickness is 0.4-3.0 mm; the impregnating solution consists of vinyl monomer, initiator, cross-linking agent, polyol and water, wherein the mass ratio of the vinyl monomer to the initiator to the cross-linking agent to the polyol to the water=100:0.1-1.0:0.1-3.0:10-90:10-90; the vinyl monomer contained in the impregnating solution is any one or a mixture of acrylic acid, acrylamide, 2-hydroxyethyl acrylate and hydroxypropyl acrylate; the initiator contained in the impregnating solution is any one of ammonium persulfate, potassium persulfate and azodiisobutyronitrile; the cross-linking agent contained in the impregnating solution is any one of N, N' -methylene bisacrylamide and polyethylene glycol diacrylate; the polyhydric alcohol contained in the impregnating solution is any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 4-butanediol, mannitol and sorbitol.
The preparation method of the transparent leather provided by the invention has the following advantages:
firstly, the impregnating solution contains a polymerizable vinyl monomer, fully permeates into gaps of skin collagen fibers through mechanical treatment, and is subjected to in-situ polymerization on the surfaces and gaps of the skin collagen fibers to form a polymer crosslinked network during heating and curing, and meanwhile, the polymer crosslinked network and an original skin collagen fiber skeleton in the bare skin form a network interpenetrating structure, so that polyol is well fixed in leather, the problems that the polyol dissolves out and runs off when meeting water and the transparency of the leather is reduced are thoroughly solved.
Secondly, because the vinyl monomer is polymerized in situ on the surface and gaps of the collagen fibers of the leather to form a polymer crosslinked network, and forms a network interpenetrating structure with the original collagen fiber framework in the leather, the physical and mechanical properties of the transparent leather are greatly improved.
Third, the refractive index of the polymer formed by polymerizing the selected monomer is matched with that of the collagen fiber of the skin, and the original fiber gaps in the skin are completely filled, so that the refraction, scattering and reflection generated at each interface in the skin during light transmission are greatly reduced, and the transparency of the skin is greatly increased.
Fourth, the preparation method of the transparent leather provided by the invention has very simple process, and the used chemical materials are few in variety and low in price, so that the preparation method of the transparent leather is simple, low in cost and easy to industrialize.
Detailed Description
The following examples are given to illustrate the present invention in more detail, and it should be understood that they are not to be construed as limiting the scope of the invention, but rather as providing numerous insubstantial modifications and adaptations of the invention to those skilled in the art in light of the foregoing disclosure.
Example 1
Acrylic acid is used as a monomer, ammonium persulfate is used as an initiator, N '-methylene bisacrylamide is used as a cross-linking agent, ethylene glycol and water are used as solvents to prepare an impregnating solution, and the mass ratio of the acrylic acid to the ammonium persulfate to the N, N' -methylene bisacrylamide to the ethylene glycol to the water=100:0.1:0.6:90:10. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-limed and softened goatskin with a thickness of 0.4mm was weighed, placed in a rotating drum, added with an impregnating solution of 50% of the skin weight, and rotated at 25 ℃ for 4 hours. Taking out the soaked goat skin, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 40 ℃ (vacuum degree to 0), and heating and curing for 12 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 2
The method comprises the steps of preparing an impregnating solution by using acrylamide as a monomer, potassium persulfate as an initiator, N '-methylene bisacrylamide as a cross-linking agent and 1, 2-propanediol and water as solvents, wherein the mass ratio of the acrylamide to the potassium persulfate to the N, N' -methylene bisacrylamide to the 1, 2-propanediol to the water=100:0.2:1.0:60:40. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-ashed and softened sheep skin with a thickness of 0.5mm was weighed, put into a drum, added with an impregnating solution of 60% of the skin weight, and rotated at 20 ℃ for 5 hours. Taking out the soaked sheep skin, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 90 ℃ (the vacuum degree is 0), and heating and curing for 2 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 3
The dipping solution is prepared by taking acrylic acid-2-hydroxyethyl as a monomer, azodiisobutyronitrile as an initiator, N '-methylene bisacrylamide as a cross-linking agent and 1, 3-propanediol and water as solvents, wherein the mass ratio of the acrylic acid-2-hydroxyethyl to the azodiisobutyronitrile to the N, N' -methylene bisacrylamide to the 1, 3-propanediol to the water is 100:0.3:0.1:20:80. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-ashed and softened pig head layer skin with the thickness of 0.6mm is weighed, put into a rotary drum, added with an impregnating solution with the weight of 70% of the skin, and rotated for 10 hours at 30 ℃. Taking out the soaked pigskin, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 60 ℃ (vacuum degree is 0), and heating and curing for 4 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 4
The dipping solution is prepared by taking hydroxypropyl acrylate as a monomer, ammonium persulfate as an initiator, polyethylene glycol diacrylate (M.W.200) as a cross-linking agent and glycerol and water as solvents, wherein the mass ratio of the hydroxypropyl acrylate to the ammonium persulfate to the polyethylene glycol diacrylate (M.W.200) to the glycerol to the water=100:0.4:0.2:70:30. Stirring and dissolving at normal temperature to obtain an impregnating solution. The two layers of the pig skin after the deashing and softening with the thickness of 0.7mm are weighed, put into a rotary drum, added with an impregnating solution with the weight of 100% of the skin weight, and rotated for 18 hours at 35 ℃. Taking out the soaked pigskin, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to be 50 ℃ (the vacuum degree is 0), and heating and curing for 5 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 5
The dipping solution is prepared by taking a mixture of acrylic acid and acrylamide (the mass ratio is 1:9) as a monomer, potassium persulfate as an initiator, polyethylene glycol diacrylate (M.W.200) as a cross-linking agent and 1, 4-butanediol and water as solvents, wherein the mass ratio of the mixture of acrylic acid and acrylamide (the mass ratio is 1:9) to the mixture of potassium persulfate to the polyethylene glycol diacrylate (M.W.200) to the mixture of 1, 4-butanediol to water=100:0.5:0.8:40:60. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-limed and softened goatskin with a thickness of 0.8mm was weighed, placed in a rotating drum, added with an impregnating solution with a weight of 100% of the skin weight, and rotated at 25 ℃ for 24 hours. Taking out the soaked goat skin, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 80 ℃ (vacuum degree is 0), and heating and curing for 3 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 6
The method comprises the steps of preparing an impregnating solution by using a mixture of acrylic acid and 2-hydroxyethyl acrylate (the mass ratio is 3:7) as a monomer, azodiisobutyronitrile as an initiator, polyethylene glycol diacrylate (M.W.200) as a cross-linking agent, mannitol and water, wherein the mass ratio of the impregnating solution is that the mixture of acrylic acid and 2-hydroxyethyl acrylate (the mass ratio is 3:7) is that azodiisobutyronitrile, N' -methylenebisacrylamide, mannitol and water=100:0.6:1.4:30:70. Stirring and dissolving at normal temperature to obtain an impregnating solution. The deashed and softened head cowhide with a thickness of 0.9mm is weighed, placed in a drum, added with an impregnating solution with a weight of 100% of the weight of the hide, and rotated at 35 ℃ for 36 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 40 ℃ (vacuum degree is 0), and heating and curing for 18 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 7
The method comprises the steps of preparing an impregnating solution by using a mixture of acrylic acid and hydroxypropyl acrylate (with the mass ratio of 5:5) as a monomer, ammonium persulfate as an initiator, and polyethylene glycol diacrylate (M.W.400) as a cross-linking agent, wherein the mass ratio of sorbitol to water is the mixture of acrylic acid and hydroxypropyl acrylate (with the mass ratio of 5:5) to ammonium persulfate to polyethylene glycol diacrylate (M.W.400) to sorbitol to water=100:0.7:3.0:50:50. Stirring and dissolving at normal temperature to obtain an impregnating solution. The deashed and softened two layers of cowhide with a thickness of 1.0mm are weighed, placed in a rotating drum, added with an impregnating solution with a weight of 200% of the weight of the hide, and rotated at 20 ℃ for 36 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 70 ℃ (vacuum degree is 0), and heating and curing for 3 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 8
The method comprises the steps of preparing an impregnating solution by using a mixture of acrylamide and 2-hydroxyethyl acrylate (the mass ratio is 7:3) as a monomer, potassium persulfate as an initiator, polyethylene glycol diacrylate (M.W.400) as a cross-linking agent and ethylene glycol and water as solvents, wherein the mass ratio of the mixture of acrylamide and 2-hydroxyethyl acrylate (the mass ratio is 7:3) to the mixture of potassium persulfate to the polyethylene glycol diacrylate (M.W.400) to the mixture of ethylene glycol to water=100:0.8:2.5:90:10. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-limed and softened head cowhide with a thickness of 1.2mm was weighed, placed in a rotating drum, added with an impregnating solution of 150% of the weight of the hide, and rotated at 25 ℃ for 44 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to be 50 ℃ (the vacuum degree is 0), and heating and curing for 20 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 9
The method comprises the steps of preparing an impregnating solution by using a mixture of acrylamide and hydroxypropyl acrylate (the mass ratio is 9:1) as a monomer, azodiisobutyronitrile as an initiator, polyethylene glycol diacrylate (M.W.400) as a cross-linking agent and 1, 2-propanediol and water as solvents, wherein the mass ratio of the mixture of acrylamide and hydroxypropyl acrylate (the mass ratio is 9:1) to the azodiisobutyronitrile to the polyethylene glycol diacrylate (M.W.400) to the 1, 2-propanediol to water=100:0.9:2.8:80:20. Stirring and dissolving at normal temperature to obtain an impregnating solution. The deashed and softened two layers of cowhide having a thickness of 1.4mm were weighed, placed in a rotating drum, added with an impregnating solution having a skin weight of 100%, and rotated at 25 ℃ for 48 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 90 ℃ (vacuum degree is 0), and heating and curing for 2 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 10
Acrylic acid is used as a monomer, ammonium persulfate is used as an initiator, polyethylene glycol diacrylate (M.W.600) is used as a cross-linking agent, and 1, 3-propanediol and water are used as solvents to prepare an impregnating solution, wherein the mass ratio of the acrylic acid to the ammonium persulfate to the polyethylene glycol diacrylate (M.W.600) to the 1, 3-propanediol to the water=100:1.0:2.4:65:35. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-limed and softened head cowhide with a thickness of 1.6mm was weighed, placed in a rotating drum, added with an impregnating solution of 150% of the weight of the hide, and rotated at 25 ℃ for 36 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 40 ℃ (vacuum degree is 0), and heating and curing for 20 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 11
The method is characterized in that acrylamide is used as a monomer, potassium persulfate is used as an initiator, polyethylene glycol diacrylate (M.W.600) is used as a cross-linking agent, and glycerol and water are used as solvents to prepare an impregnating solution, wherein the mass ratio of the acrylamide to the potassium persulfate to the polyethylene glycol diacrylate (M.W.600) to the glycerol to the water=100:0.3:2.0:55:45. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-limed and softened head cowhide with a thickness of 1.8mm was weighed, placed in a rotating drum, added with an impregnating solution of 150% of the weight of the hide, and rotated at 20 ℃ for 40 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 80 ℃ (vacuum degree is 0), and heating and curing for 3 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 12
The dipping solution is prepared by taking acrylic acid-2-hydroxyethyl as a monomer, azodiisobutyronitrile as an initiator and polyethylene glycol diacrylate (M.W.600) as a cross-linking agent, and taking 1, 4-butanediol and water as solvents, wherein the mass ratio of the acrylic acid-2-hydroxyethyl to the azodiisobutyronitrile to the polyethylene glycol diacrylate (M.W.600) to the 1, 4-butanediol to the water=100:0.5:1.2:35:65. Stirring and dissolving at normal temperature to obtain an impregnating solution. The deashed and softened head cowhide with a thickness of 2.2mm is weighed, placed in a drum, added with an impregnating solution with a weight of 180% of the weight of the hide, and rotated at 25 ℃ for 40 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 65 ℃ (the vacuum degree is 0), and heating and curing for 3.5 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 13
The dipping solution is prepared by taking hydroxypropyl acrylate as a monomer, ammonium persulfate as an initiator, N '-methylene bisacrylamide as a cross-linking agent and 1, 3-propanediol and water as solvents, wherein the mass ratio of the hydroxypropyl acrylate to the ammonium persulfate to the N, N' -methylene bisacrylamide to the 1, 3-propanediol to the water=100:0.8:0.4:25:75. Stirring and dissolving at normal temperature to obtain an impregnating solution. The deashed and softened head cowhide with a thickness of 2.5mm is weighed, placed in a drum, added with an impregnating solution with a weight of 180% of the weight of the hide, and rotated at 20 ℃ for 44 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 70 ℃ (vacuum degree is 0), and heating and curing for 4 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 14
The method comprises the steps of preparing an impregnating solution by using a mixture of acrylamide and 2-hydroxyethyl acrylate (with the mass ratio of 4:6) as a monomer, potassium persulfate as an initiator, polyethylene glycol diacrylate (M.W.200) as a cross-linking agent and ethylene glycol and water as solvents, wherein the mass ratio of the mixture of acrylamide and 2-hydroxyethyl acrylate (with the mass ratio of 4:6) to the mixture of potassium persulfate to the polyethylene glycol diacrylate (M.W.200) to the mixture of ethylene glycol to water=100:0.2:1.6:75:25. Stirring and dissolving at normal temperature to obtain an impregnating solution. The deashed and softened head cowhide with a thickness of 2.7mm is weighed, placed in a drum, added with an impregnating solution with a weight of 200% of the weight of the hide, and rotated at 20 ℃ for 48 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 70 ℃ (vacuum degree is 0), and heating and curing for 3 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
Example 15
The method comprises the steps of preparing an impregnating solution by using a mixture of acrylic acid and 2-hydroxyethyl acrylate (the mass ratio is 6:4) as a monomer, azodiisobutyronitrile as an initiator, polyethylene glycol diacrylate (M.W.400) as a cross-linking agent and glycerol and water as solvents, wherein the mass ratio of the mixture of acrylic acid and 2-hydroxyethyl acrylate (the mass ratio is 6:4) to the mixture of azodiisobutyronitrile to polyethylene glycol diacrylate (M.W.400) to glycerol to water=100:0.4:2.3:80:20. Stirring and dissolving at normal temperature to obtain an impregnating solution. The de-limed and softened head cowhide with a thickness of 3.0mm was weighed, placed in a rotating drum, added with an impregnating solution of 150% of the weight of the hide, and rotated at 25 ℃ for 48 hours. Taking out the soaked cowhide, flatly spreading on a platform of a leather vacuum dryer, closing a cover plate, setting the temperature to 65 ℃ (the vacuum degree is 0), and heating and curing for 5 hours. And taking the leather out of the platform, and naturally airing to obtain the transparent leather.
For the transparent leather prepared in the above examples, the transmittance was measured by the method described in GB/T2410-2008 (determination of transmittance and haze of transparent plastic), the thickness was measured by the method described in QB/T2709-2005 (determination of physical and mechanical test thickness of leather), and the tensile strength was measured by the method described in QB/T2710-2018 (determination of physical and mechanical test tensile strength and elongation of leather), and the results are shown in Table 1.
TABLE 1
| Sample of | Transmittance (%) | Thickness (mm) | Tensile Strength (N/mm 2) |
| Example 1 | 88 | 0.4 | 20.8 |
| Example 2 | 85 | 0.5 | 13.2 |
| Example 3 | 83 | 0.6 | 17.9 |
| Example 4 | 82 | 0.7 | 16.6 |
| Example 5 | 80 | 0.8 | 28.3 |
| Example 6 | 78 | 0.9 | 29.3 |
| Example 7 | 77 | 1.0 | 23.2 |
| Example 8 | 73 | 1.2 | 32.5 |
| Example 9 | 70 | 1.4 | 29.3 |
| Example 10 | 67 | 1.6 | 37.1 |
| Example 11 | 63 | 1.8 | 39.7 |
| Example 12 | 60 | 2.2 | 42.3 |
| Example 13 | 55 | 2.5 | 45.1 |
| Example 14 | 53 | 2.7 | 48.6 |
| Example 15 | 50 | 3.0 | 54.8 |
Claims (6)
1. The preparation method of the transparent leather is characterized by comprising the following process flows: 1) Weighing the de-ashed and softened pelts, placing the pelts in a rotary drum, adding an impregnating solution with the weight of 50% -200% of the pelts, rotating for 4-48 hours at 20-35 ℃, wherein the impregnating solution consists of vinyl monomers, an initiator, a cross-linking agent, a polyol and water, and the mass ratio of the vinyl monomers to the initiator to the cross-linking agent to the polyol to the water=100:0.1-1.0:0.1-3.0:10-90:10-90; 2) Taking out the immersed bare leather, heating and curing for 2-24 hours at 40-90 ℃ under the state of keeping the bare leather flat, and naturally airing to obtain the transparent leather.
2. The method for preparing transparent leather according to claim 1, wherein the de-ashed and softened pelt used for preparing the transparent leather is any one of cow leather, pig leather, goat leather and sheep leather, and the pelt has a thickness of 0.4-3.0 mm.
3. The method for preparing transparent leather according to claim 1, wherein the vinyl monomer contained in the impregnating solution for preparing transparent leather is any one of acrylic acid, acrylamide, 2-hydroxyethyl acrylate and hydroxypropyl acrylate or a mixture thereof.
4. The method for preparing transparent leather according to claim 1, wherein the initiator contained in the impregnating solution for preparing transparent leather is any one of ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
5. The method for preparing transparent leather according to claim 1, wherein the cross-linking agent contained in the impregnating solution for preparing transparent leather is any one of N, N' -methylenebisacrylamide and polyethylene glycol diacrylate.
6. The method for preparing transparent leather according to claim 1, wherein the polyhydric alcohol contained in the impregnating solution for preparing transparent leather is any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 4-butylene glycol, mannitol and sorbitol.
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| CN104479523A (en) * | 2014-12-26 | 2015-04-01 | 佛山金智节能膜有限公司 | Highly hydrophobicuv (ultraviolet) leather surface treating agent and preparation method thereof |
| WO2017201865A1 (en) * | 2016-05-21 | 2017-11-30 | 范红梅 | Coating adhesive for leather |
| CN108998600A (en) * | 2018-08-13 | 2018-12-14 | 四川大学 | A kind of transparent leather and its manufacturing method |
| CN112322807A (en) * | 2020-10-22 | 2021-02-05 | 四川大学 | Method for preparing transparent leather based on solution refractive index |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104479523A (en) * | 2014-12-26 | 2015-04-01 | 佛山金智节能膜有限公司 | Highly hydrophobicuv (ultraviolet) leather surface treating agent and preparation method thereof |
| WO2017201865A1 (en) * | 2016-05-21 | 2017-11-30 | 范红梅 | Coating adhesive for leather |
| CN108998600A (en) * | 2018-08-13 | 2018-12-14 | 四川大学 | A kind of transparent leather and its manufacturing method |
| CN112322807A (en) * | 2020-10-22 | 2021-02-05 | 四川大学 | Method for preparing transparent leather based on solution refractive index |
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