CN116622919A - Method for preparing transparent leather by adopting chrome-free tanning blank - Google Patents
Method for preparing transparent leather by adopting chrome-free tanning blank Download PDFInfo
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- CN116622919A CN116622919A CN202310821070.2A CN202310821070A CN116622919A CN 116622919 A CN116622919 A CN 116622919A CN 202310821070 A CN202310821070 A CN 202310821070A CN 116622919 A CN116622919 A CN 116622919A
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- 239000010985 leather Substances 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 241000283707 Capra Species 0.000 claims description 7
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 241001494479 Pecora Species 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 19
- 238000011282 treatment Methods 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 11
- 102000008186 Collagen Human genes 0.000 description 9
- 108010035532 Collagen Proteins 0.000 description 9
- 229920001436 collagen Polymers 0.000 description 9
- 241001465754 Metazoa Species 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- -1 aldehyde compounds Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- 230000008570 general process Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 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
- 238000009958 sewing Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
-
- 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
Abstract
The invention relates to a method for preparing transparent leather by adopting chrome-free tanning leather crust. The method adopts chrome-free tanning blank as a raw material, and is soaked in an impregnating solution consisting of a monomer, an initiator and a solvent for 1 to 120 hours at the temperature of 10 to 40 ℃, then heated for 1 to 72 hours at the temperature of 40 to 90 ℃ and dried to obtain transparent leather. The chrome-free tanning blank adopted by the method is a fully tanned product in leather industry, can endow the obtained transparent leather with excellent chemical physical and mechanical properties, and can realize effective regulation and control of the chemical physical and mechanical properties of the transparent leather by regulating and controlling the types of the blank and the monomer, thereby meeting the requirements of different application environments. The method adopts the chrome-free tanning blank, monomer and other chemical raw materials which are easy to obtain, has low cost and is easy to realize industrialization.
Description
Technical Field
The invention relates to the technical field of transparent leather, in particular to a method for preparing transparent leather by adopting chrome-free tanning blanks as raw materials through a dipping and polymerization two-step method.
Background
The leather making process is to process animal skin, such as cow leather, sheep skin, pig skin, etc. into leather product in the preparation section, tanning section, wet treatment section after tanning and finishing section. Among them, tanning is a process of changing animal skins from leather to leather, and various types of tanning agents including metal tanning agents typified by chrome tanning and aluminum tanning, organic tanning agents typified by aldehyde tanning agents and plant tanning agents, and combination tanning agents composed of them, etc. can be used. The leather crust obtained after tanning treatment not only maintains the original fiber structure of animal skin, but also has excellent physical and chemical properties, such as greatly improved wet and heat stability of collagen fibers, reduced adhesion among fibers, increased porosity of fiber structure, reduced expansion performance in water, enhanced chemical and biological effects of acid resistance, alkali, enzyme and the like, improved extrusion deformation resistance and the like, and can be prepared into leather finished products of different types to meet different application requirements.
Transparent leather is a traditional and novel leather product. The traditional transparent leather can be used for manufacturing the shadow in the traditional shadow play, and the general process flow is to carry out simple treatments such as dehairing, liming, deliming and the like on animal skin, and then dry the hide under a leveling condition to prepare the transparent leather. The transparent leather is not subjected to tanning treatment, has poor transparency, is hard, cannot resist bending and stretching, and has a limited application range. The recently reported novel transparent leather is mainly prepared according to the principle of refractive index matching, and the general process flow is to perform proper preparation working procedure treatment on animal skin to remove non-collagenous components in the animal skin, and then fill the obtained pelt with substances such as polyalcohol, polymer and the like which are matched with the refractive index (about 1.5) of collagen fibers in the pelt, so as to prepare the transparent leather. The transparent leather of the type is also generally prepared from the raw material of the pelt which is not subjected to tanning treatment, the transparency of the pelt is different due to the matching degree and the process of the refractive index of the filled substance and the collagen fiber, the leather body is generally soft, and the leather has certain bending resistance and stretching resistance, and can be used for preparing special leather products (including bags, leather shoes, leather clothing and the like) and other non-traditional leather products (such as intelligent windows, intelligent home and decorative materials, electronic skin, flexible wearable electronic equipment and the like).
Specifically, chinese patent CN108998600A, CN111455118A and CN112322807a both use pelts (including deliming and softening pelts, pelts after conventional tanning preparation process treatment, etc.) which have not undergone tanning treatment as raw materials, and use solutions containing polyalcohol for impregnation treatment, and then prepare transparent leather after drying. Because the transparent leather is not subjected to tanning treatment, the transparent leather has certain softness, but the physical and mechanical properties of the transparent leather are not good, and the requirements of practical application are difficult to meet. Chinese patent CN112322806a discloses a method for producing transparent leather based on an organic tanning agent, which uses the organic tanning agent to pretanning, then uses a solution containing polyalcohol to impregnate, and dries to obtain transparent leather. The organic tanning agent used in the patent is any one of a polyurethane sulfonate tanning agent, a cyanuric chloride active tanning agent, tetrakis (hydroxymethyl) phosphonium sulfate and tetrakis (hydroxymethyl) phosphonium chloride. However, the amount of these tanning agents is relatively low, generally 0.5-3% of the pelt after deashing and softening, the crosslinking effect on the pelt is relatively weak, and the shrinkage temperature is far lower than that of normal organic tanned leather. Therefore, the method of this patent cannot be regarded as transparent leather prepared by normal tanning of leather crust, and the physical and mechanical properties of the transparent leather cannot well meet the application requirements. Chinese patent CN114574636a discloses an ecological color transparent soft leather and a processing method thereof. The method takes de-ashed softened leather or acid leather as raw material, and the color transparent leather is obtained after neutralization, fatliquoring, dyeing, fatliquoring filling, tanning and drying treatment. The method of the patent has complex process, and various substances are difficult to be matched with the refractive index of the collagen fiber, so that the transmittance of the prepared transparent leather is not high; in addition, the tanning process is placed at the final stage of the process, the tanning agent is also an organic tanning agent, and the tanning agent comprises organic aldehyde compounds, polyepoxy epoxy compounds, cyanuric chloride compounds and derivatives thereof, and the dosage is not high, and is only 0.05-3% of the weight of de-ashed softened skin or acid skin, so the tanning agent has the same problems as the Chinese patent CN 112322806A. Chinese CN110184398A discloses a transparent leather prepared from blue wet leather crust or dyed leather crust and a preparation method thereof. The method adopts the ionic liquid compound liquid to soak the leather blank, but the principle of making leather transparent is not clear. The main disadvantages of this method are: the ionic liquid is expensive; and the leather blank is prepared by adopting chrome tanning, so that the transparent leather is not only poor in environmental protection, but also has a darker color, thereby limiting the application range.
Based on the above analysis, it can be seen that in the current process for preparing transparent leather, either the non-tanned pelts are used as raw materials for the preparation of transparent leather, or the tanning is not carried out with a sufficient amount of chromium-free tanning agent to prepare transparent leather. Because of the lack or insufficient tanning effect, the crosslinking and stitching effect between the collagen fibers in the transparent leather is insufficient, so that the chemical and physical properties of the transparent leather reported at present, such as wet heat stability, porosity, formability, bending resistance and the like, cannot be compared with those of the leather products which are normally tanned, and the application of the transparent leather in the leather and non-leather fields is greatly limited.
Disclosure of Invention
From the above analysis, it is expected that the transparent leather prepared from the fully tanned leather crust is excellent in physical and chemical properties. Therefore, a great number of preliminary experiments are carried out, and the transparent leather with high physicochemical property can be obtained by impregnating tannage with a small molecular monomer solution and then carrying out in-situ polymerization. The method comprises the steps of taking different types of chrome-free tanning blanks as raw materials, carrying out dipping treatment on the chrome-free tanning blanks by adopting dipping solution composed of monomers, an initiator and a solvent, enabling all components to fully penetrate into the chrome-free tanning blanks and uniformly distribute in collagen fiber gaps, then carrying out heating treatment in a flat state of the leather blanks, enabling the monomers to be subjected to in-situ polymerization to form polymer networks which are fully filled in the collagen fiber gaps, and forming a network interpenetrating structure with the original collagen fiber crosslinked skeleton in the leather blanks, so that transparent leather with excellent physical and mechanical properties is prepared.
Specifically, the invention aims to provide a preparation method of transparent leather, which is characterized by comprising the following process flows: 1) Weighing chrome-free tanning blanks, placing the chrome-free tanning blanks into a rotary drum, adding an impregnating solution accounting for 50-300% of the weight of the tanning blanks, and rotating for 1-120 hours at 10-40 ℃; 2) Taking out the immersed leather blank, heating for 1-72 hours at 40-90 ℃ under the condition of keeping the leather blank flat, and drying to obtain the transparent leather. The leather seed of the chrome-free tanning blank used by the method is any one of a cow leather chrome-free tanning blank, a pig leather chrome-free tanning blank, a goat leather chrome-free tanning blank and a sheep leather chrome-free tanning blank, and the thickness of the leather blank is 0.4-4.0 mm; the type of the chrome-free tanning blank is any one of a metal chrome-free tanning blank, an organic chrome-free tanning blank and an organic-metal combined chrome-free tanning blank; the metal chrome-free tanning blank is any one of aluminum tanning blank, zirconium tanning blank, titanium tanning blank, iron tanning blank, rare earth tanning blank, zeolite tanning blank and multi-metal tanning blank; the organic chrome-free tanning crust is any one of aldehyde tanning crust, organic phosphine tanning crust, organic synthetic tanning crust and oil tanning crust; the impregnating solution for preparing the transparent leather consists of monomers, an initiator and a solvent, wherein the mass ratio of the monomers to the initiator to the solvent=100:0.01-1.0:10-300; the monomer contained in the impregnating solution is any one or a mixture of acrylic acid, methacrylic acid, acrylamide, acrylic acid-2-hydroxyethyl, acrylic acid hydroxypropyl, methacrylic acid hydroxyethyl and 1-vinyl-2-pyrrolidone; the initiator contained in the impregnating solution is any one of ammonium persulfate, potassium persulfate and azodiisobutyronitrile; the solvent contained in the impregnating solution is any one of water, ethanol, tetrahydrofuran and acetone or a mixture thereof.
The preparation method of the transparent leather provided by the invention has the following advantages:
firstly, the invention adopts the fully tanned chrome-free tanning blank as the raw material, the crosslinking and sewing effect between the leather collagen fibers is stronger, and the leather blank has good chemical physical and mechanical properties. Therefore, the transparent leather prepared by the method also has very good chemical physical and mechanical properties.
Secondly, the invention can select chrome-free tanning blanks of different leather types and tanning types as raw materials, have different chemical physical and mechanical properties, and can select different types of monomers to be polymerized in situ to form polymer networks with different properties, thereby realizing effective regulation and control of the chemical physical and mechanical properties of the final transparent leather so as to meet the requirements of different application environments.
Thirdly, the chrome-free tanning blank adopted by the invention is dependent on the existing leather industry, is easy to obtain and has low cost; the components contained in the impregnating solution are common chemical raw materials, and the formula is simple and the price is low; the preparation method provided by the invention has simple process and can be finished by depending on the existing equipment in the leather industry. Therefore, the method for preparing the transparent leather has low cost and is easy to realize industrialization.
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 to enable any person skilled in the art to make various insubstantial modifications and adaptations of the invention based on the foregoing teachings.
Example 1
Acrylic acid is used as a monomer, ammonium persulfate is used as an initiator, water and ethanol (volume ratio is 8:2) are used as solvents to prepare an impregnating solution, and the mass ratio of the acrylic acid to the initiator to the solvents is 100:0.8:120. Goat aluminum tanned leather crust with the thickness of 1.6mm is weighed, put into a rotary drum, added with 100% of impregnating solution by weight of the leather crust, and rotated for 5 hours at 28 ℃. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 45 ℃, heating for 14 hours, and naturally airing to obtain transparent leather.
Example 2
The impregnating solution is prepared by adopting acrylamide as a monomer and potassium persulfate as an initiator, and water as a solvent, wherein the mass ratio of the acrylamide to the initiator to the solvent=100:0.02:210. The two-layer titanium-tanned leather crust of ox with the thickness of 2.5mm is weighed, put into a rotary drum, added with 80% of impregnating solution by weight of the leather crust, and rotated for 1 hour at 40 ℃. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 75 ℃, heating for 4 hours, and naturally airing to obtain transparent leather.
Example 3
The dipping solution is prepared by adopting acrylic acid and acrylic acid-2-hydroxyethyl ester (the mass ratio is 2:1) as monomers and azodiisobutyronitrile as an initiator, and ethanol as a solvent, wherein the mass ratio of the monomers to the initiator to the solvent=100:0.1:170. Pig head layer zirconium tanning blanks with the thickness of 2.3mm are weighed, placed in a rotary drum, added with an impregnating solution with the weight of 140% of the weight of the blanks, and rotated at 24 ℃ for 24 hours. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 60 ℃, heating for 9 hours, and naturally airing to obtain transparent leather.
Example 4
The impregnating solution is prepared by taking hydroxyethyl methacrylate as a monomer, ammonium persulfate as an initiator and water and acetone (volume ratio is 7:3) as solvents, wherein the mass ratio of the monomers to the initiator to the solvents=100:0.05:50. The ox head zeolite tannage crust with the thickness of 1.0mm is weighed, put into a rotary drum, added with 70% of impregnating solution by weight of the crust, and rotated for 6 hours at 20 ℃. And taking out the impregnated leather crust, flatly paving the leather crust on a heating platform, setting the temperature to be 50 ℃, heating for 17 hours, and naturally airing to obtain transparent leather.
Example 5
The dipping solution is prepared by taking acrylic acid-2-hydroxyethyl as a monomer and azodiisobutyronitrile as an initiator, and water and tetrahydrofuran (the volume ratio is 5:5) as solvents, wherein the mass ratio of the monomers to the initiator to the solvents=100:0.08:100. Sheep iron tanned leather with a thickness of 0.8mm was weighed, placed in a drum, added with an impregnating solution in an amount of 50% by weight of the leather, and rotated at 30 ℃ for 2 hours. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 65 ℃, heating for 11 hours, and naturally airing to obtain transparent leather.
Example 6
The dipping solution is prepared by taking hydroxypropyl acrylate as a monomer and azodiisobutyronitrile as an initiator, and water and tetrahydrofuran (volume ratio is 1:9) as solvents, wherein the mass ratio of the monomers to the initiator to the solvents=100:0.01:140. Pig two-layer aldehyde tannage with thickness of 0.4mm is weighed, put into a rotary drum, added with impregnating solution with weight of 60% of the weight of the tannage, and rotated at 10 ℃ for 108 hours. And taking out the impregnated leather crust, flatly paving the leather crust on a heating platform, setting the temperature to be 42 ℃, heating for 52 hours, and naturally airing to obtain the transparent leather.
Example 7
1-vinyl-2-pyrrolidone is used as a monomer, azodiisobutyronitrile is used as an initiator, acetone is used as a solvent to prepare an impregnating solution, and the mass ratio of the monomer to the initiator to the solvent=100:1.0:190. Goat organophosphine tannage crust with the thickness of 0.6mm is weighed, put into a rotary drum, added with 90% of the weight of the crust dipping solution and rotated at 15 ℃ for 120 hours. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 90 ℃, heating for 2 hours, and naturally airing to obtain transparent leather.
Example 8
Methacrylic acid is used as a monomer, azodiisobutyronitrile is used as an initiator, tetrahydrofuran is used as a solvent to prepare an impregnating solution, and the mass ratio of the methacrylic acid to the initiator to the solvent=100:0.4:280. Goat rare earth tannage with the thickness of 3.8mm is weighed, put into a rotary drum, added with 200 percent of impregnating solution by weight of the tannage, and rotated for 117 hours at 25 ℃. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 70 ℃, heating for 1 hour, and naturally airing to obtain transparent leather.
Example 9
The dipping solution is prepared by adopting acrylic acid and acrylamide (the mass ratio is 3:7) as monomers and potassium persulfate as an initiator, and water as a solvent, wherein the mass ratio of the acrylic acid to the acrylamide to the initiator is 100:0.03:300. The pig head layer synthetic tanning agent tannage with the thickness of 4.0mm is weighed, put into a rotary drum, added with an impregnating solution with the weight of 120% of the weight of the tannage, and rotated for 114 hours at 12 ℃. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 40 ℃, heating for 72 hours, and naturally airing to obtain transparent leather.
Example 10
The impregnating solution is prepared by adopting acrylamide and hydroxypropyl acrylate (the mass ratio is 5:5) as monomers and azodiisobutyronitrile as an initiator, and ethanol as a solvent, wherein the mass ratio of the monomers to the initiator to the solvent=100:0.2:260. The ox head layer zirconium-aluminum-titanium combined tannage with the thickness of 3.4mm is weighed, put into a rotary drum, added with 300 percent of impregnating solution by weight of the tannage, and rotated for 56 hours at 20 ℃. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 45 ℃, heating for 68 hours, and naturally airing to obtain transparent leather.
Example 11
The impregnating solution was prepared using methacrylic acid and 1-vinyl-2-pyrrolidone (mass ratio of 4:6) as monomers, potassium persulfate as initiator, water and acetone (volume ratio of 6:4) as solvents, the mass ratio of which was monomer to initiator to solvent=100:0.6:240. The two-layer pork-tanning crust with the thickness of 2.9mm is weighed, put into a rotary drum, added with an impregnating solution accounting for 180% of the crust weight and rotated at 18 ℃ for 98 hours. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 47 ℃, heating for 30 hours, and naturally airing to obtain transparent leather.
Example 12
The dipping solution is prepared by adopting hydroxypropyl acrylate and 1-vinyl-2-pyrrolidone (the mass ratio is 3:7) as monomers, ammonium persulfate as an initiator and water and ethanol (the volume ratio is 5:5) as solvents, wherein the mass ratio of the monomers to the initiator to the solvents=100:0.01:10. Sheep zeolite-aldehyde combined tannage with a thickness of 0.7mm was weighed, placed in a drum, added with an impregnating solution in an amount of 270% by weight of the tannage, and rotated at 10 ℃ for 10 hours. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 63 ℃, heating for 5 hours, and naturally airing to obtain transparent leather.
Example 13
The dipping solution is prepared by adopting methacrylic acid and hydroxyethyl methacrylate (the mass ratio is 2:8) as monomers and azodiisobutyronitrile as an initiator, and tetrahydrofuran as a solvent, wherein the mass ratio of the monomers to the initiator to the solvent=100:0.5:250. Goat titanium-aldehyde combined tannage with the thickness of 1.8mm is weighed, put into a rotary drum, added with an impregnating solution with 220% of the weight of the tannage, and rotated at 32 ℃ for 4 hours. Taking out the impregnated leather crust, flatly paving the leather crust on a heating platform, setting the temperature to be 85 ℃, heating for 3 hours, and naturally airing to obtain transparent leather.
Example 14
The dipping solution is prepared by adopting acrylamide and 1-vinyl-2-pyrrolidone (the mass ratio is 2:8) as monomers and potassium persulfate as an initiator, and water as a solvent, wherein the mass ratio of the monomers to the initiator to the solvent=100:0.04:70. The beef two-layer iron-organic phosphine combined tannage with the thickness of 1.4mm is weighed, put into a rotary drum, added with an impregnating solution accounting for 240% of the weight of the tannage, and rotated for 8 hours at 37 ℃. Taking out the impregnated leather crust, flatly laying on a heating platform, setting the temperature to 72 ℃, heating for 6 hours, and naturally airing to obtain transparent leather.
Example 15
The impregnating solution is prepared by using acrylic acid and hydroxypropyl acrylate (the mass ratio is 3:7) as monomers, ammonium persulfate as an initiator, and water and ethanol (the volume ratio is 9:1) as solvents, wherein the mass ratio of the acrylic acid to the hydroxypropyl acrylate to the initiator to the solvent=100:0.3:200. Goat aldehyde-synthetic tanning agent with the thickness of 2.0mm is combined with tanning crust, weighed into a rotary drum, added with an impregnating solution with the weight of 150% of the crust, and rotated at 14 ℃ for 86 hours. And taking out the impregnated leather crust, flatly paving the leather crust on a heating platform, setting the temperature to be 45 ℃, heating for 63 hours, and naturally airing to obtain transparent leather.
For the transparent leather prepared in the above examples, its transmittance was measured by the method described in GB/T2410-2008 (determination of transmittance and haze of transparent plastic), its thickness was measured by the method described in QB/T2709-2005 (determination of physical and mechanical test thickness of leather), and its tensile strength was measured by the method described in QB/T2710-2018 (determination of tensile strength and elongation of leather physical and mechanical test), and the results are shown in Table 1.
TABLE 1
| Sample of | Transmittance (%) | Thickness (mm) | Tensile Strength (N/mm) 2 ) |
| Example 1 | 83 | 1.6 | 88.2 |
| Example 2 | 77 | 2.5 | 125.6 |
| Example 3 | 79 | 2.3 | 118.7 |
| Example 4 | 87 | 1.0 | 65.8 |
| Example 5 | 88 | 0.8 | 58.9 |
| Example 6 | 93 | 0.4 | 43.5 |
| Example 7 | 92 | 0.6 | 50.3 |
| Example 8 | 69 | 3.8 | 158.4 |
| Example 9 | 67 | 4.0 | 172.6 |
| Example 10 | 70 | 3.4 | 152.7 |
| Example 11 | 74 | 2.9 | 133.4 |
| Example 12 | 90 | 0.7 | 52.1 |
| Example 13 | 81 | 1.8 | 98.7 |
| Example 14 | 85 | 1.4 | 75.5 |
| Example 15 | 80 | 2.0 | 108.2 |
Claims (9)
1. The preparation method of the transparent leather is characterized by comprising the following process flows: 1) Weighing chrome-free tanning blanks, placing the chrome-free tanning blanks into a rotary drum, adding an impregnating solution accounting for 50-300% of the weight of the tanning blanks, and rotating for 1-120 hours at 10-40 ℃; 2) Taking out the immersed leather blank, heating for 1-72 hours at 40-90 ℃ under the condition of keeping the leather blank flat, and drying to obtain the transparent leather.
2. The method for producing transparent leather according to claim 1, wherein the chrome-free tanned leather crust for producing transparent leather is any one of a cowhide chrome-free tanned leather crust, a pigskin chrome-free tanned leather crust, a goat skin chrome-free tanned leather crust and a sheep skin chrome-free tanned leather crust, and the crust thickness is 0.4 to 4.0mm.
3. A method of producing a transparent leather according to claims 1 and 2, characterized in that the chrome-free tannage used for producing a transparent leather is any one of a metal chrome-free tannage, an organic chrome-free tannage and an organic-metal combined chrome-free tannage.
4. A method of producing a transparent leather according to claims 1 and 3, characterized in that the metal chrome-free tanning crust for producing a transparent leather is any one of aluminum tanning crust, zirconium tanning crust, titanium tanning crust, iron tanning crust, rare earth tanning crust, zeolite tanning crust and multi-metal tanning crust.
5. A method of producing a transparent leather according to claims 1 and 3, characterized in that the organic chrome-free tanning crust for producing a transparent leather is any one of aldehyde tanning crust, organic phosphine tanning crust, organic synthetic tanning crust and oil tanning crust.
6. The method for preparing transparent leather according to claim 1, wherein the impregnating solution for preparing transparent leather is composed of monomers, initiator and solvent in a mass ratio of monomers to initiator to solvent=100:0.01-1.0:10-300.
7. A method for preparing transparent leather according to claims 1 and 6, characterized in that the monomer contained in the impregnating solution used for preparing transparent leather is any one of acrylic acid, methacrylic acid, acrylamide, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 1-vinyl-2-pyrrolidone or a mixture thereof.
8. A method for producing a transparent leather according to claims 1 and 6, characterized in that the initiator contained in the impregnating solution for producing a transparent leather is any one of ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
9. A method for producing a transparent leather according to claims 1 and 6, characterized in that the solvent contained in the impregnating solution for producing a transparent leather is any one of water, ethanol, tetrahydrofuran, acetone or a mixture thereof.
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