CN110817786A - Leather product, preparation method thereof and watch - Google Patents
Leather product, preparation method thereof and watch Download PDFInfo
- Publication number
- CN110817786A CN110817786A CN201910968901.2A CN201910968901A CN110817786A CN 110817786 A CN110817786 A CN 110817786A CN 201910968901 A CN201910968901 A CN 201910968901A CN 110817786 A CN110817786 A CN 110817786A
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- China
- Prior art keywords
- leather
- treating agent
- leather product
- soaking
- methacrylate
- Prior art date
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- Granted
Links
- 239000010985 leather Substances 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 238000002791 soaking Methods 0.000 claims abstract description 32
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- -1 fluoroacrylate compound Chemical class 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000009958 sewing Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004026 adhesive bonding Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 3
- GWYSWOQRJGLJPA-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(C)(F)F GWYSWOQRJGLJPA-UHFFFAOYSA-N 0.000 claims description 3
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 3
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 238000004140 cleaning Methods 0.000 abstract description 6
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 238000004332 deodorization Methods 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 44
- 239000000047 product Substances 0.000 description 31
- 239000011787 zinc oxide Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 17
- 230000001681 protective effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LBTSNEJGMVFUEW-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,8,8,8-dodecafluorooctoxy-dimethoxy-propylsilane Chemical compound FC(C(C(C(C(F)(F)CO[Si](OC)(OC)CCC)(F)F)(F)F)(F)F)CC(F)(F)F LBTSNEJGMVFUEW-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- 241000270722 Crocodylidae Species 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- LNNWVNGFPYWNQE-GMIGKAJZSA-N desomorphine Chemical compound C1C2=CC=C(O)C3=C2[C@]24CCN(C)[C@H]1[C@@H]2CCC[C@@H]4O3 LNNWVNGFPYWNQE-GMIGKAJZSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B68—SADDLERY; UPHOLSTERY
- B68F—MAKING ARTICLES FROM LEATHER, CANVAS, OR THE LIKE
- B68F1/00—Making articles from leather, canvas, or the like
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
- A44C5/0053—Flexible straps
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a preparation method of a leather watchband, which comprises the following steps: providing a leather product body; sequentially soaking the leather product body in a first treating agent and a second treating agent for ultrasonic treatment; drying the leather product body after soaking treatment to obtain the leather product; wherein the first treating agent is a fluoroacrylate compound, and the relative molecular weight of the first treating agent is 200-400; the second treating agent is fluoro-alkyl-trialkoxysilane, and the relative molecular weight of the second treating agent is 500-800. The invention discloses a leather watchband and a watch. The preparation method of the invention forms the protective layer with complete structure on the surface of the leather product body, so that the leather product has better water resistance, and simultaneously has excellent antifouling, weather resistance, friction resistance, deodorization and self-cleaning performances.
Description
Technical Field
The invention relates to the field of leather surface treatment, in particular to a leather product and a preparation method thereof, and further relates to a watch comprising a leather watchband.
Background
Leather products are very common in everyday life, such as leather bags, leather shoes, belts, leather watchbands, and the like. Whether the leather product has waterproofness or not in the using process is an important index of the performance. In addition, during the manufacturing process of leather products, the leather usually needs to be sewn, glued and/or perforated to obtain the desired leather product. Such treatment has a certain deterioration of the integrity of the leather wristband against water.
Taking a leather watchband as an example, the leather watchband is a belt-shaped ornament which is specially used for watches and is prepared from genuine leather (cow leather, crocodile skin and the like) and artificial leather. Generally, leather watchbands are composed of three layers, namely a top layer (usually dyed in various colors, most commonly black, brown, white, red and the like), a middle layer (filler, usually made of leather leftover materials with poor quality and easy water absorption) and a bottom layer (classified into a waterproof bottom layer and a non-waterproof bottom layer according to waterproof performance), and the three layers are combined by sewing and/or gluing. In addition, leather watchbands are generally divided into long sides, which are usually perforated, and short sides, which are provided with a clasp and a clasp.
In the process of manufacturing the leather watchband by adopting sewing and gluing processes, the integrity of the leather materials at the sewing position (the sewing needle hole), the joint of the watch buckle and the hoop, the shaft hole end and the belt hole on the long edge is damaged to a certain degree. Whether the leather watchband adopts waterproof leather or non-waterproof leather, because the integrality of leather watchband receives the damage, therefore its waterproof performance will all receive very big influence. Water vapor and/or water (or sweat) can permeate into the leather watchband through the damaged part of the leather watchband, and the leather watchband does not have a waterproof function; in particular, leather watchbands contain fillers inside, which are not only not waterproof but also absorb water easily. When water vapor and/or water (or sweat) enter the inside of the leather watchband, the leather watchband starts to corrode and damage from the inside, so that the wearing service life of the leather watchband is shortened. The problems with leather watchbands are also present in other leather articles.
Disclosure of Invention
Therefore, it is necessary to provide a leather watch strap and a preparation method thereof for solving the problems of poor waterproof performance and short service life of leather products.
The invention provides a preparation method of a leather watchband, which comprises the following steps:
providing a leather product body;
sequentially soaking the leather product body in a first treating agent and a second treating agent for ultrasonic treatment; and
drying the leather product body after soaking treatment to obtain the waterproof leather watchband;
wherein the first treating agent is a fluoroacrylate compound, and the relative molecular weight of the first treating agent is 200-410; the second treating agent is fluoro-alkyl-trialkoxysilane, and the relative molecular weight of the second treating agent is 500-800.
In one embodiment, the relative molecular weight of the fluoroacrylate compound may be selected to be 220, 240, 250, 260, 280, 300, 320, 340, 360, 380, 400.
In one embodiment, the relative molecular weight of the fluoroacrylate compound may be selected to be 550, 600, 650, 700, 750.
In one embodiment, the first treating agent is selected from one or more of hexafluorobutyl acrylate, octafluoropentyl acrylate, nonafluorohexyl acrylate, dodecafluoroheptyl acrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, nonafluorohexyl methacrylate, and dodecafluoroheptyl methacrylate.
In one embodiment, the second treating agent is selected from one or more of dodecafluoroheptylpropyltriethoxysilane, dodecafluoroheptyltriethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.
In one embodiment, the providing the first and second treating agents comprises: cooling the first treating agent and the second treating agent to 4-8 ℃.
In one embodiment, the soaking ultrasonic temperature is less than or equal to 20 ℃.
In one embodiment, before the leather product body is sequentially soaked and ultrasonically treated in the first treating agent and the second treating agent, the method further comprises the following steps: and (3) soaking the leather product body in an alcohol dispersion liquid of ZnO nano particles for ultrasonic treatment.
In one embodiment, the alcohol is an alcohol having 1 to 4 carbon atoms.
In one embodiment, the alcohol is selected from one or more of methanol, ethanol, propanol, isopropanol, and butanol.
In one embodiment, before the soaking and ultrasonic treatment step of the leather product body in the alcohol dispersion liquid of the ZnO nanoparticles, the method further comprises cooling the alcohol dispersion liquid of the ZnO nanoparticles to 4-8 ℃.
In one embodiment, the nano zinc oxide has a particle size of 1nm to 10nm, and the ZnO nanoparticles have a mass concentration of 2% to 5% in the alcoholic dispersion of the ZnO nanoparticles.
In one embodiment, the providing the leather article body comprises sewing, gluing and perforating the leather article body.
The invention also provides a leather watchband which is prepared according to the preparation method.
The invention also provides a watch comprising the leather watchband.
The watch band precursor obtained after sewing, gluing and/or perforating can be used directly for making watches after the preparation process of the invention has been completed. The preparation method of the invention forms a protective layer with a complete structure on the surface of the leather product body, thereby improving the waterproofness of the leather product. The leather body obtained after sewing, gluing and/or punching is subjected to the treatment of the invention, and the damaged part of the leather product leather material is protected, so that the leather watchband has good waterproof performance, and simultaneously has excellent antifouling, weather-resistant, friction-resistant, deodorizing and self-cleaning performances.
Detailed Description
The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of a leather watchband, which comprises the following steps:
s10, providing a leather product body;
s20, soaking the leather product body in a first treating agent and a second treating agent in sequence for ultrasonic treatment; and
s30, drying the leather product body after soaking treatment to obtain the leather product;
wherein the first treating agent is a fluoroacrylate compound, and the relative molecular weight of the first treating agent is 200-400; the second treating agent is fluoro-alkyl-trialkoxysilane, and the relative molecular weight of the second treating agent is 500-800.
The preparation method of the invention forms the protective layer with complete structure on the surface of the leather product body, so that the leather product has better water resistance, and simultaneously has excellent antifouling, weather resistance, friction resistance, deodorization and self-cleaning performances.
In the embodiment of the invention, the leather product body is sequentially soaked and ultrasonically treated in two different treating agents, wherein the fluoroacrylate compound has high weather resistance, stain resistance and self-cleaning performance. The fluorocarbon radical trialkoxysilane has the advantages of high heat resistance, high chemical stability, low surface free energy and the like. In the embodiment of the invention, two treating agents are sequentially adopted to carry out ultrasonic soaking treatment on the leather product body, and test verification shows that the waterproof performance of the leather product is obviously improved. In the soaking ultrasonic process, the first layer of protective film is generated by polymerization reaction in the first treating agent, and when the second treating agent is adopted for further treatment, the second layer of protective film is generated on the surface of the first layer of protective film, and meanwhile, polymerization is generated between the surface of the first layer of protective film and the second treating agent, so that the first layer of protective film and the second layer of protective film are connected more stably. Meanwhile, the molecular weight of the first treating agent is smaller, and the molecular weight of the second treating agent is larger, so that the first treating agent and the second treating agent are complementary to form a more stable protective film layer.
In one embodiment, the first treating agent is selected from one or more of hexafluorobutyl acrylate, octafluoropentyl acrylate, nonafluorohexyl acrylate, dodecafluoroheptyl acrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, nonafluorohexyl methacrylate, and dodecafluoroheptyl methacrylate.
In one embodiment, the second treatment agent is selected from one or more of dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropyltriethoxysilane, dodecafluoroheptyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.
Further preferably, the first treating agent is hexafluorobutyl methacrylate, and the second treating agent is tridecafluorooctyltriethoxysilane.
The combination performance can be complemented, and the leather watchband is suitable for the leather watchband, and has excellent hydrophobic, anti-fouling and self-cleaning performances.
In one embodiment, the temperature of the first treating agent and the second treating agent is 4 ℃ to 8 ℃. In the present embodiment, the first treating agent and the second treating agent are cooled, and preferably cooled to 4 to 8 ℃. The temperature of the soaking ultrasound can be controlled below 20 ℃ through the treatment, so as to ensure that the soaking ultrasound does not influence the performance of the leather product, such as the bonding performance of glue on a leather watchband.
In an embodiment, between the soaking and ultrasonic-treating the leather product body in the first treating agent and the second treating agent in sequence, the method further comprises the following steps: and (3) soaking the leather product body in an alcohol dispersion liquid of ZnO nano particles for ultrasonic treatment. The operation of soaking the ultrasonic waves by the alcohol dispersion liquid of the ZnO nanoparticles is arranged between the two treating agents for soaking the ultrasonic waves, so that the ZnO nanoparticles with the antibacterial effect are added between the protective film layer formed by the first treating agent and the protective film layer formed by the second treating agent, the ZnO nanoparticles are uniformly distributed in the whole protective film layer, and the obtained leather watchband has good ultraviolet shielding property and excellent antibacterial and bacteriostatic properties.
In one embodiment, the alcohol is an alcohol having 1 to 4 carbon atoms.
In one embodiment, the alcohol is selected from one or more of methanol, ethanol, propanol, isopropanol, and butanol.
In one embodiment, the temperature of the alcoholic dispersion of ZnO nanoparticles is 4 ℃ to 8 ℃.
In one embodiment, the ZnO nanoparticles have a particle size of 1nm to 10nm and a mass concentration of 2% to 5% in the alcohol dispersion of the ZnO nanoparticles.
In one embodiment, the providing the leather article body comprises at least one of sewing, gluing, and perforating the leather article body. In the embodiment, the leather body obtained after sewing, gluing and/or punching is subjected to the treatment of the invention, and the damaged part of the leather product upper leather material is protected, so that the leather watchband has better waterproofness and simultaneously has excellent antifouling, weather resistance, friction resistance, deodorization and self-cleaning performances.
The invention also provides a leather product prepared according to the preparation method.
Further, the leather product is a leather watchband.
The invention also provides a watch comprising the leather watchband.
In the embodiment of the invention, in the invention, PCS represents a unit of the number of the belts, and 100PCS represents that 100 watchbands are tested.
In the examples of the present invention, the reagents used were: isopropanol (analytically pure, the content is more than or equal to 99.7%), hexafluorobutyl methacrylate (the purity is more than or equal to 96% and the water content is less than or equal to 0.5%), tridecafluorooctyltriethoxysilane (the purity is more than or equal to 95% and the water content is less than or equal to 0.5%), and ZnO nanoparticles (1-10 nm). The apparatus used was: ultrasonic cleaner, leather watchband waterproof performance check out test set.
Example 1
(1) Test specimen
Waterproof bottom leather watchband x 100 PCS.
(2) Test procedure
① freezing ZnO nanoparticle dispersion liquid (ZnO concentration: 5 wt.%) containing hexafluorobutyl methacrylate, tridecafluorooctyltriethoxysilane and isopropanol to 4 deg.C;
② soaking the leather watchband (long and short sides) in hexafluorobutyl methacrylate for 4min at 60HZ (frequency, 20 deg.C or lower);
③ placing ② leather watchband wetted by hexafluorobutyl methacrylate into ZnO nanoparticle dispersion liquid (ZnO concentration: 5 wt.%) dispersed by isopropanol, ultrasonically soaking (frequency 60HZ, ultrasonic soaking temperature is less than or equal to 20 ℃) for 8min, taking out, and naturally drying for 40 min;
④ the leather watch band ③ is placed in tridecafluorooctyltriethoxysilane for ultrasonic soaking (frequency 60HZ, ultrasonic soaking temperature is less than or equal to 20 ℃) for 6min, and then taken out and naturally dried in a ventilated kitchen for 24 h.
Example 2
(1) Test specimen
Waterproof bottom leather watchband × 100 PCS.
(2) Test procedure
① cooling ZnO nanoparticle dispersion liquid (ZnO concentration: 2 wt.%) containing hexafluorobutyl methacrylate, tridecafluorooctyltriethoxysilane and isopropanol to 8 deg.C;
② soaking leather watchbands (long and short edges, 100 leather watchbands containing long and short edges) in hexafluorobutyl methacrylate for 1min at 50HZ (frequency: 20 deg.C or lower);
③ placing ② leather watchband wetted by hexafluorobutyl methacrylate into ZnO nanoparticle dispersion liquid (ZnO concentration: 2 wt.%) dispersed by isopropanol, ultrasonically soaking (frequency 50HZ, ultrasonic soaking temperature is less than or equal to 20 ℃) for 3min, taking out, and naturally drying for 20 min;
④ soaking ③ leather watch strap in tridecafluorooctyltriethoxysilane at 50HZ and 20 deg.C for 1min, taking out, and naturally drying in a ventilated kitchen for 24 h.
Comparative example 1
The same untreated water repellent leather watch band X100 PCS as in example 1 was taken.
Comparative example 2
The same untreated water-repellent back leather watchband X100 PCS was taken as in example 2.
Examples of the experiments
The leather watch bands in the example 1, the example 2, the comparative example 1 and the comparative example 2 are respectively subjected to water absorption rate detection, and the specific steps are as follows:
a. testing the conductivity of the deionized water by using a conductivity tester with the resolution of 0.1 mu S/cm, testing the pH value of the deionized water by using a pH meter with the resolution of 0.1, and selecting the deionized water with qualified conductivity and pH value (the conductivity is 1.0 mu S/cm-5.0 mu S/cm, and the pH value is 5.0-7.0);
b. washing the leather watchband waterproof performance detection equipment water tank cleaned by tap water with deionized water with qualified conductivity and pH value for 2-3 times until the conductivity and the pH value of the deionized water in the water tank are 1.87 muS/cm and 6.4 respectively and the water temperature is 22 ℃ for later use;
c. placing the short edge of the waterproof bottom leather watchband in an oven at 40 ℃ for constant temperature drying for 30 DEG Cmin and weigh m1To the nearest 0.01 g;
d. shearing a felt of soft wool (wherein the felt of soft wool is defined by Chinese invention of 12 months and 21 days in 2018) into a size of 100mm multiplied by 30mm multiplied by 10mm, soaking the felt in the deionized water provided in the step a until the felt adsorbs saturated deionized water, taking out the felt, placing the felt in a clean PVC water tank of a waterproof performance detection device of a leather watchband, and adding the deionized water with the height of 1.5mm into the water tank;
e. placing leather watchband with its short side bottom leather facing downwards on soft wool felt, pressing a 304 stainless steel block (100mm × 25mm × 10mm) with a mass of 200g on the leather watchband, standing for 15min, taking out the leather watchband, absorbing water drops on the surface with filter paper, and weighing2To the nearest 0.01 g;
f. the water absorption η ═ of the leather watchband was calculated (m)2-m1)/m1×100％。
Specific detection results are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | |
| Water absorption η | 8％～20％ | 3％～6％ | 60％～80％ | 20％～30％ |
As can be seen from the comparison of the water absorption results of the leather watchband of the invention example 1 and the leather watchband of the comparative example 1 in Table 1, the water absorption of the leather watchband with the waterproof bottom leather of the invention example is reduced from more than 60% to 8% -20%. As can be seen from the comparison of the water absorption results of the leather watchbands in the example 2 of the invention and the comparative example 2 in Table 1, the water absorption of the leather watchband with the waterproof bottom leather in the example of the invention is reduced from more than 20-30% to 3-6%. It can be seen that the water repellency of the leather watchband is significantly enhanced after the leather watchband is treated by the method in the embodiment of the invention.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. A method of making a leather article, comprising the steps of:
providing a leather product body;
sequentially soaking the leather product body in a first treating agent and a second treating agent for ultrasonic treatment; and
drying the leather product body after soaking treatment to obtain the leather product;
wherein the first treating agent is a fluoroacrylate compound, and the relative molecular weight of the first treating agent is 200-410; the second treating agent is fluoro-alkyl-trialkoxysilane, and the relative molecular weight of the second treating agent is 500-800.
2. The production method according to claim 1, wherein the first treating agent is one or more selected from the group consisting of hexafluorobutyl acrylate, octafluoropentyl acrylate, nonafluorohexyl acrylate, dodecafluoroheptyl acrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, nonafluorohexyl methacrylate, and dodecafluoroheptyl methacrylate.
3. The method of claim 1, wherein the second treatment agent is selected from the group consisting of
One or more of dodecafluoroheptylpropyltriethoxysilane, dodecafluoroheptyltriethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.
4. The production method according to claim 1, wherein the temperatures of the first treating agent and the second treating agent are each 4 ℃ to 8 ℃.
5. The method of claim 1, wherein the soaking ultrasound temperature is 20 ℃ or less.
6. The method for preparing the leather product of any one of claims 1 to 5, wherein, between the soaking and ultrasonic treatment of the leather product body in the first treating agent and the second treating agent in sequence, the method further comprises the following steps: and (3) soaking the leather product body in an alcohol dispersion liquid of ZnO nano particles for ultrasonic treatment.
7. The method according to claim 6, wherein the alcohol is an alcohol having 1 to 4 carbon atoms.
8. The method according to claim 7, wherein the alcohol is one or more selected from the group consisting of methanol, ethanol, propanol, isopropanol, and butanol.
9. The production method according to claim 6, wherein the temperature of the alcoholic dispersion of ZnO nanoparticles is 4 to 8 ℃.
10. The method according to claim 6, wherein the ZnO nanoparticles have a particle size of 1 to 10nm and a mass concentration of 2 to 5% in the alcohol dispersion of the ZnO nanoparticles.
11. The method of claim 1, wherein the providing the leather body includes at least one of sewing, gluing, and hole punching the leather body.
12. Leather product, characterized in that it is obtained according to the process of any one of claims 1 to 11.
13. Leather product according to claim 12, characterized in that it is a leather watch strap.
14. A wristwatch comprising the leather wristband of claim 13.
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| CN111575414A (en) * | 2020-06-16 | 2020-08-25 | 遂昌润德皮饰有限公司 | Tensile leather surface layer water treatment process |
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| CN103744281A (en) * | 2013-11-30 | 2014-04-23 | 成都兆益科技发展有限责任公司 | GPS watch |
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| CN103744281A (en) * | 2013-11-30 | 2014-04-23 | 成都兆益科技发展有限责任公司 | GPS watch |
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| 肖文静等: "超声促进聚合物合成研究进展", 《江苏化工》 * |
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| CN111575414A (en) * | 2020-06-16 | 2020-08-25 | 遂昌润德皮饰有限公司 | Tensile leather surface layer water treatment process |
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