CN105155292A - Production method of environmentally friendly leather imitation synthetic leather - Google Patents
Production method of environmentally friendly leather imitation synthetic leather Download PDFInfo
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- CN105155292A CN105155292A CN201510415314.2A CN201510415314A CN105155292A CN 105155292 A CN105155292 A CN 105155292A CN 201510415314 A CN201510415314 A CN 201510415314A CN 105155292 A CN105155292 A CN 105155292A
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Abstract
The invention discloses a production method of environmentally friendly leather imitation synthetic leather in order to solve the problems of residual toxic and harmful substances in present synthetic leather products, and harmfulness for environmental protection and the health of human bodies. The production method of the environmentally friendly leather imitation synthetic leather synthetic leather comprises the steps of wet base production, dry dosing, dry surface lamination and post-treatment, bentonite is modified by benzyltrimethylammonium chloride, the obtained modified bentonite is used as a filler for producing a wet base, and the modified bentonite can effectively adsorb harmful substances in the synthetic leather products, so the synthetic leather produced through adopting the method is safe and environmentally-friendly. The produced synthetic leather is post-treated by adopting a delustering agent, so the appearance and the hand feeling of the synthetic leather are improved, and the soft luster and the natural leather-like hand feeling are given to the synthetic leather.
Description
Technical field
The present invention relates to synthetic leather field, particularly relate to a kind of preparation method of environment-friendly type real leather intimating synthetic leather.
Background technology
Synthetic leather is the Nomenclature Composition and Structure of Complexes of simulation natural leather and can be used as the plastic products of its substitute material.Usually with through dipping nonwoven fabric for lamina reticularis, microvoid polyurethane layer as grain layer obtain.Its positive and negative is all quite similar with leather, and has certain gas permeability, than ordinary people fabricate-leather closer to natural leather.Synthetic leather in occupation of very consequence, is widely used in producing the aspects such as case and bag, clothes, footwear and Che Nei ornaments in the daily life of the mankind.
In existing synthetic leather manufactures, polyurethane resin adds wood powder or other packing materials through dilution, through infiltration, levelling, froth breaking, the technical process such as to solidify, according to the performance of polyurethane resin, can adopt wet method and dry method two kinds of methods production synthetic leather.Dry technology for production is the industrial process that Synthetic Leather is developed the earliest, and the synthetic leather produced is powerful excellent, and bonding is firm, but permeability is relatively poor; Wet process technique is the brand-new synthetic method grown up after dry method, and the synthetic leather produced has good moisture-inhibiting, permeability, soft, plentiful, is more imbued with style and the outward appearance of natural leather.No matter which kind of production technology, in the production process of synthetic leather and in Final finishing process, owing to employing a large amount of chemical assistants, cause in synthetic leather product with a certain amount of poisonous and harmful substance, as formaldehyde, benzene, pentachlorophenol, heavy metal ion etc., these remain in the harmful substance in synthetic leather product, and Long-Time Service can damage health.Along with progress and the growth in the living standard of society, people also along with raising, there has also been higher requirement to synthetic leather product that is healthy, environmental protection to material requirement.
Chinese patent notification number CN102899915A discloses a kind of environmental synthetic leather preparation method, comprise dry mixed batching and dry method veneer two steps, in dry mixed batching, adopt the polyurethane cover, butanone, auxiliary agent and the toner high-speed stirred that do not contain dimethyl formamide even, obtained not containing the dry method binder of dimethyl formamide, then obtained dry method binder is coated in release liners, is obtained the synthetic leather product of environmental protection by steps such as oven dry, bondings.The method is produced in synthetic leather process and is not used dimethyl formamide, avoid the pollution of dimethyl formamide to environment and the injury of workman, but the method employs a large amount of chemical assistant in process of production, cause in synthetic leather product containing a certain amount of poisonous and harmful substance, these remain in the harmful substance in synthetic leather product, and Long-Time Service can damage health.
Summary of the invention
The object of the invention is to overcome residual poisonous and harmful substance in existing synthetic leather product, be unfavorable for the problem of environmental protection and health, a kind of not only environmental protection be provided but also there is the outward appearance of similar natural leather and the synthetic leather preparation method of sense of touch.
Concrete technical scheme of the present invention is: a kind of preparation method of environment-friendly type real leather intimating synthetic leather, comprises the following steps:
(1) wet method bass preparation
A. by 10 ~ 15 weight portion dimethyl formamides and 2 ~ 5 weight portion mill base mix and blend 30 ~ 40min, then filter;
B. by 40 ~ 50 weight portion dimethyl formamides, 5 ~ 20 part by weight modified bentonites and 20 ~ 30 weight portion lignocellulose mix and blend 30 ~ 40min, then fully swelling 20 ~ 30min;
C. the mixture filtered in step a is added step b swelling after mixture in, stir, then add 50 ~ 60 parts by weight of polyurethane resins, stir 30 ~ 40min, deaeration 20 ~ 30min;
D. the mixture of deaeration in step c is coated with and scrapes on base cloth, then to immerse mass fraction be solidify in the dimethyl formamide solution of 15 ~ 17%, then through washing, dry, obtain wet method bass;
(2) dry mixing
By 30 ~ 40 parts by weight of polyurethane resins, 15 ~ 20 weight portion dimethyl formamides, 10 ~ 14 weight portion butanone, 5 ~ 10 weight portion toners, 0.2 ~ 0.5 weight portion levelling agent mixing stirs evenly, and stirs 20 ~ 25min;
(3) dry method veneer
Being coated with by the dry method slurry prepared in step (2) scrapes in release liners, in 100 ~ 120 DEG C of oven dry, cooling, form dry method veneer, then by adhesive, the wet method bass in step (1) is adhered to dry method veneer, after drying cooling, release liners is peeled off, obtains synthetic leather base material;
(4) post processing
On synthetic leather base material, evenly coat delustering agent with coating roller, 100 ~ 130 DEG C of oven dry, after cooling, namely obtain environment-friendly type real leather intimating synthetic leather.
The clay rock of bentonite to be a kind of with montmorillonite be essential mineral, montmorillonite has higher cation exchange capacity and good adsorption capacity, at normal temperatures and pressures, ion, salt and organic matter can both come in and go out montmorillonite mineral interlayer and adsorbed.Because natural montmorillonite surface silicon oxide structure has the hydrolysis of extremely strong hydrophily and a large amount of exchangeable cation of interlayer, its surface is made usually to there is the thin moisture film of one deck, and can not effective adsorb both hydrophobic organic matter.In order to improve the ability of bentonite adsorption organic pollution, the present invention adopts benzyltrimethylammonium chloride modified natural bentonite, and using the filler of modified bentonite as preparation wet method bass, modified bentonite effectively can adsorb the harmful substance such as formaldehyde, benzene in synthetic leather product, adopts the safer environmental protection of synthetic leather prepared by the present invention.Meanwhile, the present invention also adopts the synthetic leather of delustering agent to preparation to carry out post processing, improves outward appearance and the feel of synthetic leather, imparts the feel of the soft gloss of synthetic leather and similar natural leather.
As preferably, described method for preparing modified bentonite is as follows:
A. by after the pulverizing of bentonite original soil, oven dry, grinding, 200 ~ 300 mesh sieves are crossed;
B. the benzyltrimethylammonium chloride solution being 30 ~ 40% by the bentonite after sieving and mass fraction mixes, be placed in microwave applicator to heat, bentonite and benzyltrimethylammonium chloride solution quality are than being 1:1.5 ~ 2, and controlling benzyltrimethylammonium chloride pH value of solution is 8 ~ 9;
C. heat complete, by product suction filtration, wash 1 ~ 2 time with the sodium hydroxide solution that pH is 8 ~ 9, with distilled water washing 2 ~ 3 times, by filter cake freeze drying, then activate 1 ~ 1.5h at 200 ~ 250 DEG C, ground 200 ~ 300 mesh sieves, obtain modified alta-mud.
The present invention adopts benzyltrimethylammonium chloride modified alta-mud, and use microwave reaction mixed liquor, the strong fuel factor of microwave makes the mixture of bentonite and benzyltrimethylammonium chloride solution rise to higher temperature rapidly, thus accelerated reaction is carried out, shorten the time of ion-exchange equilibrium, there is reduction energy consumption, time-saving advantage.
As preferably, described microwave applicator power is 700 ~ 1000W, and heat time heating time is 3 ~ 5min.Affect microwave power and heat time heating time bentonite and benzyltrimethylammonium chloride ion-exchange speed and exchange capacity, microwave power is large, and ion-exchange speed is fast, and heat time heating time is long, ion exchange capacity increase.
As preferably, described steps d setting temperature is 30 ~ 45 DEG C, and setting time is 8 ~ 10min.Too high temperature can make coating failure intensity decline, and surface uniform degree is deteriorated.
As preferably, the upper doses of mixture on base cloth of described steps d deaeration is 110 ~ 140g/m
2.
As preferably, described step (3) uses scraper to be coated with by dry method slurry to scrape in release liners, and scraper gap is 13 ~ 18mm.Control scraper gap to control the thickness of dry method veneer.
As preferably, described step (4) delustering agent is made up of the raw material of following weight portion: 30 ~ 40 parts of aqueous polyurethanes, 10 ~ 14 parts of aerosils, 0.5 ~ 1 part of paraffin, 12 ~ 18 parts of ethyl acetate, 10 ~ 20 parts of toluene, 0.3 ~ 0.8 part of silane coupler.Synthetic leather surface is shinny, has very strong to mould sense, and in order to make the outward appearance of synthetic leather and feel more close to natural leather, the present invention adopts the synthetic leather of delustering agent to preparation to carry out delustring process, thus gives the feel of the soft gloss of synthetic leather and similar natural leather.
The invention has the beneficial effects as follows: the present invention adopts benzyltrimethylammonium chloride modified natural bentonite, and using the filler of modified bentonite as preparation wet method bass, modified bentonite effectively can adsorb the harmful substance in synthetic leather product, adopts the safer environmental protection of synthetic leather prepared by the present invention.The present invention simultaneously also adopts delustering agent, carries out post processing, improve outward appearance and the feel of synthetic leather, impart the feel of the soft gloss of synthetic leather and similar natural leather the synthetic leather of preparation.
Detailed description of the invention
Below by specific embodiment, technical scheme of the present invention is described further.
The levelling agent that the present invention uses is DOW CORNING DC-3 levelling agent, and by Dow corning, company produces; Polyurethane resin is solvent type polyurethane resin, is commercially available prod; Benzyltrimethylammonium chloride is purchased from Beijing Xing Fu fine chemistry research institute; Silane coupler is silane coupler kh560, is produced by Zhejiang Hua Jin Science and Technology Co., Ltd..
If not other raw materials of the present invention and equipment refer in particular to, all can to buy from market or this area is conventional, the method in embodiment, if no special instructions, is the conventional method of this area.
Embodiment 1
A preparation method for environment-friendly type real leather intimating synthetic leather, comprises the following steps:
(1) wet method bass preparation
A. by 10 weight portion dimethyl formamides and 2 weight portion mill base (commercially available) mix and blend 30min, then filter;
B. by 40 weight portion dimethyl formamides, 5 part by weight modified bentonites and 20 weight portion lignocellulose mix and blend 30min, then abundant swelling 20min;
C. the mixture filtered in step a is added step b swelling after mixture in, stir, then add 50 parts by weight of polyurethane resins, stir 30min, deaeration 20min;
D. by the mixture of deaeration in step c with 110g/m
2upper doses be coated with and scrape on base cloth, then to immerse mass fraction be solidify 8min in the dimethyl formamide solution of 15%, and setting temperature is 30 DEG C, then through washing, dry, obtains wet method bass;
(2) dry mixing
By 30 parts by weight of polyurethane resins, 15 weight portion dimethyl formamides, 10 weight portion butanone, 5 weight portion toners, 0.2 weight portion levelling agent mixing stirs evenly, and stirs 20min;
(3) dry method veneer
Being coated with by the dry method slurry scraper prepared in step (2) scrapes in release liners, scraper gap is 13mm, in 100 DEG C of oven dry, cooling, form dry method veneer, then by adhesive, the wet method bass in step (1) is adhered on dry method veneer, after drying cooling, release liners is peeled off, obtains synthetic leather base material;
(4) post processing
On synthetic leather base material, evenly coat delustering agent with coating roller, the upper doses of delustering agent is 30g/m
2, 100 DEG C of oven dry, after cooling, namely obtain environment-friendly type real leather intimating synthetic leather.Delustering agent is made up of the raw material of following weight portion: 30 parts of aqueous polyurethanes (production of Zhong Fang auxiliary reagent factory of Taixing City), 10 parts of aerosils, 0.5 part of paraffin, 12 parts of ethyl acetate, 10 parts of toluene, 0.3 part of silane coupler.
Wherein, method for preparing modified bentonite is as follows:
A. by after the pulverizing of bentonite original soil, oven dry, grinding, 200 mesh sieves are crossed;
B. the benzyltrimethylammonium chloride solution being 30% by the bentonite after sieving and mass fraction mixes, be placed in microwave applicator and heat 3min, microwave power is 700W, and bentonite and benzyltrimethylammonium chloride solution quality are than being 1:1.5, and controlling benzyltrimethylammonium chloride pH value of solution is 8;
C. heat complete, by product suction filtration, wash 1 time, wash 2 times with distilled water with the sodium hydroxide solution that pH is 8, by filter cake freeze drying, then activate 1h at 200 DEG C, ground 200 mesh sieves, obtain modified alta-mud.
Embodiment 2
A preparation method for environment-friendly type real leather intimating synthetic leather, comprises the following steps:
(1) wet method bass preparation
A. by 12 weight portion dimethyl formamides and 4 weight portion mill base mix and blend 35min, then filter;
B. by 45 weight portion dimethyl formamides, 10 part by weight modified bentonites and 25 weight portion lignocellulose mix and blend 35min, then abundant swelling 25min;
C. the mixture filtered in step a is added step b swelling after mixture in, stir, then add 55 parts by weight of polyurethane resins, stir 35min, deaeration 25min;
D. by the mixture of deaeration in step c with 125g/m
2upper doses be coated with and scrape on base cloth, then to immerse mass fraction be solidify 9min in the dimethyl formamide solution of 16%, and setting temperature is 35 DEG C, then through washing, dry, obtains wet method bass;
(2) dry mixing
By 35 parts by weight of polyurethane resins, 17 weight portion dimethyl formamides, 12 weight portion butanone, 8 weight portion toners, 0.3 weight portion levelling agent mixing stirs evenly, and stirs 22min;
(3) dry method veneer
Being coated with by the dry method slurry scraper prepared in step (2) scrapes in release liners, scraper gap is 15mm, in 110 DEG C of oven dry, cooling, form dry method veneer, then by adhesive, the wet method bass in step (1) is adhered to dry method veneer, after drying cooling, release liners is peeled off, obtains synthetic leather base material;
(4) post processing
On synthetic leather base material, evenly coat delustering agent with coating roller, the upper doses of delustering agent is 35g/m
2, 110 DEG C of oven dry, after cooling, namely obtain environment-friendly type real leather intimating synthetic leather.Delustering agent is made up of the raw material of following weight portion: 35 parts of aqueous polyurethanes, 12 parts of aerosils, 0.7 part of paraffin, 15 parts of ethyl acetate, 15 parts of toluene, 0.6 part of silane coupler.
Wherein, method for preparing modified bentonite is as follows:
A. by after the pulverizing of bentonite original soil, oven dry, grinding, 250 mesh sieves are crossed;
B. the benzyltrimethylammonium chloride solution being 35% by the bentonite after sieving and mass fraction mixes, be placed in microwave applicator and heat 4min, microwave power is 800W, and bentonite and benzyltrimethylammonium chloride solution quality are than being 1:1.8, and controlling benzyltrimethylammonium chloride pH value of solution is 8.5;
C. heat complete, by product suction filtration, wash 2 times, wash 2 times with distilled water with the sodium hydroxide solution that pH is 8.5, by filter cake freeze drying, then activate 1.5h at 250 DEG C, ground 250 mesh sieves, obtain modified alta-mud.
Embodiment 3
A preparation method for environment-friendly type real leather intimating synthetic leather, comprises the following steps:
(1) wet method bass preparation
A. by 15 weight portion dimethyl formamides and 5 weight portion mill base mix and blend 40min, then filter;
B. by 50 weight portion dimethyl formamides, 20 part by weight modified bentonites and 30 weight portion lignocellulose mix and blend 40min, then abundant swelling 30min;
C. the mixture filtered in step a is added step b swelling after mixture in, stir, then add 60 parts by weight of polyurethane resins, stir 40min, deaeration 20 ~ 30min;
D. by the mixture of deaeration in step c with 125g/m
2upper doses be coated with and scrape on base cloth, then to immerse mass fraction be solidify 10min in the dimethyl formamide solution of 17%, and setting temperature is 45 DEG C, then through washing, dry, obtains wet method bass;
(2) dry mixing
By 40 parts by weight of polyurethane resins, 20 weight portion dimethyl formamides, 14 weight portion butanone, 10 weight portion toners, 0.5 weight portion levelling agent mixing stirs evenly, and stirs 25min;
(3) dry method veneer
Being coated with by the dry method slurry scraper prepared in step (2) scrapes in release liners, scraper gap is 18mm, in 120 DEG C of oven dry, cooling, form dry method veneer, then by adhesive, the wet method bass in step (1) is adhered to dry method veneer, after drying cooling, release liners is peeled off, obtains synthetic leather base material;
(4) post processing
On synthetic leather base material, evenly coat delustering agent with coating roller, the upper doses of delustering agent is 40g/m
2, 130 DEG C of oven dry, namely obtain environment-friendly type real leather intimating synthetic leather after cooling.Delustering agent is made up of the raw material of following weight portion: 40 parts of aqueous polyurethanes, 14 parts of aerosils, 1 part of paraffin, 18 parts of ethyl acetate, 20 parts of toluene, 0.8 part of silane coupler.
Wherein, method for preparing modified bentonite is as follows:
A. by after the pulverizing of bentonite original soil, oven dry, grinding, 300 mesh sieves are crossed;
B. the benzyltrimethylammonium chloride solution being 40% by the bentonite after sieving and mass fraction mixes, be placed in microwave applicator and heat 5min, microwave power is 1000W, and bentonite and benzyltrimethylammonium chloride solution quality are than being 1:2, and controlling benzyltrimethylammonium chloride pH value of solution is 9;
C. heat complete, by product suction filtration, wash 2 times, wash 3 times with distilled water with the sodium hydroxide solution that pH is 9, by filter cake freeze drying, then activate 1.5h at 250 DEG C, ground 300 mesh sieves, obtain modified alta-mud.
According to GB/T19941-2005 " mensuration of leather and fur chemical experiment content of formaldehyde ", adopt AAS to record in environment-friendly type real leather intimating synthetic leather prepared by the present invention, the content of free formaldehyde is less than 100mg/kg.
Claims (7)
1. a preparation method for environment-friendly type real leather intimating synthetic leather, is characterized in that comprising the following steps:
(1) wet method bass preparation
A. by 10 ~ 15 weight portion dimethyl formamides and 2 ~ 5 weight portion mill base mix and blend 30 ~ 40min, then filter;
B. by 40 ~ 50 weight portion dimethyl formamides, 5 ~ 20 part by weight modified bentonites and 20 ~ 30 weight portion lignocellulose mix and blend 30 ~ 40min, then fully swelling 20 ~ 30min;
C. the mixture filtered in step a is added step b swelling after mixture in, stir, then add 50 ~ 60 parts by weight of polyurethane resins, stir 30 ~ 40min, deaeration 20 ~ 30min;
D. the mixture of deaeration in step c is coated with and scrapes on base cloth, then to immerse mass fraction be solidify in the dimethyl formamide solution of 15 ~ 17%, then through washing, dry, obtain wet method bass;
(2) dry mixing
By 30 ~ 40 parts by weight of polyurethane resins, 15 ~ 20 weight portion dimethyl formamides, 10 ~ 14 weight portion butanone, 5 ~ 10 weight portion toners, 0.2 ~ 0.5 weight portion levelling agent mixing stirs evenly, and stirs 20 ~ 25min;
(3) dry method veneer
Being coated with by the dry method slurry prepared in step (2) scrapes in release liners, in 100 ~ 120 DEG C of oven dry, cooling, form dry method veneer, then by adhesive, the wet method bass in step (1) is adhered to dry method veneer, after drying cooling, release liners is peeled off, obtains synthetic leather base material;
(4) post processing
On synthetic leather base material, evenly coat delustering agent with coating roller, 100 ~ 130 DEG C of oven dry, after cooling, namely obtain environment-friendly type real leather intimating synthetic leather.
2. the preparation method of a kind of environment-friendly type real leather intimating synthetic leather according to claim 1, it is characterized in that, described method for preparing modified bentonite is as follows:
A. by after the pulverizing of bentonite original soil, oven dry, grinding, 200 ~ 300 mesh sieves are crossed;
B. the benzyltrimethylammonium chloride solution being 30 ~ 40% by the bentonite after sieving and mass fraction mixes, be placed in microwave applicator to heat, bentonite is 1: 1.5 ~ 2 with benzyltrimethylammonium chloride solution quality ratio, and controlling benzyltrimethylammonium chloride pH value of solution is 8 ~ 9;
C. heat complete, by product suction filtration, wash 1 ~ 2 time with the sodium hydroxide solution that pH is 8 ~ 9, with distilled water washing 2 ~ 3 times, by filter cake freeze drying, then activate 1 ~ 1.5h at 200 ~ 250 DEG C, ground 200 ~ 300 mesh sieves, obtain modified alta-mud.
3. the preparation method of a kind of environment-friendly type real leather intimating synthetic leather according to claim 2, is characterized in that, described microwave applicator power is 700 ~ 1000W, and heat time heating time is 3 ~ 5min.
4. the preparation method of a kind of environment-friendly type real leather intimating synthetic leather according to claim 1, is characterized in that, described steps d setting temperature is 30 ~ 45 DEG C, and setting time is 8 ~ 10min.
5. the preparation method of a kind of environment-friendly type real leather intimating synthetic leather according to claim 1, is characterized in that, the upper doses of mixture on base cloth of described steps d deaeration is 110 ~ 140g/m
2.
6. the preparation method of a kind of environment-friendly type real leather intimating synthetic leather according to claim 1, is characterized in that, described step (3) uses scraper to scrape in release liners by the painting of dry method slurry, and scraper gap is 13 ~ 18mm.
7. the preparation method of a kind of environment-friendly type real leather intimating synthetic leather according to claim 1, it is characterized in that, described step (4) delustering agent is made up of the raw material of following weight portion: 30 ~ 40 parts of aqueous polyurethanes, 10 ~ 14 parts of aerosils, 0.5 ~ 1 part of paraffin, 12 ~ 18 parts of ethyl acetate, 10 ~ 20 parts of toluene, 0.3 ~ 0.8 part of silane coupler.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106192439A (en) * | 2016-08-17 | 2016-12-07 | 华伦皮塑（苏州）有限公司 | A kind of preparation method of environmental protection easy decontamination synthetic leather |
| CN107385944A (en) * | 2017-09-11 | 2017-11-24 | 苏州瑞高新材料有限公司 | A kind of automobile gear sheath removes from office manufacture method |
| CN107761404A (en) * | 2017-12-06 | 2018-03-06 | 吴宗文 | A kind of preparation method of high abrasion-proof PU synthetic leather fabric |
| CN111543753A (en) * | 2020-06-05 | 2020-08-18 | 杭州天龙手袋股份有限公司 | Handbag with cowhide finishing layer |
| CN112482039A (en) * | 2020-11-24 | 2021-03-12 | 桐乡市汇中纺织有限公司 | Environment-friendly imitated leather fabric and preparation process thereof |
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| CN102899921A (en) * | 2011-07-29 | 2013-01-30 | 昆山协孚人造皮有限公司 | Manufacturing method of powder-wax synthetic leather |
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| CN104652137A (en) * | 2015-03-13 | 2015-05-27 | 厦门信得利投资发展有限公司 | Preparation method of environment-friendly silica gel synthetic leather |
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| JPS56382A (en) * | 1979-06-13 | 1981-01-06 | Kunimine Kogyo Kk | Production of artificial leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107385944A (en) * | 2017-09-11 | 2017-11-24 | 苏州瑞高新材料有限公司 | A kind of automobile gear sheath removes from office manufacture method |
| CN107761404A (en) * | 2017-12-06 | 2018-03-06 | 吴宗文 | A kind of preparation method of high abrasion-proof PU synthetic leather fabric |
| CN107761404B (en) * | 2017-12-06 | 2020-02-11 | 扬州市德运塑业科技股份有限公司 | Preparation method of high-wear-resistance PU synthetic leather fabric |
| CN111543753A (en) * | 2020-06-05 | 2020-08-18 | 杭州天龙手袋股份有限公司 | Handbag with cowhide finishing layer |
| CN111543753B (en) * | 2020-06-05 | 2022-07-12 | 杭州天龙手袋股份有限公司 | Handbag with cowhide finishing layer |
| CN112482039A (en) * | 2020-11-24 | 2021-03-12 | 桐乡市汇中纺织有限公司 | Environment-friendly imitated leather fabric and preparation process thereof |
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