CN108360269A - A kind of preparation method of ox hair powder filler modified water-soluble dry method polyurethane bass - Google Patents
A kind of preparation method of ox hair powder filler modified water-soluble dry method polyurethane bass Download PDFInfo
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- CN108360269A CN108360269A CN201810356752.XA CN201810356752A CN108360269A CN 108360269 A CN108360269 A CN 108360269A CN 201810356752 A CN201810356752 A CN 201810356752A CN 108360269 A CN108360269 A CN 108360269A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The present invention relates to a kind of preparation methods of ox hair powder filler modified water-soluble dry method polyurethane bass, include the following steps：（1）Ox hair cleans（2）Ox hair powder filler it is crude（3）Ox hair powder filler refines（4）Prepare the aqueous polyurethane slurry containing ox hair powder filler（5）The preparation of ox hair powder filler modified water-soluble dry method polyurethane bass.Ox hair filler particle size prepared by this method is small, and light weight, water absorption rate is big, and the aqueous dry method polyurethane bass of preparation has good foam structure and permeability.The addition of the ox hair powder filler, provides not only the effective way of a discarded ox hair recycling, and improves the sanitation performance of waterborne polyurethane synthetic leather and ecological degradability.
Description
Technical field
The invention belongs to the biological material utilizations of resources and leather/synthetic leather field, and in particular to a kind of ox hair powder is filled out
Expect the preparation method of modified water-soluble dry method polyurethane bass.
Background technology
In recent years, the booming horizontal raising for people's lives of leather industry provides strong material guarantee.
But due to the particularity of leather-making technology, industry is set to also result in certain problem of environmental pollution while rapid development, such as
The discarding of the solid waste containing chromium, the high ammonia nitrogen such as liming depilation, dyeing and fat-liquoring, the discharge of high chroma waste liquid and terminal leather-making mud
Accumulation problem.With the enhancing of social environment consciousness, the entirety of national research strength is soaring, some emerging tanning technologies are answered
With such as being recycled without chrome tanning, liming chroming waste liquor, process hides institute has been effectively relieved in the use etc. of high-selenium corn dyeing and fat-liquoring material
The environmental pressure faced, people are not than today closer to the concept of leather green manufacturing.Although the sequentially implementation of green technology,
The filthy stereotype of traditional leather industry is greatly changed, but the problem after some New technical uses starts to float recently
It is existing, the rapid popularization for the guarantor's hair dehairing process for " ruining the rotten hair method of hair " in traditional ox-hide leather production is especially substituted, although significantly drop
COD, BOD value in low waste water, but these discarded ox hairs taken off are difficult to have place to show one's prowess for the moment, start bulk deposition,
The thorny problem that must be faced as process hides dealer.
On the other hand, the supplement of artificial leather, synthetic leather as natural leather, not only designs and varieties are various, but also price is just
Preferably, liking for people is received always on the market.Nowadays, artificial leather, synthetic leather have quantitatively surmounted limited corium already
Product, or even also it is better than natural leather in intensity, but polar group or peptide bond due to lacking natural collagen,
Permeable penetrability is insufficient, poor with the sympathy of skin, often not as good as corium on sanitation performance.It is aqueous dry in synthetic leather manufacture
Method polyurethane bass（BASE）, referring to can be with the principle of mechanical foaming, with sending out the polyurethane steeped using water-base resin（PU）Slurry
Material carries out direct coating to synthetic leather base cloth, forms the synthetic leather semi-finished product with foam structure, soft coating after drying.Shellfish
This can become polyurethane and synthesize after dry method veneer or surface finish, such as after surface printing, embossing, mill skin technique
Remove from office finished product.The primary raw material of production waterborne polyurethane synthetic leather dry method bass has waterborne polyurethane resin, filler material, surface-active
The materials such as agent.For preparing the filler of bass at present, with wood powder（Microcrystalline cellulose）It is the most universal, followed by lightweight carbonic acid
Calcium, calcium sulfate, wollastonite etc., these fillers are as one of natural resources, and often limited amount, exploitation or preparation are more tired
It is difficult.
Invention content
The problems such as processing to solve discarded ox hair is disposed and common synthetic leather water vapor permeability is poor, and fill resources are limited, it is real
Now discard ox hair resource high added value conversion and aqueous dry method polyurethane bass it is function modified, the present invention provides a kind of oxen
The preparation method of hair powder filler modified water-soluble dry method polyurethane bass, synthetic leather bass foam structure made of the method is apparent,
Vapor pervious performance is good, and sanitation performance is good, can be used for the manufacture of aqueous ecological synthetic leather.
A kind of method of the aqueous dry method polyurethane bass of ox hair powder modification, includes the following steps：
（1）Ox hair cleans：Ox hair 20min-40min is impregnated with 15-25 times of the clear water rinsing of ox hair weight, picks the wood to float in the water surface
It considers and sinks to bottom insoluble impurities to be worth doing, dried hair with centrifuge；It is fitted into ultrasonic cleaning machine, immersion, rinsing 2-3 times, every time
30min removes soluble impurity, obtained wet ox hair is placed in pallet, is uniformly spread out, puts dry in baking oven；
（2）Ox hair powder it is crude：It will be through step（1）The ox hair of removal of impurities is put into pulverizer, sieving；
（3）Ox hair powder refines：By step（2）Ox hair powder, be put into ball grinder, be added solution；Seal ball milling；Choose
Abrading-ball, by slurry spraying drying powder-forming；
（4）The preparation of aqueous polyurethane slurry：Foaming agent, thickener, foam stabilizer and step are added in hydrotropism's polyurethane（3）System
Standby ox hair powder filler, mechanical agitation is uniform, foams；
（5）The preparation of aqueous dry method polyurethane bass：In the upper clearance gauge of clean base fabric two edges pad by plating, with coated rod edge
It is longitudinal by step clearance gauge（4）Slurry scratch in base fabric, be subsequently placed into baking oven gradient increased temperature drying to get aqueous dry method
Polyurethane bass.
The step（1）Middle soaking solution is the aqueous solution containing 2% neopelex that ox hair weighs 20 times.
The step（3）In, ball grinder is any one in ceramic pot, agate pot, stainless cylinder of steel, tetrafluoroethene tank；
Abrading-ball is any one in cobblestone ball, agate ball, zirconia ball, stainless steel ball.
The step（3）In, solution is any one in water, acetone, ethyl alcohol；The matter of the ox hair, abrading-ball, solution
Amount is than being 1：150-250：100-200；The Ball-milling Time is 6-12h, rotating speed 35-45Hz.
The step（4）In, the solid content of aqueous polyurethane is 35-50%；The foaming agent, thickener, foam stabilizer and ox
The addition of hair powder filler, in terms of polyurethane resin quality, respectively 3-5%, 0.5-3%, 0.5-5%, 1-4%.
The step（4）In, mechanical agitation rotating speed is 1200-2500 r/min, and the mechanical foaming time is 20-50min.
The step（5）In, 60-110 DEG C of the drying temperature of baking oven, drying time 20-30min.
Description of the drawings
The common wood powder fillers of Fig. 1（It is left）And ox hair powder filler（It is right）Apparent form；
The common wood powder fillers of Fig. 2（On）With ox hair powder filler（Under）Grain size distribution；
Fig. 3 common water borne PU bass（It is left）With ox hair powder filler modified water-soluble dry method PU bass（It is right）SEM cross-section morphologies.
Beneficial effects of the present invention：
（1）After the present invention cleans discarded ox hair, it is changed into ox hair powder and is used as waterborne polyurethane synthetic leather dry method bass
Filler is turned waste into wealth, and the recycling to discard ox hair provides new thinking and approach.
（2）The physics modes such as integrated use crushing of the present invention, mechanical ball mill avoid the traditional chemical processing excessive water of ox hair
The problem of solution, keratin resource wastes indirectly and chemical reagent use easily leads to secondary pollution, realize the height of discarded ox hair
Effect and high level conversion.
（3）The present invention prepares water-soluble polyurethane leather beth powder filler with leather-making waste ox hair（See the right sides Fig. 1）, replace
For traditional wood powder（See the left sides Fig. 1）, the materials such as calcium carbonate, saved natural resources, reduced production cost, be leather,
Synthetic leather industry creates another economic benefit, has preferable application prospect.
（4）Compared with conventional wet polyurethane bass or aqueous dry method polyurethane bass, aqueous poly- ammonia prepared by the present invention
Lipase absobed remove from office bass, due to the addition of natural ox hair protein powder filler, and with good moisture absorption penetrability, sanitation performance and
Ecological degradability.
Specific implementation mode
It is as described below to be only the preferred embodiment of the present invention, it is used only for the description present invention, should not be understood as to the present invention
Range limitation.
Embodiment 1：
A kind of method of the aqueous dry method polyurethane bass of ox hair powder modification, includes the following steps：
（1）Ox hair pre-treatment：After impregnating ox hair 20min with the clear water rinsing of 20 times of gross weight, picks and float in the sawdust of the water surface and heavy
Hair is dried in insoluble impurities such as rock ballast, the meat pieces of bottom, then with centrifuge.It is clear that ox hair through tentatively cleaning is packed into ultrasound
It washes in device, with the aqueous solution soaking containing 2% neopelex of 20 times of gross weight, rinsing 3 times, while being aided with ultrasonic vibration,
30 minutes every time, to remove the soluble impurities such as degreasing, sulfide, obtained wet ox hair is placed in pallet, uniformly spreads out, puts
It is dry in baking oven.
（2）Ox hair powder filler it is crude：Ox hair of the step 1 after processed is put into pulverizer, crush as 1mm with
Under, cross 20 mesh sieve.
（3）Ox hair powder filler refines：Ox hair of the step 2 after processed is put into the stainless steel ball of planetary ball mill
In grinding jar, stainless steel ball is put into, water, wherein ox hair are added：Abrading-ball：The mass ratio of water is 1：250：200, with 45Hz after sealing
Speed ball milling 6h.Choose abrading-ball, by slurry spraying drying powder-forming.
（4）Prepare the aqueous polyurethane slurry for being mixed with ox hair powder filler：Admittedly the aqueous polyurethane for containing 35% is placed in drying
In PE plastic beakers, ox hair powder filler prepared by 5% foaming agent, 3% thickener, 5% foam stabilizer and 1% step 3 is added（With PU trees
Lipid gauge）, stirred evenly with the rotating speed machinery of 2500r/min, and mechanical foaming 20min.
（5）The preparation of ox hair powder filler modified water-soluble dry method polyurethane bass：On the clean base fabric both sides by plating
Clearance gauge on edge pad is scratched in base fabric along longitudinal slurry for preparing step 4 of clearance gauge with coated rod, is subsequently placed into baking oven
Drying, gradient increased temperature is to 110 DEG C since 70 DEG C for drying temperature, drying time 20min.
Embodiment 2:
A kind of method of the aqueous dry method polyurethane bass of ox hair powder modification, includes the following steps：
（1）Ox hair pre-treatment：After impregnating ox hair 30min with the clear water rinsing of 25 times of gross weight, picks and float in the sawdust of the water surface and heavy
Hair is dried in insoluble impurities such as rock ballast, the meat pieces of bottom, then with centrifuge.It is clear that ox hair through tentatively cleaning is packed into ultrasound
It washes in device, with the aqueous solution soaking containing 2% neopelex of 20 times of gross weight, rinsing 2 times, while being aided with ultrasonic vibration,
30 minutes every time, to remove the soluble impurities such as degreasing, sulfide, obtained wet ox hair is placed in pallet, uniformly spreads out, puts
It is dry in baking oven.
（2）Ox hair powder filler it is crude：Ox hair of the step 1 after processed is put into pulverizer, crush as 1mm with
Under, cross 20 mesh sieve.
（3）Ox hair powder filler refines：Ox hair of the step 2 after processed is put into the ceramic ball milling of planetary ball mill
In tank, zirconia ball is put into, ethyl alcohol, wherein ox hair are added：Abrading-ball：The mass ratio of ethyl alcohol is 1：150：100, after sealing with
40Hz speed ball millings 10h.Choose abrading-ball, by slurry spraying drying powder-forming.
（4）Prepare the aqueous polyurethane slurry for being mixed with ox hair powder filler：Admittedly the aqueous polyurethane for containing 45% is placed in drying
In PE plastic beakers, ox hair powder filler prepared by 4% foaming agent, 2% thickener, 3% foam stabilizer and 2% step 3 is added（With PU trees
Lipid gauge）, stirred evenly with the rotating speed machinery of 2000r/min, and mechanical foaming 30min.
（5）The preparation of ox hair powder filler modified aqueous polyurethane synthetic leather bass：In the clean base fabric two by plating
Clearance gauge on edge pad is scratched in base fabric along longitudinal slurry for preparing step 4 of clearance gauge with coated rod, is subsequently placed into baking oven
Middle drying, gradient increased temperature is to 110 DEG C since 80 DEG C for drying temperature, drying time 25min.
Embodiment 3:
A kind of method of the aqueous dry method polyurethane bass of ox hair powder modification, includes the following steps：（1）Ox hair pre-treatment：With hair
Weigh after 15 times of clear water rinsing impregnates ox hair 40min, pick float the water surface sawdust and to sink to the rock ballast of bottom, meat piece etc. insoluble
Property impurity, then dried hair with centrifuge.Ox hair through tentatively cleaning is fitted into ultrasonic cleaning machine, contains 2% with 20 times of gross weight
The aqueous solution soaking of neopelex, rinsing 3 times, while being aided with ultrasonic vibration, 30 minutes every time, with remove degreasing,
Obtained wet ox hair is placed in pallet, uniformly spreads out by the soluble impurities such as sulfide, puts dry in baking oven.
（2）Ox hair powder filler it is crude：Ox hair of the step 1 after processed is put into pulverizer, crush as 1mm with
Under, cross 20 mesh sieve.
（3）Ox hair powder filler refines：Ox hair of the step 2 after processed is put into the agate ball milling of planetary ball mill
In tank, agate ball is put into, acetone, wherein ox hair are added：Abrading-ball：The mass ratio of acetone is 1：200：150, with 35Hz after sealing
Speed ball milling 12h.Choose abrading-ball, by slurry spraying drying powder-forming.
（4）Prepare the aqueous polyurethane slurry for being mixed with ox hair powder filler：Admittedly the aqueous polyurethane for containing 50% is placed in drying
In PE plastic beakers, ox hair powder filler prepared by 3% foaming agent, 0.5% thickener, 2% foam stabilizer and 4% step 3 is added（With PU
Resinite gauge）, stirred evenly with the rotating speed machinery of 1800r/min, and mechanical foaming 50min.
（5）The preparation of ox hair powder filler modified aqueous polyurethane synthetic leather bass：In the clean base fabric two by plating
Clearance gauge on edge pad is scratched in base fabric along longitudinal slurry for preparing step 4 of clearance gauge with coated rod, is subsequently placed into baking oven
Middle drying, gradient increased temperature is to 105 DEG C since 60 DEG C for drying temperature, drying time 30min.
Comparative example
A kind of method of aqueous dry method polyurethane bass, includes the following steps：
（1）Prepare the aqueous polyurethane slurry for being mixed with ox hair powder filler：Admittedly the aqueous polyurethane for containing 45% is placed in dry PE modelings
Expect in beaker, 4% foaming agent, 2% thickener, 3% foam stabilizer and 2% wood powder is added（With PU resinite gauge）, with 2000r/min
Rotating speed machinery stir evenly, and mechanical foaming 30min.
（2）The preparation of ox hair powder filler modified aqueous polyurethane synthetic leather bass：In the clean base fabric two by plating
Clearance gauge on edge pad is scratched in base fabric along longitudinal slurry for preparing step 4 of clearance gauge with coated rod, is subsequently placed into baking oven
Middle drying, gradient increased temperature is to 110 DEG C since 80 DEG C for drying temperature, drying time 25min.
The ox hair powder filler developed to commercially available common wood powder and the present invention with micron-sized laser particle size analyzer has carried out grain
Diameter is analyzed, and the results are shown in Figure 2；As shown in Figure 2, the ox hair powder filler that prepared by the present invention is similar to common wooden powder diameter,
Average grain diameter is at 45 μm or so, and the particle diameter distribution of most particles is within 20-100 μm.
And Electronic Speculum is scanned to the section of the product of embodiment 2 and comparative example（SEM）Analysis, the results are shown in Figure 3；By
Fig. 3 it is found that with common wood powder filler prepare aqueous dry method bass compared with, ox hair powder filler be modified the poly- ammonia of aqueous dry method
Ester bass has pass structure not of uniform size, there is the pore-creating effect similar to wet-process coating technique, has better soft hand
Sense, and bass coating surface has trepanning, has the sanitation performances such as good permeable moisture-inhibiting.
Claims (7)
1. a kind of method of the aqueous dry method polyurethane bass of ox hair powder modification, which is characterized in that include the following steps：
（1）Ox hair cleans：Ox hair 20min-40min is impregnated with 15-25 times of the clear water rinsing of ox hair weight, picks the wood to float in the water surface
It considers and sinks to bottom insoluble impurities to be worth doing, dried hair with centrifuge；It being fitted into ultrasonic cleaning machine, solution is impregnated, is rinsed 2-3 times,
Each 30min removes soluble impurity, obtained wet ox hair is placed in pallet, is uniformly spread out, puts dry in baking oven；
（2）Ox hair powder it is crude：It will be through step（1）The ox hair of removal of impurities is put into pulverizer, sieving；
（3）Ox hair powder refines：By step（2）Ox hair powder, be put into ball grinder, be added solution；Seal ball milling；Choose
Abrading-ball, by slurry spraying drying powder-forming；
（4）The preparation of aqueous polyurethane slurry：Foaming agent, thickener, foam stabilizer and step are added in hydrotropism's polyurethane（3）System
Standby ox hair powder filler, mechanical agitation is uniform, foams；
（5）The preparation of aqueous dry method polyurethane bass：In the upper clearance gauge of clean base fabric two edges pad by plating, with coated rod edge
It is longitudinal by step clearance gauge（4）Slurry scratch in base fabric, be subsequently placed into baking oven gradient increased temperature drying to get aqueous dry method
Polyurethane bass.
2. preparation method according to claim 1, which is characterized in that step（1）Described in the solution that impregnates be ox hair weight
20 times of the aqueous solution containing 2% neopelex.
3. preparation method according to claim 1, which is characterized in that the step（3）In, ball grinder is ceramic pot, agate
Any one in Nao tanks, stainless cylinder of steel, tetrafluoroethene tank；Abrading-ball is cobblestone ball, agate ball, zirconia ball, stainless steel ball
In any one.
4. preparation method according to claim 1, which is characterized in that the step（3）In, solution is water, acetone, ethyl alcohol
In any one；The ox hair, abrading-ball, solution mass ratio be 1：150-250：100-200；The Ball-milling Time is
6-12h, rotating speed 35-45Hz.
5. preparation method according to claim 1, which is characterized in that the step（4）In, the solid content of aqueous polyurethane
For 35-50%；The addition of the foaming agent, thickener, foam stabilizer and ox hair powder filler, in terms of polyurethane resin quality, point
It Wei not 3-5%, 0.5-3%, 0.5-5%, 1-4%.
6. preparation method according to claim 1, which is characterized in that the step（4）In, mechanical agitation rotating speed is
1200-2500 r/min, mechanical foaming time are 20-50min.
7. preparation method according to claim 1, which is characterized in that the step（5）In, the drying temperature 60- of baking oven
110 DEG C, drying time 20-30min.
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| CN201810356752.XA CN108360269B (en) | 2018-04-20 | 2018-04-20 | Preparation method of cow hair powder filler modified aqueous dry-method polyurethane base |
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| CN201810356752.XA CN108360269B (en) | 2018-04-20 | 2018-04-20 | Preparation method of cow hair powder filler modified aqueous dry-method polyurethane base |
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| CN108360269B CN108360269B (en) | 2020-05-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110204679A (en) * | 2019-05-20 | 2019-09-06 | 齐鲁工业大学 | A kind of preparation method of modified environment-friendly aqueous polyurethane and its polyurethane of preparation |
| CN115323803A (en) * | 2022-08-17 | 2022-11-11 | 广东汇齐新材料有限公司 | Completely-recyclable environment-friendly thermoplastic foaming artificial leather material and preparation method thereof |
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| CN106118034A (en) * | 2016-08-16 | 2016-11-16 | 合肥科天水性科技有限责任公司 | A kind of dry method clothing leather bass and preparation technology thereof |
| CN106478957A (en) * | 2016-10-12 | 2017-03-08 | 温州大学 | The preparation method of keratin grafting water-based polyurethane polymer leather retanning packing material |
| CN107190349A (en) * | 2017-05-10 | 2017-09-22 | 天津中智科技发展有限公司 | A kind of method that utilization yak hair prepares nanofiber |
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| CN102182066A (en) * | 2010-11-30 | 2011-09-14 | 江苏宝泽高分子材料股份有限公司 | Soft crazy-horse resin for clothing leather and preparation method thereof |
| CN102080332A (en) * | 2010-12-27 | 2011-06-01 | 陕西科技大学 | Preparation method of waterborne polyurethane synthetic leather base |
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| CN110204679A (en) * | 2019-05-20 | 2019-09-06 | 齐鲁工业大学 | A kind of preparation method of modified environment-friendly aqueous polyurethane and its polyurethane of preparation |
| CN110204679B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of modified environment-friendly waterborne polyurethane and polyurethane prepared by same |
| CN115323803A (en) * | 2022-08-17 | 2022-11-11 | 广东汇齐新材料有限公司 | Completely-recyclable environment-friendly thermoplastic foaming artificial leather material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN108360269B (en) | 2020-05-12 |
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