CN105992847B - A kind of production method of non-solvent foamed type polyurethane synthetic leather - Google Patents
A kind of production method of non-solvent foamed type polyurethane synthetic leather Download PDFInfo
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- CN105992847B CN105992847B CN201580002437.1A CN201580002437A CN105992847B CN 105992847 B CN105992847 B CN 105992847B CN 201580002437 A CN201580002437 A CN 201580002437A CN 105992847 B CN105992847 B CN 105992847B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
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- Dispersion Chemistry (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The present invention provides a kind of production methods of non-solvent foamed type polyurethane synthetic leather, and surface layer slurry is taken to be coated in release paper, drying；Then it takes polyalcohol, catalyst and functional aid to be placed in a head tank of solvent-free slurry perfusion machine, isocyanate ester compound is taken to be placed in another head tank, two tank feedstock transportations are then mixed to get foamed slurry；Foamed slurry is coated on surface layer slurry layer, oven heat；Cloth is fitted on foamed slurry layer, is dried；It is cooling, remove release paper to get.The present invention reduces the wet process techniques of conventional urethane, reduce the use of organic solvent, greatly reduce the consumption of the human and material resources of production, process is simple, equipment aspect only needs to carry out original dry process production line a small amount of add-assembly, it will not influence the production of original production line and old technology, save improvement cost.And the peel strength of Synthetic Leather obtained is high, hydrolytic resistance is good, and organic solvent content is extremely low, best in quality.
Description
Technical field
The invention belongs to Synthetic Leather technical fields, and in particular to a kind of non-solvent foamed type polyurethane synthetic leather
Production method.
Background technique
Synthetic Leather is the institutional framework and service performance for simulating natural leather, and can be used as natural leather substitute
Composite material.Lamina reticularis is usually simulated with non-woven fabrics, with microvoid polyurethane coating simulation grain layer, obtained synthetic leather
Positive and negative are all quite similar with leather, and have certain gas permeability, than common artificial leather closer to natural leather, use extensively
In production shoes, boots, luggage and ball etc..
It is shown according to national statistics office data: the above enterprise of artificial leather synthetic leather scale (the new criteria for classifying: year in 2011
20,000,000 or more enterprise of income from sales) 495,2,410,000 tons of yield, increase by 9.57%；925.35 hundred million yuan of total industrial output value, increase
Long 29.55%；69.85 hundred million yuan of profits tax, increase by 32.12%；47.86 hundred million yuan of total profit, increase by 36.15%.All in all, exist
In the case where big economic environment recovery, China's Synthetic Leather shows rapid growth momentum.
Currently, the production of Synthetic Leather mainly uses solvent type production system, by wet process technique and dry method
Production technology two parts complete the production of product, wet process technique process (referring to Fig.1): using according to different product demands
The wet process use that production is made in organic solvent, filler material and functional aid after mixing is added in different polyurethane resins
Polyurethane slurry, then cloth after over cleaning, by polyurethane slurry be coated in cloth cover on, and enter containing 17~30% it is organic
It is solidified in the sink of solvent (DMF), using clean water by after the organic solvent elution in material, drying removes solvent, finally
Semi-finished product are produced in cooling.Dry technology for production process (referring to Fig. 2): different polyurethane is used according to different product demands
The dry method polyurethane slurry of production is made after mixing, applies in release paper for resin, addition organic solvent, functional aid
Cover polyurethane slurry as surface layer, polyurethane slurry then coated in surface layer as adhesive layer, be dried to it is half-dried, by wet production
Semi-finished product be bonded by combined wheels, dry, it is cooling, separate release paper to get.
Conventionally produced synthetic leather there are the problem of: the polyurethane that traditional handicraft synthetic leather uses first contains largely
Organic solvent, the content of basic organic solvent is all 50~80% or so, and the ingredient of organic solvent is mostly toluene, dimethyl
Formamide (DMF), ethyl acetate (EAC), butanone (MEK) etc. can all escape into transport, production outer with a certain amount of volatilization
Boundary's environment, influences environment, causes certain environmental problem, and these organic solvents can all endanger the health of worker.Followed by
Production process is complicated, at least will be through 2 procedures, and the 1st is wet process process, and the 2nd is dry method, and there are also be exactly wet process process
The semi-finished product of production contain large quantity of moisture, and dry method production contains a large amount of organic solvent, this large amount of moisture and process need
Want a large amount of energy consumption.The complicated influence for also bringing another aspect of process, when process is more, the human resources of consumption are more, tradition
The manpower that technique expends is novel process more than 2 times.
Summary of the invention
It is an object of the invention to solve deficiency in the prior art, a kind of non-solvent foamed type polyurethane synthetic leather is provided
Production method, be able to solve DMF, TOL, MEK, THF equal solvent generated in the production of current solvent borne polyurethane synthetic leather
Product safety problem caused by the residual of product DMF in problem of environmental pollution and Synthetic Leather production, additionally it is possible to solve molten at present
Process is more in the production of dosage form Synthetic Leather, and human resources consume big problem etc..
The first aspect of the invention is to provide the production method of non-solvent foamed type polyurethane synthetic leather, including following step
It is rapid:
(1) take surface layer slurry be coated in release paper on, drying, wherein the surface layer slurry in percentage by weight by
It is mixed with one 0.1-0.2% of functional aid and polyurethane resin surplus；
(2) foamed slurry is taken, the foamed slurry is made of component A and B component, and in parts by weight, component A includes
80~120 parts of polyalcohol, 0.1~2.0 part of catalyst and 2 0.5~5 parts of functional aid, B component includes isocyanates
Close 10~100 parts of object；Component A and B component are respectively placed in two head tanks of solvent-free slurry perfusion machine, then pass through conciliation
Component A and B component conveying are mixed to get foamed slurry by the metering pump of head tank；Foamed slurry is coated in surface layer slurry layer
On, 1~2min is heated at 80~150 DEG C；
(3) cloth is fitted on foamed slurry layer, 130 DEG C of 1~2min of baking, then 40~80 DEG C of 4~15min of baking；
(4) cooling, remove release paper to get.
Further, the catalyst is amines catalyst or organometallic catalysts.
Further, in parts by weight, component A includes 100 parts of polyalcohol, 0.5~1.0 part of catalyst and functionality
2 1.0~3.0 parts of auxiliary agent, B component includes 10~100 parts of isocyanate ester compound.
Further, the functional aid two in component A includes levelling agent, foaming agent and foam stabilizer.Levelling agent, foaming agent
It can rule of thumb take the circumstances into consideration to add with additive amount those skilled in the art of foam stabilizer.
Further, in parts by weight, functional aid two includes 0.1~2 part of levelling agent, foaming in component A
0.1~2 part and 0.1~2 part of foam stabilizer of agent.
Further, the functional aid one is surfactant.
The present invention is not defined the type of polyalcohol, workable polyalcohol in polyurethane production, such as poly-
One or more of ether glycol, polyether triol, heats liquefied polyester-diol or base polyurethane prepolymer for use as with hydroxyl etc..
The present invention is not defined isocyanate ester compound, workable isocyanates chemical combination in polyurethane production
In object, such as toluene di-isocyanate(TDI), liquefaction diphenylmethylene diisocyanate or isophorone diisocyanate etc.
One or more.
The present invention is not to amines catalyst, organometallic catalysts, levelling agent, foaming agent, foam stabilizer and surface-active
Agent is defined, workable in polyurethane production.
The second aspect of the invention is to provide a kind of non-solvent foamed type polyurethane synthetic leather, using the present invention first
Any one production method described in aspect is prepared.
This invention simplifies traditional process flows, reduce the wet process technique of conventional urethane, directly reduce wet
The energy consumption of method production line reduces the use of organic solvent, reduces the recycling energy consumption of organic solvent indirectly, simplifies the people of production
The consumption of power resource.Process is simple, and equipment aspect only needs to carry out original dry process production line a small amount of add-assembly, will not
Original production line is impacted, the production of old technology can be still carried out, saves improvement cost.And polyurethane synthesis obtained
The peel strength of leather is high, and hydrolytic resistance is good, and organic solvent content is extremely low, best in quality.
Detailed description of the invention
Fig. 1 is the wet process technique process in the production system of traditional solvent-borne；
Fig. 2 is the dry technology for production process in the production system of traditional solvent-borne；
Fig. 3 is the technological process of production of the invention.
Specific embodiment
Below with reference to specific embodiment, the invention will be further described, to better understand the invention.
Embodiment 1
(1) firstly, in percentage by weight, surfactant 0.1% and polyurethane resin 99.9% is taken to be mixed into face
Layer slurry, is coated in release paper, and drying is used as surface layer, and drying temperature is at 130 DEG C or more.
(2) secondly, in parts by weight, take 100 parts of polyalcohol, 0.8 part of catalyst, 1 part of levelling agent, 1 part of foaming agent,
1 part of foam stabilizer, 80 parts of isocyanate ester compound, wherein polyalcohol, catalyst, levelling agent, foaming agent and foam stabilizer mixing are equal
During an even raw material for being placed on solvent-free slurry perfusion machine as component A fills, isocyanate ester compound is placed as B component
In another raw material of solvent-free slurry perfusion machine fills, when production bottler placer according to the linear speed of production line, coating thickness come into
Component A and B component conveying are mixed to get foamed slurry by row metering mixing, the metering pump by reconciling head tank.
Foamed slurry is coated on surface layer slurry layer, baking oven heating, traditional handicraft heats will be in polyurethane slurry
Organic solvent evaporation, and heating is to accelerate reacting for polyalcohol and isocyanates in the present embodiment, warm temperature is according to production line
Speed is set, and 1~2min is heated at general 80~150 DEG C.
(3) cloth is fitted on foamed slurry layer, 130 DEG C of 1~2min of baking after fitting, the hair in promotion functions auxiliary agent
Infusion foaming, then 40~80 DEG C of 4~15min of baking, accelerate the cross-linking reaction of solvent-free slurry.
(4) finally, it is cooling, release paper is removed, non-solvent foamed type polyurethane synthetic leather is obtained.
Detect to the performance of non-solvent foamed type polyurethane synthetic leather made from the present embodiment: peel strength is
7kg.f/cm；For anti-hydrolytic performance at the immersion of 10% sodium hydroxide solution 48 hours or more, peel strength only reduced by 1%；DMF (two
Methylformamide) content be 0ppm.
Embodiment 2
(1) firstly, in percentage by weight, surfactant 0.2% and polyurethane resin 99.8% is taken to be mixed into face
Layer slurry, is coated in release paper, and drying is used as surface layer, and drying temperature is at 130 DEG C or more.
(2) secondly, in parts by weight, taking 100 parts of polyalcohol, 0.5 part of catalyst, 0.5 part of levelling agent, foaming agent 1
Part, 1.5 parts of foam stabilizer, 100 parts of isocyanate ester compound, wherein polyalcohol, catalyst, levelling agent, foaming agent and foam stabilizer
It is uniformly mixed and is placed in the raw material filling of solvent-free slurry perfusion machine as component A, isocyanate ester compound is as B group
Another raw material for point being placed on solvent-free slurry perfusion machine fills, and bottler placer is according to the linear speed of production line, coating thick when production
For degree to carry out metering mixing, component A and B component conveying are mixed to get foamed slurry by the metering pump by reconciling head tank.
Foamed slurry is coated on surface layer slurry layer, baking oven heating, traditional handicraft heats will be in polyurethane slurry
Organic solvent evaporation, and heating is to accelerate reacting for polyalcohol and isocyanates in the present embodiment, warm temperature is according to production line
Speed is set, and 1~2min is heated at general 80~150 DEG C.
(3) cloth is fitted on foamed slurry layer, 130 DEG C of 1~2min of baking after fitting, the hair in promotion functions auxiliary agent
Infusion foaming, then 40~80 DEG C of 4~15min of baking, accelerate the cross-linking reaction of solvent-free slurry.
(4) finally, it is cooling, release paper is removed, non-solvent foamed type polyurethane synthetic leather is obtained.
Detect to the performance of non-solvent foamed type polyurethane synthetic leather made from the present embodiment: peel strength is
6.5kg.f/cm；For anti-hydrolytic performance at the immersion of 10% sodium hydroxide solution 48 hours or more, peel strength only reduced by 1.5%；DMF
The content of (dimethylformamide) is 0ppm.
Embodiment 3
(1) firstly, in percentage by weight, surfactant 0.2% and polyurethane resin 99.8% is taken to be mixed into face
Layer slurry, is coated in release paper, and drying is used as surface layer, and drying temperature is at 130 DEG C or more.
(2) secondly, in parts by weight, taking 100 parts of polyalcohol, 1.0 parts of catalyst, 0.8 part of levelling agent, foaming agent
0.2 part, 0.1 part of foam stabilizer, 10 parts of isocyanate ester compound, wherein polyalcohol, catalyst, levelling agent, foaming agent and foam stabilizing
Agent is uniformly mixed to be placed in the raw material filling of solvent-free slurry perfusion machine as component A, and isocyanate ester compound is as B
During another raw material that component is placed on solvent-free slurry perfusion machine fills, linear speed of the bottler placer according to production line, coating when production
Thickness carries out metering mixing, and component A and B component conveying are mixed to get foamed slurry by the metering pump by reconciling head tank.
Foamed slurry is coated on surface layer slurry layer, baking oven heating, traditional handicraft heats will be in polyurethane slurry
Organic solvent evaporation, and heating is to accelerate reacting for polyalcohol and isocyanates in the present embodiment, warm temperature is according to production line
Speed is set, and 1~2min is heated at general 80~150 DEG C.
(3) cloth is fitted on foamed slurry layer, 130 DEG C of 1~2min of baking after fitting, the hair in promotion functions auxiliary agent
Infusion foaming, then 40~80 DEG C of 4~15min of baking, accelerate the cross-linking reaction of solvent-free slurry.
(4) finally, it is cooling, release paper is removed, non-solvent foamed type polyurethane synthetic leather is obtained.
Detect to the performance of non-solvent foamed type polyurethane synthetic leather made from the present embodiment: peel strength is
6.8kg.f/cm, for anti-hydrolytic performance at the immersion of 10% sodium hydroxide solution 48 hours or more, peel strength only reduced by 1.3%；Not
Detect DMF (dimethylformamide).
Embodiment 4
(1) firstly, in percentage by weight, surfactant 0.1% and polyurethane resin 99.9% is taken to be mixed into face
Layer slurry, is coated in release paper, and drying is used as surface layer, and drying temperature is at 130 DEG C or more.
(2) secondly, in parts by weight, taking 80 parts of polyalcohol, 2.0 parts of catalyst, 2 parts of levelling agent, foaming agent 1.5
Part, 1.5 parts of foam stabilizer, 10 parts of isocyanate ester compound, wherein polyalcohol, catalyst, levelling agent, foaming agent and foam stabilizer are mixed
It closes and is uniformly placed in the raw material filling of solvent-free slurry perfusion machine as component A, isocyanate ester compound is as B component
Another raw material for being placed on solvent-free slurry perfusion machine fills, linear speed, coating thickness of the bottler placer according to production line when production
Carry out metering mixing, component A and B component conveying are mixed to get foamed slurry by the metering pump by reconciling head tank.
Foamed slurry is coated on surface layer slurry layer, baking oven heating, traditional handicraft heats will be in polyurethane slurry
Organic solvent evaporation, and heating is to accelerate reacting for polyalcohol and isocyanates in the present embodiment, warm temperature is according to production line
Speed is set, and 1~2min is heated at general 80~150 DEG C.
(3) cloth is fitted on foamed slurry layer, 130 DEG C of 1~2min of baking after fitting, the hair in promotion functions auxiliary agent
Infusion foaming, then 40~80 DEG C of 4~15min of baking, accelerate the cross-linking reaction of solvent-free slurry.
(4) finally, it is cooling, release paper is removed, non-solvent foamed type polyurethane synthetic leather is obtained.
Detect to the performance of non-solvent foamed type polyurethane synthetic leather made from the present embodiment: peel strength is
6.2kg.f/cm；For anti-hydrolytic performance at the immersion of 10% sodium hydroxide solution 48 hours or more, peel strength only reduced by 1.7%；Not
Detect DMF (dimethylformamide).
Embodiment 5
(1) firstly, in percentage by weight, surfactant 0.2% and polyurethane resin 99.8% is taken to be mixed into face
Layer slurry, is coated in release paper, and drying is used as surface layer, and drying temperature is at 130 DEG C or more.
(2) secondly, in parts by weight, taking 120 parts of polyalcohol, 0.1 part of catalyst, 0.5 part of levelling agent, foaming agent 2
Part, 2 parts of foam stabilizer, 100 parts of isocyanate ester compound, wherein polyalcohol, catalyst, levelling agent, foaming agent and foam stabilizer are mixed
It closes and is uniformly placed in the raw material filling of solvent-free slurry perfusion machine as component A, isocyanate ester compound is as B component
Another raw material for being placed on solvent-free slurry perfusion machine fills, linear speed, coating thickness of the bottler placer according to production line when production
Carry out metering mixing, component A and B component conveying are mixed to get foamed slurry by the metering pump by reconciling head tank.
Foamed slurry is coated on surface layer slurry layer, baking oven heating, traditional handicraft heats will be in polyurethane slurry
Organic solvent evaporation, and heating is to accelerate reacting for polyalcohol and isocyanates in the present embodiment, warm temperature is according to production line
Speed is set, and 1~2min is heated at general 80~150 DEG C.
(3) cloth is fitted on foamed slurry layer, 130 DEG C of 1~2min of baking after fitting, the hair in promotion functions auxiliary agent
Infusion foaming, then 40~80 DEG C of 4~15min of baking, accelerate the cross-linking reaction of solvent-free slurry.
(4) finally, it is cooling, release paper is removed, non-solvent foamed type polyurethane synthetic leather is obtained.
Detect to the performance of non-solvent foamed type polyurethane synthetic leather made from the present embodiment: peel strength is
5.8kg.f/cm；For anti-hydrolytic performance at the immersion of 10% sodium hydroxide solution 48 hours or more, peel strength only reduced by 19%；It does not examine
Measure DMF (dimethylformamide).
Comparative example 1
Using traditional solvent-borne prepared by Synthetic Leather preparation process, process flow referring to Figures 1 and 2 because
It is the prior art, herein without repeating.To the performance of synthetic leather made from traditional solvent-borne Synthetic Leather preparation process
It is detected: 0.3~1.5kg.f/cm of peel strength；The immersion of 10% sodium hydroxide solution 48 hours or more, peel strength reduced
10~20%；The content of DMF (dimethylformamide) is substantially all at 200~600ppm (< 1000ppm).
By the performance test results of comparative example 1~5 and comparative example 1, it can be seen that, traditional handicraft is compared, using this
The peel strength of synthetic leather made from invented technology greatly enhances, and anti-hydrolytic performance is excellent, and organic solvent content is extremely low.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (4)
1. a kind of production method of non-solvent foamed type polyurethane synthetic leather, which comprises the following steps:
(1) take surface layer slurry be coated in release paper on, drying, wherein the surface layer slurry in percentage by weight by and function
Energy property auxiliary agent one 0.1~0.2% and polyurethane resin surplus mix；The functional aid one is surfactant；
(2) take foamed slurry, wherein the foamed slurry is made of component A and B component, in parts by weight, component A by
80~120 parts of polyalcohol, 0.1~2.0 part of catalyst and 2 0.5~5 parts of functional aid compositions, B component is by isocyanates
10~100 parts of compound compositions；Component A and B component are respectively placed in two head tanks of solvent-free slurry perfusion machine, are then led to
Component A and B component conveying are mixed to get foamed slurry by the metering pump for crossing conciliation head tank；Foamed slurry is starched coated in surface layer
On the bed of material, 1~2min is heated at 80~150 DEG C；In component A functional aid two by 0.1~2 part of levelling agent, foaming agent 0.1~
2 parts and 0.1~2 part of foam stabilizer compositions；
(3) cloth is fitted on foamed slurry layer, 130 DEG C of 1~2min of baking, then 40~80 DEG C of 4~15min of baking；
(4) cooling, remove release paper to get.
2. production method according to claim 1, which is characterized in that the catalyst is amines catalyst or organic gold
Belong to class catalyst.
3. production method according to claim 1, which is characterized in that in parts by weight, component A includes polyalcohol
100 parts, 0.5~1.0 part of catalyst and 2 1.0~3.0 parts of functional aid, B component include isocyanate ester compound 10~
100 parts.
4. a kind of non-solvent foamed type polyurethane synthetic leather, which is characterized in that using described in any one of claims 1 to 3
Production method be prepared.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2015/080025 WO2016187857A1 (en) | 2015-05-28 | 2015-05-28 | Production method of solvent-free foamed polyurethane synthetic leather |
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| Publication Number | Publication Date |
|---|---|
| CN105992847A CN105992847A (en) | 2016-10-05 |
| CN105992847B true CN105992847B (en) | 2018-12-18 |
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| CN201580002437.1A Active CN105992847B (en) | 2015-05-28 | 2015-05-28 | A kind of production method of non-solvent foamed type polyurethane synthetic leather |
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| WO (1) | WO2016187857A1 (en) |
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| CN107759759B (en) * | 2017-11-07 | 2020-10-23 | 陕西科技大学 | Preparation method and application of closed solvent-free polyurethane for synthetic leather |
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| CN113846491A (en) * | 2021-09-26 | 2021-12-28 | 南通中豪超纤制品有限公司 | High-solid-content self-foaming environment-friendly synthetic leather |
| CN115287913B (en) * | 2022-08-10 | 2024-04-02 | 苏州瑞高新材料股份有限公司 | Soft suede basketball synthetic leather and preparation method thereof |
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| CN103015220B (en) * | 2012-12-20 | 2014-06-04 | 陕西科技大学 | Preparation method of thermoplastic polyurethane synthetic leather |
| CN103031736B (en) * | 2012-12-20 | 2014-07-02 | 陕西科技大学 | Method for preparing solvent-free multicomponent polyurethane synthetic leather based on steam injection coating |
| CN104088161B (en) * | 2014-07-07 | 2016-05-25 | 旭川化学（苏州）有限公司 | A kind of preparation method of solvent-free environment-friendly polyurethane automobile leather |
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2015
- 2015-05-28 CN CN201580002437.1A patent/CN105992847B/en active Active
- 2015-05-28 WO PCT/CN2015/080025 patent/WO2016187857A1/en active Application Filing
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| WO2016187857A1 (en) | 2016-12-01 |
| CN105992847A (en) | 2016-10-05 |
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