CN104479102B - Environment-friendly polyurethane clothing leather and preparation method thereof - Google Patents
Environment-friendly polyurethane clothing leather and preparation method thereof Download PDFInfo
- Publication number
- CN104479102B CN104479102B CN201410797159.0A CN201410797159A CN104479102B CN 104479102 B CN104479102 B CN 104479102B CN 201410797159 A CN201410797159 A CN 201410797159A CN 104479102 B CN104479102 B CN 104479102B
- Authority
- CN
- China
- Prior art keywords
- component
- molecular weight
- average molecular
- environment
- clothing leather
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- D06N3/145—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 two or more layers of 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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
-
- 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
- D06N3/146—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 characterised by the macromolecular diols used
-
- 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
- D06N3/147—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 characterised by the isocyanates used
-
- 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 invention relates to environment-friendly polyurethane clothing leather and a preparation method thereof. The environment-friendly polyurethane clothing leather is composed of a base cloth layer, a binding resin layer fitted on the base cloth layer and a surface resin layer fitted on the binding resin layer, wherein the binding resin layer is formed by solvent-free polyurethane resin, and the surface resin layer is formed by waterborne polyurethane resin. The environment-friendly polyurethane clothing leather has the advantages that specific solvent-free polyurethane resin is taken as a binding layer, specific waterborne polyurethane resin is taken as surface resin, the prepared leather product has excellent hydrolysis resistance, low temperature flexibility, soft handfeel and strong true leather feeling and is wearproof, scrap-proof, and overall performance is excellent; meanwhile, all the raw materials in a formula are available, cost is low, and the environment-friendly polyurethane clothing leather can be produced by adopting the existing equipment and technological conditions, so that production cost is low; besides, no organic solvent is used or discharged in a production process, so that no pollution is produced to the environment; no organic solvent is volatilized from the leather product, so that the leather product is safe and reliable when used.
Description
Technical field
The present invention relates to a kind of polyurethane clothing leather and preparation method thereof.
Background technology
In prior art, according to the difference of purposes, synthetic leather can be divided into polyurethane clothing leather, footwear synthetic leather, automobile leather,
Sofa artificial leather etc..Different applications is different for the performance requirement of leather.Wherein clothing leather for comfortableness and functional will
Ask the requirement of particularly comfortableness higher.It is desirable to the breathability that had of leather for comfortableness, voluptuousness, low-temperature flexibility and
Soft feel；It is desirable to remove from office the hydrolytic resistance having had, wear-resisting scratch resistance, extensibility etc. for feature.Additionally, price
Factor is also the key factor of impact leather goods application, therefore, when developing clothing leather product, except pursuing its performance
Lifting outer it is necessary to effective control cost.Additionally, people's growing interest health and environmental protection today, clothing leather goods itself and
Whether environmental protection also will be the whether welcome key factor with popularization and application of this product to production technology.
In prior art with regard to the research of clothing leather mainly all concentrate on certain or some in terms of performance lifting.Patent
Cn 101381448 discloses a kind of polyurethane resin for water proof and breathable clothing leather product and has high moisture-inhibiting high water pressure resistance, performance
Reach external product level, but it lays particular emphasis on the breathability of leather goods.Patent cn 101050265 a discloses a kind of synthesis
Leather wet mild polyurethane resin and preparation method thereof, this invention is used for clothing or case and bag, and after frosted, fine hair sense is strong, exhibition
Color is good, does not provide advantage in the performances such as hydrolysis, peel strength for this invention.Patent cn 1816579a and patent
Cn101851325 a individually discloses the low temperature resistant polyurethane synthetic leather resin of heat-resisting hydrolysis and wet-method synthetic leather polyester-type
Hydrolysis high-peel-strength polyurethane resin and preparation method thereof, but raw materials used cost intensive, are unfavorable for promoting.
Entitled " a kind of clothing leather wet polyurethane resin and preparation method thereof ", the disclosure being proposed by the applicant
Number disclose a kind of clothing leather wet polyurethane resin for the patent application of cn 103351456a, had by design specific
The ester ether copolymer polyhydric alcohol of molecular structure and molecular weight, passes through first to synthesize the polyurethane resin of a kind of viscosity and solid content simultaneously
Intermediate, then this intermediate is added in final polyurethane resin, has obtained preferable pliability, wet and slippery sense, plentiful
Feel, stronger kishke feel, there are the hydrolysis required by clothing leather field, high peel off, the product of the performance requirement such as super softness
Product.However, this polyurethane resin must be using the organic solvent accounting for formula proportion more than 50% in formula, production process and institute
Product processed can not meet environmental requirement.
Cn 104088161 a discloses a kind of preparation method of solvent-free environment-friendly polyurethane automobile leather, and the method adopts two
The solvent-free environment-friendly polyurethane resin of kind of different formulations comes surface layer and foaming layer respectively as automobile leather it is achieved that automobile leather
Solvent free produces.But, the synthetic leather compliance of the formula disclosed in this patent and method preparation is poor, and Boardy Feeling is it is impossible to expire
Sufficient clothing leather application requirement.Additionally, also using substantial amounts of PCDL in this patent, significantly increase cost,
It is unfavorable for promoting.
Waterborne polyurethane resin compares solvent type polyurethane resin, with water as disperse medium, need not have in process
Machine solvent, and in product system, do not contain poisonous nco group, therefore environmentally safe, to operator's no health hazard, and
And waterborne polyurethane resin abnormal smells from the patient is little, nonflammable, the course of processing is safe and reliable；Its ratio of viscosities is with the solvent type resin of solid content
Lower it is easy to process operation.But the physical property by aqueous polyurethane itself and in release paper application performance limited, at present also
Have no the product of batch application, also there is no the precedent of successful Application particularly on clothing leather.Although cn203160038u reports
Waterborne polyurethane resin to be prepared clothing leather as tack coat, but does not wherein relate to joining of waterborne polyurethane resin
Side and how to prepare clothing leather and the performance of prepared clothing leather.And very it is apparent that in leather production, aqueouss are gathered
Urethane resin has its fatal inferior position as adhesive layer.With water as solvent, adhesive layer is less useful for water between surface layer and base fabric
The drying dividing, and the heat of evaporation needing in drying course is higher, the baking time of therefore leather making process needs to extend, baking temperature
Degree needs to improve, and this will substantially reduce the production efficiency in leather making process, and the cost increasing leather making process is and it needs to enter to equipment
Row is revised.
In sum it is necessary to provide a kind of excellent combination property, product itself and the equal environmental protection of product processes and one-tenth
This relatively low clothing leather.
Content of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, provides a kind of excellent combination property, product
Product itself and the equal environmental protection of product processes and lower-cost polyurethane clothing leather.
The present invention also provides a kind of preparation method of environment-friendly polyurethane synthetic leather simultaneously.
For solving above-mentioned technical problem, a kind of technical scheme that the present invention takes is:
A kind of environment-protecting polyurethane clothing leather, this clothing leather is by base cloth layer, the binding resin layer being fitted on base cloth layer, patch
The surface layer resin layer being combined in binding resin layer is constituted, and binding resin layer is formed by solvent-free polyurethane resin, surface layer resin layer
Formed by waterborne polyurethane resin, wherein:
Described solvent-free polyurethane resin is reacted in the presence of the first catalyst by component a and component b and obtains, wherein group
Part a is hydroxy-end capped polyol component, and component b is isocyanate-terminated pre-polymer component, and component a is fed intake with component b's
Mass ratio is 2:1.4～1.9；
In parts by weight, the composition of raw materials of component a is: the polyoxypropyleneglycol 70- of number-average molecular weight 2000～3000
90 parts, 5～15 parts of the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 300～1000, number-average molecular weight 1000～2000 ester ether altogether
Poly-dihydric alcohol 20-30 part, 1.5～6 parts of small molecule glycol chain extender, 0.5～6 part of glycerol, 0.2～2 part of water, the second catalysis
0.2～1.5 part of agent, 0.5～3 part of auxiliary agent, the wherein hydroxyl value of ester ether copolymerization dihydroxylic alcohols are 55-106mgkoh/g, by adipic acid, number
The polyether Glycols of average molecular weight 200～300, small molecule dihydroxylic alcohols three reaction are obtained, number-average molecular weight 200～300 poly-
Ether dihydroxylic alcohols, the molar ratio of small molecule dihydroxylic alcohols are 1:1～2；
In parts by weight, the composition of raw materials of component b is: mdi50-70 part, liquefaction mdi4-15 part, number-average molecular weight 2000
～3000 polyoxypropyleneglycol 20-30 part, 5～15 parts of the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 300～1000；
In parts by weight, the composition of raw materials of described waterborne polyurethane resin is: poly- the four of number-average molecular weight 1000～2000
Hydrogen furan dihydroxylic alcohols 20-30 part, ester ether copolymer 10-20 part of number-average molecular weight 3000～4000, first chain extender 3-5 part,
Second chain extender 1-3 part, the 3rd chain extender 0.5-2 part, isocyanates 10-20 part, nertralizer 1-3 part, acetone 2-5 part, water 45-
55 parts, levelling agent 0.5-2 part, thickening agent 0.5-2 part, defoamer 0.5-1.5 part, the wherein first chain extender be dmpa, dmba or
Combination, the second chain extender is small molecule dihydroxylic alcohols or ternary alcohols chain extender, and the 3rd chain extender is small molecule diamine
Class chain extender, ester ether copolymer is the PEPA of number-average molecular weight 500-1000, the polyethers of number-average molecular weight 200～300
The ester ether copolymerization dihydroxylic alcohols that dihydroxylic alcohols and adipic acid copolyreaction obtain, hydroxyl value are 27-37mgkoh/g, isocyanates are tdi,
Mdi or combination；
The first described catalyst, the second catalyst independently are one of amines catalyst, organo-metallic catalyst
Or multiple combinations.
According to the present invention, the consumption of the first catalyst, using conventional addition, is specifically as follows component a and component b total
The 0.5 ‰ -1.5 ‰ of weight.
Further, in component a, small molecule glycol chain extender can for ethylene glycol, diethylene glycol, butanediol, hexanediol,
The combination of one or more of neopentyl glycol.
Further, component a is obtained as follows: by formula, all raw materials is put into the reactor with stirring
In, it is warming up to 50-75 DEG C, isothermal reaction to reaction system viscosity is 200～450cp/25 DEG C, moisture content is less than or equal to 0.5%, knot
Shu Fanying, obtains final product component a.
Further, component b is obtained as follows: by formula, mdi and liquefaction mdi is put into the reaction with stirring
In device, then sequentially add the polyoxypropyleneglycol of number-average molecular weight 2000～3000 and number-average molecular weight 300～1000
Polyoxypropylene trihydroxylic alcohol, is maintained at isothermal reaction at temperature 55-80 DEG C and is 200～450cp/25 DEG C to reaction system viscosity,
Ncowt% is 16～22%, terminates reaction, obtains final product component b.
In the present invention, ester ether copolymerization dihydroxylic alcohols as raw material and ester ether copolymer all can by conventional method synthesis or
Person passes through to be commercially available.
Further, described waterborne polyurethane resin is obtained as follows: by PolyTHF dihydroxylic alcohols, ester ether altogether
Polymers is put in the reactor with stirring, temperature control device and chuck heater, heats up, and biodiversity is treated in vacuum dehydration
After content is less than 300ppm, is cooled to 40-50 DEG C and adds isocyanates, the first chain extender and the second chain extender, acetone, react to
After ncowt% measured value is 1-2%, it is cooled to 40-50 DEG C, add nertralizer, then gained resin is emulsifiable in water, then drips
Enter the 3rd chain extender, complete chain extension under agitation, last vacuum distillation removes acetone, add levelling agent, thickening by formula proportion
Agent, defoamer, obtain final product the waterborne polyurethane resin that viscosity is 4000-6000cp/25 DEG C.
Preferably, described nertralizer is triethylamine.
Further, described second chain extender can for ethylene glycol, diethylene glycol, butanediol, hexanediol, tmp, new penta 2
The combination of one or more of alcohol, glycerol, Oleum Ricini.
Further, described 3rd chain extender can be the combination of one or more of ethylenediamine, hexamethylene diamine, ipda.
Further, the auxiliary agent in component a generally includes foam stabilizer and stabilizer etc., is specifically as follows commonly used in the art
Those, be not particularly limited.
The another technical scheme that the present invention takes is: a kind of preparation method of above-mentioned environment-protecting polyurethane clothing leather, its
Comprise the following steps:
(1) waterborne polyurethane resin is spread evenly across in release paper with the thickness of 0.1～0.25mm, dries, form face
Layer resin bed；
(2), after component a being mixed with the first catalyst, add component b mixing, after mix homogeneously, with 0.1～0.25mm's
Thickness is uniformly coated on the surface layer resin of step (1), is placed in 70-80 DEG C of air dry oven and is dried 10-20 second, obtains
The half-dried bonding resin layer having certain wire drawing shape；
(3) by laminating for step (1) gained surface layer resin layer on step (2) gained bonding resin layer and be compacted, it is placed in 70-
1-2 minute is dried in 110 DEG C of drying baker, throws off release paper, obtain final product described clothing leather.
Preferably, described base fabric is woven fabric non-woven fabrics.
Due to the enforcement of above technical scheme, the present invention compared with prior art has the advantage that
The present invention using specific solvent-free polyurethane resin as tack coat, using specific waterborne polyurethane resin as face
Layer resin, the leather goods being formed have excellent hydrolytic resistance and low-temperature flexibility, wear-resisting scratch resistance, soft, kishke feel
By force, excellent combination property, meets the requirements of garment industry application；In formula, whole raw material sources are extensive simultaneously, and price is low
Honest and clean, and can be produced using existing equipment and process conditions, production cost is relatively low.Additionally, in production technology of the present invention
There is not use and the discharge of organic solvent, environment is not resulted in any pollution problem；The synthetic leather product of preparation is no any
The volatilization of organic solvent, reliable using process safety.
Specific embodiment
Below to be described in further details to the present invention in conjunction with specific embodiments.It should be understood that these embodiments are used for
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.Adopt in embodiment
Implementation condition can be done according to specific requirement and adjust further, and not marked implementation condition is usually the condition in normal experiment.
Embodiment is raw materials used to be industrial goods.Wherein, liquefaction mdi be Carbodiimide-Modified mdi, it with pure mdi as raw material,
Heat-treated prepared in the presence of catalyst.This patent uses mdi-100ll, and storage is more stable, because containing in its structure
There is-n=c=n- so that product propertiess are physical property, anti-fire is all improved.
Embodiment 1
This example provides a kind of solvent-free polyurethane resin, and it is reacted in the presence of the first catalyst by component a and component b
Obtain, wherein component a is hydroxy-end capped polyol component, component b is isocyanate-terminated pre-polymer component, component a with
The mass ratio that feeds intake of component b is 2:1.5.
In parts by weight, the composition of raw materials of component a is: 90 parts of the polyoxypropyleneglycol of number-average molecular weight 2000, number are all
10 parts of the polyoxypropylene trihydroxylic alcohol of molecular weight 1000,25 parts of ester ether copolymerization dihydroxylic alcohols, 3 parts of ethylene glycol, 1 part of glycerol, 1 part of water,
Second 0.5 part of catalyst, 0.2 part of foam stabilizer, 1 part of stabilizer, wherein ester ether copolymerization dihydroxylic alcohols are by adipic acid, number-average molecular weight
300 PTMG, hexanediol reaction are obtained, adipic acid, PTMG, the feeding intake mole of hexanediol
Than for 2:1.05:1.1.Reaction detailed process is as follows: adipic acid, PTMG, hexanediol are added to equipped with machine
Survey after being gradually heating to 220 DEG C of constant temperature 15h in the four round flask that tool stirring, nitrogen, temperature controller, condensing reflux are equipped
Trial product hydroxyl value is standby for lowering the temperature after 65mgkoh/g.
In parts by weight, the composition of raw materials of component b is: mdi50 part, liquefaction mdi10 part, the polyoxy of number-average molecular weight 2000
Change 25 parts of propylene glycol, 8 parts of the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 1000.
The preparation method of component a is as follows: puts into all raw materials in the reactor with stirring by formula, is warming up to 50-
55 DEG C of isothermal reactions are 265cp/25 DEG C to reaction system viscosity, and moisture content is less than or equal to 0.45%, terminate reaction, obtain final product component a.
The preparation method of component b is as follows: puts in the reactor with stirring by formula by mdi and liquefaction mdi, Ran Houyi
The secondary addition polyoxypropyleneglycol of number-average molecular weight 2000 and the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 1000, are maintained at temperature
At 55-65 DEG C of degree, isothermal reaction is 320cp/25 DEG C to reaction system viscosity, and ncowt% is 18.5%, terminates reaction, obtains final product group
Part b.
The first above-mentioned catalyst, the second catalyst can be appointing in organic amine catalyst, organo-metallic catalyst
One or more of combination.
Component a, component b and the first catalyst independent packaging.During practical application, after component a is mixed with the first catalyst,
Obtain solvent-free polyurethane resin with component b hybrid reaction again.
Embodiment 2
This example provides a kind of solvent-free polyurethane resin, and it is reacted in the presence of the first catalyst by component a and component b
Obtain, wherein component a is hydroxy-end capped polyol component, component b is isocyanate-terminated pre-polymer component, component a with
The mass ratio that feeds intake of component b is 2:1.9.
In parts by weight, the composition of raw materials of component a is: 70 parts of the polyoxypropyleneglycol of number-average molecular weight 3000, number are all
15 parts of the polyoxypropylene trihydroxylic alcohol of molecular weight 300,20 parts of ester ether copolymerization dihydroxylic alcohols, 3 parts of ethylene glycol, 1 part of glycerol, 1 part of water,
Two 0.5 part of catalyst, 0.2 part of foam stabilizer, 1 part of stabilizer, wherein ester ether copolymerization dihydroxylic alcohols are by adipic acid, number-average molecular weight 200
PTMG, hexanediol reaction be obtained, adipic acid, PTMG, the molar ratio of hexanediol
For 2:1.06:1.5.Reaction detailed process is as follows: adipic acid, PTMG, hexanediol are added to equipped with machinery
Test after being gradually heating to 220 DEG C of constant temperature 15h in the four round flask that stirring, nitrogen, temperature controller, condensing reflux are equipped
Product hydroxyl value is standby for lowering the temperature after 95mgkoh/g.
In parts by weight, the composition of raw materials of component b is: mdi70 part, liquefaction mdi5 part, the polyoxy of number-average molecular weight 3000
Change 20 parts of propylene glycol, 12 parts of the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 300.
The preparation method of component a is as follows: puts into all raw materials in the reactor with stirring by formula, is warming up to 65-
70 DEG C of isothermal reactions are 316cp/25 DEG C to reaction system viscosity, and moisture content is less than or equal to 0.45%, terminate reaction, obtain final product component a.
The preparation method of component b is as follows: puts in the reactor with stirring by formula by mdi and liquefaction mdi, Ran Houyi
The secondary addition polyoxypropyleneglycol of number-average molecular weight 3000 and the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 300, are maintained at temperature
At 65-75 DEG C of degree, isothermal reaction is 360cp/25 DEG C to reaction system viscosity, and ncowt% is 19.3%, terminates reaction, obtains final product group
Part b.
The first above-mentioned catalyst, the second catalyst can be appointing in organic amine catalyst, organo-metallic catalyst
One or more of combination.
Component a, component b and the first catalyst independent packaging.During practical application, after component a is mixed with the first catalyst,
Obtain solvent-free polyurethane resin with component b hybrid reaction again.
Embodiment 3
This example provides a kind of waterborne polyurethane resin, and in parts by weight, the composition of raw materials of waterborne polyurethane resin is: number is all
30 parts of the PolyTHF dihydroxylic alcohols of molecular weight 1000,10 parts of the ester ether copolymer of number-average molecular weight 3000, dmpa4 part, second two
2 parts of alcohol, 1 part of hexamethylene diamine, tdi15 part, 2 parts of triethylamine, 3 parts of acetone, 50 parts of water, 1 part of levelling agent, 1 part of thickening agent, defoamer 1
Part, wherein ester ether copolymer is the PEPA of number-average molecular weight 600 and the PTMG of number-average molecular weight 300
And adipic acid copolyreaction obtain ester ether copolymerization dihydroxylic alcohols, hydroxyl value be 35mgkoh/g.
Waterborne polyurethane resin is obtained as follows: by formula proportion by PolyTHF dihydroxylic alcohols, ester ether copolymerization
Thing is put in the reactor with stirring, temperature control device and chuck heater, heats up, and vacuum dehydration treats that biodiversity contains
Amount adds tdi, dmpa and ethylene glycol, acetone etc. less than after 300ppm, being cooled to 40-50 DEG C, reacts and to ncowt% measured value is
After 1-2%, it is cooled to 40-50 DEG C, add triethylamine, then gained resin is emulsifiable in remaining water, then instills hexamethylene diamine,
Complete chain extension under stirring, last vacuum distillation removes acetone, add levelling agent, thickening agent, defoamer by formula proportion, obtain final product viscous
Spend the waterborne polyurethane resin for 5500cpscp/25 DEG C.
Embodiment 4
This example provides a kind of waterborne polyurethane resin, and in parts by weight, the composition of raw materials of waterborne polyurethane resin is: number is all
20 parts of the PolyTHF dihydroxylic alcohols of molecular weight 2000,20 parts of the ester ether copolymer of number-average molecular weight 4000, dmba4 part, glycerol 2
Part, 1 part of ethylenediamine, mdi15 part, 2 parts of triethylamine, 5 parts of acetone, 48 parts of water, 1 part of levelling agent, 1 part of thickening agent, 1 part of defoamer,
Ester ether copolymer is with embodiment 3.
The preparation process of this example waterborne polyurethane resin is with embodiment 3.The viscosity of gained waterborne polyurethane resin is
4500cp/25℃.
Embodiment 5
This example provides a kind of Synthetic Leather, and it is obtained as follows:
(1) waterborne polyurethane resin of embodiment 3 is spread evenly across in release paper with the thickness of 0.1mm, dries, formed
Surface layer resin layer；
(2), after the component a of embodiment 1 being mixed with the first catalyst, add component b mixing, after mix homogeneously, with
The thickness of 0.1mm is uniformly coated on the surface layer resin of step (1), is placed in 70-80 DEG C of air dry oven and 10-20 second is dried
Clock, obtains the half-dried bonding resin layer having certain wire drawing shape；
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed in base fabric, are placed in 70-80 DEG C of drying baker
1-2 minute is dried, throws off release paper, obtain final product described clothing leather, wherein base fabric is woven fabric non-woven fabrics.
Embodiment 6
This example provides a kind of Synthetic Leather, and it is obtained as follows:
(1) waterborne polyurethane resin of embodiment 3 is spread evenly across in release paper with the thickness of 0.2mm, dries, formed
Surface layer resin layer；
(2), after the component a of embodiment 2 being mixed with the first catalyst, add component b mixing, after mix homogeneously, with
The thickness of 0.15mm is uniformly coated on the surface layer resin of step (1), is placed in 70-80 DEG C of air dry oven and 10-20 is dried
Second, obtain the half-dried bonding resin layer having certain wire drawing shape；
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed in base fabric, are placed in 70-80 DEG C of drying baker
1-2 minute is dried, throws off release paper, obtain final product described clothing leather, wherein base fabric is woven fabric non-woven fabrics.
Embodiment 7
This example provides a kind of Synthetic Leather, and it is obtained as follows:
(1) waterborne polyurethane resin of embodiment 4 is spread evenly across in release paper with the thickness of 0.25mm, dries, shape
Become surface layer resin layer；
(2), after the component a of embodiment 1 being mixed with the first catalyst, add component b mixing, after mix homogeneously, with
The thickness of 0.20mm is uniformly coated on the surface layer resin of step (1), is placed in 70-80 DEG C of air dry oven and 10-20 is dried
Second, obtain the half-dried bonding resin layer having certain wire drawing shape；
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed in base fabric, are placed in 70-80 DEG C of drying baker
1-2 minute is dried, throws off release paper, obtain final product described clothing leather, wherein base fabric is woven fabric non-woven fabrics.
Embodiment 8
This example provides a kind of Synthetic Leather, and it is obtained as follows:
(1) waterborne polyurethane resin of embodiment 4 is spread evenly across in release paper with the thickness of 0.2mm, dries, formed
Surface layer resin layer；
(2), after the component a of embodiment 2 being mixed with the first catalyst, add component b mixing, after mix homogeneously, with
The thickness of 0.15mm is uniformly coated on the surface layer resin of step (1), is placed in 70-80 DEG C of air dry oven and 10-20 is dried
Second, obtain the half-dried bonding resin layer having certain wire drawing shape；
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed in base fabric, are placed in 70-80 DEG C of drying baker
1-2 minute is dried, throws off release paper, obtain final product described clothing leather, wherein base fabric is woven fabric non-woven fabrics.
Performance test
The performance of the resin to above-described embodiment and clothing leather is tested, specific as follows.
(1), tensile strength and test of elongation rate: by the resin of embodiment 3 and 4 in flat glass plate or politef
On plate, uniform paving, makes the thin film of thickness 0.5mm, then tests the percentage elongation of epithelium using tensilon.Test condition
Standard is: cupping machine should meet the regulation of 5.1.2～5.1.5 bar in gb/t1040.1-2006, and test procedure and result are pressed
The 9th chapter regulation in gb/t1040.3-2006 is carried out, and wherein from for 100mm, test speed is 200mm/ to sample distance between bench marks
min±10mm/min.The tensile strength recording embodiment 3 and 4 is respectively 28 and 30n/3cm, and percentage elongation is respectively 560% He
680%.
(2), feel test: be directly subject to the clothing leather of embodiment 5-8 with feel, result show these clothing leather feels all than
More soft, kishke feel is strong, by contrast, product described in above-mentioned publication, its feel is harder, does not meet and makees clothing leather
Index request.
(3), the anti-hydrolytic performance peel load of the clothing leather of testing example 5-8:
Hydrolytic resistance method of testing: according to qb/t2888-2007 standard, test specimen size: 100mm × 20mm, in temperature
Spend for 23 DEG C ± 2 DEG C, under conditions of relative humidity 45%～55%, sample is immersed in 10%naoh aqueous solution, place 24h
With tweezers, sample is taken out afterwards, and rinsed well with water, after 100 DEG C of ± 2 DEG C of drying in oven, observe strip and corrode Testudiniss
Split situation or the peel load of test sample.
Peel strength test method: cupping machine should meet the rule of 5.1.2～5.1.5 bar in gb/t1040.1-2006
Determine, test procedure and result are carried out by the regulation of the 5.9th article in gb/t8949-1995.
Result is referring to table 1.
(4), folding fastness method of testing: the folding fastness of the clothing leather of testing example 5-8, according to qb/t1646-
2007 standard regulations are carried out, respectively by each group sample at 23 DEG C ± 2 DEG C and -10 DEG C ± 2 DEG C, by sample front folded inward,
Observe positive and negative two sides by changing that folding part is divided.Result is referring to table 1.
(5), wearability test measures:
The abrasion resistance test method of the clothing leather of embodiment 5-8: the regulation according to qb/t2726-2005 is carried out.Loading is
1000g, from h-22 emery wheel, setting speed is 60r/min, and rotating speed is 500r.Tested specimen surface is observed after off-test
Change.Result is referring to table 1.
Table 1
Above the present invention is described in detail, its object is to allow the personage being familiar with this art will appreciate that this
The content of invention is simultaneously carried out, and can not be limited the scope of the invention with this, all spirit institutes according to the present invention
The equivalence changes made or modification, all should cover within the scope of the present invention.
Claims (10)
1. a kind of environment-protecting polyurethane clothing leather it is characterised in that: described clothing leather by base cloth layer, be fitted on described base cloth layer
Binding resin layer, the surface layer resin layer that is fitted in described binding resin layer constitute, described binding resin layer is by solvent-free
Polyurethane resin is formed, and described surface layer resin layer is formed by waterborne polyurethane resin, wherein:
Described solvent-free polyurethane resin is reacted in the presence of the first catalyst by component a and component b and obtains, wherein component a
For hydroxy-end capped polyol component, component b is isocyanate-terminated pre-polymer component, the quality that feeds intake of component a and component b
Than for 2:1.4 ~ 1.9；
In parts by weight, the composition of raw materials of component a is: polyoxypropyleneglycol 70-90 part of number-average molecular weight 2000 ~ 3000,
5 ~ 15 parts of the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 300 ~ 1000, the ester ether copolymerization dihydroxylic alcohols of number-average molecular weight 1000 ~ 2000
20-30 part, 1.5 ~ 6 parts of small molecule glycol chain extender, 0.5 ~ 6 part of glycerol, 0.2 ~ 2 part of water, the second catalyst 0.2 ~ 1.5
Part, 0.5 ~ 3 part of auxiliary agent, the wherein hydroxyl value of ester ether copolymerization dihydroxylic alcohols are 55-106mgkoh/g, by adipic acid, number-average molecular weight 200
~ 300 polyether polyol, small molecule dihydroxylic alcohols three reaction are obtained, the polyether polyol of number-average molecular weight 200 ~ 300, little point
The molar ratio of sub- dihydroxylic alcohols is 1:1 ~ 2；
In parts by weight, the composition of raw materials of component b is: mdi 50-70 part, liquefaction mdi 4-15 part, number-average molecular weight 2000 ~
3000 polyoxypropyleneglycol 20-30 part, 5 ~ 15 parts of the polyoxypropylene trihydroxylic alcohol of number-average molecular weight 300 ~ 1000；
In parts by weight, the composition of raw materials of described waterborne polyurethane resin is: the PolyTHF of number-average molecular weight 1000 ~ 2000
Dihydroxylic alcohols 20-30 part, ester ether copolymer 10-20 part of number-average molecular weight 3000 ~ 4000, first chain extender 3-5 part, the second chain extension
Agent 1-3 part, the 3rd chain extender 0.5-2 part, isocyanates 10-20 part, nertralizer 1-3 part, acetone 2-5 part, water 45-55 part, stream
Flat agent 0.5-2 part, thickening agent 0.5-2 part, defoamer 0.5-1.5 part, the wherein first chain extender is dmpa, dmba or the group of the two
Close, the second chain extender is small molecule dihydroxylic alcohols or ternary alcohols chain extender, the 3rd chain extender is small molecule binary amine chain extender,
Ester ether copolymer is the PEPA of number-average molecular weight 500-1000, the polyether Glycols Radix Chloranthi Serrati of number-average molecular weight 200 ~ 300
Ester ether copolymerization dihydroxylic alcohols that diacid copolyreaction obtains, hydroxyl value are 27-37mgkoh/g, isocyanates be tdi, mdi or the two
Combination；
The first described catalyst, the second catalyst independently are one of amines catalyst, organo-metallic catalyst or many
The combination planted.
2. environment-protecting polyurethane clothing leather according to claim 1 it is characterised in that: in component a, small molecule dihydroxylic alcohols expand
Chain agent is the combination of one or more of ethylene glycol, diethylene glycol, butanediol, hexanediol, neopentyl glycol.
3. environment-protecting polyurethane clothing leather according to claim 1 it is characterised in that: component a is obtained as follows:
By formula, all raw materials are put in the reactor with stirring, be warming up to 50-75 DEG C, isothermal reaction to reaction system viscosity is
200 ~ 450 cp/25 DEG C, moisture is less than or equal to 0.5%, terminates reaction, obtains final product component a.
4. environment-protecting polyurethane clothing leather according to claim 1 it is characterised in that: component b is obtained as follows:
By formula, mdi and liquefaction mdi is put in the reactor with stirring, then sequentially add number-average molecular weight 2000 ~ 3000
The polyoxypropylene trihydroxylic alcohol of polyoxypropyleneglycol and number-average molecular weight 300 ~ 1000, is maintained at constant temperature at temperature 55-80 DEG C anti-
Should be 200 ~ 450 cp/25 DEG C to reaction system viscosity, ncowt% is 16 ~ 22%, terminates reaction, obtains final product component b.
5. environment-protecting polyurethane clothing leather according to claim 1 it is characterised in that: described waterborne polyurethane resin passes through
Following steps are obtained: PolyTHF dihydroxylic alcohols, ester ether copolymer are put into stirring, temperature control device and chuck heating dress
In the reactor put, heat up, vacuum dehydration, it is less than after 300ppm after biodiversity content, be cooled to 40-50 DEG C of addition Carbimide.
Ester, the first chain extender and the second chain extender, acetone, react after being 1-2% to ncowt% measured value, are cooled to 40-50 DEG C, add
Nertralizer, then gained resin is emulsifiable in water, then instills the 3rd chain extender, completes chain extension under agitation, and finally decompression is steamed
Evaporate removing acetone, add levelling agent, thickening agent, defoamer by formula proportion, obtain final product the water that viscosity is cp/25 DEG C of 4000-6000
Property polyurethane resin.
6. according to claim 1 or 5 environment-protecting polyurethane clothing leather it is characterised in that: described nertralizer be three second
Amine.
7. according to claim 1 or 5 environment-protecting polyurethane clothing leather it is characterised in that: described second chain extender be second
The combination of one or more of glycol, diethylene glycol, butanediol, hexanediol, tmp, neopentyl glycol, glycerol, Oleum Ricini.
8. according to claim 1 or 5 environment-protecting polyurethane clothing leather it is characterised in that: described 3rd chain extender be second
The combination of one or more of diamidogen, hexamethylene diamine, ipda.
9. the preparation method of the environment-protecting polyurethane clothing leather as described in a kind of claim as any one of claim 1 to 8, its
It is characterised by comprising the following steps:
(1) waterborne polyurethane resin is spread evenly across in release paper with the thickness of 0.1 ~ 0.25mm, dries, form surface layer resin
Layer；
(2), after component a being mixed with the first catalyst, add component b mixing, after mix homogeneously, with the thickness of 0.1 ~ 0.25 mm
It is uniformly coated on the surface layer resin of step (1), is placed in 70-80 DEG C of air dry oven and is dried 10-20 second, obtain half-dried
The bonding resin layer having certain wire drawing shape；
(3) by laminating for step (1) gained surface layer resin layer on step (2) gained bonding resin layer and be compacted, it is placed in 70-110
DEG C drying baker in 1-2 minute is dried, throw off release paper, obtain final product described clothing leather.
10. preparation method according to claim 9 it is characterised in that: described base fabric be woven fabric non-woven fabrics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410797159.0A CN104479102B (en) | 2014-12-19 | 2014-12-19 | Environment-friendly polyurethane clothing leather and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410797159.0A CN104479102B (en) | 2014-12-19 | 2014-12-19 | Environment-friendly polyurethane clothing leather and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104479102A CN104479102A (en) | 2015-04-01 |
| CN104479102B true CN104479102B (en) | 2017-01-18 |
Family
ID=52753718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410797159.0A Active CN104479102B (en) | 2014-12-19 | 2014-12-19 | Environment-friendly polyurethane clothing leather and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104479102B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105970639A (en) * | 2016-06-24 | 2016-09-28 | 江苏国信复合材料科技股份有限公司 | Spandex garment leather and preparation method thereof |
| CN106397722B (en) * | 2016-08-31 | 2019-05-17 | 合肥安利聚氨酯新材料有限公司 | A kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin and its preparation method and application |
| CN106397728A (en) * | 2016-08-31 | 2017-02-15 | 合肥安利聚氨酯新材料有限公司 | Environment-friendly low-VOC two-component polyurethane resin for totally-dry-bonding bonding layer of synthetic leather and preparation method thereof |
| CN106380575B (en) * | 2016-09-21 | 2018-11-27 | 无锡市莱瑟新材料科技有限公司 | A kind of aero-mechanical foaming type polyurethane bass is resin dedicated and preparation method thereof |
| CN106928421A (en) * | 2017-04-13 | 2017-07-07 | 合肥科天水性科技有限责任公司 | A kind of clothing leather soft bed material and preparation method thereof |
| KR102406170B1 (en) * | 2017-05-18 | 2022-06-07 | 현대자동차주식회사 | Eco-friendly artificial leather for interior of automobile and manufacturing method thereof |
| CN107012692B (en) * | 2017-05-19 | 2019-02-12 | 陕西科技大学 | A kind of production method of biology base no-solvent polyurethane synthetic leather |
| CN107629670A (en) * | 2017-09-07 | 2018-01-26 | 旭川化学（苏州）有限公司 | It is a kind of to feel solvent-free polyurethane resin and preparation method and application without modeling |
| CN108824017A (en) * | 2018-07-18 | 2018-11-16 | 华伦皮塑（苏州）有限公司 | Solvent-free shoes leather of a kind of loopful water-retaining property and preparation method thereof |
| CN109457496A (en) * | 2018-11-14 | 2019-03-12 | 南京边城体育用品股份有限公司 | A kind of fire-resistant waterproof ventilation moisture-permeable shell fabric and preparation method thereof |
| CN109880504B (en) * | 2019-03-06 | 2021-06-08 | 上海金狮化工有限公司 | Leather isolation layer coating agent, preparation method thereof and leather |
| WO2021012139A1 (en) * | 2019-07-22 | 2021-01-28 | Dow Global Technologies Llc | Polyurethane compositions, products prepared with same and preparation methods thereof |
| CN110607694A (en) * | 2019-09-25 | 2019-12-24 | 晋江全亿无纺布有限责任公司 | Water-based microfiber non-woven fabric capable of replacing genuine leather |
| CN110684171A (en) * | 2019-10-29 | 2020-01-14 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN111155325B (en) * | 2020-01-22 | 2022-08-30 | 黎明化工研究设计院有限责任公司 | Three-dimensional composite nano carbon material, environment-friendly polyurethane synthetic leather with high folding fastness prepared from three-dimensional composite nano carbon material and preparation method of environment-friendly polyurethane synthetic leather |
| CN111304924B (en) * | 2020-04-06 | 2022-07-15 | 湖南工程学院 | Environment-friendly moisture-absorbing and heating finishing agent |
| CN115057990B (en) * | 2022-07-20 | 2023-11-03 | 浙江华峰合成树脂有限公司 | Polyurethane resin for adhesive layer and preparation method and application thereof |
| CN115322319A (en) * | 2022-08-30 | 2022-11-11 | 浙江禾欣科技有限公司 | Solvent-free polyurethane synthetic leather and preparation method thereof |
| CN115895431A (en) * | 2022-12-18 | 2023-04-04 | 现代纺织技术创新中心(鉴湖实验室) | Low-viscosity biomass bi-component solvent-free polyurethane coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654738A (en) * | 2004-02-13 | 2005-08-17 | 三芳化学工业股份有限公司 | Environmental protection artificial leather and its manufacturing method |
| CN103351456A (en) * | 2013-05-28 | 2013-10-16 | 江苏华大新材料有限公司 | Wet method polyurethane resin for clothing leather, and preparation method thereof |
| CN103755917A (en) * | 2013-12-26 | 2014-04-30 | 浙江华峰合成树脂有限公司 | Polyurethane bonding layer resin for clothing leather, and preparation method and application thereof |
-
2014
- 2014-12-19 CN CN201410797159.0A patent/CN104479102B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654738A (en) * | 2004-02-13 | 2005-08-17 | 三芳化学工业股份有限公司 | Environmental protection artificial leather and its manufacturing method |
| CN103351456A (en) * | 2013-05-28 | 2013-10-16 | 江苏华大新材料有限公司 | Wet method polyurethane resin for clothing leather, and preparation method thereof |
| CN103755917A (en) * | 2013-12-26 | 2014-04-30 | 浙江华峰合成树脂有限公司 | Polyurethane bonding layer resin for clothing leather, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104479102A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104479102B (en) | Environment-friendly polyurethane clothing leather and preparation method thereof | |
| JP6291011B2 (en) | Dispersion and film containing aqueous polyurethaneurea composition | |
| CN1228497C (en) | Fabric structure body comprising organic polysiloxane-polyurea-polyurethane block copolymer | |
| CN102712736B (en) | Polyester polyol, polyurethane utilizing the polyester polyol and process for production thereof, and polyurethane molded article | |
| KR101624018B1 (en) | Solvent Free Aqueous Polyurethane Dispersions and Shaped Articles Therefrom | |
| CN104031225B (en) | A kind of aqueous pu dispersions for synthetic leather adhesive and preparation method thereof | |
| CN100540582C (en) | Breathable polyurethanes, blend, and goods | |
| CN100366818C (en) | Method for manufacturing light-proof leatheroid and leatheroid thereof | |
| CN101443373B (en) | Microporous coating based on polyurethane-polyurea | |
| US20150284902A1 (en) | Polyurethane dispersion based synthetic leathers having improved embossing characteristics | |
| CN101717487A (en) | Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof | |
| KR101907333B1 (en) | Aqueous polyurethaneurea compositions including dispersions and films | |
| CN102159165A (en) | Wound dressing with a polyurethane foam layer and a cover layer made of thermoplastic polymer | |
| CN109160994B (en) | Polyurethane dispersion for dry coating primer, and preparation method and application thereof | |
| CN106496514A (en) | A kind of waterborne polyurethane resin | |
| CN109312043A (en) | Contact gluing product, its preparation and corresponding contact adhesive based on polyurethane-urea | |
| CN110452350A (en) | A kind of preparation of leather polyurethane dry method surface layer resin and its application in vacuum pattern absorbing leather making process | |
| JP7123907B2 (en) | Aqueous polyurethane dispersions, prepolymers, and shaped articles made therefrom | |
| KR101818751B1 (en) | Aqueous polyurethane dispersion for coating-glove, method for manufacturing thereof and coating glove coated with the same | |
| CN111533875B (en) | Preparation method of cationic waterborne polyurethane, leather bottom sealing resin and leather coating | |
| CN105603758B (en) | A kind of elastic force moving fabric | |
| JP2017519075A (en) | Aqueous polyurethaneurea composition comprising dispersion and film | |
| CN116478359B (en) | Polysiloxane material for preventing jean fabric from losing elasticity, preparation method and application | |
| CN107857869B (en) | Aqueous polyurethane and its preparation method and application | |
| CN109705310B (en) | Polyurethane resin for waterproof breathable leather and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230418 Address after: 235200 YONGGU Light Chemical Industrial Park, Xiaoxian County, Suzhou City, Anhui Province Patentee after: ANHUI HUADA CHEMICALS Co.,Ltd. Address before: No. 28 Shengyu Avenue, Changshu New Materials Industrial Park, Suzhou City, Jiangsu Province, 215500 Patentee before: JIANGSU HUADA NEW MATERIAL Co.,Ltd. |