CN106397722B - A kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin and its preparation method and application - Google Patents
A kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin and its preparation method and application Download PDFInfo
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- CN106397722B CN106397722B CN201610798749.4A CN201610798749A CN106397722B CN 106397722 B CN106397722 B CN 106397722B CN 201610798749 A CN201610798749 A CN 201610798749A CN 106397722 B CN106397722 B CN 106397722B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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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
- D06N3/0086—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
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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- 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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- 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
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
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- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
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- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
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Abstract
The invention belongs to synthetic leather fields, provide a kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin, carry out mixing by component A and B component 2:1-1:2 in mass ratio and constitute；Component A is made of 5-15 parts of aliphatic diisocyanate, 50-60 parts of oligomer dihydric alcohol, 10-20 parts of organosilicon polyalcohol, 3-10 parts of small molecule dihydric alcohol, 0.5-5 parts of small molecule trihydroxylic alcohol, 0.1-1.5 parts of catalyst, 0.5-2.5 parts of light heat stabilizer, 0.02-0.5 parts of levelling agent, 0.01-0.2 parts of defoaming agent, 0.1-0.5 parts of deicer, 0.5-5.0 parts of carbon fiber；B component is made of 40-50 parts of aliphatic diisocyanate, 0-10 parts of aliphatic triisocyanate, 35-50 parts of polytetrahydrofuran dihydric alcohol, 0.5-5 parts of small molecule dihydric alcohol, 0-2 parts of small molecule trihydroxylic alcohol, 0.5-1.0 parts of light heat stabilizer；The present invention also provides the preparation method and applications of the resin.Resin involucra angle tear strength is up to 130kN/m or more after carbon fiber modifying；No-solvent type sports shoe leather made from the method for the present invention, peel strength is up to 90N/3cm or more, anti-hydrolytic performance up to 10 weeks or more.
Description
Technical field
This technology belongs to synthetic leather field, is related to a kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin
And its preparation method and application.
Background technique
With the continuous improvement of living standards, people propose sport footwear comfort, aesthetics and environmentally protective performance
Increasingly higher demands.Sports shoe leather mainly uses solvent borne polyurethane synthetic leather currently on the market, and processing method is by wet process
Technique and dry process two parts composition, are determined by finished leather processing features, the processing of wet process finished leather and dry method bond processing
Used organic solvent n,N-Dimethylformamide (DMF) is difficult to eliminate completely during process, causes in resultant Leather
DMF has certain residual.
European Union is also year by year plus tight to the control of DMF content in resultant Leather, until banning the use of DMF before the year two thousand twenty.European Union
It is the main base of China's synthetic leather outlet, this forces synthetic leather enterprise, China just to need to control DMF in the fabrication process
System can just meet the standard of outlet European Union.In addition China has also formulated corresponding synthetic leather standard successively.It develops more environmentally protective
Synthetic Leather it is very urgent.
One of the important species that no-solvent polyurethane sports shoe leather is removed from office as Future movement shoes, it is necessary to using physical property,
The various aspects of performance such as chemical property and ecological, environmental protective performance are able to satisfy the no-solvent polyurethane tree of sports shoe leather processing request
Rouge is as premise；Therefore, it is extremely urgent to develop a sports shoe leather no-solvent polyurethane surface layer resin.
Summary of the invention
The present invention is intended to provide a kind of carbon fiber modifying no-solvent polyurethane surface layer resin, with and preparation method thereof with answer
With.No matter from peel strength, anti-hydrolytic performance or the processing technology closed with cloth base junction angularly for, be all satisfied solvent-free
The requirement of polyurethane sport shoes leather.
The present invention provides a kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resins, by component A and B
Component 2:1-1:2 in mass ratio is mixed:
The component A includes that following components is prepared by mass fraction:
The B component includes that following components is prepared by mass fraction:
The aliphatic diisocyanate is isophorone diisocyanate (IPDI), hexamethylene diisocyanate
(HDI), 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12One or more of) MDI mixture；Aliphatic three is different
Cyanate is HDI trimer；
The oligomer dihydric alcohol be molecular weight be 1000-3000 polytetrahydrofuran dihydric alcohol, polycarbonate glycol,
The mixture of one or more of polycaprolactone diols, polyester diol；
The organosilicon polyalcohol is OFX-0930, NiaxL-1160, OHX 4010, in OHX 4081, OFOH702E
One or more kinds of mixtures；
The small molecule dihydric alcohol is ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, neopentyl glycol, one
Diglycol ethylene, 3- methyl-1, in bis- (2- ethoxy) ethers of 5- pentanediol, 1,6-HD, 1,4 cyclohexane dimethanol quinhydrones
One or more kinds of mixtures；
The small molecule trihydroxylic alcohol is one or both of glycerine, trimethylolpropane；
The catalyst be delaying type catalyst, such as organometallic catalysts be BiCAT 8106, BiCAT8108,
BiCAT 8124、BiCAT 3228、Borchi Kat 22、Borchi Kat 24、BiCAT 4130、BiCAT 4232、MB20
Deng；
The light heat stabilizer is ultraviolet absorbing agent, hindered amine light stabilizer；Wherein ultraviolet absorbing agent is UV-
1, UV-320, UV-1130, UV-P, UV-1164 or UV-234；Hindered amine light stabilizer be 292,622,770,944,5050,
5060 or 5151.
The antioxidant is antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or anti-
The mixture of one or more of oxygen agent 3114.
The levelling agent is silicone levelling agent, such as BYK-322, BYK-333, BYK-345, BYK-361N；
The defoaming agent is the mixing of one or more of BYK-054, TEGO Airex 900, BYK-1790
Object；
The deicer be one or both of ALT-201, ALT-202, Incozol 2, Zoldine MS-PLus with
On mixture；
The carbon fiber is short fine coiled carbon fibers.
The present invention also provides the preparation method of the solvent-free surface layer polyurethane resin of above-mentioned carbon fiber modifying, the preparation methods
The following steps are included:
(1) preparation of component A: oligomer dihydric alcohol, organosilicon polyalcohol are put into reaction kettle, is warming up to 100-120
DEG C, be dehydrated 2-4h under -0.08MPa~-0.1MPa vacuum condition, after be cooled to 30-40 DEG C, small molecule dihydric alcohol and rouge is added
Fat race isocyanates maintains to react 2-4h at 75-90 DEG C of temperature；Then it is cooled to 30-40 DEG C, sequentially adds small molecule ternary
Alcohol, catalyst, light heat stabilizer, levelling agent, defoaming agent, deicer, coiled carbon fibers；It is warming up to 60-80 DEG C of stirring 2-4h
Afterwards, hydroxyl value and moisture content are detected, can be prepared by component A after qualified, sealed package is stand-by；
(2) preparation of B component: aliphatic diisocyanate, aliphatic triisocyanate and light heat are put into kettle and is stablized
Oligomer polytetrahydrofuran dihydric alcohol, small molecule dihydric alcohol and small molecule trihydroxylic alcohol is added in agent, and stirs instead at 80-90 DEG C
2.5-4.5h is answered, NCO content is detected, can be prepared by B component after qualified, sealed package is stand-by；
(3) preparation of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin: by obtained above-mentioned component A
It is sufficiently mixed with B component 2:1-1:2 in mass ratio, casting is coated in above-mentioned release paper after mixing, in 90-130
The solvent-free surface layer polyurethane resin of carbon fiber modifying can be obtained in DEG C drying；
The present invention also provides the applications of above-mentioned no-solvent type surface layer polyurethane resin, which is used for sports shoe leather
In.Obtained component A and B component 2:1-1:2 in mass ratio are sufficiently mixed at 90-130 DEG C one section of pre-reaction when use
Time is bonded screen cloth after pre-reaction, then in 110-150 DEG C of the reaction was continued 5-10min, form its crosslinking curing；Gu
It is wound after chemical conversion type and removes release paper, obtain no-solvent type sports shoe leather.
Specifically, compared with prior art, the present invention has following obvious advantage:
(1) carbon fiber modifying no-solvent polyurethane surface layer resin prepared by the present invention makes as the surface layer of sports shoe leather
With, and may also function as the effect of bonding simultaneously, so that eliminating wet process and dry method bonding process link in finished leather process has
The feature of environmental protection of sports shoe leather has been effectively ensured in the use of solvent；
(2) component A passes through the appropriate aliphatic diisocyanate progress pre-polymerization synthesis of introducing, one side effectively solution in the present invention
Consistency problem in component A of having determined between oligomer dihydric alcohol and small molecule polyol；On the other hand A, B can effectively be adjusted
The parameters such as viscosity, molecular weight between two-component material, to guarantee the stability of A/B material proportion when production and processing；
(3) component A of the present invention is synthesized by introducing appropriate organosilicon polyalcohol, and organic silicon on the one hand can be improved
The compatibility of auxiliary agent and main body polyalcohol；On the other hand double component solvent-free surface layer resin and the removing of release paper difficulty be can solve
Problem；
(4) moisture prevents from reacting generation bubble with B component in deicer consumption component A, and defoaming agent inhibitor eliminates physics
Machinery bubble；Short fibre coiled carbon fibers improve the tearing strength of solvent-free surface layer resin；
(5) resin of the present invention uses carbon fiber modifying aliphatic poly carbon-polyester-polyether-organosilicon copolymerization system, meets fortune
While dynamic shoes leather product anti-hydrolytic performance, can be effectively ensured sports shoe leather low temperature, high-temperature durable performance and peel strength,
The mechanical properties such as tearing strength；Sports shoe leather product peel strength obtained is up to 90N/3cm or more, anti-hydrolytic performance up to 10
Week；
(6) when resin of the present invention is produced for sports shoe leather, continuous production operability and reactivity has been fully ensured that, has been passed through
Time processing, that is, plastic is not necessarily to curing process, effectively shortens the production cycle, reduces energy consumption.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it should be understood that reality of the invention
It applies specific material proportion, process conditions and result described in example and is merely to illustrate the present invention, this can not be limited with this
The protection scope of invention, the equivalent change or modification that all Spirit Essences according to the present invention are done, should all cover in this hair
Within bright protection scope.
Embodiment 1:
A kind of sports shoe leather carbon fiber modifying no-solvent type surface layer polyurethane resin, the resin is by hydroxy component A and different
Isocyanate component B composition:
The component A is constituted as follows in mass fraction ratio:
The B component is constituted as follows in mass fraction ratio:
Wherein, the component A is mixed with B component 1:1.4 in mass ratio.
IPDI in component A is the isophorone diisocyanate of Bayer A.G's production, and T5652 is Japanese Asahi Chemical Industry
The polycarbonate glycol of the number-average molecular weight 2000 of chemicals Co., Ltd. production, SP-2013 are that Amway polyurethane in Hefei is new
The polyester diol of the number-average molecular weight 2000 of Materials Co., Ltd's production, EG, glycerol are commercial product, and OFOH702E is advanced in years
The hydroxy silicon oil that the hydroxyl value of figure new high-tech material Group Co., Ltd production is 50mgKOH/g, MB20 are US Air gasification chemical product
The organic bismuth catalyst of company's production, Tinuvin 1130 are the ultraviolet absorbing agent of BASF Corp. of Germany's production, Chisorb
292 light stabilizers produced for Taiwan Double Bond Chemical Ind.,Co.,Ltd., BYK-322 are that BYK company, Germany produces organic silicon
Levelling agent, BYK-054 are that BYK company, Germany produces no-solvent type defoaming agent, and ALT-201 is the production of Ai Lite Chemical Co., Ltd.
Oxazole alkanes deicer；
N3300 in component B is the HDI trimer of Bayer A.G's production, and Poly THF 2000 is Germany BASF public
The polytetrahydrofuran diol of the number-average molecular weight 2000 of production is taken charge of, Chinox 1010 is Taiwan Double Bond Chemical Ind.,Co.,Ltd.
The antioxidant of production；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin,
The preparation method the following steps are included:
(1) poly- carbon dihydric alcohol T5652, polyester diol SP-2013 and organic the preparation of component A: are put into reaction kettle
Silicon polyalcohol OFX-0930 is warming up to 120 DEG C, is dehydrated 4h under -0.08MPa~-0.1MPa vacuum condition, after be cooled to 40
DEG C, small molecule dihydric alcohol EG and aliphatic diisocyanate IPDI is added, maintains 90 DEG C of reaction 2h of temperature；Then 40 are cooled to
DEG C, sequentially add small molecule trihydric alcohol glycerin, catalyst MB20, light heat stabilizer T inuvin 1130 and Chisorb 292,
Levelling agent BYK-322, defoaming agent BYK-054, deicer ALT-201, coiled carbon fibers, after being warming up to 60 DEG C of stirring 2h, detection
Hydroxyl value and moisture content can be prepared by component A after qualified, and sealed package is stand-by；
(2) aliphatic diisocyanate IPDI, triisocyanate N3300 and light heat the preparation of B component: are put into kettle
Polytetrahydrofuran dihydric alcohol Poly THF 2000, small molecule dihydric alcohol EG is added in stabilizer Chinox 1010, and at 80 DEG C
It is stirred to react 4.5h, NCO content is detected, can be prepared by B component after qualified, sealed package is stand-by；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin: by obtained above-mentioned component A
It is sufficiently mixed with B component 2:1 in mass ratio, casting is coated in release paper after mixing, can be obtained in 130 DEG C of drying
To no-solvent type sports shoe leather surface layer polyurethane resin；
The present invention also provides the applications of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin；Make
120 DEG C of obtained A, B component pre-reactions for a period of time, are bonded screen cloth by the used time after pre-reaction, then continued in 150 DEG C anti-
It answers, forms its crosslinking curing.It is wound after curing molding and removes release paper, obtain no-solvent type sports shoe leather.
Embodiment 2
A kind of sports shoe leather carbon fiber modifying no-solvent type surface layer polyurethane resin, the resin is by hydroxy component A and different
Isocyanate component B composition:
The component A is constituted as follows in mass fraction ratio:
The B component is constituted as follows in mass fraction ratio:
Wherein, the component A is mixed with B component 1:1 in mass ratio.
H in component A12MDI is that the hydrogenation MDI, T5652 of Yantai Wanhua company production are Japanese Asahi Chemical Industry chemicals strain formula
The polycarbonate glycol of the number-average molecular weight 2000 of commercial firm's production, SP-2313 are the limited public affairs of Hefei Amway polyurethane new material
The polyester diol of the number-average molecular weight 2000 of production is taken charge of, OFX-0930 is that the hydroxyl value of Dow Corning Corporation's production is 130mgKOH/g
Hydroxy silicon oil, Isosorbide-5-Nitrae-BG and trimethylolpropane TMP are commercial product, and BiCAT 8108 is the leading chemical company in the U.S.
Organic bismuth catalyst, Chisorb P and Chisorb 944 be respectively Taiwan double bond Chemical Co., Ltd. ultraviolet absorbing agent and
Light stabilizer, BYK-345 are that BYK company, Germany produces silicone levelling agent, and BYK-1790 is that BYK company, Germany produces without molten
Dosage form defoaming agent, Zoldine MS-PLus are the oxazole alkanes deicer of U.S. Angus chemical company production；
H in component B12MDI is that the hydrogenation MDI, TPA-100 of Yantai Wanhua company production are Japanese Asahi Kasei Corporation
The HDI trimer of production, Poly THF 2000 are the polytetrahydrofuran two of the number-average molecular weight 2000 of BASF Corp. of Germany's production
Alcohol, Chinox 1010 are the antioxidant of Taiwan Double Bond Chemical Ind.,Co.,Ltd. production；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin,
The preparation method the following steps are included:
(1) poly- carbon dihydric alcohol T5652, polyester diol SP-2313 and OFX- the preparation of component A: are put into reaction kettle
0930, be warming up to 100 DEG C, be dehydrated 2h under -0.08MPa~-0.1MPa vacuum condition, after be cooled to 30 DEG C, small molecule is added
Dihydric alcohol 1,4-BG and diisocyanate H12MDI maintains 75 DEG C of reaction 4h of temperature；Then 30 DEG C are cooled to, sequentially adds small point
Sub- trihydroxylic alcohol TMP, catalyst BiCAT 8108, light heat stabilizer Chisorb P and Chisorb 944, levelling agent BYK-345,
Defoaming agent BYK-1790, deicer Zoldine MS-PLus, coiled carbon fibers, after being warming up to 80 DEG C of stirring 4h, detect hydroxyl value and
Moisture content can be prepared by component A after qualified, and sealed package is stand-by；
(2) aliphatic diisocyanate H the preparation of B component: is put into kettle12MDI, triisocyanate TPA-100 and light/
Polytetrahydrofuran dihydric alcohol Poly THF 2000, small molecule dihydric alcohol Isosorbide-5-Nitrae-BG and small is added in heat stabilizer Chinox 1010
Molecule trihydroxylic alcohol TMP, and 2.5h is stirred to react at 90 DEG C, NCO content is detected, can be prepared by B component, sealed package after qualified
For use；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin: by obtained above-mentioned component A
It is sufficiently mixed with B component 1:2 in mass ratio, casting is coated in release paper after mixing, can be obtained in 130 DEG C of drying
To no-solvent type sports shoe leather surface layer polyurethane resin；
The present invention also provides the applications of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin；Make
120 DEG C of obtained A, B component pre-reactions for a period of time, are bonded screen cloth by the used time after pre-reaction, then continued in 150 DEG C anti-
It answers, forms its crosslinking curing.It is wound after curing molding and removes release paper, obtain no-solvent type sports shoe leather.
Embodiment 3:
A kind of sports shoe leather carbon fiber modifying no-solvent type surface layer polyurethane resin, the resin is by hydroxy component A and different
Isocyanate component B composition:
The component A is constituted as follows in mass fraction ratio:
The B component is constituted as follows in mass fraction ratio:
Wherein, the component A is mixed with B component 2:1 in mass ratio.
IPDI in component A is the isophorone diisocyanate of Bayer A.G's production, and T5652 is Japanese Asahi Chemical Industry
The polycarbonate glycol of the number-average molecular weight 2000 of chemicals Co., Ltd. production, SP-2013 are that Amway polyurethane in Hefei is new
The polyester diol of the number-average molecular weight 2000 of Materials Co., Ltd's production, EG, glycerol are commercial product, and OFOH702E is advanced in years
The hydroxy silicon oil that the hydroxyl value of figure new high-tech material Group Co., Ltd production is 50mgKOH/g, MB20 are US Air gasification chemical product
The organic bismuth catalyst of company's production, Tinuvin 1130 are the ultraviolet absorbing agent of BASF Corp. of Germany's production, Chisorb
292 light stabilizers produced for Taiwan Double Bond Chemical Ind.,Co.,Ltd., BYK-322 are that BYK company, Germany produces organic silicon
Levelling agent, BYK-054 are that BYK company, Germany produces no-solvent type defoaming agent, and ALT-201 is the production of Ai Lite Chemical Co., Ltd.
Oxazole alkanes deicer；
N3300 in component B is the HDI trimer of Bayer A.G's production, and Poly THF 2000 is Germany BASF public
The polytetrahydrofuran diol of the number-average molecular weight 2000 of production is taken charge of, Chinox 1010 is Taiwan Double Bond Chemical Ind.,Co.,Ltd.
The antioxidant of production；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin,
The preparation method the following steps are included:
(1) poly- carbon dihydric alcohol T5652, polyester diol SP-2013 and organic the preparation of component A: are put into reaction kettle
Silicon polyalcohol OFX-0930 is warming up to 120 DEG C, is dehydrated 4h under -0.08MPa~-0.1MPa vacuum condition, after be cooled to 40
DEG C, small molecule dihydric alcohol EG and aliphatic diisocyanate IPDI is added, maintains 90 DEG C of reaction 2h of temperature；Then 40 are cooled to
DEG C, sequentially add small molecule trihydric alcohol glycerin, catalyst MB20, light heat stabilizer T inuvin 1130 and Chisorb 292,
Levelling agent BYK-322, defoaming agent BYK-054, deicer ALT-201, coiled carbon fibers, after being warming up to 60 DEG C of stirring 2h, detection
Hydroxyl value and moisture content can be prepared by component A after qualified, and sealed package is stand-by；
(2) aliphatic diisocyanate IPDI, triisocyanate N3300 and light heat the preparation of B component: are put into kettle
Polytetrahydrofuran dihydric alcohol Poly THF 2000, small molecule dihydric alcohol EG is added in stabilizer Chinox 1010, and at 80 DEG C
It is stirred to react 4.5h, NCO content is detected, can be prepared by B component after qualified, sealed package is stand-by；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin: by obtained above-mentioned component A
It is sufficiently mixed with B component 2:1 in mass ratio, casting is coated in release paper after mixing, can be obtained in 130 DEG C of drying
To no-solvent type sports shoe leather surface layer polyurethane resin；
The present invention also provides the applications of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin；Make
120 DEG C of obtained A, B component pre-reactions for a period of time, are bonded screen cloth by the used time after pre-reaction, then continued in 150 DEG C anti-
It answers, forms its crosslinking curing.It is wound after curing molding and removes release paper, obtain no-solvent type sports shoe leather.
Embodiment 4
A kind of sports shoe leather carbon fiber modifying no-solvent type surface layer polyurethane resin, the resin is by hydroxy component A and different
Isocyanate component B composition:
The component A is constituted as follows in mass fraction ratio:
The B component is constituted as follows in mass fraction ratio:
Wherein, the component A is mixed with B component 1:2 in mass ratio.
H in component A12MDI is that the hydrogenation MDI, T5652 of Yantai Wanhua company production are Japanese Asahi Chemical Industry chemicals strain formula
The polycarbonate glycol of the number-average molecular weight 2000 of commercial firm's production, SP-2313 are the limited public affairs of Hefei Amway polyurethane new material
The polyester diol of the number-average molecular weight 2000 of production is taken charge of, OFX-0930 is that the hydroxyl value of Dow Corning Corporation's production is 130mgKOH/g
Hydroxy silicon oil, Isosorbide-5-Nitrae-BG and trimethylolpropane TMP are commercial product, and BiCAT 8108 is the leading chemical company in the U.S.
Organic bismuth catalyst, Chisorb P and Chisorb 944 be respectively Taiwan double bond Chemical Co., Ltd. ultraviolet absorbing agent and
Light stabilizer, BYK-345 are that BYK company, Germany produces silicone levelling agent, and BYK-1790 is that BYK company, Germany produces without molten
Dosage form defoaming agent, Zoldine MS-PLus are the oxazole alkanes deicer of U.S. Angus chemical company production；
H in component B12MDI is that the hydrogenation MDI, TPA-100 of Yantai Wanhua company production are Japanese Asahi Kasei Corporation
The HDI trimer of production, Poly THF 2000 are the polytetrahydrofuran two of the number-average molecular weight 2000 of BASF Corp. of Germany's production
Alcohol, Chinox 1010 are the antioxidant of Taiwan Double Bond Chemical Ind.,Co.,Ltd. production；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin,
The preparation method the following steps are included:
(1) poly- carbon dihydric alcohol T5652, polyester diol SP-2313 and OFX- the preparation of component A: are put into reaction kettle
0930, be warming up to 100 DEG C, be dehydrated 2h under -0.08MPa~-0.1MPa vacuum condition, after be cooled to 30 DEG C, small molecule is added
Dihydric alcohol 1,4-BG and diisocyanate H12MDI maintains 75 DEG C of reaction 4h of temperature；Then 30 DEG C are cooled to, sequentially adds small point
Sub- trihydroxylic alcohol TMP, catalyst BiCAT 8108, light heat stabilizer Chisorb P and Chisorb 944, levelling agent BYK-345,
Defoaming agent BYK-1790, deicer Zoldine MS-PLus, coiled carbon fibers, after being warming up to 80 DEG C of stirring 4h, detect hydroxyl value and
Moisture content can be prepared by component A after qualified, and sealed package is stand-by；
(2) aliphatic diisocyanate H the preparation of B component: is put into kettle12MDI, triisocyanate TPA-100 and light/
Polytetrahydrofuran dihydric alcohol Poly THF 2000, small molecule dihydric alcohol Isosorbide-5-Nitrae-BG and small is added in heat stabilizer Chinox 1010
Molecule trihydroxylic alcohol TMP, and 2.5h is stirred to react at 90 DEG C, NCO content is detected, can be prepared by B component, sealed package after qualified
For use；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin: by obtained above-mentioned component A
It is sufficiently mixed with B component 1:2 in mass ratio, casting is coated in release paper after mixing, can be obtained in 130 DEG C of drying
To no-solvent type sports shoe leather surface layer polyurethane resin；
The present invention also provides the applications of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin；Make
120 DEG C of obtained A, B component pre-reactions for a period of time, are bonded screen cloth by the used time after pre-reaction, then continued in 150 DEG C anti-
It answers, forms its crosslinking curing.It is wound after curing molding and removes release paper, obtain no-solvent type sports shoe leather.
Comparative example
Remove coiled carbon fibers on that basis of example 1, specific as follows:
A kind of sports shoe leather no-solvent type surface layer polyurethane resin, the resin is by hydroxy component A and isocyanate component B
Composition:
The component A is constituted as follows in mass fraction ratio:
The B component is constituted as follows in mass fraction ratio:
Wherein, the component A is mixed with B component 1:1.25 in mass ratio.
IPDI in component A is the isophorone diisocyanate of Bayer A.G's production, and T5652 is Japanese Asahi Chemical Industry
The polycarbonate glycol of the number-average molecular weight 2000 of chemicals Co., Ltd. production, SP-2013 are that Amway polyurethane in Hefei is new
The polyester diol of the number-average molecular weight 2000 of Materials Co., Ltd's production, EG, glycerol are commercial product, and OFOH702E is advanced in years
The hydroxy silicon oil that the hydroxyl value of figure new high-tech material Group Co., Ltd production is 50mgKOH/g, MB20 are US Air gasification chemical product
The organic bismuth catalyst of company's production, Tinuvin 1130 are the ultraviolet absorbing agent of BASF Corp. of Germany's production, Chisorb
292 light stabilizers produced for Taiwan Double Bond Chemical Ind.,Co.,Ltd., BYK-322 are that BYK company, Germany produces organic silicon
Levelling agent, BYK-054 are that BYK company, Germany produces no-solvent type defoaming agent, and ALT-201 is the production of Ai Lite Chemical Co., Ltd.
Oxazole alkanes deicer；
N3300 in component B is the HDI trimer of Bayer A.G's production, and Poly THF 2000 is Germany BASF public
The polytetrahydrofuran diol of the number-average molecular weight 2000 of production is taken charge of, Chinox 1010 is Taiwan Double Bond Chemical Ind.,Co.,Ltd.
The antioxidant of production；
The present invention also provides the preparation method of above-mentioned no-solvent type sports shoe leather surface layer polyurethane resin, the preparation methods
The following steps are included:
(1) poly- carbon dihydric alcohol T5652, polyester diol SP-2013 and organic the preparation of component A: are put into reaction kettle
Silicon polyalcohol OFX-0930 is warming up to 120 DEG C, is dehydrated 4h under -0.08MPa~-0.1MPa vacuum condition, after be cooled to 40
DEG C, small molecule dihydric alcohol EG and aliphatic diisocyanate IPDI is added, maintains 90 DEG C of reaction 2h of temperature；Then 40 are cooled to
DEG C, sequentially add small molecule trihydric alcohol glycerin, catalyst MB20, light heat stabilizer T inuvin 1130 and Chisorb 292,
Levelling agent BYK-322, defoaming agent BYK-054, deicer ALT-201 after being warming up to 60 DEG C of stirring 2h, detect hydroxyl value and moisture contain
Amount can be prepared by component A after qualified, and sealed package is stand-by；
(2) aliphatic diisocyanate IPDI, triisocyanate N3300 and light heat the preparation of B component: are put into kettle
Polytetrahydrofuran dihydric alcohol Poly THF 2000, small molecule dihydric alcohol EG is added in stabilizer Chinox 1010, and at 80 DEG C
It is stirred to react 4.5h, NCO content is detected, can be prepared by B component after qualified, sealed package is stand-by；
(3) preparation of no-solvent polyurethane sports shoe leather surface layer resin: obtained above-mentioned component A is pressed with B component
Mass ratio 2:1 is sufficiently mixed, and casting is coated in release paper after mixing, can be obtained in 130 DEG C of drying solvent-free
Type sports shoe leather surface layer polyurethane resin；
The present invention also provides the applications of above-mentioned no-solvent type sports shoe leather surface layer polyurethane resin；It will be made when use
120 DEG C of A, B component pre-reactions for a period of time, screen cloth is bonded after pre-reaction, then the reaction was continued in 150 DEG C, makes its friendship
Join curing molding.It is wound after curing molding and removes release paper, obtain no-solvent type sports shoe leather.
The no-solvent type polyurethane sport shoes leather and comparative example of carbon fiber modifying obtained in above-described embodiment are made
Sports shoe leather carry out peel strength (GB/T 8949) and anti-hydrolytic performance (jungle test) test (QB/T4671), it is specifically several
According to following table:
Embodiment 1-4 performance can meet sports shoe leather use, not have the humidification of coiled carbon fibers in comparative example, just
Beginning peel strength deviation is just up to standard, removes after jungle test in ten weeks and is not able to satisfy use.
Embodiment described above is only that preferred embodiments of the present invention will be described, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (9)
1. a kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin, which is characterized in that by component A and B component
2:1-1:2 is mixed in mass ratio:
The component A includes that following components is prepared by mass fraction:
The B component includes that following components is prepared by mass fraction:
2. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, feature
Be: the aliphatic diisocyanate is isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '-two hexamethylenes
The mixture of one or more of dicyclohexylmethane diisocyanate；The aliphatic triisocyanate is that hexa-methylene two is different
Cyanate tripolymer.
3. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, feature
Be: the oligomer dihydric alcohol is the polytetrahydrofuran dihydric alcohol, polycarbonate glycol, poly- that molecular weight is 1000-3000
The mixture of one or more of ester dihydric alcohol；
The organosilicon polyalcohol is one of OFX-0930, NiaxL-1160, OHX 4010, OHX 4081, OFOH702E
Or two or more mixture；
The small molecule dihydric alcohol is ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, neopentyl glycol, a contracting two
Ethylene glycol, 3- methyl-1, one in bis- (2- ethoxy) ethers of 5- pentanediol, 1,6-HD, 1,4 cyclohexane dimethanol quinhydrones
Kind or two or more mixtures；
The small molecule trihydroxylic alcohol is one or both of glycerine, trimethylolpropane.
4. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, feature
Be: the catalyst be BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228, Borchi Kat 22,
At least one of the delaying type catalyst of Borchi Kat 24, BiCAT 4130, BiCAT 4232, MB20.
5. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, feature
Be: the light heat stabilizer is ultraviolet absorbing agent, hindered amine light stabilizer；Wherein ultraviolet absorbing agent be UV-1,
UV-320, UV-1130, UV-P, UV-1164 or UV-234；Hindered amine light stabilizer be 292,622,770,944,5050,
5060 or 5151.
6. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, feature
Be: the levelling agent is silicone levelling agent；
The defoaming agent is the mixture of one or more of BYK-054, TEGO Airex 900, BYK-1790；
The deicer is one or more of ALT-201, ALT-202, Incozol's 2, Zoldine MS-PLus
Mixture；
The coiled carbon fibers are short fine coiled carbon fibers.
7. a kind of sports shoe leather according to claim 6 carbon fiber modifying no-solvent polyurethane surface layer resin, feature
Be: the levelling agent is BYK-322, BYK-333, BYK-345 or BYK-361N.
8. preparing a kind of described in any item sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resins of claim 1-7
Method, which is characterized in that the preparation method the following steps are included:
(1) preparation of component A: into reaction kettle put into oligomer dihydric alcohol, organosilicon polyalcohol, be warming up to 100-120 DEG C ,-
Be dehydrated 2-4h under 0.08MPa~-0.1MPa vacuum condition, after be cooled to 30-40 DEG C, small molecule dihydric alcohol and aliphatic is added
Isocyanates maintains to react 2-4h at 75-90 DEG C of temperature；Then it is cooled to 30-40 DEG C, small molecule trihydroxylic alcohol is sequentially added, urges
Agent, light heat stabilizer, levelling agent, defoaming agent, deicer, coiled carbon fibers；After being warming up to 60-80 DEG C of stirring 2-4h, detection
Hydroxyl value and moisture content can be prepared by component A after qualified, and sealed package is stand-by；
(2) preparation of B component: putting into aliphatic diisocyanate, aliphatic triisocyanate and light heat stabilizer into kettle,
Polytetrahydrofuran dihydric alcohol, small molecule dihydric alcohol and small molecule trihydroxylic alcohol is added, and is stirred to react 2.5- at 80-90 DEG C
4.5h detects NCO content, can be prepared by B component after qualified, sealed package is stand-by；
(3) preparation of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin: by obtained above-mentioned component A and B
Component 2:1-1:2 in mass ratio is sufficiently mixed, and casting is coated in release paper after mixing, is in 90-130 DEG C of drying
The solvent-free surface layer polyurethane resin of carbon fiber modifying can be obtained.
9. a kind of described in any item sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resins of claim 1-7 are answered
With, it is characterised in that: obtained component A and B component 2:1-1:2 in mass ratio are sufficiently mixed in 90-130 DEG C of pre-reaction
For a period of time, screen cloth is bonded after pre-reaction, then in 110-150 DEG C of the reaction was continued 5-10min, make its crosslinking curing at
Type；It is wound after curing molding and removes release paper, obtain no-solvent type sports shoe leather.
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| CN107446100A (en) * | 2017-08-18 | 2017-12-08 | 江苏宝泽高分子材料股份有限公司 | A kind of environment-friendly type solvent-free polyurethane material and preparation method thereof |
| CN108252115B (en) * | 2017-12-29 | 2020-09-29 | 浙江华峰合成树脂有限公司 | Solvent-free high-transparency and high-flexibility-resistant polyurethane resin for leather, and preparation method and application thereof |
| CN108164674B (en) * | 2017-12-29 | 2020-11-24 | 浙江华峰合成树脂有限公司 | Solvent-free non-yellowing high-transparency and bending-resistant polyurethane leather resin and preparation method and application thereof |
| ES2959980T3 (en) * | 2018-01-18 | 2024-02-29 | Evonik Operations Gmbh | Solvent-free multi-component system |
| CN109679064B (en) * | 2019-01-08 | 2020-08-11 | 合肥安利聚氨酯新材料有限公司 | Solvent-free polyurethane surface layer slurry and preparation method and application method thereof |
| CN110204885B (en) * | 2019-05-24 | 2021-02-12 | 合肥安利聚氨酯新材料有限公司 | Solvent-free polyurethane resin leather film, preparation method thereof and shoe leather |
| CN110407997A (en) * | 2019-07-25 | 2019-11-05 | 南通万顺化工科技有限公司 | A kind of uninanned platform leather polyurethane resin and preparation method thereof |
| CN110483718A (en) * | 2019-08-21 | 2019-11-22 | 福建国邦新材料有限公司 | A kind of carbon fiber modifying no-solvent polyurethane surface layer resin |
| CN110804156A (en) * | 2019-11-07 | 2020-02-18 | 中天科盛（上海）企业发展股份有限公司 | High-strength anti-aging thermoplastic polyurethane elastomer and preparation method thereof |
| CN115976854B (en) * | 2022-12-14 | 2024-01-05 | 安徽安利材料科技股份有限公司 | High-molecular polymer microporous foaming filling mesh cloth composite material and preparation method thereof |
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| CN104088161A (en) * | 2014-07-07 | 2014-10-08 | 旭川化学（苏州）有限公司 | Preparation method of solvent-free environment-friendly polyurethane automobile leather |
| CN104086738A (en) * | 2014-07-07 | 2014-10-08 | 旭川化学（苏州）有限公司 | Solvent-free environment-friendly polyurethane automobile leather surface resin as well as preparation method and application thereof |
| CN104479102A (en) * | 2014-12-19 | 2015-04-01 | 江苏华大新材料有限公司 | Environment-friendly polyurethane clothing leather and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104088161A (en) * | 2014-07-07 | 2014-10-08 | 旭川化学（苏州）有限公司 | Preparation method of solvent-free environment-friendly polyurethane automobile leather |
| CN104086738A (en) * | 2014-07-07 | 2014-10-08 | 旭川化学（苏州）有限公司 | Solvent-free environment-friendly polyurethane automobile leather surface resin as well as preparation method and application thereof |
| CN104479102A (en) * | 2014-12-19 | 2015-04-01 | 江苏华大新材料有限公司 | Environment-friendly polyurethane clothing leather and preparation method thereof |
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