CN106397722A - Carbon fiber modified non-solvent polyurethane surface layer resin for sports shoe leather, as well as preparation method and application of carbon fiber modified non-solvent polyurethane surface layer resin - Google Patents

Carbon fiber modified non-solvent polyurethane surface layer resin for sports shoe leather, as well as preparation method and application of carbon fiber modified non-solvent polyurethane surface layer resin Download PDF

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CN106397722A
CN106397722A CN201610798749.4A CN201610798749A CN106397722A CN 106397722 A CN106397722 A CN 106397722A CN 201610798749 A CN201610798749 A CN 201610798749A CN 106397722 A CN106397722 A CN 106397722A
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component
carbon fiber
surface layer
sports shoe
shoe leather
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CN106397722B (en
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李晓飞
王海峰
姚克俭
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C—CHEMISTRY; METALLURGY
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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
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
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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
    • C08G18/28—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
    • C08G18/61—Polysiloxanes
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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
    • C08G18/28—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
    • C—CHEMISTRY; METALLURGY
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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
    • C08G18/6633—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • 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
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1664—Releasability
    • 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
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • 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 belongs to the field of synthetic leather, and provides carbon fiber modified non-solvent polyurethane surface layer resin for sports shoe leather. The resin is formed by mixing a component A and a component B according to mass percent being 2:1 to 1:2, wherein the component A comprises 5 to 15 parts of aliphatic diisocyanate, 50 to 60 parts of low polymer dihydric alcohol, 10 to 20 parts of organosilicone polyhydric alcohol, 3 to 10 parts of micromolecule dihydric alcohol, 0.5 to 5 parts of micromolecule trihydric alcohol, 0.1 to 1.5 parts of a catalyst, 0.5 to 2.5 parts of a light/heat stabilizer, 0.02 to 0.5 part of a flatting agent, 0.01 to 0.2 part of a defoamer, 0.1 to 0.5 part of a dehydrator, and 0.5 to 5.0 parts of carbon fiber; the component B comprises 40 to 50 parts of aliphatic diisocyanate, 0 to 10 parts of triisocyanate, 35 to 50 parts of polytetrahydrofuran dihydric alcohol, 0.5 to 5 parts of micromolecule dihydric alcohol, 0 to 2 parts of micromolecule trihydric alcohol, and 0.5 to 1.0 part of a light/heat stabilizer. The invention further provides a preparation method and application of the resin. The tangential breaking strength of carbon fiber modified resin coating can reach 130kN/m or above; for non-solvent sports shoe leather prepared through the method, the peeling strength can reach 90N/3 cm or above and the hydrolysis resistance can reach 10 weeks or above.

Description

A kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin and its preparation Methods and applications
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 technology
With the continuous improvement of living standard, people propose to sport shoess comfortableness, aesthetic property and environmental protection performance Higher and higher requirement., mainly using solvent borne polyurethane synthetic leather, its processing mode is by wet method for sports shoe leather in the market Technique and dry process two parts composition, are determined by finished leather processing features, wet method finished leather is processed and dry method bond processing The organic solvent DMF (DMF) being used during operation is difficult to eliminate completely, leads 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 of China to be accomplished by the fabrication process DMF is controlled System, just can meet the standard of outlet European Union.In addition China has also formulated corresponding synthetic leather standard successively.Exploitation more environmental protection Synthetic Leather very urgent.
One of important kind that no-solvent polyurethane sports shoe leather is removed from office as Future movement footwear it is necessary to using physical property, The various aspects of performance such as chemical property and ecological, environmental protective performance all can meet the no-solvent polyurethane tree of sports shoe leather processing request Fat is as premise；Therefore, develop a sports shoe leather extremely urgent with no-solvent polyurethane surface layer resin.
Content 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 should With.No matter from the peel strength closed with cloth base junction, anti-hydrolytic performance, or processing technique angularly for, be satisfied by solvent-free The use requirement of polyurethane sport footwear leather.
The invention provides a kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin, it is by component A and B Component in mass ratio 2:1-1:2 are mixed：
Described component A includes following components and is prepared from by mass fraction：
Described B component includes following components and is prepared from by mass fraction：
Described aliphatic diisocyanate is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12One of) or two or more mixture MDI；Aliphatic three is different Cyanate is HDI trimer；
Described oligomer dihydroxylic alcohols for molecular weight be the PolyTHF dihydroxylic alcohols of 1000-3000, PCDL, One of polycaprolactone diols, polyester diol or two or more mixture；
Described organosilicon polyhydric alcohol is OFX-0930, NiaxL-1160, OHX 4010, in OHX 4081, OFOH702E One or more mixture；
Described small molecule dihydroxylic alcohols be ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, neopentyl glycol, one Diglycol ethylene, 3- methyl isophthalic acid, in double (2- ethoxy) ether of 5- pentanediol, 1,6-HD, 1,4 cyclohexane dimethanol hydroquinone One or more mixture；
Described small molecule trihydroxylic alcohol is one of glycerol, trimethylolpropane or two kinds；
Described 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；
Described light heat stabilizer is UV absorbent, hindered amine light stabilizer；Wherein UV absorbent is UV- 1st, UV-320, UV-1130, UV-P, UV-1164 or UV-234；Hindered amine light stabilizer be 292,622,770,944,5050, 5060 or 5151.
Described antioxidant is antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or anti- One of oxygen agent 3114 or two or more mixture.
Described levelling agent is silicone levelling agent, such as BYK-322, BYK-333, BYK-345, BYK-361N etc.；
Described defoamer is one of BYK-054, TEGO Airex 900, BYK-1790 or two or more mixing Thing；
Described deicer be one of ALT-201, ALT-202, Incozol 2, Zoldine MS-PLus or two kinds with On mixture；
Described carbon fiber is short fibre coiled carbon fibers.
Present invention also offers the preparation method of the solvent-free surface layer polyurethane resin of above-mentioned carbon fiber modifying, this preparation method Comprise the following steps：
(1) preparation of component A：Put into oligomer dihydroxylic alcohols, organosilicon polyhydric alcohol in reactor, be warming up to 100-120 DEG C, be dehydrated 2-4h under the vacuum condition of -0.08MPa～-0.1MPa, after be cooled to 30-40 DEG C, add small molecule dihydroxylic alcohols and fat Fat race isocyanates, maintain and react 2-4h at temperature 75-90 DEG C；Then it is cooled to 30-40 DEG C, sequentially add small molecule ternary Alcohol, catalyst, light heat stabilizer, levelling agent, defoamer, deicer, coiled carbon fibers；It is warming up to 60-80 DEG C of stirring 2-4h Afterwards, detection hydroxyl value and moisture, qualified after can be prepared by component A, pack stand-by；
(2) preparation of B component：Put into aliphatic diisocyanate, aliphatic triisocyanate and light heat stable into kettle Agent, adds oligomer PolyTHF dihydroxylic alcohols, small molecule dihydroxylic alcohols and small molecule trihydroxylic alcohol, and stirs anti-at 80-90 DEG C Answer 2.5-4.5h, detect NCO content, qualified after can be prepared by B component, pack stand-by；
(3) the sports shoe leather preparation of carbon fiber modifying no-solvent polyurethane surface layer resin：By obtained above-mentioned component A With B component in mass ratio 2:1-1:2 are sufficiently mixed, and cast after mix homogeneously is coated in above-mentioned release paper, in 90-130 DEG C dry and can get the solvent-free surface layer polyurethane resin of carbon fiber modifying；
Present invention also offers the application of above-mentioned no-solvent type surface layer polyurethane resin, this resin is used for sports shoe leather In.By obtained component A and B component in mass ratio 2 during use:1-1:2 are sufficiently mixed in one section of 90-130 DEG C of pre-reaction Time, pre-reaction is fitted after terminating screen cloth, continues reaction 5-10min so as to crosslinking curing molding with after 110-150 DEG C；Gu Wind after chemical conversion type and release paper is peeled off, obtain no-solvent type sports shoe leather.
Specifically, compared with prior art, the present invention has following obvious advantage：
(1) the carbon fiber modifying no-solvent polyurethane surface layer resin of present invention preparation makes as the surface layer of sports shoe leather With, and may also function as the effect of bonding, thus eliminate wet method and dry method bonding process link in the finished leather course of processing having simultaneously The use of machine solvent, has been effectively ensured the feature of environmental protection of sports shoe leather；
(2) in the present invention, component A carries out pre-polymerization synthesis by introducing appropriate aliphatic diisocyanate, on the one hand effectively solves Consistency problem between oligomer dihydroxylic alcohols and small molecule polyol in component A of having determined；On the other hand A, B can effectively be adjusted The parameters such as the viscosity between double-component material, molecular weight, thus ensure the stability of A/B material proportioning during production and processing；
(3) component A of the present invention is synthesized by introducing appropriate organosilicon polyhydric alcohol, on the one hand can improve silicone Auxiliary agent and the compatibility of main body polyhydric alcohol；On the other hand double component solvent-free surface layer resin and the difficult stripping of release paper can be solved Problem；
(4) deicer consumes moisture in component A and prevents from reacting generation bubble with B component, and froth breaking 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 adopts carbon fiber modifying aliphatic poly carbon-polyester-polyether-organosilicon copolymerization system, meets fortune While dynamic footwear leather product anti-hydrolytic performance, can be effectively ensured the low temperature of sports shoe leather, high-temperature durable performance and peel strength, The mechanical properties such as tearing strength；Prepared sports shoe leather product peel strength reaches more than 90N/3cm, anti-hydrolytic performance up to 10 Week；
(6), when resin of the present invention is used for sports shoe leather production, has fully ensured that continuous production operation and reactivity, passed through Time processing is plastic, without curing process, effectively shortens the production cycle, reducing energy consumption.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it should be understood that the reality of the present invention Apply the specific material proportion described in example, process conditions and result and be merely to illustrate the present invention, this can not be limited with this The protection domain of invention, equivalence changes or modification that every spirit according to the present invention is done, all should cover at this Within bright protection domain.
Embodiment 1：
A kind of sports shoe leather carbon fiber modifying no-solvent type surface layer polyurethane resin, this resin is by hydroxy component A and different Isocyanate component B forms：
Described component A, in mass fraction ratio, constitutes as follows：
Described B component, in mass fraction ratio, constitutes as follows：
Wherein, described component A and B component in mass ratio 1:1.4 are mixed.
The isophorone diisocyanate that IPDI in component A produces for Bayer A.G, T5652 is Japanese Asahi Chemical Industry The PCDL of the number-average molecular weight 2000 that chemicals Co., Ltd. produces, SP-2013 is that Hefei Amway polyurethane is new The polyester diol of the number-average molecular weight 2000 that Materials Co., Ltd produces, EG, glycerol are commercially available prod, and OFOH702E is advanced in years The hydroxyl value that figure new high-tech material Group Co., Ltd produces is the hydroxy silicon oil of 50mgKOH/g, and MB20 is US Air gasification chemical product The organic bismuth catalyst that company produces, the UV absorbent that Tinuvin 1130 produces for BASF Corp. of Germany, Chisorb 292 light stabilizers producing for Taiwan Double Bond Chemical Ind.,Co.,Ltd., BYK-322 is that German BYK company produces silicone Levelling agent, BYK-054 is that German BYK company produces no-solvent type defoamer, and ALT-201 produces for Ai Lite Chemical Co., Ltd. Oxazole alkanes deicer；
The HDI trimer that N3300 in component B produces for Bayer A.G, Poly THF 2000 is that German BASF is public The polytetrahydrofuran diol of the number-average molecular weight 2000 that department produces, Chinox 1010 is Taiwan Double Bond Chemical Ind.,Co.,Ltd. The antioxidant producing；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin, This preparation method comprises the following steps：
(1) preparation of component A：Poly- carbon dihydroxylic alcohols T5652, polyester diol SP-2013 and organic is put into in reactor Silicon polyhydric alcohol OFX-0930, is warming up to 120 DEG C, is dehydrated 4h under the vacuum condition of -0.08MPa～-0.1MPa, after be cooled to 40 DEG C, add small molecule dihydroxylic alcohols EG and aliphatic diisocyanate IPDI, maintain 90 DEG C of reaction 2h of temperature；Then it is cooled to 40 DEG C, sequentially add small molecule trihydric alcohol glycerin, catalyst MB20, light heat stabilizer T inuvin 1130 and Chisorb 292, Levelling agent BYK-322, defoamer BYK-054, deicer ALT-201, coiled carbon fibers, after being warming up to 60 DEG C of stirring 2h, detection Hydroxyl value and moisture, qualified after can be prepared by component A, pack stand-by；
(2) preparation of B component：Aliphatic diisocyanate IPDI, triisocyanate N3300 and light heat is put into into kettle Stabilizer Chinox 1010, adds PolyTHF dihydroxylic alcohols Poly THF 2000, small molecule dihydroxylic alcohols EG, and at 80 DEG C Stirring reaction 4.5h, detect NCO content, qualified after can be prepared by B component, pack stand-by；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin：By obtained above-mentioned component A With B component in mass ratio 2:1 is sufficiently mixed, and cast after mix homogeneously is coated in release paper, dries at 130 DEG C To no-solvent type sports shoe leather surface layer polyurethane resin；
Present invention also offers the application of surface layer polyurethane resin of above-mentioned carbon fiber modifying no-solvent type sports shoe leather；Make Used time, pre-reaction was fitted after terminating screen cloth, anti-with continuing after 150 DEG C by obtained A, 120 DEG C of pre-reactions of B component for a period of time Should be so as to crosslinking curing molding.Wind after curing molding and release paper is peeled off, 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, this resin is by hydroxy component A and different Isocyanate component B forms：
Described component A, in mass fraction ratio, constitutes as follows：
Described B component, in mass fraction ratio, constitutes as follows：
Wherein, described component A and B component in mass ratio 1:1 is mixed.
H in component A12MDI is the hydrogenation MDI that Yantai Wan Hua company produces, and T5652 is Japanese Asahi Chemical Industry chemicals strain formula The PCDL of the number-average molecular weight 2000 that commercial firm produces, SP-2313 is the limited public affairs of Hefei Amway polyurethane new material The polyester diol of the number-average molecular weight 2000 that department produces, OFX-0930 is 130mgKOH/g for the hydroxyl value that Dow Corning Corporation produces Hydroxy silicon oil, Isosorbide-5-Nitrae-BG and trimethylolpropane TMP are commercially available prod, and BiCAT 8108 is the leading chemical company of the U.S. Organic bismuth catalyst, Chisorb P and Chisorb 944 be respectively Taiwan double bond Chemical Co., Ltd. UV absorbent and Light stabilizer, BYK-345 is that German BYK company produces silicone levelling agent, and BYK-1790 produces no molten for German BYK company Dosage form defoamer, Zoldine MS-PLus is the oxazole alkanes deicer that Angus chemical company of the U.S. produces；
H in component B12MDI is the hydrogenation MDI that Yantai Wan Hua company produces, and TPA-100 is Japanese Asahi Kasei Corporation The HDI trimer producing, the PolyTHF two of the number-average molecular weight 2000 that Poly THF 2000 produces for BASF Corp. of Germany Alcohol, the antioxidant that Chinox 1010 produces for Taiwan Double Bond Chemical Ind.,Co.,Ltd.；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin, This preparation method comprises the following steps：
(1) preparation of component A：Poly- carbon dihydroxylic alcohols T5652, polyester diol SP-2313 and OFX- is put into in reactor 0930, be warming up to 100 DEG C, be dehydrated 2h under the vacuum condition of -0.08MPa～-0.1MPa, after be cooled to 30 DEG C, add small molecule Dihydroxylic alcohols 1,4-BG and diisocyanate H12MDI, maintains 75 DEG C of reaction 4h of temperature；Then it is cooled to 30 DEG C, sequentially add little point Sub- trihydroxylic alcohol TMP, catalyst BiCAT 8108, light heat stabilizer Chisorb P and Chisorb 944, levelling agent BYK-345, Defoamer BYK-1790, deicer Zoldine MS-PLus, coiled carbon fibers, be warming up to 80 DEG C stirring 4h after, detection hydroxyl value and Moisture, qualified after can be prepared by component A, pack stand-by；
(2) preparation of B component：Aliphatic diisocyanate H is put into into kettle12MDI, triisocyanate TPA-100 and light/ Heat stabilizer Chinox 1010, adds PolyTHF dihydroxylic alcohols Poly THF 2000, small molecule dihydroxylic alcohols Isosorbide-5-Nitrae-BG and little Molecule trihydroxylic alcohol TMP, and stirring reaction 2.5h at 90 DEG C, detect NCO content, qualified after can be prepared by B component, pack Stand-by；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin：By obtained above-mentioned component A With B component in mass ratio 1:2 are sufficiently mixed, and cast after mix homogeneously is coated in release paper, dries at 130 DEG C To no-solvent type sports shoe leather surface layer polyurethane resin；
Present invention also offers the application of surface layer polyurethane resin of above-mentioned carbon fiber modifying no-solvent type sports shoe leather；Make Used time, pre-reaction was fitted after terminating screen cloth, anti-with continuing after 150 DEG C by obtained A, 120 DEG C of pre-reactions of B component for a period of time Should be so as to crosslinking curing molding.Wind after curing molding and release paper is peeled off, 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, this resin is by hydroxy component A and different Isocyanate component B forms：
Described component A, in mass fraction ratio, constitutes as follows：
Described B component, in mass fraction ratio, constitutes as follows：
Wherein, described component A and B component in mass ratio 2:1 is mixed.
The isophorone diisocyanate that IPDI in component A produces for Bayer A.G, T5652 is Japanese Asahi Chemical Industry The PCDL of the number-average molecular weight 2000 that chemicals Co., Ltd. produces, SP-2013 is that Hefei Amway polyurethane is new The polyester diol of the number-average molecular weight 2000 that Materials Co., Ltd produces, EG, glycerol are commercially available prod, and OFOH702E is advanced in years The hydroxyl value that figure new high-tech material Group Co., Ltd produces is the hydroxy silicon oil of 50mgKOH/g, and MB20 is US Air gasification chemical product The organic bismuth catalyst that company produces, the UV absorbent that Tinuvin 1130 produces for BASF Corp. of Germany, Chisorb 292 light stabilizers producing for Taiwan Double Bond Chemical Ind.,Co.,Ltd., BYK-322 is that German BYK company produces silicone Levelling agent, BYK-054 is that German BYK company produces no-solvent type defoamer, and ALT-201 produces for Ai Lite Chemical Co., Ltd. Oxazole alkanes deicer；
The HDI trimer that N3300 in component B produces for Bayer A.G, Poly THF 2000 is that German BASF is public The polytetrahydrofuran diol of the number-average molecular weight 2000 that department produces, Chinox 1010 is Taiwan Double Bond Chemical Ind.,Co.,Ltd. The antioxidant producing；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin, This preparation method comprises the following steps：
(1) preparation of component A：Poly- carbon dihydroxylic alcohols T5652, polyester diol SP-2013 and organic is put into in reactor Silicon polyhydric alcohol OFX-0930, is warming up to 120 DEG C, is dehydrated 4h under the vacuum condition of -0.08MPa～-0.1MPa, after be cooled to 40 DEG C, add small molecule dihydroxylic alcohols EG and aliphatic diisocyanate IPDI, maintain 90 DEG C of reaction 2h of temperature；Then it is cooled to 40 DEG C, sequentially add small molecule trihydric alcohol glycerin, catalyst MB20, light heat stabilizer T inuvin 1130 and Chisorb 292, Levelling agent BYK-322, defoamer BYK-054, deicer ALT-201, coiled carbon fibers, after being warming up to 60 DEG C of stirring 2h, detection Hydroxyl value and moisture, qualified after can be prepared by component A, pack stand-by；
(2) preparation of B component：Aliphatic diisocyanate IPDI, triisocyanate N3300 and light heat is put into into kettle Stabilizer Chinox 1010, adds PolyTHF dihydroxylic alcohols Poly THF 2000, small molecule dihydroxylic alcohols EG, and at 80 DEG C Stirring reaction 4.5h, detect NCO content, qualified after can be prepared by B component, pack stand-by；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin：By obtained above-mentioned component A With B component in mass ratio 2:1 is sufficiently mixed, and cast after mix homogeneously is coated in release paper, dries at 130 DEG C To no-solvent type sports shoe leather surface layer polyurethane resin；
Present invention also offers the application of surface layer polyurethane resin of above-mentioned carbon fiber modifying no-solvent type sports shoe leather；Make Used time, pre-reaction was fitted after terminating screen cloth, anti-with continuing after 150 DEG C by obtained A, 120 DEG C of pre-reactions of B component for a period of time Should be so as to crosslinking curing molding.Wind after curing molding and release paper is peeled off, 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, this resin is by hydroxy component A and different Isocyanate component B forms：
Described component A, in mass fraction ratio, constitutes as follows：
Described B component, in mass fraction ratio, constitutes as follows：
Wherein, described component A and B component in mass ratio 1:2 are mixed.
H in component A12MDI is the hydrogenation MDI that Yantai Wan Hua company produces, and T5652 is Japanese Asahi Chemical Industry chemicals strain formula The PCDL of the number-average molecular weight 2000 that commercial firm produces, SP-2313 is the limited public affairs of Hefei Amway polyurethane new material The polyester diol of the number-average molecular weight 2000 that department produces, OFX-0930 is 130mgKOH/g for the hydroxyl value that Dow Corning Corporation produces Hydroxy silicon oil, Isosorbide-5-Nitrae-BG and trimethylolpropane TMP are commercially available prod, and BiCAT 8108 is the leading chemical company of the U.S. Organic bismuth catalyst, Chisorb P and Chisorb 944 be respectively Taiwan double bond Chemical Co., Ltd. UV absorbent and Light stabilizer, BYK-345 is that German BYK company produces silicone levelling agent, and BYK-1790 produces no molten for German BYK company Dosage form defoamer, Zoldine MS-PLus is the oxazole alkanes deicer that Angus chemical company of the U.S. produces；
H in component B12MDI is the hydrogenation MDI that Yantai Wan Hua company produces, and TPA-100 is Japanese Asahi Kasei Corporation The HDI trimer producing, the PolyTHF two of the number-average molecular weight 2000 that Poly THF 2000 produces for BASF Corp. of Germany Alcohol, the antioxidant that Chinox 1010 produces for Taiwan Double Bond Chemical Ind.,Co.,Ltd.；
The present invention also provides the preparation method of above-mentioned carbon fiber modifying no-solvent type sports shoe leather surface layer polyurethane resin, This preparation method comprises the following steps：
(1) preparation of component A：Poly- carbon dihydroxylic alcohols T5652, polyester diol SP-2313 and OFX- is put into in reactor 0930, be warming up to 100 DEG C, be dehydrated 2h under the vacuum condition of -0.08MPa～-0.1MPa, after be cooled to 30 DEG C, add small molecule Dihydroxylic alcohols 1,4-BG and diisocyanate H12MDI, maintains 75 DEG C of reaction 4h of temperature；Then it is cooled to 30 DEG C, sequentially add little point Sub- trihydroxylic alcohol TMP, catalyst BiCAT 8108, light heat stabilizer Chisorb P and Chisorb 944, levelling agent BYK-345, Defoamer BYK-1790, deicer Zoldine MS-PLus, coiled carbon fibers, be warming up to 80 DEG C stirring 4h after, detection hydroxyl value and Moisture, qualified after can be prepared by component A, pack stand-by；
(2) preparation of B component：Aliphatic diisocyanate H is put into into kettle12MDI, triisocyanate TPA-100 and light/ Heat stabilizer Chinox 1010, adds PolyTHF dihydroxylic alcohols Poly THF 2000, small molecule dihydroxylic alcohols Isosorbide-5-Nitrae-BG and little Molecule trihydroxylic alcohol TMP, and stirring reaction 2.5h at 90 DEG C, detect NCO content, qualified after can be prepared by B component, pack Stand-by；
(3) preparation of carbon fiber modifying no-solvent polyurethane sports shoe leather surface layer resin：By obtained above-mentioned component A With B component in mass ratio 1:2 are sufficiently mixed, and cast after mix homogeneously is coated in release paper, dries at 130 DEG C To no-solvent type sports shoe leather surface layer polyurethane resin；
Present invention also offers the application of surface layer polyurethane resin of above-mentioned carbon fiber modifying no-solvent type sports shoe leather；Make Used time, pre-reaction was fitted after terminating screen cloth, anti-with continuing after 150 DEG C by obtained A, 120 DEG C of pre-reactions of B component for a period of time Should be so as to crosslinking curing molding.Wind after curing molding and release paper is peeled off, obtain no-solvent type sports shoe leather.
Comparative example
Remove coiled carbon fibers on the basis of embodiment 1, specific as follows：
A kind of sports shoe leather no-solvent type surface layer polyurethane resin, this resin is by hydroxy component A and isocyanate component B Composition：
Described component A, in mass fraction ratio, constitutes as follows：
Described B component, in mass fraction ratio, constitutes as follows：
Wherein, described component A and B component in mass ratio 1:1.25 being mixed.
The isophorone diisocyanate that IPDI in component A produces for Bayer A.G, T5652 is Japanese Asahi Chemical Industry The PCDL of the number-average molecular weight 2000 that chemicals Co., Ltd. produces, SP-2013 is that Hefei Amway polyurethane is new The polyester diol of the number-average molecular weight 2000 that Materials Co., Ltd produces, EG, glycerol are commercially available prod, and OFOH702E is advanced in years The hydroxyl value that figure new high-tech material Group Co., Ltd produces is the hydroxy silicon oil of 50mgKOH/g, and MB20 is US Air gasification chemical product The organic bismuth catalyst that company produces, the UV absorbent that Tinuvin 1130 produces for BASF Corp. of Germany, Chisorb 292 light stabilizers producing for Taiwan Double Bond Chemical Ind.,Co.,Ltd., BYK-322 is that German BYK company produces silicone Levelling agent, BYK-054 is that German BYK company produces no-solvent type defoamer, and ALT-201 produces for Ai Lite Chemical Co., Ltd. Oxazole alkanes deicer；
The HDI trimer that N3300 in component B produces for Bayer A.G, Poly THF 2000 is that German BASF is public The polytetrahydrofuran diol of the number-average molecular weight 2000 that department produces, Chinox 1010 is Taiwan Double Bond Chemical Ind.,Co.,Ltd. The antioxidant producing；
The present invention also provides the preparation method of above-mentioned no-solvent type sports shoe leather surface layer polyurethane resin, this preparation method Comprise the following steps：
(1) preparation of component A：Poly- carbon dihydroxylic alcohols T5652, polyester diol SP-2013 and organic is put into in reactor Silicon polyhydric alcohol OFX-0930, is warming up to 120 DEG C, is dehydrated 4h under the vacuum condition of -0.08MPa～-0.1MPa, after be cooled to 40 DEG C, add small molecule dihydroxylic alcohols EG and aliphatic diisocyanate IPDI, maintain 90 DEG C of reaction 2h of temperature；Then it is cooled to 40 DEG C, sequentially add small molecule trihydric alcohol glycerin, catalyst MB20, light heat stabilizer T inuvin 1130 and Chisorb 292, Levelling agent BYK-322, defoamer BYK-054, deicer ALT-201, after being warming up to 60 DEG C of stirring 2h, detection hydroxyl value and moisture contain Amount, qualified after can be prepared by component A, pack stand-by；
(2) preparation of B component：Aliphatic diisocyanate IPDI, triisocyanate N3300 and light heat is put into into kettle Stabilizer Chinox 1010, adds PolyTHF dihydroxylic alcohols Poly THF 2000, small molecule dihydroxylic alcohols EG, and at 80 DEG C Stirring reaction 4.5h, detect NCO content, qualified after can be prepared by B component, pack 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 cast after mix homogeneously is coated in release paper, can get solvent-free in 130 DEG C of drying Type sports shoe leather surface layer polyurethane resin；
Present invention also offers the application of surface layer polyurethane resin of above-mentioned no-solvent type sports shoe leather；Will be made during use A, 120 DEG C of pre-reactions of B component for a period of time, pre-reaction terminate after fit screen cloth, with after 150 DEG C continue reaction so as to hand over Connection curing molding.Wind after curing molding and release paper is peeled off, obtain no-solvent type sports shoe leather.
The no-solvent type polyurethane sport footwear leather of obtained carbon fiber modifying in above-described embodiment and comparative example are obtained Sports shoe leather carry out peel strength (GB/T 8949) and anti-hydrolytic performance (jungle test) test (QB/T4671), specifically count According to following table：
Embodiment 1-4 performance can meet sports shoe leather and use, and do not have the potentiation of coiled carbon fibers, just in comparative example Beginning peel strength deviation is just up to standard, peels off and can not meet use after jungle test in ten weeks.
The above embodiment is only that the preferred embodiment of the present invention is described, the not model to the present invention Enclose and be defined, on the premise of without departing from design spirit of the present invention, the technical side to the present invention for the those of ordinary skill in the art Various modifications and improvement that case is made, all should fall in the protection domain of claims of the present invention determination.

Claims (10)

1. a kind of sports shoe leather with carbon fiber modifying no-solvent polyurethane surface layer resin it is characterised in that by component A and B component In mass ratio 2:1-1:2 are mixed：
Described component A includes following components and is prepared from by mass fraction：
Described B component includes following components and is prepared from by mass fraction：
2. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, its feature It is：Described aliphatic diisocyanate is isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '-two hexamethylenes One of dicyclohexylmethane diisocyanate or two or more mixture；Described aliphatic triisocyanate is that hexa-methylene two is different Cyanate trimer.
3. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, its feature It is：Described oligomer dihydroxylic alcohols for molecular weight be the PolyTHF dihydroxylic alcohols of 1000-3000, PCDL, poly- One of caprolactone dihydroxylic alcohols, polyester diol or two or more mixture；
Described organosilicon polyhydric alcohol is OFX-0930, NiaxL-1160, OHX 4010, one of OHX 4081, OFOH702E Or two or more mixture；
Described small molecule dihydroxylic alcohols be ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, neopentyl glycol, one contracting two Ethylene glycol, 3- methyl isophthalic acid, in double (2- ethoxy) ether of 5- pentanediol, 1,6-HD, 1,4 cyclohexane dimethanol hydroquinone Plant or two or more mixture；
Described small molecule trihydroxylic alcohol is one of glycerol, trimethylolpropane or two kinds.
4. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, its feature It is：Described catalyst be BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228, Borchi Kat 22, At least one in Borchi Kat 24, BiCAT 4130, BiCAT 4232, the delaying type catalyst of MB20.
5. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, its feature It is：Described light heat stabilizer is UV absorbent, hindered amine light stabilizer；Wherein UV absorbent 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, its feature It is：Described antioxidant is antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or antioxygen One of agent 3114 or two or more mixture.
7. a kind of sports shoe leather according to claim 1 carbon fiber modifying no-solvent polyurethane surface layer resin, its feature It is：Described levelling agent is silicone levelling agent.
Described defoamer is one of BYK-054, TEGO Airex 900, BYK-1790 or two or more mixture；
Described deicer is one of ALT-201, ALT-202, Incozol 2, Zoldine MS-PLus or two or more Mixture；
Described carbon fiber is short fibre coiled carbon fibers.
8. a kind of sports shoe leather according to claim 7 carbon fiber modifying no-solvent polyurethane surface layer resin, its feature It is：Described levelling agent is BYK-322, BYK-333, BYK-345 or BYK-361N.
9. a kind of sports shoe leather carbon fiber modifying no-solvent polyurethane surface layer resin described in preparation any one of claim 1-8 Method it is characterised in that this preparation method comprises the following steps：
(1) preparation of component A：To in reactor put into oligomer dihydroxylic alcohols, organosilicon polyhydric alcohol, be warming up to 100-120 DEG C ,- Be dehydrated 2-4h under the vacuum condition of 0.08MPa～-0.1MPa, after be cooled to 30-40 DEG C, add small molecule dihydroxylic alcohols and aliphatic Isocyanates, maintain and react 2-4h at temperature 75-90 DEG C；Then it is cooled to 30-40 DEG C, sequentially add small molecule trihydroxylic alcohol, urge Agent, light heat stabilizer, levelling agent, defoamer, deicer, carbon fiber；After being warming up to 60-80 DEG C of stirring 2-4h, detect hydroxyl value And moisture, qualified after can be prepared by component A, pack stand-by；
(2) preparation of B component：Put into aliphatic diisocyanate, aliphatic triisocyanate and light heat stabilizer into kettle, Add PolyTHF dihydroxylic alcohols, small molecule dihydroxylic alcohols and small molecule trihydroxylic alcohol, and stirring reaction 2.5- at 80-90 DEG C 4.5h, detect NCO content, qualified after can be prepared by B component, pack stand-by；
(3) the sports shoe leather preparation of carbon fiber modifying no-solvent polyurethane surface layer resin：By obtained above-mentioned component A and B Component in mass ratio 2:1-1:2 are sufficiently mixed, and cast after mix homogeneously is coated in release paper, in 90-130 DEG C of drying is Can get the solvent-free surface layer polyurethane resin of carbon fiber modifying.
10. the carbon fiber modifying no-solvent polyurethane surface layer resin of a kind of sports shoe leather described in any one of claim 1-8 Application it is characterised in that：By obtained component A and B component in mass ratio 2:1-1:2 be sufficiently mixed pre- anti-at 90-130 DEG C Should a period of time, pre-reaction terminate after fit screen cloth, with after 110-150 DEG C continue reaction 5-10min so as to crosslinking curing become Type；Wind after curing molding and release paper is peeled off, obtain no-solvent type sports shoe leather.
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