CN109627409A - A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method - Google Patents
A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method Download PDFInfo
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- CN109627409A CN109627409A CN201811566688.4A CN201811566688A CN109627409A CN 109627409 A CN109627409 A CN 109627409A CN 201811566688 A CN201811566688 A CN 201811566688A CN 109627409 A CN109627409 A CN 109627409A
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- Prior art keywords
- aqueous polyurethane
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- added
- dumb light
- polyurethane
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 92
- 239000004814 polyurethane Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 26
- 229920001971 elastomer Polymers 0.000 claims abstract description 26
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 26
- 239000000806 elastomer Substances 0.000 claims abstract description 25
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000004359 castor oil Substances 0.000 claims abstract description 14
- 235000019438 castor oil Nutrition 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960004194 lidocaine Drugs 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 26
- 238000011017 operating method Methods 0.000 claims description 17
- 238000009736 wetting Methods 0.000 claims description 13
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 6
- -1 neutralizer Substances 0.000 abstract description 6
- KQIGMPWTAHJUMN-UHFFFAOYSA-N 3-aminopropane-1,2-diol Chemical compound NCC(O)CO KQIGMPWTAHJUMN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002649 leather substitute Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 1
- XGIKILRODBEJIL-UHFFFAOYSA-N 1-(ethylamino)ethanol Chemical compound CCNC(C)O XGIKILRODBEJIL-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to the technical fields of high molecular material, more particularly to a kind of aqueous polyurethane, including the following raw material: polynary amino alcohol, isocyanic acid, thermoplastic polyurethane elastomer, chain extender, neutralizer, deionized water and hydrazine hydrate, polynary amino alcohol is diethylaminoethanol, 3- amino -1,2- propylene glycol or 3- lignocaine -1- propyl alcohol, the dosage of neutralizer is that the pH of control mixed liquor is 7.5-9, has the advantages that wear-resisting, water resistance is good and wellability is good;The aqueous polyurethane that castor oil is added is additionally provided, the wellability of aqueous polyurethane is further improved;Additionally provide the preparation method of dumb light aqueous polyurethane after two kinds of aqueous polyurethanes to be added to flatting silicas and preparation method thereof and two kinds of aqueous polyurethanes, the dumb light aqueous polyurethane made, while improving leather surface gloss, delustering agent can be made not to be stripped out from film, extend the effective acting time of flatting silica.
Description
Technical field
The present invention relates to the technical fields of high molecular material, and in particular to a kind of aqueous polyurethane, dumb light aqueous polyurethane
And preparation method.
Background technique
A large amount of leathers are used in automobile, luggage and shoe-making field, to improve leather surface aesthetics, corrosion resistance and wear-resisting
Performance often uses coating and carries out top finishing.
Synthetic Leather is the most promising natural leather substitute after artificial polyvinyl chloride leather.Synthetic Leather
It compensates for artificial polyvinyl chloride leather and substrate adhesive fastness is poor, be easy to peel off, the disadvantages of feel is stiff has gloss naturally soft
With, adhesive property is good, it is wear-resistant the advantages that.
Existing low gloss leather finishing agent mostly uses greatly waterborne polyurethane resin, and aqueous polyurethane is a kind of plastic particle
Evenly dispersed thinlyfluid in water forms the sequential like being evenly distributed by fusion between polymer particles and applies when in use
Film;When film forming, show especially with the volatilization of solvent, the thinning silica dioxide granule for shrinking, being suspended in resin of film in film item
Layer forms a micro-roughened surface, which can make incident light, thus obtain low gloss effect with
Soft sense of touch.But it is monomer that current aqueous polyurethane, which mostly uses polyether polyol, water resistance is poor with wearability;And its
Wellability is poor, although can obtain low gloss effect by the delustering agent for adding such as silica etc, with pushing away for time
It moves, these duller particles are easy to be stripped out from film, thus bring to the weatherability of film and ultraviolet-resistant performance
Negative effect.
Summary of the invention
In view of the deficienciess of the prior art, the first purpose of this invention is that providing one kind has wear-resisting, water resistance
The good aqueous polyurethane of energy.
The first purpose of this invention is achieved through the following technical solutions:
A kind of aqueous polyurethane, the raw material including following parts by weight: polynary amino alcohol 40-60 parts, 35-55 parts of isocyanic acid, thermoplastic
15-30 parts of polyurethane elastomer of property, 8-15 parts of chain extender, neutralizer, 5-15 parts of deionized water and 1-3 parts of hydrazine hydrate are described more
First amino alcohol is diethylaminoethanol, 3- amino -1,2-PD or 3- lignocaine -1- propyl alcohol, the dosage of the neutralizer
It is 7.5-9 to control the pH of mixed liquor.
By using above-mentioned technical proposal, diethylaminoethanol (English name Diethylaminoethanol) also known as 2-
(diethylin) ethyl alcohol [2- (diethylamino)-Ethano1].It is colourless liquid under room temperature, has ammonia taste, there is hygroscopicity.It is main
To be used as sour gas in medicine intermediate, softening agent, emulsifier, curing agent etc. and organic synthesis raw material and natural gas
Scavenger.3- amino -1,2-PD (3-Amino-1,2-propanediol) is used as emulsifier, organic intermediate.3- bis-
Ethylamino -1- propyl alcohol, nickname N, N- diethylpropanolamine, 3- diethyl amino -1- propyl alcohol, 3- (lignocaine) -1- propyl alcohol are colourless
To yellow liquid.Hydrazine hydrate is also known as hydrazine hydrate, is a kind of important fine chemical material.Thermoplastic polyurethane elastomer is also known as
Thermoplastic polyurethane rubber, with the comprehensive performance that high intensity, high tenacity, wear-resisting, oil resistant etc. are excellent, processing performance is good.Pass through
Polynary amino alcohol and isocyanate reaction obtain polyurethane, compared to using polyether polyol as the polyurethane of monomer, water resistance with
Wear-resisting property is greatly improved.And the introducing of hydrazine hydrate, by the polymer of polynary amino alcohol and isocyanate reaction with
High-intensitive, high tenacity and the crosslinking of the thermoplastic polyurethane elastomer of wear-resisting property mix, and have the two by chemical bond
Machine combines, and further improves the wear-resisting property of aqueous polyurethane.
Preferably, the chain extender is 1-4- butanediol or 2,2- dihydromethyl propionic acid.
By using above-mentioned technical proposal, chain extender is also known as chain extender, and being can be with the functional group on linear polymer chain
The substance for reacting and increasing strand extension, molecular weight.It is usually used in improving the mechanical property and work of the products such as polyurethane, polyester
Skill performance.2,2- dihydromethyl propionic acids are both chain extender in aqueous polyurethane manufacture and make polyurethane obtained from emulsibility
Can, it can be made into the self-emulsifying aqueous polyurethane of excellent in stability.
Second object of the present invention is to provide a kind of preparation method of the aqueous polyurethane of first goal of the invention, packet
Include following operating procedure:
Isocyanic acid is added after polynary amino alcohol is carried out vacuum dehydration processing, at 75-85 DEG C, reacts 1-3h;Chain extender is added,
At 80-90 DEG C, 2-4h is reacted;Add neutralizer at salt, deionized water and hydrazine hydrate is added, is dispersed with the revolving speed of 2000r/min
3-5min is stirred, later at 20-50 DEG C, reacts 30-40min;It is down to 20-25 DEG C, stirs 40-60min, stands 30-
48h obtains aqueous polyurethane.
Third object of the present invention is to provide a kind of wearability and the high aqueous polyurethane of wetting property.
Third object of the present invention is achieved through the following technical solutions:
A kind of aqueous polyurethane, the raw material including each parts by weight in first goal of the invention further include 5-15 parts of castor oil.
By using above-mentioned technical proposal, castor oil is the polyol compound of natural reproducible, longer non-in component
Polarity aliphatic chain has good hydrophobic effect, can further improve the water resistance and flexibility of water-base polyurethane material.And
And it further can make aqueous polyurethane preferably spread in substrate surface, to further increase the infiltration of aqueous polyurethane
Property, to improve the wear-resisting property of film.
Fourth object of the present invention is to provide a kind of preparation method of the aqueous polyurethane of third goal of the invention, wrap
Include following operating procedure:
Isocyanic acid and castor oil is added after polynary amino alcohol is carried out vacuum dehydration processing, at 80-85 DEG C, reacts 1-3h;Add
Enter chain extender, at 80-90 DEG C, reacts 2-4h: neutralizer being added to be neutralized into salt, deionized water and hydrazine hydrate is added, with 2000r/
The revolving speed dispersion stirring 3-5min of min reacts 30-40min later at 20-50 DEG C;It is down to 20-25 DEG C, stirs 40-
60min stands 30-48h, obtains aqueous polyurethane.
Fifth object of the present invention is to provide a kind of dumb light aqueous polyurethanes, for that can make leather in leather paint
The softer beauty of the gloss on surface, and cooperate the aqueous polyurethane in the present invention, remove delustering agent will not from film
Out.
5th purpose of the invention is realized by following technical solution:
A kind of dumb light aqueous polyurethane, the raw material including following parts by weight: first or third goal of the invention aqueous polyurethane
85-95 parts, 20-40 parts of deionized water, 1-3 parts of flatting silica, 5-10 parts of thermoplastic polyurethane elastomer, 0.1-1 parts of levelling agent, profit
0.1-1 parts of hygroscopic water powder, 0.1-1 parts of defoaming agent and 0.5-1.5 parts of thickener.
It is good with the high-wearing feature, high waterproofness and wetting property prepared in the present invention by using above-mentioned technical proposal
Aqueous polyurethane, flatting silica and auxiliary agent in addition, to obtain the leather finishing agent with photoextinction;Due to the present invention
Aqueous polyurethane wetting property it is good, duller particle can be very good infiltration in finally obtained film, to be not easy
It is stripped out from film, to realize the delustring treatment effect to leather products surface long term.
Preferably, the flatting silica is the silica that partial size is 5-10 μm.
By using above-mentioned technical proposal, the fineness of silica is controlled, improves its square dispersing uniformity in film, from
And further avoid it and detached from film, improve the delustring stability of dumb light aqueous polyurethane.
Of the invention the 6th is designed to provide a kind of preparation side of the dumb light aqueous polyurethane of 5th goal of the invention
Method, including following operating procedure: the aqueous polyurethane in first or third goal of the invention, deionized water are sufficiently mixed
It is even, flatting silica is added and stirs 25-35min, thermoplastic polyurethane elastomer is added and stirs 25-35min, levelling agent, wetting is added
Dispersing agent stirs 15-20min, and defoaming agent is added and thickener stirs 5-15min, obtains dumb light aqueous polyurethane.
In conclusion the invention has the following beneficial effects:
(1) polymer for obtaining polynary amino alcohol and isocyanate reaction, cooperation hydrazine hydrate and high-intensitive, high tenacity and wearability
The thermoplastic polyurethane elastomer crosslinking of energy mixes, and the polymer and thermoplastic polyurethane elastomer is made to pass through chemical bond
It organically combines, while improving the wetting property of aqueous polyurethane, further improves the wear-resisting property of aqueous polyurethane;
(2) by the way that the polyol compound castor oil of natural reproducible is added, obtained it is a kind of have better water resistance and
Flexible water-base polyurethane material;The material can make aqueous polyurethane preferably spread in substrate surface, to further mention
The wellability of high aqueous polyurethane;
(3) by the way that two kinds of above-mentioned aqueous polyurethanes are added upper flatting silica and auxiliary agent, obtain having the leather of photoextinction to apply
Agent is adornd, since the wetting property of two kinds of aqueous polyurethanes is good, duller particle can be very good infiltration in finally obtained painting
In film, to be not easy to be stripped out from film, to realize the delustring treatment effect to leather products surface long term.
Specific embodiment
Each raw material and chemical reagent used in the present invention are commercial product.Wherein thermoplastic polyurethane elastomer is selected
Polyester-type spherical particle.Wetting dispersing agent is nonionic surface active agent, and nonionic surface active agent, which can improve, to be helped
Agent dispersion performance, the present invention in wetting dispersing agent select Air Prod & Chem, the U.S. the trade mark be Surfynol 104 table
Face activating agent.Defoaming agent selects silicone emulsion, and thickener selects hydroxypropyl methyl cellulose.
Embodiment 1
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, be heated under vacuum conditions 110 DEG C be carried out dehydrating 1.5h (dehydration for this
The conventional technical means in field), isocyanic acid 35g is then added, at 75 DEG C, reacts 1h, obtains mixed liquor A;
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 80 DEG C, reacts 2h, obtains
To the mixed liquid B of polymerization reaction;
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 7.5, and deionized water 5g, hydrazine hydrate is added
1g, and be dispersed with stirring under the mixing speed of 2000r/min, emulsify 3min, then at 20 DEG C, 30min is reacted, is mixed
Liquid C;
(4) by mixed liquor C at 20 DEG C, the mixing speed of 2400r/min stirs 40min, stands 30h and is hardened, obtains water
Property polyurethane.
Embodiment 2
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, it is heated to 110 DEG C under vacuum conditions and is carried out dehydrating 2h (dehydration is ability
The conventional technical means in domain), isocyanic acid 35g is then added, at 80 DEG C, reacts 2h, obtains mixed liquor A;
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 85 DEG C, reacts 3h, obtains
To mixed liquid B;
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 8.5, and deionized water 5g, hydrazine hydrate is added
1g, and the stirring and emulsifying 5min under the mixing speed of 2000r/min react 40min, obtain mixed liquor C then at 35 DEG C;
(4) by mixed liquor C at 25 DEG C, the mixing speed of 4000r/min stirs 50min, stands 48h, obtains aqueous poly- ammonia
Ester.
Embodiment 3
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, be heated under vacuum conditions 110 DEG C be carried out dehydrating 1.5h (dehydration for this
The conventional technical means in field), isocyanic acid 35g is then added, at 85 DEG C, reacts 3h, obtains mixed liquor A;
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 90 DEG C, reacts 4h, obtains
To mixed liquid B;
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 9, and deionized water 5g, hydrazine hydrate is added
1g, and the stirring and emulsifying 4min under the mixing speed of 2000r/min react 30min, obtain mixed liquor C then at 50 DEG C;
(4) by mixed liquor C at 25 DEG C, the mixing speed of 5000r/min stirs 60min, stands 48h, obtains aqueous poly- ammonia
Ester.
Embodiment 4
Embodiment 4 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: 3-
Amino -1,2-PD 50g, isocyanic acid 40g, thermoplastic polyurethane elastomer 25g, 2,2- dihydromethyl propionic acid 10g, deionization
Water 10g and hydrazine hydrate 2g.
Embodiment 5
Embodiment 5 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: 3-
Lignocaine -1- propyl alcohol 55g, isocyanic acid 45g, thermoplastic polyurethane elastomer 20g, methyl pyrrolidone 12g, deionized water
13g and hydrazine hydrate 2.5g.
Embodiment 6
Embodiment 6 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: two
Ethylaminoethanol 45g, isocyanic acid 50g, thermoplastic polyurethane elastomer 25g, methyl pyrrolidone 15g, deionized water 15g and water
Close hydrazine 3g.
Embodiment 7
Embodiment 7 is identical as the operating procedure of embodiment 1, and difference is only that, in step (1), while isocyanic acid is added, adds
Enter 5g castor oil, at 80 DEG C, reacts 1h, obtain mixed liquor A;Remaining is same as Example 1.
Embodiment 8
Embodiment 8 is identical as the operating procedure of embodiment 2, and difference is only that, in step (1), while isocyanic acid is added, adds
Enter 5g castor oil, remaining is same as Example 2.
Embodiment 9
Embodiment 9 is identical as the operating procedure of embodiment 3, and difference is only that, in step (1), while isocyanic acid is added, adds
Enter 5g castor oil, remaining is same as Example 3.
Embodiment 10
Embodiment 10 is identical as the operating procedure of embodiment 4, and difference is only that, in step (1), while isocyanic acid is added,
8g castor oil is added, remaining is same as Example 4.
Embodiment 11
Embodiment 11 is identical as the operating procedure of embodiment 5, and difference is only that, in step (1), while isocyanic acid is added,
12g castor oil is added, remaining is same as Example 5.
Embodiment 12
Embodiment 12 is identical as the operating procedure of embodiment 6, and difference is only that, in step (1), while isocyanic acid is added,
15g castor oil is added, remaining is same as Example 6.
Embodiment 13
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared
85g, deionized water 20g are sufficiently mixed uniformly, and the 1g silica that partial size is 5-10 μm, the revolving speed stirring of 1000r/min is added
Thermoplastic polyurethane elastomer 5g is added in 25min, stirs 25min, and carboxymethyl cellulose 0.1g, wetting dispersing agent 0.1g is added,
15min is stirred, defoaming agent 0.1g and thickener 0.5g is added, 5min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 14
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared
90g, deionized water 30g are sufficiently mixed uniformly, and the 2g silica that partial size is 5-10 μm, the revolving speed stirring of 1300r/min is added
Thermoplastic polyurethane elastomer 8g is added in 30min, stirs 30min, and carboxymethyl cellulose 0.5g, wetting dispersing agent 0.5g is added,
15min is stirred, defoaming agent 0.5g and thickener 1g is added, 10min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 15
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared
95g, deionized water 40g are sufficiently mixed uniformly, and the 3g silica that partial size is 5-10 μm, the revolving speed stirring of 1500r/min is added
Thermoplastic polyurethane elastomer 10g is added in 35min, stirs 35min, and carboxymethyl cellulose 1g, wetting dispersing agent 1g is added, stirs
20min is mixed, defoaming agent 1g and thickener 1.5g is added, 15min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 16
Embodiment 16 and the difference of embodiment 13 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation
Example 13 is identical.
Embodiment 17
Embodiment 17 and the difference of embodiment 14 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation
Example 14 is identical.
Embodiment 18
Embodiment 18 and the difference of embodiment 15 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation
Example 15 is identical.
Comparative example 1
Comparative example 1 and the difference of embodiment 5 are do not have thermoplastic polyurethane elastomer in the raw material in comparative example 1, remaining with
Embodiment 5 is identical.
Comparative example 2
Comparative example 2 and the difference of embodiment 5 are do not have hydrazine hydrate in the raw material in comparative example 2, remaining is same as Example 5.
Comparative example 3
Comparative example 3 and the difference of embodiment 5 are do not have polynary amino alcohol and isocyanic acid in the raw material in comparative example 3, also without
The operation step of the two, remaining is same as Example 5.
Comparative example 4
Comparative example 4 and the difference of embodiment 17 are do not have thermoplastic polyurethane elastomer in the raw material in comparative example 4, remaining
It is identical as embodiment 17.
Performance test
According to following test method to embodiment 1-18, comparative example the 1-4 aqueous polyurethane prepared or dumb light aqueous polyurethane into
Row test, test result are shown in Tables 1 and 2.Wherein blank group is the sample without smearing any leather finishing agent.
Film rub resistance: according to GB/T8949-2008 " polyurethane dry method artificial leather " in Scott type rubbing test machine
Upper measurement.Experimental method is as follows: unidirectional 2 pieces of sample cloth covers being overlapped, being then charged into grip separation is 30mm's
In rubbing test machine clamp.The distance for gradually reducing fixture applies load, spacing contracting after contacting the cloth cover of 2 pieces of samples gently
It is small to load be 1kg until.It is 120 times/min in frequency, under conditions of stroke 50mm, reciprocal 1000 times, observes artificial leather table
Face whether there is or not glossiness variation, crackle, damage or Bu Ji and apply UF membrane phenomena such as.If there is having above-mentioned phenomenon on 1 piece of sample, then
The rub resistance for sentencing the sample is unqualified.Experimental sample is in (23 ± 2) DEG C, the standard environment and one of relative humidity (50 ± 10) %
As carry out the sample status adjustment of no less than 4h in deviation range, and tested with this condition.
Film wearability: carrying out according to QB/T2537-2001 " leather color fastness test reciprocating friction color fastness ", this mark
Standard is equal to ISO11640.The wear-resisting property of film is with leather surface colour fastness test tester to the resistance to dry of each finished leather film
Wet rubbing is tested, and then determines its grade by regulation with gray scale.Experiment condition is 20 DEG C of temperature, relative humidity 80%,
Measuring head gross mass is 1000g, and xerotripsis number is 50 times, and wet rubbing number is 200 times.
Water-resistance property of coating: materialsing 2 pieces, is put into the water that temperature is 25 DEG C, and water all submerges sample, if sample floating is difficult
Then apply external force with submergence to guarantee in sample immersion water.Observe variation of the sample in 72h.
Apply it is film modified after leather glossiness: with the daylight light irradiation specimen surface of 30W, observe gloss.
The performance test results of each aqueous polyurethane of table 1
The performance test results of each dumb light aqueous polyurethane of table 2
By Tables 1 and 2 it is found that aqueous polyurethane prepared by the present invention and dumb light aqueous polyurethane all have good wearability
And water resistance, and rub resistance can be strong, it, can be right using the aqueous polyurethane and dumb light aqueous polyurethane in the present invention
Leather and fur products plays preferable protective effect, and the raising of wear-resisting property can further improve the defect that flatting silica is easily detached from.
And the wear-resisting property for being added to the aqueous polyurethane of castor oil is better than un-added.By comparative example 1-3 in table 1 it is found that
Thermoplastic polyurethane elastomer, hydrazine hydrate, polynary amino alcohol and isocyanic acid have water resistance, wear-resisting property very big in the present invention
Influence;Lack three's any component, then will lead to it is water-fast, wear-resisting property substantially reduce or even effect is equal to blank group,
Prove that thermoplastic polyurethane elastomer in the present invention, hydrazine hydrate, polynary amino alcohol and isocyanic acid mutual cooperation play synergistic effect,
Improve the wear-resisting and water resistance of aqueous polyurethane of the present invention.As shown in Table 2, the delustring of dumb light aqueous polyurethane of the invention
Effect is obvious, can effectively improve the appearance and gloss of product using leather and fur products.By comparative example 4 in table 2 it is found that the present invention
Thermoplastic polyurethane elastomer in dumb light aqueous polyurethane has the wear-resisting and waterproof performance of dumb light aqueous polyurethane very big just
To effect.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology
Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as
All by the protection of Patent Law in scope of the presently claimed invention.
Claims (8)
1. a kind of aqueous polyurethane, which is characterized in that the raw material including following parts by weight: polynary amino alcohol 40-60 parts, isocyanic acid
35-55 parts, 15-30 parts of thermoplastic polyurethane elastomer, 8-15 parts of chain extender, neutralizer, 5-15 parts of deionized water and hydrazine hydrate
1-3 parts, the polynary amino alcohol be diethylaminoethanol, 3- amino -1,2-PD or 3- lignocaine -1- propyl alcohol, it is described
The dosage of neutralizer is that the pH of control mixed liquor is 7.5-9.
2. aqueous polyurethane according to claim 1, it is characterised in that: the chain extender is 1-4- butanediol or 2,2- bis-
Hydroxymethyl propionic acid.
3. a kind of preparation method of aqueous polyurethane of any of claims 1 or 2, which is characterized in that including following operating procedure:
Isocyanic acid is added after polynary amino alcohol is carried out vacuum dehydration processing, at 75-85 DEG C, reacts 1-3h;Chain extender is added,
At 80-90 DEG C, 2-4h is reacted;Add neutralizer at salt, deionized water and hydrazine hydrate is added, is dispersed with the revolving speed of 2000r/min
3-5min is stirred, later at 20-50 DEG C, reacts 30-40min;It is down to 20-25 DEG C, stirs 40-60min, stands 30-
48h obtains aqueous polyurethane.
4. aqueous polyurethane according to claim 1, it is characterised in that: further include 5-15 parts of castor oil.
5. a kind of preparation method of aqueous polyurethane as claimed in claim 4, which is characterized in that including following operating procedure:
Isocyanic acid and castor oil is added after polynary amino alcohol is carried out vacuum dehydration processing, at 80-85 DEG C, reacts 1-3h;Add
Enter chain extender, at 80-90 DEG C, reacts 2-4h;Add neutralizer to be neutralized into salt, deionized water and hydrazine hydrate is added, with 2000r/
The revolving speed dispersion stirring 3-5min of min reacts 30-40min later at 20-50 DEG C;It is down to 20-25 DEG C, stirs 40-
60min stands 30-48h, obtains aqueous polyurethane.
6. a kind of dumb light aqueous polyurethane, which is characterized in that the raw material including following parts by weight: claim 1 or 4 it is aqueous poly-
85-95 parts of urethane, 20-40 parts of deionized water, 1-3 parts of flatting silica, 5-10 parts of thermoplastic polyurethane elastomer, levelling agent 0.1-1
Part, 0.1-1 parts of wetting dispersing agent, 0.1-1 parts of defoaming agent and 0.5-1.5 parts of thickener.
7. dumb light aqueous polyurethane according to claim 6, it is characterised in that: the flatting silica is that partial size is 5-10 μm
Silica.
8. a kind of preparation method of dumb light aqueous polyurethane as claimed in claim 6, which is characterized in that including operating step as follows
It is rapid: the aqueous polyurethane of claim 1 or 4, deionized water being sufficiently mixed uniformly, flatting silica is added and stirs 25-35min, adds
Enter thermoplastic polyurethane elastomer stirring 25-35min, levelling agent is added, wetting dispersing agent stirs 15-20min, addition defoaming agent
5-15min is stirred with thickener, obtains dumb light aqueous polyurethane.
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Application publication date: 20190416 |