CN105482678A - Modified waterborne polyurethane wood lacquer with excellent water-resistant performance - Google Patents
Modified waterborne polyurethane wood lacquer with excellent water-resistant performance Download PDFInfo
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- CN105482678A CN105482678A CN201511024505.2A CN201511024505A CN105482678A CN 105482678 A CN105482678 A CN 105482678A CN 201511024505 A CN201511024505 A CN 201511024505A CN 105482678 A CN105482678 A CN 105482678A
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- 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
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- C09D175/08—Polyurethanes from polyethers
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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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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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
- C08G18/48—Polyethers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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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
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- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a modified waterborne polyurethane wood lacquer with excellent water-resistant performance. The modified waterborne polyurethane wood lacquer with the excellent water-resistant performance is prepared from modified waterborne polyurethane, poly-glycol, diglycol, polyether polyol, polytetramethylene ether glycol, methyl methacrylate, ethidene diamine, asbestos, propylene glycol, aminosilane, trimethylolpropane, aluminum dipropyl phosphinic acid, diacetone alcohol, zinc oxide, linseed oil, toluene diisocyanate and hexametaphosphate. The wood lacquer has the excellent water-resistant performance.
Description
Technical field
The present invention relates to a kind of wood lacquer, particularly relate to a kind of modified aqueous polyurethane wood lacquer with excellent water repelling property.
Background technology
Aqueous polyurethane is a kind of urethane resin containing hydrophilic radical in the molecular chain of urethane, has very strong affinity, adopt specific technique can make it disperse in water and form stable system with glassware for drinking water.Because the reactive behavior of base polyurethane prepolymer for use as is higher, during the mixture of material handling and pigment after the addition, the combination of pigment and performed polymer molecular chain is more difficult, greatly have impact on pigment add after color developing, make the reproduction effect of coating color after a procedure poor.Aqueous polyurethane is mainly used in the aspects such as leather finish, textile printing and dyeing, paper-making industry, building coating, tackiness agent, steel moulder's paint, involved is nearly all inflammable material, these materials as without fire-retardant finish, must become the potential safety hazard of initiation fire in use.Aqueous polyurethane flame-retarded is one of important directions of aqueous polyurethane functionalization.
In prior art, the water repelling property of polyurethanes wood lacquer cannot meet the demand in actual use procedure, therefore needs a kind of polyurethane carpentry paint with excellent water repelling property of exploitation badly.
Summary of the invention
For solving the technical problem existed in background technology, the present invention proposes a kind of modified aqueous polyurethane wood lacquer with excellent water repelling property, has excellent water repelling property.
A kind of modified aqueous polyurethane wood lacquer with excellent water repelling property that the present invention proposes, its raw material comprises by weight: modified aqueous polyurethane 80-120 part, poly-dihydric alcohol 50-80 part, glycol ether 30-40 part, polyether glycol 10-30 part, polytetramethylene ether diol 5-15 part, methyl methacrylate 2-8 part, quadrol 1-5 part, asbestos 2-6 part, propylene glycol 3-9 part, aminosilane 1-4 part, tricarboxylic methylpropane 5-9 part, dipropyl phospho acid aluminium 4-8 part, diacetone alcohol 2-8 part, zinc oxide 4-8 part, oleum lini 1-9 part, tolylene diisocyanate 2-4 part, hexa metaphosphoric acid 3-6 part.
Preferably, modified aqueous polyurethane is prepared by following technique: polytetrahydrofuran is obtained material a in the dry 0.5-1.5h of 110-113 DEG C of vacuum decompression; Then in material a, add isoflurane chalcone diisocyanate and butyleneglycol mixes, then drip dibutyltin dilaurate catalyst, after stirring, be warming up to 75-85 DEG C, insulation 0.5-1.5h, then adds dicarboxyl methylpropanoic acid and collagen protein mixes, and is cooled to 50-60 DEG C, add in triethylamine and 0.4-0.6h, then use washing with acetone, precipitation, gets filtrate after filtration, with distilled water emulsification 0.3-0.6h, leave standstill froth breaking, removing acetone, is cooled to room temperature and obtains modified aqueous polyurethane.
Preferably, the weight ratio of polytetrahydrofuran, isoflurane chalcone diisocyanate, butyleneglycol, dibutyltin dilaurate catalyst, dicarboxyl methylpropanoic acid, collagen protein, triethylamine and distilled water is 5-15:2-8:1-5:3-6:2-5:4-8:1-4:1-3.
Preferably, the weight ratio of modified aqueous polyurethane, poly-dihydric alcohol, glycol ether, polyether glycol and polytetramethylene ether diol is 85-115:55-75:32-38:15-25:8-12.
Preferably, the weight ratio of methyl methacrylate, quadrol, asbestos, propylene glycol, aminosilane, tricarboxylic methylpropane, dipropyl phospho acid aluminium, diacetone alcohol, zinc oxide, oleum lini, tolylene diisocyanate and hexa metaphosphoric acid is 3-7:2-4:3-5:4-8:2-3:6-8:5-7:3-7:5-7:2-8:2.5-3.5:4-5.
Preferably, its raw material comprises by weight: modified aqueous polyurethane 85-115 part, poly-dihydric alcohol 55-75 part, glycol ether 32-38 part, polyether glycol 15-25 part, polytetramethylene ether diol 8-12 part, methyl methacrylate 3-7 part, quadrol 2-4 part, asbestos 3-5 part, propylene glycol 4-8 part, aminosilane 2-3 part, tricarboxylic methylpropane 6-8 part, dipropyl phospho acid aluminium 5-7 part, diacetone alcohol 3-7 part, zinc oxide 5-7 part, oleum lini 2-8 part, tolylene diisocyanate 2.5-3.5 part, hexa metaphosphoric acid 4-5 part.
Preferably, its raw material comprises by weight: modified aqueous polyurethane 100 parts, poly-dihydric alcohol 65 parts, glycol ether 35 parts, polyether glycol 20 parts, polytetramethylene ether diol 10 parts, methyl methacrylate 5 parts, quadrol 3 parts, 4 parts, asbestos, propylene glycol 6 parts, aminosilane 2.5 parts, tricarboxylic methylpropane 7 parts, 6 parts, dipropyl phospho acid aluminium, diacetone alcohol 5 parts, 6 parts, zinc oxide, oleum lini 5 parts, tolylene diisocyanate 3 parts, hexa metaphosphoric acid 4.5 parts.
Raw material of the present invention comprises modified aqueous polyurethane, poly-dihydric alcohol, glycol ether, polyether glycol, polytetramethylene ether diol, methyl methacrylate, quadrol, asbestos, propylene glycol, aminosilane, tricarboxylic methylpropane, dipropyl phospho acid aluminium, diacetone alcohol, zinc oxide, oleum lini, tolylene diisocyanate and hexa metaphosphoric acid, take wherein modified aqueous polyurethane as major ingredient, modified aqueous polyurethane is as filmogen and poly-dihydric alcohol, glycol ether, polyether glycol, polytetramethylene ether diol and methyl methacrylate coordinate, conservative control harmonic proportion each other, make wood lacquer of the present invention have excellent water repelling property, and by adding quadrol, asbestos, propylene glycol, aminosilane, tricarboxylic methylpropane, dipropyl phospho acid aluminium, diacetone alcohol, zinc oxide, oleum lini, tolylene diisocyanate and hexa metaphosphoric acid are as auxiliary agent, effectively improve the over-all properties of wood lacquer of the present invention, in the modifying process of wherein aqueous polyurethane, collagen protein and polyurethane backbone there occurs graft reaction, and adding of collagen protein makes the particle diameter of polyaminoester emulsion increase, and makes the crystallization trend of polyurethane laminate increase, surfaceness reduces, the mechanical property of aqueous polyurethane and water repelling property obtain maximized raising, thus make wood lacquer of the present invention have excellent water repelling property.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail; should understand; embodiment is only for illustration of the present invention, instead of for limiting the present invention, any amendment, equivalent replacement etc. made on basis of the present invention is all in protection scope of the present invention.
Embodiment 1
A kind of modified aqueous polyurethane wood lacquer with excellent water repelling property that the present invention proposes, its raw material comprises by weight: modified aqueous polyurethane 100 parts, poly-dihydric alcohol 65 parts, glycol ether 35 parts, polyether glycol 20 parts, polytetramethylene ether diol 10 parts, methyl methacrylate 5 parts, quadrol 3 parts, 4 parts, asbestos, propylene glycol 6 parts, aminosilane 2.5 parts, tricarboxylic methylpropane 7 parts, 6 parts, dipropyl phospho acid aluminium, diacetone alcohol 5 parts, 6 parts, zinc oxide, oleum lini 5 parts, tolylene diisocyanate 3 parts, hexa metaphosphoric acid 4.5 parts.
Modified aqueous polyurethane is prepared by following technique: by weight 10 parts of polytetrahydrofurans are obtained material a in the dry 1.0h of 111.5 DEG C of vacuum decompressions; Then in material a, 5 parts of isoflurane chalcone diisocyanates are added and 3 parts of butyleneglycols mix, then 4.5 parts of dibutyltin dilaurate catalysts are dripped, 80 DEG C are warming up to after stirring, insulation 1.0h, then interpolation 3.5 parts of dicarboxyl methylpropanoic acids and 6 parts of collagen proteins mix, be cooled to 55 DEG C, add in 2.5 parts of triethylamines and 0.5h, then use washing with acetone, precipitation, gets filtrate after filtration, with 2 parts of distilled water emulsification 0.45h, leave standstill froth breaking, removing acetone, is cooled to room temperature and obtains modified aqueous polyurethane.
Embodiment 2
A kind of modified aqueous polyurethane wood lacquer with excellent water repelling property that the present invention proposes, its raw material comprises by weight: modified aqueous polyurethane 80 parts, poly-dihydric alcohol 80 parts, glycol ether 30 parts, polyether glycol 30 parts, polytetramethylene ether diol 5 parts, methyl methacrylate 8 parts, quadrol 1 part, 6 parts, asbestos, propylene glycol 3 parts, aminosilane 4 parts, tricarboxylic methylpropane 5 parts, 8 parts, dipropyl phospho acid aluminium, diacetone alcohol 2 parts, 8 parts, zinc oxide, oleum lini 1 part, tolylene diisocyanate 4 parts, hexa metaphosphoric acid 3 parts.
Modified aqueous polyurethane is prepared by following technique: by weight 5 parts of polytetrahydrofurans are obtained material a in the dry 0.5h of 113 DEG C of vacuum decompressions; Then in material a, 8 parts of isoflurane chalcone diisocyanates are added and 1 part of butyleneglycol mixes, then 6 parts of dibutyltin dilaurate catalysts are dripped, 75 DEG C are warming up to after stirring, insulation 1.5h, then interpolation 2 parts of dicarboxyl methylpropanoic acids and 8 parts of collagen proteins mix, be cooled to 50 DEG C, add in 4 parts of triethylamines and 0.4h, then use washing with acetone, precipitation, gets filtrate after filtration, with 3 parts of distilled water emulsification 0.3h, leave standstill froth breaking, removing acetone, is cooled to room temperature and obtains modified aqueous polyurethane.
Embodiment 3
A kind of modified aqueous polyurethane wood lacquer with excellent water repelling property that the present invention proposes, its raw material comprises by weight: modified aqueous polyurethane 120 parts, poly-dihydric alcohol 50 parts, glycol ether 40 parts, polyether glycol 10 parts, polytetramethylene ether diol 15 parts, methyl methacrylate 2 parts, quadrol 5 parts, 2 parts, asbestos, propylene glycol 9 parts, aminosilane 1 part, tricarboxylic methylpropane 9 parts, 4 parts, dipropyl phospho acid aluminium, diacetone alcohol 8 parts, 4 parts, zinc oxide, oleum lini 9 parts, tolylene diisocyanate 2 parts, hexa metaphosphoric acid 6 parts.
Modified aqueous polyurethane is prepared by following technique: by weight 15 parts of polytetrahydrofurans are obtained material a in the dry 1.5h of 110 DEG C of vacuum decompressions; Then in material a, 2 parts of isoflurane chalcone diisocyanates are added and 5 parts of butyleneglycols mix, then 3 parts of dibutyltin dilaurate catalysts are dripped, 85 DEG C are warming up to after stirring, insulation 0.5h, then interpolation 5 parts of dicarboxyl methylpropanoic acids and 4 parts of collagen proteins mix, be cooled to 60 DEG C, add in 1 part of triethylamine and 0.6h, then use washing with acetone, precipitation, gets filtrate after filtration, with 1 part of distilled water emulsification 0.6h, leave standstill froth breaking, removing acetone, is cooled to room temperature and obtains modified aqueous polyurethane.
Embodiment 4
A kind of modified aqueous polyurethane wood lacquer with excellent water repelling property that the present invention proposes, its raw material comprises by weight: modified aqueous polyurethane 85 parts, poly-dihydric alcohol 75 parts, glycol ether 32 parts, polyether glycol 25 parts, polytetramethylene ether diol 8 parts, methyl methacrylate 7 parts, quadrol 2 parts, 5 parts, asbestos, propylene glycol 4 parts, aminosilane 3 parts, tricarboxylic methylpropane 6 parts, 7 parts, dipropyl phospho acid aluminium, diacetone alcohol 3 parts, 7 parts, zinc oxide, oleum lini 2 parts, tolylene diisocyanate 3.5 parts, hexa metaphosphoric acid 4 parts.
Modified aqueous polyurethane is prepared by following technique: by weight 8 parts of polytetrahydrofurans are obtained material a in the dry 0.8h of 112 DEG C of vacuum decompressions; Then in material a, 7 parts of isoflurane chalcone diisocyanates are added and 2 parts of butyleneglycols mix, then 5 parts of dibutyltin dilaurate catalysts are dripped, 78 DEG C are warming up to after stirring, insulation 1.2h, then interpolation 3 parts of dicarboxyl methylpropanoic acids and 7 parts of collagen proteins mix, be cooled to 52 DEG C, add in 3 parts of triethylamines and 0.45h, then use washing with acetone, precipitation, gets filtrate after filtration, with 2.5 parts of distilled water emulsification 0.4h, leave standstill froth breaking, removing acetone, is cooled to room temperature and obtains modified aqueous polyurethane.
Embodiment 5
A kind of modified aqueous polyurethane wood lacquer with excellent water repelling property that the present invention proposes, its raw material comprises by weight: modified aqueous polyurethane 115 parts, poly-dihydric alcohol 55 parts, glycol ether 38 parts, polyether glycol 15 parts, polytetramethylene ether diol 12 parts, methyl methacrylate 3 parts, quadrol 4 parts, 3 parts, asbestos, propylene glycol 8 parts, aminosilane 2 parts, tricarboxylic methylpropane 8 parts, 5 parts, dipropyl phospho acid aluminium, diacetone alcohol 7 parts, 5 parts, zinc oxide, oleum lini 8 parts, tolylene diisocyanate 2.5 parts, hexa metaphosphoric acid 5 parts.
Modified aqueous polyurethane is prepared by following technique: by weight 12 parts of polytetrahydrofurans are obtained material a in the dry 1.2h of 111 DEG C of vacuum decompressions; Then in material a, 3 parts of isoflurane chalcone diisocyanates are added and 4 parts of butyleneglycols mix, then 4 parts of dibutyltin dilaurate catalysts are dripped, 82 DEG C are warming up to after stirring, insulation 0.8h, then interpolation 4 parts of dicarboxyl methylpropanoic acids and 5 parts of collagen proteins mix, be cooled to 58 DEG C, add in 2 parts of triethylamines and 0.55h, then use washing with acetone, precipitation, gets filtrate after filtration, with 1.5 parts of distilled water emulsification 0.5h, leave standstill froth breaking, removing acetone, is cooled to room temperature and obtains modified aqueous polyurethane.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (7)
1. one kind has the modified aqueous polyurethane wood lacquer of excellent water repelling property, it is characterized in that, its raw material comprises by weight: modified aqueous polyurethane 80-120 part, poly-dihydric alcohol 50-80 part, glycol ether 30-40 part, polyether glycol 10-30 part, polytetramethylene ether diol 5-15 part, methyl methacrylate 2-8 part, quadrol 1-5 part, asbestos 2-6 part, propylene glycol 3-9 part, aminosilane 1-4 part, tricarboxylic methylpropane 5-9 part, dipropyl phospho acid aluminium 4-8 part, diacetone alcohol 2-8 part, zinc oxide 4-8 part, oleum lini 1-9 part, tolylene diisocyanate 2-4 part, hexa metaphosphoric acid 3-6 part.
2. the modified aqueous polyurethane wood lacquer with excellent water repelling property according to claim 1, it is characterized in that, modified aqueous polyurethane is prepared by following technique: polytetrahydrofuran is obtained material a in the dry 0.5-1.5h of 110-113 DEG C of vacuum decompression; Then in material a, add isoflurane chalcone diisocyanate and butyleneglycol mixes, then drip dibutyltin dilaurate catalyst, after stirring, be warming up to 75-85 DEG C, insulation 0.5-1.5h, then adds dicarboxyl methylpropanoic acid and collagen protein mixes, and is cooled to 50-60 DEG C, add in triethylamine and 0.4-0.6h, then use washing with acetone, precipitation, gets filtrate after filtration, with distilled water emulsification 0.3-0.6h, leave standstill froth breaking, removing acetone, is cooled to room temperature and obtains modified aqueous polyurethane.
3. the modified aqueous polyurethane wood lacquer with excellent water repelling property according to claim 1 and 2, it is characterized in that, the weight ratio of polytetrahydrofuran, isoflurane chalcone diisocyanate, butyleneglycol, dibutyltin dilaurate catalyst, dicarboxyl methylpropanoic acid, collagen protein, triethylamine and distilled water is 5-15:2-8:1-5:3-6:2-5:4-8:1-4:1-3.
4. the modified aqueous polyurethane wood lacquer with excellent water repelling property according to any one of claim 1-3, it is characterized in that, the weight ratio of modified aqueous polyurethane, poly-dihydric alcohol, glycol ether, polyether glycol and polytetramethylene ether diol is 85-115:55-75:32-38:15-25:8-12.
5. the modified aqueous polyurethane wood lacquer with excellent water repelling property according to any one of claim 1-4, it is characterized in that, the weight ratio of methyl methacrylate, quadrol, asbestos, propylene glycol, aminosilane, tricarboxylic methylpropane, dipropyl phospho acid aluminium, diacetone alcohol, zinc oxide, oleum lini, tolylene diisocyanate and hexa metaphosphoric acid is 3-7:2-4:3-5:4-8:2-3:6-8:5-7:3-7:5-7:2-8:2.5-3.5:4-5.
6. the modified aqueous polyurethane wood lacquer with excellent water repelling property according to any one of claim 1-5, it is characterized in that, its raw material comprises by weight: modified aqueous polyurethane 85-115 part, poly-dihydric alcohol 55-75 part, glycol ether 32-38 part, polyether glycol 15-25 part, polytetramethylene ether diol 8-12 part, methyl methacrylate 3-7 part, quadrol 2-4 part, asbestos 3-5 part, propylene glycol 4-8 part, aminosilane 2-3 part, tricarboxylic methylpropane 6-8 part, dipropyl phospho acid aluminium 5-7 part, diacetone alcohol 3-7 part, zinc oxide 5-7 part, oleum lini 2-8 part, tolylene diisocyanate 2.5-3.5 part, hexa metaphosphoric acid 4-5 part.
7. the modified aqueous polyurethane wood lacquer with excellent water repelling property according to any one of claim 1-6, it is characterized in that, its raw material comprises by weight: modified aqueous polyurethane 100 parts, poly-dihydric alcohol 65 parts, glycol ether 35 parts, polyether glycol 20 parts, polytetramethylene ether diol 10 parts, methyl methacrylate 5 parts, quadrol 3 parts, 4 parts, asbestos, propylene glycol 6 parts, aminosilane 2.5 parts, tricarboxylic methylpropane 7 parts, 6 parts, dipropyl phospho acid aluminium, diacetone alcohol 5 parts, 6 parts, zinc oxide, oleum lini 5 parts, tolylene diisocyanate 3 parts, hexa metaphosphoric acid 4.5 parts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106366889A (en) * | 2016-08-31 | 2017-02-01 | 阜南县大自然工艺品有限公司 | Waterborne polyurethane antiseptic paint for hydrolyzed collagen compound rattan handiwork and preparation method of waterborne polyurethane antiseptic paint |
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| CN110256651B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of collagen-based papermaking functional sizing agent |
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