CN116478605A - Water-based PU paint and preparation method and application thereof - Google Patents
Water-based PU paint and preparation method and application thereof Download PDFInfo
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- CN116478605A CN116478605A CN202310659974.XA CN202310659974A CN116478605A CN 116478605 A CN116478605 A CN 116478605A CN 202310659974 A CN202310659974 A CN 202310659974A CN 116478605 A CN116478605 A CN 116478605A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003973 paint Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 93
- 238000000576 coating method Methods 0.000 claims abstract description 69
- 239000011248 coating agent Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 239000006184 cosolvent Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 25
- -1 hexadecanol ester Chemical class 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 239000004033 plastic Substances 0.000 claims abstract description 8
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000002562 thickening agent Substances 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 239000000080 wetting agent Substances 0.000 claims description 19
- 229920002635 polyurethane Polymers 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 16
- 238000001723 curing Methods 0.000 claims description 14
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 abstract description 17
- 238000001035 drying Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000007921 spray Substances 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 description 15
- 239000013530 defoamer Substances 0.000 description 14
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- 229920000570 polyether Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000010276 construction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a water-based PU paint, a preparation method and application thereof, wherein the water-based PU paint comprises the following components in parts by weight: 20-30 parts of aqueous hydroxy acrylic dispersion resin, 35-45 parts of modified aqueous polyurethane dispersion resin, 2-6 parts of cosolvent, 0.1-0.3 part of catalyst and other auxiliary agents; the cosolvent is a mixture of alcohol ester dodecanol and hexadecanol ester; the catalyst is one or any combination of organic tin, organic cobalt and organic bismuth. The invention solves the problem of low yield caused by paint slag bonding at the spray gun mouth due to high surface drying speed during continuous spraying of paint, improves the yield of the produced products and reduces the production cost. The coating disclosed by the invention can be baked at a low temperature, is very friendly to the current 3C electronic plastic light and thin substrate, and can ensure the appearance quality and yield of the product and achieve good performance.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to a water-based PU paint, and a preparation method and application thereof.
Background
In recent years, along with the rapid development of the 3C electronic industry, the more the coating amount for protecting and decorating the surfaces of various products is, the more the water-based coating amount is increased along with the improvement of environmental awareness of people. The 3C electronic product is generally sprayed by using a Spindle automatic line, so that the productivity is high and the cost is low. However, the Spindle wire body is limited by the field, the oven is shorter, the effective baking time is only 10-15 min, and the drying and solidification of the water paint are not facilitated. In addition, as the requirements of consumers are continuously improved, products are designed and manufactured in the light and thin direction, but the light and thin base material cannot resist high-temperature baking in the production and manufacturing process, so the paint formula needs to select self-crosslinking resin or low-hydroxyl resin with high drying speed for designing the formula so as to meet the baking, curing and drying under shorter baking time and low temperature.
The applicant researches find that in the practical construction application process, the paint is sprayed out from a muzzle through compressed air during continuous spraying, and the self-crosslinking resin or low-hydroxyl resin has high surface drying volatilization speed, so that the paint is dry and adhered on a metal muzzle, paint slag is easy to form at the muzzle, the muzzle paint slag is accumulated more and more along with the time extension of spraying, and finally the paint slag can fall off on the surface of a sprayed product when accumulated to a certain amount, so that paint points and defective particles are formed. When the gun is serious, more paint is adhered to the gun mouth for about 15 minutes, so that the gun is blocked, and the gun can be recovered after cleaning, so that the coating effect is poor, the production efficiency is also influenced, the construction period is prolonged, and the yield and the production cost in batch production are seriously influenced.
To solve this problem, the patent CN110511658A adopts the scheme of matching PU (polyurethane) resin with UV resin, and utilizes the characteristic that the UV resin cannot be cured by baking at normal temperature or low temperature and only can be cured by irradiation of UV lamp, so that the problem of gun muzzle paint slag blocking is solved by blending part of UV resin into PU resin. However, UV curing is not suitable for PU+PU process, and high temperature baking at 70-80 ℃ and 1200-1400 mj/cm are required 2 Is not suitable for applications with thin and light substrates. In order to solve the problems, development of a water-based PU coating which is not easy to slag at a muzzle and is not blocked and can be cured at a low temperature is urgently needed to meet market demands.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects and the shortcomings in the background art, and provides a water-based PU coating which is not easy to slag at muzzle, does not block gun and can be cured at low temperature, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the water-based PU coating comprises the following components in parts by weight: 20-30 parts of aqueous hydroxy acrylic dispersion resin, 35-45 parts of modified aqueous polyurethane dispersion resin, 2-6 parts of cosolvent, 0.1-0.3 part of catalyst and other auxiliary agents;
the cosolvent is a mixture of alcohol ester dodecanol and hexadecanol ester; the catalyst is one or any combination of organic tin, organic cobalt and organic bismuth.
As a further improvement, the modified aqueous polyurethane dispersion resin is a polyurethane/urea polymer composite dispersion.
As a further improvement, the mass ratio of alcohol ester twelve to hexadecanol ester in the cosolvent is (1.6-2.4): 1.
as a further improvement, the addition amount of the cosolvent is 3-5 parts; and/or the catalyst is added in an amount of 0.2 to 0.3 part.
As a further improvement, the addition amount of the cosolvent is 3.5-4.5 parts, and the addition amount of the catalyst is 0.25-0.3 parts.
As a further improvement, the other auxiliary agents comprise the following components in parts by weight: 0.2 to 1.0 part of thickening agent, 0.1 to 0.2 part of defoaming agent, 1.0 to 2.5 parts of base material wetting agent, 0.2 to 0.5 part of dispersing agent, 15 to 25 parts of filler, 0.5 to 1.0 part of leveling agent and the balance of water, wherein the total weight is 100 parts.
The invention also provides a preparation method of the water-based PU paint, which comprises the following steps:
s1, stirring and dispersing aqueous hydroxy acrylic dispersion resin and modified aqueous polyurethane dispersion resin;
s2, adding a thickening agent, a defoaming agent, a base material wetting agent and a dispersing agent in sequence under stirring;
s3, adding filler to disperse the mixture under stirring;
and S4, adding the leveling agent, the cosolvent, the catalyst and deionized water in sequence under stirring, dispersing and mixing uniformly, and filtering to obtain the water-based PU coating.
The invention also provides application of the water-based PU coating in 3C electronic products.
As a further improvement, the application includes: and adding a curing agent and deionized water into the water-based PU coating for dilution, spraying the water-based PU coating on the surface of a plastic substrate, and then baking and curing.
As a further improvement, the baking and curing temperature is 50-60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention achieves the purpose of reducing the volatilization speed of the surface of the coating and solving the problem of muzzle slag bonding during continuous construction by adding a proper amount of alcohol ester twelve and hexadecyl alcohol ester. In order to improve the baking and actual drying reaction speed of the paint in a short time, a small amount of catalyst is added into the formula, so that the reaction speed during baking is improved, the production efficiency is improved, and the performance of the paint after baking and curing is ensured.
The invention solves the problem of low yield caused by paint slag bonding at the spray gun mouth due to high surface drying speed during continuous spraying of paint, improves the yield of the produced products and reduces the production cost. In addition, the coating can be baked at low temperature, is very friendly to the current 3C electronic plastic light and thin substrate, and can ensure the appearance quality and yield of the product and achieve good performance.
In addition, the invention adopts water as the diluent, effectively reduces the VOC content in the paint, ensures that the PU paint has no pollution in the spraying process, greatly improves the construction environment and is environment-friendly. Meanwhile, the coating disclosed by the invention is simple and easy to prepare and wide in application. The water-based PU paint can be used for preparing a single-coating process coating and also can be used as a primer for preparing PU+UV or PU+UV process coating.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of the present invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The water-based PU coating of some embodiments of the invention comprises the following components in parts by weight: 20 to 30 parts of aqueous hydroxyl acrylic dispersion resin, 35 to 45 parts of modified aqueous polyurethane dispersion resin, 0.2 to 1.0 part of thickener, 0.1 to 0.2 part of defoamer, 1.0 to 2.5 parts of base material wetting agent, 0.2 to 0.5 part of dispersant, 15 to 25 parts of filler, 0.5 to 1.0 part of flatting agent, 2 to 6 parts of cosolvent, 0.1 to 0.3 part of catalyst and the balance of water, wherein the total weight is 100 parts.
In a preferred embodiment, the composition comprises the following components in parts by weight: 25 parts of aqueous hydroxy acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of thickener, 0.1 part of defoamer, 1.3 parts of base material wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 4 parts of cosolvent, 0.3 part of catalyst and 8.1 parts of water.
In some embodiments, the aqueous hydroxyacrylic dispersion resin has a solids content of 38 to 42 weight percent and a hydroxyl number of 30 to 35mgKOH/g. The hydroxyl value was 33mgKOH/g in the following examples.
In some embodiments, the modified aqueous polyurethane dispersion resin is a polyurethane/urea polymer composite dispersion having a solids content of 39 to 41wt%.
The main body of the aqueous PU coating consists of two resins, namely aqueous hydroxy acrylic dispersion resin and modified aqueous polyurethane dispersion resin (PUA). The aqueous hydroxyacrylic dispersion resin can provide good chemical resistance, water resistance, wear resistance and high hardness. The modified aqueous polyurethane dispersion resin (polyurethane/urea polymer composite dispersion) has the characteristics of good adhesive force on different plastic substrates, strong universality, high drying speed, suitability for low-temperature baking, excellent adhesive force on various plastic substrates including PET, PA, GF, PC, TPU, ABS, excellent flexibility, and no cracking after being cured when being bent for 180 degrees on soft materials such as TPU (thermoplastic polyurethane). The two resins can meet the appearance and performance requirements of different plastic substrates and different color systems. However, both resins are easy to block gun at muzzle slag and influence yield when being constructed due to high drying speed.
In some embodiments, the thickener is an aqueous polyurethane associative thickener having a pseudoplastic fluid flow characteristic.
In some embodiments, the defoamer is one or more of polyether defoamers.
In some embodiments, the substrate wetting agent is a modified polyether siloxane copolymer.
In some embodiments, the dispersant is a solution of a nonionic modified fatty acid derivative.
In some embodiments, the filler is one or more of titanium dioxide, talc, fumed silica.
In some embodiments, the leveling agent is one or more of polyether siloxane copolymer and ethoxypolydimethylsiloxane.
In some embodiments, the catalyst is one of organotin, organocobalt, and organobismuth.
In some embodiments, the cosolvent is a mixture of alcohol ester dodecyl and hexadecyl alcohol ester, and the mass ratio of the cosolvent to the hexadecyl alcohol ester is preferably (1.6-2.4): 1, more preferably 2:1.
the key point of the invention is that a proper amount of alcohol ester dodecyl (2, 4-trimethyl 1, 3-pentanediol monoisobutyrate) and hexadecyl alcohol ester (2, 4-trimethyl-1, 3-pentanediol diisobutyrate) high-boiling point mixed solvent are added into the paint formula, so as to achieve the purpose of reducing the surface drying volatilization speed of the paint and solving the problem of muzzle slag formation during continuous construction. In addition, the addition of the cosolvent can effectively reduce the Minimum Film Forming Temperature (MFFT) of the resin and adapt to construction under different environments.
The alcohol ester has good twelve hydrolysis stability, can be used together with various emulsions including pure propionic acid emulsion with high pH, can effectively coalesce emulsion particles, has low freezing point, does not need special treatment in winter, and has good low temperature resistance. The paint film can obviously improve the film forming performance, the glossiness, the strength and the powder resistance of the paint film, the leveling property is improved, the paint film is endowed with good flexibility and elasticity, and the freeze-thawing stability of the emulsion paint can be improved. But in practical application, the problem of muzzle paint slag bonding cannot be completely solved. The hexadecyl alcohol ester has higher boiling point (281 ℃ C., 760 mmHg) so that the hexadecyl alcohol ester has good water-retaining property, and a small amount of the hexadecyl alcohol ester can prevent slag and crust formation during paint construction, and according to European Union decoration paint guide specification 2004/42/EC; a EU solvent emission command; it is not VOC, is environment-friendly solvent with China national environmental protection agency. However, the high boiling point does not allow for substantial addition which can affect the final cure of the coating.
Therefore, the two cosolvents are mixed and added into the paint formula according to a proper proportion, so that the film forming and curing of the paint in the construction process can be ensured, and the problem of muzzle paint slag in the continuous production process can be solved.
Meanwhile, in order to improve the baking and actual drying reaction speed of the paint in a short time, a small amount of catalyst is added into the formula, so that the reaction speed during baking is improved, and the performance of the paint after baking and curing is ensured.
Through the cross verification of different addition amounts of the cosolvent and the drier, the relationship between the performance and the gun plugging can be balanced. The preferable addition amount of the cosolvent is 3-5 parts, and the preferable addition amount of the catalyst is 0.2-0.3 parts. In a preferred embodiment, the amount of co-solvent is 3.5 to 4.5 parts and the amount of catalyst is 0.25 to 0.3 parts.
In some embodiments, the preparation method of the aqueous PU coating comprises the following steps:
s1, adding aqueous hydroxy acrylic dispersion resin and modified aqueous polyurethane dispersion resin into a dispersion container;
s2, stirring at 600-900 rpm, and sequentially adding a thickening agent, a defoaming agent, a substrate wetting agent and a dispersing agent;
s3, stirring at 800-1000 rpm, adding filler to disperse for 10-15 minutes, and dispersing the fineness below 20 um;
s4, stirring at 800-1000 rpm, adding a leveling agent, a cosolvent, a catalyst and deionized water, dispersing and mixing uniformly at 800-1000 rpm, and filtering at 250-350 meshes to obtain the water-based PU coating.
In some embodiments, the application of the aqueous PU coating includes: and (3) adding an HDI isocyanate curing agent accounting for 2-5% of the weight of the water-based PU coating and a proper amount of deionized water into the water-based PU coating for dilution, dispersing, filtering, spraying the water-based PU coating on the surface of the plastic substrate wiped by alcohol, and baking and curing the water-based PU coating to obtain the coating with the film thickness of 15-20 mu m.
In some embodiments, the spray gas pressure is 3kgf/cm 2 ～4kgf/cm 2 The baking and curing temperature is 50-60 ℃. Specifically, if the single-coated PU process coating is manufactured, the product is subjected to forced drying for 50-60 ℃ for 3-4 hours or is placed at room temperature for more than 7 days before testing. If the two-coating process coating is prepared, the water-based PU coating is solidified for 10-20 min at 50-60 ℃, PU or UV finish paint is directly sprayed on the water-based PU coating, and the product is subjected to forced drying for 50-60 ℃ for 3-4 h or standing at room temperature for more than 7 days before testing, so that the water-based PU coating is tested.
In the present invention, the aqueous hydroxyacrylic acid dispersion resin may be any one selected from the group consisting of QiSend 8219B, tongde 3AH0562W, ke Lisen KN 3793F. The modified aqueous polyurethane dispersion resin (polyurethane/urea polymer composite dispersion) may be selected from any one of Baojie SH-295ACN, baobaodi AC3600, baobaodi AC2403, and Wanhua chemistry 6140. The catalyst may be selected from any one of Borchers Deca Zinc aqua, borchers LH 10, borchers KAT 315. In the examples below, the aqueous hydroxyacrylic dispersion resin was Ke Lisen KN3793F, the polyurethane/urea polymer composite dispersion was Wanhua chemistry 6140, and the catalyst was Borchers LH 10.
Example 1
The aqueous PU coating of the embodiment comprises the following components in percentage by weight:
25 parts of aqueous hydroxy acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of substrate wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 2 parts of cosolvent, 0.1 part of catalyst and 10.3 parts of water. Specifically, the results are shown in Table 1.
TABLE 1 addition level of aqueous PU coating
The preparation method of the water-based PU coating comprises the following steps:
s1, adding modified aqueous polyurethane dispersion resin while stirring aqueous hydroxyl acrylic dispersion resin, wherein the stirring speed is 700 revolutions per minute, so as to obtain a mixture A;
s2, adding a polyurethane association thickener, a polyether defoamer, a polyether siloxane copolymer wetting agent and a nonionic modified fatty acid derivative solution dispersing agent into the mixed solution A while stirring at the stirring speed of 700 revolutions per minute, and uniformly mixing to obtain a mixture B;
s3, adding titanium dioxide into the mixed solution B while stirring at the stirring rotating speed of 1000 revolutions per minute, and dispersing until the fineness is less than 20 mu m to obtain a mixture C;
s4, adding a polyether siloxane copolymer flatting agent into the mixed solution C while stirring at the stirring rotating speed of 800 revolutions per minute to obtain a mixture D;
s5, adding alcohol ester twelve-hexadecanol ester mixture cosolvent into the mixed solution D while stirring at the stirring rotating speed of 800 revolutions per minute, and dispersing for 10 minutes to obtain a mixture E;
s6, adding the catalyst and water into the mixed solution E while stirring at the stirring speed of 800 revolutions per minute, and uniformly mixing. Filtering with 250 mesh screen to obtain the water-based PU paint.
Example 2
The aqueous PU coating of the embodiment comprises the following components in percentage by weight:
25 parts of aqueous acrylic emulsion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of base material wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 4 parts of cosolvent, 0.1 part of catalyst and 8.3 parts of water. As shown in table 2.
TABLE 2 addition of Water-based PU coating
The preparation method of the aqueous PU paint is the same as that of the example 1.
Example 3
The aqueous PU coating of the embodiment comprises the following components in percentage by weight:
25 parts of aqueous hydroxy acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of substrate wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 6 parts of cosolvent, 0.1 part of catalyst and 6.3 parts of water. Specifically, the results are shown in Table 3.
TABLE 3 addition of Water-based PU coating
The preparation method of the aqueous PU paint is the same as that of the example 1.
Example 4
The aqueous PU coating of the embodiment comprises the following components in percentage by weight:
25 parts of aqueous hydroxy acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of substrate wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 2 parts of cosolvent, 0.3 part of catalyst and 10.1 parts of water. Specifically, the results are shown in Table 4.
TABLE 4 addition level of aqueous PU coating
The preparation method of the aqueous PU paint is the same as that of the example 1.
Example 5
The aqueous PU coating of the embodiment comprises the following components in percentage by weight:
25 parts of aqueous hydroxy acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of substrate wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 4 parts of cosolvent, 0.3 part of catalyst and 8.1 parts of water. Specifically, the results are shown in Table 5.
TABLE 5 addition level of aqueous PU coating
The preparation method of the aqueous PU paint is the same as that of the example 1.
Example 6
The aqueous PU coating of the embodiment comprises the following components in percentage by weight:
25 parts of aqueous hydroxy acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of substrate wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 6 parts of cosolvent, 0.3 part of catalyst and 6.1 parts of water. Specifically, the results are shown in Table 6.
TABLE 6 addition level of Water-based PU coating
The preparation method of the aqueous PU paint is the same as that of the example 1.
Comparative example 1
The aqueous PU coating of the comparative example comprises the following components in percentage by weight:
25 parts of aqueous hydroxyl acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of substrate wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 4 parts of alcohol ester twelve-cosolvents, 0.3 part of catalyst and 8.1 parts of water. Specifically, the results are shown in Table 7.
TABLE 7 addition of Water-based PU coating
The preparation method of the water-based PU coating comprises the following steps:
s1, adding modified aqueous polyurethane dispersion resin while stirring aqueous hydroxyl acrylic dispersion resin, wherein the stirring speed is 700 revolutions per minute, so as to obtain a mixture A;
s2, adding a polyurethane association thickener, a polyether defoamer, a polyether siloxane copolymer wetting agent and a nonionic modified fatty acid derivative solution dispersing agent into the mixed solution A while stirring at the stirring speed of 700 revolutions per minute, and uniformly mixing to obtain a mixture B;
s3, adding titanium dioxide into the mixed solution B while stirring at the stirring rotating speed of 1000 revolutions per minute, and dispersing until the fineness is less than 20 mu m to obtain a mixture C;
s4, adding a polyether siloxane copolymer flatting agent into the mixed solution C while stirring at the stirring rotating speed of 800 revolutions per minute to obtain a mixture D;
s5, adding alcohol ester twelve-ingredient solvent into the mixed solution D while stirring at the stirring speed of 800 revolutions per minute, and dispersing for 10 minutes to obtain a mixture E;
s6, adding the catalyst and water into the mixed solution E while stirring at the stirring speed of 800 revolutions per minute, and uniformly mixing. Filtering with 250 mesh screen to obtain the water-based PU paint.
Comparative example 2
The aqueous PU coating of the comparative example comprises the following components in percentage by weight:
25 parts of aqueous hydroxy acrylic dispersion resin, 40 parts of modified aqueous polyurethane dispersion resin, 0.2 part of aqueous polyurethane thickener, 0.1 part of defoamer, 1.3 parts of base material wetting agent, 0.5 part of dispersing agent, 20 parts of filler, 0.5 part of leveling agent, 4 parts of hexadecyl alcohol ester cosolvent, 0.3 part of catalyst and 6.1 parts of water. As shown in table 8.
Table 8 amount of aqueous PU coating added
The preparation method of the water-based PU coating comprises the following steps:
s1, adding modified aqueous polyurethane dispersion resin while stirring aqueous hydroxyl acrylic dispersion resin, wherein the stirring speed is 700 revolutions per minute, so as to obtain a mixture A;
s2, adding a polyurethane association thickener, a polyether defoamer, a polyether siloxane copolymer wetting agent and a nonionic modified fatty acid derivative solution dispersing agent into the mixed solution A while stirring at the stirring speed of 700 revolutions per minute, and uniformly mixing to obtain a mixture B;
s3, adding titanium dioxide into the mixed solution B while stirring at the stirring rotating speed of 1000 revolutions per minute, and dispersing until the fineness is less than 20 mu m to obtain a mixture C;
s4, adding a polyether siloxane copolymer flatting agent into the mixed solution C while stirring at the stirring rotating speed of 800 revolutions per minute to obtain a mixture D;
s5, adding hexadecanol ester cosolvent into the mixed solution D while stirring at the stirring speed of 800 revolutions per minute, and dispersing for 10 minutes to obtain a mixture E;
s6, adding the catalyst and water into the mixed solution E while stirring at the stirring speed of 800 revolutions per minute, and uniformly mixing. Filtering with 250 mesh screen to obtain the water-based PU paint.
The aqueous PU coatings of the examples 1 to 6 and the comparative examples 1 to 2 are diluted by adding 3% of HDI isocyanate curing agent and a proper amount of deionized water according to the mass ratio of 100:3: 10-20, stirring for 3min at 300 rpm, and filtering with 200 mesh sieve. The spray gun used was a DEVILBISS 1.2mm caliber water paint special spray gun with a spray air pressure of 3kgf/cm 2 ～4kgf/cm 2 The spray booth temperature was controlled at 25℃and humidity was controlled at 50% RH. And (3) continuously spraying each embodiment for 60 minutes, observing the muzzle paint forming condition, controlling the film thickness to be 15-20 mu m, baking for 20 minutes at the temperature of 55 ℃, fully detecting the yield of each embodiment after the product is baked for 3 hours at the temperature of 55 ℃, and performing performance test on the product of each embodiment.
The yields and performances of the coatings formed from the aqueous PU coatings of examples 1 to 6 and comparative examples 1 to 2 were measured as shown in Table 9.
Table 9 performance test
The aqueous PU coating products of the examples 1 to 6 and the comparative examples 1 to 2 were subjected to yield test and performance test. As shown in the above Table 9, the yield and performance of example 5 are best, the yield is 90%, the adhesion between conventional and boiled products is stable and can reach the 0-grade standard, the pencil hardness is 500g/3H, no scratch is generated, the RCA is abrasion-resistant for 60 times, no substrate is present, no foaming or discoloration is generated after high-temperature high-humidity ring measurement, and the adhesion is not reduced and can reach the 0-grade standard.
Through the comparison verification of the addition amounts of different cosolvents in examples 1-3, the higher the addition amount of the cosolvent is, the less slag is formed at the muzzle, the higher the yield is (the yield is improved by 40%), but RCA, hardness and high-temperature and high-humidity performance can be reduced along with the increase of the slow-drying solvent.
Examples 4-6 the addition of the drier was increased based on examples 1-3, so that the performance was not lowered and the yield was also ensured.
The alcohol ester twelve-or sixteen-carbon alcohol ester cosolvent is added in the comparative example 1-2, wherein the alcohol ester twelve-solvent is added in the comparative example 1, muzzle slagging is obviously of grade 3, and the yield is 60%; in comparative example 2, only the hexadecanol ester solvent is added, slag formation at the muzzle is not obviously 1 grade, the yield is 95%, but the performance test is poor, the conventional adhesive force is 3 grade, the adhesive force for boiling and high-temperature high-humidity severe foaming is 4 grade, the RCA is only 15 times, and the main reason is that the hexadecanol ester solvent has a high boiling point, and the coating cannot be completely dried within a short time after a large amount of addition, so that the performance is reduced. The performance of independently adding alcohol ester twelve is superior to that of independently adding hexadecyl alcohol ester solvent in the comprehensive comparison examples 1 and 2, but the muzzle slag bonding is serious and the yield is low. On the contrary, the sixteen carbon alcohol ester solvent is added singly, the yield is high but the performance is poor, so that the two solvents cannot be added singly and are needed to be added in a matched mode according to a certain proportion.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.
Claims (10)
1. The water-based PU coating is characterized by comprising the following components in parts by weight: 20-30 parts of aqueous hydroxy acrylic dispersion resin, 35-45 parts of modified aqueous polyurethane dispersion resin, 2-6 parts of cosolvent and 0.1-0.3 part of catalyst;
the cosolvent is a mixture of alcohol ester dodecanol and hexadecanol ester; the catalyst is one or any combination of organic tin, organic cobalt and organic bismuth.
2. The aqueous PU coating according to claim 1, wherein the modified aqueous polyurethane dispersion resin is a polyurethane/urea polymer composite dispersion.
3. The water-based PU paint according to claim 1 or 2, wherein the mass ratio of alcohol ester twelve to hexadecyl alcohol ester in the cosolvent is (1.6-2.4): 1.
4. the aqueous PU coating according to claim 3, wherein the addition amount of the cosolvent is 3 to 5 parts; and/or the catalyst is added in an amount of 0.2 to 0.3 part.
5. The aqueous PU coating according to claim 4, wherein the addition amount of the cosolvent is 3.5 to 4.5 parts and the addition amount of the catalyst is 0.25 to 0.3 parts.
6. The aqueous PU coating according to claim 1 or 2, characterized in that the coating further comprises the following components in parts by weight: 0.2 to 1.0 part of thickening agent, 0.1 to 0.2 part of defoaming agent, 1.0 to 2.5 parts of base material wetting agent, 0.2 to 0.5 part of dispersing agent, 15 to 25 parts of filler, 0.5 to 1.0 part of leveling agent and the balance of water, wherein the total weight is 100 parts.
7. A method for preparing the aqueous PU coating according to any one of claims 1 to 6, comprising the steps of:
s1, stirring and dispersing aqueous hydroxy acrylic dispersion resin and modified aqueous polyurethane dispersion resin;
s2, adding a thickening agent, a defoaming agent, a base material wetting agent and a dispersing agent in sequence under stirring;
s3, adding filler to disperse the mixture under stirring;
and S4, adding the leveling agent, the cosolvent, the catalyst and deionized water in sequence under stirring, dispersing and mixing uniformly, and filtering to obtain the water-based PU coating.
8. Use of the aqueous PU coating of any one of claims 1-6 in 3C electronic products.
9. The use according to claim 8, characterized in that it comprises: and adding a curing agent and deionized water into the water-based PU coating for dilution, spraying the water-based PU coating on the surface of a plastic substrate, and then baking and curing.
10. The use according to claim 9, wherein the bake-curing temperature is 50-60 ℃.
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