CN101538441B - Improved amino baking varnish inverse emulsion, preparation method thereof, and method for preparing baking varnish coating by using improved amino baking varnish inverse emulsion - Google Patents
Improved amino baking varnish inverse emulsion, preparation method thereof, and method for preparing baking varnish coating by using improved amino baking varnish inverse emulsion Download PDFInfo
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- CN101538441B CN101538441B CN2009100028006A CN200910002800A CN101538441B CN 101538441 B CN101538441 B CN 101538441B CN 2009100028006 A CN2009100028006 A CN 2009100028006A CN 200910002800 A CN200910002800 A CN 200910002800A CN 101538441 B CN101538441 B CN 101538441B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 221
- 239000002966 varnish Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 title claims description 37
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title abstract 6
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 158
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 229920001214 Polysorbate 60 Polymers 0.000 claims abstract description 43
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001593 sorbitan monooleate Substances 0.000 claims abstract description 21
- 235000011069 sorbitan monooleate Nutrition 0.000 claims abstract description 21
- 229940035049 sorbitan monooleate Drugs 0.000 claims abstract description 21
- -1 formaldehyde, benzene compounds Chemical class 0.000 claims abstract description 10
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 118
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 93
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 84
- 150000001875 compounds Chemical class 0.000 claims description 77
- 125000003368 amide group Chemical group 0.000 claims description 55
- 239000008346 aqueous phase Substances 0.000 claims description 52
- 238000012986 modification Methods 0.000 claims description 43
- 230000004048 modification Effects 0.000 claims description 43
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical group CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
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- 239000002253 acid Substances 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052742 iron Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 100
- 229910010413 TiO 2 Inorganic materials 0.000 description 31
- 238000003756 stirring Methods 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 19
- 239000007921 spray Substances 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000005303 weighing Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
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- 239000003795 chemical substances by application Substances 0.000 description 4
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- 239000008098 formaldehyde solution Substances 0.000 description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 4
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- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- MPDGHEJMBKOTSU-YKLVYJNSSA-N 18beta-glycyrrhetic acid Chemical compound C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C(O)=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](O)C1(C)C MPDGHEJMBKOTSU-YKLVYJNSSA-N 0.000 description 2
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- OZZOVSQSDIWNIP-UHFFFAOYSA-N acetic acid;azane Chemical compound [NH4+].[NH4+].CC([O-])=O.CC([O-])=O OZZOVSQSDIWNIP-UHFFFAOYSA-N 0.000 description 1
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- KDRHKDNXHXANOQ-UHFFFAOYSA-N formaldehyde pentane-2,3-dione Chemical compound C(C)C(=O)C(=O)C.C=O KDRHKDNXHXANOQ-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention relates to improved amino baking varnish inverse emulsion and a preparation method thereof. The inverse emulsion comprises a water phase system of nano-titanium dioxide, amino baking varnish emulsion, a composite emulsifier and an assistant emulsifier, wherein the composite emulsifier is the mixture of polyoxyethylene 20 sorbitan monostearate and sorbitan monooleate. The baking varnish prepared by the improved amino baking varnish inverse emulsion greatly reduces the volatilization of organic substances, has the efficacy of degrading harmful gases such as formaldehyde, benzene compounds and the like and can release negative air ions of more than 800/cm<3> to play the functions of purifying and cleaning air. In addition, the invention also relates to a method for preparing baking varnish coatings by using the improved amino baking varnish inverse emulsion.
Description
Technical field
The present invention relates to a kind of amino-stoving varnish reversed-phase emulsion of modification, particularly, the present invention relates to a kind of nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion that uses.In addition, the invention still further relates to a kind of method for preparing this modified amido baking vanish reversed-phase emulsion, and a kind of method of using this modified amido baking vanish reversed-phase emulsion to prepare the baking vanish coating.
Background technology
People expect to invent the coating that is similar to the green plants effect always: can reduce the discharging of organic volatile, reduce organic harm such as formaldehyde, benzene series, purify air etc.
Amino-stoving varnish, mainly comprise acrylic-amino baking vanish, alcohol acid amido baking vanish and polyester amino-stoving varnish etc., they have very outstanding film-forming properties, weathering resistance and resistance to air loss, be widely used in exterior coating, baking finish for car, wood furniture and indoor decoration, water-proof sheet material application etc., but they often discharge a large amount of organic volatile contaminate environment such as benzene series in use towards periphery, even adopted expensive additive to reduce the technology of organic volatile discharging, but it is not ideal enough also to produce effects, and also influences the cost performance of coating significantly.
As everyone knows, nano titanium oxide has the effect of degradation of formaldehyde, benzene compounds.If nano titanium oxide is included in the amino-stoving varnish emulsion, then can be so that this amino-stoving varnish emulsion has the effect of degradation of formaldehyde extraly.Yet, when people attempt to add to nano titanium oxide in the amino-stoving varnish emulsion, always can't compatible well nano titanium oxide be separated out in the amino-stoving varnish emulsion with nano titanium oxide, the result obtains the not good nano-titanium dioxide modified amino-stoving varnish emulsion of stability.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the field of the amino-stoving varnish emulsion being carried out modification with nano titanium oxide, is well dispersed in modified amido baking vanish in the conventional amino-stoving varnish emulsion in the hope of obtaining a kind of nano titanium oxide.Found that, by means of a kind of specific compound emulsifying agent (being the mixture of polyoxyethylene 20 sorbitan monostearate and sorbitan monooleate) and assistant for emulsifying agent, can realize the good distribution of nano titanium oxide in conventional amino-stoving varnish emulsion and stable.The present invention just is being based on aforementioned discovery and is being accomplished.
The present invention adopts the reversed-phase emulsion technology, by means of the mixture of polyoxyethylene 20 sorbitan monostearate and sorbitan monooleate as compound emulsifying agent and assistant for emulsifying agent, successfully that nano titanium oxide is compatible in the amino-stoving varnish emulsion, obtain having the composite coating of nanostructure after the curing.Adopt antiphase emulsifiable method to prepare nano-TiO
2The modification reversed-phase emulsion of/amino-stoving varnish emulsion has W/O (modification) micellar dimensional controllability, forms " pond " system uniformly.This system has solved a key difficult problem for preparing nano-titanium dioxide modified amino-stoving varnish emulsion, and promptly amino-stoving varnish emulsion and nano titanium oxide are difficult to a compatible difficult problem, makes them reach fully compatible, and has the stable and dispersed of height.
Therefore, an object of the present invention is to provide a kind of nano-titanium dioxide modified modified amido baking vanish emulsion, this modified emulsion is a reversed-phase emulsion.
Another object of the present invention provides a kind of method for preparing modified amido baking vanish reversed-phase emulsion of the present invention.
A further object of the present invention provides a kind ofly uses modified amido baking vanish reversed-phase emulsion of the present invention to prepare the method for baking vanish coating.
One aspect of the present invention provides a kind of nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion, and it comprises:
A) aqueous phase system of nano titanium oxide;
B) amino-stoving varnish emulsion;
C) compound emulsifying agent, it is the mixture of polyoxyethylene 20 sorbitan monostearate and sorbitan monooleate; And
D) assistant for emulsifying agent.
The present invention provides a kind of method for preparing modified amido baking vanish reversed-phase emulsion of the present invention on the other hand, and it comprises the following steps:
I) aqueous phase system of preparation nano titanium oxide;
Ii) will mix with the amino-stoving varnish emulsion with the mixture and the assistant for emulsifying agent of sorbitan monooleate as the polyoxyethylene 20 sorbitan monostearate of compound emulsifying agent; And
Iii) under agitation, will be in step I) in the aqueous phase system of the nano titanium oxide that makes dropwise join at step I i) in the mixture that makes, obtain nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion.
Further aspect of the present invention provides a kind of and has used modified amido baking vanish reversed-phase emulsion of the present invention to prepare the method for baking vanish coating, and it comprises the steps:
I) aqueous phase system of preparation nano titanium oxide;
Ii) will mix with the amino-stoving varnish emulsion with the mixture and the assistant for emulsifying agent of sorbitan monooleate as the polyoxyethylene 20 sorbitan monostearate of compound emulsifying agent;
Iii) under agitation, will be in step I) in the aqueous phase system of the nano titanium oxide that makes dropwise join at step I i) in the mixture that makes, obtain nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion; And
Iv) will carry out spraying paint and the baking vanish step of baking vanish technology, obtain the baking vanish coating at the modified amido baking vanish reversed-phase emulsion that step I makes in ii).
According to the present invention, by using above-mentioned specific compound emulsifying agent and assistant for emulsifying agent that nano titanium oxide is scattered in the conventional amino-stoving varnish emulsion, found that, even conventional amino-stoving varnish emulsion contains organic solvent still less, can not influence the coating property of this modified amido baking vanish reversed-phase emulsion yet and apply performance.Especially, can in the amino-stoving varnish prescription, reduce the consumption of benzene class organic solvent according to compatible technique of the present invention, thereby reduce organic volatile to the pollution of environment (according to " hazardous and noxious substances is limited the quantity of in the indoor decorating material interior wall coating " standard (GB 18582-2001) regulation, VOC value of limiting the quantity of of the modification baking vanish of the present invention that records≤200g/L).For example, not used according to the invention nano-titanium dioxide modified before, the VOC value of amino-stoving varnish coating is 250g/L, use nano-titanium dioxide modified after, the VOC value of this amino-stoving varnish coating is reduced to 180g/L, and compatible technique promptly of the present invention makes the VOC value be reduced to 180g/L from 250g/L.In addition, use nano-titanium dioxide modified after, can make that the dimethylbenzene consumption reduces 40% in the baking vanish prescription, and whole system viscosity unaffected (maintaining between the 30-45PaS), thereby guarantee the normal construction and the coating property of baking vanish.Therefore, compatible technique of the present invention can reduce the add-on of the organic solvent of amino-stoving varnish, thereby greatly reduces the organism volatile quantity.In addition, this coating also has the effect of obnoxious flavoures such as degradation of formaldehyde, benzene compounds (according to GB18883-2002 " IAQ (indoor air quality) examination criteria ", 24 hours Degradation Formaldehyde rates of modified amido baking vanish of the present invention are 80.7%), and can discharge 800/cm
3Above negative aeroion plays the effect of purification and fresh air.
These and other purposes of the present invention, feature and advantage will be easy to be understood by those of ordinary skill after considering the present invention in conjunction with following accompanying drawing integral body.
The accompanying drawing summary
Fig. 1 schematically shows the preferred flow charts of the processing step of preparation modified amido baking vanish reversed-phase emulsion of the present invention.
Fig. 2 shows the prepared nano-TiO of the embodiment of the invention 1
2The acrylic-amino baking vanish coating of modification is about the degradation rate of formaldehyde.
Fig. 3 shows acrylic-amino baking vanish (that is the acrylic-amino baking vanish emulsion of using among each embodiment of the application (Changzhou XinGang GaoLi chemical engineering Co., Ltd provides)) without modification of the present invention about the natural decay rate of formaldehyde.
Fig. 4 and Fig. 5 show transmission electron microscope (TEM) photo of the prepared reversed-phase emulsion of the embodiment of the invention 1, and wherein Fig. 4 amplifies 10,000 times TEM photo for reversed-phase emulsion, and Fig. 5 amplifies 100,000 times TEM photo for reversed-phase emulsion.
Fig. 6 is the TEM photo of the reversed-phase emulsion of preparation in the embodiment of the invention 2.
Fig. 7 is the TEM photo of the reversed-phase emulsion of preparation in the embodiment of the invention 3.
Fig. 8 does not wherein add assistant for emulsifying agent for the TEM photo of the reversed-phase emulsion of preparation in the Comparative Examples 4 of the present invention.
Fig. 9 is the TEM photo of the reversed-phase emulsion of preparation in the Comparative Examples 5, wherein adds conventional emulsifier.
Figure 10 is the TEM photo of the reversed-phase emulsion of preparation in the Comparative Examples 6, and wherein the emulsifying agent consumption is not enough.
Figure 11 also is the TEM photo of the reversed-phase emulsion of preparation in the Comparative Examples 6, and just magnification is bigger.
From the amplification picture of Figure 11 as can be seen: under the not enough situation of emulsifying agent consumption, titania is reunited obviously, and its growth crystal grain is excessive, much contains TiO
2The water drop obviously surpass 100nm, the photocatalytic activity of the titanium dioxide of Sheng Chenging is extremely low in this case, the titanium dioxide granule of this form extremely is unfavorable for the coating of emulsifying agent to titanium dioxide nanoparticle, be unfavorable for the stable of inverted emulsion equally, corresponding reversed-phase emulsion also should not be used.
Figure 12 is its concentration of series of standards concentration formaldehyde solution and the linear formaldehyde typical curve of absorbancy.
Detailed Description Of The Invention
Component A
In nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion of the present invention, comprise the aqueous phase system (hereinafter sometimes using " W " expression) of nano titanium oxide. The nano titanium oxide that uses in this aqueous phase system can be any nano titanium oxide, and for example its average grain diameter is no more than 110nm, as is 60-110nm, even littler, as is 5-30nm. In principle, this nano titanium oxide can be titanium dioxide compound itself, without any modification, also can be any nano titanium oxide through modification. Preferably through the nano titanium oxide of modification. In the methods of the invention, for example can use the nano titanium oxide of being produced by the Huada Tianrui Nano-Material Technology Co., Ltd., Beijing, such as the RECH type.
Nano titanium oxide as modification, preferably, it is to use nano titanium oxide that semi-conducting material mixes as matrix and further use the nano titanium oxide of conjugated system organic matter surface modification, its photocatalytic effect has been broken through the restriction of ultraviolet light, has reached near infrared light, visible light, ultraviolet light and all can excite light-catalysed effect. The information of relevant this modified nano-titanium dioxide and preparation thereof sees also the inventor's the open CN 1448214A (or ZL 02 1 03829.5) of Chinese patent application, and the document is incorporated in this specification as a reference in full.
In a preferred embodiment of the invention, the modified nano-titanium dioxide of the present invention's use uses the nano titanium oxide of semi-conducting material doping as matrix. In described matrix, used semi-conducting material can be those skilled in the art well-known those, such as the oxide of niobium, tungsten, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc etc., the oxide of preferred iron, zinc, vanadium, tin etc. In described matrix, the weight ratio of titanium dioxide and semi-conducting material (take metal oxide) is 60: 40-96: 4, preferred 65: 35-90: 10. The matrix used particle size of the present invention is nanoscale, and preferred average grain diameter is in the 100nm, more preferably in the 50nm.
In another preferred embodiment of the present invention, the conjugated system organic matter in the modified nano-titanium dioxide is selected from maleic acid and salt, fumaric acid and salt thereof, alkene sulfonic acid (such as vinyl sulfonic acid, acrylic sulfonic acid, allyl sulphonic acid etc.) and salt, DBSA and salt thereof, chooses the acrylic acid and the salt thereof that replace wantonly. The organic content of described conjugated system is 0.01-20% weight based on the weight of the nm TiO 2-base body that described semi-conducting material mixes, preferred 0.05-15% weight, more preferably 0.1-10% weight.
In order to obtain the aqueous phase system of the nano titanium oxide that the present invention uses, under agitation, nano titanium oxide is dispersed in the aqueous medium. For this nano titanium oxide stably is dispersed in the aqueous medium, also can add surfactant. To this, can use any surfactant that is suitable for this purpose. Preferably use anion surfactant as surfactant at this, more preferably use neopelex and/or dodecyl sodium sulfate, especially use neopelex. In addition, as required, also can add the pH value that pH adjusting agent is regulated the aqueous dispersion of nano titanium oxide. For example, can add NH3·H
2O regulates the pH value. The pH of gained aqueous dispersion can select according to the pH of the system of the amino-stoving varnish emulsion of using, it should be so that the final modified amido baking vanish reversed-phase emulsion that obtains be neutral basically, perhaps be faintly acid or alkalescent, for example pH is 5-9, preferred 6-8, more preferably 6.5-7.5 especially is 6.8-7.2.
In nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion of the present invention, the nano titanium oxide that comprises has photocatalytic activity, the effectively degraded of catalysis formaldehyde, thereby reduce and not wish the formaldehyde (pollutant) that exists, the formaldehyde in the environment for example purifies and the purpose of clean air thereby reach.
For the aqueous phase system that comprises nano titanium oxide, the content of nano titanium oxide wherein can be selected according to concrete needs. Usually, the content of nano titanium oxide is the 0.5-9 % by weight based on the weight of aqueous medium, preferred 1-8 % by weight, and especially preferred 2-6 % by weight for example is 1 % by weight, 4 % by weight or 7 % by weight. In nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion of the present invention, gross weight based on this modified amido baking vanish reversed-phase emulsion, the content of the aqueous phase system of nano titanium oxide is generally the 15-45 % by weight, preferred 20-40 % by weight, especially 25-32 % by weight.
Component C
In nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion of the present invention, also comprise compound emulsifying agent, to realize the good compatible of amino-stoving varnish emulsion and aqueous phase system and to disperse. This compound emulsifying agent is the combination of polyoxyethylene 20 sorbitan monostearate emulsifying agent and sorbitan monooleate emulsifying agent.
In the preferred embodiment of modified amido baking vanish reversed-phase emulsion of the present invention, the polyoxyethylene 20 sorbitan monostearate emulsifier component in the compound emulsifying agent of use both can be commercial, also can be by the preparation of the known method in this area. For example can use Tween60, its main component is polyoxyethylene 20 sorbitan monostearate, there is the polyoxyethylene segment in its structural formula (being shown below), water there is good affinity, composite hydrophilic lipophilic balance HLB value is 14.9, but hydrophilic head is too big, is unfavorable for forming the protruding w/o type emulsion to oil phase in hydrophobic side.
x+y+z+w＝20
Sorbitan monooleate emulsifier component in the compound emulsifying agent both can be commercial, also can be by the preparation of the known method in this area. For example can use Span80, its main component is the sorbitan monooleate shown in the following formula, and composite hydrophilic lipophilic balance HLB value is 4.3.
When except adding the polyoxyethylene 20 sorbitan monostearate emulsifying agent, also add a certain amount of sorbitan monooleate, during such as Span 80 (compound HLB value is 4.3), variation has taken place in the structure of emulsifying agent film: owing to there are two keys in the structure of Span 80, its molecule becomes fold-line-shaped, the molecule of this broken line shape inserts the polyoxyethylene 20 sorbitan monostearate emulsifier component, the rete of Tween 60 for example, the hydrophobic end volume is increased, from geometry, be conducive to form the protruding rete to oil phase of lipophilic group, obtain the w/o type emulsion. But add too many polyoxyethylene 20 sorbitan monostearate emulsifier component, for example Tween60 can form local ordered arrangement, has lost the effect that the hybrid films hydrophobic group is increased. Therefore, when mixing a small amount of polyoxyethylene 20 sorbitan monostearate emulsifier component, for example Tween60 is so that the HLB value of compound emulsifying agent when being 12-14, and diagram of system reveals good water emulsification solubilizing power, obtains transparent, stable reversed-phase emulsion; When adding more sorbitan monooleate emulsifier component, for example during Span80, the HLB value of compound emulsifying agent diminishes, and the water emulsification solubilizing power of system will weaken. Therefore in the compound emulsifying agent that the present invention uses, the proportioning of polyoxyethylene 20 sorbitan monostearate emulsifying agent and sorbitan monooleate emulsifying agent is most important to the good formation of emulsion, its proportioning should be so that the composite hydrophilic lipophilic balance HLB value of gained compound emulsifying agent be 12-14, being preferably 12.5-13.5, especially is 12.8-13.2.
The proportioning of this compound emulsifying agent can be determined according to hydrophilic-lipophilic balance (HLB) method (HLB method). For example, for the hydrophile-lipophile balance HLB value that realizes compound emulsifying agent is 13, the Span80 of 82 % by weight can be mixed with the Tween60 of 18 % by weight, its composite hydrophilic lipophilic balance HLB value=82% * 14.9+18% * 4.3=13, other situation the like.
In the present invention, adopt polyoxyethylene 20 sorbitan monostearate emulsifying agent (for example Tween60) and the composite compound emulsifying agent that forms of these two kinds of emulsifying agents of sorbitan monooleate emulsifying agent (for example Span80). Because in water-oil-emulsifier system, emulsifying agent not only will have strong affinity with decentralized photo, and to stronger affinity be arranged with decentralized medium, the requirement that takes into account simultaneously this two aspect is that any single emulsifier is beyond one's reach, and the effect of two kinds of composite uses of emulsifying agent is better than using single emulsifier. So select to carry out composite with polyoxyethylene 20 sorbitan monostearate emulsifying agent (for example Tween60) and these two kinds of emulsifying agents of sorbitan monooleate emulsifying agent (for example Span80).
The relative consumption of compound emulsifying agent needs as mentioned above so that the composite hydrophilic lipophilic balance HLB value of this compound emulsifying agent is 12-14, is preferably 12.5-13.5, especially is 12.8-13.2. In nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion of the present invention, based on the gross weight of this modified amido baking vanish reversed-phase emulsion, the content of compound emulsifying agent is generally the 20-60 % by weight, preferred 22-45 % by weight, especially 24-40 % by weight.
Component D
In modified amido baking vanish reversed-phase emulsion of the present invention, for fine dispersion and the stabilisation that realizes emulsion, except using compound emulsifying agent, also to additionally use the assistant for emulsifying agent as component D. Assistant for emulsifying agent mainly plays three kinds of effects in the forming process of emulsion, and the one, reduce surface tension, more emulsifying agent is adsorbed on the interface; The 2nd, reduce the rigidity at interface, increase the flexibility at interface, make the interface be easier to flow, required bending energy when reducing emulsion and generating generates emulsion droplets easily; The 3rd, can play the effect of fine setting emulsifying agent HLB. Therefore, select suitable assistant for emulsifying agent that the formation speed of emulsion is accelerated, the drop that makes is more even. For the purpose of the present invention, suitable assistant for emulsifying agent is selected from the fat alcohol compound with 4-12 carbon atom, the example of this fat alcohol compound comprises n-butanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, Decanol, n-dodecanol etc., and preferred assistant for emulsifying agent is n-hexyl alcohol. Based on the gross weight of assistant for emulsifying agent and compound emulsifying agent, the consumption of assistant for emulsifying agent is the 5-20 % by weight, preferred 12-18 % by weight.
In modified amido baking vanish reversed-phase emulsion of the present invention,, preferably use n-hexyl alcohol as assistant for emulsifying agent when the combination of using Span80 and Tween60 during as compound emulsifying agent.At this moment, the consumption of Span80 and Tween60 should make the composite hydrophilic lipophilic balance HLB value of the compound emulsifying agent that they constitute satisfy requirement of the present invention, is 12-14, is preferably 12.5-13.5, especially is 12.8-13.2; And the consumption of assistant for emulsifying agent is 5-20 weight % based on the gross weight of this assistant for emulsifying agent and compound emulsifying agent, preferred 12-18 weight %.
B component
Of the present invention by nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion in, comprise the amino-stoving varnish emulsion.This amino-stoving varnish emulsion obviously should not be according to of the present invention or be not the amino-stoving varnish reversed-phase emulsion that obtains according to compatible technique of the present invention, amino-stoving varnish emulsion as B component is conventional amino-stoving varnish emulsion, this emulsion both can be those commercially available amino-stoving varnish emulsions, also can prepare by the known mode in amino-stoving varnish field itself.The composition in the amino-stoving varnish emulsion and the selection of composition thereof all are conventional.
Usually, the amino-stoving varnish emulsion is the emulsion that aminoresin and nondrying oil modified resin (comprising Synolac, acrylic resin etc.) form as main component.For acrylic-amino baking vanish emulsion, adopt acrylic resin usually as nondrying oil modified resin.Be different from acrylic-amino baking vanish emulsion, the Synolac as nondrying oil modified resin that alcohol acid amido baking vanish emulsion comprises is the tetramethylolmethane of soya-bean oil modification and the polycondensate of Tetra hydro Phthalic anhydride under the most common situation, it uses with the solution in No. 200 petrolic solvents usually.Certainly, various amino-stoving varnish emulsions also can comprise various auxiliary agents, for example pigment, flow agent or the like, and this is well-known to those skilled in the art.
In a preferred embodiment of the invention, use acrylic-amino baking vanish emulsion, more preferably use to comprise thermosetting acrylic resin and propyl carbinol etherify melamine resin acrylic-amino baking vanish emulsion as host as B component.Further preferably, this amino-stoving varnish emulsion is the acrylic-amino baking vanish emulsion that is provided by Changzhou XinGang GaoLi chemical engineering Co., Ltd.The host of this emulsion is thermosetting acrylic resin (9360) and butyl ether aminoresin 5860 (propyl carbinol etherify melamine resin), auxiliary agent is 1-Methoxy-2-propyl acetate (PMA), dimethylbenzene, 601A (Resins, epoxy of three wood), 415 (flow agent, manufacturer's enlightening height) or the like.Details about this amino-stoving varnish emulsion are described referring to this specification sheets embodiment part relevant " raw material ".
In nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion of the present invention, based on the gross weight of this modified amido baking vanish reversed-phase emulsion, the content of amino-stoving varnish emulsion is generally 20-55 weight %, preferred 28-51 weight %, especially 34-45 weight %.
Preferably, in nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion of the present invention, gross weight based on this modified amido baking vanish reversed-phase emulsion, content as the aqueous phase system of the nano titanium oxide of component A is 15-45 weight %, be 20-55 weight % and be 20-60% as the content of the amino-stoving varnish emulsion of B component as the content of the compound emulsifying agent of component C.More preferably, based on the gross weight of this modified amido baking vanish reversed-phase emulsion, the content of component A is 20-40 weight %, and the content of B component is that the content of 28-51 weight % and component C is 22-45 weight %.Particularly preferably be, based on the gross weight of this modified amido baking vanish reversed-phase emulsion, the content of component A is 25-32 weight %, and the content of B component is that the content of 34-45 weight % and component C is 24-40 weight %.
In another aspect of this invention, also provide a kind of method for preparing modified amido baking vanish reversed-phase emulsion of the present invention, it comprises the following steps:
I) aqueous phase system of preparation nano titanium oxide;
Ii) will mix with the amino-stoving varnish emulsion with the mixture and the assistant for emulsifying agent of sorbitan monooleate as the polyoxyethylene 20 sorbitan monostearate of compound emulsifying agent; And
Iii) under agitation, will be in step I) in the aqueous phase system of the nano titanium oxide that makes dropwise join at step I i) in the mixture that makes, obtain nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion.
Step I)
In step I) in, under stirring or ultrasonication, nano titanium oxide mentioned above is dispersed in the water medium, thus the aqueous phase system of acquisition nano titanium oxide.For nano titanium oxide stably is dispersed in the water medium, also can add tensio-active agent.To this, can use any tensio-active agent that is suitable for this purpose.Preferably use anion surfactant as tensio-active agent at this, more preferably use Sodium dodecylbenzene sulfonate and/or sodium laurylsulfonate, especially use Sodium dodecylbenzene sulfonate.In addition, as required, also can add the pH value that gained nano titanium oxide water dispersion is regulated in the pH regulator agent.For example, can add NH
3H
2O regulates the pH value.
For this aqueous phase system, the content of nano titanium oxide wherein can be selected according to concrete needs.Usually, the content of nano titanium oxide is 0.5-9 weight % based on the weight of water medium, preferred 1-8 weight %, and preferred especially 2-6 weight % for example is 1 weight %, 4 weight % or 7 weight %.
For in order to stablize the tensio-active agent that this water dispersion adds, the selection of its consumption is well known by persons skilled in the art, as long as can stablize the gained water suspension, generally, its consumption is 0.1-2 weight % based on the weight of water medium.The pH of gained water dispersion can select according to the pH of the system of the amino-stoving varnish emulsion of using, it should make the modified amido baking vanish reversed-phase emulsion of final acquisition be neutral basically, perhaps be slightly acidic or weakly alkaline, for example pH is 5-9, preferred 6-8, more preferably 6.5-7.5 especially is 6.8-7.2.
For step I) the middle nano titanium oxide that uses, in principle, this nano titanium oxide can be a titanium dioxide compound itself, without any modification, also can be any nano titanium oxide through modification.For example, the information of the preparation of relevant this nano titanium oxide sees also the inventor's the open CN 1448214A (ZL 02 1 03829.5) of Chinese patent application, and the document is incorporated in this specification sheets as a reference in full.
Step I i)
At step I i) in, compound emulsifying agent and assistant for emulsifying agent are mixed with the amino-stoving varnish emulsion, obtain the mixture of compound emulsifying agent, assistant for emulsifying agent and amino-stoving varnish emulsion.This mixture prepares by interpolation compound emulsifying agent of the present invention and assistant for emulsifying agent in the amino-stoving varnish emulsion.For example, at ambient temperature, be compound emulsifying agent with Span80 and Tween60, hexalin is an assistant for emulsifying agent, and the amino-stoving varnish emulsion is added in aforementioned compound emulsifying agent and the assistant for emulsifying agent.For example, be about Span80 and the Tween60 that 4: 1 part by weight takes by weighing certain mass respectively by Span80: Tween60, hydrophile-lipophile balance value (compound HLB) by compound emulsifying agent is about 13, HLB=4/5 * 14.9+1/5 * 4.3=12.78 (calculate with the massfraction that accounts for compound emulsifying agent, take by weighing at every turn and guarantee that hydrophile-lipophile balance value is about about 13); Again by (Span80+Tween60) (S): hexalin (A) is about 5: 1 part by weight, adds hexalin, stirs half an hour, makes it to become compound emulsifying agent system (S+A); By the predetermined weight ratio adding amino-stoving varnish emulsion (O) of this compound emulsifying agent system (S+A), continue to stir one hour subsequently with acrylic-amino baking vanish emulsion; Make the mixture (S+A+O) of compound emulsifying agent, assistant for emulsifying agent and amino-stoving varnish emulsion.
Step I ii)
Step I ii) in, under agitation, will be in step I) in the aqueous phase system of the nano titanium oxide that makes dropwise join at step I i) in the mixture that makes, obtain nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion.
In one side more of the present invention, the present invention also provides a kind of and has used modified amido baking vanish reversed-phase emulsion of the present invention to prepare the method for baking vanish coating, and it comprises the steps:
I) aqueous phase system of preparation nano titanium oxide;
Ii) will mix with the amino-stoving varnish emulsion with the mixture and the assistant for emulsifying agent of sorbitan monooleate as the polyoxyethylene 20 sorbitan monostearate of compound emulsifying agent;
Iii) under agitation, will be in step I) in the aqueous phase system of the nano titanium oxide that makes dropwise join at step I i) in the mixture that makes, obtain nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion; And
Iv) will carry out spraying paint and the baking vanish step of baking vanish technology, obtain the baking vanish coating at the modified amido baking vanish reversed-phase emulsion that step I makes in ii).
Step I in the aforesaid method)-iii) with above about included step I in the method for preparing modified amido baking vanish reversed-phase emulsion of the present invention)-iii) identical, repeat no more herein.
Above-mentioned steps iv) in, will carry out spraying paint and the baking vanish step of baking vanish technology at the modified amido baking vanish reversed-phase emulsion that step I makes in ii), obtain the baking vanish coating.Described spray paint and baking vanish technology for the those of ordinary skill in baking vanish or the amino-stoving varnish field, be conventional.Spray paint and comprise hand spray, electrostatic spraying and dip-coating etc.; After spraying paint, carry out baking vanish, obtain the baking vanish coating.In the present invention, for example the modified amido baking vanish reversed-phase emulsion through the modifying titanium dioxide modification can be stirred set aside for use 30 minutes.With the spray speed of GREEN W-71-3G type spray gun with 210cc/min this modified amido baking vanish reversed-phase emulsion is sprayed on the ground, spray gun at the uniform velocity translational speed is 1m/s, and gun slot is 10cm from the distance of plate.Ageing 2 hours is placed in the spraying back, but will be sprayed with the tube furnace that the ground of filming is put into temperature programming then, rises to 200 ℃ with 6 ℃/second heat-up rates, and is incubated 1 hour.Afterwards, cool to room temperature with the furnace, on ground, can obtain the amino-stoving varnish coating.
In a preferred embodiment, the processing step for preparing the method for modified amido baking vanish reversed-phase emulsion of the present invention can schematically illustrate with accompanying drawing 1, wherein S represents compound emulsifying agent (for example Span80+Tween60), A represents assistant for emulsifying agent (as n-hexyl alcohol), S+A represents compound emulsifying agent+assistant for emulsifying agent, O represents the amino-stoving varnish emulsion, the S+A+O representative mixed system of S+A by the amino-stoving varnish emulsion preparation, and W represents the aqueous phase system of nano titanium oxide.
The nano titanium oxide that wherein comprises has photocatalytic activity by nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion for of the present invention, degradable formaldehyde, thus play the purpose that purifies air.In addition, modified amido baking vanish reversed-phase emulsion of the present invention has excellent sterilization effect, and in bactericidal assay, antibiotic rate reaches 97%; In addition, the amino-stoving varnish coating surface light that uses modified amido baking vanish reversed-phase emulsion of the present invention to obtain, color and luster unanimity, film strong adhesion.And the surface microhardness of composite membrane still can reach modification requirement before.
Compare with the amino-stoving varnish of prior art, the purifying air baking vanish of anti-discolouring of the present invention, long-acting degraded obnoxious flavour has following advantage:
(1) solved the problem that traditional photocatalysis air-cleaning material is introduced the baking vanish variable color;
(2) degraded obnoxious flavour process is a kind of photocatalytic process of non-stripping, has therefore overcome degraded limited shortcoming of obnoxious flavour life-span;
(3) the reversed-phase emulsion technology of preparing make nano titanium oxide in baking vanish homodisperse and the size distribution of nano titanium oxide in baking vanish less than 100nm; With
(4) antimicrobial efficiency reaches more than 90%.
The test of the degradation of formaldehyde performance of amino-stoving varnish:
The formaldehyde detection method
This detection method is carried out according to GB/T15516-1995 " mensuration of Air quality formaldehyde-methyl ethyl diketone spectrophotometry ".Formaldehyde gas with the methyl ethyl diketone effect, generates stable yellow compound rapidly under the boiling water bath condition in acetate-ammonium acetate buffer solution of pH=6 after water absorbs, measure at wavelength 413nm place.
The reagent that adopts:
Ammonium acetate (Beijing chemical reagent factory);
Acetate (Shantou Xilong Chemical Industry Co., Ltd);
Methyl ethyl diketone (Shantou Xilong Chemical Industry Co., Ltd);
0.1000mol/L iodine solution;
The 1mol/L sodium hydroxide solution;
0.5mol/L sulphuric acid soln;
0.1000mol/L sodium thiosulfate standard solution;
0.5% starch solution;
Deionized water; With
Vaseline (Beijing chemical reagent factory).
The detecting instrument that adopts:
PU 5000 liquid-transfering guns (Propette company);
Volumetric flask;
Rubber suction bulb;
Water-bath;
722S type spectrophotometer (Shanghai Precision Scientific Apparatus Co., Ltd's analytical instrument head factory);
Fritted glass disk bubbler (the brilliant glass laboratory apparatus in Jintan City, Jiangsu Province factory); And
CD-1 type portable type air sampler (Instr Ltd. is analysed by Jintan City, Jiangsu section);
Detect step
(1) making of typical curve
Be mixed with the standard formaldehyde solution of a series of 10mL concentration known with the formaldehyde standardized solution of demarcating concentration, add 0.25% methyl ethyl diketone solution 2.0mL, mixing, place boiling water bath to heat 3min, taking-up is cooled to room temperature, using the 1cm cuvette, is reference with water, measures absorbancy in wavelength 412nm place.According to the making method of typical curve in the experimental procedure, the absorbance A of the absorbance A value deduction reagent blank that series of standards concentration formaldehyde solution is recorded just obtains calibrating absorbancy y value, is X-coordinate with the y value, with formaldehyde content x (mg/m
3) be ordinate zou, be depicted as typical curve, see Figure 12.
Obtain formaldehyde typical curve equation by the formaldehyde standard curve making:
Y＝4220.6X+3.8401
A=4220.6 wherein, b=3.8401, coefficient R
2=0.9972, prove to have good linear relationship between absorbancy and the concentration of formaldehyde.
(2) Degradation Formaldehyde experiment
Four sizes are the nano-TiO that contains of 500mm * 500mm
2The amino-stoving varnish model be placed in the climate compartment, cover top surface of the glass and the edge sealed with Vaseline and adhesive tape.By the heating and gasifying instrument environmental chamber and thorough mixing even (about 30min) are injected in 1 μ l formaldehyde solution gasification back, the gas that extracts environmental chamber detects the wherein content of formaldehyde with the methyl ethyl diketone spectrophotometry, and control group is not for containing nano-TiO
2The amino-stoving varnish model.
Degradation Formaldehyde rate (%)=(control group formaldehyde content-test group formaldehyde content)/photograph group formaldehyde content * 100%
(3) formaldehyde of the control group experiment that decays naturally
In order accurately to investigate the degradation property of titania modified amino-stoving varnish of the present invention for formaldehyde, the contriver has at first done the blank test that the formaldehyde of control group is decayed naturally, obtaining formaldehyde is natural decay rate under 50% condition 25 ℃ and humidity, as following table 1 and shown in Figure 3.This blank test is adopted and is not contained nano-TiO of the present invention
2Amino-stoving varnish contrast model, detect by above-mentioned detection method.
The blank natural attenuation test table of table 1
Time-temperature humidity absorbancy time concentration of formaldehyde natural decay rate
(hour) (℃) (%) (hour) (mg/m
3) (%)
0 27.5 48.9 0.245 0 1.688 9.88＊10
-6
1 28.1 47.4 0.233 1 1.603 5.00
2 28.4 47.1 0.190 2 1.301 22.93
3 28.5 47.4 0.187 3 1.280 24.18
4 28.6 47.7 0.186 4 1.273 24.59
5 28.7 48.0 0.184 5 1.259 25.43
6 28.8 48.5 0.182 6 1.244 26.26
7 28.7 48.6 0.180 7 1.230 27.09
8 28.8 50.1 0.178 8 1.216 27.93
9 28.8 50.5 0.175 9 1.195 29.18
Embodiment
The present invention below will be described in more detail by embodiment, but protection scope of the present invention is not limited to these embodiment.
Raw material
In following each embodiment, used following raw material:
(1) Tween60 (east, Wenzhou City rises chemical reagent factory, chemical pure), composite hydrophilic lipophilic balance HLB value is 14.9.
(2) Span80 (Shanxi Province's Yongji County chemical industry two factories, chemical pure), compound HLB value is 4.3.
(3) n-hexyl alcohol (Chinese Medicine Shanghai chemical reagent factory, chemical pure) is as assistant for emulsifying agent.
(4) acrylic-amino baking vanish emulsion (Changzhou XinGang GaoLi chemical engineering Co., Ltd provides), it is the emulsion of amino-stoving varnish.Shown in the component of this product and the table composed as follows thereof:
| Amount (weight part) | Percentage composition (%) | |
| Thermosetting acrylic resin (9360) | 225.5 | 72.64 |
| 1-Methoxy-2-propyl acetate (PMA) | 12 | 3.87 |
| Dimethylbenzene | 5 | 1.61 |
| 601A (Resins, epoxy of three wood) | 9 | 2.90 |
| Butyl ether aminoresin 5860 (propyl carbinol etherify melamine resin) | 58.35 | 18.79 |
| 415 (flow agents that enlightening is high) | 0.6 | 0.19 |
| 310.45 | 100.00 |
(5) ammoniacal liquor (Chinese Medicine Shanghai chemical reagent factory, analytical pure).
(6) nano-TiO
2, this nano-TiO
2R for Huada Tianrui Nano-Material Technology Co., Ltd., Beijing's production
TechRayType nano titanium oxide, its particle size range are 6-30nm.
(7) sodium laurylsulfonate (Beijing Raw Materials Company of Chemical Industry, analytical pure), tensio-active agent.
(1) nano-TiO
2The preparation of aqueous phase system
Get 100ml H
2O adds 0.15g sodium laurylsulfonate and 3g nano-TiO
2, grind, and add an amount of NH
3H
2O carries out ultra-sonic dispersion then so that the pH value is adjusted to 8.5, obtains nano-TiO
2Aqueous phase system.
(2) preparation of the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent
(hydrophile-lipophile balance value of this compound emulsifying agent (compound HLB) is 12.99:HLB=82% * 14.9+18% * 4.3=12.99) and the hexalin assistant for emulsifying agent of 1.5g to take by weighing the Span80 of 8.2g and 1.8g Tween60 respectively, the three is at room temperature mixed and stir half an hour, add 10g acrylic-amino baking vanish emulsion subsequently, at room temperature continue to stir one hour, make the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent.
(3) preparation of modification reversed-phase emulsion
In the mixture that step (2) makes, dropwise add the 8g nano-TiO that step (1) makes
2Aqueous phase system, and stir fully, make stable modification reversed-phase emulsion.The transmission electron microscope photo of this modification reversed-phase emulsion as shown in Figure 4 and Figure 5.Fig. 4 photo shows: nano-TiO
2Aqueous phase system presents 100 nano particle sizes basically with interior little drop, and evenly compound with vinylformic acid baking vanish organic phase; Fig. 5 photo further shows: nano-TiO
2Powder is dispersed in aqueous phase with the form of nano particle, and the form with the little drop of water is dispersed in the vinylformic acid baking vanish organic phase subsequently, obtains TiO thus
2Nanoparticulate dispersed compound modified amido baking vanish reversed-phase emulsion.
(4) preparation of acrylic-amino baking vanish coating
The modification reversed-phase emulsion that makes in the step (3) was stirred set aside for use 30 minutes.With the spray speed of GREENW-71-3G type spray gun with 210cc/min described modification reversed-phase emulsion is sprayed on the steel plate, spray gun at the uniform velocity translational speed is 1m/s, and gun slot is 10cm from the distance of steel plate.Ageing 2 hours is placed in the spraying back, but will be sprayed with the tube furnace that the steel plate of filming is put into temperature programming then, rises to 200 ℃ with 6 ℃/second heat-up rates, and is incubated 1 hour.Afterwards, cool to room temperature with the furnace, on steel plate, can obtain acrylic-amino baking vanish coating.
The degradation efficiency of this acrylic-amino baking vanish coating PARA FORMALDEHYDE PRILLS(91,95) is summarised in the following table 2.
Table 2
The time-temperature humidity sampling extinction concentration nature decay concentration of definitely degrading is degraded relatively
(hour) (℃) be amount (g) degree (mg/m (%)
3) rate (%) (mg/m
3) rate (%)
0 27.5 48.9 3 0.245 1.688
2 18.7 41.2 3 0.042 0.2596 84.62 1.301 80.05
4 21.7 34.7 4.5 0.042 0.1731 89.74 1.273 86.40
6 23.5 40 6 0.044 0.1369 91.89 1.244 89.00
8 22.9 18.7 6 0.044 0.1369 91.89 1.216 88.74
10 19.1 50.1 6 0.043 0.1333 92.10
Fig. 2 shows the degradation rate of this acrylic-amino baking vanish coating about formaldehyde.Contrast Fig. 3 (the natural extinction curve of formaldehyde) by Fig. 2, the starting point concentration of formaldehyde is 1.688mg/m
3, 2 hours absolute degradation efficiency of this baking vanish PARA FORMALDEHYDE PRILLS(91,95) degraded is 84.62%, degradation efficiency is 80.05% relatively, along with the increase of degradation time, degradation efficiency increases, and residual formaldehyde concentration is more and more littler, during degradation time to 8 hour, the formaldehyde residual concentration is 0.1369mg/m
3, absolute degradation efficiency reaches 91.89%, and concentration of formaldehyde is 1.216mg/m on the natural extinction curve at this moment
3, degradation efficiency is 88.74% relatively.Test result illustrates that this acrylic-amino baking vanish PARA FORMALDEHYDE PRILLS(91,95) pollutent has degradation effect.
(1) nano-TiO
2The preparation of aqueous phase system
Get 100ml H
2O adds 0.1g sodium laurylsulfonate and 2g nano-TiO
2, grind, and add an amount of NH
3H
2O carries out ultra-sonic dispersion then so that the pH value is adjusted to 8.5, obtains nano-TiO
2Aqueous phase system.
(2) preparation of the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent
(hydrophile-lipophile balance value of this compound emulsifying agent (compound HLB) is 13.31:HLB=85% * 14.9+15% * 4.3=13.31) and the hexalin assistant for emulsifying agent of 1.5g to take by weighing the Span80 of 8.5g and 1.5g Tween60 respectively, the three is at room temperature mixed and stir half an hour, add 16g acrylic-amino baking vanish emulsion subsequently, at room temperature continue to stir one hour, make the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent.
(3) preparation of modification reversed-phase emulsion
In the mixture that step (2) makes, dropwise add the 12g nano-TiO that step (1) makes
2Aqueous phase system, and stir fully, make stable modification reversed-phase emulsion.The transmission electron microscope photo of this modification reversed-phase emulsion as shown in Figure 6.By this photo as can be seen: this embodiment 2 is identical with embodiment 1, nano-TiO
2Powder is dispersed in aqueous phase with the form of nano particle, and the form with the little drop of water is dispersed in the vinylformic acid baking vanish organic phase subsequently, obtains TiO thus
2Nanoparticulate dispersed compound modified amido baking vanish reversed-phase emulsion.
(4) preparation of acrylic-amino baking vanish coating
The modification reversed-phase emulsion that makes in the step (3) was stirred set aside for use 30 minutes.With the spray speed of GREENW-71-3G type spray gun with 210cc/min described modification reversed-phase emulsion is sprayed on the steel plate, spray gun at the uniform velocity translational speed is 1m/s, and gun slot is 10cm from the distance of steel plate.Ageing 2 hours is placed in the spraying back, but will be sprayed with the tube furnace that the steel plate of filming is put into temperature programming then, rises to 200 ℃ with 6 ℃/second heat-up rates, and is incubated 1 hour.Afterwards, cool to room temperature with the furnace, on steel plate, can obtain acrylic-amino baking vanish coating.
Embodiment 3
(1) nano-TiO
2The preparation of aqueous phase system
Get 100ml H
2O adds 0.08g Sodium dodecylbenzene sulfonate and 1g nano-TiO
2, grind, and add an amount of NH
3H
2O carries out ultra-sonic dispersion then so that the pH value is adjusted to 8.5, obtains nano-TiO
2Aqueous phase system.
(2) preparation of the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent
(hydrophile-lipophile balance value of this compound emulsifying agent (compound HLB) is 12.78:HLB=80% * 14.9+20% * 4.3=12.78) and the hexalin assistant for emulsifying agent of 1.5g to take by weighing the Span80 of 8.0g and 2.0g Tween60 respectively, the three is at room temperature mixed and stir half an hour, add 20g acrylic-amino baking vanish emulsion subsequently, at room temperature continue to stir one hour, make the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent.
(3) modification reversed-phase emulsion preparation
In the mixture that step (2) makes, dropwise add the 16g nano-TiO that step (1) makes
2Aqueous phase system, and stir fully, make stable modification reversed-phase emulsion.The transmission electron microscope photo of this modification reversed-phase emulsion as shown in Figure 7.By this photo as can be seen: this embodiment 3 is identical with preceding 2 embodiment, nano-TiO
2Powder is dispersed in aqueous phase with the form of nano particle, and the form with the little drop of water is dispersed in the vinylformic acid baking vanish organic phase subsequently, obtains TiO thus
2Nanoparticulate dispersed compound modified amido baking vanish reversed-phase emulsion.
(4) preparation of acrylic-amino baking vanish coating
The modification reversed-phase emulsion that makes in the step (3) was stirred set aside for use 30 minutes.With the spray speed of GREENW-71-3G type spray gun with 210cc/min described modification reversed-phase emulsion is sprayed on the steel plate, spray gun at the uniform velocity translational speed is 1m/s, and gun slot is 10cm from the distance of steel plate.Ageing 2 hours is placed in the spraying back, but will be sprayed with the tube furnace that the steel plate of filming is put into temperature programming then, rises to 200 ℃ with 6 ℃/second heat-up rates, and is incubated 1 hour.Afterwards, cool to room temperature with the furnace, on steel plate, can obtain acrylic-amino baking vanish coating.
Comparative Examples 4 (not having assistant for emulsifying agent)
(1) nano-TiO
2The preparation of aqueous phase system
Get 100ml H
2O adds 0.15g sodium laurylsulfonate and 3g nano-TiO
2, grind, and add an amount of NH
3H
2O carries out ultra-sonic dispersion then so that the pH value is adjusted to 8.5, obtains nano-TiO
2Aqueous phase system.
(2) preparation of the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent
(hydrophile-lipophile balance value of this compound emulsifying agent (compound HLB) is 12.99:HLB=82% * 14.9+18% * 4.3=12.99) to take by weighing the Span80 of 8.2g and 1.8g Tween60 respectively, both are at room temperature mixed and stir half an hour, add 10g acrylic-amino baking vanish emulsion subsequently, at room temperature continue to stir one hour, make the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent.
(3) modification reversed-phase emulsion preparation
In the mixture that step (2) makes, dropwise add the 8g nano-TiO that step (1) makes
2Aqueous phase system, and stir fully, make the modification reversed-phase emulsion of less stable.The transmission electron microscope photo of this modification reversed-phase emulsion as shown in Figure 8.Contrast Comparative Examples 4 and embodiment 1 owing to do not add the assistant for emulsifying agent hexalin, cause nano-TiO
2The consistency variation of aqueous phase system and vinylformic acid organic phase, drop become big, and titanium dioxide reunion phenomenon is more serious, by this photo as can be seen: nano-TiO
2Water and vinylformic acid organic phase do not reach evenly compound, the emulsion that obtains thus, and nano titanium oxide does not have scattered, and stability of emulsion is not good.
(4) preparation of vinylformic acid baking vanish coating
The modification reversed-phase emulsion that makes in the step (3) was stirred set aside for use 30 minutes.With the spray speed of GREENW-71-3G type spray gun with 210cc/min described modification reversed-phase emulsion is sprayed on the steel plate, spray gun at the uniform velocity translational speed is 1m/s, and gun slot is 10cm from the distance of steel plate.Ageing 20 minutes is placed in the spraying back, but will be sprayed with the tube furnace that the steel plate of filming is put into temperature programming immediately then, rises to 200 ℃ with 15 ℃/second heat-up rates, and is incubated 1 hour.Afterwards, cool to room temperature with the furnace, on steel plate, can obtain vinylformic acid baking vanish coating.This coating is rough, and the finding of naked eye flaw is more.Comparative Examples 5 (common emulsifying agent)
(1) nano-TiO
2The preparation of aqueous phase system
Get 100ml H
2O adds 0.1g sodium laurylsulfonate and 2g nano-TiO
2, grind, and add an amount of NH
3H
2O carries out ultra-sonic dispersion then so that the pH value is adjusted to 8.5, obtains nano-TiO
2Aqueous phase system.
(2) preparation of the mixture of acrylic-amino baking vanish emulsion and conventional emulsifier
Take by weighing paraoctyl phenol Soxylat A 25-7 (belonging to typical nonionic emulsifying agent) and the 1.5g hexalin of 10g respectively, at room temperature stir, add 16g acrylic-amino baking vanish emulsion, at room temperature continue to stir one hour, make the mixture of acrylic-amino baking vanish emulsion and conventional emulsifier.
(3) preparation of modification reversed-phase emulsion
In the mixture that step (2) makes, dropwise add the 12g nano-TiO that step (1) makes
2Aqueous phase system, and stir fully, churning time is longer than embodiment 2, makes unsettled modification reversed-phase emulsion.Its reason may be: after changing the emulsifying agent of embodiment 2 into common emulsifying agent (paraoctyl phenol Soxylat A 25-7), the water drop of titanium dioxide is reunited easily, be difficult for and the vinylformic acid organic phase evenly compound, the transmission electron microscope photo of this emulsion is as shown in Figure 9.
Comparative Examples 6 (the emulsifying agent consumption is not enough, (S+A)/(S+A)+(O)=15%)
(1) nano-TiO
2The preparation of aqueous phase system
Get 100ml H
2O adds 0.08g sodium laurylsulfonate and 1g nano-TiO
2, grind, and add an amount of NH
3H
2O carries out ultra-sonic dispersion then so that the pH value is adjusted to 8.5, obtains nano-TiO
2Aqueous phase system.
(2) preparation of the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent
(hydrophile-lipophile balance value of this compound emulsifying agent (compound HLB) is 12.78:HLB=80% * 14.9+20% * 4.3=12.78) and the hexalin assistant for emulsifying agent of 0.5g to take by weighing the Span80 of 2.0g and 0.5g Tween60 respectively, the three is at room temperature mixed and stir half an hour, add 17g acrylic-amino baking vanish emulsion subsequently, at room temperature continue to stir one hour, make the mixture of acrylic-amino baking vanish emulsion and compound emulsifying agent and assistant for emulsifying agent.
(3) modification reversed-phase emulsion preparation
In the mixture that step (2) makes, dropwise add the 12g nano-TiO that step (1) makes
2Aqueous phase system, and stir fully, but the emulsion instability that makes, oil phase and aqueous phase system are difficult to compatible.The transmission electron microscope photo of this reversed-phase emulsion as shown in figure 10.From Figure 10 obviously as seen, nano-TiO
2Water is blended in the vinylformic acid organic phase with large size drop state, nano-TiO
2Disperse well, but be the state of reunion, this reversed-phase emulsion is defective.
Claims (18)
1. the amino-stoving varnish reversed-phase emulsion of a modification, it comprises:
A) aqueous phase system of nano titanium oxide;
B) amino-stoving varnish emulsion;
C) compound emulsifying agent, it is the mixture of polyoxyethylene 20 sorbitan monostearate and sorbitan monooleate, the hydrophilic-lipophilic balance HLB value of this compound emulsifying agent is 12-14; And
D) assistant for emulsifying agent, this assistant for emulsifying agent is selected from the fat alcohol compound with 4-12 carbon atom.
2. as the desired modified amido baking vanish of claim 1 reversed-phase emulsion, wherein the polyoxyethylene 20 sorbitan monostearate emulsifying agent is Tween60.
3. as the desired modified amido baking vanish of claim 1 reversed-phase emulsion, wherein the sorbitan monooleate emulsifying agent is Span80.
4. as the desired modified amido baking vanish of claim 2 reversed-phase emulsion, wherein the sorbitan monooleate emulsifying agent is Span80.
5. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein the hydrophilic-lipophilic balance HLB value of compound emulsifying agent is 12.5-13.5.
6. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein the hydrophilic-lipophilic balance HLB value of compound emulsifying agent is 12.8-13.2.
7. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein said amino-stoving varnish emulsion is acrylic-amino baking vanish, alcohol acid amido baking vanish or polyester amino-stoving varnish emulsion.
8. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein based on the gross weight of this modified amido baking vanish reversed-phase emulsion, content as the aqueous phase system of the nano titanium oxide of component A is 15-45 weight %, content as the amino-stoving varnish emulsion of B component is 20-55 weight %, with the content as the compound emulsifying agent of component C be 20-60%, and based on the gross weight of assistant for emulsifying agent and compound emulsifying agent, the consumption of assistant for emulsifying agent is 5-20 weight %.
9. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein based on the gross weight of this modified amido baking vanish reversed-phase emulsion, content as the aqueous phase system of the nano titanium oxide of component A is 20-40 weight %, content as the amino-stoving varnish emulsion of B component is 28-51 weight %, with the content as the compound emulsifying agent of component C be 22-45 weight %, and based on the gross weight of assistant for emulsifying agent and compound emulsifying agent, the consumption of assistant for emulsifying agent is 5-20 weight %.
10. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein assistant for emulsifying agent is a n-hexyl alcohol.
11. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein the nano titanium oxide in the aqueous phase system of nano titanium oxide is the nano titanium oxide of modification, it comprises the adulterated nano titanium oxide of semiconductor material as matrix and coated conjugated system organism on described matrix surface, wherein titanium dioxide and semiconductor material are 60 with the weight ratio that metal oxide calculates in described matrix: 40-96: 4 and the particle size of described matrix be in the 100nm, the organic content of wherein said conjugated system is 0.01-20% weight based on the weight of the adulterated nm TiO 2-base body of described semiconductor material.
12. as the desired modified amido baking vanish of claim 11 reversed-phase emulsion, wherein titanium dioxide and semiconductor material are 65 with the weight ratio that metal oxide calculates in described matrix: 35-90: 10 and the particle size of described matrix be in the 50nm, the organic content of wherein said conjugated system is 0.05-15% weight based on the weight of the adulterated nm TiO 2-base body of described semiconductor material.
13. as the desired modified amido baking vanish of claim 12 reversed-phase emulsion, wherein said semiconductor material is selected from the oxide compound of tungsten, niobium, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc.
14. as the desired modified amido baking vanish of claim 12 reversed-phase emulsion, wherein said conjugated system organism is selected from toxilic acid and salt, fumaric acid and salt thereof, alkene sulfonic acid and salt thereof, Witco 1298 Soft Acid and salt thereof, chooses the vinylformic acid and the salt thereof that replace wantonly.
15. as the desired modified amido baking vanish of claim 13 reversed-phase emulsion, wherein said conjugated system organism is selected from toxilic acid and salt, fumaric acid and salt thereof, alkene sulfonic acid and salt thereof, Witco 1298 Soft Acid and salt thereof, chooses the vinylformic acid and the salt thereof that replace wantonly.
16. as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-4, wherein the amino-stoving varnish emulsion as B component is an acrylic-amino baking vanish emulsion, and this emulsion comprises thermosetting acrylic resin and propyl carbinol etherify melamine resin as host.
17. a method for preparing as each desired modified amido baking vanish reversed-phase emulsion among the claim 1-16, it comprises the following steps:
I) aqueous phase system of preparation nano titanium oxide;
Ii) will mix with the amino-stoving varnish emulsion with the mixture and the assistant for emulsifying agent of sorbitan monooleate as the polyoxyethylene 20 sorbitan monostearate of compound emulsifying agent; And
Iii) under agitation, will be in step I) in the aqueous phase system of the nano titanium oxide that makes dropwise join at step I i) in the mixture that makes, obtain nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion.
18. each desired modified amido baking vanish reversed-phase emulsion prepares the method for baking vanish coating among use such as the claim 1-16, it comprises the steps:
I) aqueous phase system of preparation nano titanium oxide;
Ii) will mix with the amino-stoving varnish emulsion with the mixture and the assistant for emulsifying agent of sorbitan monooleate as the polyoxyethylene 20 sorbitan monostearate of compound emulsifying agent;
Iii) under agitation, will be in step I) in the aqueous phase system of the nano titanium oxide that makes dropwise join at step I i) in the mixture that makes, obtain nano-titanium dioxide modified modified amido baking vanish reversed-phase emulsion; And
Iv) will carry out spraying paint and the baking vanish step of baking vanish technology, obtain the baking vanish coating at the modified amido baking vanish reversed-phase emulsion that step I makes in ii).
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| CN105693104A (en) * | 2015-09-06 | 2016-06-22 | 广州叶子环保科技有限公司 | Use methods of nano titanium dioxide in ceramics, glass and furniture |
| CN107141984A (en) * | 2017-06-30 | 2017-09-08 | 四川锦泓佳建筑装饰工程有限公司 | One kind removes methanal paint |
| CN111072996A (en) * | 2019-12-09 | 2020-04-28 | 兴业皮革科技股份有限公司 | Polyurethane micro-powder emulsification method, polyurethane micro-powder emulsion, leather mending agent and application thereof |
| CN112973437B (en) * | 2021-02-20 | 2022-08-26 | 武汉绿知行环保科技有限公司 | Formaldehyde removal master batch for air purification device and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1448214A (en) * | 2002-03-29 | 2003-10-15 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
| EP1397441B1 (en) * | 2001-06-01 | 2005-07-27 | BASF Coatings AG | Pigmented powder paint suspensions (pigmented powder slurries ), production method and utilization thereof |
| CN1814629A (en) * | 2005-02-05 | 2006-08-09 | 广州宏昌胶粘带厂 | Inorganic nano-particle-containing nucleocapsid inorganic-organic composite pressure-sensitive adhesive emulsion, and its preparing method and use |
| US20070009453A1 (en) * | 2005-07-11 | 2007-01-11 | L'oreal | Photoprotective compositions comprising an aqueous phase and a low melting point apolar wax |
| CN101220228A (en) * | 2007-04-26 | 2008-07-16 | 天津兆阳纳米科技有限公司 | Method for producing stable nano-scale water dispersible pigment dispersion with ultrasound wave |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1397441B1 (en) * | 2001-06-01 | 2005-07-27 | BASF Coatings AG | Pigmented powder paint suspensions (pigmented powder slurries ), production method and utilization thereof |
| CN1448214A (en) * | 2002-03-29 | 2003-10-15 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
| CN1814629A (en) * | 2005-02-05 | 2006-08-09 | 广州宏昌胶粘带厂 | Inorganic nano-particle-containing nucleocapsid inorganic-organic composite pressure-sensitive adhesive emulsion, and its preparing method and use |
| US20070009453A1 (en) * | 2005-07-11 | 2007-01-11 | L'oreal | Photoprotective compositions comprising an aqueous phase and a low melting point apolar wax |
| CN101220228A (en) * | 2007-04-26 | 2008-07-16 | 天津兆阳纳米科技有限公司 | Method for producing stable nano-scale water dispersible pigment dispersion with ultrasound wave |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2004-269582A 2004.09.30 |
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