CN107141869A - A kind of novel colorful stone similar paint and preparation method thereof - Google Patents
A kind of novel colorful stone similar paint and preparation method thereof Download PDFInfo
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- CN107141869A CN107141869A CN201710258801.1A CN201710258801A CN107141869A CN 107141869 A CN107141869 A CN 107141869A CN 201710258801 A CN201710258801 A CN 201710258801A CN 107141869 A CN107141869 A CN 107141869A
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- similar paint
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- 239000003973 paint Substances 0.000 title claims abstract description 118
- 239000004575 stone Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- 229920002678 cellulose Polymers 0.000 claims abstract description 48
- 239000001913 cellulose Substances 0.000 claims abstract description 48
- 239000000839 emulsion Substances 0.000 claims abstract description 46
- 239000002270 dispersing agent Substances 0.000 claims abstract description 39
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 29
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000006004 Quartz sand Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000080 wetting agent Substances 0.000 claims description 36
- 239000002562 thickening agent Substances 0.000 claims description 35
- 235000010215 titanium dioxide Nutrition 0.000 claims description 31
- 239000003755 preservative agent Substances 0.000 claims description 24
- 230000002335 preservative effect Effects 0.000 claims description 24
- 239000004408 titanium dioxide Substances 0.000 claims description 24
- 239000013530 defoamer Substances 0.000 claims description 21
- -1 hydroxyl Ethyl Chemical group 0.000 claims description 16
- 239000003002 pH adjusting agent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 31
- 238000000576 coating method Methods 0.000 abstract description 21
- 159000000000 sodium salts Chemical class 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000000470 constituent Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004035 construction material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000126 substance Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000007888 film coating Substances 0.000 description 7
- 238000009501 film coating Methods 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000002421 anti-septic effect Effects 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000004579 marble Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 241000533950 Leucojum Species 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- QVBODZPPYSSMEL-UHFFFAOYSA-N dodecyl sulfate;2-hydroxyethylazanium Chemical compound NCCO.CCCCCCCCCCCCOS(O)(=O)=O QVBODZPPYSSMEL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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 present invention relates to construction material, belong to wall building coating technical field.The invention provides a kind of novel colorful stone similar paint, pass through the selection to raw material and constituent optimization, under interaction particularly between kaolin, modified cellulose, sodium salt dispersant, pure-acrylic emulsion and levelling agent, the colorful stone similar paint particle for making product formation stable.Compared with prior art, have on product storage stability and be obviously improved, obtain that a kind of stability is good, particle dispersion is good, not stratified novel colorful stone similar paint, the traffic coverage of novel colorful stone similar paint is expanded significantly and scope is used.Simultaneously present invention also offers the preparation method of the novel colorful stone similar paint, control adds speed during modified cellulose is added, it is to avoid conglomeration, influences the performance of colorful stone similar paint particle.
Description
Technical field
The present invention relates to construction material, belong to wall building coating technical field, and in particular to a kind of novel colorful is imitated
Mineral varnish and preparation method thereof.
Background technology
Colorful stone similar paint is that a kind of decorative effect exactly likes marble, granitic thick matter exterior wall decorating coating.It is main to use
The base paint particle of a variety of colors is formulated.Building after colorful stone similar paint finishing, with natural real natural colour,
Graceful, harmonious, serious aesthetic feeling is given, is suitable for the indoor and outdoor decoration of all kinds of buildings, particularly on curved-surface building thing
Decoration, can receive vivid, effect of back to nature.Simultaneously as component is largely snowflake sand in colorful stone similar paint,
With fire prevention, waterproof, acid and alkali-resistance, anti-pollution, nontoxic, tasteless, bonding force by force, the features such as good weatherability, can effectively it prevent outer
Erosion of boundary's adverse circumstances to building, extends the life-span of building.
Meanwhile, the research for the colorful stone similar paint is also gushed out like the mushrooms after rain.As in patent 201510478043.5
Disclose a kind of preparation method of new type water bag watercolor mineral varnish, using pigment, calcium carbonate, defoamer, dispersant, coalescents,
Thickener, ammoniacal liquor, preservative, cellulose, resin emulsion etc. are mixed, and are prepared for a kind of water-water colored stone paint.Such as patent
A kind of preparation technology of liquid marble paint is disclosed in CN201010582918.3, it is with deionized water, multifunctional assistant, ammonium salt
Prepared by the components such as dispersant, wetting agent, defoamer, anatase titanium dioxide, kaolin, emulsion, obtain a kind of colorful stone similar paint,
And it is tested.But the product that is obtained of these technical schemes is easily swollen in product particle, product layering substantially,
Storage stability is poor.
Although existing product on the market also has the colorful stone similar paint building coating of different brands, the temperature of these coating
It is qualitative poor, it is not easy to maintain, even occurred to go bad (1 week or so) short period, lower leaf in appearance has a strong impact on coating
Workability.Particularly when south or summer temperature are higher, the holding time is shorter, greatly limit it and applies model
Enclose.Fig. 1 is colorful stone similar paint coating photo on the market, it can be seen that significantly upper lower leaf occur, Fig. 2 is the technology of the present invention side
The product of case embodiment 1.Fig. 3 is the schematic diagram of the stone similar paint paint coatings of technical solution of the present invention product formation.
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of novel colorful stone similar paint, it has preferable combination property, and
Stability is good, and particle dispersion is good, not stratified, and the traffic coverage of novel colorful stone similar paint is expanded significantly and scope is used.
In order to realize the technical purpose of the present invention, the present invention is adopted the following technical scheme that.
A kind of novel colorful stone similar paint, by mass, including 530-620 parts of water, 10-15 parts of modified cellulose, dispersant
1-5 parts, 5-10 parts of preservative, 10-15 parts of titanium dioxide, 40-55 parts of kaolin, 12-18 parts of coalescents, pure-acrylic emulsion 280-
300 parts, 80-100 parts of levelling agent, 1.5-2 parts of PH conditioning agents, 10-12 parts of antifreezing agent, 5-8 parts of wetting agent, quartz sand 500-520
Part, 5-8 parts of thickener, 3-5 parts of defoamer.
It is preferred that, a kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, dispersant 3
Part, 7 parts of preservative, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, pH is adjusted
Save 1.5 parts of agent, 10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
It is preferred that, the modified cellulose is hydroxyethyl modified cellulose.The addition of cellulose can cause paint film water resistance
Decline, hydroxyethyl modified cellulose is used in the present invention, control is no more than 15 mass parts, with preferable water resistance.Its base
In the hydrophobic main chain on cellulose and surrounding water molecules through hydrogen bond association, the fluid body of colorful stone similar paint particle in itself is improved
Product, reduces the space of Particle free activity, so as to improve the stability of system.When content of cellulose is relatively low or is not added with completely
When, the colorful stone similar paint particle obtained is smaller, unstable, easily layering, is difficult long-term preservation.Using hydroxyethyl cellulose
Non- use hydroxypropyl methyl cellulose or methylcellulose are because it in the present invention there is colloid more more preferable than the latter to protect
Ability and stability.
It is preferred that, the titanium dioxide is that specific surface area is 80-145m2/ g anatase titanium dioxides.More preferably R95 or
The titanium dioxide of 996 anatase models, makes coating have optimal performance in whiteness and covering power.While specific surface area control is
80-145m2/ g because if specific surface area is excessive, can cause when in use water absorption rate it is higher, powder is difficult to point
Dissipate.
It is preferred that, the pure-acrylic emulsion is acrylate modified or epoxy resin modification pure-acrylic emulsion.Because this
Using pure-acrylic emulsion with there is more preferable paint film mildness using other kinds of emulsion (such as silicone acrylic emulsion) in invention, while
In the stability for testing colorful stone similar paint, it may have more excellent performance.
It is preferred that, the quartz sand is the quartz sand of 40-100 mesh.It is furthermore preferred that the color of the quartz sand can be white
Color, brown, black, yellow etc., are arranged in pairs or groups according to the requirement of basic colorful stone similar paint.Quartz sand selects the original of the mesh of 40 mesh -100
Because being the too small easy blocking spray gun of one side quartz sand mesh number, follow-up painting membrane process is influenceed；Other quartz sand mesh number is too big
Talk about, significant change occurs in surface gloss etc., and the visual impression of imitation marble paint has larger decline.It is furthermore preferred that in the present invention
Quartz sand is arranged in pairs or groups：90 mesh, which account for 14.8%, 80 mesh and account for 7.4%, 70 mesh, accounts for 7.8%, and remainder is 60 mesh quartz sands, with optimal table
Face glossiness and class marble vision sense of touch.
It is preferred that, the wetting agent is cationic wetting agent, can be amine salt or quaternary ammonium salt cationic wetting agent.Amine salt
Cationic wetting agent can be specifically fatty amine salt (R-R1-R2- N-H-X, wherein R are C10-C18Alkyl, R1、R2For low molecule
Alkyl, methyl, ethyl, benzyl or hydrogen atom；X be halogen, inorganic salts or organic acid), ethanolamine salt (triethanolamine, diethyl
Hydramine, MEA, dodecyl sulphate monoethanolamine etc.), polyethylene polyamines salt (N- alkyl polyamines, N- alkyl Diethylenetriamine).
Quaternary ammonium salt cationic type wetting agent can be specifically R1(or CH3)-R2-R3(or CH3)-N+-CH3X-, wherein R1、R2For ethyl, benzyl
Base.
It is preferred that, the thickener is alkali swollen thickener, specifically refers to acrylic acid, the homopolymer of methacrylic acid or common
Copolymer emulsion thickener.Because such thickener is acid in itself, therefore need to adjust pH value to 8-9, ability when in use
There can be good thickening effect.
It is preferred that, the pH adjusting agent is one kind in ammoniacal liquor or saleratus.
It is preferred that, the kaolin is that average grain diameter is that between 0.5~2 μm, kaolin on the one hand can be with water combination shape
Into after pug, with higher plasticity, colorful stone similar paint particle is set to deform in the effect of external force, external force is deformed after removing
The characteristic of disappearance, in the granular size for the colorful stone similar paint for increasing acquisition to a certain degree.In addition, kaolinite soil granularity is to its mud
Ion exchange capacity, binding ability in viscosity, mud etc. all have a very big impact.In the present invention, kaolinic particle diameter is less than 2
Preferable plasticity and quartz sand associativity μm can be obtained, selection is at 0.5 μm above is because the less height of one side granularity
Ridge soil improves a lot and performance change is not obvious in cost, and still further aspect is in order at that kaolinite soil granularity is meticulous can also be due to
Specific surface area is excessive when colorful stone similar paint coating is dried, and causes formed paint film to shrink excessive, discontinuous disconnected line occurs,
Influence the drastically deterioration attractive in appearance and causing water resistance of product.
It is preferred that, the LX-150 that preservative can be DOW Chemical is added, the antiseptic property of product is improved.
It is preferred that, the coalescents are Luo Diya or DOW Chemical DIB coalescents.
It is preferred that, the levelling agent is cross-linking type fluororesin levelling agent, can improve the weatherability of colorful stone similar paint, is improved
The rheological property of colorful stone similar paint particle, contributes to reinforcement to form monodisperse particles, prevents flocculation, and product layering is improved
The storage stability of product.
It is preferred that, the dispersant is sodium salt dispersant.In the present invention, sodium salt dispersant has preferable viscosity stability
And water resistance, the colorful stone similar paint product storge quality after disperseing can be lifted.Sodium salt dispersant content control 5 parts with
Under, be because while sodium salt dispersant can improve it is scattered after colorful stone similar paint product storage stability, it is but excessive
Sodium salt dispersant can cause the water resistance for the colorful stone similar paint paint film being ultimately formed to decline.
A kind of preparation method of novel colorful stone similar paint, comprises the following steps：(1) by water, preservative, dispersant, titanium white
Powder, kaolin, a part of defoamer are added in reactor, and stirring 2-5 minute is uniform to material, continues to add under stirring
Enter modified cellulose, continue to stir 5 minutes；(2) add after coalescents, antifreezing agent and disperse 2 minutes；(3) add pure-acrylic emulsion,
Thickener, wetting agent and remaining defoamer, continue to stir 5 minutes to uniform；(4) quartz sand is added, continues to stir 5 minutes,
Levelling agent and PH conditioning agents are added, stirring is shut down standby after 2 minutes.
It is preferred that, to be slowly added to during the addition of modified cellulose in the step (1), it is to avoid agglomerating caking.
The beneficial effects of the invention are as follows：
The invention provides a kind of novel colorful stone similar paint, by the selection to raw material and constituent optimization, particularly kaolin,
Under interaction between modified cellulose, sodium salt dispersant, pure-acrylic emulsion and levelling agent, make the colorful of product formation stabilization
Stone similar paint particle.Compared with prior art, have on product storage stability and be obviously improved, it is good to obtain a kind of stability,
Particle dispersion is good, not stratified novel colorful stone similar paint, and the traffic coverage of novel colorful stone similar paint is expanded significantly with using
Scope.Present invention also offers the preparation method of the novel colorful stone similar paint simultaneously.
Figure of description
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with the accompanying drawings
The present invention will be described in further detail.
Fig. 1 is colorful stone similar paint coating photo on the market；
Fig. 2 is the product of technical solution of the present invention embodiment 1；
Fig. 3 is the schematic diagram of the stone similar paint paint coatings of 1-4 of embodiment of the present invention formation；
Fig. 4 is the schematic diagram of the stone similar paint paint coatings of comparative example 1-2 formation of the present invention；
Fig. 5 is the schematic diagram of the stone similar paint paint coatings of the formation of comparative example 3 of the present invention；
Fig. 6 is the schematic diagram of the stone similar paint paint coatings of the formation of comparative example 5 of the present invention；
Fig. 7 is comparative example 4 of the present invention, the schematic diagram of the stone similar paint paint coatings of comparative example 6-8 formation；
Fig. 8 is the schematic diagram for the stone similar paint paint coatings that commercially available prod is formed.
Wherein 1#-4# represents the picture of embodiment 1-4 paint film coatings successively, and 5#-12# represents comparative example 1-8 successively respectively
Paint film coating picture.
Embodiment
In order to be better understood from the present invention, invention is described in detail with reference to specific embodiment.It should be appreciated that this
The specific embodiment of place description does not limit the present invention only to explain the present invention.
Embodiment 1
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
It is preferred that, the modified cellulose is hydroxyethyl modified cellulose.
It is preferred that, the titanium dioxide is that specific surface area is 80-145m2/ g anatase titanium dioxides.
It is preferred that, the pure-acrylic emulsion is acrylate modified or epoxy resin modification pure-acrylic emulsion.
It is preferred that, the kaolin is that average grain diameter is between 0.5~2 μm.
It is preferred that, the thickener is alkali swollen thickener, specifically refers to acrylic acid, the homopolymer of methacrylic acid or common
Any one in copolymer emulsion thickener.
It is preferred that, the quartz sand is the quartz sand of 40-100 mesh, and the color of the quartz sand can be carried out according to demand
Selection.
It is preferred that, the pH adjusting agent is one kind in ammoniacal liquor or saleratus.
It is preferred that, the wetting agent is cationic wetting agent, can be amine salt or quaternary ammonium salt cationic wetting agent.
It is preferred that, the LX-150 that preservative can be DOW Chemical is added, the antiseptic property of product is improved.
It is preferred that, the coalescents are Luo Diya or DOW Chemical DIB coalescents.
It is preferred that, the levelling agent is cross-linking type fluororesin levelling agent.
It is preferred that, the dispersant is sodium salt dispersant.
Embodiment 2
A kind of novel colorful stone similar paint, by mass, including 550 parts of water, 12 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 12,55 parts of kaolin, 12 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 5 parts of thickener, 3 parts of defoamer.
It is preferred that, the modified cellulose is hydroxyethyl modified cellulose.
It is preferred that, the titanium dioxide is that specific surface area is 80-145m2/ g anatase titanium dioxides.
It is preferred that, the pure-acrylic emulsion is acrylate modified or epoxy resin modification pure-acrylic emulsion.
It is preferred that, the kaolin is that average grain diameter is between 0.5~2 μm.
It is preferred that, the thickener is alkali swollen thickener, specifically refers to acrylic acid, the homopolymer of methacrylic acid or common
Any one in copolymer emulsion thickener.
It is preferred that, the quartz sand is the quartz sand of 40-100 mesh, and the color of the quartz sand can be carried out according to demand
Selection.
It is preferred that, the pH adjusting agent is one kind in ammoniacal liquor or saleratus.
It is preferred that, the wetting agent is cationic wetting agent, can be amine salt or quaternary ammonium salt cationic wetting agent.
It is preferred that, the LX-150 that preservative can be DOW Chemical is added, the antiseptic property of product is improved.
It is preferred that, the coalescents are Luo Diya or DOW Chemical DIB coalescents.
It is preferred that, the levelling agent is cross-linking type fluororesin levelling agent.
It is preferred that, the dispersant is sodium salt dispersant.
Embodiment 3
A kind of novel colorful stone similar paint, by mass, including 600 parts of water, 15 parts of modified cellulose, 5 parts of dispersant, preservative
10 parts, 15 parts of titanium dioxide, 40 parts of kaolin, 12 parts of coalescents, 290 parts of pure-acrylic emulsion, 100 parts of levelling agent, PH conditioning agents
1.5 parts, 12 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 8 parts of thickener, 5 parts of defoamer.
It is preferred that, the modified cellulose is hydroxyethyl modified cellulose.
It is preferred that, the titanium dioxide is that specific surface area is 80-145m2/ g anatase titanium dioxides.
It is preferred that, the pure-acrylic emulsion is acrylate modified or epoxy resin modification pure-acrylic emulsion.
It is preferred that, the kaolin is that average grain diameter is between 0.5~2 μm.
It is preferred that, the thickener is alkali swollen thickener, specifically refers to acrylic acid, the homopolymer of methacrylic acid or common
Any one in copolymer emulsion thickener.
It is preferred that, the quartz sand is the quartz sand of 40-100 mesh, and the color of the quartz sand can be carried out according to demand
Selection.
It is preferred that, the pH adjusting agent is one kind in ammoniacal liquor or saleratus.
It is preferred that, the wetting agent is cationic wetting agent, can be amine salt or quaternary ammonium salt cationic wetting agent.
It is preferred that, the LX-150 that preservative can be DOW Chemical is added, the antiseptic property of product is improved.
It is preferred that, the coalescents are Luo Diya or DOW Chemical DIB coalescents.
It is preferred that, the levelling agent is cross-linking type fluororesin levelling agent.
It is preferred that, the dispersant is sodium salt dispersant.
Embodiment 4
A kind of novel colorful stone similar paint, by mass, including 620 parts of water, 15 parts of modified cellulose, 1 part of dispersant, preservative 5
Part, 10 parts of titanium dioxide, 55 parts of kaolin, 18 parts of coalescents, 300 parts of pure-acrylic emulsion, 90 parts of levelling agent, 2 parts of PH conditioning agents are prevented
Freeze 10 parts of agent, 8 parts of wetting agent, 520 parts of quartz sand, 7 parts of thickener, 3 parts of defoamer.
It is preferred that, the modified cellulose is hydroxyethyl modified cellulose.
It is preferred that, the titanium dioxide is that specific surface area is 80-145m2/ g anatase titanium dioxides.
It is preferred that, the pure-acrylic emulsion is acrylate modified or epoxy resin modification pure-acrylic emulsion.
It is preferred that, the kaolin is that average grain diameter is between 0.5~2 μm.
It is preferred that, the thickener is alkali swollen thickener, specifically refers to acrylic acid, the homopolymer of methacrylic acid or common
Any one in copolymer emulsion thickener.
It is preferred that, the quartz sand is the quartz sand of 40-100 mesh, and the color of the quartz sand can be carried out according to demand
Selection.
It is preferred that, the pH adjusting agent is one kind in ammoniacal liquor or saleratus.
It is preferred that, the wetting agent is cationic wetting agent, can be amine salt or quaternary ammonium salt cationic wetting agent.
It is preferred that, the LX-150 that preservative can be DOW Chemical is added, the antiseptic property of product is improved.
It is preferred that, the coalescents are Luo Diya or DOW Chemical DIB coalescents.
It is preferred that, the levelling agent is cross-linking type fluororesin levelling agent.
It is preferred that, the dispersant is sodium salt dispersant.
Comparative example 1 (under conditions of content of cellulose is more than 15 parts)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 25 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Comparative example 2 (content of cellulose is less than in the case of 5 parts)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 3 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Comparative example 3 (uses silicone acrylic emulsion)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of silicone acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Comparative example 4 (sodium salt dispersion dosage is more than 10 parts)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, 15 parts of dispersant, preservative
7 parts, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Comparative example 5 (influence of kaolinite soil granularity, average grain diameter is less than 0.3 μm of kaolin)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Comparative example 6 (does not contain levelling agent)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 1.5 parts of pH adjusting agent, 10 parts of antifreezing agent, profit
5 parts of humectant, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Comparative example 7 (does not contain wetting agent)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Comparative example 8 (uses methylcellulose)
A kind of novel colorful stone similar paint, by mass, including 530 parts of water, 10 parts of modified cellulose, 3 parts of dispersant, preservative 7
Part, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, 280 parts of pure-acrylic emulsion, 80 parts of levelling agent, 1.5 parts of pH adjusting agent,
10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener, 4 parts of defoamer.
Coating paint film is made in the colorful stone similar paint particle obtained to above example and comparative example, and it is surveyed
Examination, as a result as shown in table 1.
Performance test between each embodiment of table 1 and comparative example
Test condition：
Product Status：It is dispersed on scraper plate, is estimated.
Storage stability：Stood at 25 DEG C, observe whether it is layered, if the phenomenons such as muddiness occur, record weekly once.
Paint film application property：Blade coating or spray gun coating, observe it and whether there is the phenomenon for blocking spray gun or falling paint.
Paint film state：Paint film coating is made into, after natural drying, whether observation coating surface state is continuous, whether deposit
In the defect such as crackle and stomata.
Paint film water resistance：Paint film is applied to be placed at 15-20 DEG C in water and soaked, its situations such as turning white of whether fading is observed,
Record once within every 7 days, using the data result of 30 days as final water resistance test result.
Preferably, storage time is longer, not stratified, not muddy, and particle is larger for embodiment 1-4 result product stability,
Disperse between grain and particle, the paint film coating formed is soft, without defects such as disconnected lines, with preferable water resistance, expand significantly
The traffic coverage of novel colorful stone similar paint and use scope.
It is due to add although the stability of the colorful stone similar paint particle of addition in comparative example 1 due to cellulose is more excellent
Modified fibre cellulose content it is more so that cause paint film water resistance decline.The content of cellulose added in comparative example 2 is too low, though
So the performance in water resistance is not deteriorated, but the less stable of the colorful stone similar paint particle obtained, during preservation
Between it is shorter, and the colorful stone similar paint particle obtained is smaller, easily layering.Methylcellulose is used in comparative example 8, can be seen
Colorful stone similar paint particle to its acquisition will be weaker than on storage stability using hydroxyethyl modified cellulose.
Silicone acrylic emulsion rather than pure-acrylic emulsion are used in comparative example 3, the paint film that the colorful stone similar paint particle obtained is made is applied
Layer mildness be not high, the defect such as easily there is micropore, wrinkles, meanwhile, the paint film obtained is also deteriorated in water resistance.This hair
In bright, sodium salt dispersant has preferable viscosity stability and water resistance, can lift the colorful stone similar paint product storage after disperseing
Sustainability energy, improves the storage stability of the colorful stone similar paint product after disperseing, but sodium salt dispersant exceedes in comparative example 4
10 parts, the water resistance for ultimately resulting in the colorful stone similar paint paint film to be formed declines.
Product particle obtained in comparative example 5 is larger, product stability preferably, but by colorful stone similar paint particle system
During lacquering membrane coat, dried paint film is excessive due to shrinking, and discontinuous disconnected line easily occurs, influences the attractive in appearance of product, and
And the water resistance of paint film is also drastically deteriorated.
Levelling agent is not contained in comparative example 6, the colorful stone similar paint particle obtained disperses in product storage stability, particle
Compared with embodiment 1-4 weak points in property.And the water resistance of its paint film coating finally obtained is also not so good as in embodiment
The paint film coating obtained.Wetting agent is not contained in comparative example 7, the colorful stone similar paint particle finally obtained is smaller, storage is steady
It is qualitative bad, easily it is layered, the defect such as the paint film coating surface presence obtained is wrinkled, Bark mark, surface mildness is poor.
According to above-described embodiment and comparative example data, it is apparent that imitating stone the invention provides a kind of novel colorful
Paint, by the selection to raw material and constituent optimization, particularly kaolin, modified cellulose, sodium salt dispersant, pure-acrylic emulsion with
Under interaction between levelling agent, the colorful stone similar paint particle for making product formation stable.Compared with prior art, in product
Have on storage stability and be obviously improved, obtain that a kind of stability is good, particle dispersion is good, not stratified novel colorful imitates stone
Paint, expands the traffic coverage of novel colorful stone similar paint and uses scope significantly.Present invention also offers the novel colorful simultaneously
The preparation method of stone similar paint, control adds speed during modified cellulose is added, it is to avoid conglomeration, influences colorful stone similar paint
The performance of particle.
The basic principles, principal features and advantages of the present invention have been shown and described above.The technical staff of the industry should
Understand, the invention is not limited in any way for above-described embodiment, it is all to be obtained by the way of equivalent substitution or equivalent transformation
Technical scheme, all falls within protection scope of the present invention.
Claims (8)
1. a kind of novel colorful stone similar paint, it is characterised in that by mass, including 530-620 parts of water, modified cellulose 10-15
Part, 1-5 parts of dispersant, 5-10 parts of preservative, 10-15 parts of titanium dioxide, 40-55 parts of kaolin, 12-18 parts of coalescents, pure third
280-300 parts of emulsion, 80-100 parts of levelling agent, 1.5-2 parts of PH conditioning agents, 10-12 parts of antifreezing agent, 5-8 parts of wetting agent, quartz sand
500-520 parts, 5-8 parts of thickener, 3-5 parts of defoamer.
2. a kind of novel colorful stone similar paint according to claim 1, it is characterised in that by mass, including 530 parts of water,
10 parts of modified cellulose, 3 parts of dispersant, 7 parts of preservative, titanium dioxide 10,50 parts of kaolin, 14 parts of coalescents, pure-acrylic emulsion
280 parts, 80 parts of levelling agent, 1.5 parts of PH conditioning agents, 10 parts of antifreezing agent, 5 parts of wetting agent, 500 parts of quartz sand, 6 parts of thickener disappears
4 parts of infusion.
3. a kind of novel colorful stone similar paint according to claim 1 or 2, it is characterised in that：The modified cellulose is hydroxyl
Ethyl modified cellulose.
4. a kind of novel colorful stone similar paint according to claim 1 or 2, it is characterised in that：The titanium dioxide is to compare surface
Product is 80-145m2/ g anatase titanium dioxides.
5. a kind of novel colorful stone similar paint according to claim 1 or 2, it is characterised in that：The pure-acrylic emulsion is propylene
Acid esters modification or the pure-acrylic emulsion of epoxy resin modification.
6. a kind of novel colorful stone similar paint according to claim 1 or 2, it is characterised in that：The quartz sand is 40-100
Purpose quartz sand.
7. a kind of preparation method of novel colorful stone similar paint according to claim any one of 1-6, it is characterised in that including
Following steps：(1) water, preservative, dispersant, titanium dioxide, kaolin, a part of defoamer are added in reactor, stirred
2-5 minutes uniform to material, and continuation adds modified cellulose under stirring, continues to stir 5 minutes；(2) film forming is added to help
Disperse 2 minutes after agent, antifreezing agent；(3) pure-acrylic emulsion, thickener, wetting agent and remaining defoamer are added, continues to stir 5 points
Clock is to uniform；(4) quartz sand is added, continues to stir 5 minutes, levelling agent and pH adjusting agent is added, stirring is shut down standby after 2 minutes
With.
8. a kind of preparation method of novel colorful stone similar paint according to claim 7, it is characterised in that：The step (1)
To be slowly added to during the addition of middle modified cellulose, it is to avoid agglomerating caking.
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| CN116285514A (en) * | 2023-03-22 | 2023-06-23 | 广东美洲宝实业有限公司 | Waterproof anti-fouling stone-like paint and preparation method thereof |
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Address after: No. 9, First Floor, Building B, No. 137 Weimin Road, Shenglong Village, Xiaolan Town, Zhongshan City, Guangdong Province, 528415 Patentee after: Guangdong Nantian New Material Technology Co.,Ltd. Country or region after: China Address before: No. 105 Zhuyuan Baoyuan Road, Xiaolan Town, Zhongshan City, Guangdong Province, 528415 Patentee before: GUANGDONG NANTIAN PAINT CO.,LTD. Country or region before: China |