CN105925024B - Inorganic mineral environment-friendlyfireproof fireproof paint and preparation method thereof - Google Patents
Inorganic mineral environment-friendlyfireproof fireproof paint and preparation method thereof Download PDFInfo
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- CN105925024B CN105925024B CN201610309698.4A CN201610309698A CN105925024B CN 105925024 B CN105925024 B CN 105925024B CN 201610309698 A CN201610309698 A CN 201610309698A CN 105925024 B CN105925024 B CN 105925024B
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- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
- C09D7/44—Combinations of two or more thickening agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of inorganic mineral environment-friendlyfireproof fireproof paint and preparation method thereof, the inorganic mineral environment-friendlyfireproof fireproof paint is prepared by the raw material of following weight parts：15 35 parts of potassium silicate solution, 1 1.5 parts of dispersant, 2.5 parts of thickener 1 part, 13 parts of dimethicone, 39 parts of emulsion, 1 10 parts of titanium dioxide, 19 parts of iron oxide, 19 parts of sepiolite, 16 parts of zinc oxide, 18 parts of tourmaline, 14 parts of kaolin, 0.5 2.5 parts of Ludox, 10 50 parts of water.A kind of inorganic mineral environment-friendlyfireproof fireproof paint of the present invention and preparation method thereof, by by reasonably matching, it is preferred that go out the species and dosage of suitable exterior coating thickener, dispersant, improve coating waterproofing, Scratch Resistance, stain resistance, gas permeability, weatherability, avoid peeling, fade, there is the advantages of not long mildew of fire protection flame retarding, automatic sterilization function, environmentally friendly simultaneously, and easy construction, environmental suitability are more preferable.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of inorganic mineral environment-friendlyfireproof fireproof paint and preparation method thereof.
Background technology
Paint finishing can very well bond with matrix material in body surface and form the material of complete and tough and tensile diaphragm, claim
For coating.Coating and paint are identical concepts.Paint is people's custom title used for a long time, just sharp always after introducing China
Used in building trade.The effect of coating may be summarized to be three aspects：Protective effect, decoration function, specific function effect.Coating
General composition：Include film forming matter, color stuffing, solvent, auxiliary agent.
There is building coating decoration functions, defencive function and livability to improve function.Proportion shared by various functions is because making
It is not quite similar with purpose difference.Decoration functions are to improve the function of its appearance value by the beautification of building.Mainly
Design design and the design of three-dimensional pattern design in terms of including plane color, pattern and gloss.But will be with building in itself
The size and shape of moulding and base material in itself is engaged, and just can fully play out.
It is polyurethanes water-repellent paint that the waterproof material of in the market, which is typically, and this kind of material is usually by polyurethane and coal tar
Oil is made as raw material.The tar gas toxicity that it is volatilized is big, and does not allow easy-clear, therefore is prohibited in 2000 in China
Use.It is to be used as raw material instead of coal tar by the use of pitch still in the polyurethane water-proof paint of sale.But when using this coating,
It is general to be diluted using the organic solvents such as toluene, dimethylbenzene are contained, thus also containing toxic.
The invention provides a kind of inorganic mineral environment-friendlyfireproof fireproof paint, have good water proofing property, Negative ion disengagement,
The not long mildew of automatic sterilization function, Scratch Resistance, stain resistance, while there is the advantages of fire protection flame retarding, environmentally friendly, especially suitable for resident
The occasions such as building, commercial building, public building, and easy construction, environmental suitability is more preferable, has broad application prospects.
The content of the invention
For the deficiencies in the prior art, one of the technical problems to be solved by the invention are to provide a kind of inorganic ore deposit
Thing environment-friendlyfireproof fireproof paint.
The two of the technical problems to be solved by the invention are to provide a kind of preparation method of inorganic mineral environment-friendlyfireproof fireproof paint.
The present invention seeks to what is be achieved through the following technical solutions：
A kind of inorganic mineral environment-friendlyfireproof fireproof paint, is prepared by the raw material of following weight parts：
Potassium silicate solution 15-35 parts, dispersant 1-1.5 parts, thickener 1-2.5 parts, dimethicone 1-3 parts, emulsion 3-9
Part, titanium dioxide 1-10 parts, iron oxide 1-9 parts, sepiolite 1-9 parts, zinc oxide 1-6 parts, tourmaline 1-8 parts, kaolin 1-4
Part, Ludox 0.5-2.5 parts, water 10-50 parts.
Preferably, described thickener be hydroxypropul starch, CMS, one kind in hydroxypropyl methyl cellulose or
A variety of mixtures.
It is highly preferred that described thickener is made up of hydroxypropul starch, CMS, hydroxypropyl methyl cellulose, institute
It is (1-3) to state hydroxypropul starch, CMS, the mass ratio of hydroxypropyl methyl cellulose：(1-3)：(1-3).
Preferably, described dispersant is mixing one or more in calgon, sodium pyrophosphate, sodium tripolyphosphate
Thing.
It is highly preferred that described dispersant is made up of calgon, sodium pyrophosphate, sodium tripolyphosphate, the six inclined phosphorus
Sour sodium, sodium pyrophosphate, the mass ratio of sodium tripolyphosphate are (1-3)：(1-3)：(1-3).
Preferably, described emulsion is acrylic emulsion, vinyl acetate-ethylene copolymerization emulsions, Styrene maleic acid
One kind in acid anhydride-acrylate polymer emulsion, SAN emulsion.
The mass concentration of the potassium silicate solution is 25-35wt%.
Present invention also offers the preparation method of above-mentioned inorganic mineral environment-friendlyfireproof fireproof paint, comprise the following steps：
(1) each component is added in Scattered Kettle, 0.5-1 hours is stirred under 500-1000 revs/min of rotating speed, obtain slurries；
(2) slurries are injected into grinder, grinds 0.5h；
(3) iron oxide is added after the completion of grinding, 0.5-1 hours are stirred under 100-500 revs/min of rotating speed.
A kind of inorganic mineral environment-friendlyfireproof fireproof paint of the present invention and preparation method thereof, by reasonably matching, preferably goes out
It is adapted to exterior coating thickener, the species and dosage of dispersant, improves coating waterproofing, Scratch Resistance, stain resistance, ventilative
Property, weatherability, avoid peeling, fade, while there is the advantages of not long mildew of fire protection flame retarding, automatic sterilization function, environmentally friendly, Er Qieshi
Work is easy, and environmental suitability is more preferable.
Embodiment
With reference to embodiment, the present invention is described further, as described below, is only the preferable implementation to the present invention
Example, is not limited the present invention, any person skilled in the art is possibly also with the disclosure above
Technology contents be changed to the equivalent embodiment changed on an equal basis.It is every of the invention without departing from the present invention program content, foundation
Technical spirit any simple modification that following examples are made or equivalent variations, all fall within protection scope of the present invention.
Each raw material introduction in embodiment：
Hydroxypropul starch, No. CAS：9049-76-7, the Zhengzhou biochemical chemical product Co., Ltd of dragon provide.
CMS, No. CAS：9063-38-1, Jinan Yuan Tong Chemical Co., Ltd.s provide.
Hydroxypropyl methyl cellulose, No. CAS：9004-65-3, Jinan Yuan Tong Chemical Co., Ltd.s provide.
Calgon, No. CAS：10124-56-8.
Sodium pyrophosphate, No. CAS：13472-36-1.
Sodium tripolyphosphate, No. CAS：7758-29-4.
Dimethicone, No. CAS：63148-62-9.
Acrylic emulsion, No. CAS：79-10-7, provided by Shandong Kaitai Petrochemical Co., Ltd..
Titanium dioxide, No. CAS：1317-80-2, particle diameter 20-40nm.
Iron oxide, No. CAS：1309-37-1.
Sepiolite, provided by Lingshou County Ling Ze mineral products processings factory.
Zinc oxide, No. CAS：1314-13-2, particle diameter 20-40nm.
Tourmaline, the crystal tourmaline produced using Lingshou County rock forming mineral powder factory, the mesh of specification 80.
Kaolin, Shanghai jump river titanium white heavy chemicals Co., Ltd provide, the mesh of specification 4000.
Ludox, using number of patent application：201210235302.8 prepared by the method for middle embodiment 2.
Potassium silicate solution, using number of patent application：In 90109316.5 prepared by the method for embodiment 1, and mass concentration is
28%.
Embodiment 1
Weigh each raw material (parts by weight)：Potassium silicate solution 3000g, dispersant 150g, thickener 150g, dimethicone
300g, acrylic emulsion 600g, titanium dioxide 1000g, iron oxide 600g, 600 parts of sepiolite, zinc oxide 500g, tourmaline
600g, kaolin 300g, Ludox 200g, water 2000g.
Described thickener by 50g hydroxypropul starch, 50g CMSs, 50g hydroxypropyl methyl celluloses mixing and
Into.
Described dispersant is mixed by 50g calgons, 50g sodium pyrophosphates, 50g sodium tripolyphosphates.
Prepared by inorganic mineral environment-friendlyfireproof fireproof paint, comprise the following steps：
(1) by potassium silicate solution 3000g, dispersant 150g, thickener 150g, dimethicone 300g, acrylic emulsion
600g, titanium dioxide 1000g, iron oxide 600g, 600 parts of sepiolite, zinc oxide 500g, tourmaline 600g, kaolin 300g, silicon
Colloidal sol 200g, water 2000g are added in Scattered Kettle, are stirred 0.5 hour under 800 revs/min of rotating speed, are obtained slurries；
(3) slurries are injected into disc grinder and (uses the disk of Shandong Fang Bang bio tech ltd model 001
Formula grinder), grind 0.5h；
(4) iron oxide 600g is added after the completion of grinding, is stirred 0.5 hour under 100-500 revs/min of rotating speed.
Embodiment 2
Inorganic mineral environment-friendlyfireproof fireproof paint is prepared by the raw material proportioning and method of embodiment 1, is differed only in：Described increasing
Thick dose is mixed by 75g hydroxypropul starch, 75g CMSs.Obtain the inorganic mineral environment-friendlyfireproof fireproof paint of embodiment 2.
Embodiment 3
Inorganic mineral environment-friendlyfireproof fireproof paint is prepared by the raw material proportioning and method of embodiment 1, is differed only in：Described increasing
Thick dose by 75g hydroxypropul starch, 75g hydroxypropyl methyl celluloses.Obtain the inorganic mineral environment-friendlyfireproof fireproof paint of embodiment 3.
Embodiment 4
Inorganic mineral environment-friendlyfireproof fireproof paint is prepared by the raw material proportioning and method of embodiment 1, is differed only in：Described institute
The thickener stated is mixed by 75g CMSs, 75g hydroxypropyl methyl celluloses.Obtain the inorganic mineral ring of embodiment 4
Protect fireproof coating.
Embodiment 5
Inorganic mineral environment-friendlyfireproof fireproof paint is prepared by the raw material proportioning and method of embodiment 1, is differed only in：Described point
Powder is mixed by 75g calgons, 75g sodium pyrophosphates.Obtain the inorganic mineral environment-friendlyfireproof fireproof paint of embodiment 5.
Embodiment 6
Inorganic mineral environment-friendlyfireproof fireproof paint is prepared by the raw material proportioning and method of embodiment 1, is differed only in：Described point
Powder is mixed by 75g calgons, 75g sodium tripolyphosphates.Obtain the inorganic mineral environment-friendlyfireproof fireproof paint of embodiment 6.
Embodiment 7
Inorganic mineral environment-friendlyfireproof fireproof paint is prepared by the raw material proportioning and method of embodiment 1, is differed only in：Described point
Powder is mixed by 75g sodium pyrophosphates, 75g sodium tripolyphosphates.Obtain the inorganic mineral environment-friendlyfireproof fireproof paint of embodiment 7.
Test case 1
The water resistance for the inorganic mineral environment-friendlyfireproof fireproof paint that embodiment 1-7 is prepared is tested.
This test is in strict accordance with GB 18445-2012 to its upstream face impermeability pressure, upstream face secondary impermeability pressure, backwater
Face impermeability pressure is tested, and concrete outcome is shown in Tables 1 and 2.
Table 1：Upstream face water resistance test data table
Table 2：Back side impermeability pressure test data table
| Impermeability pressure/MPa | |
| Embodiment 1 | 1.7 |
| Embodiment 2 | 0.9 |
| Embodiment 3 | 0.8 |
| Embodiment 4 | 1.0 |
| Embodiment 5 | 0.8 |
| Embodiment 6 | 1.1 |
| Embodiment 7 | 0.9 |
Comparing embodiment 1 and embodiment 2-4, embodiment 1 (hydroxypropul starch, CMS, hydroxypropyl methyl cellulose
Compounding) water resistance is substantially better than embodiment 2-4 (any two kinds of hydroxypropul starch, CMS, hydroxypropyl methyl celluloses
Compounding).Comparing embodiment 1 and embodiment 5-7, embodiment 1 (calgon, sodium pyrophosphate, tripolyphosphate compounding) water proofing property
Embodiment 5-7 (the two any compounding in calgon, sodium pyrophosphate, tripolyphosphate) can be substantially better than.
Test case 2
The anti-microbial property for the inorganic mineral environment-friendlyfireproof fireproof paint that embodiment 1-7 is prepared is tested, anti-microbial property
Surveyed by GB/T21866-2008 antibiotic paint anti-microbial property assay methods and antibacterial effect, HG/T 3980-2007 antibiotic paints
Fixed, detection project is antibacterial test and fungus-proof test.
Antibacterial test：Escherichia coli ATYCC 25922, staphylococcus aureus ATCC 6538.
Specific test result is shown in Table 3.
Table 3：Inorganic mineral environment-friendlyfireproof fireproof paint anti-microbial property test data
Comparing embodiment 1 and embodiment 2-4, in the case of antiseptic adds total amount identical, (hydroxypropyl forms sediment embodiment 1
Powder, CMS, hydroxypropyl methyl cellulose compounding) anti-microbial property be substantially better than embodiment 2-4 (hydroxypropul starch, carboxylic
The two any compounding of methyl starch, hydroxypropyl methyl cellulose).Comparing embodiment 1 and embodiment 5-7, (the six inclined phosphorus of embodiment 1
Sour sodium, sodium pyrophosphate, tripolyphosphate compounding) anti-microbial property is substantially better than embodiment 5-7 (calgon, sodium pyrophosphate, trimerization
The two any compounding in phosphoric acid).
Test case 3
Using《HG/T 4109-2009 anion function coating》Standard, the inorganic mineral environmental protection prepared to embodiment 1-7
Fireproof coating carries out negative aeroion and induces measurement examination, and specific test data is shown in Table 4.
Table 4：Negative aeroion induces measurement examination tables of data
| Sample name | The negative aeroion amount of inducing, individual/scm2 |
| Embodiment 1 | 1620 |
| Embodiment 2 | 1430 |
| Embodiment 3 | 1410 |
| Embodiment 4 | 1460 |
| Embodiment 5 | 1510 |
| Embodiment 6 | 1500 |
| Embodiment 7 | 1510 |
Comparing embodiment 1-4, embodiment 1 (hydroxypropul starch, CMS, hydroxypropyl methyl cellulose compounding) air
The anion amount of inducing (is adopted any in hydroxypropul starch, CMS, hydroxypropyl methyl cellulose apparently higher than embodiment 2-4
The two is compounded)；Comparing embodiment 1 and embodiment 5-7, embodiment 1 (calgon, sodium pyrophosphate, tripolyphosphate compounding) are empty
The gas anion amount of inducing is apparently higher than embodiment 5-7 (in calgon, sodium pyrophosphate, tripolyphosphate any the two compound).
Test case 4
Using《HG/T 4109-2009 anion function coating》Standard, the inorganic mineral environmental protection prepared to embodiment 1-7
Fireproof coating carries out Fire retardance and the time test of resistance to combustion, Fire retardance：Tested by GB/T15442.4 regulation, the resistance to combustion time：
Tested by GB/T15442.2 regulation.Specific test data is shown in Table 5.
Table 5：Fire retardance and resistance to combustion time test tables of data
Comparing embodiment 1-4, embodiment 1 (hydroxypropul starch, CMS, hydroxypropyl methyl cellulose compounding) back-fire relief
Property and the resistance to combustion time be substantially better than embodiment 2-4 and (adopt in hydroxypropul starch, CMS, hydroxypropyl methyl cellulose any
The two is compounded)；Comparing embodiment 1 and embodiment 5-7, embodiment 1 (calgon, sodium pyrophosphate, tripolyphosphate compounding) resistance
Fire and resistance to combustion time are substantially better than embodiment 5-7 (the two any compounding in calgon, sodium pyrophosphate, tripolyphosphate).
Claims (3)
1. a kind of inorganic mineral environment-friendlyfireproof fireproof paint, it is characterised in that be prepared by the raw material of following weight parts：Potassium silicate is molten
Liquid 15-35 parts, dispersant 1-1.5 parts, 1 part -2.5 parts of thickener, dimethicone 1-3 parts, emulsion 3-9 parts, titanium dioxide 1-
10 parts, iron oxide 1-9 parts, sepiolite 1-9 parts, zinc oxide 1-6 parts, tourmaline 1-8 parts, kaolin 1-4 parts, Ludox 0.5-
2.5 parts, water 10-50 parts；
Described thickener is made up of hydroxypropul starch, CMS, hydroxypropyl methyl cellulose, the hydroxypropul starch,
CMS, the mass ratio of hydroxypropyl methyl cellulose are (1-3)：(1-3)：(1-3)；
Described dispersant is made up of calgon, sodium pyrophosphate, sodium tripolyphosphate, the calgon, sodium pyrophosphate,
The mass ratio of sodium tripolyphosphate is (1-3)：(1-3)：(1-3).
2. inorganic mineral environment-friendlyfireproof fireproof paint as claimed in claim 1, it is characterised in that the emulsion be acrylic emulsion,
Vinyl acetate-ethylene copolymerization emulsions, phenylethylene-maleic anhydride-acrylate polymer emulsion, styrene-acrylonitrile polymerization
One kind in thing emulsion.
3. the preparation method of the inorganic mineral environment-friendlyfireproof fireproof paint as described in claim any one of 1-2, it is characterised in that including
Following steps：
(1) each component is added in Scattered Kettle, 0.5-1 hours is stirred under 500-1000 revs/min of rotating speed, obtain slurries；
(2) slurries are injected into grinder, grinds 0.5h；
(3) iron oxide is added after the completion of grinding, 0.5-1 hours are stirred under 100-500 revs/min of rotating speed.
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| CN110330821A (en) * | 2019-07-23 | 2019-10-15 | 苏州弗美斯环保科技有限公司 | Inorganic environment-friendly fire prevention mineral coating and its preparation process |
| CN112280345A (en) * | 2019-07-25 | 2021-01-29 | 富思特新材料科技发展股份有限公司 | Preparation method of damp-proof, mildew-proof and fire-resistant organic-inorganic composite coating for underground garage |
| CN111218136A (en) * | 2020-03-06 | 2020-06-02 | 成都虹润制漆有限公司 | Organic-inorganic hybrid fireproof coating and preparation method thereof |
| CN112680004A (en) * | 2021-01-19 | 2021-04-20 | 河南圣德哥尔无机水性涂料有限公司 | Inorganic interior wall antibacterial coating, spraying dispersion equipment and spraying dispersion method |
| CN113512312A (en) * | 2021-08-07 | 2021-10-19 | 简达康 | Waterproof and heat-insulating inorganic building coating |
| CN114106602A (en) * | 2021-10-12 | 2022-03-01 | 杜齐宝 | Inorganic coating and preparation method thereof |
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| KR100791052B1 (en) * | 2006-05-10 | 2008-01-03 | 우성테크 주식회사 | Fireproof Paint Composition and Manufacturing Method of using thereof for Fireproof Paint |
| CN102765925A (en) * | 2012-06-08 | 2012-11-07 | 高培元 | Mineral paint formula and manufacturing method thereof |
| CN103937302A (en) * | 2014-03-28 | 2014-07-23 | 珠海哥拜耳涂料有限公司 | Inorganic mineral coating and manufacturing method thereof |
| CN104559507A (en) * | 2014-12-29 | 2015-04-29 | 三棵树涂料股份有限公司 | Organic-inorganic composite paint and preparation method thereof |
| CN105130369A (en) * | 2015-07-22 | 2015-12-09 | 河北晨阳工贸集团有限公司 | Aqueous internal wall inorganic coating and preparation method thereof |
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