WO2008072492A1 - Pigment anti-rouille et composition de revêtement anti-corrosion contenant celui-ci - Google Patents

Pigment anti-rouille et composition de revêtement anti-corrosion contenant celui-ci Download PDF

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Publication number
WO2008072492A1
WO2008072492A1 PCT/JP2007/073202 JP2007073202W WO2008072492A1 WO 2008072492 A1 WO2008072492 A1 WO 2008072492A1 JP 2007073202 W JP2007073202 W JP 2007073202W WO 2008072492 A1 WO2008072492 A1 WO 2008072492A1
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WIPO (PCT)
Prior art keywords
mass
pigment
antifungal
amorphous inorganic
range
Prior art date
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PCT/JP2007/073202
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English (en)
Japanese (ja)
Inventor
Yutaka Kinose
Yasuyuki Tanaka
Minoru Yokoyama
Yasushi Yamakage
Heiji Uchiyama
Original Assignee
Nippon Chemical Industrial Co., Ltd.
Toho Ganryo Kogyo Co., Ltd.
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Application filed by Nippon Chemical Industrial Co., Ltd., Toho Ganryo Kogyo Co., Ltd. filed Critical Nippon Chemical Industrial Co., Ltd.
Publication of WO2008072492A1 publication Critical patent/WO2008072492A1/fr

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust

Definitions

  • Antifouling pigment and antifouling paint composition containing the same
  • the present invention relates to a pollution-free antifouling pigment that imparts excellent antifungal properties to a metal material, and an antifouling coating composition containing the same.
  • Conventional antifungal pigments include chromate (strontium chromate, basic zinc chromate, basic potassium potassium chromate, etc.) and lead compounds (lead red, lead suboxide, cyanamide lead, lead acidity) Noresium etc.) were used. These anti-bacterial pigments have excellent anti-corrosion performance for metals, but are toxic. As chromium and lead have been regulated as environmental pollutants, it is expected to provide new anti-fouling pigments to replace these materials.
  • Non-lead and non-chromium anti-bacterial pigments currently on the market include, for example, metal phosphates, phosphites, phosphosilicates, borosilicates, borates, metaborates, molybdenum
  • acid salts and polyphosphates As these metal cations, for example, calcium, strontium, norlium, zinc, anorium, magnesium and the like are used.
  • silica that has undergone ion exchange such as silica that has undergone calcium exchange, is also commercially available.
  • Patent Document 1 below discloses an antifungal pigment containing a phosphonic acid having a chelating ability.
  • Patent Document 2 discloses an antifungal pigment containing an organo-substituted phosphonic acid or a polyvalent metal salt of phosphonocarboxylic acid.
  • Patent Document 1 Japanese Patent Publication No. 11 512126
  • Patent Document 2 JP-A-7-207182
  • Patent Document 3 Japanese Patent Application Laid-Open No. 57-92588
  • Patent Document 4 Japanese Patent Laid-Open No. 57-149885
  • Patent Document 5 Japanese Unexamined Patent Publication No. 57-200279
  • Patent Document 6 Japanese Patent Laid-Open No. 58-69794
  • Patent Document 7 JP-A-58-89939
  • Patent Document 8 Japanese Patent Laid-Open No. 58-145681
  • Patent Document 9 JP-A-60-65785
  • Patent Document 10 Japanese Patent Laid-Open No. 62-270484
  • Patent Document 11 JP-A-8-295584
  • Patent Document 12 Japanese Patent Laid-Open No. 53-18636
  • antifouling pigments are mainly composed of aluminum tripolyphosphate or zinc phosphate.
  • anti-pigmenting pigments such as aluminum tripolyphosphate and zinc phosphate do not necessarily reach the same level of performance compared to chromium-based and lead-based anti-fading pigments. ⁇ Improved performance is required.
  • an object of the present invention is to provide a pollution-free antifouling pigment capable of imparting excellent antifungal properties to a metal material, and an antifouling coating composition containing the same.
  • An antifungal pigment comprising an amorphous inorganic composition containing 2 5 2 and MgO has a coating composition containing the antifungal pigment, in which the antifungal effect component in the pigment is slightly eluted in water.
  • the first invention to be provided by the present invention is that P 2 O, CaO, SiO, and MgO are used.
  • a second invention to be provided by the present invention is an antifouling paint composition comprising the antifouling pigment of the first invention.
  • a pollution-free fender capable of imparting excellent fender resistance to a metal material.
  • a pigment and an antifungal coating composition containing the pigment can be provided.
  • the antifungal pigment of the present invention contains PO, CaO, SiO, and MgO, and a preferred combination thereof.
  • the composition consists of (1) Phosphoric acid component P 0 10-30% by mass, preferably 15-25% by mass, (2) Force
  • Silicate component As a lucium ingredient. ⁇ 20-40% by mass, preferably 25-35% by mass, (3) Silicate component as Si ⁇ 10-30% by mass, preferably 15-25% by mass, (4) M as magnesium component
  • gO is 10 to 20% by mass, 12 to 17% by mass, and is characterized by comprising an amorphous inorganic composition that shows amorphous in X-ray diffraction analysis.
  • the antifouling pigment of the present invention comprising the amorphous inorganic composition has a stable pigment characteristic while each component elutes slightly, and a coating composition containing the antifouling pigment is used as a metal material table. When applied to the surface, it can provide excellent antifungal properties comparable to conventional coating compositions containing chromium or lead antifungal pigments.
  • the anti-glare pigment of the present invention if the proportion of each component is out of the range of the composition, crystallization of the inorganic composition occurs, and the elution of the component from the pigment tends to be easily lost. , There is a tendency that it does not function as an antifungal pigment, and it becomes difficult to obtain the effect of the present invention.
  • the antifungal pigment of the present invention contains 5% by mass or more of B 2 O if necessary in addition to the components (1) to (4).
  • Mn ⁇ can be contained in the range of 5 mass% or less, and Fe ⁇ , A1 ⁇ , Na
  • Components such as O can be contained in the range of 5% by mass or less.
  • the amorphous inorganic composition used in the anti-mold pigment of the present invention has a water content measured in accordance with JIS K5101-16-1 in the range of 0.;! To 1% by mass. It is more preferable that it is in the range of 0.1 to 0.6% by mass. If the water content is less than the above range, the metal material surface has an insufficient antifungal effect due to the components eluted in water, and if the water content exceeds the above range, the elution of the components is too fast and the antifungal effect is not good. It will not last long. Further, the phosphoric acid content to be dissolved is 0.001% or more as PO, preferably 0.001 to;
  • the content is from 0.002 to 0.5% by mass because the antifouling performance can be further improved.
  • the amorphous inorganic composition used in the anti-mold pigment of the present invention has a volume average particle size determined by measurement by a laser diffraction scattering method in the range of 0.5 to 15 m. More preferably, it is in the range of! To 5 in.
  • the volume average particle size of the amorphous inorganic composition is in the range of 0.5 to 15 111, the coating film applied to the surface of the metal material when the antifouling coating composition is prepared using this pigment is used. Appearance, strength and durability are good.
  • the amorphous inorganic composition used in the anti-mold pigment of the present invention preferably has a sieve residue of 1.0% by mass or less as measured in accordance with JIS K5101-14 1 More preferably, it is 5% by mass or less.
  • the sieve measured according to JIS K5101-14-l! / The residue is the sieve measured using a 45 m mesh! /, The residue, This value corresponds to the content of particles having a diameter of 45 m or more. If the sieve residue exceeds 1.0% by mass, the appearance, strength and durability of the coating applied to the surface of the metal material deteriorates when an antifouling paint composition is prepared using this pigment. To do.
  • the amorphous inorganic composition used for the anti-mold pigment of the present invention is produced by heating and melting a mixture containing a magnesium source, a calcium source, a phosphoric acid source and a silicic acid source, and then rapidly cooling the mixture. It is preferable in that it can prevent crystallization (mainly apatite formation) and elution of components such as phosphoric acid within the above range when in contact with water.
  • the mixture containing the magnesium source, calcium source, phosphoric acid source, and silicic acid source may be a mixture of compounds containing these components, or a compound containing two or more of these components. Or minerals may be used.
  • a particularly preferred amorphous inorganic composition has a molar compositional power of 1 ⁇ 2 MgO′yCaO.
  • the amorphous inorganic composition used in the antifungal pigment of the present invention can be produced by using a typical production method of molten phosphorus fertilizer, and is described in, for example, Patent Documents 3 to 11 and the like. It can be manufactured using a method or the like.
  • this amorphous inorganic composition can be produced by mixing and melting the raw materials containing the respective components, then rapidly cooling, and if necessary, pulverizing and classifying.
  • Contains each of the above ingredients For example, industrial raw materials such as calcium phosphate, magnesium phosphate, silica (natural products, synthetic products), calcium silicate, and natural raw materials (silica stone, quartz sand, phosphate rock, serpentinite, peridotite, etc.) are used. Can be manufactured.
  • (A) Phosphorous ore as a phosphorus-containing component is mixed with serpentinite or peridotite silicate and nickel slag containing both components as a main raw material. After adding a small amount of additive components such as gun or boron, heat melting at 1200 ° C or higher, preferably 1400 ⁇ ; 1500 ° C in a melting furnace such as an electric furnace or flat furnace, and then the melt is granulated and dried.
  • additive components such as gun or boron
  • the antifungal pigment according to the present invention is a metal compound containing one or more metal elements selected from the group consisting of Ca, Mg, Zn and Si in addition to the amorphous inorganic composition. When used together, the anti-fouling performance can be improved.
  • these metal powders and oxides, carbonates, hydroxides, phosphates, and phosphites of these metals can be used. It may be a thing. Of these, metal powders, metal oxides, and carbonates are preferably used because of their high synergistic effect, and zinc powder, zinc oxide, calcium carbonate, magnesium phosphite, amorphous silicic acid are particularly preferred.
  • One or more selected from the group consisting of The physical properties and the like of the metal compound are not particularly limited, but the volume average particle size determined by measurement by a laser diffraction scattering method is preferably in the range of 0.5 to 15 m, and 1 to 5 mm. A range of m is more preferable.
  • the volume average particle diameter is in the range of 0.5 to 15 11 m
  • an antifouling paint composition using this metal compound and the antifungal pigment When prepared, the appearance, strength and durability of the coating applied to the surface of the metal material become good.
  • these metal compounds can be included in a range of 5 to 100 parts by mass with respect to 100 parts by mass of the amorphous inorganic powder.
  • the metal compound to be used in combination may be prepared in advance as a uniform mixture with the antifungal pigment, and in the case of a coating composition to be described later, it should be added separately to the coating composition. tomorrow.
  • the anti-mold pigment and the metal compound are optionally surface-treated with an organic phosphate compound selected from acidic phosphate esters and / or phosphonic acids having chelate ability, or derivatives thereof.
  • Acid phosphates include, for example, methyl acid phosphate, dimethenorea acid phosphate, ethenorea acid phosphate, jetino acid acid phosphate, methyl ethyl acid phosphate, mono- or isopropyl acid phosphate, regular or isodipropyl acid phosphate , Methyl butyrate, positive or isooctyl acid phosphate, positive or isooctyl acid phosphate, positive decyl acid phosphate, positive decyl acid phosphate, positive laurinorea acid phosphate, positive sylaurino acid phosphate, positive or Is isocecylic acid phosphate, uni- or iso-decyl acyl
  • Typical examples of the phosphonic acid compound having chelating ability include aminoalkylenephosphonic acid, ethylenediaminetetraalkylenephosphonic acid, alkylmethane 1-hydroxy 1,1-diphosphonic acid, and 2-hydroxyphosphonoacetic acid. It is mentioned as.
  • examples of the aminoalkylenephosphonic acid include nitrilotristyrene phosphonic acid, nitrilotripropylenephosphonic acid, nitrilojetylmethylenephosphonic acid, nitrilopropylpropylmethylenephosphonic acid, and the like.
  • Examples of ethylenediaminetetraalkylene phosphonic acid include ethylenediaminetetramethylene phosphonic acid, ethylene Examples include amine tetraethylene phosphonic acid and ethylene diamine tetrapropylene phosphonic acid.
  • Examples of alkylene-1-hydroxy-1-, 1-diphosphonic acid include methane-1-hydroxy-1,1,1-diphosphonic acid, ethane-1-hydroxy-1,1,1-diphosphonic acid, propane 1-hydroxy L 1, 1-diphosphonic acid.
  • An acid etc. are mentioned, Mg, Ca, Sr, Ba, Zn or A of these compounds may be one or two or more complex salts selected, but it is not limited to these compounds.
  • the above acidic phosphate ester and phosphonic acid compound having chelating ability may be used alone or in combination of two or more.
  • the amount of acidic phosphate ester and / or phosphonic acid having chelating ability relative to phosphorus oxyacid salt is not uniform depending on the physical properties and type of the compound used, but is usually 0.;! To 30% by mass, preferably Is;! -10 mass%.
  • the anti-mold pigment and the metal compound may be further surface-treated with a higher fatty acid or a derivative thereof, a surfactant, or a silane coupling agent for the purpose of improving dispersibility.
  • the anti-mold pigment may be an inorganic cation exchanger such as hydrated calcite or hydrated talcite, or a nitrite alkali metal nitrite, an alkali metal nitrite, or an alkaline earth metal nitrite.
  • the force S is added so that the nitrate is added in an amount that does not impair the effects of the present invention.
  • the antifouling paint composition of the present invention contains the antifouling pigment and the paint vehicle.
  • a paint vehicle refers to a medium in which paint components are dispersed. That is, a polymer material such as a polymer oil, a natural or synthetic resin, an inorganic binder, a fiber or a rubber derivative, and the like, which are coating film forming components, or those dissolved in a solvent.
  • a polymer material such as a polymer oil, a natural or synthetic resin, an inorganic binder, a fiber or a rubber derivative, and the like, which are coating film forming components, or those dissolved in a solvent.
  • Examples of the synthetic resin include phenol resin, alkyd resin, melamine resin, guanazine resin, bull resin, epoxy resin, polyamine resin, acrylic resin, polybutadiene resin, polyester resin, urethane resin, and key resin. Fluoro resin etc. are mentioned, These may be mixed system or modified resin as needed.
  • examples of the inorganic binder include water-soluble silicates, modified aqueous silicates, alkyl silicates, alkoxy silicates, coupling agents, colloidal silica, and the like.
  • the water-soluble silicate is represented by the general formula MO -xSiO -yH ⁇ , where ⁇ is sodium.
  • Alkali metals such as lithium and potassium, N (CH OH), N (CH OH), N (CH OH), N (CH OH).
  • alkali metal silicates such as sodium silicate, potassium silicate and lithium silicate, triethanolamine silicate, tetramethanol silicate, tetraethanol ammonium silicate and the like.
  • the water-soluble silicate is a metal oxide, hydroxide, fluoride, silica selected from aluminum, magnesium, calcium, norlium, strontium, zinc, zirconium and vanadium. Modified with one or more of fluorides, or modified with sodium silicofluoride, potassium trisilicofluoride zincate, fluoroaluminum complex, fluorozinc complex (Patent Document 12) For example).
  • alkyl silicate is represented by the general formula: SiR or SiXR, wherein R is
  • X represents an alkoxy group, a bur group, an epoxy group, an amino group, a methacryl group, or a mercapto group.
  • alkyl group examples include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propino group, and a butyl group.
  • Specific examples of the alkyl group include tetramethyl Examples thereof include silicate, tetraethyl silicate, tetrapropyl silicate, tetraptyl silicate and the like.
  • the alkoxysilane is represented by the general formula: Si (OR) or SiX (OR) or SiR (OR).
  • R represents an alkyl group
  • X represents a bur group, an epoxy group, an amino group, a methacrylol group, or a mercapto group.
  • alkyl group include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples thereof include tetramethyloxysilicate, tetraethoxysilicate, tetrapropoxysilicate, tetrabutoxysilicate and the like.
  • Examples of the coupling agent include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropinoremethinolegoxysilane, ⁇ - (3,4 epoxy cyclohexylenesilane, and ⁇ mercapto.
  • Silane coupling agents such as propyltrimethoxysilane, isopropyl
  • titanium coupling agents such as sulfonyl titanate, aluminum coupling agents, zirconium coupling agents and the like.
  • the colloidal silica usually has a particle size of about 2 to 100 nm and a solid content of 20 to
  • Colloidal silica stabilized by the above can be used.
  • the coating film components may be used alone or in combination of two or more.
  • diluents water, alcohols, ketones, benzenes, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as liquefied paraffin are generally used in the field of paints.
  • the solvents that are used can be applied.
  • the blending amount of the antifungal pigment of the present invention with respect to the paint vehicle is usually 2 to 50% by mass, preferably 5 to 20% by mass.
  • the blending amount is less than 2% by mass, the fender resistance is lowered, and when it exceeds 50% by mass, preferable coating properties cannot be obtained.
  • the antifouling coating composition of the present invention may be used by incorporating various additives generally used in the coatings field as components other than those described above.
  • the antifouling coating composition of the present invention improves the antifouling performance by using in combination with a metal compound containing one or more metal elements selected from Ca, Mg, Zn and Si described above. It is preferable in that it can be performed.
  • the antifouling paint composition according to the present invention can be used for brushing, roller coating, spray coating, electrostatic coating, powder coating, roll coater, curtain flow coater, datebing coating, electrodeposition coating, and the like. .
  • the anti-fouling mechanism of the anti-fouling pigment according to the present invention is very complicated and has yet to be elucidated, the slightly eluted phosphate ions and silicate ions are It is presumed that magnesium ions and calcium ions stabilize metal materials while reacting with iron and zinc to form a strong passive film.
  • amorphous inorganic powder sample the amorphous inorganic composition that is the main component of the antifungal pigment of the present invention.
  • the water content of the obtained amorphous inorganic powder sample was measured according to JIS K5101-16-l. As a result, the water content was 0.31% by mass. Furthermore, as a result of analyzing the water-soluble component, it was found that 0.005% by mass of phosphate ions and silicate ions were mainly contained in the water-soluble components.
  • the antibacterial pigment was prepared by operating the amorphous inorganic powder sample prepared above and the metal compound at 2000 rpm for 5 minutes using a high speed mixer.
  • strontium chromate or antifungal pigment was prepared as described above.
  • zinc oxide has an average particle size of 1
  • im calcium carbonate has an average particle size of 1 ⁇ m
  • strontium chromate has an average particle size of 1 m
  • zinc phosphate has an average particle size of 5, im. It was used.
  • galvanized steel sheet • JIS G3302 SGCC hot dip galvanized steel sheet (hereinafter referred to as “galvanized steel sheet”)
  • the blending ratio of each test paint is as follows.
  • Alkyd resin 21 3 parts
  • Alkyd resin Beccosol P—470—70 (Dainippon Ink Chemical Co., Ltd.) Dryer: Dick Nate (Dainippon Ink Chemical Co., Ltd.)
  • Antifungal pigments 4. 4 parts
  • Epoxy resin Epicoat 1001X75 (Japanepoxy Resin)
  • Each steel plate of 0. 8 mm X 70 mm X I 50 mm was degreased with solvent, and each test paint was applied with a bar coater with a dry coating thickness set to 30 microns, and allowed to dry at room temperature for 1 week. After drying, the back and end surfaces of the coated steel plate were sealed with masking tape, and a cross cut was placed on the test painted surface.
  • a 5% NaCl aqueous solution was subjected to a spray test for 240 hours on a test coating plate under conditions of 35 ° C in the salt spray tester and 1 kg / cm 2 spray pressure.
  • the salt spray test results were evaluated for fouling performance by the following five-step evaluation method. The results are shown in Table 2.
  • Evaluation 4 Rust and blister occur within 2mm on one side from the cross cut part.
  • Evaluation 3 Rust and blister occur within 6mm on one side from the cross cut part.
  • Evaluation 2 Rust or blister occurs within 12mm on one side from the cross cut part.
  • Evaluation 1 Rust or blister occurs at 12mm or more on one side from the cross cut part.

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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)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention propose un pigment antirouille non polluant qui confère une excellente caractéristique anticorrosion à des matières métalliques et des compositions de revêtement anticorrosion contenant le pigment. Les compositions de revêtement anticorrosion sont caractérisées par le fait qu'elles consistent en une composition inorganique non cristalline contenant P2O5, CaO, SiO2 et MgO, de préférence consistant en une composition inorganique non cristalline contenant de 10 à 30 % en masse de P2O5, 20 à 40 % en masse de CaO, 10 à 30 % en masse de SiO2, et 10 à 20 % en masse de MgO.
PCT/JP2007/073202 2006-12-13 2007-11-30 Pigment anti-rouille et composition de revêtement anti-corrosion contenant celui-ci WO2008072492A1 (fr)

Applications Claiming Priority (2)

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JP2006-335635 2006-12-13
JP2006335635A JP5014762B2 (ja) 2006-12-13 2006-12-13 防錆顔料及びこれを含有する防錆塗料組成物

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WO2008072492A1 true WO2008072492A1 (fr) 2008-06-19

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WO2011024758A1 (fr) * 2009-08-24 2011-03-03 菊水化学工業株式会社 Revêtement anti-corrosion
JP2017137499A (ja) * 2010-10-15 2017-08-10 ブンゲ アモルプヒク ソルトイオンス エルエルシー 耐食性を有するコーティング組成物
JP2017141460A (ja) * 2010-10-15 2017-08-17 ブンゲ アモルプヒク ソルトイオンス エルエルシー 耐食性を有するコーティング組成物

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US20120094130A1 (en) * 2010-10-15 2012-04-19 Universidade Estadual De Campinas Coating Compositions With Anticorrosion Properties
TWI476273B (zh) 2012-12-04 2015-03-11 Dainippon Ink & Chemicals Liquid crystal display device
WO2014128885A1 (fr) 2013-02-21 2014-08-28 Dic株式会社 Dispositif d'affichage à cristaux liquides
WO2014203326A1 (fr) 2013-06-18 2014-12-24 Dic株式会社 Dispositif d'affichage à cristaux liquides
KR101545667B1 (ko) 2013-11-29 2015-08-19 디아이씨 가부시끼가이샤 액정 표시 장치
CN106590034B (zh) * 2016-12-13 2019-01-01 广西壮族自治区化工研究院 一种纳米氧化物无机包膜的亚磷酸盐粉体及含有该粉体的水性涂料
CN107673620A (zh) * 2017-11-08 2018-02-09 常熟市永达化工设备厂 搪玻璃管件
JP7357251B2 (ja) * 2019-02-04 2023-10-06 株式会社イーエスティージャパン 錆抑制塗料及びその製造方法
CN110591416A (zh) * 2019-08-23 2019-12-20 广州凌玮科技股份有限公司 一种无定形二氧化硅防锈颜料的制备方法

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