WO2017004904A1 - 一种常温固化型无机涂料及其制造方法 - Google Patents

一种常温固化型无机涂料及其制造方法 Download PDF

Info

Publication number
WO2017004904A1
WO2017004904A1 PCT/CN2015/091625 CN2015091625W WO2017004904A1 WO 2017004904 A1 WO2017004904 A1 WO 2017004904A1 CN 2015091625 W CN2015091625 W CN 2015091625W WO 2017004904 A1 WO2017004904 A1 WO 2017004904A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic
weight
inorganic coating
solution
functional
Prior art date
Application number
PCT/CN2015/091625
Other languages
English (en)
French (fr)
Inventor
刘晓东
Original Assignee
刘晓东
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 刘晓东 filed Critical 刘晓东
Priority to SG11201800116XA priority Critical patent/SG11201800116XA/en
Publication of WO2017004904A1 publication Critical patent/WO2017004904A1/zh

Links

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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/80—Processes for incorporating ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups

Definitions

  • the present invention relates to a coating material, and more particularly to a room temperature curing type inorganic coating material and a method for producing the same. More specifically, alkoxysilane (Alkoxy-Silane) and silica (SiO 2 ) particles are dispersed in water for water decomposition reaction. Thereafter, a polycondensation polymerization reaction is carried out, and then a filler, an inorganic pigment powder, and other curing accelerators are added to the solution in order to impart physicochemical properties to form a room temperature curable inorganic coating material.
  • the existing general coatings are used to protect structures, buildings, extend life and maintain aesthetics over a long period of time. Therefore, the coating (or coating agent) has good gloss, is easy to construct and tasteless, and the coating needs to be maintained for a long time. , with high chemical resistance (solvent resistance, drug resistance, weather resistance, water resistance, antibacterial, etc.) and beneficial physical properties (non-combustible, flame retardant, waterproof, adhesive, insulating, etc.), and harmless to the body or No environmental pollution, ensuring safety. These factors are the ultimate goal of the coating or coating agent.
  • various inorganic coatings are composed of four major factors: adhesives, pigments, solvents, additives, etc.
  • the so-called ceramic coatings contain adhesives, using silicon or epoxy.
  • An organic polymer such as polyester resin is filled with ceramic powder or acetone, benzene, toluene, xylene and An organic solvent such as ethyl acetate, and most of the additives are also organic.
  • the present invention provides a room temperature curing type inorganic coating and a manufacturing method thereof.
  • the room temperature curable inorganic coating can be cured at room temperature, and does not release organic gas after film formation, which is environmentally friendly.
  • the present invention adopts the following technical solutions:
  • the invention provides a room temperature curing type inorganic coating material, and the raw material of the inorganic coating material comprises the following components:
  • a functional auxiliary selected from potassium titanate, alumina or a combination thereof;
  • the raw material of the solution comprises the following components: 30-40% by weight of organoalkoxysilane (abbreviated as alkoxysilane, or simply organosilane), 15-20% by weight of organic solvent, 25-30% by weight of silica sol ;
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the invention provides a room temperature curing type inorganic coating material, and the raw material of the inorganic coating material comprises the following components:
  • a functional auxiliary selected from potassium titanate, alumina or a combination thereof;
  • the raw material of the inorganic solution comprises the following components: 30-40% by weight of organoalkoxysilane (abbreviated as alkoxysilane, or simply organosilane), 15-20% by weight of organic solvent, 25-30% by weight of silicon Sol
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the above inorganic coating material contains deionized water.
  • inorganic coatings may be referred to as inorganic ceramic coatings.
  • the organoalkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , the R 1 is selected from an alkyl group, and the R 2 is selected from an alkyl group.
  • the alkyl group has the formula C n H 2n+1 ; n is a positive integer, n ranges from 1-10; the total number of R 1 and OR 2 described above is 4, m is a non-negative integer, and m ranges from 0 to 3.
  • the organoalkoxysilane comprises a methyl group, an ethyl group, a phenyl group, a CF 3 CH 2 CH 2 , a CF 3 (CF 2 ) 5 CH 2 CH 2 , or a CF 3 ( One or a combination of at least two of CF 2 ) 7 CH 2 CH 2 .
  • the organoalkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , m is a non-negative integer, and m ranges from 0 to 3.
  • the R 1 is selected from the group consisting of methyl, ethyl, phenyl, CF 3 CH 2 CH 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 , or CF 3 (CF 2 ) 7 CH 2 CH 2 Or a combination of at least two.
  • the R 2 is selected from the group consisting of methyl, ethyl, phenyl, CF 3 CH 2 CH 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 , or CF 3 (CF 2 ) 7 CH 2 CH 2 Or a combination of at least two.
  • the silica sol comprises 20-40% of silica particles (SiO 2 ), and the particle diameter of the silica particles is nanometer to micrometer; the inorganic coating further includes Ionic water.
  • the inorganic pigment is selected from the group consisting of titanium oxide, chrome yellow, iron blue, cadmium red, cadmium yellow, carbon black, iron oxide red, iron oxide yellow, or a combination of at least two thereof.
  • the other functional auxiliary agent is selected from one or a combination of tourmaline, rare earth ore.
  • the functional additive includes 3-5 wt% of potassium titanate.
  • the potassium titanate is a needle-like potassium titanate having a particle size of 1-100 nm.
  • OR 2 is a hydrolyzable alkoxy group, which is decomposed by water (water in the coating, or moisture in the air or moisture on the surface of the substrate) to form a silicon hydroxide (Si-OH).
  • Si-OH silicon hydroxide
  • the above-mentioned silicon oxyhydroxide forms a Si-OM bond on the surface (M-OH) of the substrate, and strongly bonds with the substrate.
  • M represents a substrate.
  • the alkoxysilane is selected from the group consisting of one or a combination of methyltrimethoxysilane, tetraethoxysilane, and phenyltrimethoxysilane.
  • the organic solvent is selected from one or a combination of at least two of methanol, ethanol or isopropyl alcohol.
  • the invention also provides a method for preparing the inorganic coating, the method is as follows:
  • the raw materials of the inorganic coating are separately combined to prepare a main agent and a hardener;
  • the preparation method of the main agent is as follows: stirring the silica sol first, adding the organic solvent, continuing to stir, adding deionized water to continue stirring; controlling the reaction temperature to not exceed 50 ° C;
  • the above organic solvent is selected from the group consisting of methanol, ethanol, and different a propanol or a combination of at least two thereof;
  • the preparation method of the hardener is as follows: the organoalkoxysilane, the functional auxiliary, the inorganic pigment, and other functional additives are added to the deionized water to be stirred and uniformly mixed.
  • the raw materials of the inorganic coating are separately combined to prepare a main agent and a hardener;
  • the preparation method of the main agent is as follows: stirring the silica sol first, gradually adding the organic solvent, continuing to stir, and continuously adding deionized water; the process of mixing the silica gel and the deionized water generates heat, and the temperature of the reactor needs to be controlled. Not more than 50 ° C; the above organic solvent is selected from the group consisting of methanol, ethanol, isopropanol or a combination of at least two of these, which generally affects the drying speed after coating, but can compensate for the defects of drying speed and can improve the main agent Storage capacity.
  • the viscosity of the primary agent is usually measured with a Ford cup and the viscosity is usually 14-15 seconds.
  • the preparation method of the hardener is as follows: the organosilane, the functional auxiliary, the inorganic pigment, and other functional additives are added to the deionized water to be stirred and uniformly mixed.
  • the main agent and the hardener are uniformly mixed in a ratio of 1:1, filtered through a mesh of 325-1000 mesh, and filtered to obtain the inorganic coating.
  • a mixture of silica gel, deionized water, and ethanol is prepared by first stirring a silica gel, gradually adding ethanol, continuing to stir, and continuously adding deionized water.
  • the phenomenon of heat generation during the mixing of silica gel and deionized water requires control of the reactor temperature not exceeding 50 °C.
  • the above-mentioned main agent further contains methanol or isopropyl alcohol, which generally affects the drying speed after coating, but the invention can compensate for the defects of the drying speed and can improve the storage ability of the main agent.
  • the invention provides a further preparation method of the inorganic coating, the method comprising the following steps:
  • Preparation solution 30-40 wt% of organoalkoxysilane, 15-20 wt% of organic solvent, 25-30% of silica sol are mixed together, and stirred at a temperature of 40-50 ° C for 5-10 minutes. , making a solution in a sol state;
  • the functional auxiliary agent is one of potassium titanate, aluminum oxide or a combination thereof.
  • an inorganic solution is prepared: 30-40% by weight of alkoxysilane, 15-20% by weight of an organic solvent, and 25-30% of a silica sol are mixed together at a temperature of 40-50 ° C. The mixture was stirred for 5 to 10 minutes to prepare an inorganic solution in a sol state.
  • the method includes the following steps:
  • potassium titanate In order to improve the hardness of the inorganic coating, potassium titanate is used, which has the image of fiber, so it is rich in the toughness of the material.
  • a metal oxide can be used for the colored inorganic pigment.
  • the above organosilane is preferably one of methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane, or a combination of at least two.
  • inorganic coatings are also referred to as inorganic ceramic coatings.
  • the method for producing the above inorganic ceramic coating composition is as follows: 1. a stage of preparing an inorganic solution in a sol state: mixing 25-30% by weight of a silica sol into 30-40% by weight of one or two or more organosilanes, Stirring at a temperature of 40 ° C to 50 ° C for about 5-10 minutes to obtain an inorganic solution in a sol state; 2.
  • Stirring and mixing stage 70-80 wt% of the obtained inorganic solution, potassium titanate and/or alumina functional auxiliary 5-10wt%, pigment powder composed of titanium oxide 10-20wt%, and other functional additives 0.5-2.0wt%, put together in the reactor and stir mixing;
  • Filtration The material homogenized in the above stage is filtered in a 325-1000 mesh to remove large particles, and the obtained Inorganic ceramic coatings.
  • methanol, ethanol, isopropanol or a mixture thereof is added to adjust the viscosity and reaction rate of the solution.
  • 3-5 wt% of potassium titanate having a particle size of 1-100 nm is contained.
  • the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , R 1 is an alkyl group, methyl, ethyl, phenyl, CF 3 CH 2 CH 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 , CF 3 (CF 2 ) 7 CH 2 CH 2 , etc., OR 2 is a hydrolyzable alkoxy group, which is hydrolyzed by water or moisture in the air or water on the surface of the substrate to form a silicon hydroxide (Si- OH), the above-mentioned silicon oxyhydroxide forms a bonding bond of Si-OM on the surface (M-OH) of the substrate, and strongly bonds with the substrate (M).
  • Si- OH silicon hydroxide
  • the stable inorganic axis composed of silicon-oxygen has higher binding energy than other bonding degrees, exhibits weathering, chemical resistance, wear resistance, high hardness, etc., and flexibility due to silicon-oxygen bonding. And elastic has cold resistance and strong thermal shock, as shown in Table 1 below:
  • the organosilane is hydrolyzed and polycondensed in the presence of silicon oxide to form an inorganic solution containing Si-OH, which forms a strong binding force (Si-OM) from Si-OH.
  • the inorganic solution itself has a strong binder function.
  • the organosilane includes one of tetraethoxysilane, methyltrimethoxysilane or a mixture of the above two substances, and 20-30% of a silica sol is added and stirred to prepare the above inorganic solution. If the proportion of silica gel exceeds the specified range, the bonding strength of (Si-O-M) will decrease, and peeling of the coating film will occur in a high heat environment. It is recommended to mix within the specified range.
  • methanol, ethanol, isopropanol or a mixture thereof may be added.
  • Any of the compounds can adjust the viscosity of the solution, the reaction rate, and the like.
  • functional aids such as potassium titanate or alumina can be used, and these materials are needle-like or plate-like, and have the effect of preventing the porcelain from sticking or adjusting the viscosity. It is recommended that the filler be in the range of 5 to 10% by weight, such as less than 5% by weight, the performance is remarkably lowered, and the surface of the coating film may be rough, such as higher than 10% by weight, and the gloss or adhesion is low.
  • the composition of the inorganic ceramic coating of the present invention can replace the conventional paint.
  • the color needs to be varied.
  • most of the paints have been added with organic pigments or dyes for various colors, but the organic matter causes various problems.
  • the inorganic ceramic coating composition is added with a metal oxide pigment in order to embody both inorganic and multi-colored colors. It is recommended that such a pigment powder accounts for about 10-20% by weight, such as less than 10-20% by weight, and the gloss may be lowered. If it exceeds this range, the adhesion of the coating film to the substrate may be weakened. Further, in order to impart various properties to the coating film, the inorganic ceramic coating composition of the present invention contains 0.5 to 2.0% by weight of other functional auxiliary.
  • titanium dioxide may be added to the above inorganic coating, and titanium dioxide is activated by light, and has a function of converting various pollutants into harmless substances.
  • an appropriate other functional auxiliary may be added to the above inorganic coating.
  • Other functional auxiliaries include materials that release anions. Recently, commonly used anions that release anions are mainly tourmaline and rare earth ore.
  • the above inorganic ceramic coating composition is produced in the following four stages.
  • the preparation of the inorganic solution in the stage of preparing the inorganic solution, more than 1-2 kinds of organosilanes are selected, in particular one of methyltrimethoxysilane or tetraethoxysilane or a mixture of the two substances is selected. . 30-40% by weight of organosilane, 15-20% by weight of ethanol, 25-30% of silica sol are mixed together, and stirred at a temperature of 40-50 ° C for about 5-10 minutes, at which time a mixed solution of organosilane and silica gel A chemical reaction occurs, and a phenomenon of heat generation occurs, and the state of turbidity gradually changes to a transparent state during the reaction.
  • stirring the mixed solution in the stage of stirring the mixed solution, one of the inorganic solution (70-80 wt%), potassium titanate or alumina prepared in the previous stage is selected as a functional auxiliary (5-10 wt%),
  • the pigment powder (10-20% by weight) composed of titanium oxide and other functional assistants (0.5-2.0% by weight) are mixed and stirred to form an inorganic ceramic mixture.
  • homogenization In the homogenization stage, the agitated material is placed in a homogenizer, and the particles are homogenized by stirring at a high speed for 1-2 hours.
  • the inorganic coating provided by the invention imparts flexibility to the coating film by adding functional additives, prevents cracking, and solves the phenomenon of thick film, and is used for producing a pure inorganic coating which is cured at room temperature, and is subjected to condensation polymerization by using a silica sol and an alkoxysilane. It is cured at room temperature, and forms an inorganic coating film which is harmless to the body and has no environmental pollution.
  • the room temperature curable inorganic coating provided by the present invention has an unprecedented excellent property. That is, it solves the problem of the normal temperature curing of an inorganic coating. When it is sprayed on a large structure, it does not need to have a large baking equipment, so it does not need a boiler and other parts and equipment, and can also save fuel costs, is also beneficial to the environment, and can improve production. effectiveness.
  • the room temperature curing type inorganic coating provided by the invention does not contain harmful organic components, is easy to construct, has no odor, is excellent in chemical and physical properties, can maintain the coating film for a long time, is harmless to the human body, does not induce environmental pollution, and ensures safety, Provide useful results.
  • the occurrence of new house syndrome can be prevented, and all the constituents after film formation are inorganic substances, so environmental pollution can be minimized after disposal, and because it can be prevented Peeling or fading can maintain a beautiful appearance for a long time and is resistant to heat and ultraviolet rays.
  • the invention provides an inorganic coating, the preparation method of the coating is as follows:
  • a mixture of one or both of methyltrimethoxysilane or tetraethoxysilane is 30 wt%
  • ethanol is 15 wt%
  • silica sol (abbreviated as silica gel) is 30 wt%.
  • the mixture was mixed and stirred at a temperature of 40 to 50 ° C for about 5 to 10 minutes, and a mixture of the alkoxysilane and the silica sol was chemically reacted, and a heat generation phenomenon occurred, and gradually changed from a turbid state to a transparent liquid as the reaction progressed.
  • one of methanol, ethanol, isopropyl alcohol or a mixture thereof is selected, and after these steps, an inorganic solution in a sol state is produced.
  • one of the inorganic solution, potassium titanate or alumina prepared in the above stage is selected as a functional additive 9 wt%, titanium oxide pigment powder 15 wt% and other functional additives 1 wt.
  • the % mixture was stirred together to form an inorganic ceramic mixture.
  • the agitated substance is placed in a homogenizer, and the mixture is stirred at a high speed for 1-2 hours to homogenize the particles.
  • the material which has been homogenized in the above stage is filtered on a filter mesh of a certain size, and after the particles are extracted, the paint is finally completed.
  • the invention provides an inorganic coating material, which comprises the following ingredients:
  • the raw material of the inorganic solution comprises the following components: 30 wt% of tetraethoxysilane, 15 wt% of ethanol, 25 wt% of silica sol;
  • the functional additive is a combination of potassium titanate and aluminum oxide, wherein the content of potassium titanate is 3 wt%;
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the invention provides an inorganic coating material, which comprises the following ingredients:
  • the raw material of the inorganic solution comprises the following components: 40 wt% of tetraethoxysilane and methyltrimethoxysilane composition, weight ratio of tetraethoxysilane and methyltrimethoxysilane Is 1:1, 15wt% ethanol, 25wt% silica sol;
  • the functional additive is a combination of potassium titanate and aluminum oxide, wherein the content of potassium titanate is 4%;
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the invention provides an inorganic coating material, which comprises the following ingredients:
  • the raw material of the inorganic solution comprises the following components: 30 wt% of methyltrimethoxysilane, 20 wt% of ethanol, and 30 wt% of silica sol;
  • the functional additive is a combination of potassium titanate and aluminum oxide, wherein the content of potassium titanate is 5%;
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the invention provides an inorganic coating material, which comprises the following ingredients:
  • the raw material of the inorganic solution comprises the following components: 30 wt% of methyltriethoxysilane, 15 wt% of ethanol, and 29.5 wt% of silica sol;
  • the functional additive is potassium titanate
  • the other functional auxiliaries are rare earth ores.
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the invention provides an inorganic coating material, which comprises the following ingredients:
  • the raw material of the inorganic solution comprises the following components: 35 wt% of alkoxysilane, 15 wt% of ethanol, 27 wt% of silica sol;
  • the functional additive is potassium titanate
  • the other functional auxiliaries are a combination of tourmaline and rare earth ore, the weight ratio of the two is 1:1.
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • Example 6 An inorganic coating as provided in Example 6, wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , the R 1 is CF 3 CH 2 CH 2 ; the R 2 is CF 3 CH 2 CH 2 . m is 1.
  • Example 6 wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , and the R 1 is CF 3 (CF 2 ) 5 CH 2 CH 2 ; R 2 is CF 3 (CF 2 ) 5 CH 2 CH 2 . m is 2.
  • Example 6 wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , and the R 1 is CF 3 (CF 2 ) 7 CH 2 CH 2 ; R 2 is CF 3 (CF 2 ) 7 CH 2 CH 2 . m is 3.
  • Example 6 The inorganic coating material as provided in Example 6, wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , the R 1 is a methyl group; and the R 2 is a phenyl group. m is 1.
  • Example 6 An inorganic coating as provided in Example 6, wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , the R 1 is an ethyl group; and the R 2 is CF 3 CH 2 CH 2 . m is 1.
  • Example 6 An inorganic coating as provided in Example 6, wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , the R 1 is a phenyl group; and the R 2 is CF 3 (CF 2 ) 7 CH 2 CH 2 . m is 2.
  • Example 6 As the inorganic coating provided, wherein said alkoxysilane of the formula R 1 m Si (OR 2) 4-m represents the R 1 is CF 3 CH 2 CH 2; R 2 is the A base. m is 3.
  • Example 6 wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , and the R 1 is CF 3 (CF 2 ) 5 CH 2 CH; R 2 is a combination of a methyl group and an ethyl group. m is 2.
  • Example 6 wherein the alkoxysilane is represented by the formula R 1 m Si(OR 2 ) 4-m , and the R 1 is CF 3 (CF 2 ) 7 CH 2 CH 2 ; R 2 is a phenyl group. m is 1.
  • the inorganic coating obtained in the above examples was applied onto a substrate to form a coating film having a film thickness of 30 ⁇ 5 ⁇ m and a substrate: an aluminum plate.
  • the size of the substrate test piece was 15 cm ⁇ 7.5 cm, and it was allowed to stand at room temperature for 7 days after film formation to form a strong coating film.
  • Example 1 45-55 7-9H Level 0
  • Example 2 45-55 7-9H Level 0
  • Example 3 35-45 8-9H Level 1
  • Example 4 45-55 7-9H Level 1
  • Example 5 40-50 7-9H Level 0
  • Example 6 40-50 7-9H Level 0
  • Example 7 40-50 7-9H Level 0
  • Example 8 45-55 7-9H Level 0
  • Example 9 30-35 6-9H Level 0
  • Example 10 30-35 6-9H Level 1
  • Example 11 45-50 7-9H Level 0
  • Example 12 45-55 7-9H Level 0
  • Example 13 25-30 6-8H Level 1
  • Example 14 30-35 7-8H Level 0
  • Example 15 40-50 7-9H Level 0
  • Example 16 40-50 7-9H Level 0
  • Pencil hardness test The pencil for the experiment was clamped on the hardness tester at an angle of 45°, and the load (1 kg) was applied to advance the test. A Mitsubishi pencil was used.
  • Abrasion resistance test Using the wear tester (Model KPM-042), the wheel used was CS-10wheel, put the test piece on the wear tester, hang the load of 500g, rotate 500 times, and then use the UV spectrophotometer. At 370 nm, the absorbance was measured to see if the surface became blurred, and the wear resistance was finally detected.
  • the room temperature curing type inorganic coating provided by the invention can be cured at room temperature, and the formed coating film has high hardness, good acid resistance, alkali resistance, salt water resistance and weather resistance. And the adhesion is better.
  • the room temperature curable inorganic coating provided by the invention can be widely used in architectural coatings and anticorrosive coatings.
  • the invention provides an inorganic coating material, the raw material of the inorganic coating material comprising the following components:
  • the raw material of the solution comprises the following components: 35 wt% methyltrimethoxysilane, 15 wt% propanol, 25 wt% silica sol;
  • the functional additive is potassium titanate
  • the other functional auxiliaries are rare earth ores.
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the inorganic coating provided in this embodiment is coated in a metal pot to form a coating, and the coating meets the requirements of the US FDA for the content of the resin and polymer coating extract.
  • the specific test methods and results are as follows:
  • the invention provides an inorganic coating material, the raw material of the inorganic coating material comprising the following components:
  • the raw material of the inorganic solution comprises the following components: 30 wt% of tetraethoxysilane, 20 wt% of ethanol, 30 wt% of silica sol;
  • the functional additive is a combination of potassium titanate and aluminum oxide, wherein the content of potassium titanate is 5%;
  • the above percentages are the weight percentage of each raw material to the total weight of the inorganic coating.
  • the inorganic coating provided in this embodiment is coated on a metal plate to form a coating according to Articles 30 and 31 of the German Food and Commodity Law (LFGB), the European Commission Regulation AP(2004)1 and the BfR proposal LI2006APR1 and DIN51032:1986.
  • the coating was tested as described below and the results showed that the coating was Articles 30 and 31 of the LFGB, European Commission Regulations AP (2004) 1 on the sensory, and PFOS, PFOA safety limit requirements, and DIN51032: 1986 requirements for ceramic lead cadmium cobalt dissolution safety limits.
  • Test conditions 100 ° C, 240 hours
  • Test medium deionized water
  • Test method Refer to EN1388-1/2: 1995 dissolution test of lead and cadmium on ceramic ware or silicate surface, and analyze by atomic absorption spectrometer.
  • Test method The sample was extracted with olive oil at 175 ° C for 120 minutes, and the extract was analyzed by high performance liquid chromatography.
  • Test method Refer to EPA3550C:2007, extract the extract by high performance liquid chromatography

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)
  • Silicon Compounds (AREA)

Abstract

一种常温固化型无机涂料及其制造方法，该无机涂料的原料包括：70-80wt％的溶液；5-10 wt％的功能助剂，该功能助剂选自钛酸钾、氧化铝或者二者的组合物；10-20wt％的无机颜料；0.5-2.0wt％的其它功能助剂；该溶液的原料包括下述成份：30-40wt％的烷氧基硅烷，15-20wt％的有机溶剂，25-30wt％的硅溶胶。该常温固化型无机涂料能够在常温固化，且成膜后不会释放有机气体，利于环保。

Description

一种常温固化型无机涂料及其制造方法 技术领域
本发明涉及涂料，特别涉及一种常温固化型无机涂料及其制造方法，更详细地说，烷氧基硅烷(Alkoxy-Silane)和二氧化硅(SiO2)粒子分散在水中，进行水分解反应后，接着进行缩聚合(Polycondensation polymeR1ization)反应，之后在此溶液里为了赋予物理化学性能，添加填充剂、无机颜料粉和其他固化促进剂，形成一种常温固化型无机涂料。
背景技术
现有一般的涂料(或者涂层剂)的作用是保护结构物、建筑物，延长寿命和长期维持美观，因此涂料(或者涂层剂)光泽度要好，便于施工且无味，涂层要长期维持，具有高耐化学性(耐溶剂性，耐药物性，耐候性，耐水性，抗菌等)和有益的物理性能(不燃，难燃，防水，附着，绝缘性等)，且对身体无害或无环境污染，确保安全性。这些因素是涂料或涂层剂要追求的最终目标。
传统的防腐蚀或者建筑涂料从原油里提取有机物，再混合多种化学药品而制作，含大量的有机成分，施工后过一段时间，在涂层上形成的龟裂缝里会繁殖微生物，会出现剥离的现象，如长时间暴露在紫外线的环境下会褪色，且防污效果下降。并且，大部分涂料里具有各种对人体有害的污染物质，由此会诱发皮肤病，头疼，呕吐等环境性疾病。并且，石油的储藏量有限，但需求急剧增加，生产涂料时所需原料的供求也越来越紧张。同时，为了解决上述传统涂料出现的问题，提出的各种无机涂料由粘合剂、颜料、溶剂、添加剂等四大因素组成，平时所谓的陶瓷涂料包含粘合剂，是使用硅或者环氧，涤纶树脂之类的有机高分子填充陶瓷粉或者使用丙酮、苯、甲苯、二甲苯及 乙酸乙酯等有机溶剂，且大部分的添加剂也都是有机物。
另外，传统的陶瓷涂料或涂层剂大部分硬性强，容易出现严重的龟裂现象，不易涂上去，尤其是近期推出的无机陶瓷涂层剂需在200℃下加热干燥，在现场施工，会有很多问题。
发明内容
为了解决有机涂料不环保，传统的陶瓷涂料硬性强，现场施工不方便的问题，本发明提供一种常温固化型无机涂料及其制造方法。该常温固化型无机涂料能够在常温固化，且成膜后不会释放有机气体，利于环保。
为了解决上述技术问题，本发明采用下述技术方案：
本发明提供一种常温固化型无机涂料，所述无机涂料的原料包括下述成份：
70-80wt％的溶液；
5-10wt％的功能助剂，所述功能助剂选自钛酸钾、氧化铝或者二者的组合物；
10-20wt％的无机颜料；
0.5-2.0wt％的其它功能助剂；
所述溶液的原料包括下述成份：30-40wt％的有机烷氧基硅烷(简称为烷氧基硅烷，或简称为有机硅烷)，15-20wt％的有机溶剂，25-30wt％的硅溶胶；
上述百分比为各原料占无机涂料总重的重量百分比。
本发明提供一种常温固化型无机涂料，所述无机涂料的原料包括下述成份：
70-80wt％的无机溶液；
5-10wt％的功能助剂，所述功能助剂选自钛酸钾、氧化铝或者二者的组合物；
10-20wt％的无机颜料；
0.5-2.0wt％的其它功能助剂；
所述无机溶液的原料包括下述成份：30-40wt％的有机烷氧基硅烷(简称为烷氧基硅烷，或简称为有机硅烷)，15-20wt％的有机溶剂，25-30wt％的硅溶胶；
上述百分比为各原料占无机涂料总重的重量百分比。
进一步的，上述无机涂料中含有去离子水。
上述无机涂料可称为无机陶瓷涂料。
进一步的，所述的无机涂料中，所述有机烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1选自烷基，所述R2选自烷基，烷基的通式为CnH2n+1；n是正整数，n的范围是1-10；上述R1和OR2的总数量是4，m是非负整数，m的范围是0-3。
进一步的，所述无机涂料中，所述有机烷氧基硅烷包含有甲基、乙基、苯基、CF3CH2CH2、CF3(CF2)5CH2CH2、或CF3(CF2)7CH2CH2中的一种或至少两种的组合。
进一步的，所述有机烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，m是非负整数，m的范围是0-3。所述R1选自甲基、乙基、苯基、CF3CH2CH2、CF3(CF2)5CH2CH2、或CF3(CF2)7CH2CH2中的一种或至少两种的组合。所述R2选自甲基、乙基、苯基、CF3CH2CH2、CF3(CF2)5CH2CH2、或CF3(CF2)7CH2CH2中的一种或至少两种的组合。
进一步的，所述无机涂料中，所述硅溶胶包括20-40％的二氧化硅粒子(SiO2)，所述二氧化硅粒子的粒径是纳米至微米级；所述无机涂料还包括去离子水。
进一步的，所述无机颜料选自氧化钛、铬黄、铁蓝、镉红、镉黄、炭黑、氧化铁红、氧化铁黄中的一种或其中至少两种的组合。
进一步的，所述无机涂料中，所述其它功能助剂选自电气石，稀土类原矿石中的一种或两种的组合。
进一步的，所述无机涂料中，所述功能助剂中包括3-5wt％的钛酸钾。进一步的，所述钛酸钾为针状的粒度为1-100nm的钛酸钾。
进一步的，所述无机涂料中，OR2为加水分解性烷氧基，被水(涂料中的水、或者空气中的水分或者基材表面的水分)分解，形成硅氢氧根(Si-OH)，上述的硅氢氧根在基材的表面(M-OH)上形成Si-O-M的结合，与基材强有力的结合。M表示基材。
进一步的，所述无机涂料中，烷氧基硅烷选自甲基三甲氧基硅烷、四乙氧基硅烷、苯基三甲氧基硅烷中的一种或两种的组合物。进一步的，所述有机溶剂选自甲醇，乙醇或者异丙醇中的一种或至少两种的组合。
本发明还提供所述的无机涂料的制备方法，所述方法如下：
将所述无机涂料的原料分别组合制备成主剂和硬化剂；
所述主剂的制备方法如下：先搅拌硅溶胶，添加有机溶剂后继续进行搅拌，再添加去离子水继续进行搅拌；控制反应温度不超过50℃；上述的有机溶剂选自甲醇、乙醇、异丙醇或者其中至少两种的组合物；
所述硬化剂的制备方法如下：将有机烷氧基硅烷，功能助剂，无机颜料，以及其他功能助剂加入去离子水中搅拌，混合均匀。
进一步的，所述方法如下：
将所述无机涂料的原料分别组合制备成主剂和硬化剂；
所述主剂的制备方法如下：先搅拌硅溶胶，渐渐地添加有机溶剂后继续进行搅拌，再持续添加去离子水；硅胶和去离子水混合的过程中会产生发热现象，需要控制反应器温度不超过50℃；上述的有机溶剂选自甲醇、乙醇、异丙醇或者其中至少两种的组合物，这些一般会影响涂装后的干燥速度，但可弥补干燥速度的缺陷而且可提高主剂的储藏能力。
所述主剂的粘度通常是用福特杯(Ford cup)检测，粘度通常是14-15秒。
所述硬化剂的制备方法如下：将有机硅烷，功能助剂，无机颜料，以及其他功能助剂加入去离子水中搅拌，混合均匀。
在使用时，将主剂和硬化剂按照1：1的比例混合均匀，经325-1000目的网过滤，过滤后所得即所述的无机涂料。
进一步的，上述的无机涂料的制备方法中，由硅胶及去离子水，乙醇构成的混合物的制作方法是先搅拌硅胶，渐渐地添加乙醇后继续进行搅拌，再持续添加去离子水。硅胶和去离子水混合的过程中会产生发热现象，需要控制反应器温度不超过50℃。上述的主剂里还包含有甲醇或者异丙醇，这些一般会影响涂装后的干燥速度，但此发明可弥补干燥速度的缺陷而且可提高主剂的储藏能力。
本发明提供所述的无机涂料的又一种制备方法，所述方法包括下述步骤：
(1)制作溶液：将30-40wt％的有机烷氧基硅烷、15-20wt％的有机溶剂、25-30％的硅溶胶混合一起，在40-50℃的温度下，搅拌5-10分钟，制作成溶胶状态的溶液；
(2)搅拌混合溶液：将上述步骤(1)制得的无机溶液、5-10wt％的功能助剂,10-20wt％的无机颜料，0.5-2.0wt％的其它功能助剂混合在一起搅拌，形成无机陶瓷混合物；
(3)均匀：把上述步骤(2)制得的无机陶瓷混合物放进均质器，高速搅拌1-2小时使混合物搅拌均匀；
(4)提取涂料：将上述步骤(3)制得的已搅拌均匀的物质在325-1000目的过滤网上过滤，经过滤后的物质即为所述的无机涂料。
进一步的，所述功能助剂是钛酸钾、氧化铝中的一种或其组合。
进一步的，上述步骤(1)中，制作无机溶液：将30-40wt％的烷氧基硅烷、15-20wt％的有机溶剂、25-30％的硅溶胶混合一起，在40-50℃的温度下，搅拌5-10分钟，制作成溶胶状态的无机溶液。
进一步的，所述方法包括下述步骤：
(1)制作无机溶液：将30-40wt％的烷氧基硅烷、15-20wt％的有机溶剂、25-30％的硅溶胶混合一起，在40-50℃温度下，搅拌5-10分钟，这时烷氧基 硅烷(简称有机硅烷)和硅胶的混合溶液产生化学反应，出现发热现象，在反应过程中由浑浊的状态逐渐变为透明的状态；加入有机溶剂的目的是为了调节溶液的粘度和反应速度，经过这样的工序，制作成溶胶状态的无机溶液；
(2)搅拌混合溶液：将60-70wt％的上述步骤(1)制得的无机溶液、5-10wt％的钛酸钾或者氧化铝,10-20wt％的颜料，0.5-2.0wt％的其它功能助剂混合在一起搅拌，形成无机陶瓷混合物；
(3)均匀：把上述步骤(2)制得的无机陶瓷混合物放进均质器，高速搅拌1-2小时使混合物搅拌均匀；
(4)提取涂料：将上述步骤(3)制得的已搅拌均匀的物质在325-1000目的过滤网上过滤，经过滤后的物质即为所述的无机涂料。
为了改善无机涂料的硬性，使用钛酸钾，它具有纤维的形象，所以富有增强材料韧性的功能。着色的无机颜料可使用金属氧化物。
上述有机硅烷优选甲基三甲氧基硅烷、甲基三乙氧基硅烷、苯基三甲氧基硅烷中的一种或至少两种的组合。
上述的无机涂料也称为无机陶瓷涂料。
制作上述的无机陶瓷涂料组合物的方法是：一、制作溶胶状态的无机溶液的阶段：向一种或两种或两种以上的有机硅烷30-40wt％里混合25-30wt％的硅溶胶，在40℃-50℃的温度下搅拌约5-10分钟，得到溶胶状态的无机溶液；二、搅拌混合阶段：将得到的无机溶液70-80wt％，钛酸钾和/或氧化铝功能助剂5-10wt％，由氧化钛构成的颜料粉10-20wt％，以及其它功能助剂0.5-2.0wt％，一同放入反应器里搅拌混合；三、均匀化阶段：将上述阶段中搅拌混合的物质放进均质器里高速搅拌1-2小时使使粒子均匀化；四、过滤：把在上述阶段里均匀化的物质在325-1000目的网里过滤，除去大颗粒粒子，得到所述的无机陶瓷涂料。
进一步的，在制作无机溶液的阶段，加入甲醇、乙醇、异丙醇或者其混合物，以调节溶液的粘度和反应速度。进一步的，在上述的搅拌混合阶段， 加入的5-10wt％功能助剂当中包含粒子大小为1-100nm的钛酸钾3-5wt％。
下面详细说明关于此发明的构成及制作过程。
上述无机溶液的物质结构和原理如下：
烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，R1为烷基，甲基、乙基、苯基、CF3CH2CH2、CF3(CF2)5CH2CH2、CF3(CF2)7CH2CH2等，OR2为加水分解性烷氧基，被水或者空气中的水分或者基材表面的水分加水分解，形成硅氢氧根(Si-OH)，上述的硅氢氧根在基材的表面(M-OH)上形成Si-O-M的结合键，与基材(M)强有力的结合。由硅-氧构成的稳定的无机轴，结合能量比其他结合度偏高，表现出耐候性、耐化学性、耐磨性、高硬度等的特性，同时由于硅-氧结合而产生的柔韧性及弹性具有耐寒性及强热震性，如下面表1所示：
表1：各原子之间的化学键的能量及化学键的长度
Figure PCTCN2015091625-appb-000001
Figure PCTCN2015091625-appb-000002
是长度单位：埃。
在本发明里，有机硅烷在氧化硅的存在下，进行加水分解、及缩聚合反应形成无机溶液，此无机溶液含Si-OH，由Si-OH形成结合力强的(Si-O-M)，所以无机溶液本身有强力的粘合剂的作用。
进一步的，所述有机硅烷包括四乙氧基硅烷，甲基三甲氧基硅烷中的一种或者上述两种物质的混合物，添加20-30％的硅溶胶搅拌而制作出上述无机溶液。如硅胶的比例超过指定的范围，(Si-O-M)的结合力会下降，以至在高热环境下会出现涂膜剥离现象，建议在指定范围内混合。
同时，上述无机溶液制作工程中，可添加甲醇、乙醇、异丙醇或者其混 合物中的任意一种，可调节溶液的粘度及反应速度等。
而且，为了改善涂膜的物理化学性能，可使用钛酸钾或氧化铝等功能助技，这些物质是针状或者板状，有防止绷瓷或调节粘度的作用。建议填充剂在5-10wt％的范围内，如低于5wt％，性能明显下降，而且涂膜的表面会粗糙，如高于10wt％，光泽度或者附着力低下。
本发明的无机陶瓷涂料的组合物可代替以往的油漆，为了达到这个目的，颜色需多样，以往的涂料为了颜色多样，大部分添加了有机颜料或染料，但有机物导致各种问题，本发明的无机陶瓷涂料组合物为了体现既是无机物也能体现多种颜色而添加了金属氧化物颜料。建议此类的颜料粉占约10-20wt％，如低于10-20wt％，光泽度会低下，如超过此范围会导致弱化涂膜与基材的结合力。并且，为了赋予涂膜多种性能，本发明的无机陶瓷涂料组合物含有0.5-2.0wt％的其它功能助剂。
举个例子，为了体现光触媒性能，上述无机涂料中可添加二氧化钛，二氧化钛通过光而活化，具有把各种污染物转换为无害物质的作用。
而且根据需求，为了赋予远紫外线放射或排放阴离子等性能，上述无机涂料中可添加适当的其它功能助剂。其它功能助剂包括能释放阴离子的物质。近来，普遍使用的能释放阴离子的物质主要有电气石和稀土类原矿石。
进一步的，上述的无机陶瓷涂料组合物通过以下4个阶段来制作。
第一、无机溶液的制作：在制作无机溶液的阶段，选1-2种以上的有机硅烷，尤其选择甲基三甲氧基硅烷或四乙氧基硅烷中的一种或者这两种物质的混合物。将30-40wt％的有机硅烷、15-20wt％的乙醇、25-30％的硅溶胶混合一起，在40-50℃温度下，搅拌大约5-10分钟，这时有机硅烷和硅胶的混合溶液产生化学反应，出现发热现象，在反应过程中由浑浊的状态逐渐变为透明的状态。此时，为了调节溶液的粘度和反应速度，在甲醇、乙醇、异丙醇或者其混合物中选择一个放进去，经过这样的工序，制作成溶胶状态的无机溶液。
第二、搅拌混合溶液：在搅拌混合溶液的阶段，把上阶段制作出的无机溶液(70-80wt％)、钛酸钾或者氧化铝当中挑选一个作为功能助剂(5-10wt％),由氧化钛构成的颜料粉(10-20wt％)和其他功能助剂(0.5-2.0wt％)混合一起搅拌，形成无机陶瓷混合物。
第三、均匀化：在均匀化阶段，把搅拌的物质放进均质器，高速搅拌1-2小时使粒子均匀化。
第四、过滤：在过滤阶段，将上述阶段里已均匀化的物质在325-1000目的过滤网上经过过滤，除去大粒子后，最终得到无机涂料。
本发明提供的无机涂料，通过添加功能助剂赋予了涂膜柔韧性，防止龟裂，解决了厚膜现象，为制造常温固化的纯无机涂料，利用硅溶胶与烷氧基硅烷进行缩聚合反应，在常温下实现固化，且形成对身体无害，无环境污染的物性优异的无机涂膜。
与现有技术相比，本发明所提供的常温固化型无机涂料具有前所未有的优异特性。即，解决了一个无机涂料的常温固化的难题，喷涂在大型构筑物的时候不需要具备大型烘烤设备，所以也不需要锅炉等零件设备，也可节省燃料费用，对环境也有益，可提高生产效率。而且，本发明所提供的常温固化型无机涂料不包含有害有机成分，易施工，无味，耐化学物理性能优异，可长时间维持涂膜，对人体无害，不诱发环境污染，确保安全性，提供有用的效果。进一步的，因阻隔voc或者甲醛等有害物质的排放，可防止新房综合征的发生，而且成膜后的所有构成物都是无机物，所以废弃后也可使环境污染最小化，并且因为可防止剥离或者褪色的现象，可长时间维持美丽的外观，对于热和紫外线具有耐性。
具体实施方式
下面通过实施例对本申请的技术方案进一步详细说明，但目的不是限制本申请的保护范围。
实施例1：
本发明提供一种无机涂料，所述涂料的制备方法如下：
(1)在本发明的制作无机溶液的阶段，将甲基三甲氧基硅烷或者四乙氧基硅烷种中的一种或二者的混合物30wt％，乙醇15wt％，硅溶胶(简称硅胶)30wt％混合一起，在40-50℃温度下搅拌约5-10分钟，烷氧基硅烷和硅溶胶的混合液产生化学反应，出现发热现象，随着反应进行，从浑浊状态逐渐变为透明液体。此时，为了调节溶液的粘度和反应速度，在甲醇、乙醇、异丙醇或者其混合物中选择一种放进去，经过这些工序，制作成溶胶状态的无机溶液。
(2)在本发明的混合液搅拌阶段，把上阶段制作出的无机溶液、钛酸钾或者氧化铝当中挑选一种作为功能助剂9wt％，氧化钛颜料粉15wt％和其他功能助剂1wt％混合一起搅拌，形成无机陶瓷混合液。
(3)在均匀化阶段，把搅拌的物质放进均质器，高速搅拌1-2小时使粒子均匀化。
(4)提取涂料的阶段，在上述阶段里已均匀化的物质在一定大小的过滤网上经过过滤，提取粒子后，最终完成涂料。
实施例2
本发明提供的一种无机涂料，所述无机涂料的原料包括下述成份：
70wt％的无机溶液；所述无机溶液的原料包括下述成份：30wt％的四乙氧基硅烷，15wt％的乙醇，25wt％的硅溶胶；
10wt％的功能助剂，所述功能助剂为钛酸钾和氧化铝的组合物，其中，钛酸钾的含量是3wt％；
19.5wt％的无机颜料；
0.5wt％的其它功能助剂；所述其它功能助剂为电气石。
上述百分比为各原料占无机涂料总重的重量百分比。
实施例3
本发明提供的一种无机涂料，所述无机涂料的原料包括下述成份：
80wt％的无机溶液；所述无机溶液的原料包括下述成份：40wt％的四乙氧基硅烷和甲基三甲氧基硅烷组合物，四乙氧基硅烷和甲基三甲氧基硅烷的重量比是1:1，15wt％的乙醇，25wt％的硅溶胶；
5wt％的功能助剂，所述功能助剂为钛酸钾和氧化铝的组合物，其中，钛酸钾的含量是4％；
13wt％的无机颜料；
2wt％的其它功能助剂；所述其它功能助剂为电气石。
上述百分比为各原料占无机涂料总重的重量百分比。
实施例4
本发明提供的一种无机涂料，所述无机涂料的原料包括下述成份：
80wt％的无机溶液；所述无机溶液的原料包括下述成份：30wt％的甲基三甲氧基硅烷，20wt％的乙醇，30wt％的硅溶胶；
6wt％的功能助剂，所述功能助剂为钛酸钾和氧化铝的组合物，其中，钛酸钾的含量是5％；
13wt％的无机颜料；
1wt％的其它功能助剂；所述其它功能助剂为稀土类原矿石。
上述百分比为各原料占无机涂料总重的重量百分比。
实施例5
本发明提供的一种无机涂料，所述无机涂料的原料包括下述成份：
74.5wt％的无机溶液；所述无机溶液的原料包括下述成份：30wt％的甲基三乙氧基硅烷，15wt％的乙醇，29.5wt％的硅溶胶；
5wt％的功能助剂，所述功能助剂为钛酸钾；
20wt％的无机颜料；
0.5wt％的其它功能助剂；所述其它功能助剂为稀土类原矿石。
上述百分比为各原料占无机涂料总重的重量百分比。
实施例6
本发明提供的一种无机涂料，所述无机涂料的原料包括下述成份：
77wt％的无机溶液；所述无机溶液的原料包括下述成份：35wt％的烷氧基硅烷，15wt％的乙醇，27wt％的硅溶胶；
7wt％的功能助剂，所述功能助剂为钛酸钾；
15wt％的无机颜料；
1wt％的其它功能助剂；所述其它功能助剂为电气石和稀土类原矿石的组合，二者的重量比为1:1。
上述百分比为各原料占无机涂料总重的重量百分比。
所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R2为苯基。m为0。
实施例7
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为CF3CH2CH2；所述R2为CF3CH2CH2。m为1。
实施例8
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为CF3(CF2)5CH2CH2；所述R2为CF3(CF2)5CH2CH2。m为2。
实施例9
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为CF3(CF2)7CH2CH2；所述R2为CF3(CF2)7CH2CH2。m为3。
实施例10
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为甲基；所述R2为苯基。m为1。
实施例11
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为乙基；所述R2为CF3CH2CH2。m为1。
实施例12
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为苯基；所述R2为CF3(CF2)7CH2CH2。m为2。
实施例13
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为CF3CH2CH2；所述R2为甲基。m为3。
实施例14
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为CF3(CF2)5CH2CH；所述R2为甲基和乙基的组合。m为2。
实施例15
如实施例6提供的无机涂料，其中，所述烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1为CF3(CF2)7CH2CH2；所述R2为苯基。m为1。
实施例16
如实施例6提供的无机涂料，其中，所述烷氧基硅烷是苯基三甲氧基硅烷。
将上述实施例得到的无机涂料涂布在基材上形成涂膜，涂膜的膜厚：30±5μm，基材：铝板。基材试片大小为15cm×7.5cm，成膜后在常温下放置7天，可形成坚固的涂膜。
本发明实施例1-16提供的无机涂料形成的涂膜的性能测试结果如下面表2和表3所示：
表2 本发明实施例1-16提供的无机涂料形成的涂膜的性能测试结果
Figure PCTCN2015091625-appb-000003
Figure PCTCN2015091625-appb-000004
表3 本发明实施例1-16提供的无机涂料形成的涂膜的性能测试数值
序号 光泽度 铅笔硬度 附着力
实施例1 45-55 7-9H 0级
实施例2 45-55 7-9H 0级
实施例3 35-45 8-9H 1级
实施例4 45-55 7-9H 1级
实施例5 40-50 7-9H 0级
实施例6 40-50 7-9H 0级
实施例7 40-50 7-9H 0级
实施例8 45-55 7-9H 0级
实施例9 30-35 6-9H 0级
实施例10 30-35 6-9H 1级
实施例11 45-50 7-9H 0级
实施例12 45-55 7-9H 0级
实施例13 25-30 6-8H 1级
实施例14 30-35 7-8H 0级
实施例15 40-50 7-9H 0级
实施例16 40-50 7-9H 0级
铅笔硬度实验：把实验专用铅笔，以45°的角度夹在硬度测定仪上，施加荷重(1kg)往前推进行测试，需用三菱铅笔。
附着力实验
方法：百格法
耐磨性实验：利用耐磨试验机(Model KPM-042)，使用的轮子是CS-10wheel，把试片放在耐磨试验机，吊500g的荷重，旋转500回，再利用UV分光光度计在370nm下，检测吸光度，观察表面是否变模糊，最终检测耐磨性。
由上述实施例的测试结果可以得出，本发明提供的常温固化型无机涂料可以常温固化，且形成的涂膜具有较高的硬度，较好的耐酸、耐碱、耐盐水性，耐候性，且附着力较好。本发明所提供的常温固化型无机涂料可广泛用于建筑涂料、防腐涂料。
实施例17
本发明提供一种无机涂料，所述无机涂料的原料包括下述成份：
75wt％的溶液；所述溶液的原料包括下述成份：35wt％的甲基三甲氧基硅烷，15wt％的丙醇，25wt％的硅溶胶；
5wt％的功能助剂，所述功能助剂为钛酸钾；
19.5wt％的无机颜料；
0.5wt％的其它功能助剂；所述其它功能助剂为稀土类原矿石。
上述百分比为各原料占无机涂料总重的重量百分比。
对本实施例提供的无机涂料形成的涂层进行危险性鉴定：
爆炸危险性鉴定(Hazard of Explosion):按照联合国《关于危险货物运输的建议书——试验和标准手册》(第五修订版)甄别程序判定，本品不属爆炸品。
氧化危险性鉴定(Hazard of Oxidation):按照联合国《关于危险货物运输的建议书——试验和标准手册》(第五修订版)甄别程序判定，本品不属氧化剂。
本实施例提供的无机涂料涂在金属锅内形成涂层，涂层符合美国FDA对树脂及聚合物涂层提取物的含量要求。具体测试方法及结果如下：
测试方法：按照FDA 21 CFR 175.300规定。
表4 涂层提取物测试结果
Figure PCTCN2015091625-appb-000005
实施例18
本发明提供一种无机涂料，所述无机涂料的原料包括下述成份：
80wt％的无机溶液；所述无机溶液的原料包括下述成份：30wt％的四乙氧基硅烷，20wt％的乙醇，30wt％的硅溶胶；
6wt％的功能助剂，所述功能助剂为钛酸钾和氧化铝的组合物，其中，钛酸钾的含量是5％；
13.5wt％的无机颜料；
0.5wt％的其它功能助剂；所述其它功能助剂为电气石。
上述百分比为各原料占无机涂料总重的重量百分比。
本实施例提供的无机涂料涂在金属平板上形成涂层，根据德国《食品与日用品法》(LFGB)第30、31条，欧盟委员会法规AP(2004)1及BfR提议LI2006APR1和DIN51032:1986对涂层进行下述测试，结果表明，涂层符 合LFGB第30和31条，欧盟委员会法规AP(2004)1中对感官，和PFOS，PFOA的安全限量要求，和DIN51032:1986中对陶瓷铅镉钴溶出的安全限值的要求。
1)感官测试
测试方法：参照DIN 10955:1983(2004)
测试条件：100℃，240小时
测试介质：去离子水
人数：6
表5 感官测试结果
测试项目 测试结果 允许限值
嗅觉(级) 0 2.5
味觉(级) 0 2.5
分数评价：
0：与原始气味和味道无差别；1：与原始气味和味道极小差别
2：与原始气味和味道微弱的可察觉的差别
3：与原始气味和味道明显可察觉的差别
4：与原始气味和味道极大的差别
2)铅镉钴溶出(制备4个涂层样品用于检测)
测试方法：参考EN1388-1/2:1995陶瓷器皿或者硅酸盐表面铅镉的溶出测试，用原子吸收光谱仪分析。
表6 铅镉钴溶出测试结果
Figure PCTCN2015091625-appb-000006
Figure PCTCN2015091625-appb-000007
铅镉允许限值引用于DIN51032:1986。
表7 陶瓷，玻璃，搪瓷表面，铅镉溶出允许限值
Figure PCTCN2015091625-appb-000008
*与欧盟法规相一致。
3)PFOA溶出量测试
测试方法：样品用橄榄油在175℃提取120分钟，提取液用高效液相色谱分析
表8 PFOA溶出量测试结果
测试项目 测试结果 最大允许限值
PFOA溶出量,mg/dm2 <0.005 0.005
4)PFOS含量测试
测试方法：参照EPA3550C:2007，取提取液用高效液相色谱分析
表9 PFOS溶出量测试结果
测试项目 测试结果 最大允许限值
PFOS溶出量,μg/m2 <1 1
由实施例17和18的测试结果可以得出，本发明提供的常温固化型无机 涂料形成的涂层符合食品安全标准，安全性极高，可用于厨具及餐具。
以上所述，仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。凡是根据本发明内容所做的均等变化与修饰，均涵盖在本发明的专利范围内。

Claims (11)

  1. 一种常温固化型无机涂料，其特征在于，所述无机涂料的原料包括下述成份：
    70-80wt％的溶液；
    5-10wt％的功能助剂，所述功能助剂选自钛酸钾、氧化铝或者二者的组合物；
    10-20wt％的无机颜料；
    0.5-2.0wt％的其它功能助剂；
    所述溶液的原料包括下述成份：30-40wt％的有机烷氧基硅烷，15-20wt％的有机溶剂，25-30wt％的硅溶胶；
    上述百分比为各原料占无机涂料总重的重量百分比。
  2. 根据权利要求1所述的无机涂料，其特征在于，所述有机烷氧基硅烷以分子式R1 mSi(OR2)4-m表示，所述R1选自烷基，所述R2选自烷基，烷基的通式为CnH2n+1；n是正整数，n的范围是1-10；上述R1和OR2的总数量是4，m是非负整数，m的范围是0-3。
  3. 根据权利要求1所述的无机涂料，其特征在于，所述有机烷氧基硅烷包含有甲基、乙基、苯基、CF3CH2CH2、CF3(CF2)5CH2CH2、或CF3(CF2)7CH2CH2中的一种或至少两种的组合。
  4. 根据权利要求1所述的无机涂料，其特征在于，所述硅溶胶包括20-40％的二氧化硅粒子，所述二氧化硅粒子的粒径是纳米至微米级；所述无机涂料还包括去离子水。
  5. 根据权利要求1所述的无机涂料，其特征在于，所述其它功能助剂选自电气石，稀土类原矿石中的一种或两种的组合。
  6. 根据权利要求1所述的无机涂料，其特征在于，所述功能助剂中包括3-5wt％的钛酸钾。
  7. 根据权利要求2所述的无机涂料，其特征在于，OR2为加水分解性烷氧基，OR2被水分解，形成硅氢氧根(Si-OH)，上述的硅氢氧根在基材的表面上形成Si-O-M的结合，M表示基材。
  8. 根据权利要求1所述的无机涂料，其特征在于，所述有机烷氧基硅烷选自甲基三甲氧基硅烷、四乙氧基硅烷、苯基三甲氧基硅烷中的一种或两种的组合物。
  9. 根据权利要求1所述的无机涂料，其特征在于，所述无机涂料的原料包括下述成份：
    70-80wt％的无机溶液；
    5-10wt％的功能助剂，所述功能助剂选自钛酸钾、氧化铝或者二者的组合物；
    10-20wt％的无机颜料；
    0.5-2.0wt％的其它功能助剂；
    所述无机溶液的原料包括下述成份：30-40wt％的有机烷氧基硅烷，15-20wt％的有机溶剂，25-30wt％的硅溶胶；
    上述百分比为各原料占无机涂料总重的重量百分比。
  10. 一种权利要求1所述的无机涂料的制备方法，其特征在于，所述方法如下：将所述无机涂料的原料分别组合制备成主剂和硬化剂；
    所述主剂的制备方法如下：先搅拌硅溶胶，添加有机溶剂后继续进行搅拌，再添加去离子水继续进行搅拌；控制反应温度不超过50℃；上述的有机溶剂选自甲醇、乙醇、异丙醇或者其中至少两种的组合物；
    所述硬化剂的制备方法如下：将有机烷氧基硅烷，功能助剂，无机颜料，以及其他功能助剂加入去离子水中搅拌，混合均匀。
  11. 一种权利要求1所述的无机涂料的制备方法，其特征在于，所述方法包括下述步骤：
    (1)制作溶液：将30-40wt％的有机烷氧基硅烷、15-20wt％的有机溶剂、25-30％的硅溶胶混合一起，在40-50℃温度下，搅拌5-10分钟，制作成溶胶状态的溶液；
    (2)搅拌混合溶液：将上述步骤(1)制得的溶液、5-10wt％的功能助剂,10-20wt％的无机颜料，0.5-2.0wt％的其它功能助剂混合在一起搅拌，形成无机陶瓷混合物；
    (3)均匀：把上述步骤(2)制得的无机陶瓷混合物放进均质器，高速搅拌1-2小时使混合物搅拌均匀；
    (4)提取涂料：将上述步骤(3)制得的已搅拌均匀的物质在325-1000目的过滤网上过滤，经过滤后的物质即为所述的无机涂料。
PCT/CN2015/091625 2015-07-08 2015-10-10 一种常温固化型无机涂料及其制造方法 WO2017004904A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SG11201800116XA SG11201800116XA (en) 2015-07-08 2015-10-10 Room-temperature curable inorganic coating and manufacturing method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510396824.X 2015-07-08
CN201510396824.XA CN105038335B (zh) 2015-07-08 2015-07-08 一种常温固化型无机涂料及其制造方法

Publications (1)

Publication Number Publication Date
WO2017004904A1 true WO2017004904A1 (zh) 2017-01-12

Family

ID=54445324

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/091625 WO2017004904A1 (zh) 2015-07-08 2015-10-10 一种常温固化型无机涂料及其制造方法

Country Status (12)

Country Link
US (2) US10081731B2 (zh)
EP (1) EP3115403B1 (zh)
JP (1) JP6228637B2 (zh)
KR (2) KR20170007171A (zh)
CN (1) CN105038335B (zh)
AU (1) AU2016204613C1 (zh)
DK (1) DK3115403T3 (zh)
ES (1) ES2658338T3 (zh)
NO (1) NO3115403T3 (zh)
PL (1) PL3115403T3 (zh)
SG (1) SG11201800116XA (zh)
WO (1) WO2017004904A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10081731B2 (en) 2015-07-08 2018-09-25 Xiaodong Liu Inorganic coating composition which can be cured at low temperature and a preparation method thereof
CN113248948A (zh) * 2021-06-23 2021-08-13 河北晨阳工贸集团有限公司 一种无机内墙涂料及其制备方法

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106085155A (zh) * 2016-07-18 2016-11-09 天长市巨龙车船涂料有限公司 一种耐磨型涤纶树脂改性氯化橡胶面漆
CN106009800B (zh) * 2016-07-19 2018-12-04 上海宜瓷龙新材料股份有限公司 一种可释放负离子的易清洁烤瓷板及其制备方法
CN106977983B (zh) * 2017-04-21 2019-10-01 河北精涂科技有限公司 一种可常温固化的纳米陶瓷涂料及其制备方法
CN107868494B (zh) * 2017-10-18 2020-07-10 浙江玉釉新材料科技有限公司 一种无机纳米常温固化成釉涂料及其制备方法
CN109575656A (zh) * 2019-01-11 2019-04-05 安徽大学 一种常温固化型无机涂料及其制备方法
CN112142376B (zh) * 2019-06-28 2022-04-29 舾蒙新材料科技(上海)有限公司 一种热固性无机液体电子陶瓷材料及其制备方法
CN112625470A (zh) * 2019-09-24 2021-04-09 舾蒙新材料科技(上海)有限公司 一种常温固化无机涂料及其制备方法
CN112625467A (zh) * 2019-09-24 2021-04-09 舾蒙新材料科技(上海)有限公司 一种自脱模型模具及其制备方法
CN112625469A (zh) * 2019-09-24 2021-04-09 舾蒙新材料科技(上海)有限公司 一种采用无机涂层的耐高温金属板及其制备方法
CN112674160A (zh) * 2019-10-18 2021-04-20 海南中商馥香源农产品配送有限公司 一种果蔬专用负离子保鲜药剂及其保鲜方法
KR102297925B1 (ko) * 2020-03-19 2021-09-03 (주)힐링123 희토류 성분을 가진 환경 친화성 도료 조성물 및 그의 제조 방법
CN111995948A (zh) * 2020-06-29 2020-11-27 上海大学 室温成膜的导热陶瓷涂料及其应用
WO2022133908A1 (zh) * 2020-12-24 2022-06-30 刘晓东 陶瓷复合涂料、杀毒陶瓷复合涂料及其制备方法和涂层
CN112280344B (zh) * 2020-12-24 2021-07-06 北京银合汇新材料科技有限公司 陶瓷复合涂料、杀毒陶瓷复合涂料及其制备方法和涂层
KR102455558B1 (ko) * 2021-06-01 2022-10-21 연규승 열대차 열풍을 이용한 강제 경화형 친환경 나노 무기세라믹 도료 및 그 도장 방법
CN113527916A (zh) * 2021-06-10 2021-10-22 广西舾蒙新材料科技有限公司 一种常温固化型低VOCs无机涂料及其制备方法
KR102574505B1 (ko) * 2021-08-10 2023-09-04 배남수 일액형 세라믹 도료 조성물 및 이의 제조방법
CN114656809A (zh) * 2022-03-15 2022-06-24 北京固瑞恩科技有限公司 一种建筑耐久性防护用无机陶瓷涂料
CN114907769B (zh) * 2022-05-31 2023-03-10 紫荆花涂料（上海）有限公司 一种高硬度无机耐火仿陶瓷涂料及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008075815A1 (en) * 2006-12-19 2008-06-26 Neo Energe & Technology Co., Ltd. An inorganic-ceramic-coating-composition which can be harden under normal temperature condition and a method for manufacturing thereof
CN101481553A (zh) * 2008-11-06 2009-07-15 常州市纳罗可涂料有限公司 一种常温固化的自组装复合纳米氧化物防腐涂料
CN101668821A (zh) * 2007-04-19 2010-03-10 阿克佐诺贝尔国际涂料股份有限公司 用于金属基材的涂料组合物
CN102690536A (zh) * 2011-03-21 2012-09-26 上海宜瓷龙新材料科技有限公司 一种环保型建筑铝幕墙用陶瓷涂料及其制备方法
CN103013193A (zh) * 2012-12-13 2013-04-03 慧智科技（中国）有限公司 含钛陶瓷涂料与保护涂层
CN104559351A (zh) * 2014-11-24 2015-04-29 浙江大学自贡创新中心 用于金属铝板表面防腐的有机-无机复合溶胶的制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01163276A (ja) * 1987-12-18 1989-06-27 Hakusui Chem Ind Ltd 硬質被膜形成組成物
JPH08895B2 (ja) * 1991-09-17 1996-01-10 株式会社ダイフク 建築用鋼材の接合法
JPH10324838A (ja) * 1997-05-23 1998-12-08 Matsushita Electric Works Ltd 顔料分散組成物及び塗料組成物
KR100633177B1 (ko) * 2005-03-24 2006-10-12 김정하 ｐＨ 조절을 이용한 상온건조 무기도료 조성물과 그제조방법 및 용도
WO2012037322A2 (en) * 2010-09-15 2012-03-22 Jeld-Wen, Inc. Anti-bonding coatings for inhibiting material adhesion to equipment in thin-layer fiber composite manufacturing
JP2014205743A (ja) * 2013-04-11 2014-10-30 パナソニック株式会社 無機塗料組成物及びその塗装品
TWI492978B (zh) * 2013-07-24 2015-07-21 Grand Tek Advance Material Science Co Ltd 複合材料微粉、陶瓷塗料、保護塗層、與複合材料微粉的形成方法
CN104059398B (zh) * 2014-04-02 2016-08-24 浙江鹏孚隆科技有限公司 一种柔韧性陶瓷不粘涂层组合物及其涂覆方法
CN105038335B (zh) 2015-07-08 2017-02-01 刘晓东 一种常温固化型无机涂料及其制造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008075815A1 (en) * 2006-12-19 2008-06-26 Neo Energe & Technology Co., Ltd. An inorganic-ceramic-coating-composition which can be harden under normal temperature condition and a method for manufacturing thereof
CN101668821A (zh) * 2007-04-19 2010-03-10 阿克佐诺贝尔国际涂料股份有限公司 用于金属基材的涂料组合物
CN101481553A (zh) * 2008-11-06 2009-07-15 常州市纳罗可涂料有限公司 一种常温固化的自组装复合纳米氧化物防腐涂料
CN102690536A (zh) * 2011-03-21 2012-09-26 上海宜瓷龙新材料科技有限公司 一种环保型建筑铝幕墙用陶瓷涂料及其制备方法
CN103013193A (zh) * 2012-12-13 2013-04-03 慧智科技（中国）有限公司 含钛陶瓷涂料与保护涂层
CN104559351A (zh) * 2014-11-24 2015-04-29 浙江大学自贡创新中心 用于金属铝板表面防腐的有机-无机复合溶胶的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10081731B2 (en) 2015-07-08 2018-09-25 Xiaodong Liu Inorganic coating composition which can be cured at low temperature and a preparation method thereof
CN113248948A (zh) * 2021-06-23 2021-08-13 河北晨阳工贸集团有限公司 一种无机内墙涂料及其制备方法

Also Published As

Publication number Publication date
NO3115403T3 (zh) 2018-04-07
AU2016204613C1 (en) 2019-06-27
US20170009079A1 (en) 2017-01-12
PL3115403T3 (pl) 2018-04-30
AU2016204613A1 (en) 2017-02-02
CN105038335A (zh) 2015-11-11
CN105038335B (zh) 2017-02-01
US10081731B2 (en) 2018-09-25
ES2658338T3 (es) 2018-03-09
JP6228637B2 (ja) 2017-11-08
KR20170007171A (ko) 2017-01-18
DK3115403T3 (en) 2018-02-05
AU2016204613B2 (en) 2017-07-13
US20190016899A1 (en) 2019-01-17
EP3115403A1 (en) 2017-01-11
KR20180069771A (ko) 2018-06-25
EP3115403B1 (en) 2017-11-08
SG11201800116XA (en) 2018-02-27
JP2017020009A (ja) 2017-01-26

Similar Documents

Publication Publication Date Title
WO2017004904A1 (zh) 一种常温固化型无机涂料及其制造方法
CN102786229B (zh) 具有装饰涂层的玻璃或微晶玻璃制品
US8852333B2 (en) Multi-functional environmental coating composition with mesoporous silica nanomaterials
CN106009800B (zh) 一种可释放负离子的易清洁烤瓷板及其制备方法
CA2581474A1 (en) Non-stick ceramic coating composition and process
CN109135558A (zh) 一种陶瓷树脂及其应用
CN102719153A (zh) 一种反射隔热涂料及其制备方法
KR20080056863A (ko) 상온경화형 무기질계 세라믹 코팅제 조성물 및 그 제조방법
CN112625470A (zh) 一种常温固化无机涂料及其制备方法
RU2667546C2 (ru) Композиция для жаростойкого порошкового покрытия, способ ее получения и ее применение
CN104478392B (zh) 一种用于城市轨道交通车辆内饰板的瓷膜涂料
CN108659585A (zh) 一种制备防青苔纳米钛瓷涂料的方法
CN102746768A (zh) 水性彩色玻璃涂料及其制备方法与应用
CN109504279B (zh) 耐高温粉末涂料组合物、其制备方法及其用途
CN108129076A (zh) 一种制备纳米陶瓷真石漆的方法
CN112625469A (zh) 一种采用无机涂层的耐高温金属板及其制备方法
KR101615550B1 (ko) 분리형 유/무기 하이브리드형 보호 코팅제 조성물 및 이를 피막한 코팅 제품
JP5204142B2 (ja) 遮熱性塗料組成物
CN1169888C (zh) 纳米钛釉涂料
JP2010043188A (ja) 光触媒性塗膜形成用塗料、光触媒性塗膜及び該光触媒性塗膜を備える積層体
CN106947353A (zh) 一种环保型防水油漆及其制备工艺
JP2002036442A (ja) 高耐久性塗膜構成体
KR20090047265A (ko) 순수 무기질계 상온 경화형 코팅제 조성물 및 그 제조방법
JP2004330550A (ja) 耐汚染性，塗膜密着性に優れた光触媒塗装金属板及びその製造方法
CN106634080A (zh) 一种改进的建筑涂料

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15897560

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 11201800116X

Country of ref document: SG

122 Ep: pct application non-entry in european phase

Ref document number: 15897560

Country of ref document: EP

Kind code of ref document: A1