JP5207333B2 - Hybrid paint and products with hybrid film - Google Patents

Description

The invention also relates to a hybrid coating, to a hybrid film with the product.

  The first product having at least the surface of inorganic glass has excellent hydrophilicity. The first product may be made of an inorganic glassy material or a base material having a film made of an inorganic glassy material. Even if oily dirt adheres to this first product, it is excellent in hydrophilicity, so that the attached oily dirt can be easily removed only with water. This first product also has characteristics such as excellent heat resistance, high hardness, weather resistance, chemical resistance, and low cost. Moreover, the product which formed the membrane | film | coat which consists of inorganic glassy materials on a base material also has the characteristic that it is excellent in adhesiveness.

  On the other hand, the second product having at least the surface of a fluororesin such as polytetrafluoroethylene (PTFE) has excellent water repellency and oil repellency. The second product may be made of a fluororesin itself, or may be a product in which a film made of a fluororesin is formed on a substrate. This second product is water- and oil-repellent, it is difficult for oily dirt to adhere to it, and it is easy to wipe off oil dirt. However, when it is used in an environment where water is applied, the oily dirt tends to adhere. There is a problem. In addition, this second product has a problem in terms of environmental load because it is difficult to remove the adhered oil stains with water, and in this case, a surfactant is required.

  Under actual usage conditions, water and oil stains often coexist, making it difficult for oil stains to adhere to them, and if they do so, they can be easily removed by any method such as wiping or washing with water. There is a demand for products with excellent soiling properties.

  In this regard, the product obtained by applying the paint described in Patent Document 1 on the base material contains an oligomer having fluoroalkyl groups at both ends and a polyfunctional alkoxysilane, so that the coating is made of fluoroalkyl groups. It will have the part formed and the part formed with the silicon based on polyfunctional alkoxysilane. For this reason, this product has both hydrophilicity and oil repellency, and can exhibit excellent antifouling properties against aqueous and oily soils. In other words, this paint is a hybrid paint that can form a hybrid film that exhibits both hydrophilicity and oil repellency, and the product obtained can be said to be a product with a hybrid film.

JP 2003-253250 A

  However, the product with a hybrid film disclosed in Patent Document 1 is desired to further improve hydrophilicity, oil repellency, heat resistance, high hardness, weather resistance, chemical resistance, adhesion, low cost, etc. in the hybrid film.

  In addition, this product with a hybrid film needs to use an organic solvent in the hybrid paint, and thus VOC is released during film formation, which has a large environmental load.

  Furthermore, this product with a hybrid film uses many relatively expensive materials for the hybrid paint, and there is a problem in terms of cost when mass production is taken into consideration.

  The present invention has been made in view of the above-described conventional circumstances, has excellent antifouling properties due to hydrophilicity and oil repellency, and has heat resistance, high hardness, weather resistance, chemical resistance, adhesion, low cost, and the like. It is an issue to be solved to provide a hybrid paint capable of producing a product with a hybrid film excellent in properties and the like under a low environmental load.

  And this invention also makes it the subject which should be solved to provide such a product with a hybrid membrane | film | coat.

  The inventors have intensively studied to solve the above problems. In order to solve the problems of the present invention, the advantages of the known hybrid paint disclosed in Patent Document 1 and the advantages of the known inorganic paint disclosed in Japanese Patent Application Laid-Open No. 2000-327949 are compatible. It has been found that it is effective to develop it, and the present invention has been completed.

The hybrid paint having hydrophilicity and oil repellency of the present invention comprises a low polymer which is an oligomer and / or a co-oligomer having fluorine-containing groups at both ends in a matrix of water glass as a main component, anchor particles, And the low polymer is fixed to the anchor particles by a reaction via an ester bond, a hydrogen bond, a coordination bond, a siloxane bond or an alkoxide .

  According to the hybrid paint of the present invention, a hybrid film having an inorganic glassy matrix based on water glass and a portion formed by a fluoroalkyl group can be obtained. The inorganic vitreous matrix in this hybrid film can be densified with additives and the like as compared to the portion based on the polyfunctional alkoxysilane in the hybrid film disclosed in Patent Document 1, and has fewer organic components. Exhibits superior hydrophilicity. Thus, this hybrid film exhibits hydrophilic oil repellency due to the oil repellency, hydrophilicity and excellent hydrophilicity of the base material due to the fluorine oligomer and / or co-oligomer. It exhibits excellent antifouling properties that can easily remove oil by any method.

  In particular, this hybrid paint is an oligomer and / or a co-oligomer having a fluorine-containing group at both ends of the low-polymer, so that it depends on the hydrophilic part of the substrate and the oligomer and / or the co-oligomer depending on the environment. Hydrophilicity and oil repellency due to the fluoroalkyl groups at both ends are changed by the Flip-Flop mechanism, and oily soil can be effectively removed. In this respect, it has higher practicality than the paint disclosed in Japanese Patent Application Laid-Open No. 11-5951, which is simply a mixture of an aqueous fluororesin dispersion and water glass.

  Moreover, according to this hybrid paint, since a hybrid film having an inorganic glassy matrix based on water glass can be formed, a product excellent in heat resistance, high hardness, weather resistance, chemical resistance, adhesion, etc. is manufactured. Can do.

  Furthermore, this hybrid paint does not necessarily require the use of an organic solvent and has a low environmental load.

  In addition, since this hybrid paint uses a lot of inexpensive materials such as water glass, it is possible to reduce the cost of products with a hybrid film.

  Therefore, according to the hybrid paint of the present invention, a product with a hybrid coating having excellent antifouling properties and excellent heat resistance, high hardness, weather resistance, chemical resistance, adhesion, low cost, etc. It is possible to manufacture under.

The hybrid paint of the present invention is formed by mixing at least water glass and a low polymer. The water glass is represented by the general formula SiO ₂ · nA ₂ O · 2H ₂ O (A is an alkali, n is an integer), and various types such as soda water glass and potassium water glass can be adopted. .

The low polymer is an oligomer and / or a co-oligomer having fluorine-containing groups at both ends. Fluorine-containing groups include fluoroalkyl groups such as —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ , —C ₆ F ₁₃ , —C ₇ F ₁₅ , —CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _P OC ₃ F ₇ (wherein P is 0, 1 or 2). This low polymer may be an oligomer, a co-oligomer, or a mixture of an oligomer and a co-oligomer. Hereinafter, in some cases, an oligomer having fluorine-containing groups at both ends is referred to as a fluorine oligomer, and a co-oligomer having fluorine-containing groups at both ends is referred to as a fluorine co-oligomer.

  As specific examples of the low polymer, an oligomer shown in Chemical Formula 1 or a co-oligomer shown in Chemical Formula 2 can be employed.

In Formula 1, R _F is a fluoroalkyl group, R ₁ is a monovalent organic group, and n is a natural number.

R ₁ can be an organic group that is hydrophilic and can form a hydrogen bond, a coordination bond, a covalent bond, an ionic bond, an ester bond, or other bonds.

R ₁ is, for example, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a silanol group (≡SiOH), a hydroxyl group (—OH), an amino group (—NH ₂ ), a nitro group (—NO ₂ ). ), A carbonyl group (═C═O), an amide group (—C (═O) NH—) or an organic group containing a derivative thereof. Since these are hydrophilic and easily interact with water glass, the resulting hybrid film is bonded to the portion formed by the inorganic glassy matrix and the fluorine-containing group while maintaining hydrophilicity. This is because it is considered that the strength becomes stronger and the durability is improved. Here, the interaction means a hydrogen bond, a coordination bond, an ester bond, dehydration polycondensation, or the like. Further, since the organic group is hydrophilic, it has a function of making the hybrid film hydrophilic and improving the antifouling property.

In Formula 2, R _F is a fluoroalkyl group, R ₂ and R ₃ are monovalent organic groups, and x and y are natural numbers.

R ₂ can be hydrophilic. R _{2 is} also preferably an organic group containing, for example, a carboxyl group, a sulfo group, a silanol group, a hydroxyl group, an amino group, a nitro group, a carbonyl group, an amide group, or a derivative thereof, like R ₁ described above.

R ₃ can be selected from any organic group that can interact with and bind to water glass or other materials. This is because when these are combined with water glass or other materials, the co-oligomer is firmly fixed in the obtained hybrid film, and durability is considered to be improved. Here, the interaction means hydrogen bond, coordination bond, covalent bond, ester bond, urethane bond, amide bond, dehydration polycondensation, vinyl polymerization and other bonds.

R ₃ may be an organic group capable of forming a hydrogen bond, a coordination bond, a covalent bond, an ester bond, a urethane bond, an amide bond, a dehydration polycondensation, a vinyl polymerization, or other bonds. R ₃ is same as above R _1, R _2, for example, a carboxyl group, a sulfo group, a silanol group, a hydroxyl group, an amino group, a nitro group, a carbonyl group, in addition to obtaining an organic group containing an amide group, an alkoxy group ( M (OC _n H _{2n + 1} ) _m X _3-m ; M is Si, Ti, Al, etc., n is a natural number of 1 to 3, m is a natural number of 1 to 3, and an isocyanate group (—N═C═O ), An organic group containing a vinyl group (—CH═CH ₂ —) or the like.

  In the case of a fluorine oligomer having a carboxyl group, as shown in Chemical Formula 3, the carboxyl group of the fluorine oligomer is ester-bonded to water glass and immobilized. Carboxyl groups that are not ester-bonded with water glass show hydrophilicity, and fluoroalkyl groups at both ends of the fluorine oligomer show oil repellency. As a result, the hybrid film exhibits hydrophilicity and oil repellency.

  In the case of a fluorine oligomer having a sulfo group, as shown in Chemical formula 4, the sulfo group of the fluorine oligomer is hydrogen-bonded to water glass and immobilized. The sulfo group that does not hydrogen bond with water glass exhibits hydrophilicity, and the fluoroalkyl groups at both ends of the fluorine oligomer exhibit oil repellency. As a result, the hybrid film exhibits hydrophilicity and oil repellency.

Further, in the case of an oligomer having a functional group capable of coordinating and bonding, as shown in Chemical formula 5, the functional group of the fluorine oligomer is coordinated and fixed to Si in the water glass. It is sufficient that the fluorine oligomer has a functional group capable of coordinating and bonding to Si, and it has both a functional group capable of coordinating and a hydrophilic functional group (OH, COOH, SO ₃ H, NO ₂ , NH _2, etc.). Fluorine co-oligomer may be used. In this case, the hydrophilic functional group is hydrophilic, and the fluoroalkyl groups at both ends of the fluorine oligomer and / or fluorine co-oligomer exhibit oil repellency. As a result, the hybrid film exhibits hydrophilicity and oil repellency.

  Thus, a fluorine oligomer having a functional group capable of hydrogen bonding or a functional group capable of coordinating bonding interacts with water glass and can be immobilized on the hybrid film.

In the case of a fluorine oligomer having an alkoxysilane, as shown in Chemical formula 6, the alkoxysilane alkoxysilane has a siloxane bond to Si in water glass and is fixed. The fluorine oligomer only needs to have alkoxysilane, and may be a fluorine co-oligomer having both a functional group capable of coordinating bonding and a hydrophilic functional group (OH, COOH, SO ₃ H, NO ₂ , NH _2, etc.). In this case, the hydrophilic functional group is hydrophilic, and the fluoroalkyl groups at both ends of the fluorine oligomer and / or fluorine co-oligomer exhibit oil repellency. As a result, the hybrid film exhibits hydrophilicity and oil repellency. Any alkoxide capable of binding to water glass can be used. Any fluorine oligomer may be used as long as it has alkoxysilane in part.

  When an alkoxide is used as a binder, as shown in Chemical Formula 7 (M is a metal), an alkoxide can be used as a binder between water glass and a fluorine oligomer as long as it is a fluorine oligomer that can be bonded to an alkoxide. The alkoxide can be added in the form of a solution, and since the molecule is smaller than that of water glass, there is an advantage that the reactivity is higher.

  According to the inventors' consideration, for example, oligomers or co-oligomers of chemical formulas 8 to 15 can be employed.

  The hybrid paint of the present invention can be mixed with pigments, aggregates such as silica powder, etc. in addition to water glass and low polymer.

In the hybrid paint of the present invention, anchor particles for fixing the low polymer are mixed in a matrix made of water glass as a main component . In this case, the low polymer is fixed in the matrix by the anchor particles, and excellent durability can be exhibited.

  As the anchor particles, any solid particles, sols, and gels can be adopted as long as they can interact with the low polymer, regardless of organic or inorganic. For example, fine silica (silica sol) or fine titania (titania sol) can be employed. Anchor particles that are surface-treated with a silane coupling agent or the like are preferable.

  When the carboxyl group is ester-bonded to the anchor particle A, the carboxyl group of the fluorine oligomer is ester-bonded to the surface of the anchor particle A and fixed to the anchor particle A as shown in Chemical formula (16).

  When the sulfo group is hydrogen bonded to the anchor particle A, the sulfo group of the fluorine oligomer is hydrogen bonded to the surface of the anchor particle A as shown in Chemical formula 17, and is immobilized on the anchor particle A.

  Further, when the functional group of the fluorine oligomer is coordinated to the anchor particle A, the functional group of the fluorine oligomer is coordinated to the metal ion on the surface of the anchor particle A and fixed to the anchor particle A as shown in Chemical formula 18. It becomes.

  When the fluorine oligomer alkoxysilane reacts with the anchor particles A, as shown in Chemical formula 19, the fluorine oligomer contains an alkoxysilane by co-oligomer of a certain monomer and vinylsilane (considering an alkoxysilane having a vinyl group as a monomer). Yes, this alkoxysilane is siloxane-bonded to Si in water glass and fixed.

  When the fluorine oligomer is immobilized on the anchor particle A via the alkoxide, as shown in Chemical formula 20, the fluorine oligomer and the anchor particle A are reacted via the alkoxide.

  As a method of polymerizing the fluorine oligomer on the surface of the anchor particle A after modifying the vinyl group on the anchor particle A, the method shown in Chemical formula 21 can be adopted. In this case, fluorine oligomers are formed on the surface by synthesizing vinyl group-modified particles, monomers and fluoroalkanoyl peroxide (Polymer Collection, Vol.58, No.4 (2001) pp.147-160) in a fluorine solvent. Immobilized anchor particles A are obtained. The portion indicated by a broken line in the chemical formula is a portion that was a vinyl group-modified particle, and the other portion is a portion in which a monomer is polymerized on the vinyl group-modified particle. As a whole, anchor particles A to which a fluorine oligomer is immobilized are obtained.

  The hybrid paint of the present invention is preferably mixed with a water glass curing agent. In this case, water glass hardens early and becomes a matrix, and the hybrid film can exhibit excellent durability.

  Water glass curing agents include aluminum tripolyphosphate, aluminum phosphate, aluminum hydrogen phosphate, aluminum metaphosphate, aluminum orthophosphate, primary aluminum phosphate, secondary aluminum phosphate, zirconium phosphate, magnesium phosphate, phosphorus Zinc oxide, zinc calcium phosphate, ammonium phosphate, iron phosphate, titanium phosphate, boron phosphate, zinc white (zinc oxide), activated zinc white, magnesium oxide, calcium oxide, metallic aluminum powder, kaolinite, spodumene powder , Potassium silicofluoride, sodium silicofluoride, calcium silicofluoride, lead silicofluoride, copper silicofluoride, zinc silicofluoride, aluminum silicate, calcium silicate, dilime silicate, magnesium silicate, aluminum hydroxide, Aluminum chloride, ferrosilicon, manganese silicon , Silicon nitrite, silicon carbide, silicon borate, silicon phosphate, primary potassium phosphate, dibasic potassium phosphate, zeolite, Na artificial zeolite, Fe artificial zeolite, bentonite (mica), sepiolite, Kanuma earth, diatomaceous earth, Allophane, metakaolin, zirconium borate, sodium borate, potassium borate, silicon borate, calcium borate, acetic acid, ammonium acetate, barium acetate, magnesium acetate, aluminum acetate, manganese acetate, zinc acetate, aluminum oxalate, ammonium oxalate, calcium oxalate, magnesium oxalate , Iron (II) oxalate, manganese (II) oxalate, potassium titanium oxalate, titanium titanium oxalate, zinc oxalate, methanol, ethanol, propanol, calcined gypsum, frit etc. phosphate compounds, hydroxides, It is possible to adopt the product, and the like.

  According to the test results of the inventors, aluminum tripolyphosphate, aluminum phosphate, aluminum metaphosphate, aluminum orthophosphate, zirconium phosphate, zinc phosphate, magnesium oxide, potassium silicofluoride and calcium fluorosilicate are very preferable. In particular, there is a great difference in the water resistance, adhesion and durability of the hybrid film between the case of containing aluminum tripolyphosphate and the case of not containing it. It was confirmed that there was an effect. For this reason, it is preferable that at least a part of the curing agent for water glass is aluminum tripolyphosphate.

The hybrid paint of the present invention is preferably produced by the following production method. The method for producing this hybrid paint comprises a reaction step of reacting an anchor particle with a low polymer that is an oligomer and / or a co-oligomer having a fluorine-containing group at both ends;
And a mixing step of mixing at least the anchor particles with low polymer in water glass.

  In this case, since the obtained hybrid coating has anchor particles with a low polymer in which the low polymer and the anchor particles are reacted, the resulting hybrid film has the low polymer fixed more firmly in the matrix. , Can exhibit excellent durability.

  In the reaction step, an alkoxide such as TEOS (tetraethoxysilane), a silane coupling agent, or the like can be used.

The product with a hybrid film of the present invention comprises a substrate and a hybrid film having hydrophilicity and oil repellency formed on the substrate,
The hybrid coating is prepared by mixing an anchor particle with a low polymer that is an oligomer and / or a co-oligomer having fluorine-containing groups at both ends in an inorganic glassy matrix as a main component. The low polymer is fixed by a reaction via an ester bond, a hydrogen bond, a coordination bond, a siloxane bond or an alkoxide .

  The product with a hybrid film of the present invention has more excellent antifouling properties and is excellent in heat resistance, high hardness, weather resistance, chemical resistance, adhesion, low cost, and the like. In addition, this product with a hybrid film can realize a low environmental load during production.

Said hybrid coating, that has an anchor particles for fixing the low polymer in the matrix. In this case, the hybrid film can exhibit excellent durability.

Method for manufacturing a hybrid coating with product, and water glass, the paint preparation step of obtaining a hybrid coating material and low polymer is at least mixed with oligomeric and / or co-oligomer with a fluorine-containing group at both ends,
An application step of applying the hybrid paint on a substrate and forming a coating layer on the substrate;
It is characterized by comprising a solidification step of solidifying the coating layer into a hybrid coating.

According to this method of manufacturing a product with a hybrid film, a product with a hybrid film that has superior antifouling properties and is excellent in heat resistance, high hardness, weather resistance, chemical resistance, adhesion, low cost, etc. in a low environment Can be manufactured under load.

  Substrates include not only inorganic materials such as calcium silicate plates, cement plates, and slate plates, but also metallic materials such as steel plates, aluminum plates, stainless steel plates, galvanized steel plates, and materials with low heat resistance such as wood. Can also be adopted. Resin materials such as polyethylene, polypropylene, acrylic, and FRP can also be used as the base material. Moreover, the base material which apply | coated the primer layer, the glaze layer, etc. is also employable.

  As the coating process, various methods such as a spray method, a dipping method, a brush coating method, and a roll coating method can be performed. As a pre-stage of the coating process, it is preferable to blast the substrate.

  It is preferable that a solidification process includes the baking process which bakes a coating-film layer at the temperature of 350 degrees C or less. According to the test results of the inventors, this can more reliably evaporate water from the hybrid paint. When the coating layer is baked at a temperature exceeding 350 ° C., the low polymer is decomposed and it is difficult to obtain an effective hybrid coating.

  The solidification step preferably includes a chemical treatment step for dealkalizing the coating layer. Thereby, the durability of the matrix based on water glass is improved, and an excellent hybrid film is obtained.

  As the chemical solution that can be used, various organic acids, organic acid salts or inorganic acids, inorganic acid salts, and aqueous solutions of ammonia salts can be used. As the acid, phosphoric acid and acetic acid are particularly suitable. In the case of inorganic acid salt, one or more of phosphate and oxalate, ammonium salt, specifically sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate It is preferable to use an aqueous solution of ammonium phosphate, ammonium hydrogen phosphate, sodium oxalate, potassium oxalate, ammonium oxalate, ammonium chloride, ammonium acetate, ammonium iodide, and particularly an aqueous solution of ammonium phosphate.

  Specifically, an aqueous solution of an acid such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, oxalic acid, acetic acid, formic acid, propionic acid, butyric acid, valeric acid or the like can be used.

  In addition, zinc hydrogen phosphate, aluminum hydrogen phosphate, ammonium dihydrogen phosphate (primary ammonium phosphate), diammonium hydrogen phosphate (second ammonium phosphate), sodium ammonium hydrogen phosphate, potassium dihydrogen phosphate ( Primary potassium phosphate), dipotassium hydrogen phosphate (dibasic potassium phosphate), calcium dihydrogen phosphate (primary calcium phosphate), dicalcium hydrogen phosphate (dibasic calcium phosphate), sodium dihydrogen phosphate (primary Sodium phosphate), disodium hydrogen phosphate (dibasic sodium phosphate), magnesium hydrogen phosphate, magnesium dihydrogen phosphate, manganese dihydrogen orthophosphate (manganese dihydrogen orthophosphate, manganous acid phosphate) , Lithium dihydrogen phosphate (primary lithium phosphate), dilithium hydrogen phosphate ( Potassium diphosphate lithium), pyrophosphate, ammonium pyrophosphate, pyrophosphate, potassium pyrophosphate hydrogen, sodium hydrogen pyrophosphate, ammonium metaphosphate, an aqueous solution of soluble phosphate sodium metaphosphate and the like can be used.

  Further, aluminum acetate, ammonium acetate, cadmium acetate, potassium acetate, calcium acetate, chromium (II) acetate (chromium acetate), chromium (III) acetate (chromium acetate), germanium acetate, cobalt (II) acetate ( (Cobalt acetate), ammonium hydrogen acetate, potassium hydrogen acetate, cerium acetate, copper (I) acetate (cuprous acetate), copper (II) acetate (cupric acetate), potassium copper acetate, copper calcium acetate, acetic acid Aqueous solutions of soluble acetates such as sodium, lead (II) acetate (lead lead), nickel (II) acetate (nickel acetate), barium acetate, manganese (II) acetate (manganese acetate), lithium acetate Can be used.

  In addition, zinc nitrate, aluminum nitrate, ammonium nitrate, calcium nitrate, potassium nitrate, silver nitrate, chromium nitrate, cobalt nitrate (II) (cobalt nitrate), basic cobalt nitrate (II) (basic cobalt acetate), zirconium nitrate , Zirconium oxynitrate, mercury nitrate, scandium nitrate, tin (II) nitrate (stannous nitrate), tin (IV) nitrate (stannic nitrate), strontium nitrate, cesium nitrate, cerium (III) nitrate (first nitrate) Cerium), cerium nitrate (IV) (cerium nitrate), cerium ammonium nitrate, thallium nitrate (I) (first thallium nitrate), thallium nitrate (III) (secondary thallium nitrate), titanium nitrate, iron nitrate (II) ) (Ferrous nitrate), iron (III) nitrate (ferric nitrate), copper (II) nitrate (cupric nitrate), sodium nitrate, lead nitrate (I) ), Nickel nitrate (II), basic nickel nitrate, neodymium nitrate, neodymium nickel nitrate, neodymium magnesium nitrate, neodymium rubidium nitrate, barium nitrate, bismuth nitrate, magnesium nitrate, manganese nitrate, lanthanum nitrate, lanthanum ammonium nitrate, lanthanum potassium nitrate An aqueous solution of a soluble nitrate such as sodium lanthanum nitrate, nickel lanthanum nitrate, magnesium lanthanum nitrate, lithium nitrate, ternium nitrate, rubidium nitrate, rhodium nitrate can be used.

  In addition, soluble oxalic acid such as aluminum oxalate, ammonium oxalate, cadmium oxalate, potassium oxalate, potassium hydrogen oxalate, sodium hydrogen oxalate, barium hydrogen oxalate, lithium hydrogen oxalate, sodium oxalate, lithium oxalate An aqueous salt solution can be used.

  Also, zinc sulfate, ammonium zinc sulfate, ammonium sulfate, potassium zinc sulfate, aluminum sulfate, ammonium ammonium sulfate, potassium aluminum sulfate, aluminum thallium sulfate, sodium aluminum sulfate, antimony sulfate, ammonium sulfate, sodium ammonium sulfate, ytterbium (III) sulfate, yttrium sulfate , Potassium yttrium sulfate, sodium yttrium sulfate, iridium sulfate (IV), iridium sulfate (III), iridium sulfate (IV), iridium trisulfate (III) tripotassium, iridium (III) disulfate, cesium sulfate, iridium sulfate Thallium, indium sulfate, indium ammonium sulfate, uranyl sulfate, uranyl ammonium sulfate, uranyl potassium sulfate, uranyl sulfate Potassium, magnesium sulfate sulfate, cadmium sulfate, cadmium ammonium sulfate, potassium cadmium sulfate, potassium sulfate, gallium sulfate, gallium ammonium sulfate, potassium gallium sulfate, gallium cesium sulfate, gallium rubidium sulfate, calcium sulfate, calcium potassium sulfate, calcium sulfate Sodium, silver sulfate, chromium sulfate (II) (chromium sulfate), chromium (III) sulfate (chromium oxalate), chromium ammonium sulfate, potassium potassium sulfate, chromium rubidium sulfate, cobalt (II) sulfate (sulfuric acid Monocobalt), cobalt (III) sulfate (cobalt sulfate), cobalt ammonium sulfate, cobalt potassium sulfate, cobalt cesium sulfate, cobalt thallium sulfate, cobalt rubidium sulfate, samarium sulfate, disulfate sulfate Luconium, zirconium oxysulfate, ammonium hydrogen sulfate, potassium hydrogen sulfate, calcium hydrogen sulfate, strontium hydrogen sulfate, cesium hydrogen sulfate, thallium hydrogen sulfate, sodium hydrogen sulfate, vanadium hydrogen sulfate, barium hydrogen sulfate, bismuth hydrogen sulfate, magnesium hydrogen sulfate, Lithium hydrogen sulfate, scandium hydrogen sulfate, scandium ammonium sulfate, potassium scandium hydrogen sulfate, scandium hydrogen oxalate, tin (II) sulfate (stannous sulfate), tin (IV) sulfate (stannic sulfate), cesium sulfate , Cerium (III) sulfate (cerium sulfate), cerium (IV) sulfate (cerium sulfate), cerium ammonium sulfate, thallium sulfate (I) (thallium sulfate), thallium (III) sulfate (secondary sulfate) Thallium), titanium sulfate (I ) (Titanium sulfate), iron (II) sulfate (ferrous sulfate), iron (III) sulfate (II) (ferric ferrous sulfate), iron (III) sulfate (ferric sulfate) , Iron (II) ammonium sulfate (ammonium sulfate), iron (III) ammonium sulfate (ferric ammonium sulfate), iron thallium (II) sulfate (ferric thallium sulfate), iron (II) rubidium sulfate ( Ferrous sulfate rubidium), iron (III) sulfate rubidium (ferric sulfate rubidium), copper sulfate (I) (cuprous sulfate), copper sulfate (II) (cupric sulfate), ammonium copper sulfate, sulfuric acid Copper potassium, copper cesium sulfate, copper thallium sulfate, copper sodium sulfate, copper rubidium sulfate, thorium ammonium sulfate, potassium thorium sulfate, sodium thorium sulfate, sodium sulfate, potassium sodium sulfate, nickel sulfate, nickel sulfate ammonium Nickel, potassium potassium sulfate, nickel cesium sulfate, nickel thallium sulfate, nickel sodium sulfate, nickel rubidium sulfate, neodymium sulfate, vanadium sulfate, vanadium sulfate ammonium, vanadium sulfate, vanadium sulfate rubidium sulfate, hafnium sulfate, palladium sulfate, bismuth sulfate, sulfuric acid Hydroxyl ammonium, plutonium sulfate, beryllium sulfate, beryllium ammonium sulfate, beryllium potassium sulfate, beryllium sodium sulfate, magnesium sulfate, magnesium ammonium sulfate, magnesium potassium sulfate, magnesium calcium potassium sulfate, magnesium thallium sulfate, magnesium sodium sulfate, magnesium rubidium sulfate, sulfuric acid Manganese (II) (manganese sulfate), manganese sulfate (I I) (manganese sulfate), manganese sulfate (IV), manganese sulfate (II) ammonium (manganese ammonium sulfate), dimanganese trisulfate (II) diammonium (dimanganese trisulfate diammonium), sulfuric acid Manganese (III) ammonium (manganese ammonium sulfate), manganese (II) potassium sulfate (manganese potassium sulfate), dimanganese (II) trisulfate (dimanganese trisulfate), manganese sulfate ( III) Potassium (potassium sulfate), Manganese (II) cesium sulfate (manganese cesium sulfate), Manganese (III) cesium sulfate (manganese cesium sulfate), Manganese (II) sulfate (manganese sulfate) Sodium), manganese (II) sulfate rubidium (manganese rubidium sulfate), magnesium sulfate Of soluble sulfate such as Ngan (III) rubidium (manganese rubidium sulfate), lanthanum sulfate, lanthanum ammonium sulfate, potassium lanthanum sulfate, sodium lanthanum sulfate, lithium sulfate, ruthenium sulfate, rubidium sulfate, potassium rhodium sulfate, cesium sulfate An aqueous solution can be used.

Hereinafter, Examples 1 to 5, which embody the present invention , Reference Examples 6 to 9, and Comparative Examples 1 to 3 will be described.
( Example 1 )

An oligomer was prepared as a low polymer. This oligomer is a fluorine oligomer of acrylic acid in which R _{F in} Chemical Formula 1 is —C ₃ F ₇ and R ₁ is a carboxyl group.

  A hybrid paint was prepared by mixing 0.1 g of this fluorine oligomer, 100 g of No. 3 soda-based water glass (Nippon Chemical Industry), 10 g of Aerosil 90G (Nippon Aerosil) and 400 g of water.

As shown in FIG. 1, the hybrid paint was applied to a glass plate as the substrate 1 by a spray method. Thus, a coating layer 2a having a thickness of 30 g / m ² was formed on the substrate 1.

  The base material 1 having the coating layer 2a was heated at 150 ° C. for 30 minutes.

The coating layer 2a after the firing step was immersed in a 5% aqueous acetic acid solution for 10 minutes. In this way, as shown in FIG. 2, the hybrid film 2b was formed on the base material 1, and the product with a hybrid film was obtained.
( Example 2 )

A co-oligomer was prepared as a low polymer. This co-oligomer is a fluorine co-oligomer of dimethylacrylamide and acrylic acid in which R _{F in} Chemical Formula 2 is —C ₃ F ₇ , R ₂ is dimethylamide, and R ₃ is a carboxyl group.

A hybrid paint was prepared by mixing 0.1 g of the fluorine co-oligomer, 100 g of the soda-based water glass, 10 g of the Aerosil, and 400 g of water. And the application process, the heating process, and the chemical treatment process similar to Example 1 were performed, and the product with a hybrid film was obtained.
( Example 3 )

  A hybrid paint was prepared by mixing 0.1 g of the fluorine oligomer used in Example 1, 100 g of the soda-based water glass, 10 g of the above-mentioned Aerosil, 10 g of calcium phosphate as a curing agent for water glass, 1 g of titanium oxide pigment and 400 g of water.

As in Examples 1 and 2, the hybrid paint was applied to the glass plate as the substrate 1 by a spray method. Thus, a coating layer 2a having a thickness of 30 g / m ² was formed on the substrate 1.

The base material 1 having the coating layer 2a was heated at 150 ° C. for 30 minutes. Thus, the hybrid film 2b was formed on the substrate 1, and a product with a hybrid film was obtained.
(Comparative Example 1)

  An inorganic paint was prepared by mixing 100 g of the soda-based water glass, 10 g of the Aerosil and 400 g of water. And the application | coating process similar to Example 1, a heating process, and a chemical treatment process were performed, and the product with an inorganic membrane | film | coat was obtained.

(Comparative Example 2)

An inorganic paint was prepared by mixing 100 g of the soda-based water glass, 10 g of the Aerosil and 400 g of water. And the application | coating process similar to Example 1, the heating process, and the chemical treatment process were performed. Fluoroalkylsilane LS-160 (Shin-Etsu Chemical Co., Ltd.) as a water and oil repellent treatment agent was thinly applied onto the obtained inorganic coating, and the inorganic coating was subjected to water and oil repellent treatment. Thus, a product with an inorganic coating was obtained.
(Comparative Example 3)

  A commercially available PTFE plate was used as it was.

(Evaluation method)
About the test piece of each product of Examples 1-3 and Comparative Examples 1-3, while measuring water contact angle (degree) by Kyowa Interface Science CA-X and evaluating hydrophilicity, oil contact angle (degree) Was measured to evaluate oil repellency. In addition, the oil-in-water contact angle (°) was measured by Kyowa Interface Science CA-X to evaluate the oil stain removability in water.

Moreover, each test piece was arrange | positioned 40 cm above the oil heated at 180 degreeC, and the amount of oil vapor adhesion (g / m < ² >) was calculated | required by measuring the quantity of the adhered oil.

As a test for removing the adhered oil in water, oleic acid was applied to each test piece so as to be 20 g / m ² and then immersed in water at 25 ° C. for 15 minutes. From the weight change after immersion, the removal rate (%) of oleic acid was measured.

  As the hot water resistance, each test piece was immersed in water at 90 ° C. for 8 hours and 50 hours, and the change in the film was visually evaluated. In the evaluation, a test piece that did not change at all was rated as ◎, a test piece that changed slightly was marked as ◯, a test piece that changed was marked as △, and a test piece that changed markedly was marked as x.

  These are shown in Table 1. Although the test piece of Examples 1 and 2 is especially excellent, it turns out that the test piece of Example 3 is also a favorable result compared with the test piece of Comparative Examples 1-3 corresponding to the conventional product.

  The test pieces of Comparative Examples 1 to 3 also correspond to those often used as antifouling products. In the test piece of Comparative Example 1, the adhered oil stains are easy to remove with water (that is, the oil-in-water contact angle is high), but the oil is easy to adhere in air (that is, the oil contact angle is low). I understand that. The test piece of Comparative Example 3 is hard to adhere to oil and easy to wipe off (that is, the oil contact angle is high), but oil is difficult to remove by washing with water (that is, the oil-in-water contact angle is low). . The test piece of Comparative Example 2 was obtained by subjecting the test piece of Comparative Example 1 to water and oil repellency treatment, but lost the original good properties (advantages of Comparative Example 1), and had the same properties as Comparative Example 3. You can see that That is, all the test pieces of Comparative Examples 1 to 3 have disadvantages.

On the other hand, the test pieces of Examples 1 to 3 have the advantages of Comparative Examples 1 to 3, and the oil is difficult to adhere (that is, the oil contact angle is high and the oil is repelled so that it can be easily wiped off). Even if it adheres, it is easy to remove with water (that is, the oil-in-water contact angle is high and the oil is easily removed with water).
( Example 4 )

A blasted aluminum grease filter substrate 1 was prepared, and the hybrid paint of Example 2 was applied to the substrate 1 by a spray method. Thus, a coating layer 2a having a thickness of 30 g / m ² was formed on the substrate 1. And the solidification process similar to Example 1 was performed, and the grease filter was obtained.

When this grease filter was used, the oil vapor was less likely to adhere, and the adhered oil stain could be easily removed with water, and the labor for maintenance was reduced.
( Example 5 )

  A hybrid paint was prepared by mixing 0.1 g of the fluorine oligomer used in Example 1, 100 g of the soda-based water glass, 10 g of the Aerosil, 5 g of the titanium oxide pigment, and 400 g of water.

A blasted stainless steel kitchen sink base material 1 was prepared, and the hybrid paint was applied to the base material 1 by a spray method. Thus, a coating layer 2a having a thickness of 200 g / m ² was formed on the substrate 1. And after performing the baking process similar to Example 1, the coating layer 2a after a baking process was immersed in 5% phosphoric acid aqueous solution for 10 minutes as a chemical | medical agent treatment process. Thus I got a kitchen sink.

When this kitchen sink is used, the oily dirt generated in the kitchen is difficult to adhere (that is, the oily dirt is repelled), and the attached oily dirt can be easily removed with water, and the maintenance labor is reduced.
(Reference Example 1)

  0.5 g of the fluorine oligomer used in Example 1, 5 g of methanol silica sol (Nissan Chemical), 0.5 g of TEOS (Wako Special Grade) and 0.5 ml of 25% aqueous ammonia were reacted in 25 ml of ethanol for 2 hours. Thus, a fluorine oligomer-modified silica sol in which the fluorine oligomer of Example 1 was immobilized on the surface was obtained. This fluorine oligomer modified silica sol is an anchor particle with a low polymer.

  Fluoro-oligomer modified silica sol 0.5g, 2K potassium water glass 50g, aluminum phosphate (Pacific Chemical) 10g as a hardener for water glass, titanium oxide pigment 1g, silica stone powder (SP-3, snow mark) 5g as aggregate And 20 g of water were mixed to prepare a hybrid paint.

This hybrid paint was applied to an aluminum plate as the substrate 1 by a spray method. Thus, a coating layer 2a having a thickness of 200 g / m ² was formed on the substrate 1. The substrate 1 having the coating layer 2a was heated at 220 ° C. for 1 hour. Thus, the hybrid film 2b was formed on the substrate 1, and a product with a hybrid film was obtained.
(Reference Example 2)

  Glass frit 10g (Nippon frit) as anchor particles, 0.5g TEOS (Wako special grade), 0.5ml bind silane (Amersham) and 0.5ml 25% aqueous ammonia solution (Kanto Chemical) into 50ml acetone (Wako Pure Chemical) The mixture was added, stirred for 24 hours, and treated with bind silane on a glass frit.

  10 g of this bound silane-treated glass frit, 5 g of acrylic acid monomer, and 100 g of perfluorooxide were reacted in 150 g of a fluorine solvent (Asaclean AK225 (Asahi Glass)). Thus, a glass frit having a surface modified with a fluorine oligomer of acrylic acid was obtained. This modified glass frit is an anchor particle with a low polymer.

  5 g of this modified glass frit, 50 g of the above potassium-based water glass, 10 g of aluminum pyrophosphate (Pacific Chemical) as a curing agent for water glass, 1 g of dipyroxide black (# 9565, Dainichi Seikagaku) as a pigment, and 20 g of water Mixed to prepare a hybrid paint.

This hybrid paint was applied to a stainless steel plate as the substrate 1 by a spray method. Thus, a coating layer 2a having a thickness of 200 g / m ² was formed on the substrate 1. The substrate 1 having the coating layer 2a was heated at 180 ° C. for 1 hour. Thus, the hybrid film 2b was formed on the substrate 1, and a product with a hybrid film was obtained.
(Reference Example 3)

  10 g of the above silica stone powder as anchor particles, 0.5 g of TEOS (Wako Special Grade), 0.5 ml of the above bound silane, 0.5 ml of 25% aqueous ammonia solution (Kanto Chemical) are added to 50 ml of acetone (Wako Pure Chemical Industries) and 24 hours. Stir and bind silane treatment on the silica powder.

  10 g of this bound silane-treated silica powder, 5 g of acrylic acid monomer, and 100 g of perfluorooxide were reacted in 150 g of a fluorine solvent (Asaclean AK225 (Asahi Glass)). This modified silica powder is an anchor particle with a low polymer.

  A hybrid paint was prepared by mixing 5 g of this modified silica powder, 50 g of the potassium-based water glass, 1 g of the titanium oxide pigment, and 20 g of water.

This hybrid paint was applied to a galvanized steel sheet as the substrate 1 by a spray method. Thus, a coating layer 2a having a thickness of 200 g / m ² was formed on the substrate 1. The substrate 1 having the coating layer 2a was heated at 200 ° C. for 3 hours. Furthermore, it was immersed in 3% phosphoric acid aqueous solution for 4 hours. Thus, the hybrid film 2b was formed on the substrate 1, and a product with a hybrid film was obtained.
(Reference Example 4)

  A hybrid paint was prepared by mixing 1.0 g of the fluorine oligomer used in Example 1, 100 g of the soda-based water glass, 50 g of colloidal silica (ST-XS, Nissan Chemical), 10 g of zirconium phosphate as a pigment, and 100 g of water. .

This hybrid paint was applied to a glass plate as the substrate 1 by a spray method. Thus, the coating layer 2a having a thickness of 80 g / m ² was formed on the substrate 1. The base material 1 having the coating layer 2a was heated at 150 ° C. for 30 minutes. Further, it was immersed in a 10% aqueous ammonium phosphate solution for 3 hours. Thus, the hybrid film 2b was formed on the substrate 1, and a product with a hybrid film was obtained.

In the above, the present invention has been described with reference to the first to fifth embodiments. However, the present invention is not limited to the first to fifth embodiments, and it can be applied as appropriate without departing from the scope of the present invention. Not too long.

  The present invention can be used for a range filter, a range hood, a fan for a ventilation fan, a kitchen bag, a white board, a building material, and the like.

It is sectional drawing of a base material and a coating-film layer in connection with Examples 1-5, Reference Examples 6-9, and Comparative Examples 1-3. It is sectional drawing of a base material and a film | membrane concerning Examples 1-5, Reference Examples 6-9, and Comparative Examples 1-3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2a ... Coating layer 2b ... Film | membrane, hybrid film

Claims (2)

A low polymer that is an oligomer and / or co-oligomer having fluorine-containing groups at both ends is mixed with anchor particles in a matrix made of water glass as the main component, and the low polymer is esterified to the anchor particles. A hybrid paint having hydrophilicity and oil repellency, which is fixed by a reaction via a bond, a hydrogen bond, a coordination bond, a siloxane bond or an alkoxide . A substrate and a hybrid film having hydrophilicity and oil repellency formed on the substrate;
The hybrid coating is prepared by mixing an anchor particle with a low polymer that is an oligomer and / or a co-oligomer having fluorine-containing groups at both ends in an inorganic glassy matrix as a main component. A product with a hybrid film, wherein the low polymer is fixed by a reaction via an ester bond, a hydrogen bond, a coordination bond, a siloxane bond or an alkoxide .

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