WO2009096492A1 - Matériau en paillettes et procédé de production correspondant - Google Patents

Matériau en paillettes et procédé de production correspondant Download PDF

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Publication number
WO2009096492A1
WO2009096492A1 PCT/JP2009/051506 JP2009051506W WO2009096492A1 WO 2009096492 A1 WO2009096492 A1 WO 2009096492A1 JP 2009051506 W JP2009051506 W JP 2009051506W WO 2009096492 A1 WO2009096492 A1 WO 2009096492A1
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WIPO (PCT)
Prior art keywords
acid
flake body
body according
dye
red
Prior art date
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PCT/JP2009/051506
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English (en)
Japanese (ja)
Inventor
Shinji Mikami
Mitsuhiro Kawazu
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Nippon Sheet Glass Company, Limited
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Publication date
Application filed by Nippon Sheet Glass Company, Limited filed Critical Nippon Sheet Glass Company, Limited
Priority to JP2009551582A priority Critical patent/JPWO2009096492A1/ja
Publication of WO2009096492A1 publication Critical patent/WO2009096492A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D7/41—Organic pigments; Organic dyes
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 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
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present invention relates to a flake body in which a fluorescent dye is dispersed and a method for producing the same.
  • a flake body containing a pigment is produced by a so-called sol-gel method.
  • JP-A-4-292430 is formed by applying a solution containing a metal compound capable of hydrolysis and dehydration condensation (for example, tetramethoxysilane) and an organic dye on a substrate and drying the solution.
  • a method for obtaining a flake body by peeling a gel from a substrate is disclosed.
  • JP-A-8-60019 is formed by using an acid dye as an organic dye, adding the organic dye to a solution containing a metal compound capable of hydrolysis and dehydration condensation, applying the solution to a substrate, and drying the solution.
  • a method for producing a flake body is disclosed, in which a gel to be peeled is peeled from a substrate and a predetermined heat treatment is performed on the gel. According to this method, a flake body containing an organic coloring matter (dye) at a high concentration (0.5 to 30% by mass) can be obtained.
  • JP-A-8-245341 a solution containing a metal compound capable of hydrolysis and dehydration condensation (condensation polymerization) is cured, and the hydrolyzed metal compound is subjected to condensation polymerization so that the degree of polymerization is 100 to 3500.
  • a method for producing a flake body in which a solution obtained by adding an acid dye to a solution is applied onto a substrate, the gel formed by drying the solution is peeled off from the substrate, and the gel is further heated. According to this method, the elution resistance of the organic dye is improved.
  • the degree of polymerization of the metal compound must be controlled within a predetermined range in the solution. For this reason, in order to mass-produce the flake body, further improvement is necessary.
  • An object of the present invention is to provide a flake body with improved elution resistance of fluorescent dyes. Another object of the present invention is to provide a method for producing the flake body.
  • a fluorescent dye-dispersed flake body excellent in elution resistance and color developability can be obtained by including at least one organic acid in the sol-gel method flake body in which the fluorescent dye is dispersed. I found it.
  • the present invention A flake body mainly composed of a metal oxide by a sol-gel method, An oxide matrix composed of the metal oxide; A fluorescent dye dispersed in the oxide matrix; An organic acid, Providing a flake body.
  • the present invention provides: Preparing a sol solution containing at least one fluorescent dye by hydrolyzing a metal compound; Applying a sol solution containing the fluorescent dye on a substrate to form a film; Separating the film from the substrate to obtain a flake body,
  • the hydrolysis provides a method for producing a flake body that is performed using at least one organic acid as a catalyst.
  • At least one kind of fluorescent dye is dispersed in an oxide matrix and contains at least one kind of organic acid.
  • organic acid By containing the organic acid, a flake body having improved elution resistance of the fluorescent dye can be obtained.
  • the flake body is excellent in mass productivity.
  • the catalyst in the sol-gel reaction is not an inorganic acid but an organic acid. For this reason, since the obtained flake body does not contain the inorganic acid which is a strong acid, it is excellent in safety.
  • the flake body of the present invention is preferably produced by a sol-gel method.
  • the metal oxide is the main component of the flake body.
  • the main component means a component contained in the flake body by 50% or more by mass. Any kind of metal oxide can be used as long as it can be produced by a sol-gel method.
  • the metal of the metal oxide inexpensive, industrially easily available metals such as silicon, titanium, aluminum and zirconium are preferable from the viewpoint of production. These metal alkoxides, chlorides, and nitrates are generally used in the sol-gel method.
  • silicon is a particularly preferable metal, and silicon alkoxide is preferable because it can be obtained at a low cost.
  • silicon alkoxide examples include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.
  • ethyl silicate 40, ethyl silicate 45, methyl silicate 51 are commercially available as polymers of dimers or more in which silicon alkoxide is partially condensed. It is also possible to use silicon alkoxide.
  • the metal oxide constituting the flake body may be silicon oxide and at least one selected from the group consisting of titanium oxide, aluminum oxide and zirconium oxide.
  • silicon alkoxide, titanium alkoxide, aluminum alkoxide, zirconium alkoxide, and the like are used in combination. That is, as the metal compound, a silicon compound and at least one selected from the group consisting of a titanium compound, an aluminum compound, and a zirconium compound can be used in the sol-gel method.
  • metal oxide fine particles described above may be used.
  • Metal oxide fine particles cannot be used as a main component due to weak bonding force between the particles, but can be added to a coating solution (a sol solution containing a fluorescent dye).
  • a coating solution a sol solution containing a fluorescent dye.
  • colloidal silica, colloidal alumina, silica sol, alumina sol and the like are commercially available.
  • the organic acid to be included in the flake body of the present invention is, for example, an acid having a functional group such as a carboxylic acid group or a sulfonic acid group and containing at least carbon in the molecule, and is generally referred to as an inorganic acid. It is an acid distinguished from hydrochloric acid, sulfuric acid and the like.
  • the organic acid used in the present invention preferably has at least one functional group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and an amino acid group. More preferably, the organic acid is a carboxylic acid or natural amino acid, or a mixture thereof.
  • organic acids examples include adipic acid, ascorbic acid, benzoic acid, oleic acid, orotic acid, capric acid, caprylic acid, citric acid, glycyrrhizic acid, gluconic acid, glycolic acid, succinic acid, acetic acid, salicylic acid, Tartaric acid, stearic acid, serotic acid, sorbic acid, tannic acid, dehydroacetic acid, nicotinic acid, valmitic acid, glacial acetic acid, phytic acid, propionic acid, behenic acid, myristic acid, lauric acid, malic acid, linoleic acid, acrylic acid, Examples include methacrylic acid, formic acid, fumaric acid, butyric acid, and oxalic acid. One of these may be used, or two or more may be mixed and used. Of these, formic acid, acetic acid, citric acid, sorbic acid, glutamic acid and gluc
  • the present inventors consider the reason why the elution resistance of the fluorescent dye is improved by using an organic acid as a catalyst in the sol-gel reaction as follows.
  • an organic acid such as hydrochloric acid or nitric acid
  • the metal oxide, inorganic salt, and fluorescent dye that are inorganic substances are separated in the drying process of the coating solution, The fluorescent dye is in an aggregated state. This deteriorates the elution resistance.
  • an organic acid is a molecule having a carboxylic acid group or a sulfonic acid group having a high affinity for a metal oxide and a portion having a strong affinity for a fluorescent dye. For this reason, the effect which connects both arises between a metal oxide and fluorescent dye, it becomes difficult to isolate
  • the acid dissociation constant pka value of the organic acid used in the present invention is preferably 2 to 4.8.
  • the pka value is an index representing the strength of acid, and the smaller the value, the stronger the acid strength. It is considered that the elution resistance of the fluorescent dye in the flake body and the acid dissociation constant of the organic acid are related. According to the organic acid having such a pka value, high elution resistance can be realized, and the stability of the coating solution is also good.
  • the acid dissociation constant (pka value) is shown about some acids among the organic acids mentioned above.
  • acid dissociation constants of inorganic acids are also shown.
  • the amount of water used in the hydrolysis may be an amount capable of hydrolyzing the hydrolyzable metal compound. Furthermore, it is desirable to use at least 1/2 equivalent of water relative to the number of reaction points of the metal compound to water. For example, when silicon alkoxide is used as the metal compound, the number of hydrolyzable reaction points is 4 per molecule, and theoretically 4 molecules of water are consumed. However, in the condensation reaction after hydrolysis, two water molecules are reproduced per metal atom. As a result, two molecules of water are consumed per molecule of silicon alkoxide. Therefore, when 2 molecules / 4 molecules or more, that is, 1/2 equivalent or more of water is used with respect to the number of reaction points of the metal compound to water, sufficient hydrolysis is possible.
  • ethyl silicate 40 In the case of a dimer or higher polymer in which silicon alkoxide is partially condensed, for example, since the metal compound of ethyl silicate 40 is an average pentamer, there are 12 water reaction points. From this, in the case of ethyl silicate 40, it is sufficient to use 6 equivalents or more of water per molecule.
  • hydrolysis may be performed using 1 ⁇ 2 equivalent or more and 1 equivalent or less of water relative to the number of reaction points of the metal compound to water. desirable.
  • the metal compound when hydrolyzed with a small amount of water, the water ratio in the sol solution is reduced, and a fluorescent dye having low solubility in water can be used.
  • the water ratio in the sol solution at this time is preferably 14% by mass or less, and more preferably 7.5% by mass or less.
  • an organic solvent such as alcohol is added to the obtained sol solution, the water ratio can be further reduced.
  • sol solution having a small water ratio because it can suppress the influence on the fluorescent dye whose absorption, light emission, and color tone are changed by the action of water.
  • the content of the organic acid in the flake body is, for example, 0.01% by mass or more and 20% by mass or less from the viewpoint of improving the elution resistance and maintaining the strength of the flake body.
  • the volatile organic acid volatilizes during the drying process of the coating solution, and the flake body may not contain 0.01% by mass or more. . Even in this case, since the formation of the network is completed, good elution resistance is maintained.
  • the organic acid in the flake body is analyzed by analyzing the functional group of the organic acid by infrared absorption spectrum or Raman absorption spectrum, or the flake body is finely pulverized and then extracted with a solvent such as water or ethanol, and subjected to liquid chromatography. , Gas chromatography, and gel permeation chromatography (Gel Permeation Chromatography).
  • the fluorescent dye is a dye that is excited by absorbing ultraviolet light, visible light, or infrared light, and emits ultraviolet light, visible light, or infrared light.
  • Such fluorescent dyes include fluorescein dyes, pyrazine dyes, coumarin dyes, naphthalimide dyes, triazine dyes, oxazine dyes, dioxazine dyes, rhodamine dyes, sulforhodamine dyes, azo compounds, azomethines.
  • Related compounds, stilbene derivatives, oxazole derivatives, benzoxazole dyes, imidazole dyes, pyrene dyes, and the like are known. One kind selected from these dyes may be used, or two or more kinds may be mixed and used.
  • fluorescent dyes in consideration of safety, a fluorescent dye selected from cosmetic legal dyes stipulated in the Japanese Pharmaceutical Affairs Law is desirable. Further, it is desirable that the fluorescent dye is registered in the FDA (Food and Drug Administration) classification.
  • fluorescent dyes purple No. 401 (D & C Violet No.2), yellow No.201 (D & C Yellow No.7), yellow No.202- (1) (D & C Yellow No.8), yellow No.202- ( 2) (D & C Yellow No.8), Yellow No.203 (D & C Yellow No.10), Orange 201 (D & C Orange No.5), Red 104- (1) (D & C Red No.28), Red No.105 -(1), Red 106, Red 230- (1) (D & C (Red No.22), Red 230- (2), Red 231, Red 232, Red 3 (FD & C Red No.3) Red 401 (EXT.D & C Red No.3), Red 213 (D & C Red No.19) and the like.
  • One kind selected from these fluorescent dyes may be used, or two or more kinds may be mixed and used.
  • the content of the fluorescent dye may be adjusted according to the absorbance, emission intensity, and intended use of the fluorescent dye, and is, for example, in the range of 0.01% by mass to less than 50% by mass.
  • the total of the content of the fluorescent dye and the content of the organic acid does not exceed 50% by mass.
  • the range of the organic acid content is 0.01 to 20% by mass
  • the upper limit of the content of the fluorescent dye is 49.9% by mass.
  • a preferable range of the content of the fluorescent dye is 0.01 to 20% by mass. According to such a range, color development by the fluorescent dye is sufficiently exhibited while appropriately maintaining the strength and elution resistance of the flake body.
  • a more preferable range of the content of the fluorescent dye is 0.5 to 5% by mass.
  • the added amount of the fluorescent dye is maintained and dispersed in the flake body.
  • the dye concentration can be analyzed by analyzing the functional group of the dye molecule with an infrared absorption spectrum or by measuring the absorption spectrum of the dye in the ultraviolet region or visible region.
  • the color developability of the fluorescent dye changes depending on pH, and the fluorescent dye changes color under strong acid conditions or alkaline conditions.
  • the degree of acid resistance and alkali resistance varies depending on the type of fluorescent dye.
  • an organic acid which is a weak acid compared to an inorganic acid is used, there is little influence on the color developability of the fluorescent dye. For this reason, a flake body containing a fluorescent dye having good color developability is obtained.
  • the coating solution may contain a surfactant.
  • surfactants include cationic surfactants and amino acid derivatives.
  • cationic surfactant at least one selected from the group consisting of alkyl betaines, quaternary alkyl ammonium salts and heterocyclic ammonium salts can be used.
  • amino acid derivative at least one selected from the group consisting of alkyl-substituted amino acids, acrylated amino acids, and alkoxylated amino acids can be used.
  • the amino acid derivative may be at least one selected from the group consisting of glutamic acid surfactants, sarcosine surfactants, glycine surfactants and lysine surfactants. Of these, glutamic acid surfactants are preferable.
  • the content of such a surfactant is 0.01% by mass or more and less than 50% by mass, preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass with respect to the flake body. is there. However, the total of the content of the fluorescent dye, the content of the organic acid, and the content of the surfactant does not exceed 50% by mass.
  • the average particle diameter of the flake body is 0.2 ⁇ m to 5 mm, preferably 1 ⁇ m to 500 ⁇ m. According to the flake body having such an average particle diameter, for example, when this flake body is contained in ink or paint, good applicability, dispersibility and uniformity can be realized. As shown in FIG. 1B, the particle size of the flake body 1 can be determined as the square root of the area S when the flake body 1 is viewed in plan. In this specification, the “average particle size” means an average value obtained by measuring the particle size of 50 flake bodies with a scanning electron microscope.
  • the average thickness of the flake body is 0.1 to 15 ⁇ m. More preferably, it is 0.1 to 10 ⁇ m, and further preferably 0.1 to 5 ⁇ m. According to the flake body having such an average thickness, when the flake body is contained in ink or paint, good slipping properties and coating properties can be realized.
  • “average thickness” means an average value obtained by measuring the thickness of 50 flake bodies with a scanning electron microscope.
  • a coating liquid containing a sol obtained by hydrolyzing a hydrolyzable metal compound, an organic acid, and a fluorescent dye is prepared. There are no particular restrictions on the procedure for preparing this solution.
  • a metal alkoxide which is a compound capable of hydrolysis and polycondensation of the hydrolyzate
  • a coating solution can be prepared by dissolving or dispersing a fluorescent dye in a metal alkoxide solution, adding an organic acid as a catalyst, and hydrolyzing the metal alkoxide to form a sol.
  • a metal alkoxide which is a compound capable of hydrolysis and polycondensation of the hydrolyzate, is dissolved in a solvent, and an organic acid is added to the metal alkoxide solution as a catalyst to form a sol. Thereafter, the coating solution may be prepared by dissolving or dispersing the fluorescent dye in the sol solution.
  • the concentration of the organic acid in the coating solution is 1 ⁇ 10 ⁇ 6 mol / g or more and 5 ⁇ 10 ⁇ 4 mol / g or less regardless of whether the acid is volatile or nonvolatile. It is desirable to be.
  • the content of the organic acid in the flake body can be 0.01% by mass or more and 20% by mass or less.
  • the organic acid content in the flake body may be less than 0.01% by mass, but since the organic acid is present in the coating solution at the time of network formation, good elution resistance Flake bodies are obtained.
  • solvent for the coating solution lower alcohols such as methanol, ethanol and isopropanol, cellosolve solvents such as ethylene glycol diethyl ether and butyl cellosolve, and glycol solvents such as propylene glycol and ethylene glycol are suitable.
  • a solvent such as glycerin or hexylene glycol, which is a low volatility solvent, may be added.
  • the prepared coating solution is applied to the substrate.
  • a base substrate
  • a resin it is preferable to select a resin material having a heat resistant temperature equal to or higher than the boiling point of the solvent contained in the coating solution.
  • the surface of the substrate on which the solution is applied is preferably smooth.
  • a stainless steel plate is mentioned as a base
  • the solution may be applied to the substrate using a known technique.
  • various coating methods such as roll coating methods (flexographic printing methods, etc.), screen printing methods, spin coating methods, spray coating methods, curtain coating methods, dip-up (dip coating) methods, flow coating (flow coating) A method, an inkjet method, or the like may be used.
  • the film formed by applying the solution is dried on the substrate.
  • the drying method is not limited, but in order to promote the removal of the solvent, the fluorescent dye contained in the flake body is not decomposed, and the substrate is heated to a temperature not higher than the heat resistance temperature of the substrate to dry the solution. It is good to let them.
  • a preferable temperature in this drying step may be 80 ° C. to 250 ° C.
  • the solution As the solution is dried, a gel film is formed on the substrate. As the drying further progresses, the film on the substrate shrinks, cracks are generated due to the stress accompanying the shrinkage, the cracks extend, and finally the film peels from the substrate to form a flake body. In order to peel and collect the flake body, it is preferable to suck or scrape it using a brush or the like. In the case where the flake body does not peel off naturally, it may be peeled off from the substrate by applying a force from the outside.
  • the method for recovering the flake body is not particularly limited, and besides the above method, a method of blowing compressed air on the membrane, a method of immersing in a solution, a method of scraping with a scraper, and the like can be shown.
  • the method according to the present invention described above is the simplest for producing the flake body of the present invention and is suitable for mass production.
  • the method for producing a flake body of the present invention is not limited to the method described above.
  • the flake body of the present invention can also be produced by, for example, forming a flat metal oxide liquid in the atmosphere by spraying a coating liquid at high speed and drying it as it is.
  • the flake body of the present invention may contain other components such as hydroxide, halide, and nitride.
  • Example 1 In Example 1, tetramethoxysilane was used as a hydrolyzable compound, and citric acid was used as an organic acid as a catalyst. Further, Tinopal CBS-X (manufactured by Ciba Pearl Chemicals, Inc., Disodium Distyrylbiphenyl Disulfonate), which is a water-soluble fluorescent dye, was used as the fluorescent dye.
  • this coating solution was applied on a stainless steel (SUS304) substrate having a size of 100 ⁇ 100 mm at a speed of 10 revolutions / second (600 rpm) by a spin coating method to form a film.
  • a stainless steel (SUS304) substrate having a size of 100 ⁇ 100 mm at a speed of 10 revolutions / second (600 rpm) by a spin coating method to form a film.
  • water and methanol released by condensation polymerization and isopropanol as a solvent are released from the membrane. After drying, a glassy flake body naturally separated from the substrate was recovered.
  • the thickness t of the obtained flake body was about 1 ⁇ m.
  • the average particle size a was about 5-50 ⁇ m (see FIGS. 1A and 1B).
  • a commercially available scanning electron microscope VE-9000 manufactured by Keyence Corporation was used. In the following Examples and Comparative Examples, the same flake bodies having t and a were obtained.
  • the citric acid used in Example 1 is non-volatile, and Tinopal® CBS-X, which is a fluorescent dye, does not volatilize.
  • the flake body contains about 5% by mass of Tinopal CBS-X and 9.5% by mass of citric acid when calculated from the components of the coating solution.
  • the dissolution property of the flake body was measured by the following method. First, 50 mg of flake bodies were weighed into a sample bottle, 10 g of water was further added, and the mixture was stirred for 1 hour with a magnetic stirrer at a speed of about 8.3 revolutions / second (500 rpm). The rotation speed of the stirrer is sufficient so that the amount of elution does not change even if stirring is performed at a speed higher than this, and the stirring speed is sufficient. After removing flake bodies from this suspension by suction filtration, an absorption peak intensity at 350 nm derived from Tinopal CBS-X was determined using an ultraviolet-visible spectrophotometer (UV-3100 manufactured by Shimadzu Corporation). From this, the amount of fluorescent dye eluted from the flake body was calculated.
  • UV-3100 ultraviolet-visible spectrophotometer
  • Example 2 is the same as Example 1 except that the amount of the fluorescent dye was changed from 1.13 g to 0.57 g and the citric acid concentration was changed to 0.1 mol / dm 3 (0.1N). Got the body.
  • Example 3 flake bodies were obtained in the same manner as in Example 1 except that the organic acid was changed to 1 mol / dm 3 (1N) acetic acid.
  • Example 4 In Example 4, a flake body was obtained in the same manner as in Example 1 except that the organic acid was changed to 0.01 mol / dm 3 (0.01 N) formic acid.
  • Comparative Example 1 flake bodies were obtained in the same manner as in Example 1 except that the acid was changed to 0.1 mol / dm 3 (0.1N) nitric acid.
  • Comparative Example 2 In Comparative Example 2, flakes were obtained in the same manner as in Example 1 except that the acid was changed to 0.05 mol / dm 3 (0.1N) sulfuric acid.
  • Example 5 In Example 5, tetramethoxysilane was used as the hydrolyzable compound, and citric acid was used as the organic acid as a catalyst. Moreover, red 104- (1) (Acid Red 92), which is a red fluorescent dye, was used as the fluorescent dye.
  • Example 6 a flake body was obtained in the same manner as in Example 5 except that the fluorescent dye was changed to Orange No. 201 (Solv. Red 72).
  • Example 7 flake bodies were obtained in the same manner as in Example 5 except that the fluorescent dye was changed to yellow 201 (Acid Yellow 73, fluorescein).
  • Example 8 To a solution containing 30.0 g of tetramethoxysilane and 41.7 g of isopropanol, 7.1 g of an aqueous citric acid solution (0.2 mol / dm 3 ) was added and stirred for 1 hour at room temperature. The obtained solution was allowed to stand in a thermostat at 50 ° C. for 48 hours, followed by hydrolysis and polymerization to obtain a sol solution.
  • this sol solution was added 0.33 g of an alcohol solution of octadecyloxypropyltrimethylammonium chloride (manufactured by Kao Corp., Cotamine 80K), 0.015 g of a fluorescent dye (orange 201), and 5.0 g of isopropanol.
  • This coating solution was applied to a stainless steel substrate (SUS304, 100 mm ⁇ 100 mm ⁇ 0.5 mm thickness) at a spin coating rotational speed of 500 rpm, and then dried for 60 seconds in a 250 ° muffle furnace, and the flakes that were naturally peeled were collected to obtain flakes.
  • the film thickness of the flakes at this time was 0.8 ⁇ m to 1.3 ⁇ m and showed good peelability.
  • Example 9 To a solution containing 46.8 g of tetramethoxysilane, 4.7 g of methyltrimethoxysilane and 72.8 g of isopropanol, 18.4 g of an aqueous citric acid solution (0.2 mol / dm 3 ) was added and stirred for 1 hour at room temperature. The obtained solution was allowed to stand in a thermostat at 50 ° C. for 48 hours, followed by hydrolysis and polymerization to obtain a sol solution. To 10 g of this sol solution, 0.015 g of a fluorescent dye (red No.
  • Table 1 shows the conditions and dissolution data of the examples and comparative examples described above. Compared to those using inorganic acids, those using organic acids showed better elution resistance regardless of the type and concentration of organic acids. In addition, Examples 8 and 9 using a surfactant also showed sufficient elution resistance.
  • the flake body of the present invention exhibits an excellent effect when it is contained in a paint, a resin composition, ink, paper, a gel composition (for example, gel ink), or the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un matériau en paillettes contenant un oxyde métallique en tant que principal composant, lequel matériau est produit selon un procédé sol-gel. Le matériau en paillettes comprend une matrice d'oxyde composée de l'oxyde métallique, d'un colorant fluorescent dispersé dans la matrice d'oxyde et d'un acide organique. En outre, l'invention concerne également un procédé permettant de produire un matériau en paillettes, lequel procédé comprend les étapes qui consistent à préparer une solution sol contenant au moins un colorant fluorescent par hydrolyse d'un composé métallique; à appliquer la solution sol contenant le colorant fluorescent sur une plaque de base afin de former une pellicule; puis à peler la pellicule de la plaque de base afin de produire le matériau en paillettes, l'hydrolyse étant réalisée au moyen d'au moins un acide organique en tant que catalyseur.
PCT/JP2009/051506 2008-01-30 2009-01-29 Matériau en paillettes et procédé de production correspondant WO2009096492A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103183988A (zh) * 2011-12-29 2013-07-03 深圳市宏商材料科技股份有限公司 一种热收缩材料喷涂示温漆及其制备方法
WO2018130827A1 (fr) * 2017-01-10 2018-07-19 The Royal Mint Limited Encre contenant un élément de sécurité

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0860019A (ja) * 1994-08-23 1996-03-05 Nippon Sheet Glass Co Ltd フレーク状粉体、その製造方法、およびそれを配合した化粧料
JP2007099859A (ja) * 2005-10-03 2007-04-19 Nippon Sheet Glass Co Ltd 蛍光色素含有フレーク体およびその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0860019A (ja) * 1994-08-23 1996-03-05 Nippon Sheet Glass Co Ltd フレーク状粉体、その製造方法、およびそれを配合した化粧料
JP2007099859A (ja) * 2005-10-03 2007-04-19 Nippon Sheet Glass Co Ltd 蛍光色素含有フレーク体およびその製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103183988A (zh) * 2011-12-29 2013-07-03 深圳市宏商材料科技股份有限公司 一种热收缩材料喷涂示温漆及其制备方法
WO2018130827A1 (fr) * 2017-01-10 2018-07-19 The Royal Mint Limited Encre contenant un élément de sécurité
GB2572119A (en) * 2017-01-10 2019-09-18 The Royal Mint Ltd Ink containing a security element
GB2572119B (en) * 2017-01-10 2020-06-03 The Royal Mint Ltd Ink containing a security element

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