WO2021235230A1 - Film de revêtement chromatique brillant et objet de revêtement équipé dudit film de revêtement - Google Patents

Film de revêtement chromatique brillant et objet de revêtement équipé dudit film de revêtement Download PDF

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Publication number
WO2021235230A1
WO2021235230A1 PCT/JP2021/017371 JP2021017371W WO2021235230A1 WO 2021235230 A1 WO2021235230 A1 WO 2021235230A1 JP 2021017371 W JP2021017371 W JP 2021017371W WO 2021235230 A1 WO2021235230 A1 WO 2021235230A1
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coating film
chromatic
brilliant
color
titanium acid
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PCT/JP2021/017371
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English (en)
Japanese (ja)
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浩一 福傳
祐介 植薄
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石原産業株式会社
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Priority to JP2022524372A priority Critical patent/JPWO2021235230A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents

Definitions

  • the present invention relates to a chromatic brilliant coating film (that is, a brilliant chromatic coating film) and an object including the coating film.
  • a coating film using a brilliant pigment is generally called a brilliant coating film, but in a brilliant coating film using an aluminum flake pigment, the reflected light intensity (that is, brightness) changes depending on the viewing angle (so-called brightness). Flip-flop property) can be obtained.
  • a paint containing an aluminum flake pigment and a chromatic pigment is applied to a base material (Patent Document 1), or a coating film containing an aluminum flake pigment and a coating film containing a chromatic pigment are laminated (Patent Document 1). By 2), a chromatic bright coating film is formed.
  • An object of the present invention is to provide a novel brilliant chromatic coating film.
  • An object of the present invention is preferably to provide a brilliant chromatic coating film capable of achieving both flip-flop property and high saturation without causing design restrictions or complication of the painting process.
  • the present inventors have conducted a diligent study in view of the problems of the prior art as described above. Then, they have found that the above-mentioned problems can be solved by using "flaky titanium acid” as a brilliant pigment to be combined with a chromatic pigment, and have completed the present invention.
  • the present invention includes the following inventions.
  • L * 15 and brightness L * 110 which is the ratio of the L * 15 / L * 110 is 1.4 or more, L * a * b * color saturation and chroma C * 45 of the coating in the color system
  • a brilliant chromatic color coating having a value of (C * 45 + C * 75) / 2, which is an average value with C * 75, of 30 or more.
  • the brilliant chromatic color coating film according to (1) which comprises a single layer containing the chromatic pigment and the flaky titanium acid.
  • the brilliant chromatic coating film of the present invention can realize a unique design feeling of high saturation from any angle while ensuring sufficient flip-flop properties.
  • the brilliant chromatic color coating film of the present invention can realize the above-mentioned design feeling without adopting a "multi-layer" structure, so that the degree of freedom in the design of the coating film can be ensured and coating can be performed. It is possible to simplify the process.
  • the inventors of the present invention described the molar absorption coefficient of flaky titanium acid at a specific wavelength and the graininess of the coating film (the presence of individual flaky titanium acid particles was conspicuously glaring). It was found that there is a certain correlation with the texture. That is, by using flaky titanium acid having a molar extinction coefficient of 500 or more at a wavelength of 265 nm, not only the flip-flop property and high saturation are compatible, but also the graininess is small (glare is suppressed and the texture is fine and precise. ) It is possible to realize a coating film with a unique design feeling.
  • FIG. 2A is a color photograph (the right half is blue) showing a state in which the bright chromatic coating film of Example 1 of the present invention is viewed from a highlight region.
  • FIG. 2B is a color photograph (the right half is blue) showing a state in which the bright chromatic coating film of Example 1 of the present invention is viewed from a shade region. It is a color photograph (the right half is a turbid blue with low saturation) showing the appearance of the brilliant chromatic color coating film of Comparative Example 1.
  • the brilliant chromatic coating film of the present invention contains at least a chromatic pigment and flaky titanium acid.
  • the chromatic pigment in the present invention is a pigment exhibiting a chromatic color (that is, a color having hue, lightness, and saturation). In other words, it is a pigment other than black, gray, and white, and is a pigment exhibiting, for example, red, orange, yellow, green, blue, and purple.
  • a chromatic color that is, a color having hue, lightness, and saturation.
  • the chromatic pigment either an inorganic pigment or an organic pigment can be used as long as it exhibits a chromatic color.
  • red pigment examples include iron oxide pigments, azolake pigments, insoluble azo pigments, condensed azo pigments and other azo pigments, anthanthrone pigments, anthracinone pigments, perylene pigments, quinacridone pigments and diketo.
  • examples thereof include pyrrolopyrrole pigments.
  • orange pigment examples include azo pigments, anthracinone pigments, perinones, slen pigments, quinacridone pigments, and indigoid pigments.
  • yellow pigment examples include isoindoline pigments, azomethine pigments, antron pigments, iron oxide pigments, benzimidazolone pigments, quinoxalindione pigments, isoindolinone pigments and the like.
  • green pigment examples include phthalocyanine pigments and azomethine pigments.
  • blue pigment examples include phthalocyanine pigments and indigoid pigments.
  • purple pigments examples include iron oxide purple, purple ultramarine, manganese purple, cobalt purple, indigoid pigments, quinacridone pigments, oxazine pigments, anthraquinone pigments, carbonium pigments, and xanthene pigments.
  • chromatic color pigment of the present invention not only one type of chromatic color pigment can be used, but also a plurality of types of chromatic color pigments can be mixed and used. Further, a chromatic pigment contained in a commercially available chromatic paint composition can also be used.
  • titanium acid is a compound composed of Ti, O and H atoms. Titanate is known to have various crystal structures, but it is preferable to use titanium acid having a layered crystal structure.
  • Titanate which has a layered crystal structure, also has various crystal structures. Its crystal form is crystallographically different from A-type (anatase-type) and R-type (rutile-type) titanium oxide.
  • the titanic acid having a layered crystal structure for example, a TiO 6 octahedron shares a ridge to form a sheet that spreads two-dimensionally in the a-axis and c-axis directions, and a layered structure containing cations is formed between them.
  • Titanate having a layered crystal structure having a skull site structure can be used. The crystal structure can be confirmed by powder X-ray diffraction.
  • flaky is a concept including what is called plate-like, sheet-like, flake-like, and scaly-like in terms of the shape of titanium acid particles, and the width and length with respect to the thickness. It has a shape with a relatively large ratio of.
  • the flaky titanium acid of the present invention preferably has a median diameter (D50) in the range of 10 to 40 ⁇ m (that is, 10 ⁇ m or more and 40 ⁇ m or less) in the volume particle size distribution measured by the laser diffraction / scattering method, and is preferably 10 to 30 ⁇ m (that is, 10 to 30 ⁇ m). It is more preferably in the range of 10 ⁇ m or more and 30 ⁇ m or less). Within such a range, the flip-flop property of the brilliant chromatic color coating film can be sufficiently ensured.
  • D50 median diameter
  • a dispersion liquid in which flaky titanium acid powder is dispersed in a dispersion medium such as water is used as a measurement sample. Measurement is performed at a refractive index of 2.50 using a laser diffraction / scattering type particle size distribution measuring device (LA-950, manufactured by HORIBA, Ltd.).
  • the inventors of the present invention are studying the reduction of the graininess of the coating film (that is, the texture in which the presence of individual flaky titanium acid particles is conspicuous). It was found that there is a correlation between the molar extinction coefficient, which is one of the physical properties, and the graininess of the coating film. Based on this finding, the flaky titanium acid of the present invention preferably has a molar extinction coefficient of 500 or more, and more preferably 1000 or more at a wavelength of 265 nm. By doing so, the graininess of the coating film can be further reduced. However, from the viewpoint of ensuring the difference in brightness (that is, L * 15 / L * 110), the value of the molar extinction coefficient of flaky titanium acid should not be too large. Therefore, the molar extinction coefficient of flaky titanium acid used in the bright chromatic coating film of the present invention is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 5,000 or less.
  • the flaky titanium acid of the present invention can be produced, for example, as follows.
  • the titanium acid metal salt uses a metal oxide or a compound decomposed into a metal oxide by heating and a compound that produces titanium oxide or titanium oxide by heating as a starting material, and these starting materials are mixed and 1050 to 1200. It is obtained by firing at about ° C. After that, it may be crushed if necessary.
  • the titanium acid metal salt is preferably a titanium acid mixed alkali metal salt produced as follows. That is, each compound is decomposed into each M 2 O and M '2 O by alkali metal oxide M 2 O and M' 2 O (M, M ' is an alkali metal and each is different from) or heating dioxide It is produced by mixing titanium or a compound that produces titanium dioxide by heating, preferably at a molar ratio of M / M'/ Ti at a ratio of 3/1/5 to 3/1/11, and firing.
  • the alkali metal oxide at least one of lithium, sodium, potassium, rubidium, and cesium oxides can be used.
  • an alkali metal carbonate, a hydroxide, a nitrate, a sulfate and the like can be used as the compound decomposed into an alkali metal oxide by heating.
  • carbonates and hydroxides are preferable.
  • the compound that produces titanium oxide by heating include hydroxide-containing titanium such as metatitanium acid and orthotitanium acid, and organic titanium compounds such as titanium alkoxide. Of these, titanium hydroxide-containing titanium is preferable.
  • the acidic compound is preferably an aqueous acid solution.
  • a metal titanic acid salt for example, after suspending a metal titanic acid salt in a solvent such as water, an aqueous acid solution is added to extract metal ions (metal ions in the metal titanic acid salt and cations in the acid are separated from each other.
  • metal ions metal ions in the metal titanic acid salt and cations in the acid are separated from each other.
  • Examples of the acid aqueous solution include an aqueous solution of an inorganic acid and an organic acid, but there is no particular limitation.
  • Examples of the inorganic acid include hydrochloric acid, sulfuric acid and the like.
  • Examples of the organic acid include acetic acid and oxalic acid. The concentration can be adjusted arbitrarily.
  • the layered titanium acid obtained in the above step is brought into contact with the basic organic compound.
  • the basic organic compound is inserted between the layers by the exchange reaction between the hydrogen ion contained in the layered titanic acid and the basic organic compound, and at least a part of the layers is swollen and / or peeled off to obtain flaky titanium acid. ..
  • the contact method is not particularly limited, and any method can be adopted.
  • a basic organic compound is added to a dispersion of layered titanium acid and mixed.
  • the pH of the aqueous dispersion of layered titanium acid may be appropriately adjusted using a pH adjuster (ammonia, sodium hydroxide, etc.).
  • the basic organic compound is not particularly limited, and any one or two or more basic organic compounds can be appropriately selected and used. Specific examples include (1) quaternary ammonium hydroxide compounds (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc.), and (2) alkylamine compounds (propylamine, (Diethylamine, etc.), (3) Alkanolamine compounds (ethanolamine, aminomethylpropanol, etc.) and the like can be mentioned. Of these, an alkanolamine compound is preferable, and aminomethylpropanol is more preferable.
  • the dispersion of flaky titanium acid thus obtained is solid-liquid separated by a known method and dried.
  • the powder of flaky titanium acid can be obtained by centrifuging the dispersion of flaky titanium acid, separating the sediment and the medium, and drying the sediment.
  • a normal centrifuge can be used for centrifugation. Centrifugation may be repeated twice or more.
  • the powder of flaky titanium acid can also be obtained by spray-drying the dispersion liquid of flaky titanium acid.
  • the precipitate after centrifugation may be spray-dried.
  • a normal spray dryer can be used for spray drying.
  • classification may be performed.
  • the classification may be performed by a wet method or a dry method.
  • the device used for classification is not particularly limited, and any classification device can be used.
  • the wet classifier include a vibrating sieve, a gravitational field classification (sickener, etc.), and a centrifugal force field classification (liquid cyclone, etc.).
  • the dry classifier include a vibrating sieve, a centrifugal force field classification (dry cyclone, etc.), and an inertial force field classification (classifier, etc.). It is preferable to contact the layered titanium acid with the basic organic compound to peel off the layered titanium acid, and then perform the classification in a wet manner as it is because the process can be simplified.
  • the absorption coefficient is controlled by the pH of the layered titanium acid dispersion when the layered titanium acid is brought into contact with the basic organic compound, the amount of the pH adjuster added, the presence or absence of a classification step, the coarse particles at the time of classification, and the fine particles. This can be done by appropriately setting conditions such as the distribution rate.
  • the brilliant chromatic coating film of the present invention contains, as appropriate, a resin component and the like in addition to the above-mentioned chromatic pigment and flaky titanium acid.
  • a resin component and the like include alkyd resin, acrylic resin, polyester resin, epoxy resin, amino resin, fluorine resin, modified silicone resin, urethane resin, vinyl resin and the like, and are appropriately selected. can.
  • These resin components are not particularly limited to organic solvent-soluble type, water-soluble type, emulsion type and the like, and the curing method is not limited to heat-curing type, room temperature curing type, ultraviolet curing type, electron beam curing type and the like.
  • resin components contained in commercially available paint compositions can also be used.
  • additives such as absorbents and antifungal agents, fillers and the like may be contained.
  • the brilliant chromatic coating film of the present invention is not limited to the form of a coating film composed of a single layer, but may take the form of a multi-layer coating film. That is, even if the brilliant chromatic color coating film of the present invention is a coating film composed of a single layer and the single layer coating film contains both the above-mentioned chromatic color pigment and flaky titanium acid.
  • the brilliant chromatic color coating film of the present invention is a coating film composed of a multi-layer coating film, and the coating film includes a coating film containing a chromatic color pigment and a coating film containing flaky titanium acid. Alternatively, it may be in the form of a multi-layer coating film.
  • a coating film containing flaky titanium acid may be laminated on a coating film containing a chromatic pigment, or a coating film containing flaky titanium acid may be laminated on the coating film containing flaky titanium acid. It may be in the form of laminating a coating film containing a chromatic pigment.
  • the bright chromatic coating film of the present invention may further have a clear layer on the outermost surface.
  • the clear layer is formed of, for example, a thermoplastic resin capable of forming a transparent coating film.
  • the clear layer is a layer located on the outermost surface of the brilliant chromatic color coating film, and is provided to improve the appearance, weather resistance, etc. of the object to which the brilliant chromatic color coating film is applied. It is a transparent layer.
  • the thermoplastic resin include acrylic resins having crosslinkable functional groups such as hydroxyl groups, carboxyl groups, silanol groups, and epoxy groups, polyester resins, alkyd resins, fluororesins, urethane resins, and silicon-containing resins.
  • the bright chromatic coating film of the present invention can be formed, for example, as follows.
  • chromatic pigment, flaky titanium acid, resin component, various additives, a solvent and the like are mixed to prepare a brilliant chromatic paint composition.
  • the solvent include organic solvents such as alcohols, esters, ethers, ketones, aromatic hydrocarbons and aliphatic hydrocarbons, water or a mixed solvent thereof and the like.
  • the solvent type can be selected according to the suitability with the resin component. More simply, a brilliant chromatic paint composition can also be obtained by mixing a commercially available chromatic paint and flaky titanium acid.
  • the brilliant chromatic paint composition thus obtained is applied to a substrate by a known method.
  • general methods such as spin coating, spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, and method of dropping droplets.
  • the instrument used for applying the brilliant chromatic paint composition can be appropriately selected from known instruments such as a spray gun, a roller, a brush, a bar coater, and a doctor blade. By doing so, a single layer of brilliant chromatic coating film is formed on the substrate.
  • a clear paint containing a thermoplastic resin capable of forming the above-mentioned transparent coating film is used and applied in layers in the same manner as described above to have a brilliant property having a clear layer on the outermost surface.
  • a chromatic coating film can be obtained.
  • Coating film manufacturing method 2 A chromatic paint composition containing the above-mentioned chromatic pigment and a brilliant paint composition containing flaky titanium acid are separately prepared. The preparation method of each coating composition is based on the above-mentioned bright chromatic coating composition.
  • the chromatic color coating composition and the brilliant coating composition thus obtained are sequentially applied to the substrate by the above-mentioned known method.
  • the base material for example, a metal material such as iron, aluminum, brass, copper, tin, stainless steel, zinc-plated steel, zinc alloy (for example, Zn-Al, Zn-Ni, Zn-Fe, etc.) plated steel; polyethylene.
  • Resins such as resins, polypropylene resins, acrylonitrile-butadiene-styrene (ABS) resins, polyamide resins, acrylic resins, vinylidene chloride resins, polycarbonate resins, polyurethane resins, epoxy resins; various plastic materials such as FRP; glass, cement, Inorganic materials such as concrete; wood; fiber materials such as paper and cloth can be mentioned. There is no limit to the order of application. Further, if necessary, by forming a clear layer on the outermost surface, a multi-layered brilliant chromatic coating film can be obtained.
  • the object to which the brilliant chromatic coating film of the present invention is applied is not particularly limited as long as it achieves the object of the present invention. , Automobile parts; Building materials; Household electrical products such as mobile phones and audio equipment, and articles such as outer panel parts such as furniture. Of these, the outer panel portion of the automobile body and the automobile parts are preferable.
  • the bright chromatic coating film of the present invention may be formed on the base material of the object.
  • L * 15 / L * 110 which is the ratio of the brightness L * 15 and the brightness L * 110 of the coating film in the L * a * b * color system, is 1.4. That is all.
  • L * in the present invention indicates the brightness based on the L * a * b * color system which is the color system adopted in JIS Z 8729.
  • a multi-angle colorimeter BYK-mac i manufactured by Big Gardner Co., Ltd.
  • the light source is set to 90 ° (normal direction of the coating film).
  • L * 15 means the brightness in the so-called highlight region
  • L * 110 means the brightness in the so-called shade region.
  • the brilliant coating film of the present invention contains flaky titanium acid having a large aspect ratio (that is, the ratio of the width and the length to the thickness of the particles), so that the incident light is strongly reflected in the specular reflection direction and the scattered light is generated. Because it is less, it becomes brighter in the highlight area (that is, the lightness L * 15 is larger) and darker in the shade area (that is, the lightness L * 110 is smaller). As a result, the L * 15 / L * 110 of the coating film becomes 1.4 or more, and the difference in brightness between the highlight region and the shade region is sufficiently secured. When the L * 15 / L * 110 of the coating film is 1.4 or more, it can be visually confirmed that sufficient flip-flop properties are exhibited. On the other hand, the larger the value of L * 15 / L * 110 of the coating film, the better, but usually, the value of L * 15 / L * 110 is about 10 or less.
  • L * 15 / L * 110 can be 2 or more. More preferably, in the blue-based and purple-based bright chromatic coating films of the present invention, L * 15 / L * 110 can be 4 or more. More preferably, in the purple-based bright chromatic coating film of the present invention, L * 15 / L * 110 can be 6 or more.
  • the "green" paint color means that the hue angle h is 120 ° or more and less than 210 ° in the L * C * h color system based on the L * a * b * color system.
  • the paint color that is within the range.
  • a "blue” paint color is a paint color having a hue angle h of 210 ° or more and less than 290 °
  • a "purple” paint color is a paint color having a hue angle h of 290 ° or more and 340 ° or more.
  • a paint color within the range of less than °, or a "reddish” paint color is a paint color having a hue angle h of 0 ° or more, less than 30 °, and 340 ° or more and less than 360 °, "orange color”.
  • the "system” paint color is a paint color in which the hue angle h is within the range of 30 ° or more and less than 60 °, and the “yellowish” paint color is the range in which the hue angle h is 60 ° or more and less than 120 °. Refers to the paint color inside.
  • the brilliant chromatic coating film of the present invention is an average value of the saturation C * 45 and the saturation C * 75 of the coating film in the L * a * b * color system (C * 45 + C * 75) /. 2 is 30 or more.
  • C * in the present invention indicates the saturation based on the L * a * b * color system, which is the color system adopted in JIS Z 8729.
  • a multi-angle colorimeter BYK-mac i manufactured by Big Gardner Co., Ltd.) (registered trademark) is used, and the light source is set to 90 ° (this value is for the coating film). It means the C * value (measured value of C * at 15 ° and 110 ° in FIG.
  • C * 45 means the saturation in the so-called face region (that is, the region between the highlight and the shade)
  • C * 75 means the saturation in the so-called shade region.
  • flaky titanium acid as a brilliant pigment has a characteristic that the flip-flop property is exhibited and the brightness is not extremely reduced in the shade region. Therefore, even when used in combination with a chromatic pigment, the shade region does not become grayish and turbid. Therefore, not only the saturation C * 45 in the face region but also the saturation C * 75 in the shade region is maintained high, and the (C * 45 + C * 75) / 2 of the coating film is 30 or more. When (C * 45 + C * 75) / 2 of the coating film is 30 or more, it can be visually confirmed that high saturation is maintained in a relatively wide range regardless of the light receiving angle (that is, the viewing angle). .. On the other hand, the larger the (C * 45 + C * 75) / 2 of the coating film, the better, but usually, the value of (C * 45 + C * 75) / 2 is about 200 or less.
  • (C * 45 + C * 75) / 2 can be 40 or more. More preferably, in the yellowish brilliant chromatic coating film of the present invention, (C * 45 + C * 75) / 2 can be 55 or more.
  • the graininess of the coating film can be further reduced when flaky titanium acid having a molar extinction coefficient of 500 or more (preferably 1000 or more) is used.
  • the G value of the coating film can be set to 3 or less.
  • the G value is an index showing the graininess of the coating film, and is calculated by detecting an image with a CCD chip under diffuse illumination and evaluating the uniformity of the area of a bright and dark region.
  • the G value in the present invention can be measured using a multi-angle colorimeter (BYK-mac i, manufactured by Big Gardner) (registered trademark).
  • Titanium oxide Tianium Oxide A-100 manufactured by Ishihara Sangyo
  • potassium carbonate and lithium carbonate both Kanto Chemical's reagents
  • Menou dairy pot at a mass ratio of 100: 40: 9.2, and then at 1150 ° C. in the air.
  • Lithium potassium titanate K 0.8 Li 0.27 Ti 1.73 O 4
  • the obtained lithium potassium titanate was crushed in an agate mortar to obtain lithium titanate powder.
  • the obtained lithium potassium titanate powder and its 14.4 times mass of 1.1N sulfuric acid aqueous solution were mixed and stirred for 30 minutes, and then the layered titanic acid solid was filtered to recover the layered titanic acid cake.
  • the recovered layered titanium acid cake was mixed with the same amount of 1.1N sulfuric acid aqueous solution again and stirred for 30 minutes, and then the layered titanium acid solid was filtered and washed to recover the layered titanium acid cake.
  • the obtained layered titanium acid cake was mixed and dispersed at a ratio of 1000 g of pure water to 100 g in terms of TiO 2 to obtain a layered titanium acid dispersion.
  • a layered titanium acid dispersion After mixing the layered titanium acid dispersion and aqueous ammonia to adjust the pH to 8.7, 21.4 g of 2-amino-2-methyl-1-propanol 90% aqueous solution per 100 g of TiO 2 (to layered titanium acid). (0.3 neutralizing equivalent) was added to the contained hydrogen ions, and the mixture was stirred at room temperature for 1 hour to obtain a flaky titanium acid dispersion.
  • a mesh with an opening of 10 ⁇ m was attached to a slurry screener (SS170 ⁇ 500 manufactured by Accor Japan Co., Ltd.), and a solution obtained by diluting the obtained flaky titanium acid dispersion with pure water 2-fold was poured at 100 L / hour.
  • the flaky titanium acid dispersion on the net and the flaky titanium acid dispersion under the net were recovered, respectively.
  • a flaky titanium acid dispersion was prepared in the same manner as in Production Example 1 except that the pH of Production Example 1 after the addition of aqueous ammonia was 10.2. Pure water is added to the flaky titanium acid dispersion to dilute it 2-fold, and a disc atomizer is sprayed using a spray dryer (L-8i manufactured by Ohkawara Kakohki Co., Ltd.), inlet temperature 190 ° C, outlet temperature 110 ° C, under the main body. , Cyclone, and bag filter were spray-dried under the conditions of three-point collection, and the powder recovered by the cyclone was mixed under the main body to obtain "flaky titanic acid powder 2".
  • a spray dryer Li-8i manufactured by Ohkawara Kakohki Co., Ltd.
  • Cyclone, and bag filter were spray-dried under the conditions of three-point collection, and the powder recovered by the cyclone was mixed under the main body to obtain "flaky titanic acid powder 2".
  • the particle size distribution of the flaky titanic acid powder obtained in Production Examples 1 and 2 was measured using a laser diffraction / scattering type particle size distribution measuring device (LA-950, manufactured by HORIBA, Ltd.). The refractive index was 2.50. Table 1 shows the 50% diameter (D50) of each flaky titanium acid powder on a volume basis.
  • Molar extinction coefficient (M -1 ⁇ cm -1 ) (absorbance at 265 nm) x 79.9 / ((diluted solid content concentration (wt%)) x 10) Table 1 shows the molar extinction coefficient of each flaky titanium acid powder.
  • the paint primary color containing the brilliant pigment shown in Table 2 (that is, the brilliant paint composition) and the paint primary color containing the chromatic pigment shown in Table 3 are formed. (That is, a chromatic color paint composition) and each were prepared.
  • the paint primary colors shown in Tables 2 and 3 the paint primary colors containing flaky titanium acid powder as a bright pigment which is a paint raw material (specifically, "fluffy titanium acid primary colors 1" and “flakes” in Table 2 "Metallic primary colors” which are the brilliant paint compositions shown in Table 2 and “Blue primary colors” which are the chromatic color paint compositions shown in Table 3 except for the primary colors of the paint (specifically, the primary colors of titanium acid 2 ").
  • the "flaky titanium acid primary color 2" which is the paint primary color containing the flaky titanic acid powder shown in Table 2, the “flaky titanium acid powder 2" obtained in Production Example 2 of the above “flaky titanium acid powder 1" is also available. It was produced by the same method as “Fluffy titanium acid primary color 1" except that it was replaced with "1".
  • the paint raw materials are mixed with a disper while stirring with a disper according to the formulations shown in Tables 2 and 3, and each of the metallic, blue, yellow, red, purple, and green paints is used. The primary colors were made.
  • each paint primary color which is the brilliant paint composition shown in Table 2
  • each paint primary color which is the chromatic color paint composition shown in Table 3
  • the bright chromatic paints P1 to P17 were prepared by hand-stirring with a spatula until the hue became uniform.
  • the numerical unit indicating the blending ratio in Tables 4 and 5 is "g" representing the weight.
  • Example 1 16 g of pure water was added to 40 g of the brilliant chromatic paint P1 to dilute it. Using Anest Iwata's spray gun (W-101-138BGC), the total amount of paint is concealed in black and white after dilution with a hand pressure of 0.125 MPa, a discharge amount opening of 1.5 rotations, an air amount opening fully open, and a pattern width opening fully open. It was applied to a rate test paper (manufactured by Reneta). After setting for 10 minutes or more, it was forcibly dried at 40 ° C. for 30 minutes.
  • W-101-138BGC Anest Iwata's spray gun
  • Retan (registered trademark) PG80III 026 clear 100 parts of Retan (registered trademark) PG80III 026 clear, 10 parts of Retan (registered trademark) PG80 curing agent, and 40 parts of Retan (registered trademark) PG thinner standard type (both manufactured by Kansai Paint) are mixed and the same.
  • the clear layer was applied with a hand pressure of 0.2 MPa, a discharge amount opening of 2.5 rotations, an air amount opening fully opened, and a pattern width opening fully opened. After setting for 10 minutes or more, the film was forcibly dried at 60 ° C. for 1 hour to prepare a brilliant chromatic coating film of Example 1.
  • Examples 2 to 12, Comparative Examples 1 to 5 Using the bright chromatic paints P2 to P12 shown in Table 4, the bright chromatic coating films of Examples 2 to 12 were prepared in the same manner as in Example 1, and the bright chromatic colors shown in Table 5 were prepared. Using the paints P13 to P17, the brilliant chromatic coating films of Comparative Examples 1 to 5 were produced in the same manner as in Example 1.
  • the value of L * 15 / L * 110 of any of the brilliant chromatic coatings also exceeds 1.4.
  • the right half (blue part) of FIG. 2A shows the bright chromatic coating film of Example 1 as viewed from the highlight region, and the right half (blue part) of FIG. 2B.
  • the part) shows the appearance of the brilliant chromatic coating film of Example 1 as viewed from the shade region.
  • FIGS. 2A and 2B in the bright chromatic coating film of Example 1, the difference in brightness between the highlight region and the shade region is secured, and sufficient flip-flop property is exhibited. You can see that there is. Similarly, it was confirmed that sufficient flip-flop properties were exhibited in the other examples.
  • the A value ( (C * 45 + C * 75) / 2) of the brilliant chromatic color coating film.
  • the A value is less than 30.
  • the right half (blue part) of FIG. 3 shows a state in which the bright chromatic coating film of Comparative Example 1 was seen.
  • the brilliant chromatic color coating film of Comparative Example 1 using aluminum flakes as the brilliant pigment has low saturation in appearance, and the original vividness (that is, saturation) of the primary color of the paint is exhibited. It was confirmed that the color was damaged and became muddy.
  • the right half (that is, the blue part) of FIG. 4 shows the state of the bright chromatic paint film of Example 1 observed from substantially the same angle side by side with the bright chromatic paint film of Comparative Example 1.
  • the bright chromatic color coating film of Example 1 using flaky titanium acid as the bright pigment is compared with the bright chromatic color coating film of Comparative Example 1 (see FIG. 3).
  • the saturation of the appearance was high, and the original vividness of the primary colors of the paint was maintained.
  • the brilliant chromatic coating film of Example 1 was viewed from all angles, it was confirmed that high saturation was maintained from any angle. A similar tendency was confirmed in other examples.
  • Example 1 which are blue-based bright chromatic coating films
  • Example 4 which are blue-based bright chromatic coating films
  • the G value of the brilliant chromatic color coating film is smaller than that of Example 4 and is 3 or less.
  • FIG. 5 shows a black-and-white photograph taken at the time of measuring the G value showing the graininess of the brilliant chromatic color coating film of Example 1
  • FIG. 6 shows the brilliant chromatic color coating film of Example 4.
  • a black-and-white photograph taken at the time of measuring the G value indicating the graininess of is shown.
  • FIG. 7 shows a black-and-white photograph taken at the time of measuring the G value indicating the graininess of the brilliant chromatic color coating film of Comparative Example 1.
  • FIG. 5 shows a black-and-white photograph taken at the time of measuring the G value indicating the graininess of the brilliant chromatic color coating film of Comparative Example 1.
  • the brilliant chromatic coating film of the present invention is useful as a brilliant chromatic coating film formed on the surface of a base material of an article such as an automobile or a home electric appliance, which requires a unique design feeling.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un film de revêtement chromatique brillant apte à obtenir à la fois des propriétés caméléon et une saturation élevée sans conférer de restrictions de conception ni compliquer le processus de revêtement.　Film de revêtement chromatique brillant contenant au moins un pigment chromatique et de l'acide titanique lamellaire, le film de revêtement étant formé sur un substrat, dans lequel : L*15/L*110, qui est le rapport de la clarté L*15 et de la clarté L*110 du film de revêtement dans le système de couleur L*a*b*, est de 1,4 ou plus ; et (C*45+C*75)/2, qui est la moyenne de la saturation C*45 et de la saturation C*75 du film de revêtement dans le système de couleur L*a*b*, est de 30 ou plus.
PCT/JP2021/017371 2020-05-19 2021-05-06 Film de revêtement chromatique brillant et objet de revêtement équipé dudit film de revêtement WO2021235230A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0967124A (ja) * 1995-08-29 1997-03-11 Natl Inst For Res In Inorg Mater 薄片状酸化チタンおよびその集合体である多孔体とそれらの製造方法
JP2006263568A (ja) * 2005-03-23 2006-10-05 Toyota Motor Corp 黄金色塗膜の形成方法および黄金色塗膜
WO2017135426A1 (fr) * 2016-02-05 2017-08-10 関西ペイント株式会社 Film de revêtement multicouche et procédé de formation d'un film de revêtement multicouche
WO2019065961A1 (fr) * 2017-09-29 2019-04-04 関西ペイント株式会社 Procédé de formation de film de revêtement multicouche

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0967124A (ja) * 1995-08-29 1997-03-11 Natl Inst For Res In Inorg Mater 薄片状酸化チタンおよびその集合体である多孔体とそれらの製造方法
JP2006263568A (ja) * 2005-03-23 2006-10-05 Toyota Motor Corp 黄金色塗膜の形成方法および黄金色塗膜
WO2017135426A1 (fr) * 2016-02-05 2017-08-10 関西ペイント株式会社 Film de revêtement multicouche et procédé de formation d'un film de revêtement multicouche
WO2019065961A1 (fr) * 2017-09-29 2019-04-04 関西ペイント株式会社 Procédé de formation de film de revêtement multicouche

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