TW202321378A - Coated plate-shaped titanate particles, method for producing same and uses thereof - Google Patents

Abstract

The present invention provides: coated plate-like titanic acid particles which are capable of forming a designed coating film that exhibits high adhesion and water resistance, while having a good silky texture and a good shaded appearance in either case where the coated plate-like titanic acid particles are added to a water-based coating material or where the coated plate-like titanic acid particles are added to an organic solvent-based coating material; and a method for producing the coated plate-like titanic acid particles. According to the present invention, the surfaces of plate-like titanic acid particles are provided with: an oxide and/or hydroxide of aluminum; and at least one substance that is selected from among a silane coupling agent, a hydrolysis product thereof, and a condensate of the silane coupling agent or the hydrolysis product. A silane coupling agent is mixed with the plate-like titanic acid particles, which have an oxide and/or hydroxide of aluminum on the particle surfaces, in a solvent and the resulting mixture is subsequently dried, thereby producing the coated plate-like titanic acid particles of the present invention.

Description

Coated platy titanic acid particles, method for producing the same, and use thereof

The present invention relates to coated plate-shaped titanic acid particles, coated plate-shaped titanic acid particle compositions using the same, their production methods, and design pigments, dispersions, and coating compositions obtained by blending them , Plastic composition.

Gloss paints are known which impart design to the surface of an article. For glossy paints, for example, glossy pigments in which a coating layer of titanium oxide is provided on the surface of scaly substrates such as natural mica, synthetic mica, and flaky alumina can be used. Conventional glossy pigments have a strong luster (brilliance of a metallic tone) and a grainy feel (a design in which individual particles can be seen to shine brightly).

In recent years, as a more luxurious design, a silk-like deep, calm and dense gloss (smooth design like silk without seams) that suppresses the graininess has been proposed, that is, a design that shows a silky feeling. As a glossy pigment that imparts a silky feel, plate-shaped (such shapes generally include, for example, flake-like and scale-like shapes) titanic acid particles are known. For example, Patent Document 1 proposes a method of producing flaky titanic acid having a thickness within a certain range by promoting the exfoliation of layered titanic acid particles by the action of a basic organic compound. Such flake-shaped titanic acid particles can impart a silky feeling with strong brilliance and shade to the coating film, and can also exhibit high weather resistance as a coating film. In addition, in Patent Document 2, a thin-flaky titanic acid particle is proposed, which is characterized in that the average major diameter is 5-30 μm, and the average thickness is 0.5-300 nm; Silica is treated and further treated with a silane coupling agent. In this way, a glossy pigment with excellent silky feeling can be provided, and the deterioration of the coating film resin and the adhesion of the coating film can be improved. In addition, Patent Document 3 proposes surface-treated titanic acid particles produced by adding a surfactant and a hydrophobicity-imparting agent to a pigment of sol-like scaly titanic acid particles, mixing them, freeze-drying, and then powdering them. For the pigment, the surface of the pigment of the scale-shaped titanic acid particle can be hydrophobized. [Prior Art Literature] [Patent Document]

Patent Document 1: International Publication No. 2019/159923 Patent Document 2: Japanese Unexamined Patent Publication No. 2006-257179 Patent Document 3: Japanese Patent Laid-Open No. 2007-153922

[Problem to be Solved by the Invention]

Since the surface of plate-shaped titanic acid particles is hydrophilic, it is relatively easy to disperse in water-based coatings, but it is not easy to disperse in organic solvent-based coatings. The difference between the lightness of the highlight and the lightness of the shade). When the plate-shaped (specifically, flaky) titanic acid particles produced in Patent Document 1 are blended with any of water-based paint and organic solvent-based paint, the water resistance of the coating film formed by the paint remains the same. Not enough. The flaky titanic acid particles of Patent Document 2 still have insufficient dispersibility to organic solvents. Moreover, the coating treatment efficiency of the silane coupling agent is also low, and a large amount of silane coupling agent needs to be added. In Patent Document 3, it is difficult to obtain the effect of improving the hydrophobicity of the scale-like titanic acid particles by organic treatment. In addition, since a freeze-drying step is required to physically adsorb the hydrophobicity-imparting agent on the surface of the scaly titanic acid particles, the production steps are complicated. As mentioned above, when a coating film obtained by using platy titanic acid particles is splashed with a large amount of water such as intense rainfall, the water penetrates between the base material and the coating film to cause swelling (bubbles). In the worst case, there is concern that the coating film will peel off from the substrate. This tendency is particularly remarkable when the above-mentioned platy titanic acid particles are blended into an organic solvent-based paint. [Means to solve the problem]

The inventors of the present invention have diligently studied in view of the above-mentioned problems of the prior art. As a result, it was found that at least one of oxides and/or hydroxides of aluminum, silane coupling agents, hydrolyzed products thereof, and condensation products thereof were present on the surface of plate-shaped titanic acid particles, thereby even when blended with In the case of any one of water-based paint and organic solvent-based paint, the platy titanic acid particles can be sufficiently dispersed. Furthermore, they found that the above-mentioned problems can be solved by applying the paint to an object to form a coating film, and completed the present invention.

That is, the present invention is the following etc.: (1) A coated plate-shaped titanic acid particle in which oxides and/or hydroxides of aluminum and at least one selected from silane coupling agents, their hydrolyzed products, and condensates thereof are present on the plate. The surface of titanic acid particles, (2) The coated plate-shaped titanic acid particles as in (1), wherein the aforementioned silane coupling agent is a compound having an organic functional group X having 8 or less carbon atoms, (3) The coated plate-shaped titanic acid particles as in (1) or (2), wherein relative to the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide, the content of the aforementioned silane coupling agent is 0.5% by mass or more and 30% by mass or less, (4) A composition of coated plate-shaped titanic acid particles, comprising: the coated plate-shaped titanic acid particles according to any one of (1) to (3), and a polysiloxane-based surfactant, (5) The coated plate-shaped titanic acid particle composition as in (4), wherein, compared to the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide, the polysiloxane-based surfactant The content is not less than 0.01% by mass and not more than 20% by mass, (6) A design pigment, which includes: the coated platy titanic acid particles according to any one of (1)~(3), or the coated platy titanic acid particles as in (4) or (5) particle composition, (7) A dispersion comprising: the coated plate-shaped titanic acid particles as described in any one of (1) to (3) or the coated plate-shaped titanic acid particles as described in (4) or (5) substances, and solvents, (8) A coating composition comprising: the coated plate-shaped titanic acid particles according to any one of (1) to (3) or the coated plate-shaped titanic acid particles according to (4) or (5) composition, and resin components, (9) A plastic composition, which includes: the coated plate-shaped titanic acid particles as described in any one of (1) to (3) or the coated plate-shaped titanic acid particles as described in (4) or (5) composition, and resin components, (10) A method for producing coated plate-shaped titanic acid particles, comprising: mixing plate-shaped titanic acid particles having aluminum oxide and/or hydroxide on the particle surface and a silane coupling agent in a solvent , (11) A method for producing coated plate-shaped titanic acid particles, comprising: mixing plate-shaped titanic acid particles having aluminum oxide and/or hydroxide on the surface of the particles, a silane coupling agent, and a polymer in a solvent. After the silicone surfactant, the drying step is carried out. [Effect of the invention]

According to the present invention, the coated plate-shaped titanic acid particle and the coated plate-shaped titanic acid particle composition can be used as a design pigment for any paint of water-based paint or organic solvent-based paint, and silky smoothness can be achieved. A design film with good texture and shadow. In addition, the coated platy titanic acid particles and the coating film of the coated platy titanic acid particle composition using the coated platy titanic acid particles not only have excellent adhesion to the substrate but also exhibit high water resistance. From this point of view, the coated plate-shaped titanic acid particles of the present invention and the coated plate-shaped titanic acid particle composition using the same are suitable for being blended in, for example, automotive coatings, etc., which are assumed to be used in harsh outdoor environments. Pigments for the paints used below.

The coated plate-shaped titanic acid particles of the present invention are made of aluminum oxides and/or hydroxides, at least one selected from silane coupling agents, their hydrolyzed products, and their condensates present in the plate-shaped titanic acid particles The superficial ones (that is, the covered ones). The "coating" in the coated plate-shaped titanic acid particles of the present invention means the presence of at least one selected from the group consisting of aluminum oxides and/or hydroxides, silane coupling agents, their hydrolyzed products, and their condensates State on the surface of plate-shaped titanic acid particles. Therefore, the oxide and/or hydroxide of aluminum and at least one selected from the group consisting of silane coupling agents, their hydrolyzed products, and their condensates not only exist throughout the entire surface of the plate-shaped titanic acid particles, For example, the case where it exists in an island-like dot shape is also included. The platy titanic acid particles have a "plate-like" shape. The so-called "plate shape" refers to concepts other than plate shape, including flake shape, sheet shape, flake shape, scale shape, etc., and refers to the particle size relative to the direction parallel to the particle plate surface , a shape with a smaller particle size (thickness) in the direction perpendicular to the plate surface.

The plate-shaped titanic acid particles are composed of Ti atoms, O atoms and H atoms. The plate-shaped titanic acid particles may also contain various trace elements (for example, Li, Na, K, Rb, Cs, etc.) derived from impurities contained in raw materials and the production method of titanic acid. The platy titanic acid particles can adopt various crystal structures, but a lamellar crystal structure is preferable. There are various structures as a layered crystal structure. For example, TiO ₆ octahedra share edges and extend two-dimensionally into sheets, and plate-shaped titanic acid particles having a lepidocite structure containing cations between these layers can be used. The crystal structure of plate-shaped titanic acid particles can be confirmed by powder X-ray diffraction.

The plate-shaped titanic acid particles have a median diameter (D50) in the volume particle size distribution measured by the laser diffraction/scattering method, preferably in the range of 10 μm to 40 μm, more preferably in the range of 15 μm to 30 μm. Thereby, it is easy to obtain a coating film showing a better shade and silky feeling. The plate-shaped titanic acid particles preferably have a cumulative 10% particle diameter (D10) in the volume particle size distribution measured by the laser diffraction/scattering method of 5 μm or more, more preferably 10 μm or more. Thereby, the abundance ratio of fine particles can be sufficiently reduced, and the fall of the shadow feeling of a coating film can be suppressed. The plate-shaped titanic acid particles preferably have a cumulative 90% particle size (D90) of 70 μm or less, more preferably 60 μm or less, in the volume particle size distribution measured by the laser diffraction/scattering method. Thereby, the abundance ratio of coarse particles can be sufficiently reduced, and the development of particle feeling at the time of coating film formation can be suppressed. Plate-shaped titanic acid particles, the measurement of the particle size distribution by the laser diffraction/scattering method uses a laser diffraction/scattering type particle size distribution measuring device (manufactured by Horiba Manufacturing Co., Ltd., LA-950), and the refractive index is set to for 2.50 to proceed.

The average thickness of the plate-shaped titanic acid particles is preferably in the range of 0.05 μm to 0.4 μm, more preferably in the range of 0.05 μm to 0.3 μm. The average thickness is to make a coating film containing plate-shaped titanic acid particles, observe the section cut with a microtome through an electron microscope, measure the thickness of 100 randomly selected plate-shaped titanic acid particles, and calculate the average value of the number.

The coated plate-shaped titanic acid particles have aluminum oxide and/or hydroxide on the surface. Aluminum oxide and/or hydroxide may coat the surface of the plate-shaped titanic acid particles, or may exist in island-like spots on the surface of the plate-shaped titanic acid particles. Examples of the crystal structure of the hydroxide of aluminum include boehmite, gibbsite, pseudoboehmite, bayerite, and the like, including hydrous oxides and hydrated oxides of aluminum. A plurality of aluminum hydroxides having different crystal structures may be present in admixture. Of course, aluminum oxides and hydroxides may exist in admixture. The crystal structure of aluminum oxide and/or hydroxide can be confirmed by powder X-ray diffraction.

In the present invention, the oxide and/or hydroxide of aluminum coated on the surface of the plate-shaped titanic acid particles can be understood to function as a foothold for the silane coupling agent to exist on the surface of the plate-shaped titanic acid particles . More specifically, the specific surface area of the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide is larger than the specific surface area of untreated plate-shaped titanic acid particles. This can be understood as ensuring more footholds for the silane coupling agent to exist on the surface of the platy titanic acid particles. What functions as a foothold for the silane coupling agent to exist on the surface of the plate-shaped titanic acid particles include, for example, silicon dioxide other than aluminum oxide and/or hydroxide. However, compared with silicon dioxide, aluminum oxide and/or hydroxide has a higher affinity for the plate-shaped titanic acid particles, so it is easy to coat the surface of the plate-shaped titanic acid particles.

Therefore, it is desirable to use aluminum oxide and/or hydroxide as a starting point for making the silane coupling agent exist on the surface of the plate-shaped titanic acid particles. Therefore, in the present invention, it is desirable to use aluminum oxide and/or Hydroxide coats the surface of the plate-shaped titanic acid particles. By coating the oxide and/or hydroxide of aluminum on the surface of the plate-shaped titanic acid particles, the amount of silane coupling agent present on the coated plate-shaped titanic acid particles increases, which can improve the surface of the plate-shaped titanic acid particles. The effect of imparting functionality (specifically, imparting hydrophobicity, water-resistant adhesion, etc.).

The content of the oxide and/or hydroxide of aluminum is preferably at least 1 mass % and at most 30 mass % in terms of Al ₂ O ₃ relative to the plate-shaped titanic acid particles. With respect to the plate-shaped titanic acid particles, the oxide and/or hydroxide of aluminum is contained at least 1% by mass, so that a sufficient amount of silane coupling agent can exist in the oxide and/or hydroxide of aluminum The surface of plate-shaped titanic acid particles. If the content of aluminum oxide and/or hydroxide is high, the silane coupling agent is more likely to exist on the surface of the plate-shaped titanic acid particles, improving the dispersibility of the coated plate-shaped titanic acid particles in an organic solvent. On the other hand, if the content is set at 30% by mass or less, it is possible to effectively avoid the situation where the effect of improving the dispersibility in an organic solvent is reduced due to excessive content of aluminum oxides and/or hydroxides. Therefore, the content of the aluminum oxide and/or hydroxide is more preferably 3% by mass or more and 25% by mass or less in terms of Al ₂ O ₃ relative to the plate-shaped titanic acid particles, and more preferably 5% by mass. The above is 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less.

The coated plate-shaped titanic acid particles have, on their surface, at least one selected from the group consisting of silane coupling agents, their hydrolyzed products, and their condensates, other than aluminum oxides and/or hydroxides. In addition, silane coupling agents, their hydrolyzed products, and their condensates are sometimes collectively referred to as silane coupling agents below. Silane coupling agent refers to an organosilicon compound that has an organic functional group (X) that is expected to react and interact with organic matter, and a hydrolyzable functional group (OR) in one molecule, and is represented by the following general formula.

General formula: X _n Si(OR) _m (However, n and m are natural numbers, satisfying n+m=4)

In the above general formula, when X is an organic functional group and n is 2 or more, they may be the same or different from each other. The organic functional group X is composed of a carbon chain part formed continuously from silane (Si) and a functional group part bonded to the end of the carbon chain part.

The carbon chain portion of the organic functional group X may include a carbon-carbon double bond in the middle, and may have a branched or cyclic structure, but is preferably a straight chain. Examples of the functional group moiety of the organic functional group X include hydrogen, vinyl, acryl, methacryl, isocyanate, epoxy, amine, mercapto, and thioether. In addition, the carbon chain part and the functional group part may be bonded through a carbon atom, or may be bonded through a heteroatom such as an oxygen atom, a nitrogen atom, and a sulfur atom.

In the above general formula, the OR part is a hydrolyzable functional group (in this case, also referred to as a hydrolyzable group), and furthermore, the R part is a hydrogen atom and/or an alkyl group with 1 to 22 carbon atoms, and when m is 2 or more, They can be the same or different from each other. The alkyl group may be any of linear, branched and cyclic structures. At least one of the hydrolyzable groups (OR) of silane coupling agents can be a hydrolyzed product, which can be condensed with the hydrolyzable groups (OR) of other silane coupling agents and the hydroxyl groups of their hydrolyzed products to form condensation products. Furthermore, the hydroxyl groups of the platy titanic acid particles, the hydroxyl groups of the oxides and/or hydroxides of aluminum existing on the surface thereof react with the silane coupling agent to form hydrolysis products.

The silane coupling agent helps to improve the water resistance of the coating film formed from the coated platy titanic acid particles. Generally speaking, the surface of the platy titanic acid particles is hydrophilic, so water is easily introduced into the coating film formed by the coating containing the platy titanic acid particles. If the coating film is immersed in water, the coating film of the substrate The adhesion is significantly reduced. Therefore, the above-mentioned silane coupling agents exist on the surface of the plate-shaped titanic acid particles through the OR part of the general formula, and the carbon chain part of the organic functional group X imparts hydrophobicity to the surface of the coated plate-shaped titanic acid particles. This improves the water resistance of the coating film formed from the coating material containing the coated platy titanic acid particles. The carbon chain part of the organic functional group X of the silane coupling agent is not as long as possible. By selecting an appropriate carbon number, the effects of adhesion and water resistance of the coating film on the substrate can be optimized. Specifically, the carbon number of the organic functional group X of the silane coupling agent is preferably 8 or less. In the present invention, "the carbon number of the organic functional group X" means the number of carbon atoms in the carbon chain part formed continuously from silane (Si).

In addition, silane coupling agents exist on the surface of plate-shaped titanic acid particles through the OR portion of the above general formula, and the carbon chain portion of the organic functional group X has a high affinity with organic solvents and resins, thereby improving the organic solvent It is based on the dispersibility of the coated plate-shaped titanic acid particles in the coating to obtain a coating film with a high sense of shadow. That is, the carbon chain part of the organic functional group X of the silane coupling agent contributes to the affinity with organic solvents and resins, so the carbon number of the organic functional group X is preferably 3 or more, more preferably 5 or more.

Due to the above, in terms of optimizing the adhesion and water resistance of the coating film formed by the coating containing the coated platy titanic acid particles in the present invention, the organic functional group X of the silane coupling agent The carbon number is preferably 8 or less. In particular, in terms of the shadow feeling of the coating film obtained by using the coated plate-shaped titanic acid particles, as well as the optimization of both the adhesion to the substrate and the water resistance, the organic functional group X of the silane coupling agent The carbon number is more preferably from 3 to 8, and still more preferably from 5 to 8.

The functional group part of the organic functional group X of the silane coupling agent can be selected according to the purpose. For example, by using silane coupling agents with hydrophobic functional group moieties (specifically, alkyl, methacryl, phenyl, vinyl, etc.), the coated plate-shaped titanic acid particles can be further improved. For the dispersibility of organic solvent-based coatings. In other words, when a silane coupling agent having a hydrophobic functional group is used, even if the carbon number of the organic functional group X is small, sufficient dispersibility to the organic solvent-based coating can be ensured. As a result, it becomes easy to optimize the shadow feeling of the coating film using the coated plate-shaped titanic acid particles, and the adhesion and water resistance to the base material. In addition, by using silane coupling agents having hydrophilic functional groups (specifically, amino groups, mercapto groups, etc.), the dispersibility of coated plate-shaped titanic acid particles to water-based coatings can be further improved. Furthermore, by using silane coupling agents having reactive functional groups (specifically, amine groups, mercapto groups, epoxy groups, isocyanate groups, etc.), the reactivity with the resin components constituting the paint is improved, and as a result , can further enhance the adhesion to the substrate.

Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 7-octenyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 8-Glycidoxyoctyltrimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, p-Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane Oxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane , N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethyl Oxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl)-2-amine Hydrochloride of ethylethyl-3-aminopropyltrimethoxysilane, ginseng-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Isocyanatopropyltriethoxysilane, Octenyltrimethoxysilane, Glycidoxyoctyltrimethoxysilane Oxysilane, Methacryloxyoctyltrimethoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane silane, decyltrimethoxysilane, 1,6-(trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, and siloxane containing hydrolyzable groups.

Examples of commercially available silane coupling agents include KBM-3063, KBM-3103C, KBM-503, KBM-5803, KBM-903, KBM-603, KBM-803, KBM-1003, KBM-1083, KBM-403, KBM-4803, KBM-6803, KBM-7103 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. The silane coupling agent may be used singly or in combination of two or more kinds (that is, two or more kinds).

The content of silane coupling agents is preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to 10% by mass, relative to the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide , and more preferably at least 1% by mass and not more than 8% by mass. The content of silane coupling agents was obtained by measuring the amount of Si element contained in the dry powder of coated plate-shaped titanic acid particles, and calculating the amount of Si element as the mass of the silane coupling agent. The amount of Si contained in the dry powder of the coated plate-shaped titanic acid particles was measured using a fluorescent X-ray analyzer (manufactured by Rigaku, ZSX Primus IV). The content of the silane coupling agents can also be referred to as the added amount of the silane coupling agents. If the content of the silane coupling agents is within the above range, a sufficient amount of the silane coupling agents can be present on the surface of the platy titanic acid particles in order to exert the effect of the invention. As a result, dispersion of coated plate-shaped titanic acid particles in organic solvents and organic solvent-based coatings becomes favorable, and high shadow and silky sensations can be realized. In addition, it can improve the adhesion and water resistance of the coating film on the substrate.

The present invention may be a coated plate-shaped titanic acid particle composition comprising the above-mentioned coated plate-shaped titanic acid particles and a polysiloxane-based surfactant. In the coated plate-shaped titanic acid particle composition, only the coated plate-shaped titanic acid particles and polysiloxane-based surfactant can be mixed, or the coated plate-shaped titanic acid particles and the polysiloxane-based interface can be physically adsorbed The active agent can also chemically adsorb coated plate-shaped titanic acid particles and polysiloxane-based surfactants. By blending polysiloxane-based surfactants, the aggregation of coated plate-shaped titanic acid particles can be suppressed, and the wettability to organic solvents and resins can be improved. In the coated plate-shaped titanic acid particle composition, in addition to the coated plate-shaped titanic acid particles and the polysiloxane-based surfactant, within the range that does not inhibit the effect of the present invention, a dispersant, Surface regulators such as leveling agents and wettability improvers, defoamers, colorants, extenders, antifungal agents, hardening aids, tackifiers, anti-settling agents and other additives or fillers.

As a polysiloxane-based surfactant, it may have a siloxane structure, or may have a hydrophilic functional group or a hydrophilic polymer chain on the side chain or end of the polysiloxane structure.

Examples of the hydrophilic functional groups and hydrophilic polymer chains of polysiloxane-based surfactants include polyether groups (polyethylene oxide and/or polypropylene oxide copolymers, etc.), polyglycerin (HO(CH ₂ CH(OH)CH ₂ O) _n- H, etc.), pyrrolidone, betaine (C ₃ H ₆ N ⁺ (C ₂ H ₄ ) ₂ -CH ₂ COO ^- , etc.), sulfate ( C ₃ H ₆ O(C ₂ H ₄ O) _n -SO ₃ Na, etc.), phosphates (C ₃ H ₆ O(C ₂ H ₄ O) _n -P(=O)OHONa, etc.), 4th grade salts ( C ₃ H ₆ N ⁺ (C ₂ H ₄ ) ₃ Cl ^- etc.) etc. However, in the aforementioned chemical formulae, n represents an integer of 1 or more. Among these, those having a polyether group are preferable as the hydrophilic functional group. In addition, the main chain of the polysiloxane-based surfactant is not limited to a siloxane structure, and may have a polysiloxane structure in a side chain or a terminal. For example, polydimethylsiloxane obtained by copolymerization of polydimethylsiloxane having a polymerizable vinyl group at the end and other monomers, which has a polysiloxane chain in the side chain, can be cited. Vinyl copolymers, etc. In this case, it is preferable to use hydrophilic monomers, such as (meth)acrylic acid or its salt, for at least a part of other monomer.

Among them, the best polysiloxane-based surfactant is a nonionic surfactant having a structure of methylpolysiloxane in the hydrophobic group and polyoxyethylene in the hydrophilic group. For example, polyether modified Polysiloxane, polysiloxane compounds containing polyoxyalkylene groups, etc.

As the polysiloxane-based surfactant, commercially available products can be used, for example, SILFACE (registered trademark) SAG005, SILFACE (registered trademark) SAG008, SILFACE (registered trademark) SAG013, SILFACE (registered trademark) SAG503A, SILFACE ( Registered trademark) SJM003 (above, made by Nissin Chemical Industry Co., Ltd.), 71ADDITIVE, 74ADDITIVE, 57ADDITIVE, 8029ADDITIVE, 8054ADDITIVE, 8211ADDITIVE, 8019ADDITIVE, 8526ADDITIVE, FZ2110, FZ-2123, FZ2166, FZ-2191, SH-377 2M, L7001 , SH-377M (above, manufactured by Dow Corning Toray Co., Ltd.), KF-945, KF-6017 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), FormBan MS-575 (manufactured by Ultra Addives Inc.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF4460 (above, manufactured by Momentive Performance Materials), TEGO (registered trademark) Wet KL245, TEGO (registered trademark) Wet 240, TEGO (registered trademark) Wet 250, TEGO (registered trademark) Wet 260, TEGO (registered trademark) Wet 265, TEGO (registered trademark) Wet 270, TEGO (registered trademark) Wet 280 (above, manufactured by Evonik Industries), BYK (registered trademark)-302, BYK (registered trademark)- 307, BYK (registered trademark)-331, BYK (registered trademark)-333, BYK (registered trademark)-345, BYK (registered trademark)-347, BYK (registered trademark)-348, BYK (registered trademark)-349, BYK (registered trademark)-375, BYK (registered trademark)-377, BYK (registered trademark)-3455 (above, manufactured by BYK-Chemie Japan Co., Ltd.), etc.

The content of the polysiloxane-based surfactant is preferably from 0.01% by mass to 20% by mass, more preferably 0.5% by mass, relative to the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide Above 10% by mass or less. If the content of the polysiloxane-based surfactant is within this range, the wettability of the coated platy titanic acid particles with respect to organic solvents can be sufficiently ensured, and the composition comprising the coated platy titanic acid particles of the present invention can be used In the case of forming a coating film with other paints, it can achieve a good silky feeling and shadow feeling. The content of the polysiloxane-based surfactant may also be referred to as the added amount of the polysiloxane-based surfactant. The content of polysiloxane-based surfactants is not easy to directly measure because the molecular structure of the commercially available products used may not be clear. Therefore, in the manufacturing process of this case, the addition amount of the polysiloxane-based surfactant used as a raw material is set as the content of the polysiloxane-based surfactant.

The coated platy titanic acid particles and the coated platy titanic acid particle composition of the present invention can be used as design pigments. If the coating film is formed by using the coated platy titanic acid particles or the coated platy titanic acid particle composition as the pigment, a good design coating film with silky feeling and shadow feeling can be realized . Furthermore, the coating film has high adhesion and water resistance, so it can fully withstand strong friction and exposure to intense rainfall during outdoor use, even in harsher environments than usual.

The coated platy titanic acid particles and the coated platy titanic acid particle composition of the present invention can be mixed with various solvents such as water and organic solvents to form a dispersion. As a mixing method, for example, a general mixer, colloid mill, ball mill, bead mill, vibrator, paint conditioner, oscillator, disperser, etc. can be used.

For the aforementioned organic solvent, the carbon number and/or functional group of the hydrocarbon can be appropriately selected according to the application. Hydrocarbons having 1 or more carbon atoms can be used as the organic solvent. These hydrocarbons may contain multiple bonds, and may have branched or cyclic structures. Furthermore, organic functional groups such as hydroxyl groups, carboxyl groups, ether groups, ketone groups, ester groups, amido groups, nitrile groups, carbonate groups, and acrylate groups, and halogen elements may be included. Also, these hydrocarbons can be used as polymer compounds. For example, hydrocarbons (hexane, heptane, octane, decane, mobile paraffin, etc.), aromatic hydrocarbons (benzene, toluene, xylene, naphthalene, etc.), alcohols (ethanol, isopropanol, 2 -butanol, glycerin, ethylene glycol, propylene glycol, etc.), carboxylic acids (acetic acid, propionic acid, lauric acid, stearic acid, lactic acid, etc.), ethers (polyethylene glycol, polytetramethylene oxide )), etc.), ketones (acetone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, glycerin fatty acid esters, etc.), amides (di Methyl phenylene, acetamide benzene, etc.), nitriles (acetonitrile, acrylonitrile, etc.), carbonates (ethyl carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), halogens (dichloromethane, chloroform, tetrachloroethylene, etc.). In addition, examples of usable organic solvents include vegetable oils such as salad oil, soybean oil, and castor oil, fluorine-modified oils, and varnish thinners. These organic solvents may be used alone or in combination of two or more.

The content of the coated plate-shaped titanic acid particles in the dispersion can be appropriately set, preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass.

The dispersion of the present invention may also contain surface regulators such as dispersants, leveling agents, wettability improvers, defoamers, colorants, extenders, anti-mold Additives or fillers such as additives, hardening aids, tackifiers, anti-settling agents, etc. Examples of the dispersant include anionic, cationic, and nonionic various surfactants and silicone-based dispersants. For example, there are: carboxylate, carboxylate salt, sulfate ester salt, sulfonate, phosphate, phosphate ester salt alkylamine salt, alkylamine type ether type, alcohol ester type, ether ester type, ester type, Nitrogen-containing alkyl modified polysiloxane, polyoxyalkylene modified polysiloxane, etc. A surface conditioner is one that controls the surface tension of an organic solvent dispersion and prevents coating film defects such as cissing and pits, for example, acrylic-based surface conditioners, vinyl-based surface conditioners, silicone-based surface conditioners, etc. Surface conditioner, fluorine-based surface conditioner, etc. The addition amount of the surface conditioner can be adjusted appropriately, but it is preferably from 0.005% by mass to 5.0% by mass, more preferably from 0.01% by mass to 2.0% by mass, relative to the coated plate-shaped titanic acid particles.

The coating composition of the present invention comprises: the above-mentioned coated platy titanic acid particles or the coated platy titanic acid particle composition of the present invention, and a coating resin component. Resin components for paints refer to resins used for making paints. Examples include hydrolyzable silanes, their hydrolyzed products or partial condensates thereof, polymerizable silicon compounds such as organopolysiloxanes, inorganic resins such as metal alkoxides, alkyd resins, acrylic resins, poly Organic resins such as ester resins, epoxy resins, amino resins, fluorine resins, modified silicone resins, urethane resins, and vinyl resins. The resin components for these paints are not subject to any restrictions regarding the applicable solvent system and curing method. In the paint composition, the blending amount of the coated platy titanic acid particles or the coated platy titanic acid particle composition can be appropriately set, preferably at least 1% by mass and not more than 50% by mass, more preferably at least 5% by mass % to 40% by mass.

In the coating composition of the present invention, in addition to the coated platy titanic acid particle or the coated platy titanic acid particle composition and the coating resin component, the aforementioned organic solvent, organic pigment, inorganic pigment, dye, etc. Colorants, extenders, surfactants, plasticizers, hardening aids, desiccants, defoamers, tackifiers, emulsifiers, flow regulators, anti-skinning agents, anti-color separation agents, UV absorbers , antifungal agent and other additives or fillers, etc. In addition, these raw materials can be blended according to known recipes to prepare paint compositions and ink compositions. Furthermore, the curing agent, the curing auxiliary agent, and the curable resin component can be prepared as a two-component paint that is mixed and used immediately before painting.

The coating film formed by coating the coating composition of the present invention by conventional methods can impart a good silky feeling and shadow feeling to the coated object. As conventional coating methods, specifically, spin coating, spray coating, roll coating, dip coating, flow coating, knife coating, electrostatic coating, rod coating, and die coating can be applied without limitation. Cloth, brushing, droplet dripping, etc. A spray gun, a roller, a bristle, a bar coater, a doctor blade, etc. can be selected suitably as the implement used for coating a coating composition.

The plastic composition of the present invention comprises the above-mentioned coated platy titanic acid particles or the coated platy titanic acid particle composition of the present invention, and a plastic resin component. Plastic resin components refer to resins used to make plastics. The resin component is not particularly limited, and known resin components for plastics can be used. Furthermore, for the purpose of improving physical properties such as impact resistance, scratch resistance, chemical resistance, and fluidity, two or more types of resin components for plastics may be used.

As the plastic resin component used in the plastic composition, for example, polyolefin resin (polyethylene, polypropylene, etc.), polyvinyl chloride resin, acrylonitrile butadiene styrene resin, polystyrene resin, methyl General-purpose plastic resins such as acrylic resins and polyvinylidene chloride resins, engineering plastics such as polycarbonate resins, polyethylene terephthalate resins, polyamide resins, polyacetal resins, modified polyphenylene ethers, and fluororesins Resin, polyphenylene sulfide resin, polyresin, polyether sulfide resin, amorphous polyarylate resin, liquid crystal polymer, polyether ether ketone resin, polyamide imide resin, polyether imide resin and other super Engineering plastic (Super Engineering Plastic) resin.

In the plastic composition of the present invention, the blending ratio of the coated platy titanic acid particles or the coated platy titanic acid particle composition to the above-mentioned resin components is not particularly limited. For example, with respect to 100 parts by mass of the resin component for plastics, the coated platy titanic acid particle or its granular composition is preferably in the range of 1 part by mass to 80 parts by mass, more preferably 1 part by mass to 60 parts by mass the following range. Also, if it is a masterbatch, the coated platy titanic acid particle or its granular composition is preferably in the range of 10 parts by mass or more and 900 parts by mass or less, and more preferably 50 parts by mass relative to 100 parts by mass of the resin component for plastics. The range of not less than 500 parts by mass. In addition, additives such as reinforcing materials such as glass fibers, stabilizers, dispersants, lubricants, antioxidants, ultraviolet absorbers, and fillers can also be added according to the application.

The above-mentioned plastic composition is obtained by adding coated plate-shaped titanic acid particles or a composition of coated plate-shaped titanic acid particles to molten plastic resin components and mixing using a kneader. As a kneading machine, intensive mixers (intensive mixers) such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll forming machine, etc. are mentioned, for example.

A plastic composition obtained by mixing coated platy titanic acid particles obtained by kneading or a coated platy titanic acid particle composition can be molded by a known method. In particular, if it is molded by applying a load to align the coated plate-shaped titanic acid particles in the resin in a fixed direction, the design of the silky and shadowy coating film can be improved. Such a molding method includes blow molding, which may be further heated and stretched.

Hereinafter, the method for producing the coated platy titanic acid particle and the coated platy titanic acid particle composition of the present invention will be described. In the coated plate-shaped titanic acid particles of the present invention, aluminum oxides and/or hydroxides are present on the surface of the plate-shaped titanic acid particles, and then treated with silane coupling agents. As the plate-shaped titanic acid particles used as a raw material, for example, those produced as follows can be used.

(Manufacturing of plate-shaped titanic acid particles) First, an alkali metal titanate is produced. Alkali metal titanate is produced by using carbonates or hydroxides of alkali metals such as Li, Na, K, Rb, and Cs, and titanium oxide as raw materials. Among the above alkali metal compounds, carbonates or hydroxides of two different alkali metals are used. Hereinafter, the first alkali metal is referred to as M1, and the second alkali metal is referred to as M2. Carbonates or hydroxides of M1 and M2, and titanium oxide are preferably mixed at a molar ratio of M1/M2/Ti=3/1/5 to 3/1/11 at about 1050°C~1200°C Carry out firing. Other firing conditions, such as heating and cooling rate, firing time, firing environment, etc. are not limited and can be set appropriately. Thereafter, if necessary, the fired product is pulverized to obtain an alkali metal titanate.

The alkali metal titanate salt obtained by firing, a part of the Ti ⁴⁺ position in the main skeleton, introduces an alkali metal ion different from that between the layers, and the composition formula is M1 _x [M2 _x/3 Ti _2-x/3 ]O ₄ (x is 0.50~1.0). The crystal structure of the alkali metal titanate is preferably a layered structure of orthorhombic crystals, ie lepidotype. The amount of alkali metal ions introduced into the Ti ⁴⁺ position in the host framework (ie, x in the composition formula) can be controlled by the molar ratio of the starting materials.

Next, the alkali metal titanate is suspended in an aqueous solvent to prepare a suspension. By adding an acidic solution to the suspension, the Ti coordination in the alkali metal titanate salt and the interlayer metal ions perform ion exchange with the cations in the acidic solution to generate layered titanic acid. As the acidic solution, inorganic acids such as hydrochloric acid and sulfuric acid, or organic acids such as acetic acid and oxalic acid can be used.

Through the above operations, the layered titanic acid with the interlayer alkali metal ions and a part of the Ti ⁴⁺ position in the main frame substituted, has the composition formula H _4x/3 Ti _2-x/3 O ₄ ･nH ₂ O( In the formula, x is 0.50~1.0, and n is 0~2). As the crystal structure of layered titanic acid, a layered structure having orthorhombic crystals is preferable. In this case, it is not necessary to replace all the alkali metal ions with ions, and the metal ions may remain within the range in which the effects of the present invention can be obtained.

Next, a layered titanic acid slurry is prepared by mixing the layered titanic acid and an aqueous solvent mainly composed of water. A water-soluble basic organic compound is mixed into the slurry. "Water solubility" in the present invention refers to the property of dissolving 10 g or more in 100 g of water. Through the above steps, the hydrogen ions contained between the layers of the layered titanic acid are ion-exchanged with the basic organic compound, at least a part of the layer of the layered titanic acid is swelled and/or peeled off to obtain a platy titanic acid slurry.

The water-soluble basic organic compound is not particularly limited, and one or more arbitrary basic organic compounds can be appropriately selected and used. Specifically, it can be cited: (1) Hydroxide grade 4 ammonium compounds (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc.) (2) Amine compounds having an alkyl group having 5 or less carbon atoms (propylamine, diethylamine, etc.) (3) Alkanolamine compounds (ethanolamine, aminomethylpropanol, etc.) and the like. Among them, alkanolamine compounds are preferred, and aminomethyl propanol is more preferred.

The degree of exfoliation of layered titanic acid can be determined by appropriately changing the type of water-soluble basic organic compound used, its addition amount, the concentration of layered titanic acid slurry, and the time when mixing the basic compound and layered titanic acid slurry. The temperature and pH of the layered titanic acid slurry, the mixing speed and mixing time of the layered titanic acid slurry are controlled. Thereby, the obtained plate-shaped titanic acid particles can be controlled to a desired thickness.

The plate-shaped titanic acid slurry obtained in this way can be separated from solid and liquid by conventional methods, and then washed and dried if necessary. For example, platy titanic acid slurry is centrifuged to separate the precipitate (plate-shaped titanic acid particles) and the solvent, and the collected precipitate is dried to obtain platy titanic acid particles. In addition, the plate-shaped titanic acid particles can also be obtained by spray-drying the plate-shaped titanic acid slurry. Furthermore, plate-shaped titanic acid particles can also be obtained by combining several known methods for separating and washing solid components.

The obtained platy titanic acid particles may be pulverized if necessary. A known pulverizer can be used for pulverization. From the viewpoint of maintaining the characteristic shape of the plate-shaped titanic acid particles, those with weak crushing force are preferred. Examples of such pulverizers include hammer mills and pin mills.

(Treatment using aluminum oxide and/or hydroxide) Aluminum oxide and/or hydroxide are present on the surface of the plate-shaped titanic acid particles. The aluminum oxide and/or hydroxide existing on the surface of the coated plate-shaped titanic acid particles can effectively function as a foothold for silane coupling agents to exist on the surface of the plate-shaped titanic acid particles . Such treatment operations can be performed in various solvents, preferably in aqueous solvents. For example, prepare platy titanic acid aqueous slurry in which platy titanic acid particles are dispersed in an aqueous solvent containing water as the main component, add an aluminum source as a raw material to the slurry, and prepare Source of mixed slurry. After that, by adjusting the pH of the mixed slurry, aluminum hydroxide is precipitated from the aluminum source, so that the aluminum hydroxide can be present on the surface of the plate-shaped titanic acid particles.

As an aluminum source of a raw material, what precipitated the hydroxide of aluminum by a neutralization reaction can be used suitably. For example, sodium aluminate, aluminum sulfate, etc. are mentioned. The amount of the aluminum source to be added in terms of _Al2O3 is preferably from 1% by mass to 30% by _mass relative to the plate-like titanic acid particles, more preferably from 3% by mass to 25% by mass, and still more preferably at least 5% by mass 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less.

Also, from the viewpoint of the surface charge of platy titanic acid, the pH of the platy titanic acid aqueous slurry when neutralizing the aluminum source is preferably in the range of pH 5-12, and more preferably in the range of pH 6-9. As mentioned above, other than aluminum oxide and/or hydroxide, other than aluminum oxide and/or hydroxide, for example, carbon dioxide can also be considered as a foothold for silane coupling agents to exist on the surface of plate-shaped titanic acid particles to effectively function. silicon etc. However, the isoelectric point of platy titanic acid is slightly acidic like that of silicon dioxide. Therefore, when treating the surface of plate-shaped titanic acid particles with silicon dioxide, if the plate-shaped titanic acid aqueous slurry is made into an alkaline environment, the surface of either plate-shaped titanic acid or silicon dioxide will be negatively charged, so It is difficult to perform silica treatment on the surface of plate-shaped titanic acid particles due to electrostatic repulsion. Also, if the platy titanic acid aqueous slurry is made into an acidic environment, the platy titanic acid will aggregate, and the desired design feeling cannot be obtained. In contrast, the isoelectric point of aluminum is relatively alkaline, so when the surface of the plate-shaped titanic acid particles is treated with aluminum hydroxide, it can be smoothly adjusted by adjusting the plate-shaped titanic acid aqueous slurry to a neutral to alkaline environment. And efficiently treat the surface of plate-shaped titanic acid particles with aluminum hydroxide. Therefore, when treating platy titanic acid particles with a compound that functions as a foothold of silane coupling agents while suppressing the aggregation of platy titanic acid, aluminum oxide and/or hydroxide is used, and The pH of the plate-shaped titanic acid aqueous slurry is set to the above-mentioned range. Thereby, the surface of the plate-shaped titanic acid can be treated with aluminum hydroxide while suppressing aggregation of the plate-shaped titanic acid particles. When adjusting the pH of the plate-shaped titanic acid water-based slurry, various acids and alkalis can be used depending on the aluminum source used. For example, when the aluminum source is sodium aluminate, sulfuric acid, hydrochloric acid, etc. can be used, and when aluminum sulfate is used, sodium hydroxide, ammonia water, etc. can be used.

The order of adding the aluminum source and the acid or base to neutralize the aluminum source is not particularly limited. For example, an aqueous slurry of aluminum-derived platy titanic acid can be added in advance to form a mixed slurry containing platy titanic acid particles and aluminum source, and acid or alkali can be added therein to adjust the pH of the slurry. In addition, acid or alkali can be added to the plate-like aqueous titanic acid slurry in advance, and an aluminum source can be added therein. Furthermore, it is possible to simultaneously add the aluminum source and acid or alkali to the plate-like aqueous titanic acid slurry, while maintaining the pH of the aforementioned slurry at a specified value.

The temperature of the plate-shaped titanic acid water-based slurry when neutralizing the aluminum source is preferably maintained at 50°C to 95°C, more preferably 70°C to 90°C. By maintaining such a temperature range, the aluminum hydroxide can be more densely present on the surface of the plate-shaped titanic acid particles. As a result, silane coupling agents tend to exist on the surface of plate-shaped titanic acid particles in the back-end process. The temperature of the plate-shaped titanic acid aqueous slurry is preferably raised to the above-mentioned temperature before the neutralization reaction of the starting aluminum source. In addition, after the neutralization reaction of the aluminum source is completed, the above-mentioned temperature may be maintained, and the plate-shaped titanic acid coated with aluminum hydroxide may be matured for several minutes to several hours.

The slurry of plate-shaped titanic acid particles coated with aluminum hydroxide subjected to the above treatment may be subjected to solid-liquid separation by a known method if necessary, followed by drying and firing. For example, spray drying can be used as a method of simultaneously performing solid-liquid separation and drying. At this time, the hydroxide of aluminum (hydrous alumina) changes to the oxide of aluminum (alumina) according to the temperature of drying and firing. For example, when the drying temperature is set at about 200°C, a part of the aluminum hydroxide (hydrous alumina) is changed to oxide (alumina), thereby becoming a mixed state of aluminum oxide and hydroxide . Also, when firing at a higher temperature (for example, 300° C. or higher), most of the hydroxides of aluminum (hydrous alumina) are changed to oxides (alumina). In this way, aluminum oxide and/or hydroxide can be present on the surface of the plate-shaped titanic acid particles.

(Silane coupling agent treatment) The plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide are treated with the above-mentioned silane coupling agents. Such a treatment operation can be performed in various solvents, preferably an aqueous solvent. For example, plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide and silane coupling agents may be mixed in the presence of various solvents. In addition, silane coupling agents may be added to the slurry containing plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide, and mixed for a predetermined period of time. Furthermore, plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide are added to a solution containing silane coupling agents, and mixed for a predetermined time to prepare a coated plate-shaped titanic acid slurry. As the solvent, water or a mixed solvent of water and an organic solvent can be used, but when using a silane coupling agent that cannot be easily dissolved in water, a mixed solvent of water, ethanol or the like and an organic solvent can be used. In addition, when treating plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide with a silane coupling agent, the product obtained by partially hydrolyzing the silane coupling agent may be mixed in advance, or mixed with Condensate obtained by condensation of silane coupling agent and its hydrolyzed products. Furthermore, by adding acid and alkali to the coated platy titanic acid slurry, adjusting the pH appropriately and adjusting the temperature appropriately, the silane coupling agents in the aforementioned slurry can be hydrolyzed, and these can also be condensed.

The amount of silane coupling agents added is preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to 10% by mass, relative to the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide or less, and more preferably at least 1% by mass and not more than 8% by mass.

When treating plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide with a silane coupling agent, the temperature of the coated plate-shaped titanic acid slurry can be appropriately set according to the type of silane coupling agent. Depending on the type of silane coupling agent, the above-mentioned coated plate-shaped titanic acid slurry can make the silane coupling agent fully exist on the surface of the plate-shaped titanic acid particles even at a temperature of 10°C to 30°C. The mixing time of the coated platy titanic acid slurry can be appropriately set in the range of several minutes to several hours. When treating plate-shaped titanic acid particles with silane coupling agents, it is preferable to treat with silane coupling agents after making aluminum oxide and/or hydroxide exist on the surface of the plate-shaped titanic acid particles. In addition, the surface of the plate-shaped titanic acid particles can be treated by simultaneously mixing the aluminum source and the silane coupling agent into the plate-shaped titanic acid aqueous slurry.

The coated plate-shaped titanic acid slurry treated with aluminum oxide and/or hydroxide and silane coupling agent can be separated from solid and liquid by conventional methods, washed and dried if necessary. For example, the coated platy titanic acid slurry is centrifuged, the precipitate (coated platy titanic acid particles) and the solvent are separated, and the recovered precipitate is dried. In addition, the coated plate-shaped titanic acid slurry may also be spray-dried. Furthermore, conventional separation methods and washing methods for solid components can be combined.

(Manufacturing method of coated plate-shaped titanic acid particle composition) The coated platy titanic acid particle composition of the present invention can be obtained by mixing platy titanic acid particles having aluminum oxide and/or hydroxide on the particle surface, a silane coupling agent, and polysiloxane in a solvent. It is produced by drying after the surfactant is added. Plate-shaped titanic acid particles having aluminum oxide and/or hydroxide on the surface of the particles and a silane coupling agent can be mixed separately, and can also be used as coated plate-shaped titanic acid particles. For example, the coated plate-shaped titanic acid particles and polysiloxane-based surfactant can be mixed in the presence of various solvents, and solid-liquid separation, washing, and drying can be carried out by conventional methods if necessary. As a method of solid-liquid separation, washing, and drying, for example, centrifuge the coated platy titanic acid particle composition slurry containing coated platy titanic acid particles and polysiloxane-based surfactants, and separate After the precipitate (coated platy titanic acid particle composition) is mixed with a solvent, the recovered precipitate is dried. Also, it is preferable to spray dry the aforementioned slurry. Furthermore, various known separation methods and cleaning methods for solid components can be combined. The coated platy titanic acid particle composition obtained in this way exists only in the state of mixing the coated platy titanic acid particles and the polysiloxane-based surfactant, or at least a part of the polysiloxane-based surfactant The state of physical adsorption or chemical adsorption on the surface of the coated plate-shaped titanic acid particles.

The order of mixing the plate-shaped titanic acid particles having aluminum oxide and/or hydroxide on the particle surface, the silane coupling agent, and the polysiloxane-based surfactant in the solution is not particularly limited. For example, coated plate-shaped titanic acid particles and a polysiloxane-based surfactant can be added to the solution and mixed. In addition, the coated platy titanic acid particles may be added to a solution containing a polysiloxane-based surfactant and mixed, or the polysiloxane-based surfactant may be added to a coated platy titanic acid slurry and mixed. Furthermore, plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide, silane coupling agents, and silicon-oxygen surfactants can be added to the solvent and mixed in any order to form a polysiloxane interface. The active agent treats the coated plate-shaped titanic acid particles.

As the polysiloxane-based surfactant, those mentioned above can be used. The amount of polysiloxane-based surfactant can be adjusted appropriately. For example, it is preferable to set the surface tension of the slurry to 50 mN/m or less. Specifically, the amount is preferably from 0.01% by mass to 20% by mass, more preferably from 0.5% by mass to 10% by mass, based on the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide. When the amount of the polysiloxane-based surfactant added is within this range, aggregation of the coated plate-shaped titanic acid particles can be sufficiently suppressed. As a result, the shadow feeling of the coating film containing the coated platy titanic acid particle composition can be improved.

In the case of spray-drying the coated plate-shaped titanic acid slurry, a polysiloxane-based surfactant can be added to the slurry in advance to prepare a coated plate-shaped titanic acid particle composition slurry. In this state, when spray drying is performed, the polysiloxane-based surfactant exists at the solid-liquid interface between the coated plate-shaped titanic acid particles and the solvent, so that aggregation of the coated plate-shaped titanic acid particles can be further suppressed. As a result, the shadow feeling of the coating film formed by the coating containing the coated plate-shaped titanic acid particle composition can be improved, so the spray-dried product obtained by pre-mixing the coated plate-shaped titanic acid slurry and the polysiloxane-based surfactant Slurry is the preferred method. [Example]

The present invention will be described in more detail by the following examples and comparative examples, but the present invention is not limited by the examples.

(Manufacture of plate titanic acid) Plate-shaped titanic acid particles used in Examples and Comparative Examples were produced in the following manner.

(Manufacturing example 1) After fully mixing titanium oxide (Ishihara Sangyo titanium oxide, A-100), potassium carbonate and lithium carbonate (both Kanto Chemical Co., Ltd.) in an agate mortar with a mass ratio of 100:40:9.2, the Calcined at 1150°C for 5 hours in the atmosphere to synthesize lithium potassium titanate (K _0.8 Li _0.27 Ti _1.73 O ₄ ) with orthorhombic lepidocite structure. The obtained lithium potassium titanate was pulverized in an agate mortar to obtain lithium potassium titanate powder.

The obtained lithium potassium titanate powder was mixed with 1.1N sulfuric acid 4 times its mass to prepare a suspension. The suspension was stirred for 30 minutes and ion-exchanged to prepare layered titanic acid slurry. The obtained layered titanic acid slurry was filtered and washed to obtain a layered titanic acid cake.

The obtained layered titanic acid cake was dispersed in pure water again, and the layered titanic acid slurry was prepared so as to be 8.5% by mass in terms of TiO ₂ . After mixing the layered titanic acid slurry and ammonia water, and adjusting the pH to 8.7, 2-amino-2-methyl-1 -Propanol aqueous solution (90%) 21.4g/(TiO ₂ 100g), stirred at room temperature for 1 hour, thereby obtaining plate-shaped titanic acid slurry.

After diluting the obtained plate-shaped titanic acid slurry by 2 times with pure water, flow it through a slurry screening machine (SS95×250 manufactured by Aco Japan Co., Ltd.) equipped with a mesh screen with a pore size of 10 μm at a volume flow rate of 18 L/hour. And recover the dispersion of plate-shaped titanic acid particles on the net.

The dispersion of the recovered plate-shaped titanic acid particles was diluted 3 times, and centrifuged using a centrifuge (manufactured by Mitsubishi Chemical Corporation, SJ10F). Pure water was added to the obtained precipitate (plate-shaped titanic acid particles) and diluted until the solid content became 10% by mass to prepare a dilution solution of plate-shaped titanic acid particles. Using a surface tensiometer (KRUSS K11 automatic surface tensiometer), the surface tension of the diluted solution was measured to be 62 mN/m. Using a spray dryer (L-8i manufactured by Okawara Chemical Machinery Co., Ltd.), spray-dry the aforementioned diluent under the conditions of disc spraying, inlet temperature 190°C, and outlet temperature 85°C to obtain plate-shaped titanic acid particle powder.

When measuring the particle size of the plate-shaped titanic acid powder, the median diameter (D50) in the volume particle size distribution is 20.4 μm, the cumulative 10% particle size (D10) is 10.1 μm, and the cumulative 90% particle size (D90) is 39.1 μm. The measurement conditions are as follows. Measuring device: Laser diffraction/scattering type particle size distribution measuring device (manufactured by Horiba Manufacturing Co., Ltd., LA-950) Refractive index: 2.50

(Example 1) (1) The powder of the plate-shaped titanic acid particles of the above-mentioned Production Example 1 was dispersed in pure water so that the solid content became 10 mass % by treatment with aluminum oxide and/or hydroxide, Make plate-shaped titanic acid aqueous slurry. The liquid temperature of the aqueous slurry was raised to 90°C, and 4.6N sulfuric acid was added to adjust the pH of the dispersion to 7.0. To the aforementioned aqueous slurry, 10% by mass of sodium aluminate aqueous solution and 1.1N sulfuric acid were added to the plate-shaped titanic acid particles in terms of Al ₂ O ₃ at the same time to make the plate-shaped titanic acid particles and the aluminum source. The mixed slurry. The pH of the mixed slurry was kept at 7.0-7.5, and the neutralization reaction was carried out at a liquid temperature of 90° C. for 4 hours. Afterwards, aging was carried out for 1 hour under the same conditions as the neutralization reaction, and the surface of the plate-shaped titanic acid particles was treated with aluminum hydroxide (hydrous aluminum oxide). Then, dilute the mixed slurry by 2 times with pure water, flow through a slurry screening machine (SS95×250 manufactured by Aco Japan Co., Ltd.) equipped with a mesh screen with a pore size of 10 μm at a volume flow rate of 18 L/hour, and recycle the slurry on the net. Dispersion A1 of plate-shaped titanic acid particles coated with aluminum hydroxide.

(2) Treatment of silane coupling agents The dispersion liquid A1 of the recovered platy titanic acid particles was diluted with pure water so that the solid content became 10% by mass. Dispersion A1 of plate-shaped titanic acid particles was added with 5% by mass of hexyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-3063) with respect to plate-shaped titanic acid particles coated with aluminum hydroxide , to make a coated plate-like titanic acid slurry. The slurry was stirred at room temperature for 1 hour to obtain a dispersion B1 of coated platy titanic acid particles.

(3) Addition of polysiloxane surfactant The polysiloxane-based surfactant (BYK-Chemie Japan Co., Ltd. made, BYK (registered trademark)-347) was diluted 200 times with pure water. While stirring the solution of the polysiloxane-based surfactant, it was added to the dispersion B1 of the coated platy titanic acid particles over 30 minutes. Afterwards, the coated platy titanic acid particle composition slurry comprising the dispersion B1 of the coated platy titanic acid particles and the polysiloxane-based surfactant was stirred for 30 minutes. Thereafter, the slurry was centrifuged at 10,000 rpm for 5 minutes, and the precipitate (coated platy titanic acid particle composition) was recovered. Next, pure water was added to the recovered precipitate to prepare a coated platy titanic acid particle composition slurry having a solid content of 5% by mass. Using a surface tensiometer (K11 automatic surface tensiometer from KRUSS Company), the surface tension of the coated platy titanic acid particle composition slurry was measured to be 38 mN/m. Next, use a spray dryer (L-8i manufactured by Okawara Chemical Machinery Co., Ltd.) to spray-dry the coated plate-shaped titanic acid particle composition slurry under the conditions of a disc spray type, an inlet temperature of 190° C., and an outlet temperature of 85° C. The powder of the coated platy titanic acid particle composition of Example 1 was obtained.

(Example 2) Except for omitting the step of adding (3) polysiloxane-based surfactant in Example 1, the powder of coated plate-shaped titanic acid particles of Example 2 was obtained in the same manner as in Example 1.

(Example 3) In addition to the treatment steps of (2) silane coupling agents in Example 1, the addition amount of hexyltrimethoxysilane is set to 0.5 relative to the plate-shaped titanic acid particles coated with aluminum hydroxide (hydrous aluminum oxide). Except for the mass %, in the same manner as in Example 1, the powder of the coated platy titanic acid particle composition of Example 3 was obtained.

(Example 4) In addition to the (3) addition step of the polysiloxane-based surfactant in Example 1, the amount of the polyether-modified siloxane added is set relative to the aluminum hydroxide (hydrous aluminum oxide)-coated plate The powder of the coated plate-shaped titanic acid particle composition of Example 4 was obtained in the same manner as in Example 1 except that the titanic acid particles were 0.5% by mass.

(Example 5) In addition to (2) silane coupling agent treatment steps in Example 1, use 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) to replace hexyltrimethoxy Except for silane, in the same manner as in Example 1, the powder of the coated platy titanic acid particle composition of Example 5 was obtained.

(Example 6) (1) The powder of the plate-shaped titanic acid particles of the above-mentioned Production Example 1 was dispersed in pure water so that the solid content became 10 mass % by treatment with aluminum oxide and/or hydroxide, Make plate-shaped titanic acid aqueous slurry. The liquid temperature of the aqueous slurry was raised to 90°C, and 17% ammonia water was added to adjust the pH of the dispersion to 8.5. To the aforementioned aqueous slurry, 6% by mass of aluminum sulfate aqueous solution and 17% ammonia water were simultaneously added to the plate-like titanic acid particles in terms of Al ₂ O ₃ to form a mixture containing the plate-like titanic acid particles and an aluminum source. slurry. The pH of the mixed slurry was kept at 8.5-9.0, and the neutralization reaction was carried out at a liquid temperature of 90° C. for 4 hours. Afterwards, aging was carried out for 1 hour under the same conditions as the neutralization reaction, and the surface of the plate-shaped titanic acid particles was treated with aluminum hydroxide (hydrous aluminum oxide). Dilute the mixed slurry 2 times with pure water, flow through a slurry screening machine (SS95×250 manufactured by Aco Japan Co., Ltd.) equipped with a mesh screen with a pore size of 10 μm at a volume flow rate of 18 L/hour, and recycle the on-line Dispersion A2 of plate-shaped titanic acid particles coated with aluminum hydroxide (hydrous alumina).

(2) Treatment of silane coupling agents The dispersion liquid A2 of the collected plate-shaped titanic acid particles was diluted with pure water so that the solid content became 7.5% by mass, and the liquid temperature was raised to 70°C. Add 5% by mass of long-chain vinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1083) to the plate-shaped titanic acid with respect to the plate-shaped titanic acid particles coated with aluminum hydroxide (hydrous alumina) Particle dispersion A2 was made into coated plate-shaped titanic acid slurry. The slurry was stirred at 70° C. for 3 hours to obtain a dispersion B2 of coated platy titanic acid particles. The dispersion B2 of the coated platy titanic acid particles was centrifuged at 10,000 rpm for 5 minutes, and the precipitate (coated platy titanic acid particles) was recovered. Next, pure water was added to the recovered precipitate to prepare a coated platy titanic acid slurry having a solid content of 5% by mass. Using a surface tensiometer (KRUSS K11 automatic surface tensiometer), the surface tension of the aforementioned slurry was measured to be 67-68 mN/m. Next, use a spray dryer (L-8i manufactured by Okawara Chemical Machinery Co., Ltd.) to spray-dry the coated plate-shaped titanic acid slurry under the conditions of nozzle spray type, inlet temperature 190° C., and outlet temperature 85° C. to obtain Example 6. Powder of coated plate-shaped titanic acid particles.

(Example 7) Except that the silane coupling agent in the treatment step of (2) silane coupling agent of Example 6 is changed to a long-chain epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-4803), the same as in Example 6 In this way, the powder of coated plate-shaped titanic acid particles of Example 7 was obtained.

(Embodiment 8) In addition to changing the silane coupling agent in the treatment step of (2) silane coupling agent in Example 6 to N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. The powder of the covered plate-shaped titanic acid particle of Example 8 was obtained in the same manner as in Example 6, except that the company manufacture, KBM-603).

(Example 9) In addition to changing the silane coupling agent in the treatment step of (2) silane coupling agents in Example 6 to 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903), the In the same manner as in Example 6, the powder of coated plate-shaped titanic acid particles in Example 8 was obtained.

(Example 10) In the same manner as in Example 6, except that the silane coupling agent in the treatment step of (2) silane coupling agents in Example 6 was changed to a long-chain aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-6803) , The powder of the coated plate-shaped titanic acid particles of Example 10 was obtained.

(comparative example 1) The powder of plate-shaped titanic acid particles in Production Example 1 was referred to as Comparative Example 1.

(comparative example 2) Except for omitting (1) treatment with aluminum oxide and/or hydroxide in Example 1, in the same manner as in Example 1, the plate-shaped titanic acid particle composition coated with a silane coupling agent in Comparative Example 2 was obtained. of powder.

(comparative example 3) In the same manner as in Example 1, the aluminum hydroxide of Comparative Example 3 was obtained except that the treatment steps of (2) silane coupling agents and (3) the addition of polysiloxane-based surfactants in Example 1 were omitted. Powder of plate-shaped titanic acid particles coated with hydrated alumina.

The treatment conditions of Examples 1-10, Comparative Examples 1-3, and the surface tension of the slurry before spray drying are shown in Table 1. In Examples 1, 3-5, polysiloxane-based surfactants were mixed, so the surface tension of the slurry before spray drying was 50 mN/m or less.

(Evaluation of the production of water-based coating films) Put the coated plate-shaped titanic acid particles of Examples 1-10 or the powder sample of the coated plate-shaped titanic acid particle composition, and the plate-shaped titanic acid particles of Comparative Examples 1-3 into a 20ml screw bottle 0.5 g of the powder sample, 5.9 g of acrylic silicone resin composition containing the components shown in Table 2, and 1.6 g of pure water were added. This was mixed with a paint shaker for 10 minutes to prepare a paint. The prepared coating was coated on a PET film (manufactured by Toray Co., Ltd., lumirror (registered trademark) T60) using an 8 mil doctor blade, and then forced to dry at 60° C. for 30 minutes to prepare a film comprising Examples 1 to 10 and The coating film for evaluation formed by the coating materials of the samples of Comparative Examples 1-3.

(Preparation of organic solvent-based coating film for evaluation) Put the coated plate-shaped titanic acid particles of Examples 1-10 or the powder sample of the coated plate-shaped titanic acid particle composition, and the plate-shaped titanic acid particles of Comparative Examples 1-3 into a 20ml screw bottle 0.5 g of the powder sample was further added with 6.9 g of acrylic resin paint (manufactured by Nippon Paint, nax (registered trademark) ADMILA (registered trademark) ALPHA 280 correction clear varnish:901 binder mass mixing ratio of 3.6:1). This was mixed with a paint shaker for 10 minutes to prepare a paint. The produced paint was prepared into an organic solvent-based coating film for evaluation in the same manner as (preparation of a water-based coating film for evaluation).

(Evaluation of shadow feeling) Touch the white background of black and white drawing paper to the back of the prepared coating film, and use a multi-angle colorimeter (BYK (registered trademark)-mac i of BYK company) to irradiate from the direction of -45° Light source, measure the lightness (L ^* ) value of the highlight (light receiving angle 15°) and shade (light receiving angle 110°). Each coating film was measured three times to obtain the average value L ^* . Calculate ΔL ^* by subtracting L ^* ₁₁₀ ° of shade from L ^* _15° of highlight to evaluate the sense of shadow. Table 3 shows the evaluation results.

In Table 3, the surface of the plate-shaped titanic acid particles in each example was treated with aluminum hydroxide (hydrous alumina) and a silane coupling agent, or a polysiloxane-based surfactant was further included. In the case of using such coated platy titanic acid particles and coated platy titanic acid particle composition to produce water-based and organic solvent-based coating films, as shown in Table 3, the value of ΔL ^* in any coating system All are above 50. Moreover, it was confirmed in the sensory test by visual observation that sufficient shading was exhibited. If the effect of polysiloxane-based surfactants is compared with Example 1 and Example 2, the organic solvent-based coating film of Example 1 has a larger value of ΔL ^* than the organic solvent-based coating film of Example 2, which can be Confirmed to have a higher sense of shadow. This can be understood because the presence of the polysiloxane-based surfactant in the coated platy titanic acid slurry lowers the surface tension of the slurry and inhibits aggregation of the coated platy titanic acid particles during spray drying.

In this regard, including the surface without coating treatment (comparative example 1), without aluminum hydroxide (hydrous aluminum oxide) treatment (comparative example 2), without silane coupling agent treatment and without adding polysiloxane interface activity In the coating film formed by the plate-shaped titanic acid particle coating of the solvent (Comparative Example 3), the value of ΔL ^* of the water-based coating film is the same as that of the example, while the value of ΔL ^* of the organic solvent-based coating film is not higher than that of the example. Full 50. Moreover, the shading feeling in the sensory test by visual inspection was not enough. It can be understood that the plate-shaped titanic acid particles of Comparative Examples 1-3 were not sufficiently modified on the surface, and could not maintain a dispersed state in organic solvent-based coatings.

(Preparation of water-based coatings for evaluation of adhesion and water resistance) In a 225ml mayonnaise bottle, put the coated plate-shaped titanic acid particles of Examples 1-10 or the powder sample of the coated plate-shaped titanic acid particle composition, and the plate-shaped titanic acid particles of Comparative Examples 1-3 2g of the powder sample, and 22.2g of the acrylic silicone resin composition containing the ingredients shown in Table 2 were added. After mixing it with a paint mixer for 5 minutes, adjust the viscosity of the paint with pure water to make a water-based paint. Regarding the viscosity of the paint, add the paint made with the above formula to a viscosity cup (NK-2 Cup manufactured by Anest Iwata) with a hole in the bottom, and the time from when the paint starts to flow out from the hole to when all the paint flows out of the cup is 20 seconds way to adjust.

(Preparation of organic solvent-based coatings for evaluation of adhesion and water resistance) In a 225ml mayonnaise bottle, put the coated plate-shaped titanic acid particles of Examples 1-10 or the powder sample of the coated plate-shaped titanic acid particle composition, and the plate-shaped titanic acid particles of Comparative Examples 1-3 3 g of the powder sample, and 33.4 g of acrylic resin paint (manufactured by Nippon Paint Co., Ltd., nax (registered trademark) ADMILA (registered trademark) ALPHA 280 correction clear varnish: 901 binder, the mass mixing ratio is 3.6:1). After mixing it with a paint shaker for 5 minutes, the viscosity of the paint was adjusted with a thinner (manufactured by Nippon Paint, nax (registered trademark) ADMILA (registered trademark) ALPHA 500 standard thinner). The viscosity of the paint was adjusted so that the time from when the paint started to flow out from the hole to when all the paint flowed out of the cup became 10 seconds in the same manner as above. A curing agent (manufactured by Nippon Paint, nax (registered trademark) super curing agent) was injected therein to prepare an organic solvent-based paint.

(Preparation of coating film for evaluation of adhesion and water resistance) Grind the surface of the 35mm×150mm×0.8mm steel plate with sandpaper (#400). Using an spray gun made by Anest Iwata (KIWAMI (registered trademark)-1-14KP6), the film thickness is 50 μm under the conditions of hand pressure 0.15 MPa, discharge opening 2.0 rotation, air volume opening, and pattern width opening. Apply acrylic urethane resin paint (manufactured by Nippon Paint, nax (registered trademark) URETHANE PRASUF PRO V1 WHITE, nax (registered trademark) #20 super hardener standard type, nax (registered trademark) MULTI #20 The standard urethane diluent NEO (the second petroleum type) is 10:1.5:3 in mass ratio) on the steel plate. Leave it for more than 10 minutes, then force dry at 60°C for 40 minutes. After that, use sandpaper (#400) to grind the coating film of acrylic urethane resin. Next, using a spray gun (W-101-138BGC) made by Anest Iwata, under the conditions of hand pressure 0.15 MPa, discharge volume opening 1.5 rotation, air volume opening, and pattern width opening, the film thickness becomes 30 μm. , Coating the paint used for evaluation on the coating film of acrylic urethane resin after grinding. Leave it for more than 30 minutes, then force dry at 60°C for 30 minutes. Use the spray gun made by Anest Iwata (KIWAMI (registered trademark)-1-14KP6), with hand pressure 0.15MPa, discharge volume opening 2.0 rotation, air volume opening fully open, and pattern width opening fully open, the film thickness is 40μm The method of coating clear paint (manufactured by Kansai Paint Co., Ltd., RETAN (registered trademark) PG80III026 clear paint, RETAN (registered trademark) PG80III026 clear paint hardener, RETAN (registered trademark) PG thinner standard type is 10:1 in mass ratio : 4) On the coating film formed by the coating used for the evaluation. It was left to stand for 30 minutes or more, and it was forced-dried at 60 degreeC for 12 hours, and this was used as the coating film for adhesiveness and water resistance evaluation.

(Evaluation of adhesion and water resistance) The adhesion and water resistance of the coating film were evaluated by the checkerboard test. A dicing knife was vertically brought into contact with the above-mentioned coating film for evaluation, and 11 parallel lines were drawn at intervals of 2 mm so as to reach the base. Then draw 11 parallel lines intersecting these lines at intervals of 2mm, and draw 100 squares of 2mm square. Thereafter, an adhesive tape (Nikiba, Nichiba CELLOTAPE (registered trademark) L Pack 24, tape width 24 mm) was adhered so as not to contain air bubbles, and was uniformly pressed against the cut surface of the coating film for evaluation. Thereafter, one end of the adhesive tape was pinched, and the adhesive tape was pulled from the evaluation coating film at an angle of 45° from the vertical surface of the evaluation coating film. The number of cells where the peeling of the coating film for evaluation was 50% or less in the interior divided into 2 mm squares was investigated, and the initial adhesion was evaluated. The larger the value of the initial adhesion, the better the adhesion. Next, pure water was added to a constant temperature water tank, and the temperature of the liquid was kept at 40° C., and more than 1/2 of the steel plate on which the coating film for evaluation was formed was immersed in warm water. After dipping for 168 hours, take it out from the constant temperature water tank, wipe off the water droplets and pollutants on the surface of the coating film for evaluation with a cloth, rag, etc., and let it stand for 12 hours. After that, a checkerboard test was performed in the same manner as above. This result was regarded as water resistance adhesion, and a larger value means higher water resistance. The test results of the above adhesion and water resistance are shown in Table 3.

As shown in Table 3, it is used in the coating film of coated plate-shaped titanic acid particles whose surface is treated with aluminum hydroxide (hydrous aluminum oxide) and silane coupling agent, aqueous system and organic solvent system The result of any checkerboard test is above 90/100, showing high initial adhesion and water resistance. It can be understood that the water resistance of the coating film is improved by imparting hydrophobicity to the surface of the plate-shaped titanic acid particles by the silane coupling agent, and by causing a cross-linking reaction with the coating resin.

On the other hand, the coating formed by the coating containing plate-shaped titanic acid particles with no surface treatment (Comparative Example 1), no silane coupling agent treatment, and no addition of polysiloxane-based surfactants (Comparative Example 3) Among the films, the adhesion of the water-based coating film after immersion in warm water was low, so it was judged that the water resistance of the coating film was not sufficient. This can be understood because the surface of the plate-like titanic acid particles is hydrophilic, so when the coating film is immersed in warm water, water is introduced into the coating film, thereby reducing the adhesion between the substrate and the coating film. In addition, in the water-based coating film of Comparative Example 2 that was not treated with aluminum hydroxide (hydrous aluminum oxide), the silane coupling agent and the polysiloxane-based surfactant were treated, so although the initial adhesion and water-resistant adhesion High performance, but the shading of the coating film using organic solvent-based coatings as mentioned above is not sufficient.

As mentioned above, it can be understood that if the surface of the plate-shaped titanic acid particles is treated with aluminum hydroxide (hydrous aluminum oxide) and a silane coupling agent, it can be applied to any system of water-based coatings and organic solvent-based coatings. The shadow sense and water resistance tightness.

[產業上之可利用性]

[Industrial availability]

The coated plate-shaped titanic acid particles of the present invention can be blended into any paint of water-based paint or organic solvent-based paint, and can realize a design coating film with a silky feeling and a high shadow feeling with the plate-shaped titanic acid particles. In addition, coated platy titanic acid particles are blended, and the coating film of the coated platy titanic acid particle composition using the same has excellent adhesion to the substrate and high water resistance. Coatings, etc., are useful for materials used in harsh outdoor environments.

Claims (11)

A coated plate-shaped titanic acid particle, which is made of aluminum oxide and/or hydroxide, and at least one selected from the group consisting of silane coupling agents, their hydrolyzed products, and their condensates present in the plate-shaped titanic acid the surface of the particles. The coated plate-shaped titanic acid particle according to claim 1, wherein the aforementioned silane coupling agent is a compound having an organic functional group X having 8 or less carbon atoms. The coated plate-shaped titanic acid particles according to claim 1 or 2, wherein the content of the aforementioned silane coupling agent is 0.5% by mass or more relative to the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide 30 Mass% or less. A coated plate-shaped titanic acid particle composition, comprising: the covered plate-shaped titanic acid particle according to any one of claims 1-3, and a polysiloxane-based surfactant. The coated plate-shaped titanic acid particle composition according to claim 4, wherein the content of the aforementioned polysiloxane-based surfactant is 0.01 relative to the plate-shaped titanic acid particles coated with aluminum oxide and/or hydroxide Mass % or more and 20 mass % or less. A design pigment, comprising: the coated plate-shaped titanic acid particle according to any one of claims 1-3, or the coated plate-shaped titanic acid particle composition according to claim 4 or 5. A dispersion comprising: the coated platy titanic acid particles according to any one of claims 1 to 3 or the coated platy titanic acid particle composition according to claim 4 or 5, and a solvent. A coating composition, comprising: the coated platy titanic acid particles according to any one of claims 1 to 3 or the coated platy titanic acid particle composition according to claim 4 or 5, and a resin component. A plastic composition, comprising: the coated platy titanic acid particles according to any one of claims 1 to 3 or the coated platy titanic acid particle composition according to claim 4 or 5, and a resin component. A method for producing coated plate-shaped titanic acid particles, which includes: mixing plate-shaped titanic acid particles with aluminum oxide and/or hydroxide on the surface of the particles and a silane coupling agent in a solvent. A method for producing coated plate-shaped titanic acid particles, which comprises: mixing plate-shaped titanic acid particles having aluminum oxide and/or hydroxide on the surface of the particles, a silane coupling agent, and polysiloxane-based particles in a solvent After the surfactant, the drying step is carried out.