JP2017101158A - Scaly composite particle, resin composition and coating article containing the same and manufacturing method of scaly composite particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black scaly composite particle with brightness.SOLUTION: A scaly composite particle is a scaly composite particle having fine particles consisting of metal or a second metal oxide adhered to one or more kind of scaly particles selected from first metal oxide, a resin, a mica and a glass, wherein the fine particles are adhered to the scaly particles with spot-like or island-like, adhesion rate to the scaly particles is 10 area% to 50 area% and average particle diameter is 1 nm to 80 nm, thickness of the scaly composite particle is 0.05 μm to 1 μm as average value and standard deviation s is 0<s≤0.2 and variation coefficient CV obtained by dividing the standard deviation s by the average value m is 0%<CV≤70%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to scaly composite particles, a resin composition and a coated product containing the same, and a method for producing scaly composite particles.

  Conventionally, metallic coatings containing colored pigments such as aluminum pigments and organic pigments and inorganic pigments used in combination with these are known, and these are used as chromatic metallic coatings or low-saturation metallic coatings such as automobile bodies. It is applied to a wide range of external design. Among other things, it is known to adjust the brightness of chromatic colors, design low-saturation colors, and express the texture with monotone colors using carbon black and iron oxide as black pigments. . Black pigments are widely applicable to automobiles, motorcycles, cosmetics, inks, etc., so there is a need for a new black-based color that has a color tone mixed with other colors instead of a single black like carbon black. Yes.

  For example, Japanese Patent Application Laid-Open No. 2010-275180 (Patent Document 1) discloses a technique related to a colored structure having glitter using metal plasmons attached to a flaky powder and utilizing the plasmon phenomenon of the metal fine particles. .

  Also, in JP 2009-242955 A (Patent Document 2), coating film formation of a coating composition containing a bright material in which nickel or silver fine particles are adhered to a substrate of alumina, mica, silica or glass flakes A method is disclosed.

  In addition, in Japanese Patent Laid-Open No. 1-108278 (Patent Document 3), a metal or alloy formed in the form of dots is island-like with respect to a base material on which an inorganic oxide is entirely attached on ceramic scaly particles. A coating film forming method using a pigment adhering as a part is disclosed.

JP 2010-275180 A JP 2009-242955 A Japanese Patent Laid-Open No. 1-108278

  The colored structure disclosed in Patent Document 1 has 1-50 nm metal fine particles attached to the surface of the flaky powder, and 20-99% of the area of the powder surface is exposed. There is a possibility that certain black pigments can be produced. However, since it is necessary to attach 30 to 100% by mass of silver to the flaky powder, there is a problem that costs are increased.

  The glitter material disclosed in Patent Document 2 has nickel or silver fine particles of 2 to 80 nm attached to inorganic flakes such as alumina in the range of 0.5 to 10% by mass. Further, in order to provide glitter, an inorganic oxide layer, which is a refractive layer (reflective layer) utilizing light interference, is adhered between the inorganic flake layer and the fine particles. However, since the particle diameter and thickness of the inorganic flakes, the particle diameter of the fine particles, and the thickness of the inorganic oxide layer greatly affect the color tone, there is a problem that it is difficult to control them. Furthermore, since it is necessary to provide an inorganic oxide layer, there exists a problem which requires manufacturing cost.

  Patent Document 3 discloses a ceramic scaly substrate, an inorganic oxide layer as a reflective layer that covers the entire surface of the substrate, and that exhibits glitter using light interference, and the inorganic oxide. A pigment is disclosed which comprises islands made of metal or alloy formed in the form of dots at 0.05 to 95 area% with respect to the entire surface of the layer. However, similarly to Patent Document 2, since the particle diameter and thickness of the scaly substrate, the particle diameter of the metal or alloy, and the thickness of the inorganic oxide layer greatly affect the color tone, there is a problem that their control is difficult. .

  Furthermore, in Patent Documents 1 to 3, although the thickness of the base material (flaky powder, inorganic flakes, scale-like base material) greatly affects the color tone, to what extent the thickness variation is allowed Neither is disclosed.

  The present invention has been made in view of the above circumstances, and its object is to easily produce a black color tone having a brilliant property, to suppress the material cost of fine particles, and to produce a reflective layer unnecessary An object of the present invention is to provide a scaly composite particle capable of reducing the cost, a resin composition and a coated product including the scaly composite particle, and a method for producing the scaly composite particle.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, metal or metal oxide fine particles are attached to the scaly particles in the form of dots or islands. The inventors found that black scale-like composite particles exhibiting luster can be obtained without providing a reflective layer by controlling variations in the thickness of the composite particles.

  Furthermore, the present inventors increase the material cost of the fine particles by controlling the particle size, the adhesion rate and the adhesion state of the fine particles adhering to the scaly particles, and the variation in the thickness of the scaly composite particles. Since the problem was solved and it was not necessary to provide a reflective layer, it was found that the manufacturing cost can be reduced.

  That is, in the present invention, fine particles made of a metal or a second metal oxide are adhered on a scaly particle containing at least one selected from the group consisting of a first metal oxide, a resin, mica and glass. Wherein the fine particles adhere to the scaly particles in the form of dots or islands, and the adhesion rate to the scaly particles is 10 area% or more and 50 area% or less, and The average particle diameter is 1 nm or more and 80 nm or less, the thickness of the scale-like composite particles is the average value m is 0.05 μm or more and 1 μm or less, and the standard deviation s is 0 <s ≦ 0.2, The coefficient of variation CV obtained by dividing the standard deviation s by the average value m is 0% <CV ≦ 70%.

  The fine particles are desirably at least one selected from the group consisting of gold, silver, copper, platinum, tin, palladium, nickel, iron, alloys thereof, and oxides thereof.

The scale-like composite particles preferably contain a catalyst component.
The scaly particles are preferably any of alumina, silica, or glass.

It is desirable that the scaly particles are alumina and the fine particles are silver.
The scale-like composite particles are desirably provided with one or more protective layers.

The resin composition according to one embodiment of the present invention preferably includes the scale-like composite particles.
The resin composition preferably further includes one or both of the scale-like particles and the scale-like aluminum particles.

The coated product according to one embodiment of the present invention preferably contains the scale-like composite particles.
The method for producing the scale-like composite particles according to one aspect of the present invention includes a step of preparing the scale-like particles and performing an activation treatment on the surface of the scale-like particles using an acidic solvent or an alkaline solvent. The step of preparing the scale-like activated particles, the step of preparing the scale-like catalyst-supported particles by supporting the catalyst on the surface of the scale-like activated particles, and the electroless plating treatment on the scale-like catalyst-supported particles Performing the step of depositing fine particles on the surface of the scaly catalyst-carrying particles to produce the scaly composite particles.

  In the method for producing the scaly composite particles, it is preferable to further include a step of protecting the surface of the scaly composite particles.

  According to the present invention, it is possible to provide scale-like composite particles that can easily exhibit a brilliant black color tone, reduce the material cost of fine particles, and can reduce the manufacturing cost by eliminating the need for a reflective layer. can do.

It is explanatory drawing which represented typically the cross section of the scale-like composite particle which concerns on this embodiment. 2 is a drawing-substituting photograph showing the surface of the scaly composite particles of Example 1. FIG. 4 is a drawing-substituting photograph showing the surface of the scaly composite particles of Example 2. FIG. 4 is a drawing-substituting photograph showing the surface of the scaly composite particles of Example 3. FIG. 4 is a drawing-substituting photograph showing the surface of the scaly composite particles of Example 4. FIG. 6 is a drawing-substituting photograph showing the surface of the scaly composite particles of Example 5. FIG. 6 is a drawing-substituting photograph showing the surface of the scaly composite particles of Example 6. FIG. 5 is a drawing-substituting photograph showing the surface of the scaly composite particles of Comparative Example 1. FIG. 6 is a drawing-substituting photograph showing the surface of the scaly composite particles of Comparative Example 2. FIG.

  Hereinafter, the scale-like composite particles of the present invention, the resin composition containing the same, and the coated material will be described in detail.

<Scaly composite particles>
The scaly composite particles according to the present invention are fine particles comprising a metal or a second metal oxide on one or more scaly particles selected from the group consisting of a first metal oxide, a resin, mica and glass. It is a scale-like composite particle to which is attached. The first metal oxide and the second metal oxide may be the same metal oxide or different metal oxides. However, from the viewpoint of obtaining clear glitter, the first metal oxide and the second metal oxide are preferably different metal oxides.

The scaly composite particles must satisfy the following conditions (A) to (D).
(A) The fine particles are attached to the scaly particles in the form of dots or islands. (B) The fine particles have an adhesion rate to the scaly particles of 10 area% to 50 area%. (C) The fine particles have an average particle diameter of 1 nm to 80 nm. (D) The thickness of the scaly composite particles has an average value m of 0.05 μm to 1 μm, and a standard deviation s of 0 <s ≦ 0. 2. The coefficient of variation CV obtained by dividing the standard deviation s by the average value m is 0% <CV ≦ 70%.

  In the present invention, by satisfying the above conditions (A) to (D), black scale-like composite particles exhibiting glitter can be obtained without providing a reflective layer such as an inorganic oxide layer. . Furthermore, by controlling the particle diameter, the adhesion rate and the adhesion state of the fine particles adhering to the scaly particles as in the above conditions (A) to (D), and the variation in the thickness of the scaly composite particles, etc. In addition, the color tone of the scale-like composite particles can be easily controlled, the cost for the fine particles can be reduced, and the production cost can be reduced because the reflective layer is not required.

  Whether the above conditions (A) to (D) are satisfied can be evaluated by the following method. That is, a sample containing scaly composite particles is 200 to 100000 times (200 times to 100000 times, using a numerical range in the present specification using “to”) by using a scanning electron microscope (SEM: Scanning Electron Microscope). When expressed, the range can be evaluated by taking a picture at a magnification of an upper limit and a lower limit), obtaining the image, and analyzing the image. The captured image for image analysis is preferably an electronic image (hereinafter also referred to as “electronic image”).

  In the present invention, the fine particles adhere to the scaly particles, that is, to the surface of the scaly particles in the form of dots or islands. Here, the “spot-like” refers to a state in which fine particles deposited by an electroless plating process, which will be described later, are uniformly scattered on the scaly particles, or an aspect thereof. The island shape means a state in which fine particles deposited by an electroless plating process, which will be described later, are aggregated with each other, and a plurality of the aggregates are present on the surface of the scaly particles or an aspect thereof. The size of the aggregate is not particularly limited. The manner in which the fine particles adhere to the scaly particles may be any of chemical adsorption, physical adsorption and chemical bonding.

  Since the fine particles adhere to the surface of the scaly particles in the form of dots or islands, the following light is mixed in the scaly composite particles and the periphery thereof.

(I) Light reflected by colliding with fine particles (ii) Light reflected by colliding with fine particles after passing through scaly particles (iii) Reflected by colliding with fine particles and further reflected by colliding with other fine particles (Iv) Light that passes through the scaly particles.

  By mixing these lights, the scaly composite particles can have sufficient glitter and black color tone without providing a reflective layer made of an inorganic oxide or the like. It should be noted that the expression “spot-like” and “island-like” indicating the state in which the fine particles are present on the scale-like particles or the mode thereof means that the fine particles do not cover the entire surface of the scale-like particles. This means that a part of the particles is exposed from between the fine particles. In other words, it means that the fine particles form a continuous layer and do not cover the scaly particles.

  The fine particles do not necessarily have to be attached in the form of dots or islands in the entire area of the surface of the scaly particles, but only in a limited area on the surface. However, as long as the effects of the present invention are exhibited, the present invention is not deviated.

  In the present invention, the adhesion rate of the fine particles adhering to the scaly particles is 10 area% or more and 50 area% or less. Thereby, the scale-like composite particles can exhibit a black color tone. When this adhesion rate is less than 10 area%, the color tone of the scaly composite particles may be tinted with fine particles adhering to the scaly particles. When the adhesion rate exceeds 50% by area, the color tone of the scaly composite particles approaches the glossy color of the metal constituting the fine particles or the color of the second metal oxide, and an intended black color tone can be obtained. It becomes difficult. The adhesion rate is desirably 15 area% or more and 40 area% or less.

  The adhesion rate (area%) of the fine particles adhering to the scaly particles represents the total area occupied by the fine particles in percentage in each of the scaly composite particles in the electronic image.

  Specifically, the adhesion rate of fine particles to scaly particles can be calculated by the following method. First, it image | photographs using SEM and obtains the electronic image of a scale-like composite particle. Next, by binarizing the electronic image, in one scale-like composite particle, the region S1 where the fine particles are not attached on the scale-like particles and the region where the fine particles are attached on the scale-like particles The area S2 can be distinguished. The electronic image can be binarized because the area where the fine particles are attached to the scale-like particles tends to have higher brightness than the area where the fine particles are not attached.

  The adhesion rate of the fine particles to the scaly particles can be calculated by substituting each area value of the region S1 and the region S2 into the following formula (1). In the present specification, 100 scale-like composite particles observed in an electronic image by SEM are picked up, and the average value of the above-mentioned adhesion rate calculated for each scale-like composite particle is called the adhesion rate of fine particles to the scale-like particles. And

  In the present invention, the average particle diameter of the fine particles is 1 nm or more and 80 nm or less. Thereby, the scale-like composite particles can exhibit a black color tone. When the average particle diameter of the fine particles is less than 1 nm, the color tone of the scaly composite particles is very low in brightness, and may have a color tone unique to the metal constituting the fine particles or the second metal oxide. . When the average particle diameter of the fine particles exceeds 80 nm, the color tone of the scaly composite particles approaches the glossy color of the metal constituting the fine particles or the color of the second metal oxide, and it is difficult to obtain the intended black color tone. Become. Furthermore, it becomes difficult to deposit the fine particles on the scaly particles in the form of dots or islands. The average particle diameter of the fine particles is desirably 5 nm or more and 70 nm or less.

  The particle diameter of the fine particles can be calculated by the following method. First, a sample is prepared by kneading scaly composite particles into a resin. Next, this sample is formed into a predetermined shape and then cut by an ion milling method. Subsequently, for example, using a field emission electron microscope (FE-SEM), a cross section of the cut sample is photographed at a magnification of, for example, 10,000 times to obtain an electronic image thereof. As the obtained electronic image, it is preferable to use an image in which a plurality of (for example, 100) scale-like composite particles are captured in a cross section. Specifically, as shown in FIG. 1, a cross section of a scaly composite particle 10 including scaly particles 11, fine particles 12 and a weather-resistant coating layer 13 as a protective layer to be described later is photographed. By analyzing this electronic image, the particle diameter of the fine particles 12 attached to the scaly particles 11 can be obtained. The average particle diameter of the fine particles can be represented by, for example, the diameter (median diameter) which is the median value of the particle size distribution obtained by calculating the particle diameter of 100 fine particles from the electronic image.

  In the present invention, the average value m of the scale-like composite particles is 0.05 μm or more and 1 μm or less. As a result, the scale-like composite particles can exhibit a blackish color tone with glitter. As for the thickness of the scale-like composite particles, the average value m is preferably 0.1 μm or more and 0.5 μm or less. When the average value m of the scale-like composite particles is less than 0.05 μm, the scale-like particles contained in the scale-like composite particles tend to become brittle, and when the average value m of the scale-like composite particles exceeds 1 μm, Cracks are likely to occur in the thickness direction.

  Here, the “thickness of the scaly composite particles” refers to the maximum thickness in the thickness direction of the scaly composite particles in a state in which fine particles are adhered on the scaly particles. Furthermore, when the scaly composite particles include a protective layer to be described later, the thickness including the protective layer is referred to as “thickness of the scaly composite particles”.

  The thickness of the scaly composite particles can be calculated by the following method. That is, since the cross-sectional observation of the scaly composite particles can be performed from the electronic image obtained by photographing with a field emission electron microscope (FE-SEM) as described above, the thickness can be measured. As described above, since the electronic image is taken in a state where a plurality of scale-like composite particles are dispersed in the resin, the maximum thickness in the thickness direction can be calculated for each scale-like composite particle.

The average value m of the scale-like composite particles has a thickness t _i (1 ≦ i ≦ N, N = 100) of a plurality of (for example, 100) scale-like composite particles whose maximum thickness has been calculated. ) Can be obtained by assigning to. Furthermore, since the standard deviation s of the thickness of the scaly composite particles can be obtained by substituting the average value m into the following (3), the dispersion s ² can be obtained, and thus is obtained by obtaining the square root of the dispersion s ^2. can do.

  In the present invention, the standard deviation s of the thickness of the scaly composite particles is 0 <s ≦ 0.2. The standard deviation s can be kept within the above-mentioned range by controlling the particle size of the fine particles adhering to the scale-like particles and the adhesion rate thereof to produce the scale-like composite particles. When the particle diameter of the fine particles adhering to the scaly particles and the adhesion rate thereof are not controlled, the variation in the thickness of the scaly composite particles becomes large, and the standard deviation s exceeds 0.2. If the standard deviation s is 0.2 or less, the scaly composite particles can exhibit a clear, bright, black color tone, but give a dull impression when the standard deviation s exceeds 0.2. There is a risk of color tone. The standard deviation s of the thickness of the scaly composite particles is more preferably 0 <s ≦ 0.17.

  Further, the coefficient of variation CV (unit: [%]) obtained by dividing the standard deviation s by the average value m can be calculated by the following formula (4). The variation coefficient CV represents a relative evaluation of the variation in thickness with respect to the average value m of the thickness. The smaller the variation coefficient CV, the smaller the variation in thickness. Accordingly, the scaly composite particles having a small coefficient of variation CV can exhibit a clear blackish color tone.

  In the present invention, the coefficient of variation CV is 0% <CV ≦ 70%. If the coefficient of variation CV exceeds 70%, the variation in the thickness of the scale-like composite particles is large, and it means that the scale-like composite particles of various colors are mixed, so that the color tone gives a blurred and dull impression. There is a fear. The value of the coefficient of variation CV is more preferably 0% <CV ≦ 60%.

<Scaly particles>
The scaly particles in the present invention are composed of one or more selected from the group consisting of a first metal oxide, a resin, mica and glass. Since the scaly particles occupy most of the scaly composite particles, they greatly contribute to the shape of the scaly composite particles and the production cost.

  One or more scale-like particles selected from the group consisting of the first metal oxide, resin, mica, and glass transmit light. In this specification, the “flaky particle” that transmits light means a flaky particle that exhibits 60% or more in total light transmittance measured in accordance with the provisions of JIS K 7361 (1997).

  Examples of the metal oxide contained in the first metal oxide include alumina, silica, titania and the like. As what is contained in resin, an epoxy resin, a polyester resin, an acrylic resin, a melamine resin etc. can be illustrated. The method for producing the scale-like particles is not particularly limited, and the scale-like particles can be produced by a known production method.

  Among them, in the present invention, the scaly particles are preferably any one of alumina, silica or glass. Alumina, silica and glass are suitable for application to the method for producing scale-like composite particles described later. Furthermore, since alumina, silica, and glass have a smaller coefficient of thermal expansion than resin, they can contribute to providing more stable and high quality scaly composite particles. From the viewpoint of ease of production and quality uniformity, the scaly particles are more preferably alumina or silica. More preferably, the scaly particles are alumina.

  Here, the scale-like particles in the present invention refer to flake-shaped or flat-shaped particles. For example, the aspect ratio expressed by dividing the average particle diameter of the scale-like particles by the average thickness is 20 or more and 60 or less. A certain particle.

  The average particle diameter of the scaly particles is preferably 0.05 μm or more and 50 μm or less, and more preferably 0.1 μm or more and 10 μm or less. When the average particle size is less than 0.05 μm, the amount of fine particles to be adhered increases, so that the productivity may decrease. When the average particle diameter exceeds 50 μm, the denseness of the coating film using the average particle diameter may be reduced. In the present invention, the average particle size of the scaly particles means the volume average particle size. The volume average particle size of the scaly particles can be determined, for example, by using a commercially available particle size distribution measuring device (for example, trade name: “LA-300”, manufactured by HORIBA, Ltd.) and the particle size of 100 scaly particles and It can be calculated by obtaining the volume and obtaining an average value weighted by the volume based on this.

  The average thickness of the scaly particles is 0.05 μm or more and 50 μm or less. When the average thickness of the scaly particles is less than 0.05 μm, the scaly particles are likely to be brittle, and when the average thickness of the scaly particles exceeds 50 μm, cracks are likely to occur in the thickness direction. The average thickness of the scale-like particles can be calculated by, for example, obtaining the thicknesses of 100 scale-like particles using a commercially available particle size distribution measuring device and obtaining the average value thereof.

<Fine particles>
The fine particles in the present invention adhere to the scaly particles in the form of dots or islands. In the present invention, as described above, the reflective layer made of an inorganic oxide layer or the like is not required by attaching the fine particles on the scaly particles, that is, on the surface of the scaly particles in the form of dots or islands. As described above, when the fine particles adhere to the scaly particles, the attachment mode may be any of chemical adsorption, physical adsorption, and chemical bonding.

  Conventionally, in this type of flaky composite particles, a reflective layer made of an inorganic oxide layer or the like is provided on the surface of the flaky particles, and fine particles are attached to the surface of the reflective layer, or the surface of the reflective layer is covered with fine particles. As a result, a blackish color tone with brilliancy was exhibited. According to the scale-like composite particles according to the present invention, as is apparent from the production method described later, fine particles are deposited in the form of dots or islands directly on the surface of the scale-like particles without covering the reflective layer. As a result, it is possible to exhibit a brilliant black color tone. The adhesion state of the fine particles can be observed using a scanning electron microscope (SEM) as described above.

  The fine particles are made of a metal or a second metal oxide. In order to exhibit a brilliant black color tone as the scale-like composite particles, the metal or the second metal oxide constituting the fine particles may be gold, silver, copper, platinum, tin, palladium, nickel, iron, or the like. It is preferable to use at least one selected from the group consisting of these alloys and their oxides. Among these, from the viewpoint of exhibiting high glitter, it is more preferable to select any of gold, silver and platinum. In particular, the fine particles are more preferably silver. In the scaly composite particles according to the present invention, it is most preferable that the scaly particles are alumina and the fine particles are silver.

  Further, in the electroless plating process described later, the present invention provides a catalyst supported on the surface of the scaly particles, and is controlled so that fine particles are deposited in the form of dots or islands using the catalyst as a nucleus. Including the adhesion of fine particles. For this reason, the scale-like composite particles according to the present invention can contain a catalyst component.

  In addition, as a 2nd metal oxide which comprises microparticles | fine-particles, a copper oxide, silver oxide, a tin oxide etc. can be illustrated.

  The fine particles are controlled so that the average particle diameter is 1 nm or more and 80 nm or less. When the average particle diameter of the fine particles is less than 1 nm, the scaly composite particles have a very small brightness and may have a color tone unique to the metal or the second metal oxide constituting the fine particles. On the other hand, when the average particle diameter of the fine particles exceeds 80 nm, the scaly composite particles obtain an intended black color tone in order to approach the glossy color of the metal constituting the fine particles or the color of the second metal oxide. Becomes difficult. It also becomes difficult to deposit the fine particles on the scaly particles in the form of dots or islands. Furthermore, there is a risk that the manufacturing cost increases due to an increase in material costs and a longer manufacturing process. The average particle diameter of the fine particles is desirably 5 nm or more and 70 nm or less. The average particle diameter of the fine particles is expressed as the median diameter as described above.

<Protective layer>
The scaly composite particles according to the present invention can have one or more protective layers. Specifically, it is preferable to provide one or more protective layers on the fine particles adhering to the surface of the scaly particles. The protective layer has a function of suppressing the corrosion of fine particles (also referred to as “corrosion-inhibiting layer” for convenience), and has a function of suppressing sulfurization or oxidation of the fine particles (for convenience, “weather-resistant coating layer”). And those having the effect of improving either or both of the dispersibility of the scaly composite particles in the paint resin constituting the coating film and the adhesion between the scaly composite particles and the paint resin (for convenience, “ For example, it may be referred to as “coated resin layer”.

(Corrosion suppression layer)
The corrosion inhibition layer preferably contains a corrosion inhibitor. Examples of the corrosion inhibitor include compounds having a corrosion inhibiting action on fine particles, for example, the compounds shown below. The corrosion-inhibiting layer can be composed of a single film made of any of the compounds shown below, or a mixture film containing two or more selected from the compounds shown below. The corrosion-inhibiting layer should provide weather resistance to the scale-like composite particles and the coating film containing the scale-like composite particles when a metal that easily undergoes an oxidation reaction or sulfurization reaction such as silver and copper is used as the fine particles. Can do.

  The method for forming the corrosion inhibiting layer is not particularly limited. For example, by adding scale-like composite particles to a suspension in a slurry state or paste state in which a corrosion inhibitor is added and stirring or kneading in a hydrophilic solvent, and further stirring or kneading, the fine particles in the scale-like composite particles A corrosion inhibiting layer can be formed on the surface.

  Any known corrosion inhibitor can be used. Among these, particularly preferred corrosion inhibitors include benzotriazole, 1-methylbenzotriazole, 4-methylbenzotriazole, 1-ethylbenzotriazole, 1-hydroxybenzotriazole, 4-carboxybenzotriazole, 1- Chlorbenzotriazole, 5-chlorobenzotriazole, N-acetyl-benzotriazole, N-butyryl-benzotriazole, N-pivaloyl-benzotriazole, N-nonanoyl-benzotriazole, N-caproyl-benzotriazole, N-caprylyl-benzo Triazole, N-lauroyl-benzotriazole, N-stearyl-benzotriazole, N-oleoyl-benzotriazole, naphthotriazole, tolyltriazole, 2- (2′-hydro Ci-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3,5'-di-tert-butylphenyl) benzotriazole, (di) ethylaminomethylbenzotriazole, (di) butylaminomethylbenzo Triazole, (di) octylaminomethylbenzotriazole, (di) tridecylaminomethylbenzotriazole, (di) octadecylaminomethylbenzotriazole, (di) cyclohexylaminomethylbenzotriazole, (di) allylaminomethylbenzotriazole, (di ) Benzotriazols such as benzylaminomethylbenzotriazole, (di) octylaminoethylbenzotriazole, (di) octylaminodecylbenzotriazole, (di) octylaminobenzylbenzotriazole 1-phenyl-5-mercaptotetrazole, tetrazole such as 3- (4,5dimethyl-2-thiazolyl) -2,5-diphenyl 2H-tetrazolium bromide, 5-amino-1H-tetrazole, 2-phenyl Imidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-propylimidazole, 2-phenyl-5-iodoimidazole, 2-benzylimidazole, 2-benzyl-4-methylimidazole, 2- (3-chloro) Benzylimidazole, 2- (3-iodo) benzylimidazole, 2-naphthylimidazole, 2-naphthyl-4-methylimidazole, 2-naphthyl-4-methyl-5-bromoimidazole, 2- (3,5-dibromo) naphthyl Imidazole, 2- (2,6-dichloro) naphthyl-4- Methylimidazole, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-amylimidazole, 2-heptylimidazole, 2-decylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 2- Imidazoles such as tetradecylimidazole, 2-heptadecylimidazole, 2-undecyl-4-methylimidazole, 2-heptadecyl-4-methylimidazole, 3-amino-1,2,4-triazole, 3-amino-5 Methyl-1,2,4-triazole, 3-amino-5-ethyl-1,2,4-triazole, 3-amino-5-propyl-1,2,4-triazole, 3-amino-5-butyl- 1,2,4-triazole, 3-amino-5 Pentyl-1,2,4-triazole, 3-amino-5-hexyl-1,2,4-triazole, 3-amino-5-heptyl-1,2,4-triazole, 3-amino-5-octyl- 1,2,4-triazole, 3-amino-5-nonyl-1,2,4-triazole, 3-amino-5-decyl-1,2,4-triazole, 3-amino-5-undecyl-1, Alkylaminotriazoles such as 2,4-triazole and 3-amino-5-dodecyl-1,2,4-triazole, glyoxal, pyraldehyde, diacetyl, 2,3-pentanedione, 3,4-hexanedione, 3 , 4-Heptanedione, 3,4-octanedione, 4,5-nonanedione, 4,5-decanedione, 5,6-undecanedione, 1,2-cyclohexa Dione, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 2,4-octanedione, 3,5-octanedione, 4,6-decanedione, 5,7-undecanedione, methylacetoacetate, ethyl Acetoacetate, 3-methyl-2,4-pentanedione, 2-acetylcyclopentanone, α-acetyl-γ-butyrolactone, 2-ethylcarbonylcyclopentanone, α-ethylcarbonyl-γ-butyrolactone, 2-propylcarbonyl Cyclopentanone, α-propylcarbonyl-γ-butyrolactone, 2-butylcarbonylcyclopentanone, α-butylcarbonyl-γ-butyrolactone, 2-acetylcyclohexanone, α-acetyl-δ-pentyrolactone, 2-ethylcarbonylcyclohexanone , Α-E Α-dicarbonyl compounds such as rucarbonyl-γ-pentyrolactone, 2-propylcarbonylcyclohexanone, α-propylcarbonyl-γ-pentyrolactone, 2-butylcarbonylcyclohexanone, α-butylcarbonyl-γ-pentyrolactone, or Examples thereof include mercaptan compounds such as mercaptoimidazolines, naphthyl mercaptans, and C6-C22 alkyl mercaptans such as β-dicarbonyl compounds or amine adducts thereof.

  Furthermore, higher alkylamines such as dodecylamine, octadecylamine, eicosylamine, nonylamine, and ethylene oxide adducts thereof can be exemplified.

  Further, 2-methylbenzothiazole, 2-mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfate Examples thereof include benzothiazoles such as phenamide and Ntert-butyl-2-benzothiazolylsulfenamide.

  The addition amount of the corrosion inhibitor is not particularly limited as long as the effects of the present invention are exhibited. For example, the addition amount of the corrosion inhibitor can be approximately 0.0001 to 5% by mass as the content in the protective layer (corrosion inhibition layer).

  The corrosion inhibitor is preferably added to the suspension along with a suitable solvent. This solvent includes water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Examples thereof include glycol monopropyl ether, ethylene glycol monoethyl ether, acetone, and benzene.

  The suspension containing the corrosion inhibitor can be used in the pH range of 1-13. However, since the effect of inhibiting corrosion is sufficiently exhibited in a weakly acidic to weakly alkaline region, it is desirable to use at pH 4 to 11 from the viewpoint of safety. In adjusting the pH, known acids and alkalis can be used. Since hydrochloric acid and nitric acid may affect scaly particles or fine particles when used in large quantities, sulfuric acid, sulfonic acid, etc. are preferably used as the acid, and sodium hydroxide, potassium hydroxide, ammonia, etc. are preferred as the alkali. Used for.

  After forming the corrosion inhibition layer, the corrosion inhibition layer can be covered with a resin. Examples of this resin include acrylic resin, alkyd resin, polyester resin, polyurethane resin, polyvinyl acetate resin, nitrocellulose resin, and fluorine resin. In this case, the resin covering the corrosion inhibition layer is referred to as a “corrosion inhibition layer”.

  The thickness of the corrosion inhibiting layer is preferably 1 to 100 nm including the thickness of the resin covering it. When the thickness is within this range, the scale-like composite particles have good corrosion inhibition and glitter, and a black color tone with glitter is well expressed. The thickness of the corrosion inhibiting layer is more preferably 1 to 50 nm. The thickness of this corrosion inhibition layer is an average value.

(Weather-resistant coating layer)
The weather-resistant coating layer can be composed of a single film made of any of oxides, hydroxides or hydrates, or a mixed film in which two or more of these are combined. In particular, a single film made of an oxide, hydroxide or hydrate containing at least one element selected from the group consisting of aluminum, silicon, and cerium, or a mixture film combining two or more of these. Preferably it consists of. In the present invention, by forming such a weather resistant coating layer composed of a single film or a mixture film, it is possible to impart a discoloration preventing effect to the scaly composite particles and improve the weather resistance. In particular, when an element or compound that easily oxidizes and sulfidizes, such as silver and copper, is employed as the fine particles, good weather resistance can be imparted to the scaly composite particles and the coating film containing the same.

  Furthermore, in the scale-like composite particles according to the present invention, when the above-described corrosion-inhibiting layer is formed together with the weather-resistant coating layer, it is preferable to form the weather-resistant coating layer on the corrosion-inhibiting layer. This is particularly advantageous in terms of improving the weather resistance effect during long-term exposure and suppressing oxidation and sulfurization due to heating.

  The method for forming the weather resistant coating layer is not particularly limited. For example, the case where the weather-resistant coating layer forms a single film or a mixture film containing at least one or both of aluminum and silicon is exemplified. First, at least one of an aluminum compound or a silicon compound is added to a hydrophilic solvent, and stirred or kneaded while keeping the pH alkaline or acidic to obtain a suspension in a slurry state or a paste state. Subsequently, the flaky composite particles are added to this suspension, and further stirred or kneaded to form a hydrated film containing at least one or both of aluminum and silicon on the surface of the flaky composite particles. Finally, it is preferable to form a weather-resistant film layer composed of a single film or a mixed film containing at least one or both of aluminum and silicon from the hydrated film by heat-treating the suspension.

  Examples of silicon compounds and aluminum compounds used in the method of forming a weather-resistant coating layer include methyltriethoxysilane, methyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane, and their condensates, γ-amino Propyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, sodium silicate, silicotungstic acid, silicomolybdic acid, triethoxyaluminum, Examples thereof include trimethoxyaluminum, triisopropoxyaluminum and the like, and condensates thereof, aluminum nitrate and the like. However, the silicon compound and the aluminum compound used in the above method are not limited to the above compounds.

  As a hydrophilic solvent used in a suspension for forming a weather-resistant coating layer, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve And propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone and the like. However, the hydrophilic solvent used for the suspension for forming the weather resistant coating layer is not limited to the hydrophilic solvent. The suspension for forming the weather resistant coating layer may contain water.

  For example, when the weather-resistant coating layer contains cerium, heat-stirring or stirring while keeping the pH alkaline by adding scale-like composite particles to a solution or suspension in which cerium acetate, cerium nitrate, cerium alkoxide, cerium sol, etc. are dissolved or dispersed Knead. Thereby, the weatherable film layer which consists of a single film | membrane containing cerium can be formed by forming the hydrated film | membrane containing cerium on the surface of scale-like composite particles, and then heat-processing.

  The thickness of the weather resistant coating layer is preferably 1 to 100 nm. When the thickness is 1 nm or more, properties such as water resistance, heat resistance, and weather resistance can be sufficiently imparted to the scaly composite particles. When the thickness is 100 nm or less, the scaly composite particles can exhibit a brilliant black color tone. The thickness of the weather resistant coating layer is more preferably 20 to 50 nm. The thickness of this weather-resistant coating layer is an average value.

Here, when the weather-resistant coating layer is formed on the scaly composite particles, the weather-resistant coating layer is preferably treated with a coupling agent, particularly a coupling agent containing at least one of silicon and titanium. Thereby, for example, when forming a coating film from a resin composition containing scaly composite particles and a paint resin, the affinity between the scaly composite particles and the paint resin is increased, and the adhesion between them is improved. Can do. As the coupling agent, for example, a silane coupling agent is preferable. As the silane coupling agent, for example, R _A —Si (OR _B ) ₃ or R _A —SiR _B (OR _B ) ₂ (R _A : C 2-18 alkyl group, aryl group or alkenyl group, R _B : An alkyl group having 1 to 3 carbon atoms) is preferable. Furthermore, _RA preferably has a functional group. Examples of functional groups possessed by _RA include amino groups, ureido groups, epoxy groups, sulfide groups, vinyl groups, methacryloxy (methacrylic) groups, acryloxy (acrylic) groups, mercapto groups, and ketimino groups.

  Preferred silane coupling agents include methyltriethoxysilane, methyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane, 3-aminopropyl-trimethoxysilane, n-methyl-3-aminopropyl-trimethoxy Silane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-tris (2-methoxy-epoxy-silane), n-aminoethyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-acryloxypropyl-trimethoxysilane, 3-glycidyloxypropyl-trimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropi - methyldimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl - tris (2-methoxyethoxy) silane, etc., and the like can be exemplified condensates thereof.

Furthermore, although there are few types of titanium coupling agents compared to silane coupling agents, they are preferred as coupling agents used to treat weathering coating layers. A titanium coupling agent generally has a hydrolyzable group as a hydrophilic group and a side chain organic functional group as a hydrophobic group. Typically, it has an alkoxyl group as a hydrolyzable group and an alkyl phosphate group, an amino group, a sulfide group, etc. as a side chain organic functional group. As a preferable commercially available product, a titanium coupling agent (trade name: “Plenact KR46B”, manufactured by Ajinomoto Fine Techno Co., Ltd.) can be exemplified. In the case of preneact KR46B, it has C ₈ H ₁₇ O— as the hydrolyzable group, HO—P— (OC ₁₃ H ₂₇ ) ₂ as the side chain organic functional group, and C ₈ H ₁₇ O— is coordinated to Ti. It has a structure.

  In the coupling process, the amount of the coupling agent to be added is adjusted to 0.1 to 30% by mass of the entire resin composition in the state before the coupling process, including the scaly composite particles and the coating resin. Is preferred. When the addition amount of the coupling agent is 0.1% by mass or more of the entire resin composition, an effect of improving the adhesion between the scaly composite particles and the coating resin can be obtained. When the addition amount of the coupling agent is 30% by mass or less of the entire resin composition, stability over time can be obtained, and for example, aggregation can be prevented. The addition amount of the coupling agent is more preferably 1 to 5% by mass with respect to the entire resin composition.

  The coupling treatment can be performed by a method in which the scaly composite particles on which the weather-resistant coating layer is formed are dispersed in a solvent such as isopropyl alcohol to make a slurry, and then a coupling agent is added.

(Coating resin layer)
The scaly composite particles according to the present invention preferably have a coating resin layer formed as the outermost layer. Thereby, for example, when a coating film is formed from a resin composition containing scaly composite particles and a coating resin, the adhesion between the scaly composite particles and the coating resin is improved, and the physical properties of the coating film are improved. . Furthermore, the chemical resistance of the coating film can be improved.

  The method for forming the coating resin layer is not particularly limited. For example, by dispersing the scaly composite particles in a nonpolar solvent, adding a polymerizable monomer and a polymerization initiator that will form the coating resin layer, and heating them while stirring to advance the polymerization reaction The coating resin layer can be formed on the surface of the scaly composite particles.

  Here, the polymerization reaction is preferably allowed to proceed in a non-oxidizing atmosphere, for example, an inert gas such as nitrogen or argon. This is because, under an oxidizing atmosphere, radicals that contribute to the polymerization reaction tend to disappear and the polymerization efficiency tends to decrease. The reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 100 ° C. When the reaction temperature is 50 ° C. or higher, the polymerization efficiency is sufficient. When the reaction temperature is 150 ° C. or lower, excessive evaporation of the solvent can be avoided and safety can be ensured.

  The nonpolar solvent used as the dispersion solvent is preferably a hydrocarbon solvent. Examples of hydrocarbon solvents include mineral spirits, petroleum benzine, solvent naphtha, isoparaffin, normal paraffin, benzene, toluene, xylene, cyclohexane, hexane, heptane, octane, chlorobenzene, trichlorobenzene, perchlorethylene, trichloroethylene, etc. be able to. By using a nonpolar solvent, a sufficiently thick coating resin layer can be formed as the outermost layer that coats the scaly composite particles.

  Although the coating resin layer is not particularly limited, for example, from the group consisting of a reactive monomer having at least one of a carboxyl group or a phosphate group, a polyfunctional acrylic ester monomer having 3 or more functions, and a polymerizable monomer having a benzene nucleus It can be exemplified that the copolymer is synthesized from at least two selected monomers.

  The following are illustrated as a reactive monomer which has at least one of a carboxyl group or a phosphate group. The addition amount is preferably 0.1 to 10% by mass of the whole monomer component to be polymerized, and more preferably 0.5 to 5% by mass of the whole monomer component to be polymerized. When the addition amount is out of this range, it tends to be difficult to impart good chemical resistance to the coating film containing scale-like composite particles.

  As reactive monomers, acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2-methacryloyloxyethyl acid phosphate, di-2-methacryloyloxyethyl acid phosphate, tri-2 -Methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, di-2-acryloyloxyethyl acid phosphate, tri-2-acryloyloxyethyl acid phosphate, diphenyl-2 -Methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl acid phosphate, dibutyl-2-methacryloyloxyethyl acid phosphate, dibutyl-2-acryloyloxyethyl acid phosphate Dioctyl-2-methacryloyloxyethyl acid phosphate, dioctyl-2-acryloyloxyethyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, bis (2-chloroethyl) vinyl phosphonate, diallyl dibutylphosphono A succinate etc. can be illustrated.

  The following are illustrated as a polyfunctional acrylic ester monomer which has 3 or more functions. The addition amount of the polyfunctional acrylate monomer is preferably 30 to 90% by mass of the whole monomer component to be polymerized, and more preferably 40 to 80% by mass of the whole monomer component to be polymerized. When the addition amount is out of this range, it tends to be difficult to impart good chemical resistance to the coating film containing scale-like composite particles. The polyfunctional acrylate monomer contributes to three-dimensional crosslinking of the resin and has an effect of insolubilizing the coating resin layer with respect to the organic solvent and water.

  As trifunctional or higher polyfunctional acrylic acid ester monomers, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane triacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane trimethacrylate, tetramethylolpropane tetramethacrylate, penta Examples include erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, and the like.

  The following are illustrated as a polymerizable monomer which has a benzene nucleus. The addition amount of the polymerizable monomer having a benzene nucleus is preferably 5 to 50% by mass of the whole monomer component to be polymerized, and more preferably 10 to 30% by mass of the whole monomer component to be polymerized. When the addition amount is outside this range, it tends to be difficult to impart good chemical resistance to the scaly composite particles. By copolymerizing a polymerizable monomer having a benzene nucleus, the chemical resistance of the coating resin layer can be further improved.

  As a polymerizable monomer having a benzene nucleus, styrene, α-methylstyrene, vinyl toluene, divinylbenzene, phenyl vinyl ketone, phenyl vinyl ether, divinylbenzene monooxide phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate, 2-hydroxy-3-phenoxy A propyl acrylate etc. can be illustrated.

  The mass of the coating resin layer is preferably 1 to 100% by mass of the scaly composite particles, and more preferably 5 to 50% by mass of the scaly composite particles. When the mass of the coating resin layer is 1% by mass or more of the scaly composite particles, good chemical resistance can be obtained. When the mass of the coating resin layer is 100% by mass or less of the scaly composite particles, the sharpness of the scaly composite particles is hardly impaired.

  Examples of the polymerization initiator include peroxides such as benzoyl peroxide, lauroyl peroxide, isobutyl peroxide, and methyl ethyl ketone peroxide, and azo compounds such as azobisisobutyronitrile.

  The blending amount of the polymerization initiator is preferably 0.1% by mass or more of the whole monomer component to be polymerized, and more preferably 0.5% by mass or more of the whole monomer component to be polymerized. Furthermore, the blending amount of the polymerization initiator is preferably 10% by mass or less of the whole monomer component to be polymerized, and more preferably 8% by mass or less of the whole monomer component to be polymerized. When the blending amount is 0.1% by mass or more of the entire monomer component to be polymerized, the polymerization reaction proceeds well and a film can be easily formed. When the blending amount is 10% by mass or less of the total monomer components to be polymerized, rapid progress of the polymerization reaction is prevented, so that free polymer particles are generated and the viscosity of the entire system is rapidly increased to solidify. Inconveniences such as the occurrence of this are less likely to occur.

  The thickness of the coating resin layer is preferably 1 to 100 nm. If the thickness is within this range, when a coating film is formed from a resin composition containing scaly composite particles and a paint resin, adhesion between the scaly composite particles and the paint resin, chemical resistance, and the like are improved. In addition, a bright blackish color tone is exhibited well. The thickness of the coating resin layer is more preferably 10 to 50 nm. The thickness of this coating resin layer is an average value.

  The main configuration of the scaly composite particles according to the present embodiment has been described above, but the scaly composite particles need only have fine particles directly attached to the surface of the scaly particles, and the effects of the present invention are not impaired. Within the range, layers other than those described above may be formed, or granular materials may be attached.

<Resin composition>
The resin composition according to the present invention includes scaly composite particles. Examples of such a resin composition include a paint, a coating film formed with the paint, ink, a printed material formed with the ink, a cosmetic, and a resin molded body. When the resin composition according to the present invention is a paint or ink, it can be configured in either an organic solvent type (oil-based) or aqueous, but improvement in light resistance and weather resistance is an important issue. It is particularly effective to construct it as a water-based paint or ink.

  The blending amount of the scaly composite particles in the resin composition is preferably 0.1 to 30% by mass of the entire resin composition. When the blending amount is 0.1% by mass or more of the entire resin composition, the decoration effect is improved. When the blending amount is 30% by mass or less of the entire resin composition, the weather resistance, corrosion resistance, mechanical strength, and the like of the resin composition are improved. As for the compounding quantity of the scale-like composite particle | grains in a resin composition, it is more preferable that it is 1-20 mass% of the whole resin composition.

  The resin composition can be obtained, for example, by appropriately adding a resin (hereinafter also referred to as “paint resin”) to the scaly composite particles when constituting a paint. Examples of the coating resin include acrylic resin, alkyd resin, polyester resin, polyurethane resin, polyvinyl acetate resin, nitrocellulose resin, and fluorine resin.

  Using such a resin composition, a coating film may be formed on an undercoat layer or an intermediate coat layer formed by electrodeposition coating or the like. An overcoat layer may be further formed on the coating film formed using the resin composition.

  The resin composition according to the present invention may further include any one or both of the scale-like particles and the scale-like aluminum particles. That is, the resin composition is obtained by blending, in a paint resin or the like, one or more scale-like particles selected from the group consisting of the first metal oxide, resin, mica and glass in addition to the scale-like composite particles. be able to. Furthermore, the resin composition can be obtained by blending the scaly composite particles, scaly particles and scaly aluminum particles in a paint resin or the like, or only scaly aluminum particles together with the scaly composite particles in the paint resin or the like. Can also be obtained. Such a resin composition is advantageous in that it is highly concealed, has an effect of increasing the glitter or metallic feeling, and can eliminate the base coating. The scaly aluminum particles have a mean particle diameter of 0.05 μm or more and 50 μm or less, and have a flake shape or a flat shape whose aspect ratio expressed by dividing the average particle diameter by the average thickness is 20 or more and 60 or less. Particles made of aluminum or aluminum alloy.

  Furthermore, the resin composition can contain other colored pigments or extender pigments or dyes. Examples of such colored pigments include phthalocyanine, quinacridone, isoindolinone, perylene, azo lake, iron oxide, chrome lead, carbon black, titanium oxide, and pearl mica. In addition to the above components, additives such as water, organic solvents, surfactants, curing agents, ultraviolet absorbers, static eliminators, thickeners and the like can be included.

  Cosmetics can be exemplified as one type of the resin composition according to the present invention. Conventionally, pearl pigments, aluminum pigments, and the like have been used in order to impart glossiness and luster to cosmetics. However, since pearl pigments have poor hiding properties and aluminum pigments exhibit a gray color, there is a tendency that a clear color tone cannot be obtained even when cosmetics are formed by blending other color pigments. Furthermore, since the aluminum pigment easily reacts with water, it cannot be applied to cosmetics containing water.

  In the present invention, a cosmetic material having excellent hiding power and exhibiting a black color tone is obtained by blending scale-like composite particles. Furthermore, since the scaly composite particles have a stable property that hardly reacts with water, it is also suitable when containing water. Although the kind of cosmetics which mix | blended scaly composite particle | grains is not specifically limited, The following cosmetics can be illustrated.

  For example, makeup cosmetics (lipstick, foundation, blusher, eye shadow, nail enamel, etc.), hair cosmetics (hair gel, hair wax, hair treatment, shampoo, hair manicure gel, etc.), basic cosmetics (base cream etc.), etc. Cosmetics.

  The cosmetic as one type of the resin composition according to the present invention can contain the following components in addition to the scaly composite particles.

(Oil)
Oils include oils and fats (olive oil, castor oil, etc.), waxes (beeswax, carnauba wax, lanolin, etc.), hydrocarbon oils (liquid paraffin, squalane, polybutene, etc.), fatty acid esters (isopropyl myristate, cetyl 2-ethylhexanoate, adipine) Diisopropyl acid, glyceryl trimyristate, etc.), higher fatty acids (oleic acid, isostearic acid, etc.), higher alcohols (isostearyl alcohol, oleyl alcohol, etc.), silicone oils (dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane) Etc.) and a fluorine compound (perfluoropolyether, etc.).

(Other ingredients)
Other components include surfactants, humectants, polyhydric alcohols, water-soluble polymers, film forming agents, water-insoluble polymers, polymer emulsions, powders, pigments, dyes, lakes, lower alcohols, UV absorbers, Vitamins, antioxidants, antibacterial agents, fragrances, water and the like can be included.

(Mixing amount)
A preferable blending amount of the scaly composite particles in the cosmetic is 0.1 to 99% by mass. More preferably, it is 1-80 mass%.

  The cosmetic according to the present invention can be produced by a conventionally known production method. As a method for dispersing the cosmetic, a method using a disper or a roll mill is suitable.

<Applied material>
The coated material according to the present invention includes scaly composite particles. The present invention includes, for example, a coated product obtained by coating any of the above resin compositions on a substrate. The raw material of the base | substrate which comprises such a coated material is not specifically limited, For example, a metal, resin, wood, paper, leather etc. can be mentioned. In addition, examples of such a coated material include printed materials such as automobiles, motorcycles, etc., lid materials, packaging materials, magazines, posters, and the like, coated materials requiring security such as banknotes, passports, licenses, and vouchers. Can be mentioned.

<Method for producing scaly composite particles>
The method for producing scale-like composite particles according to the present invention comprises a step of preparing scale-like particles (preparation step) and an activation treatment for the surface of the scale-like particles using an acidic solvent or an alkaline solvent. The step of preparing scale-like activated particles (scale-like activated particle preparation step) and the step of preparing scale-like catalyst-carrying particles by carrying the catalyst on the surface of the scale-like activated particles (scale-like catalyst carrying) Particle preparation step), and a step of producing scale-like composite particles by depositing fine particles on the surface of the scale-like catalyst-supported particles by performing electroless plating treatment on the scale-like catalyst-supported particles (scale-like composite particle preparation step) With. Hereinafter, each step will be described.

(Preparation process)
In the preparation step, scaly particles are prepared. As the scaly particles, one or more selected from the group consisting of the first metal oxide, resin, mica, and glass are employed. As the scaly particles, those having an average thickness of 0.05 μm or more and 1 μm or less and an average particle diameter of 0.05 μm or more and 50 μm or less are preferably used.

(Scale-like activated particle preparation process)
In the flaky activated particle preparation step, flaky activated particles are prepared by performing an activation treatment on the surface of the flaky particles using an acidic solvent or an alkaline solvent. Specifically, the slurry containing the scaly particles is prepared by first introducing the scaly particles into a stirring tank and further introducing a solvent such as water. Next, the surface of the scaly particles can be activated by adding an acidic solvent or an alkaline solvent to the slurry and stirring the slurry. Furthermore, the activation process can be stopped by washing the slurry. Examples of the cleaning treatment method include a method in which water is used as the cleaning liquid, and the slurry to which the cleaning liquid is added is subjected to solid-liquid separation using a centrifuge, a funnel or the like.

  Nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid can be exemplified as the acid contained in the acidic solvent, and sodium hydroxide can be exemplified as the alkali contained in the alkaline solvent. From the viewpoint of safety, the solvent component of the acidic solvent or alkaline solvent is preferably water, but an organic solvent such as alcohol may be used.

  The addition amount of the acidic solvent is preferably such that the volume ratio of the acid contained in the acidic solvent is 0.1% by volume or more and 30% by volume or less when the total amount of the scaly particles contained in the slurry is 100% by volume. When using an alkaline solvent, it is preferable that the addition amount is 0.1 volume% or more and 30 volume% or less when the total amount of scaly particles is 100 volume%. When the volume ratio of the acid or alkali exceeds 30% by volume, not only activation but also excessive etching tends to occur, and the surface of the scaly particles tends to become rough. When the volume ratio of acid or alkali is less than 0.1% by volume, activation of the surface of the scaly particles tends to be insufficient. The addition amount of the acidic solvent or alkaline solvent is such that when the total amount of the scaly particles contained in the slurry is 100% by volume, the volume ratio of the acid or alkali is 0.5% by volume or more and 10% by volume or less. preferable.

  The time required for the activation treatment is preferably from 1 minute to 30 minutes. The time required for the activation treatment is the time from the addition of the acidic solvent or the alkaline solvent to the slurry until the washing treatment. When this time exceeds 30 minutes, not only activation of the surface of the scaly particles but also excessive etching tends to occur, and the surface tends to become rough. When it is less than 1 minute, the surface activation of the scale-like particles tends to be insufficient.

  Here, in the scale-like activated particle preparation step, a silane coupling agent may be added together with the acidic solvent or the alkaline solvent. Preparation of scaly activated particles having a highly active silane group on the surface of scaly particles by attaching the silane coupling agent to the surface of scaly particles cleaned with an acidic solvent or an alkaline solvent Can do. The addition amount of the silane coupling agent is preferably such that the volume ratio of the silane coupling agent is 1% by volume or more and 20% by volume or less when the total amount of the scaly particles contained in the slurry is 100% by volume. Examples of such silane coupling agents include amino silane and epoxy silane.

(Scale-like catalyst support particle preparation process)
In the flaky catalyst-carrying particle preparation step, the flaky catalyst-carrying particles are prepared by supporting the catalyst on the surface of the flaky activated particles. Specifically, a slurry containing scale-like activated particles is prepared by putting a solvent such as water into a stirring tank and feeding the washed scale-like activated particles. Next, the catalyst can be supported on the surface of the scale-like activated particles by adding the catalyst to the slurry and stirring. Further, the catalyst loading can be stopped by washing the slurry. Examples of the cleaning treatment method include a method in which water is used as the cleaning liquid, and the slurry to which the cleaning liquid is added is subjected to solid-liquid separation using a centrifuge, a funnel or the like.

  The catalyst supported on the surface of the activated scaly particles serves as a nucleus for depositing fine particles in the electroless plating process described later. As the catalyst, a metal compound can be suitably used. For example, at least one metal selected from the group consisting of stannous chloride, stannous chloride, stannous sulfate, tin fluoride, tin oxide, and organic acid tin. Compounds can be used. For example, when primary palladium chloride is used, scaly catalyst-carrying particles having palladium ions supported on the surface of the scaly activated particles can be obtained. In the scale-like catalyst-carrying particle preparation step, a reducing agent may be used as necessary.

  The addition amount of the catalyst is preferably such that the mass ratio of the catalyst is 0.001 mass% or more and 20 mass% or less when the total amount of the activated scale-like particles contained in the slurry is 100 mass%. When the mass ratio of the catalyst exceeds 20% by mass, the catalyst is added more than necessary, so that the cost tends to increase. When the mass ratio of the catalyst is less than 0.001% by mass, the amount of fine particles adhering to the scaly particles tends to decrease due to the amount of the catalyst being too small, or the size of the fine particles becomes messy and the color tone is lowered. Tend to. As for the addition amount of a catalyst, when the total amount of the activated scale-like particle | grains contained in a slurry is 100 mass%, it is more preferable that the mass ratio of a catalyst is 0.01 mass% or more and 10 mass% or less.

  The time required for supporting the catalyst largely depends on the treatment temperature, but is preferably approximately 1 minute to 30 minutes. The time required for loading the catalyst refers to the time from the addition of the catalyst to the slurry until the washing treatment. When this time exceeds 30 minutes, productivity tends to deteriorate. When this time is less than 1 minute, there is a tendency that the catalyst is unevenly supported.

(Scale-like composite particle production process)
In the flaky composite particle production step, the flaky catalyst-carrying particles are subjected to electroless plating treatment, whereby fine particles are deposited on the surface of the flaky catalyst-carrying particles to produce flaky composite particles. Specifically, a slurry containing scaly catalyst-carrying particles can be prepared by introducing a solvent such as water into a stirring tank and introducing the scaly catalyst-carrying particles after washing treatment. Next, the electroless plating process can be advanced by introducing a plating solution containing a metal salt, a reducing agent and a complexing agent while stirring the slurry. Furthermore, the electroless plating process can be stopped by washing the slurry. Examples of the cleaning treatment method include a method in which water is used as the cleaning liquid, and the slurry to which the cleaning liquid is added is subjected to solid-liquid separation using a centrifuge, a funnel or the like.

  As a solvent for the plating treatment solution, an organic solvent, water, or a mixed solvent thereof can be used. When an organic solvent is used, the speed of the electroless plating process is slow, which is suitable for forming a dense metal layer of fine particles on the scaly particles. On the other hand, in consideration of productivity, it is preferable to use a mixed solvent composed of an organic solvent and water, or water as the solvent. The solvent used for the slurry containing the scaly catalyst-carrying particles before adding the plating solution may be water, an organic solvent, or a mixed solvent thereof.

  As a metal salt contained in the plating solution, a known salt used in an electroless plating method can be used. For example, nitrates, sulfates, nitrites, oxalates, carbonates, chlorides, acetates, lactates, sulfamates, fluorides, iodides that can be stably dissolved in organic solvents, water, mixed solvents, Cyanide can be used. The metal composing the metal salt is deposited on the scaly particles and becomes the metal composing the fine particles adhering to the scaly particles.

  As the reducing agent contained in the plating solution, a known agent used in an electroless plating method can be used. For example, sugars such as glucose and saccharose, polysaccharides such as cellulose, starch and glycogen, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, hypophosphorous acid, formaldehyde, boron hydride, dimethylamine borane, trimethylamine borane Hydrazine tartaric acid and salts thereof can be used. Of these, hydrazine tartaric acid is preferably used as an alkali metal salt.

  As the complexing agent contained in the plating solution, a known agent used in an electroless plating method can be used. For example, sugars such as glucose and sucrose, polysaccharides such as cellulose, starch and glycogen, carboxylic acids such as succinic acid, oxycarboxylic acids such as citric acid and tartaric acid, glycine, ethylenediaminetetraacetic acid (EDTA), aminoacetic acid, and these (Such as alkali metal salts and ammonium salts) can be used. By using a complexing agent, reprecipitation of the metal can be suppressed, and stable fine particle deposition can be achieved.

  The addition amount of the metal salt contained in the plating treatment liquid is appropriately determined according to the material of the scaly catalyst-carrying particles (particularly scaly particles), the properties such as the particle diameter, the kind of the metal salt to be added, and the like. The addition amount of the reducing agent and the complexing agent contained in the plating treatment liquid can be appropriately determined according to the addition amount of the metal salt contained in the plating treatment liquid.

  The time required for the electroless plating treatment is preferably 1 minute or more and 120 minutes or less. The time required for the electroless plating treatment is the time from the addition of the metal salt to the slurry until the washing treatment. When this time exceeds 120 minutes, productivity tends to deteriorate. When this time is less than 1 minute, there is a tendency that unreacted metal ions are present in the slurry.

  The pH of the plating solution is preferably adjusted as appropriate depending on the type of metal constituting the metal salt. By adding sodium hydroxide, potassium hydroxide, aqueous ammonia or the like to the plating treatment solution, the pH can be adjusted to be alkaline (pH 8 to 12). By adding sulfuric acid, nitric acid, citric acid or the like to the plating solution, the pH can be made acidic (pH 1 to 6). Furthermore, by using these together, the pH can be neutral (pH 6-8). What is necessary is just to adjust suitably pH of the reaction liquid prepared by adding a plating processing liquid to the slurry containing a scale-like catalyst carrying particle according to the kind of metal which comprises a metal salt.

  The temperature of the reaction solution when the electroless plating process proceeds is preferably adjusted as appropriate depending on the type of metal or second metal oxide deposited as fine particles. For example, when the fine particles are silver, the temperature is preferably 5 ° C. or higher and 40 ° C. or lower, and more preferably 10 ° C. or higher and 30 ° C. or lower. During the electroless plating treatment, the reaction solution is preferably stirred to such an extent that the scaly catalyst-carrying particles do not settle.

  By passing through the flaky composite particle preparation step, a slurry containing the flaky composite particles can be obtained, and by drying this, the flaky composite particles can be obtained.

The obtained scaly composite particles satisfy the following conditions (A) to (D).
(A) The fine particles are attached to the scaly particles in the form of dots or islands. (B) The fine particles have an adhesion rate to the scaly particles of 10 area% to 50 area%. (C) The fine particles have an average particle diameter of 1 nm to 80 nm. (D) The thickness of the scaly composite particles has an average value m of 0.05 μm to 1 μm, and a standard deviation s of 0 <s ≦ 0. 2. The coefficient of variation CV obtained by dividing the standard deviation s by the average value m is 0% <CV ≦ 70%.

(Protection process)
In this invention, it is preferable to provide the process of protecting the surface of a scale-like composite particle. The step of protecting the surface of the scaly composite particles can be carried out following the scaly composite particle production step. Thereby, protective layers, such as the corrosion suppression layer mentioned above, a weathering coating layer, and a coating resin layer, can be formed on the surface of scale-like composite particles.

  The method for forming the protective layer is not particularly limited, but the scale-like composite particles are put into a slurry containing a fatty acid, a fatty acid salt, a surfactant, a chelating agent, an organometallic compound, or the like that is a material for the protective layer. A method can be illustrated. A washing treatment is preferably performed after the formation of the protective layer. For example, water is used as the cleaning liquid, and the slurry-like composite particles on which the protective layer is formed can be cleaned by solid-liquid separation of the slurry to which the cleaning liquid has been added using a centrifuge, a funnel or the like.

  For example, there is a corrosion inhibiting layer forming step for forming a corrosion inhibiting layer on the surface of the scaly composite particles as the protective treatment step. Although the formation method of the corrosion suppression layer in this process is not specifically limited, For example, it can achieve by the above-mentioned method.

  Furthermore, for example, as a process for protecting treatment, there is a weather-resistant film layer forming process for forming a weather-resistant film layer on the surface of the scaly composite particles. Although the formation method of the weather-resistant film layer in this process is not specifically limited, For example, it can achieve by the above-mentioned method.

  In the case of including a weather-resistant film layer forming step as the protective treatment step, the coupling treatment step can be combined. The method of the coupling treatment in this case is not particularly limited, but can be achieved by, for example, the above-described method.

  In the method for producing the flaky composite particles according to the present invention, the obtained flaky composite particles, the coating resin necessary for constituting the resin composition, and other color pigments and constitutions added as necessary A step of mixing pigments, dyes, additives and the like by a conventionally known method can be provided. Furthermore, in the method for producing flaky composite particles according to the present invention, in order to prepare cosmetics as one kind of resin composition, the obtained flaky composite particles are mixed with other components, and a disper, a roll mill or the like is used. And a step of dispersing by a known method.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

[Manufacture of scale-like composite particles]
By carrying out the following steps, the scaly composite particles of Examples 1 to 6 and Comparative Examples 1 and 2 were produced.

<Example 1>
(Preparation process)
As the flaky particles, flaky alumina particles were prepared. The flaky alumina particles had a volume average particle diameter of 8.3 μm and an average thickness of 0.24 μm.

(Scale-like activated particle preparation process)
A slurry was prepared by adding 10 g of scaly alumina particles and 50 ml of ion-exchanged water to a stirring tank. To this slurry, an acidic solvent obtained by diluting 1 ml of 60% by volume hydrofluoric acid with 50 ml of ion exchange water was added and stirred for 3 minutes. The temperature in the stirring vessel at this time was 25 ° C. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. As a result, particles A as scale-like activated particles were obtained.

(Scale-like catalyst support particle preparation process)
Next, 50 ml of ion-exchanged water was added to another stirring tank, and the entire amount of the particles A was added and stirred for 1 minute to prepare a slurry containing the particles A. To this slurry, 0.25 g of stannous fluoride as a catalyst and 50 ml of ion-exchanged water were added and stirred for 5 minutes. The temperature in the stirring vessel at this time was 55 ° C. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. As a result, particles B as scaly catalyst-carrying particles were obtained.

(Scale-like composite particle production process)
Next, 900 ml of ion-exchanged water was added to another stirring tank, and the entire amount of the particles B was added and stirred for 1 minute to prepare a slurry containing the particles B. The following aqueous solutions (1) to (3) were added to this slurry, and the electroless plating process was advanced by stirring for 10 minutes. The temperature in the stirring tank at this time was 30 degreeC. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. Thereby, particles C as scale-like composite particles were obtained.

(1) An aqueous solution in which 1.75 g of silver nitrate and 7.8 ml of 25% by volume ammonia water are dissolved in 50 ml of ion-exchanged water (2) An aqueous solution in which 0.7 g of sodium hydroxide is dissolved in 50 ml of ion-exchanged water (3) Glucose An aqueous solution in which 10.5 g is dissolved in 50 ml of ion-exchanged water Silver nitrate corresponds to a metal salt, sodium hydroxide corresponds to a pH adjuster, glucose corresponds to a reducing agent, and aqueous ammonia corresponds to a complexing agent.

(Protection process)
Next, 100 ml of ion-exchanged water and 1 ml of New Dain Silver (manufactured by Yamato Kasei Laboratories) were added to another stirring tank, and the entire amount of particles C was added and stirred for 1 minute. . Thereby, the corrosion suppression layer as a protective layer was formed on the surface of the particle C. After stirring, the slurry was subjected to solid-liquid separation, washed with ion exchange water, and further dried in a vacuum environment at 110 ° C.

  Thus, the scaly composite particles of Example 1 were produced. The scaly composite particles of Example 1 have scaly particles made of alumina, fine particles made of silver, and a corrosion inhibition layer.

<Example 2>
Composite particles were produced in the same manner as in Example 1 except that scaly alumina particles having a volume average particle diameter of 9.5 μm and an average thickness of 0.19 μm were used.

  The scaly composite particles of Example 2 have scaly particles made of alumina, fine particles made of silver, and a corrosion inhibition layer.

<Example 3>
In the preparation step, scaly composite particles were produced by the same method as in Example 1 except that scaly alumina particles having a volume average particle diameter of 8.8 μm and an average thickness of 0.24 were used.

  The scaly composite particles of Example 3 have scaly particles made of alumina, fine particles made of silver, and a corrosion inhibition layer.

<Example 4>
(Preparation process)
As the flaky particles, flaky alumina particles were prepared. The flaky alumina particles had a volume average particle diameter of 9.6 μm and an average thickness of 0.22 μm.

(Scale-like activated particle preparation process)
200 g of scaly alumina particles prepared in a stirring tank and 1000 ml of ion-exchanged water were added to prepare a slurry. An acidic solvent obtained by diluting 20 ml of 60% by volume hydrofluoric acid with 1000 ml of ion-exchanged water was added to the slurry and stirred for 3 minutes. The temperature in the stirring vessel at this time was 25 ° C. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. Thereby, particles D as scale-like activated particles were obtained.

(Scale-like catalyst support particle preparation process)
Next, 1000 ml of ion-exchanged water was added to another stirring tank, and the entire amount of the particles D was added and stirred for 1 minute to prepare a slurry containing the particles D. To this slurry, 4 g of stannous fluoride as a catalyst and 1000 ml of ion exchange water were added and stirred for 5 minutes. The temperature in the stirring vessel at this time was 52 ° C. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. As a result, particles E as scaly catalyst-carrying particles were obtained.

(Scale-like composite particle production process)
Next, 4000 ml of ion-exchanged water was added to another stirring tank, and the entire amount of the particles E was added and stirred for 1 minute to prepare a slurry containing the particles E. The following aqueous solutions (4) to (6) were added to this slurry, and the electroless plating process was advanced by stirring for 10 minutes. The temperature in the stirring tank at this time was 30 degreeC. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. Thereby, particles F as scale-like composite particles were obtained.

(4) An aqueous solution in which 35 g of silver nitrate and 157 ml of 25% by volume ammonia water are dissolved in 1000 ml of ion-exchanged water (5) An aqueous solution in which 14 g of sodium hydroxide is dissolved in 1000 ml of ion-exchanged water (6) 210 g of glucose in 1000 ml of ion-exchanged water Dissolved aqueous solution Silver nitrate corresponds to a metal salt, sodium hydroxide corresponds to a pH adjuster, glucose corresponds to a reducing agent, and aqueous ammonia corresponds to a complexing agent.

(Protection process)
Next, in still another stirring tank, 2000 ml of ion-exchanged water and 20 ml of New Dain Silver (manufactured by Yamato Kasei Laboratories) were added, and the entire amount of particles F was added and stirred for 1 minute. . Thereby, the corrosion suppression layer as a protective layer was formed on the surface of the particle F. After stirring, the slurry was subjected to solid-liquid separation, washed with ion exchange water, and further dried in a vacuum environment at 110 ° C.

  Thus, the scaly composite particles of Example 4 were produced. The scaly composite particles of Example 4 have scaly particles made of alumina, fine particles made of silver, and a corrosion inhibition layer.

<Example 5>
(Preparation process)
As the flaky particles, flaky alumina particles were prepared. The flaky alumina particles had a volume average particle diameter of 9.6 μm and an average thickness of 0.22 μm.

(Scale-like activated particle preparation process)
10 g of scaly alumina particles prepared in the stirring tank and 50 ml of ion-exchanged water were added to prepare a slurry. An acidic solvent obtained by diluting 1 ml of 60% by volume hydrofluoric acid with 50 ml of ion exchange was added to the slurry and stirred for 3 minutes. The temperature in the stirring vessel at this time was 25 ° C. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. Thereby, particles G as scale-like activated particles were obtained.

(Scale-like catalyst support particle preparation process)
Next, 100 ml of ion-exchanged water was added to another stirring tank, and the entire amount of the particles G was added and stirred for 1 minute to prepare a slurry containing the particles G. Here, surface adjustment was performed for the purpose of facilitating adhesion of the catalyst. To this slurry, 20 ml of a surface conditioner (trade name: “Condizer SP”, manufactured by Okuno Pharmaceutical Co., Ltd.) was added and stirred for 10 minutes. The temperature in the stirring vessel at this time was 53 ° C. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. Subsequently, 0.2 g of stannous chloride as a catalyst, 1 ml of 35% by volume hydrochloric acid and 100 ml of ion-exchanged water were added to this slurry, and the mixture was stirred for 5 minutes. The temperature in the stirring tank at this time was 26 degreeC. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. Thereby, particles H as scaly catalyst-carrying particles were obtained.

  Next, 100 ml of ion-exchanged water was added to another stirring tank, and the whole amount of the particles H was added and stirred to prepare a slurry containing the particles H. To this slurry was added a palladium chloride solution prepared by dissolving 0.01 g of palladium chloride as a catalyst and 0.01 g of 35% by volume of hydrochloric acid with 1 ml of ion-exchanged water, followed by stirring for 5 minutes. The temperature in the stirring tank at this time was 40 degreeC. After stirring, the slurry was subjected to solid-liquid separation and washed with ion exchange water. As a result, particles I as further scaly catalyst-supported particles supported by a palladium catalyst were obtained.

(Scale-like composite particle production process)
Next, 100 ml of ion-exchanged water was added to yet another stirring tank, and the whole amount of the particles I was added and stirred for 1 minute to prepare a slurry containing the particles I. The aqueous solutions (7) to (9) below were added to this slurry, and the electroless plating process was advanced by stirring for 10 minutes. The temperature in the stirring vessel at this time was 68 ° C. After stirring, the slurry was subjected to solid-liquid separation, washed with ion exchange water, and further dried in a vacuum environment at 110 ° C. Thereby, particles J as scale-like composite particles were obtained.

(7) An aqueous solution in which 5 g of nickel sulfate is dissolved in 10 ml of ion-exchanged water (8) An aqueous solution in which 20 g of sodium hypophosphite is dissolved in 20 ml of ion-exchanged water (9) 3.5 sodium succinate in 50 ml of ion-exchanged water Dissolved aqueous solution Nickel sulfate corresponds to a metal salt, sodium hypophosphite corresponds to a reducing agent, and sodium succinate corresponds to a complexing agent.

  Thus, the scaly composite particles of Example 5 were produced. The scaly composite particles of Example 5 have scaly particles made of alumina and fine particles made of a nickel phosphorus alloy.

<Example 6>
In the preparation step, scaly glass particles were used as scaly particles. The scale-like glass particles had a volume average particle diameter of 12.7 μm and an average thickness of 0.52 μm. Otherwise, scale-like composite particles were produced in the same manner as in Example 1.

  The scaly composite particles of Example 6 have scaly particles made of glass, fine particles made of silver, and a corrosion-inhibiting layer.

<Comparative Example 1>
When electroless plating treatment is performed in the flaky composite particle preparation step, the aqueous solution charged into the flaky catalyst-carrying particles is 15.75 g of silver nitrate and 70 ml of 25% by volume of aqueous ammonia from (1) to (3) of Example 1, respectively. Example 1 was replaced with an aqueous solution in which 400 g of ion-exchanged water was dissolved, an aqueous solution in which 6.3 g of sodium hydroxide was dissolved in 400 ml of ion-exchanged water, and an aqueous solution in which 95 g of glucose was dissolved in 400 ml of ion-exchanged water. Scale-like composite particles were prepared in the same manner as in Example 1. The scaly composite particles of Comparative Example 1 have scaly particles made of alumina, fine particles made of silver, and a corrosion inhibition layer.

<Comparative example 2>
In the preparation step, scaly composite particles were produced by the same method as in Example 1 except that scaly alumina particles having a volume average particle diameter of 8.7 μm and an average thickness of 0.23 μm were used.

[Characteristic evaluation]
The scale-like composite particles of Examples 1 to 6 and Comparative Examples 1 to 2 were subjected to SEM, visual observation, and electronic image capturing. From the observation by SEM, the adhesion state of the fine particles was evaluated. The color tone was examined from visual observation. From the obtained electronic image, the average value m, the standard deviation s and the coefficient of variation CV, the adhesion rate of fine particles, and the average particle diameter were examined. Furthermore, the resin composition was produced using each scale-like composite particle, and the glitter was evaluated. Moreover, in order to investigate whether the raw material cost resulting from the quantity of microparticles | fine-particles was suppressed, the average coating amount of microparticles | fine-particles was investigated from the analysis by an atomic absorption photometer. Note that, as described above, the thickness of the scaly composite particles represents the thickness including the protective layer (corrosion suppressing layer) when the protective layer is included.

<SEM observation>
The scaly composite particles of Examples 1 to 6 and Comparative Examples 1 and 2 were photographed at a magnification of 10,000 using a field emission electron microscope (FE-SEM). The obtained electronic images are shown in FIGS.

(Particle adhesion state)
2 to 9 show electronic images of the scaly composite particles of Examples 1 to 6 and Comparative Examples 1 and 2, respectively. In the electronic images of the flaky composite particles shown in FIGS. 2 to 7 (Examples 1 to 6) and FIG. 9 (Comparative Example 2), the fine particles are scattered and island-like on the surface of the flaky particles. The adhering appearance was captured. In the electronic image of the scaly composite particles shown in FIG. 8 (Comparative Example 1), it was captured that the fine particles covered the entire surface of the scaly particles. The results are shown in the “attachment state” column of Table 1 below.

<Visual observation>
Further, the result of visual observation is shown in the “color tone” column of Table 1. The scale-like composite particles of Examples 1 to 6 and Comparative Example 2 exhibited a blackish color tone such as black green, black blue, dark black green, black red, and black gray, whereas the scale-like composite particles of Comparative Example 1 The composite particles had a yellowish white color tone. On the other hand, the black color tone exhibited by the scaly composite particles of Comparative Example 2 was dull and dull compared to the color of the scaly composite particles of Examples 1 to 6.

<Analysis by atomic absorption photometer>
(Average coverage of fine particles)
The scale-like composite particles of Examples 1 to 6 and Comparative Examples 1 and 2 were dissolved in a mixed acid composed of nitric acid and hydrofluoric acid to prepare measurement samples, respectively, and the mass of the fine particle component contained in each measurement sample was determined. The measurement was performed using an atomic absorption photometer (product name: “A-2000”, manufactured by Hitachi High-Tech Fielding Co., Ltd.). The measurement wavelength was 328.1 nm and the gas condition was air-acetylene. By substituting the value of the mass of the fine particle component into the following formula (5), the average coating amount (% by mass) of the fine particles in each scale-like composite particle was calculated. This result is shown in the column of “average coverage (mass%)” in Table 1 below.

In the above formula (5), W1 represents the mass of the fine particles, and W2 represents the mass of the scaly particles.
<Analysis with image processing software>
(Particle adhesion rate)
The scale-like composite particles of Examples 1 to 6 and Comparative Examples 1 and 2 were photographed at a magnification of 50000 times, and by analyzing the electronic images, the adhesion rate of fine particles adhering to the scale-like particles (area%) ) For calculation of the adhesion rate, image processing software (product name: “WinROOF”, manufactured by Mitani Corporation) was used. The results are shown in the column “attachment rate (area%)” in Table 1 below.

(Average particle size of fine particles)
Each measurement sample was prepared by kneading the scaly composite particles of Examples 1 to 6 and Comparative Examples 1 and 2 in an epoxy resin, respectively. Further, each measurement sample was formed into a predetermined shape and then cut by an ion milling method. The cut surface of each measurement sample obtained was photographed at a magnification of 10000 times using a field emission electron microscope (FE-SEM), and 100 particle diameters were selected from the obtained electronic images, and the particle diameter was calculated. The median diameter was determined. For the calculation of the particle diameter of each measurement sample, image processing software (product name: WinROOF, manufactured by Mitani Corporation) was used. The results are shown in the column of “average particle diameter (nm) of fine particles” in Table 1.

<Analysis of scaly composite particles>
(Average value m)
The thicknesses of the scaly composite particles of Examples 1 to 6 and Comparative Examples 1 to 2 were calculated from the electronic images of each measurement sample used for calculating the average particle diameter of the fine particles described above. At this time, 100 scale-like composite particles were selected per image, and the thickness t _i (1 ≦ i ≦ N, N = 100) was calculated, and the average value m was calculated based on the above formula (2). . The results are shown in the column “average value m (μm)” in Table 1.

(Standard deviation s)
The standard deviation of the thickness of the scaly composite particles of Examples 1 to 6 and Comparative Examples 1 and 2 was calculated as follows. That is, the average value m of the thickness of the scaly particles obtained as described above and the thickness t _i (1 ≦ i ≦ N, N = 100) of the 100 scaly composite particles are expressed by the above formula ( The variance s ² was obtained by substituting in 3), and the standard deviation s, which is the square root, was calculated. The result is shown in the column of “standard deviation s” in Table 1.

(Coefficient of variation CV)
The variation in the thickness of the scaly composite particles can be expressed by the standard deviation s. Furthermore, the variation can be grasped without being affected by the number of digits of the value by the coefficient of variation CV obtained by gradually reducing the standard deviation s by the average value m of the thickness. The variation coefficient CV of the thickness of the scaly composite particles of Examples 1 to 6 and Comparative Examples 1 to 2 was calculated from the above formula (4). The results are shown in the column of “Variation coefficient CV (%)” in Table 1.

<Evaluation of glitter>
Each of the scaly composite particles of Examples 1 to 6 and Comparative Examples 1 and 2 and a vehicle as a resin (trade name: “Nippe Acrylic Auto Clear Super”, manufactured by Nippon Paint Co., Ltd.) were kneaded. 6 and resin compositions corresponding to each of the scaly composite particles of Comparative Examples 1 and 2 were prepared. The compounding ratio in the resin composition is that the scale-like composite particles are 10% by mass, and the resin is 90% by mass.

  The obtained resin composition was applied to art paper (trade name: “Tanzaku Paper”, manufactured by Matsumura Printing Co., Ltd.) with an applicator, and naturally dried at room temperature to prepare a coating film.

For each coating film, from the Y value measured according to the method described in the condition a of JIS Z8722 (2009) (color measurement method-reflection and transmission object color), JIS Z8729 (2004) (color display method-L ^* a L ^* , a ^* and b ^* defined in ( ^* b ^* color system and L ^* u ^* v ^* color system) were obtained. Specifically, using a multi-angle spectrocolorimeter (trade name: “X-Rite MA-68II”, manufactured by X-Rite), L at an incident angle of 45 ° and an offset angle of 15 ° from the regular reflection direction. ^* Measured value. The larger the L ^* value, the greater the brightness. The results are shown in the “L ^* ” column of Table 1.

  In addition, in Table 1, the volume average particle diameter and the average thickness of the scale-like particles in Examples 1 to 6 and Comparative Examples 1 and 2 are also described in the column of “scale-like particles”.

[Discussion]
As shown in Table 1 from SEM observation and analysis of electronic images, the scale-like composite particles of Examples 1 to 6 satisfy the following conditions (A) to (D).

(A) The fine particles are attached to the scaly particles in the form of dots or islands. (B) The fine particles have an adhesion rate to the scaly particles of 10 area% to 50 area%. (C) The fine particles have an average particle diameter of 1 nm to 80 nm. (D) The thickness of the scaly composite particles has an average value m of 0.05 μm to 1 μm, and a standard deviation s of 0 <s ≦ 0. 2. The coefficient of variation CV obtained by dividing the standard deviation s by the average value m is 0% <CV ≦ 70%.

Furthermore, it was found that the glitter resin compositions of Examples 1 to 6 had high brightness from the value of “L ^* ”, and thus exhibited high glitter.

  In addition, since the scaly composite particles of Examples 1 to 6 have an average coating amount of fine particles of around 10% by mass of the scaly composite particles, and the amount of fine particles used can be reduced, raw material costs can be suppressed. I knew it was possible. Since the scale-like composite particles of Examples 1 to 6 do not have a reflective layer and the number of manufacturing steps is reduced, it is clear that the manufacturing cost is suppressed.

On the other hand, in the scale-like composite particles of Comparative Example 1, the adhesion rate of fine particles was 98.8 area% exceeding 50 area%, and it was found that the fine particles covered the entire surface of the scale-like particles. Furthermore, the average particle diameter of the fine particles of Comparative Example 1 was more than 80 nm and 88.3 nm. The yellowish white color tone exhibited by the scaly composite particles of Comparative Example 1 is a color tone exhibited by the total reflection of light with respect to the fine particles covering the entire surface of the scaly particles, based on FIG. It was speculated. Further, it was estimated that the high brightness derived from the value of “L ^* ” was due to a yellowish white color tone.

The scale-like composite particles of Comparative Example 2 had a thickness standard deviation s of more than 0.2 and 0.26. Further, the coefficient of variation CV obtained by dividing the standard deviation s by the average value m of the thickness was more than 70% and 77.3%. As described above, the black color tone of the scaly composite particles of Comparative Example 2 was visually dull and dull compared to Examples 1 to 6 from visual observation. The reason for this is that since the CV exceeds 70%, the variation in thickness of each scaly particle, which is a light transmission layer, is large, and as a result, the color tone exhibited varies greatly from scaly composite particle. It is considered a thing. In addition, the glittering resin composition of Comparative Example 2 was dull and lacked in glitter because the brightness was lower than that of Examples 1 to 6 and Comparative Example 1 from the value of “L ^* ”. It is understood.

  Although the embodiments and examples of the present invention have been described as described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  10 scale-like composite particles, 11 scale-like particles, 12 fine particles, 13 weather-resistant coating layer.

Claims (11)

A scaly composite particle in which fine particles comprising a metal or a second metal oxide are adhered on one or more scaly particles selected from the group consisting of a first metal oxide, a resin, mica and glass There,
The fine particles adhere to the scaly particles in the form of dots or islands, the adhesion rate to the scaly particles is 10 area% or more and 50 area% or less, and the average particle diameter is 1 nm or more and 80 nm or less. And
As for the thickness of the scale-like composite particles, the average value m is 0.05 μm or more and 1 μm or less, the standard deviation s is 0 <s ≦ 0.2, and the standard deviation s is divided by the average value m. Scale-like composite particles having a coefficient of variation CV of 0% <CV ≦ 70%.   2. The scaly composite according to claim 1, wherein the fine particles are at least one selected from the group consisting of gold, silver, copper, platinum, tin, palladium, nickel, iron, alloys thereof, and oxides thereof. particle.   The scaly composite particles according to claim 1 or 2, wherein the scaly composite particles include a catalyst component.   The scaly composite particles according to any one of claims 1 to 3, wherein the scaly particles are any one of alumina, silica, and glass. The scaly particles are alumina,
The scaly composite particles according to claim 1, wherein the fine particles are silver.   The scaly composite particles according to any one of claims 1 to 5, wherein the scaly composite particles include one or more protective layers.   A resin composition comprising the scaly composite particles according to claim 1.   The resin composition according to claim 7, wherein the resin composition further includes one or both of the scaly particles and the scaly aluminum particles.   The coating material containing the scale-like composite particle in any one of Claims 1-6. A method for producing the scaly composite particles according to any one of claims 1 to 6,
Preparing the scaly particles;
A step of preparing scaly activated particles by performing an activation treatment on the surface of the scaly particles using an acidic solvent or an alkaline solvent;
A step of preparing scale-like catalyst-carrying particles by carrying a catalyst on the surface of the scale-like activated particles;
A step of depositing the fine particles on the surface of the scale-like catalyst-carrying particles by performing electroless plating treatment on the scale-like catalyst-carrying particles to produce the scale-like composite particles. Production method.   The method for producing scale-like composite particles according to claim 10, further comprising a step of protecting the surface of the scale-like composite particles.