JP5036999B2 - Composition and method for producing the same - Google Patents

Description

The present invention relates to an inorganic powder composite having improved water dispersibility of fine inorganic particles, which is useful in the fields of paints and cosmetics, and a method for producing the same.

Most of inorganic particles such as pigments are produced in an aqueous system and are inherently hydrophilic. However, inorganic particles produced by water-based reactions begin to grow from the moment they are produced and cannot be extracted as ultrafine particles. In addition, in water, the particles tend to agglomerate with each other due to their polarity, making redispersibility difficult. A good dispersion. In order to facilitate the subsequent handling, once dried and powdered, the particle surface is activated, the particles are connected with a very strong cohesive force, and the redispersibility in polar water is further enhanced. It will be difficult. On the other hand, the use of inorganic particles such as pigments in water-based systems is infinitely equivalent to water-based paints, paints, cosmetics, foodstuffs, water-based inks and the like. In recent years, inorganic particles used in these applications have been required to be finer and more dispersible with the advancement and refinement of equipment and methods of use. To give an example of these applications, for example, titanium oxide and zinc oxide, which are often used as UV-cutting materials for cosmetic sunscreen agents, are essentially white powders that form a cloudy solution that is applied to the face and body. Then, since it becomes whitish, methods for making ultrafine particles and increasing transparency have been actively studied. Moreover, since the pigments for the ink jet printer provides clear printed image finer particles, an inorganic pigment was not used in too large so far, and inorganic pigments are noted for raising the recent weather resistance, fine particles As a result, it has been actively studied. However, in the above example, a very strong crushing force is required to make inorganic particles finely dispersed in water, and a large amount of surfactant is required to suppress dispersion and subsequent reaggregation. It is. (For example, refer to Patent Document 1) In this case, there is a limit to the fineness of the particles, and the use is limited depending on the type and amount of the active agent. There is a demand for inorganic fine particles that can be easily dispersed.

JP 2001-207060 A

  The present invention has been made under such circumstances, and an object of the present invention is to provide an inorganic powder composite having fine inorganic particles and being easily dispersible in water, and a method for producing the same.

一般式（１）
（但し、式中Ｒは水素原子、カルボキシル基、ヒドロキシル基を有していても良い、アルキル基乃至はアルケニル基を表し、Ｘは水素乃至はアルカリ金属乃至は炭素数２３以下のポリオキシエチレンを表す。）
（２）一般式（１）に表されるカルボン酸誘導体が炭素数１０以下のモノ、ジ又はトリカルボン酸のアルカリ塩もしくはポリオキシエチレン付加物であって、１種又は２種以上である（１）に記載の方法。
（３）一般式（１）に表されるカルボン酸誘導体重合物がポリアクリル酸またはポリメタアクリル酸のアルカリ塩もしくはポリオキシエチレン付加物であって、１種又は２種以上である（１）又は（２）に記載の方法。
（４）一般式（１）に表され且つ式中Ｘが水素であるカルボン酸が炭素数１０以下のモノ、ジ又は／及びトリカルボン酸の１種又は２種以上であって、一般式（１）に表されるカルボン酸誘導体が炭素数１０以下のカルボン酸のポリオキシエチレン付加物の１種又は２種以上である（１）〜（３）のいずれかに記載の方法。
（５）一般式（１）に表されるカルボン酸誘導体重合物がポリアクリル酸またはポリメタアクリル酸のアルカリ塩もしくはポリオキシエチレン付加物あって、単独または複合物である（１）〜（４）のいずれかに記載の方法。
（６）金属塩が亜鉛、鉄、アルミニウム、マグネシウム、チタニウム、バリウム、マンガン、セリウム、コバルト、カルシウム、カドミウム、ストロンチウム、銅、クロミニウム、ジルコニウム、金、銀の無機酸塩である（１）〜（５）のいずれかに記載の方法。
（７）前記無機粉体複合体中の無機粉体の粒子径が０．１μｍ以下であって、粒子同士が互いに独立して存在することを特徴とする（１）〜（６）のいずれかに記載の方法。
（８）前記有機溶媒がメタノール、エタノール、イソプロパノールの単独又は混合物である（１）〜（７）のいずれかに記載の方法。
（９）（１）〜（８）の何れかに記載の方法で無機粉体複合体を製造し、当該無機粉体複合体を含有させることを特徴とする皮膚外用剤の製造方法。
（１０）（１）〜（８）の何れかに記載の方法で無機粉体複合体を製造し、当該無機粉体複合体を含有させることを特徴とする水系ネールエナメルの製造方法。
（１１）（１）〜（８）の何れかに記載の方法で無機粉体複合体を製造し、当該無機粉体複合体を含有させることを特徴とする水系インクの製造方法。
（１２）（１）〜（８）の何れかに記載の方法で無機粉体複合体を製造し、当該無機粉体複合体を含有させることを特徴とする水系塗料の製造方法。 In view of such circumstances, the present invention has been intensively studied for an inorganic powder composite in which inorganic particles are fine and easy to disperse in water. As a result, inorganic fine particles and a carboxyl represented by the general formula (1) are obtained. The inventors have found that an inorganic powder composite comprising an acid derivative and / or a carboxylic acid derivative polymer represented by the general formula (1) has such characteristics, and has completed the invention. That is, the present invention is as follows.
(1) water and methanol, ethanol, isopropanol, Jio Le, ketone, tetrahydrofuran, a mixture of one or more organic solvents selected et al do you and ethylene glycol monobutyl ether, formula (1) the number of carbon atoms represented and Shikichu X is represented in the carboxylic acid having 10 or less carbon atoms and / or 該Ka carboxylic acid polymer and / or the general formula is hydrogen (1) and Shikichu X is other than hydrogen A method for producing an inorganic powder composite, comprising dissolving 10 or less carboxylic acid derivatives and / or a polymer of the carboxylic acid derivative and a metal salt, neutralizing or reducing the polymer, and polymerizing if necessary.

General formula (1)
(In the formula, R represents a hydrogen atom, a carboxyl group, or a hydroxyl group, and represents an alkyl group or an alkenyl group, and X represents hydrogen, an alkali metal, or polyoxyethylene having 23 or less carbon atoms. To express.)
(2) The carboxylic acid derivative represented by the general formula (1) is an alkali salt or polyoxyethylene adduct of a mono-, di- or tricarboxylic acid having 10 or less carbon atoms, and is one or two or more (1 ) Method.
(3) The carboxylic acid derivative polymer represented by the general formula (1) is an alkali salt or polyoxyethylene adduct of polyacrylic acid or polymethacrylic acid, and is one or more kinds (1) Or the method as described in (2).
(4) A generally formula (1) represented and Shikichu X is hydrogen der Luca carboxylic acids having 10 or less carbon atoms mono-, one or more di- and / or tricarboxylic acids of the general formula the method according to any of the carboxylic acid derivative represented in (1) is one or more polyoxyethylene adducts of mosquito carboxylic acids having 10 or less carbon atoms (1) to (3).
(5) The carboxylic acid derivative polymer represented by the general formula (1) is an alkali salt or polyoxyethylene adduct of polyacrylic acid or polymethacrylic acid, and is a single compound or a composite (1) to (4) ) Any one of the methods.
(6) The metal salt is an inorganic acid salt of zinc, iron, aluminum, magnesium, titanium, barium, manganese, cerium, cobalt, calcium, cadmium, strontium, copper, chromium, zirconium, gold, silver (1) to ( The method according to any one of 5).
(7) Any one of (1) to (6), wherein the inorganic powder in the inorganic powder composite has a particle diameter of 0.1 μm or less, and the particles exist independently of each other. The method described in 1.
(8) The method according to any one of (1) to (7), wherein the organic solvent is methanol, ethanol, or isopropanol alone or as a mixture.
(9) A method for producing an external preparation for skin, comprising producing an inorganic powder composite by the method according to any one of (1) to (8), and containing the inorganic powder composite.
(10) A method for producing an aqueous nail enamel, wherein an inorganic powder composite is produced by the method according to any one of (1) to (8), and the inorganic powder composite is contained.
(11) A method for producing a water-based ink, wherein an inorganic powder composite is produced by the method according to any one of (1) to (8), and the inorganic powder composite is contained.
(12) A method for producing a water-based paint, wherein an inorganic powder composite is produced by the method according to any one of (1) to (8), and the inorganic powder composite is contained.

  According to the present invention, it is possible to provide an inorganic powder composite having fine inorganic particles and being easily dispersed in water, and a method for producing the same.

The inorganic powder composite of the present invention comprises inorganic fine particles and a carboxylic acid derivative represented by the general formula (1) and / or a carboxylic acid derivative polymer represented by the general formula (1). . Here, the inorganic powder composite of the present invention comprising the inorganic fine particles and the carboxylic acid derivative represented by the general formula (1) and / or the carboxylic acid derivative polymer represented by the general formula (1) is the above-mentioned 2 It is also allowed to have a leaving molecule due to the conjugation of the components. Examples of the leaving molecule include water, alcohol, alkali metal salt, alkali metal hydroxide and the like. Here, the particle diameter refers to the maximum diameter of the inorganic fine particles, and the size is 0.1 μm or less. This range of particle child size varies depending Shito, for the purpose of coloration is generally about 0.1～0.01Myuemu, generally when seeking functions such as an ultraviolet absorber or a disinfectant to emphasize transparency 0 0.01 to 0.001 μm. Further, the inorganic fine particles exist in an independent state in the inorganic powder composite of the present invention.
Present state of the grain terminal size and in the composition of such particles is regulated by the manufacturing method detailed in inorganic type and subsequent stage. Next, the composition ratio of the inorganic fine particles of the present invention to the carboxylic acid derivative represented by the general formula (1) and / or the polymer of the carboxylic acid derivative represented by the general formula (1) is 60% of the inorganic fine particles. The above is desirable. This ratio cannot be generally described because the dispersibility in water varies depending on the type and particle size of the inorganic fine particles, but it is preferably 60% to 99%, more preferably 85% to 99%. The kind of inorganic substance used here is not particularly defined, but if it is described, zinc, iron, aluminum, magnesium, titanium, barium, manganese, cerium, cobalt, calcium, cadmium, strontium, copper, chromium, zirconium, gold, Silver, which is used alone or in the form of an oxide or / and hydroxide, and is a single type or a composite of two or more types.

The carboxylic acid derivatives represented by the general formula (1) used here include alkali salts such as potassium, sodium, lithium and amines of monocarboxylic acids, dicarboxylic acids and tricarboxylic acids, or polyoxyethylene adducts. Of these, fatty acid carbon number of 10 or less is particularly desirable because of its excellent miscibility with water. For example, alkali salts include sodium acetate, potassium propionate, sodium acrylate, triethylamine methacrylate, sodium caproate, lithium oxalate, potassium malonate, sodium succinate, potassium citrate , sodium tartrate, etc. Examples of the polyoxyethylene adduct include polyoxyethylene acrylate and polyoxyethylene methacrylate. Polymers of carboxylic acid derivatives represented by the general formula (1) include sodium acrylate, polyacrylate triethanolamine, polysodium methacrylate, polyethyltriethylamine, and the like as alkali salts. Examples of the adduct include polyoxyethylene acrylic polymer and polyoxyethylene methacrylic polymer having 23 mol or less of oxyethylene chain. The polymerization degree of these polymers is preferably 1000 or less.

(2) Manufacturing method of inorganic powder composite of the present invention The manufacturing method of the inorganic powder composite of the present invention includes a lower fatty acid or a derivative thereof, a lower fatty acid polymer or a mixture thereof in a mixed liquid of water and a water-soluble organic solvent. The derivative and the metal salt are dissolved, neutralized or reduced, and polymerized as necessary. In general, it is known that when a small amount or a large amount of an organic solvent is mixed in a process of hydrolyzing a metal salt in an aqueous system to produce a hydroxide or oxide, the hydrolyzate of the metal salt becomes an oxide. ing. The water-soluble organic solvent used in the production method of the present invention is used for directing the hydrolyzate of the metal salt directly to the oxide, and almost any organic solvent miscible with water can be used. Examples of such organic solvents include alcohols such as methanol, ethanol and isopropanol, diols such as ethanediol, propanediol and butanediol, ketones such as acetone, furans such as tetrahydrofuran, and a molecular weight of 200 or less. And ethylene glycol monoethers such as methoxyethanol and ethoxyethanol. The mixing ratio of such a water-soluble organic solvent varies depending on the type of the lower fatty acid or its derivative or the lower fatty acid polymer, its derivative or metal salt, and also varies depending on the type of the water-soluble organic solvent or reaction by-product used. Although it cannot be generally defined, the weight ratio of water: water-soluble organic solvent is generally in the range of 1: 9 to 9: 1. After completion of the reaction it is preferred to remove excess salts were washed with water or the like.
The lower fatty acid or derivative thereof or the lower fatty acid polymer or derivative thereof used in the production method of the present invention is a monocarboxylic acid as the lower fatty acid as described in detail above for the carboxylic acid derivative represented by the general formula (1). There are acids, dicarboxylic acids and tricarboxylic acids or polyoxyethylene adducts, and those having 10 or less carbon atoms are particularly desirable because of their excellent miscibility with water and water-soluble organic solvents. Examples include acetic acid, propionic acid, acrylic acid, methacrylic acid, caproic acid, oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, etc. These derivatives include polyoxyethylene acrylate, polyoxyethylene methacrylate There are polyoxyethylene adducts having 23 moles or less of oxyethylene chains. Examples of the lower fatty acid polymer include polyacrylic acid and polymethacrylic acid, and derivatives thereof include polyoxyethylene acrylic polymer and polyoxyethylene methacrylic polymer having 23 mol or less of oxyethylene chain of polyoxyethylene adduct.

  Hereinafter, the present invention will be described in more detail with reference to examples. Needless to say, the present invention is not limited to these examples.

  Zinc nitrate hexahydrate (18 g) and acrylic acid (1 g) were dissolved in a mixed solvent of methanol (134 g) and water (41 g) to obtain Liquid A. 3N Caustic soda (56 g) was gradually poured into the liquid A with stirring at room temperature, and heated immediately after the entire amount was poured. When the temperature reached 50 ° C., azobisisobutyronitrile (0.02 g) was added and the temperature was raised as it was. Was continued at the reflux temperature for 1 hour and cooled. After cooling, decantation and filtration were repeated three times using water, and the resulting precipitate was dried at 90 ° C. for 4 hours to obtain a dried product (5.2 g). This was 95% wurtzite zinc oxide. The photomicrograph of this is shown in FIG. It can be seen that fine spherical zinc oxide forms a complex with acrylic acid.

  Zinc chloride (9 g) and polyacrylic acid (degree of polymerization 5000) (2 g) were dissolved in a mixed solvent of ethanol (116 g) and water (91 g) to obtain Liquid A. 6N caustic soda (31 g) was gradually poured into the liquid A under stirring at room temperature, and heating was started 20 minutes after the completion of the total injection, and the mixture was maintained at the reflux temperature for 1 hour and cooled. After cooling, decantation and filtration were repeated three times using water, and the resulting precipitate was dried at 90 ° C. for 4 hours to obtain a dried product (5.9 g). This was 85% wurtzite zinc oxide.

Iron chloride (10 g) and methyl methacrylic acid (2.3 g) were dissolved in a mixed solvent of ethoxyethanol (116 g) and water (140 g) to obtain Liquid A. Slowly inject 6N caustic soda (37 g) into solution A at room temperature with stirring, warm immediately after the total amount is injected, add azobisisobutyronitrile (0.04 g) when the temperature reaches 50 ° C., and heat up as it is Was continued at the reflux temperature for 1 hour and cooled. After cooling, decantation and filtration were repeated three times using water, and the resulting precipitate was dried at 90 ° C. for 4 hours to obtain a dried product (5.6 g). This was 75% Fe ₂ O ₃ type iron oxide.

  A solution A was prepared by dissolving titanium tetrachloride (12 g) and polyoxyethylene (9) acrylate (2.5 g) in ethanol (165 g). Slowly inject 6N caustic soda (51 g) into solution A at room temperature with stirring, warm immediately after the entire amount is added, and add sodium persulfate (0.04 g) when the temperature reaches 50 ° C., and continue at that temperature for 16 hours I let you. Thereafter, the mixture was filtered while maintaining the temperature at 60 ° C., and decantation and filtration were repeated three times using separately prepared water at 60 ° C., and the obtained precipitate was dried at 90 ° C. for 4 hours to obtain a dried product (5 0.1 g) was obtained. This was 80% rutile titanium oxide.

Solution A was prepared by dissolving gold chloride (1 g) in a mixed solvent of isopropanol (100 g) and water (300 g). Separately, trisodium citrate (0.65 g) was dissolved in water (100 g) to obtain solution B. The liquid A was heated to the reflux temperature, the liquid B was added dropwise with stirring, and the liquid was maintained at the same temperature for 1 hour and cooled. After cooling, decantation and filtration were repeated three times using water, and the resulting precipitate was dried at 90 ° C. for 4 hours to obtain a dried product (0.6 g). This was 70% colloidal gold.

Of dry matter Example 1 (0.58 g) with water (300 ml), placed in a 500ml beaker, propeller-type stirrer (blade length 4 cm), and stirred for 1 hour at a rotation speed of 200 rpm, were dispersed, the dispersion A And 100 g of the dispersion A was collected, and water was added to make a total of 1000 g to obtain an aqueous paint 1A. The rest of the dispersion A was redispersed by stirring for 6 minutes at a rotational speed of 6000 rpm with a disper-type stirrer (blade length 3 cm), then 100 g was collected, water was added to make 1000 g as a whole, and the aqueous paint 1B was added. Obtained.

  The dried product (0.176 g) of Example 2 was treated in the same manner as Example 6 to obtain aqueous paints 2A and 2B.

The dried product (0.2 g) of Example 3 was treated in the same manner as in Example 6 to obtain aqueous paints 3A and 3B.

  The dried product of Example 4 (0.188 g) was treated in the same manner as in Example 6 to obtain aqueous paints 4A and 4B.

  The dried product (0.1 g) of Example 5 was treated in the same manner as in Example 6 to obtain aqueous paints 5A and 5B.

According to the following procedure, to create a comparative example 1-4, by using a laser diffraction scattering particle size distribution meter (wet), the with an aqueous paints 1A to 5 A and 1B ～5B, measuring an average particle diameter (mu m) did. The results are shown in Table 1. From the table, water-based paints 1A to 5A and 1B to 5B using the composition of the present invention by the production method of the present invention can easily reach the primary particles even with extremely weak stirring force regardless of the stirring strength at the time of dispersion. It can be seen that they are dispersed. This indicates that the inorganic particles exist independently of each other even in the powder state. On the other hand, the commercially available inorganic particles of Comparative Examples 1 to 4 have not reached the catalog value even when intense stirring force is applied. That is, the commercially available inorganic particles of Comparative Examples 1 to 4 form strong aggregates in the powder state and indicate that they cannot be easily dispersed .

<Comparative Example 1>
Commercially available fine zinc oxide powder (average particle diameter = 0.03 microns m catalog value) 0.15g harvested, 0.01% sodium polyacrylate (degree of polymerization 3000), placed in a 500ml beaker with water (300 ml), propeller stirrer (blade length 4 cm), and stirred for 1 hour at a rotation speed of 200 rpm, were dispersed, and the dispersion liquid F. 100 g of the dispersion F was collected, and water was added thereto to make a total of 1000 g, which was designated as Comparative Example 1A. After redispersing the rest of the dispersion F under Condition 2, 100 g was collected, and water was added thereto to make a total of 1000 g to obtain Comparative Example 1B.

<Comparative example 2>
Commercially available fine titanium oxide powder (average particle size = 0.023μ m catalog value) 0.15g collected and treated in the same manner as in Comparative Example 1 was obtained with Comparative Example 2B and Comparative Example 2A.

<Comparative Example 3>
Commercially available fine iron oxide powder (average particle size = 0.06μ m catalog value) 0.15g collected and treated in the same manner as in Comparative Example 1 was obtained with Comparative Example 3B and Comparative Example 3A.

<Comparative example 4>
Gold colloidal dispersion of a commercial product (average particle size = 0.01 micron m catalog value) using a 10 × 10 mm cell, when measured in an integrating sphere with the spectrometer, as the transmittance of the wavelength 700nm is 80% And diluted with water to obtain Comparative Example 4B.

  The present invention can be applied to paints and cosmetics.

2 is a view showing a micrograph of the composite of Example 1. FIG. (Drawing substitute photo)

Claims (12)

Water and methanol, ethanol, isopropanol, Jio Le, ketone, tetrahydrofuran, in a mixture with one or more organic solvents selected et al do you and ethylene glycol monomethyl ether, table general formula (1) is and Shikichu X is a carboxylic acid having 10 or less carbon atoms and / or 該Ka carboxylic acid polymer and / or represented in the general formula (1) and Shikichu X is 10 or less carbon atoms is other than hydrogen is hydrogen A method for producing an inorganic powder composite, comprising: dissolving a carboxylic acid derivative and / or a polymer of the carboxylic acid derivative and a metal salt, neutralizing or reducing the carboxylic acid derivative, and polymerizing if necessary.

General formula (1)
(In the formula, R represents a hydrogen atom, a carboxyl group, or a hydroxyl group, and represents an alkyl group or an alkenyl group, and X represents hydrogen, an alkali metal, or polyoxyethylene having 23 or less carbon atoms. To express.) The carboxylic acid derivative represented by the general formula (1) is an alkali salt or polyoxyethylene adduct of mono-, di- or tricarboxylic acid having 10 or less carbon atoms, and is one or more kinds. the method of. The carboxylic acid derivative polymer represented by the general formula (1) is polyacrylic acid, an alkali salt of polymethacrylic acid or a polyoxyethylene adduct, and is one or more kinds. The method described. A generally formula (1) represented and Shikichu X is hydrogen der Luca carboxylic acids having 10 or less carbon atoms mono-, one or more di- and / or tricarboxylic acids of the general formula (1) the method according to any one of claims 1 to 3 carboxylic acid derivative represented is one or more polyoxyethylene adducts of mosquito carboxylic acids having 10 or less carbon atoms in the. The carboxylic acid derivative polymer represented by the general formula (1) is an alkali salt or polyoxyethylene adduct of polyacrylic acid or polymethacrylic acid, and is a single compound or a composite. 2. The method according to item 1. The metal salt is an inorganic acid salt of zinc, iron, aluminum, magnesium, titanium, barium, manganese, cerium, cobalt, calcium, cadmium, strontium, copper, chromium, zirconium, gold, or silver. 2. The method according to item 1. The particle diameter of the inorganic powder in the inorganic powder composite is 0.1 μm or less, and the particles are present independently of each other. Method. The method according to any one of claims 1 to 7, wherein the organic solvent is methanol, ethanol, or isopropanol alone or as a mixture. The manufacturing method of the skin external preparation characterized by manufacturing an inorganic powder composite_body | complex by the method of any one of Claims 1-8, and containing the said inorganic powder composite_body | complex. The manufacturing method of the water-based nail enamel which manufactures an inorganic powder composite body by the method of any one of Claims 1-8, and contains the said inorganic powder composite body. An inorganic powder composite is manufactured by the method according to any one of claims 1 to 8, and the inorganic powder composite is contained. An inorganic powder composite is manufactured by the method according to any one of claims 1 to 8, and the inorganic powder composite is contained.

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