JPH0812319A - Inorganic powder having low refractive index, its production and liquid detergent composition and transparent dentifrice composition using the same - Google Patents

Abstract

PURPOSE:To produce a liq. detergent and a dentifrice excellent in washing power and polishing power and having substantially a transparent appearance on a visual sense. CONSTITUTION:In an inorg. powder having low refractive index and the liq. detergent and the dentifrice using this powder as an abrasive material, this inorg. powder having low refractive index of <=1.40 in an aqueous medium is composed of porous particles consisting essentially of SiO2 or SiO2 and Al2O3 and having 1-50mum average grain size in which fine pores having substantially <=100nm diameter occupies 8-80vol.% of the vol. of each particle, and the fine pores are blocked off at the vicinity of the particle surface and a communication with the outside is interrupted.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel low refractive index inorganic powder, a method for producing the same, a liquid detergent composition and a dentifrice composition using the same. More specifically,
The present invention contains an inorganic powder which does not impair the transparency when blended as a polishing agent in a liquid detergent composition or a dentifrice composition having a transparent appearance, a method for producing the same, and an inorganic powder. The present invention relates to a liquid detergent composition and a dentifrice composition.

[0002]

2. Description of the Related Art Liquid detergents for kitchen use for washing vegetables and tableware have hitherto been dominated by those containing only a surfactant as an active ingredient. However, such liquid cleaners show good cleaning power for washing vegetables and liquid or semi-solid oil and dirt attached to dishes, but they are not suitable for cooking food or for a long time. Detergency is insufficient when removing solid oil that has been denatured on cooking utensils when left to stand and dirt that is firmly attached to tableware. For this reason, a kitchen liquid cleaning agent and a powder or paste cleanser are commonly used for cleaning cooking utensils and tableware having solid waste that is difficult to remove.

[0003] By the way, as for the toilet cleaner for bathrooms and bathrooms, there has been a liquid detergent composition in which an abrasive is blended with a liquid detergent to facilitate removal of adhered dirt by utilizing an abrasive action. Proposed. Such a liquid detergent composition has both the detergency of a surfactant and the abrading power of an abrasive and exhibits an excellent detergency effect. However, since it contains an insoluble substance, it becomes cloudy and has an appearance. It is inevitable that the value will decrease.

In order to improve such a defect, an abrasive having a refractive index substantially equal to that of the vehicle is mixed with a transparent vehicle containing a surfactant and other additives to maintain the transparency of the appearance. A liquid containing cleaning agent has been proposed (JP-A-60-110794). By the way, in such an abrasive-containing liquid cleaning agent, the refractive index is 1.
Although it is necessary to use an abrasive having a refractive index of 35 to 1.55, it is actually possible to use a refractive index of 1.44 to 1.4.
Since it is only the amorphous silicic acid anhydride of No. 5, the composition range of the vehicle to be used becomes narrower for a transparent liquid detergent,
It has the drawback of being limited in terms of performance.

Generally, liquid detergents include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ethers, alkyl tertiary amine oxides and the like. It is mainly composed of an aqueous solution containing the nonionic surfactant, and its refractive index is usually about 1.37 to 1.40.
As the abrasive to be added to this, those having a refractive index of 1.40 or less are preferable.

However, the refractive index of amorphous silica and aluminosilicate that have been used as abrasives so far is 1.44 to 1.46, calcium carbonate is 1.66, and those of 1.40 or less are unknown.

That is, as the inorganic powder for abrasives having a low refractive index which has been proposed so far, for example, an extender pigment having a refractive index of 1.42 to 1.53 containing zeolite particles as a main component (JP-A-59). -133265 publication), refractive index 1.4
In the range of 30 to 1.433, there are amorphous silica (Japanese Patent Laid-Open No. 5-208808) having a transmittance of at least 70%, and as an inorganic powder-containing liquid composition having a transparent appearance, An abrasive-containing liquid detergent composition having a transparent appearance (JP-A-60-110794),
In addition to a surfactant, a skin cleanser containing liquid oil and a powder having a refractive index difference with the liquid oil within 0.1 (JP-A-4-91018), a refractive index of 1.35. ~ 1.44
Makeup cosmetics (Japanese Patent Laid-Open No. 63-166819) containing the synthetic flaky metal oxide are known.

[0008] On the other hand, in a dentifrice composition containing an abrasive such as silica, it is also attempted to impart transparency to enhance the commercial value.
What was used after firing at 0 ° C. (JP-A-55-92308), refractive index 1.42 to 1.4 having a specific surface area
No. 5 using silica (Japanese Patent Laid-Open No. 59-163306), one containing an abrasive having a refractive index close to that of a liquid vehicle having a refractive index of 1.36 to 1.47 (Japanese Patent Laid-Open No. Sho 5).
9-23310), refractive index 1.410-1.4.
40 containing synthetic amorphous silica (US Pat. No. 3,939,262, US Pat. No. 4,0072,260), water-soluble or water-insoluble alkali metal phosphate having a refractive index of 1.435 to 1.465 Those containing a salt (British Patent No. 1424034), those containing spherical fine silica gel (JP-A-62-87507) and the like have been proposed.

Further, when an abrasive is mixed in a liquid detergent or a liquid toothpaste, its dispersion stability is usually not good,
In order to improve the dispersion stability, it is necessary to add a dispersant that does not have a cleaning action or to use a component that has a thickening action in combination. However, using a wide variety of components makes it difficult to adjust the physical properties. On top of that, the high cost due to the addition of extra components is unavoidable.

One of the causes of such poor dispersibility of the abrasive is that the density of the inorganic powder used as the abrasive is 2 g / cm ³ or more, which is about the density of the vehicle of the liquid detergent composition. It is considerably larger than 1 g / cm ³ . Therefore, in order to improve the dispersion stability of the abrasive in the liquid cleaning agent, it is desirable to reduce the density of the abrasive so as to approach the density of the vehicle.

As described above, with respect to the abrasives mixed in the liquid detergent and the liquid toothpaste, the general range of the refractive index is, for example, 1.35 to 1.55 and the numerical value of 1.40 or less. Even though the above description is made, there is no known substance that actually exhibits a refractive index of 1.40 or less in the aqueous vehicle.

As described above, the synthetic flaky metal oxide compounded in the makeup cosmetics, the zeolite used as the light diffusing agent, or the heat-treated zeolite has a refractive index of 1.40 or less. It is known that powders exist, but these show a refractive index of 1.40 or less in a non-aqueous medium such as oil or an organic solvent, but in an aqueous medium, that is, a medium containing water or water. Refractive index 1.40
Have been confirmed to be larger than. For example, JP-A-63
Amorphous silica described in JP-A-166819 as a refractive index of 1.38 has a refractive index of 1.43 in a mixture of water and glycerin, and JP-A-5-27951.
Zeolite, which has been described as a refractive index of 1.37 in Japanese Patent No. 0, had a refractive index of 1.46 in the same aqueous medium.

The phenomenon that the refractive index becomes larger in the aqueous medium than in the non-aqueous medium can be explained as follows.

Usually, amorphous silica contains water or hydroxyl groups in a proportion of several wt% or more, and zeolite has water of crystallization. For example, in the case of NaA type, its content is 2%.
It is as high as 2% by weight. Further, these have pores, and those dried to reduce water content are used as a desiccant. This utilizes the fact that the water present in the air is adsorbed in these pores from which water has been removed. Therefore, once the water is removed by the heat treatment, the pores are filled with air, and when the organic solvent is used as the immersion liquid when measuring the refractive index, air is present in the pores. It is considered to be in the same state as it was. On the other hand, when an aqueous medium is used as the immersion liquid, it is considered that water enters the pores again and is replaced with air.

A substance having pores, which is sufficiently smaller than the wavelength of light, has a refractive index which is an average of the original value of the substance and the value of the contents of the pores. It is considered that there is a difference in the refractive index depending on the contents of. Therefore, the refractive index of water is 1.333, whereas that of air is 1.33.
From 0003, it can be understood that when an aqueous medium is used as the immersion liquid, the refractive index when water enters the pores becomes high.

[0016]

Under the above circumstances, the present invention has a low refractive index in an aqueous medium which is suitable as an abrasive-containing liquid detergent having a transparent appearance and an abrasive for liquid toothpaste. The purpose of the present invention is to provide a low-density inorganic powder having a high rate and a transparent liquid detergent composition and a liquid dentifrice composition containing the same.

[0017]

Means for Solving the Problems The present inventors have conducted various studies on abrasives for blending in liquid detergents and liquid toothpaste, and as a result, have found that SiO ₂ having a specific amount of pores of a specific diameter.
Alternatively, with respect to a powder composed of porous particles containing SiO ₂ and Al ₂ O ₃ as main components, the pores are closed near the surface so that the pores are blocked from communicating with the outside of the particles, and When the refractive index is adjusted to 1.40 or less, it is possible to maintain a visually substantially transparent appearance even when blended with a liquid composition containing water such as a liquid detergent or a liquid toothpaste, and the inorganic particles Contains air, its density is reduced and shows good dispersion stability, and such a porous particle is obtained by heat-treating the raw material particles at a specific temperature, It was found that this can be obtained by performing a blocking treatment in the vicinity of the surface in order to block the communication with and, and the present invention has been completed based on this finding.

That is, the present invention relates to SiO ₂ or SiO ₂
And Al ₂ O ₃ as main components, and pores having a diameter of substantially 100 nm or less occupy 8 to 80% by volume of average particle diameter 1 to
Low refraction characterized by comprising 50 μm porous particles, the pores being blocked near the particle surface to block communication with the outside, and having a refractive index of 1.40 or less in an aqueous medium. Rate inorganic powder.

This low-refractive-index inorganic powder is, for example, SiO ₂
Or substantially 100 containing SiO ₂ and Al ₂ O ₃ as main components
The water-insoluble porous particles having an average particle size of 1 to 50 μm in which pores having a diameter of nm or less account for 8 to 80% by volume are
It can be produced by heat-treating at 1000 ° C. until the water content in the pores is substantially completely removed, and then performing pore-blocking treatment.

The inorganic powder of the present invention is substantially 100 nm.
It is composed of porous particles having pores of the following diameters, and when the pore diameter is substantially larger than 100 nm, the particles as a whole do not exhibit a uniform refractive index. Even if dispersed in an aqueous medium having such a composition, the appearance cannot be made transparent. The structure of the pores is not particularly limited, and may be independent pores, a network-structured tunnel structure or well-type pores.

Further, in the inorganic powder of the present invention, the pores must occupy 8 to 80% by volume of the particles. The smaller the pore volume, the main component SiO ₂
Alternatively, the ratio of the refractive index of SiO ₂ and Al ₂ O ₃ contributing to the refractive index of the particles increases, and the refractive index of the inorganic powder increases. When the pore volume is less than 8% by volume, the refractive index of 1.40 or less cannot be obtained in the aqueous medium even if the pores are blocked from communicating with the outside. On the other hand, when the pore volume exceeds 80% by volume, it becomes practically difficult to manufacture the inorganic powder.

The inorganic powder of the present invention has the above-mentioned pore diameter and pore volume, and contains SiO ₂ or SiO ₂ and Al ₂ O ₃ as main components. These components are water-insoluble inorganic substances having a refractive index in the air of about 1.55 or less,
The raw material is inexpensive and the above-mentioned pore diameter and pore volume can be easily obtained.

The inorganic powder containing SiO ₂ or SiO ₂ and Al ₂ O ₃ as main components is not particularly limited as long as it can easily obtain the above-mentioned pore size and pore volume. Further, it may have any crystal structure or composition, but amorphous silica, silica gel, natural or synthetic zeolite are particularly preferable.

As the amorphous silica or silica gel having the above-mentioned pore diameter and pore volume, those commercially available in general can be used, and known methods such as (1) can be used.
A vapor phase method in which SiCl ₄ or the like is vaporized and then hydrolyzed with high temperature steam, (2) an acid treatment method in which aluminum is leached from an aluminosilicate such as zeolite by acid treatment, (3) silica gel is treated with an acid A sol agglomeration method of obtaining a porous body by aggregating with an electrolyte, heat, etc., (4) an alkoxide method of hydrolyzing a silicon alkoxide,
(5) Water glass (sodium silicate aqueous solution) is used as a main raw material, and an acid, alcohol or the like is added thereto to aggregate the silica content. (6) Water glass is W / O
B ₂ O and Na ₂ O are eluted by an interfacial reaction method in which the treatment is carried out in the same manner as in (5) above, (7) for example, by acid treatment of B ₂ O ₅ —Na ₂ O—SiO ₂ phase-separated glass fine particles. Then, it can be easily produced by using a chemical dissolution treatment method of making the material porous.

Among the above production methods, the water glass agglomeration method (5) is frequently used for the production of porous silica. According to this method, the average pore diameter is about 0.5 to several hundreds nm, A silica porous material having a pore volume of about 1 to 85% by volume can be easily produced, and the pore diameter and the pore volume can be controlled by the pH during the reaction. Those are suitable as the inorganic porous particles in the present invention.

Natural or synthetic zeolite can also be used as the inorganic porous particles in the present invention. Zeolite is naturally defined by its crystal structure in its pore diameter and pore volume, and all zeolites have a pore diameter of 0.8 nm or less and a pore volume of 10 to 50% by volume. It is suitable as the inorganic porous particle in the invention.

The inorganic porous particles in the present invention are SiO
₂ or SiO ₂ and Al ₂ O ₃ are the main components, but various additives can be added to the inorganic porous particles as desired components depending on the purpose of use. But,
Addition of an element having a large atomic weight (heavy element) tends to increase the refractive index of the inorganic porous particles, and is not preferable, and even if it is added, it should be added in a small amount.

By adding an additive, the pore diameter and / or the pore volume of the inorganic porous particles can be controlled. When the above-mentioned zeolite is used as the inorganic porous particles, it is possible to change the pore diameter and the pore volume by ion-exchanging the exchangeable cations in the zeolite crystal lattice. For example, Na
Although the pore size of A-type zeolite is 0.4 nm, it can be changed to 0.3 nm by replacing Na with K, and can be changed to 0.5 nm by replacing it with Ca.

The inorganic powder of the present invention comprises the above components,
The pores of the inorganic porous particles having a pore size and a pore volume are
It is necessary to perform a blocking treatment near the surface so as to block the communication with the outside of the particle, and make the refractive index in the underwater medium 1.40 or less. The term "communication" as used herein means a state in which water does not enter the pores. Therefore, even if there is an opening having a diameter smaller than the molecular diameter of water (0.28 nm), the communication with the outside is blocked. Further, when the refractive index exceeds 1.40, a compound having a visually substantially transparent appearance cannot be obtained when compounded with a liquid detergent as an abrasive.

Next, the inorganic powder of the present invention having the above-mentioned properties can be manufactured, for example, as follows. Water is usually adsorbed and present in the pores of the inorganic porous particles. In this way, when water is present in the pores, the refractive index of the inorganic porous particles is higher than 1.40, and water remains in the pores even when the communication with the outside of the pores is blocked. Therefore, it is difficult to set the refractive index of the inorganic powder to 1.40 or less. Therefore, in the method of the present invention,
Before performing the treatment of blocking the communication of the inorganic porous particles with the outside of the pores, an operation of removing water in the pores is performed. As an operation for removing water in the pores, 100 to 1
A heat treatment operation is performed at a temperature in the range of 000 ° C. If the heat treatment temperature is lower than 100 ° C, the removal of water in the pores may be insufficient, and if it exceeds 1000 ° C, the crystal structure changes and the pore volume decreases. The maximum temperature allowed by the heat treatment is determined within the range in which the pores of the inorganic porous particles maintain the above-mentioned pore diameter and pore volume. For example, in the case of NaA-type zeolite, when the heat treatment is performed at a temperature of 800 ° C. or higher, the crystal structure changes, and as a result, the pores disappear, so the maximum temperature that can be used in the heat treatment is 800 ° C. In the case of amorphous porous silica,
No change in crystal structure is observed, but the pore volume is significantly reduced by heat treatment at a temperature higher than 1000 ° C,
It cannot be used as the inorganic porous particle of the present invention. As for the pore structure of the inorganic porous particles containing SiO ₂ or SiO ₂ and Al ₂ O ₃ as the main components, the pore volume is remarkably reduced by the heat treatment at a temperature higher than 1000 ° C. as described above. This heat treatment can also be done under vacuum to complete the removal of water.

Immediately after the heat treatment, when the refractive index of the inorganic porous powder in an aqueous solution is measured, there are some which show a value of 1.40 or less as the object of the present invention. When the time course is examined while the body is dispersed in an aqueous medium, the refractive index rises within a few days at the latest. This is considered to indicate that although the pore size of the inorganic porous powder is reduced by the heat treatment and the penetration of water molecules is hindered to some extent, water penetrates into the pores over time.

In the method of the present invention, the porous particles thus heat-treated are subjected to a plugging treatment near the surface in order to block the communication between the pores and the outside of the particles. As this treatment, a method of reacting an organosilicon compound having one or more functional groups capable of reacting with a hydroxyl group, a method of coating a water-insoluble polymer compound, SiO ₂ or Si
Examples include a method of coating a water-insoluble amorphous inorganic compound containing O ₂ and Al ₂ O ₃ as main components.

First, a method of reacting an organosilicon compound having at least one functional group capable of reacting with a hydroxyl group will be described.

The surface of the inorganic porous particles containing SiO ₂ or SiO ₂ and Al ₂ O ₃ as main components is usually a surface hydroxyl group represented by -M-OH (M is a metal element contained in the inorganic porous particles). Exists. This surface hydroxyl group is, for example, -SiX (X is an element of Group VIIb in the periodic table) of an organosilicon compound,
SiOR (R is an alkyl group), -SiNH, -SiOH
It can easily react with functional groups such as to form chemical bonds. Examples of the organosilicon compound having at least one functional group capable of reacting with the surface hydroxyl group of such particles include, for example, alkylalkoxysilane, fluoroalkylsilane, alkylchlorosilane, alkyldisilazane, fluorodisilazane, 2,4,6,6. Examples thereof include cyclic siloxanes such as 8-tetramethylcyclotetrasiloxane and compounds generally used as silane coupling agents. Among these, those which react with the inorganic porous particles, and adjacent organic silicon compounds react with each other to form a polymer film on the surface of the particles are also included. The silane coupling agent is a compound having an organic functional group and a hydrolyzable group bonded to a silicon atom in one molecule represented by the following formula.

[0035]

Embedded image

In the above general formula (I), Z is hydrolyzed.
Groups, specifically halogen groups such as chloro,
Inorganic groups such as alkoxy groups such as Si group and ethoxy group
It is possible to react with the surface hydroxyl groups of the porous particles.
n is usually 2 or 3. R ¹Is a monovalent hydrocarbon group, R²
Is a divalent hydrocarbon group connecting Y and a silicon atom. Y
Is an organic functional group such as vinyl group, amino group, methacrylic group
Group, epoxy group, mercapto group and the like.

Examples of such silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, 3-chloropropyltrimethoxysilane and 3
-Aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. be able to.
In the present invention, two or more kinds of these organosilicon compounds may be used at the same time. Further, the reaction between the organosilicon compound and the surface hydroxyl group of the inorganic porous particles can be easily carried out by a liquid phase or a gas phase reaction.

Next, the method of coating with a water-insoluble polymer compound is as follows.
A method for coating the surface of porous particles with polymethylmethacrylate, urea resin, polyethylene, polycarbonate, polypropylene, polyvinyl chloride, nylon, ABS resin, polymethylmethacrylate, tetrahydrofuran, silicone, which is highly water-insoluble. In order to coat the surface of the inorganic porous particles with a molecular compound, a method of dissolving or dispersing the water-insoluble polymer compound in a solvent and then dispersing the inorganic porous particles to be adsorbed on the particle surface, or inorganic In a solvent in which the porous particles are dispersed, a method of polymerizing the polymer compound in question to coat the surface, or
A method is used in which the inorganic porous particles are placed in the presence of a polymerizable substance (gas phase or liquid phase) and a polymerization reaction is carried out on the surface of the particles.

The solvent used when treating the inorganic porous particles is preferably one that does not penetrate into the pores. Such a solvent is preferably selected from those having a molecular cross-sectional area larger than the pore size of the particles to be treated.

The inorganic porous particles treated by the above method are washed or heat-treated for the purpose of removing unreacted substances under the condition that the pores of the inorganic porous particles do not communicate with the outside. be able to.

Further, in order to form a dense film on the inorganic porous surface with SiO ₂ or a water-insoluble amorphous inorganic compound containing SiO ₂ and Al ₂ O ₃ as main components, for example, inorganic porous particles can be used. In the liquid phase in which the above is dispersed, a method for coating the surface of the porous particles with amorphous silica by the sol agglomeration method, the alkoxide method, the water glass agglomeration method, etc., mentioned above in the method for producing porous silica, or the like. During the treatment, a method in which an aluminum compound coexists, or a water-insoluble amorphous inorganic compound film containing SiO ₂ or SiO ₂ and Al ₂ O ₃ as main components is formed by a gas phase reaction method such as sputtering or CVD. There are ways. After such a treatment, a heat treatment is performed to make the surface of the water-insoluble amorphous compound layer containing SiO ₂ or SiO ₂ and Al ₂ O ₃ newly coated on the surface more dense. You can also This heat treatment is preferably performed in the range of 100 to 1000 ° C. in order that the pore diameter and the pore volume of the inorganic porous particles are within the above range.

The thus treated SiO ₂ or SiO ₂ and A having pores of 100 nm or less of 8 to 80% by volume is used.
Inorganic porous particles containing l ₂ O ₃ as a main component block the communication between the pores and the outside. As a result, even if this inorganic powder is dispersed in water, water will not enter the pores. The refractive index of the particles in water is an average value of the particle body and the air in the pores, and can be 1.40 or less in a stable state.

According to the invention, also with 3-40% by weight of at least one surface-active agent, the abovementioned inorganic powders 3-
A liquid detergent composition having a substantially transparent appearance containing 70% by weight is provided.

In this liquid detergent composition, the inorganic powder of the present invention acts as an abrasive, but the average particle size is smaller than 1 μm, and the content in the composition is 3 μm.
If it is less than 50% by weight, sufficient polishing power cannot be obtained. On the contrary, if it is more than 50 μm, the object to be washed is easily scratched, and if it is more than 70% by weight, it remains on the object to be washed after rinsing. It increases and is not preferable. On the other hand, when the content of the surfactant is less than 3% by weight, the detergency is insufficient and 40% by weight
If it exceeds, not only is the rinsing time lengthened, but it is likely to remain on the article to be washed after rinsing, resulting in nulliness.

In order for the liquid detergent composition to have a substantially transparent appearance, the difference in refractive index between the inorganic powder to be blended and the other portions of the liquid detergent composition is ± 0.01. Must be within range. If there is a difference in refractive index between the two, it is difficult to obtain a transparent appearance.

The surfactants used in the present invention include anionic, nonionic, cationic and amphoteric surfactants. As the anionic surfactants, usual sulfonate, sulfate and phosphate anions are used. A cationic surfactant is used. The sulfonate anionic surfactant among these anionic surfactants, such as linear or branched alkyl (C ₈ ~C ₂₃₎ benzenesulfonate, long chain alkyl (C ₈ ~C ₂₂₎ sulfonates, such as long chain olefins (C ₈ ~C ₂₂₎ sulfonate and the like. Further, examples of the sulfate type anionic surfactant include long chain monoalkyl (C _8- ).
C ₂₂ ) Sulfate ester salt, polyoxyethylene (1 to 6 mol) long chain ester (C _{8 to} C ₂₂ ) ether sulfate ester salt, polyoxyethylene (1 to 6 mol) alkyl (C ₈
To C ₁₈ ) phenyl ether sulfate ester salt and the like, and examples of the phosphate-based anionic surfactant include long-chain monoalkyl, dialkyl or sesqui (wherein each alkyl group has 8 to 22 carbon atoms) phosphorus. Acid salt,
Polyoxyethylene (1 to 6 mol) monoalkyl, dialkyl or sesquialkyl (each alkyl group has 8 to 8 carbon atoms)
22) phosphate and the like. The cation as a counter ion of these anionic surfactants is, for example, an alkyl metal or alkaline earth metal ion such as sodium, potassium and magnesium, an alkanolamine ion such as monoethanolamine, diethanolamine and triethanolamine. .

Examples of the nonionic surfactant include polyoxyethylene (1 to 20 mol) long-chain alkyl (primary or secondary C _{8 to} C ₂₂ ) ether, polyoxyethylene (1 to 20 mol) alkyl. (C ₈ ~C ₁₈₎ phenyl ether, polyoxyalkylene adducts of such polyoxyethylene polyoxypropylene block copolymer, higher fatty acid alkanolamides or alkylene oxide adducts thereof, long chain tertiary amine oxides (C ₁₂ ~C ₁₄₎ And so on.

Examples of the cationic surfactant include quaternary ammonium salts such as long-chain alkyltrimethylammonium salt, long-chain alkyldimethylbenzylammonium salt and long-chain alkylpyridinium salt.

Examples of the amphoteric surfactant include dimethyl long-chain alkyl (C ₈ -C ₁₈ ) -carboxymethylammonium betaine, di-long-chain alkyl (C ₈ -C ₁₈ ) aminoalkylcarboxylate, 2-alkyl-1. -Carboxymethyl-1-hydroxyethyl imidazolinium betaine and the like can be mentioned. These surfactants may be used alone or in combination of two or more.

In the liquid detergent composition of the present invention, in addition to the above-mentioned essential components, polyhydric alcohols such as glycerin and polyethylene glycol may be added, if necessary, within a range that does not impair the effects of the present invention. A lower aryl sulfonate such as xylene sulfonate or toluene sulfonate, a solubilizing agent such as ethanol, a fragrance, a dye, a water-soluble polymer compound or the like can be added.

Further, according to the present invention, there is provided a liquid dentifrice composition having a substantially transparent appearance, which comprises 5 to 50% by weight of the above-mentioned inorganic powder in a transparent aqueous vehicle. The transparent aqueous vehicle used in the liquid dentifrice composition of the present invention is generally one in which water is used as a medium and a viscosity modifier and a binder are mixed.

As this viscosity improver, for example, glycerin, sorbitol, polyethylene glycol, ethylene glycol, propylene glycol, xylitol and other commonly used viscosity modifiers for transparent liquid dentifrice are used. These may be used alone or in combination of two or more. Usually, this viscosity modifier is used in the range of 20 to 70% by weight, preferably 25 to 50% by weight, based on the total amount of the composition.

As the binder, water-soluble polymer compounds such as carrageenan, sodium alginate, carboxymethyl cellulose, xanthan gum, polyvinyl alcohol, polymers of acrylate or methacrylate, and polyvinylpyrrolidone are used. These may be used alone or in combination of two or more. These binders are usually used in the range of 0.1 to 5% by weight based on the total amount of the composition.

This transparent vehicle contains, if desired, higher alkyl sulfate ester salt containing an alkyl group having 8 to 18 carbon atoms such as sodium lauryl sulfate, sodium myristyl sulfate, α-oregin sulfonate, sodium lauryl monoglyceride sulfonate, C10 to C18 higher fatty acid monoglyceride sulfonates such as coconut monoglyceride sodium sulfonate and higher fatty acid monoglyceride sodium sulfate, N-methyl-N-palmityl taurate sodium phosphate, N-lauroyl sarcosine sodium, N-lauroyl -Anionic surfactants such as N-long chain acyl amino acid salts such as β-alanine sodium, diethanolamide of C10-16 fatty acids, stearyl monoglyceride, sucrose mono or dilaurate Sucrose ester of fatty acid having 12 to 18 carbon atoms, lactose fatty acid ester, lactitol fatty acid ester, maltitol fatty acid ester, 60 mol adduct of sorbitan monostearate with ethylene glycol, polymer of ethylene oxide and propylene oxide, polyoxyethylene poly Nonionic surfactants such as oxypropylene monolauryl ester, essential oils such as peppermint and spearmint, perfumes such as l-menthol, carvone, eugenol and anethole, sodium saccharin, stevioside, neohesperidyl dihydrochalcone, glycyrrhizin, perillartin, p-methoxy. Contains sweeteners such as cinnamic aldehyde, preservatives such as sodium dihydroacetate, p-hydroxymethylbenzoic acid and p-hydroxybutylbenzoic acid. Rukoto can.

Furthermore, dextranase, amylase,
Enzymes such as proteases, mutanases, phosphatases, lysozymes and lytechenzymes, sodium monofluorophosphate, alkali metal monofluorophosphates such as potassium monofluorophosphate, stannous compounds such as stannous fluoride, fluorine Of sodium chloride, chlorhexidine hydrochloride, chlorhexidine salts such as chlorhexidine sulfonate, copper chlorophyllin sodium, hinokitiol, ε-aminocaproic acid, tranexamic acid, ethanedihydroxydiphosphonate, allantoin chlorhydroxyaluminum, dihydrocholesterol, glycyrrhetinic acid, azulene, chamomile Such as crude drug, chlorophyll, chelate-forming phosphate compound such as glycerophosphate, sodium chloride, water-soluble inorganic phosphate compound etc. alone Or it may be formulated in combination of two or more. In addition, the components commonly used as an additive component for a normal transparent liquid dentifrice may be optionally added as desired. Further, the blending amounts of these components can be selected in the same manner as in the case of the conventionally known transparent liquid dentifrice.

In the dentifrice composition of the present invention, a transparent vehicle containing these components and the above-mentioned inorganic powder,
It is advantageous to maintain transparency that the refractive index is selected and mixed so as to be as close as possible. When the difference in refractive index between the two is 0.01 or more, the appearance becomes opaque.

[0057]

INDUSTRIAL APPLICABILITY The inorganic powder of the present invention has a refractive index of 1.40 or less even in water, and is excellent in dispersion stability. Therefore, it is possible to polish a liquid detergent containing an abrasive having a transparent appearance. It is useful as a material. It can also be used as an abrasive for tooth brushing. Further, the liquid detergent composition and the dentifrice composition containing the above-mentioned inorganic powder are excellent in detergency and abrading power and have a visually substantially transparent appearance, and have high commercial value.

[0058]

Next, the present invention will be described in more detail with reference to examples. In addition, the measurement of physical properties and performance evaluation in the examples were performed in the following manner.

(1) Pore Volume The pore volume of amorphous silica is FlowSo manufactured by Shimadzu Corporation.
It was measured using rbII2300. The conversion from the pore volume (cm ³ / g) to the pore volume (volume%) was based on the following formula with the density of the amorphous silica being 2.2 (g / cm ³ ).

[0060]

[Equation 1]

(2) Pore size Calculated by the following formula.

[0062]

[Equation 2]

(3) Particle size Measured using a Coulter counter.

(4) Refractive index [Liquid composition] Abbe's refractometer (IL-2 manufactured by Atago)
8607) and was measured at 25 ° C.

[Inorganic powder] The refractive index after the sample preparation is 1.3.
From 33 to 1.475, the refractive index (2
It was measured by the immersion method using various concentrations of glycerin aqueous solutions (25 ° C.) having an Abbe refractometer at 5 ° C.).

The refractive index after aging was determined by measuring the sample with LES-Na2.
Add to 5 wt% in 0 wt% aqueous solution, apply ultrasonic waves for 10 minutes to disperse, and after 14 days, a part of the dispersion is sampled and particles are not observed while observing with an optical microscope (solution And glycerin until the particles have the same refractive index),
The refractive index of the solution at that time was determined by measuring with an Abbe refractometer.

(5) Transparency 100 ml of the liquid detergent composition was placed in a transparent glass bottle having a diameter of 5 cm, and after 14 days, when the letters placed on the opposite side through the liquid could be identified, the case was identified, and the case where they could not be identified was indicated by x.

(6) Detergency: 3 liters of a 0.15 wt% composition aqueous solution (25 ° C.) was placed in a pad having a diameter of 30 cm and a depth of 13 cm, and 0.5 g of butter was applied to each dish to sponge. Scrubbing was performed 10 times with, and the feeling of finish after the washing of the seventh sheet was visually determined, and when it was good, it was evaluated as ◯. The case of failure such as the presence of oil (film) was rated as x.

(7) Polishing power 0.25 g of lard and 1 soy sauce were placed in a frying pan (diameter 26 cm).
For the stains that were mixed with 0cc and burnt for 3 minutes, 5g of the composition was attached to a nylon non-woven fabric containing 10g of water and rubbed 30 times to remove the stains. The thing was marked as x.

(8) Dispersion Stability The sample prepared in the above transparency test was left at room temperature as it was,
After storage for one month, the judgment was made by observing a boundary line in the liquid (a boundary between a portion where the abrasive is present and a portion where the abrasive is not present) caused by the sedimentation of the abrasive. The case where no boundary line was generated or the height of the liquid in the liquid was reduced by 1/4 or less from the upper end was determined as ◯, and the others were evaluated as x.

Example 1 Silica gel (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name; Sylbead N, average particle size; 20 μm) was placed in an alumina crucible and heat-treated at 700 ° C. for 1 hour.
The content was 0% by volume, the average pore diameter was 4 nm, and the refractive index measured with an aqueous glycerin solution was 1.440. 25 g of this heat-treated silica gel was placed in a stainless steel autoclave reactor together with 25 g of 1,1,1,3,3,3-hexamethyldisilazane and 1500 g of n-hexane to obtain 200
The reaction was carried out while stirring at 12 ° C at 12 ° C. The reaction was completed after 1 hour and cooled to room temperature. Next, it was filtered, washed with n-hexane, and then air dried. When the refractive index of the obtained powder was measured with an aqueous glycerin solution, it was 1.378, and the refractive index after aging maintained 1.378.

Example 2 Up to the heat treatment, the same procedure as in Example 1 was performed. S on this sample surface
A dense film of iO ₂ is formed. 5 g of this sample is 3% by weight
It was dispersed in 200 ml of ethanol containing HCl. Separately from this, a solution was prepared by adding tetraethoxysilane to 300 ml of ethanol dehydrated using molecular sieve 5A, added to the sample dispersion liquid at room temperature, and then directly
After stirring for a time, the mixture was filtered and then washed with ethanol. Vacuum drying was performed at 60 ° C. to obtain the desired inorganic powder. When the refractive index was measured using an aqueous glycerin solution, it was found to be 1.3.
The refractive index after 80 days was 1.380.

Example 3 NaA type zeolite (manufactured by Nippon Kagaku Kogyo KK, trade name; NA)
-100P, average particle size; 3 μm) was heat-treated at 700 ° C. for 1 hour. The refractive index measured with an aqueous glycerin solution was 1.460. The pore size calculated from the crystal structure of NaA zeolite is 0.22 nm and 0.42 nm.
It is known that the pore volume is 47% by volume. Next, polystyrene coating of this sample is performed. 1 g of this heat-treated sample was put in a glass cell and attached to an apparatus capable of vacuum evacuation. It was heated from the outside of the cell, heated to 100 ° C. and evacuated. Separately from this, a container containing styrene was connected to the same vacuum device via a cock that can be opened and closed with the sample cell. After evacuation of the sample cell,
Squeeze the cock installed beforehand between the vacuum exhaust line and the sample cell, gradually open the cock on the cell side containing styrene,
Styrene was introduced into the sample cell. 100 sample cells
The reaction was carried out for 6 hours while maintaining the temperature at ℃. After the reaction, the product was washed with n-hexane and then air dried. The refractive index of this inorganic powder measured with an aqueous glycerin solution was 1.370, and it was 1.370 even after the elapse of days.

Comparative Example 1 When the silica gel used in Example 1 was heat treated at 1200 ° C. for 1 hour, the pore volume was 0.5% by volume or less, and the refractive index measured with an aqueous glycerin solution was 1.430.

Comparative Example 2 The NaA type zeolite used in Example 3 was mixed at 850 ° C. for 1 hour.
When heat-treated for 0 minutes, the refractive index became 1.368. However, the refractive index after aging was 1.456 and the stability was poor.

COMPARATIVE EXAMPLE 3 The samples prepared in Comparative Example 1 were replaced with 1,1,1,3,3,3-
Hexamethyldisilanezan was treated as in Example 1. The refractive index of the obtained inorganic powder was 1.462 in the aqueous glycerin solution.

Examples 4 to 8 and Comparative Examples 4 to 7 Liquid detergent compositions having the compositions shown in Tables 1 and 2 were prepared using the inorganic powders prepared in Examples 1 to 3 and Comparative Examples 1 to 3 as abrasives. The product was prepared and its transparency, detergency, polishing power and dispersion stability were determined. The results are shown in Tables 1 and 2. The inorganic powder used in Comparative Example 4 had an average particle size of 0.1 μm,
Same as Example 1 except that the refractive index is 1.376.

[0078]

[Table 1]

[0079]

[Table 2] (Note) AOS-Na: sodium alpha-olefin sulfonate (alkyl chain length 14) LES-Na: polyoxyethylene (3 mol) alkyl (C ₁₃ ) ether sulfate sodium LAS-Na: sodium linear alkylbenzene sulfonate (alkyl chain) Length 12) Amine oxide: Lauryl dimethyl amine oxide

Example 9 A transparent liquid dentifrice was prepared using the components shown below. As the inorganic powder, the refractive index obtained in Example 1 was 1.37.
8 silica powder was used. Ingredient content (% by weight) Inorganic powder 20.0 Sodium carboxymethyl cellulose 0.4 Propylene glycol 2.0 Solbit (60%) 35.0 Glycerin (85%) 9.0 Saccharin sodium 0.1 Sodium fluoride 0.0 2 Sodium lauryl sulfate 1.5 Butyl paraoxybenzoate 0.01 Perfume 1.0 Purified water Residual 100.0

Example 10 Using the same inorganic powder as in Example 7, a transparent liquid dentifrice having the following composition was prepared. Ingredient content (% by weight) Inorganic powder 10.0 Xanthan gum 0.3 Sodium polyacrylate 0.5 Propylene glycol 3.0 Sorbit (60%) 20.0 Glycerin (85%) 25.0 Saccharin sodium 0.1 Cetylpyridinium chloride 0.01 Dye (Brilliant Blue) 0.001 Sodium lauryl sulfate 2.0 Methyl paraoxybenzoate 0.02 Perfume 1.0 Purified water Residual 100.0

Example 11 Using the same inorganic powder as in Example 7, a transparent liquid toothpaste having the following composition was prepared. Ingredient content (% by weight) Inorganic powder 15.0 Carrageenan 0.5 Propylene glycol 2.0 Solbit (60%) 35.0 Glycerin (85%) 8.5 Saccharin sodium 0.1 Sodium tripolyphosphate 1.0 Dye (Brilliant blue) 0.001 Sodium lauryl sulfate 1.2 Ethyl paraoxybenzoate 0.02 Fragrance 1.0 Purified water Residual 100.0

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C09K 3/14 550D C11D 3/14

Claims (9)

[Claims] 1. A pore containing SiO ₂ or SiO ₂ and Al ₂ O ₃ as main components and having a diameter of substantially 100 nm or less is 8 to 10.
It is composed of porous particles having an average particle diameter of 1 to 50 μm, which occupies 80% by volume, and the pores are closed near the surface of the particles to block communication with the outside.
A low-refractive-index inorganic powder having a refractive index of 40 or less. 2. The low refractive index inorganic powder according to claim 1, wherein the water-insoluble porous particles are amorphous silica particles. 3. The low refractive index inorganic powder according to claim 1, wherein the water-insoluble porous particles are zeolite particles. 4. The number of pores having SiO ₂ or SiO ₂ and Al ₂ O ₃ as main components and having a diameter of substantially 100 nm or less is 8 to 8.
The water-insoluble porous particles occupying 0% by volume and having an average particle diameter of 1 to 50 μm are heat-treated at 100 to 1000 ° C. until the water in the pores is substantially completely removed, and then the pores are closed. 1.40 in an aqueous medium characterized by
A method for producing a low refractive index inorganic powder having the following refractive index. 5. The method according to claim 4, wherein the particles are reacted with an organosilicon compound having a hydroxyl-reactive functional group to close the pores. 6. The method according to claim 4, wherein the surface of the particles is covered with a water-insoluble polymer compound to close the pores. 7. SiO ₂ or SiO ₂ and A on the surface of the particles
The method according to claim 4, wherein a film of a water-insoluble amorphous inorganic compound containing l ₂ O ₃ as a main component is formed to close the pores. 8. A liquid detergent composition having a substantially transparent appearance, comprising 3-40% by weight of at least one surfactant and 3-70% by weight of the inorganic powder of claim 1. 9. A dentifrice composition having a substantially transparent appearance containing 5 to 50% by weight of the inorganic powder of claim 1 in a transparent aqueous vehicle.