JPH05255456A - Clouding agent - Google Patents

Abstract

PURPOSE:To obtain a clouding agent for making a liquid substance such as water, oily substance or waster/oil dispersion turbid, having high clouding effects and excellent dispersion stability, comprising hollow or porous polymer particles having specific particle diameters. CONSTITUTION:A crosslinked polymer comprising a combination of methyl methacrylate/divinylbenzene/methacrylic acid, etc., having 0.1-10mum (preferably 0.1-0.6mum) particle diameter is formed into hollow or porous particles to give the objective clouding agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a clouding agent for imparting turbidity to liquid substances such as water, oily substances or water / oil dispersions.

[0002]

2. Description of the Related Art Toiletry products such as bath salts, cosmetics, liquid detergents, perfumes, and liquid fragrances or drinks, soft drinks, some foods, and liquid industrial products require turbidity in appearance. .. Conventionally, for this purpose, inorganic particles such as calcium carbonate, talc and titanium oxide, or organic polymer particles such as polystyrene, styrene / divinylbenzene copolymer and styrene / vinylpyrrolidone copolymer have been used. However, inorganic particles have a large specific gravity, which causes significant sedimentation,
There was a problem that shaking had to be carried out frequently during use.

On the other hand, in conventional polymer particles, although the specific gravity of particles is small, the refractive index is small, so that the cloudiness of the particles is small, and further, the dispersion stability of the particles in an oil medium is poor, and therefore the particles aggregate. There was a problem with it.

[0004]

DISCLOSURE OF THE INVENTION The present invention is to find a whitening agent having good dispersion stability and a large whitening effect in a liquid substance such as oil, water or an oil / water dispersion.

[0005]

The present invention uses hollow or porous polymer particles as clouding particles. The hollow polymer particle of the present invention is a polymer particle having a particle diameter of 0.1 to 10 μm and having one or a plurality of inner pore diameters having an inner pore diameter of 1/10 or more of the outer diameter of the particle inside. The method for producing the particles is not particularly limited, but is preferably JP-A-62-1
27336 and JP-A-61-185505. By using such hollow polymer particles, the effect of making the transparent substance cloudy due to the scattering of light in the pores inside the particles becomes large, and the effect of preventing sedimentation due to the decrease in the specific gravity in the pores can get.

Here, the particle diameter of the hollow polymer particles is 0.
If it is 1 μm or less, a sufficient clouding effect cannot be expected. On the other hand, if the particle diameter of the hollow polymer particles exceeds 10 μm, the particles will increase in sedimentation, which causes troubles in use. In the present invention, the hollow or porous polymer particles have a particle size of 0.1.
Although it is 10 μm, it is preferably 0.
It is 1 to 1 μm, and more preferably 0.1 to 0.6 μm. There is no particular limitation on the polymer composition of the hollow or porous polymer particles, but from the viewpoint of stability of the particles in the perfume, it is preferably a cross-linked polymer, and more specifically a combination example of constituent monomers is shown, Methyl methacrylate / divinylbenzene / methacrylic acid, methyl methacrylate / divinylbenzene / styrene and / or α-methylstyrene / methacrylic acid, styrene and / or α-methylstyrene / divinylbenzene /
Methacrylic acid and the like.

The method of adding the clouding agent of the present invention to oil, water or an oil / water dispersion is not particularly limited, but the pH of the water dispersion is preferably 2 to 4. The substance to which the clouding agent of the present invention can be added is preferably a liquid,
Oils, water, oil / water dispersions. Of these, water and oil / water dispersions are particularly preferred. Here, it is assumed that the oil / water dispersion also contains a solubilized product in which oil is finely mixed in water with a nonionic surfactant to be in a transparent state.

Specific examples of applications to which the clouding agent of the present invention can be suitably added are described below. Bath salts (liquid and solid), fragrances, water dispersions of fragrances, solubilized products of fragrances in water with nonionic surfactants, fragrance gels, liquid cosmetics, liquid detergents, shampoos, hair rinses, waxes, soft drinks , Medicine,
Examples include pesticides, adhesives, gasoline, oil, polymer solutions, etc. The amount of the clouding agent of the present invention added to the liquid substance is 0.001 to 5% by weight, preferably 0.05 to 2% by weight based on the solid content of particles. This is significantly smaller than the amount required for a whitening agent composed of general non-hollow polymer particles. Here, even if added in excess of 5% by weight, there is no particular change in the clouding effect, and the effect of large addition is small. If the addition amount is 0.001% by weight or less, there is no substantial effect.

It is also possible to add the clouding agent of the present invention to a high concentration in advance and dilute it at the time of use to lower the concentration. Furthermore, the addition method of the present invention includes adding to a solid substance before being liquefied and then liquefying it by dissolving, melting or the like at the time of use. In addition, conventional colorants and dyes are added in combination with the whitening agent of the present invention,
It is also possible to add color. Furthermore, when the present invention is used as a clouding agent for perfumes, the hollow particles have a clouding effect, and in addition to absorbing a perfume inside the particles, a sustained release effect for the perfume can be utilized.

The present invention will be described in more detail below with reference to examples.

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Also, hereinafter, "part" means "part by weight" and "%" means "% by weight". Example 1 98 parts of styrene, 2 parts of methacrylic acid, and 10 parts of t-dodecyl mercaptan were added to an aqueous solution prepared by dissolving 0.5 part of sodium lauryl sulfate and 1.0 part of potassium persulfate in 200 parts of water, and stirring the mixture to 70 parts. Polymerization was performed at 8 ° C. for 8 hours to obtain polymer particles. This polymer particle has an average particle diameter of 0.22.
μm, toluene insoluble content 3%, number average molecular weight by GPC 4,100, ratio M of weight average molecular weight to number average molecular weight
It was w / Mn = 2.4.

Next, the polymer particles were used as a seed polymer, and the polymer particles were used in a solid content of 10 parts, polyoxyethylene nonylphenyl ether 0.1 part, sodium lauryl sulfate 0.3 part and potassium persulfate 0.5. Parts were dispersed in 900 parts of water. A mixture of 80 parts of methyl methacrylate, 10 parts of divinylbenzene (pure product), and 10 parts of threthin was added thereto and stirred at 30 ° C. for 1 hour, and the above substance was almost completely absorbed by the seed polymer particles. This was polymerized as it was at 70 ° C. for 5 hours to obtain an aqueous dispersion of hollow crosslinked polymer particles having a polymerization yield of 98% and a pH of 3.0.

When the particles were observed with a transmission electron microscope, it was confirmed that the particles were hollow polymer particles having a single inward in the central part of the inside of the particles. The outer diameter of the particles is 0.50
μm, and the inner pore diameter was 0.30 μm. Next, the effect of the particles as a clouding agent was examined.

100 parts by weight of the limonene-based oily fragrance, 100 parts by weight of ethanol, and 50 parts by weight of a nonionic surfactant (Kao, Emulgen 910) were mixed, and 300 parts by weight of water and an aqueous dispersion of the hollow polymer particles previously synthesized were mixed. When the mixture of the body (3 parts by weight in terms of solid content) was mixed with good stirring, the system became clear and cloudy. As an indication of the turbidity of this white turbid material, the visible light spectrophotometer was used to measure the light transmittance (%) at a cell wavelength of 5 cm at a wavelength of 500 mμ, and used as a measure of the turbidity. The clouding agent of the present invention has a larger clouding effect than the conventional ones with the same addition amount. Furthermore, when the system was allowed to stand at 50 ° C. for 30 days as an evaluation of storage stability, no precipitate was generated.

Examples 2 to 3 and Comparative Examples 1 to 3 Particle size 0.2 synthesized according to Example 1 as a clouding agent
Example 1 using hollow and 2 μm hollow polymer particles
Water-soluble solubilized fragrances were prepared in the same manner as in Example 2 and used as Examples 2 and 3. In addition, a non-hollow polystyrene particle (particle diameter 0.5 μm) as a comparative example and titanium oxide (particle diameter 0.5 μm) and calcium carbonate (particle diameter 2 μm) as inorganic particles were used in the same manner as in Example 1 to produce the fragrance. The solubilized product of was prepared and used as Comparative Examples 1, 2, and 3. In the non-hollow polymer particles of Comparative Example 1, the whitening ability was small and the dispersion stability in perfume was poor. The titanium oxide of Comparative Example 2 had good turbidity, but the sedimentation during storage was extremely poor. The calcium carbonate of Comparative Example 3 had poor turbidity and sedimentation.

[0016]

The clouding agent of the present invention is water, oil or oil /
It has a large clouding effect on liquid products consisting of an aqueous dispersion and has excellent dispersion stability. The present invention is a fragrance, a bath agent,
It can be usefully used as a clouding agent in toiletries such as cosmetics and detergents, beverages, foods, pharmaceuticals, agricultural chemicals, and general industrial products.

[Table 1]

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location A61K 7/50 9051-4C C08F 2/44 MCS 7442-4J C10L 1/32 D 6958-4H C11D 3/37 / / A23L 2/00 L C11B 9/00 Z 2115-4H

Claims (1)

[Claims] 1. A clouding agent comprising hollow or porous polymer particles having a particle size of 0.1 to 10 μm.