JPH0931492A - Cleaning agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleaning agent composition having excellent physical cleaning effect and massaging effect, giving extremely low stimulation and damage to the surface of the cleaning object and applying good feeling in cleaning. SOLUTION: This cleaning agent composition contains (1) particles having an average particle diameter of 5-500μm in 5wt.% aqueous solution of sodium chloride and an elastic modulus of >5×10<5> dyne/cm<2> in the above aqueous solution and (2) particles of crosslinked polymer having an elastic modulus of 1×10<3> to 5×10<5> dyne/cm<2> in 5wt.% aqueous solution of sodium chloride. The compounding weight ratio of (1):(2) is 1:100 to 10:1 and the ratio of the average particle diameters of (1) to (2) is 1:(10-1).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition which gives an object to be cleaned an excellent cleaning power and a feeling of massaging, while having low irritation and low damage.

[0002]

2. Description of the Related Art Conventionally, a detergent composition containing hard polymer particles has been known as a detergent for the purpose of physically cleaning and massaging the skin and the like. However, such a detergent composition, although hard polymer particles, can provide a feeling of massage and detergency during washing,
The skin was strongly irritated and there was a risk of damaging the skin surface, and these were unsuitable as a skin cleansing composition. Also, those with low irritation and low damage to the skin had a weak detergency, and a sufficient massage feeling could not be obtained.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to maintain the feeling of massage and the cleansing power, while
An object of the present invention is to provide a detergent composition having low irritation and low damage.

[0004]

Under such circumstances, the inventors of the present invention have conducted diligent studies on the relationship between the physical properties of polymer particles and the detergency, and as a result, have found that the particles having appropriate hardness and particle size have suitable softness. By blending particles having a specificity in a specific ratio, it has been found that a detergent composition can be obtained which retains a high massage feeling and a detergency, and is less likely to cause irritation and damage to the skin. It came to completion.

That is, the present invention provides the following components (1) and (2); (1) an average particle size in a 5 wt% sodium chloride aqueous solution of 5 to 500 μm, and a modulus of elasticity in the aqueous solution. Having a particle size of more than 5 × 10 ⁵ dyne / cm ² , (2) an elastic modulus in a 5 wt% sodium chloride aqueous solution of 1 × 10 ^{3 to} 5 × 1
The cross-linking polymer particles having an amount of 0 ⁵ dyne / cm ² are included, and the weight mixing ratio of (1) and (2) is 1: 100 to 10 :.
1, the average particle size ratio of (1) and (2) is 1:10 to 1: 1.
A cleaning composition is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The particles of component (1) used in the present invention have an average particle size of 5 to 500 μm in a 5 wt% (hereinafter simply referred to as “%”) sodium chloride aqueous solution, and The particles having an elastic modulus of more than 5 × 10 ⁵ dyne / cm ² may be hydrophilic or lipophilic, and are not particularly limited, but those having an average particle size in a 5% sodium chloride aqueous solution of 50 to 250 μm Is preferable, and the elastic modulus is 5 ×
Polymer particles having a particle size of more than 10 ⁵ and not more than 1 × 10 ⁹ dyne / cm ² are preferable. Examples of these particles include hydrocarbon polymers such as polyethylene, polystyrene and polypropylene; polyamide polymers such as nylon; vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; polyethylene terephthalate and polybutylene terephthalate. Polyester-based polymer, reaction product of ethylene glycol and hexamethylene diisocyanate, polyurethane-based polymer such as polyethylene adipyldiurethane and copolymers thereof, or those obtained by forming cross-linked products thereof as described below, and walnut shell particles , Natural products such as apricot shell particles, carnauba wax particles, and the like, and one or more kinds thereof may be used in combination as necessary. Of these, polyethylene, polystyrene and polypropylene are particularly preferable.

Here, the elastic modulus of the polymer particles means that the polymer particles immersed in an aqueous 5% sodium chloride solution for 1 hour or more are spread on a sample base made of aluminum so as to form a single layer, and thermal stress strain measurement is performed. Device (Seiko Denshi Kogyo Co., Ltd., T
According to MA / SS10), a cylindrical expansion / compression probe (made of quartz) with a cross-sectional area of 7.1 mm ² at room temperature was applied with a load of 3 g as a balance in advance, and from this, a sine curve with an amplitude of 1 g and a period of 0.005 Hz was formed. It is a value obtained by applying stress and measuring the strain.

Further, the particle size is measured by filling a preparation (a hemocytometer, etc.) having a concave portion in the center with a 5% sodium chloride aqueous solution, and inserting polymer particles swollen in the same solution for 1 hour into the cover. Cover with glass 5 with optical microscope
It was performed by taking a photograph magnified about 0 to 100 times. Since the particle shape is not particularly limited, a polymer obtained by bulk polymerization or the like can be crushed to a predetermined particle size and used. Examples of preferable particle shape include a spherical shape and an ellipsoidal shape.

The polymer particles of the component (1) used in the present invention may be granules granulated with a water-insoluble binder, and can be used comfortably from the start to the end of washing and massage. Here, examples of the water-insoluble binder include acetyl cellulose, nitrocellulose, vinyl acetate resin and the like in addition to ethyl cellulose.

The granulation method is not particularly limited, and examples thereof include a method in which these binders are dissolved in a solvent and granulation is performed by, for example, a fluidized granulation method or a stirring granulation method. That is, it is preferable to spray the above-mentioned non-water-soluble binder as a solution of an optimal solvent by a method such as spraying on powder that is being stirred in a fluidized bed or the like. It may be selected according to the particle size of the granules to be used. As the solvent used at that time, any one is selected depending on the binder used or the granulation method, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, and esters. General-purpose organic solvents such as compounds, ethers, ketones, etc.
More than one species can be used in combination.

The average particle size of the granules granulated with the water-insoluble binder is also 5 to 500 μm, preferably 50 to 250 μm.
It is.

The particles of the component (1) used in the present invention are preferably incorporated in the detergent composition in an amount of 0.1 to 10%,
It is particularly preferably 1 to 5%.

The crosslinkable high component (2) used in the present invention
Molecular particles have an elastic modulus of 1 in a 5% aqueous sodium chloride solution.
× 10^Three~ 5 × 10^Fivedyne / cm^TwoIf so, hydrophilic, lipophilic
It can be used without any restriction on the sex, etc., especially 1 × 10^Four~ 1
× 10^Fivedyne / cm^TwoThe elastic modulus of is preferable. 1x1
0^Threedyne / cm^TwoIf it is less than 5, the cleaning effect is small and 5 × 10.^Five
dyne / cm^TwoIf it exceeds, there is a risk of damaging the skin and
Not good. Also, the average particle size in 5% sodium chloride
Is preferably 50 to 500 μm, particularly preferably 10
It is 0 to 300 μm. Cleaning effect is less than 50 μm
Is less than 500 μm, discomfort and skin irritation occur if it exceeds 500 μm
It is not good to show. Crosslinking of component (2) used in the present invention
Hydrophilic polymer, lipophilic high content
You can use either of these, and mix these two types of polymers
It can also be used.

As the hydrophilic polymer, for example, a hydrous gel derived from carrageenan, gelatin, agar, tragacanth gum, viscose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, etc. is stabilized by adding a polyvalent metal salt. Acrylic acid or methacrylic acid [hereinafter, abbreviated as "(meth) acrylic acid"], salts of (meth) acrylic acid such as sodium and ammonium;
(Meth) acrylamide; N-substituted (meth) acrylamide, 2- (meth) acryloylethanesulfonic acid or its salt, styrenesulfonic acid or its salt, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, vinyl methyl ether. , A homopolymer of polyethylene oxide (meth) acrylic acid ester or the like, or a crosslinked product of a copolymer using two or more kinds of these monomers; vinyl acetate-methyl acrylate copolymer saponification product, vinyl acetate-monomethyl maleate Crosslinked products such as saponified copolymers, saponified isobutylene-maleic anhydride copolymers; starch-acrylic acid graft polymers, polysaccharides-acrylic acid graft polymers, hydrolysates of starch-acrylonitrile graft polymers, etc. Can be mentioned.

As a method for forming a crosslinked product, the above-mentioned monomer or mixture of monomers is treated with a polyfunctional vinyl monomer or a functional group other than at least two vinyl groups in the molecule, such as an epoxy group. There is also a method in which a polymer having an appropriate elasticity is obtained by mixing with a cross-linking agent which is contained and polymerizing by a known method. Further, after obtaining a homopolymer or a copolymer, a crosslinking agent may be reacted by a known method to obtain a polymer having an appropriate elasticity.

Examples of the polyfunctional vinyl monomer include N, N'-methylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, and trimethylolpropane triacrylate. Examples of the cross-linking agent having at least two functional groups other than vinyl groups in the molecule include glycidyl ether-based, isocyanate-based,
Examples of the crosslinking agent include maleimide-based crosslinking agents, and examples of the glycidyl ether-based crosslinking agent include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and triglycidyl isocyanurate;
As the isocyanate type, methylenebis (4-phenylisocyanate), 2,6-tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and the like; as the dimaleimide type, N, N′-1,4-phenylenediamine Examples include, but are not limited to, dimaleimide, N, N'-1,2-phenylenediamine dimaleimide, N, N'-hexamethylenediamine dimaleimide, N, N'-tetramethylenediamine dimaleimide, and the like. is not.

Further, a copolymer of the above hydrophilic monomer and a hydrophobic monomer such as styrene (meth) acrylic acid ester is used within a range not significantly impairing the physical properties such as elastic modulus of the resulting polymer. Although it can be used, a polymer made of one or more hydrophilic monomers is preferable in order to obtain a preferable expansion coefficient.

Of these hydrophilic polymers, those having a coefficient of expansion of 1.2 to 5 times in a 5% aqueous sodium chloride solution are preferably used. The expansion rate is represented by the ratio of the particle size after swelling to the dry particle size.

Examples of the lipophilic polymer include (a) alkyl (meth) acrylate, alkyl substituted with (meth) acrylic acid,
Monovinyl monomers that form homopolymers having a glass transition point of 25 ° C. or less, such as fatty acid vinyl esters, (b) mixtures of these monovinyl monomers, or (c) these monovinyl monomers and these monovinyl monomers. The following A which can be copolymerized
Polymers obtained by a known suspension polymerization method of the mixture of the monovinyl monomer and the polyfunctional vinyl monomer described above in the presence or absence of an organic solvent can be used.

Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, etc .; acrylic acid As substituted alkyl, 2-ethoxyethyl acrylate, acrylic acid 2
-Cyanoethyl, benzyl acrylate and the like; as the alkyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate and the like; and as the fatty acid vinyl ester,
Examples include fatty vinyl, vinyl propionate, and cyclohexyl vinyl acetate.

Examples of the monovinyl monomer A which can be polymerized with the above monovinyl monomer include styrene and p
-Styrene-based monomers such as methylstyrene and p-chlorostyrene; and homopolymers having a glass transition point of 25 ° C or higher such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and t-butyl acrylate ( (Meth) acrylic acid ester; acrylonitrile, methacrylonitrile, vinyl chloride and the like can be mentioned, and these can be added within a range that does not impair the physical properties such as elastic modulus of the resulting polymer.

As the polyfunctional vinyl monomer, divinylbenzene, trivinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate,
Examples include trimethylolpropane triacrylate.

In addition, the above-mentioned monovinyl monomer and a monomer to which the above-mentioned monovinyl monomer of A which can be copolymerized with these monovinyl monomers is added within a range not impairing the physical properties of the resulting polymer, and 2-chloro Monomers having functional groups such as monomers having a halogenated methyl group such as ethyl vinyl ether and chloromethylstyrene, monomers having an epoxy group such as glycidyl methacrylate, monomers having a carboxy group such as acrylic acid and methacrylic acid. Examples of the polymer include a reactive polymer obtained by copolymerization with one of the monomers and cross-linked by a known method.

Further, as the lipophilic polymer, ethylene rubber (EPM), propylene rubber (EPDM), natural rubber,
Styrene butadiene rubber (SBR), butadiene rubber (BR), silicone rubber and the like can also be used. Among the above hydrophilic polymers or lipophilic polymers, considering the versatility of the raw material and the ease of controlling the elastic modulus, the hydrophilic polymer may be sodium (meth) acrylate, ammonium, or the like. It is preferable that the salt contains a (meth) acrylic acid ester as the lipophilic polymer. In particular, in order to obtain a desired elastic modulus, the polymer containing (meth) acrylic acid salt or (meth) acrylic acid ester is preferably 50% or more.

The crosslinkable polymer particles of the component (2) used in the present invention are preferably incorporated in the detergent composition in an amount of 0.1 to 30%, particularly preferably 1 to 15%.

In the present invention, the weight ratio of component (1) to component (2) is 1: 100 to 10: 1, preferably 1:50 to 3: 1. When it is less than 1: 100, the massage feeling cannot be improved, and when it exceeds 10: 1, irritation to the skin becomes too strong, which is not preferable.

In the present invention, the component (1) and the component (2)
The average particle size ratio of 5% in 5% sodium chloride is 1:10
It is 1: 1 and preferably 1: 5 to 1: 1. 1:
If it is less than 10, the massage feeling cannot be improved, and 1:
When it exceeds 1, irritation to the skin becomes too strong, which is not preferable.

The main surfactant used in the detergent composition of the present invention is not particularly limited, but examples thereof include anionic surfactants such as fatty acid soaps, phosphoric acid esters, acylated amino acids, sulfosuccinic acids and taurate surfactants. , Alkyl saccharides, nonionic surfactants such as EO addition type surfactants, and the like. Among them, phosphoric acid esters, acylated amino acids, alkyl saccharides and the like are preferable because they cause less skin irritation.

The content of the main surfactant is not particularly limited, but when the detergent is solid, it is 60 to 90%, when it is paste, it is 40 to 70%, when it is gel, it is 40 to 70%, and when it is liquid, it is 10%. It is preferable to blend -50%. Further, in addition to the main surfactant, it is also preferable to use an amine oxide or imidazoline-based surfactant as a foaming property improving agent.

In addition to the above-mentioned components, the detergent composition of the present invention contains the usual components used for detergents, for example, thickeners, wetting agents, colorants, preservatives, touch improvers, fragrances, anti-inflammatory agents, An ultraviolet absorber or the like can be used within a range that does not impair the effects of the present invention. The detergent composition of the present invention can be widely used in, for example, facial cleansers, whole body cleansing agents, skin cleansing agents such as bar soaps, shampoos and the like.

[0031]

The cleaning composition of the present invention is excellent in physical cleaning effect and massage effect, and has extremely low irritation and low damage to the surface of the object to be cleaned such as skin and scalp. The touch is excellent and excellent.

[0032]

EXAMPLES The present invention will be described in more detail below with reference to synthesis examples and examples, but the present invention is not limited thereto.

Synthesis Example 1 100 g of 2-ethylhexyl acrylate, ethylene glycol
5 g of recall dimethacrylate and lauroyl peroxide
1.0 g of the dissolved mixture and polyvinyl alcohol (Japan
Synthetic Chemical Industry Co., Ltd., Gohsenol GH-17) 2.
33 g and a dissolved mixture of 230.7 g of deionized water
11 Charge into a four-necked flask and stir-disperse at 1000 rpm.
Then, raise the temperature of the system to 80 ° C, and at 8 o'clock
It took a while to complete the polymerization. The dispersion of the obtained crosslinked product
Purified by steam distillation, 2-ethylhexyl polyacrylate
Crosslinked beads (average particle size 90μm, elastic modulus 4.2 ×
10 ⁶dyne / cm^Two) Got.

Synthetic Example 2 510 g of 80% acrylic acid aqueous solution was neutralized with 360 g of 30% sodium hydroxide aqueous solution at a temperature of 35 ° C. or lower, and 0.9 g of potassium persulfate and 12.2 g of ethylene glycol diglycidyl ether (acrylic acid was added). 3.0%) was added and dissolved. This monomer aqueous solution was added dropwise to a solution of 5.0 g of ethyl cellulose and cyclohexane (1600 ml) kept at 75 ° C. under stirring in a nitrogen atmosphere over 1.5 hours for polymerization. Furthermore, stirring was continued at a temperature of 70 to 75 ° C. for 1.0 hour to complete the polymerization. Then, the water content in the polymer suspended in cyclohexane was controlled to 25% by azeotropic dehydration (cyclohexane was refluxed), and then cyclohexane was removed, at 80 ° C to 100 ° C.
After drying under reduced pressure, a beaded polymer of sodium polyacrylate having an average particle size of 100 to 250 μm (average particle size of 20
0 μm, elastic modulus 6.0 × 10 ⁴ dyne / cm ² ) was obtained.

Example 1 2-Ethylhexyl polyacrylate obtained in Synthesis Example 1, sodium polyacrylate obtained in Synthesis Example 2, polystyrene (manufactured by Sumitomo Chemical Co., Ltd., Fine Pearl PB-310)
0, 3400), polyethylene (NL-200 manufactured by Mitsui Petrochemical Co., Ltd.) and walnut shell particles, and the elastic modulus and average particle diameter were measured by the following methods. The results are shown in Table 1. Then, these beads are listed in Table 2.
The cleaning improvement rate, the skin rash score, and the feeling of use were measured by the following method. The results are shown in Table 3.

(Measurement of Elastic Modulus) Polymer particles were immersed in an aqueous 5% sodium chloride solution for 1 hour and spread over an aluminum sample stand so as to form a single layer, and a thermal stress strain measuring device (Seiko Denshi Kogyo ( Co., Ltd., TMA / SS10)
With a cylindrical expansion and compression probe (made of quartz) with a cross-sectional area of 7.1 mm ² at room temperature, 3 g as a balance in advance
Was applied, stress of a sine curve with an amplitude of 1 g and a period of 0.005 Hz was applied, and the strain was measured.

[0037]

[Table 1]

[0038]

[Table 2]

(Measurement of cleaning improvement rate) 1-on dry pig skin
A solid fat dyed with [(p-phenylazo) -phenyl] azo [2-naphthol] was applied to a diameter of 15 mm and a thickness of 0.1 mm, and cleaning agent 1 containing 5% of polymer particles or polymer particles was purified water. Was subjected to a cleaning treatment with the cleaning agent 1 replaced with, and the absorbance of the remaining solid fat dissolved in an organic solvent was measured,
The cleaning rate was determined by comparing the measured value with the absorbance of the unwashed solid fat. The cleaning improvement rate was calculated by the following equation.

[0040]

## EQU1 ## W = (W ₁ -W ₀ ) × 100 / (100-W ₀ ), where W = cleaning improvement rate W ₁ = cleaning rate of cleaning agent 1 containing polymer particles W ₀ = polymer particles Cleaning rate of cleaning agent 1 with purified water replaced

(Measurement of skin rash score) A cleaning agent was applied to a specific site on the forearm with a Teflon stick for each morning and evening.
Each time, 14 times in succession, the naked eye was observed for drop and gloss, and the result was taken as the average of the scores (n = 1.
0). 0: No change 1: Mild. 2: Medium. 3: Severe.

(Evaluation of the feeling of use) The face was washed with 1 g of the cleaning agent, and the feeling of massage and the feeling of use were measured by the panelist 10.
Evaluation was performed according to the following evaluation criteria by name. A: Very good. ：: good. Δ: Normal. X: Feeling uncomfortable and stimulating.

[0043]

[Table 3]

Example 2 (Soap) A soap having the following composition was produced.

[0045]

[Table 4]% Beads of Synthesis Example 1 2.0 Beads of Synthesis Example 2 5.0 Palm oil / beef tallow fatty acid soda 82.0 Dibutylhydroxytoluene 0.1 Cetanol 5.0 Fragrance amount Dye amount Amount of purified water Balance total 100.0

Example 3 (facial cleansing foam) A cleansing foam having the following composition was produced by a conventional method.

[0047]

Table 5% Beads of Synthesis Example 1 1.0 Beads of Synthesis Example 2 3.0 Potassium laurate 40.0 Glycerin 8.0 Propylene glycol 3.0 Sodium benzoate 0.1 Perfume Finely purified water Balance total 100 .0

Example 4 (Body shampoo) A body shampoo having the following composition was produced by a conventional method.

[0049]

[Table 6]% Beads of Synthesis Example 1 2.0 Beads of Synthesis Example 2 5.0 Monolauryl phosphate triethanolamine salt 45.0 Ethanol 10.0 Propylene glycol 10.0 Perfume Finely purified water Balance total 100.0

Each of the cleaning agents of Examples 2 to 4 had good massage feeling and good cleansing property, and had low irritation to the skin.

Claims (5)

[Claims] 1. The following components (1) and (2): (1) The average particle size in a 5 wt% sodium chloride aqueous solution is 5 to 500 μm, and the elastic modulus in the aqueous solution is 5 × 10 5. Particles exceeding ⁵ dyne / cm ² , (2) Elastic modulus in 5 wt% sodium chloride aqueous solution of 1 × 10 ^{3 to} 5 × 1
The cross-linking polymer particles having an amount of 0 ⁵ dyne / cm ² are included, and the weight mixing ratio of (1) and (2) is 1: 100 to 10 :.
1, the average particle size ratio of (1) and (2) is 1:10 to 1: 1.
A cleaning composition comprising: 2. The detergent composition according to claim 1, wherein the particles of (1) are granules granulated with a water-insoluble binder. 3. The particles of (2) have an average particle size of 50 to 500 μm in a 5 wt% sodium chloride aqueous solution, and have an elastic modulus of 1 × 10 ⁴ to 1 × 10 ⁵ dyne in the aqueous solution.
The cleaning composition according to claim 1, which is cross-linked polymer particles having a density of 1 / cm ² . 4. The weight mixing ratio of (1) and (2) is 1:50.
The cleaning composition according to any one of claims 1 to 3, wherein the cleaning composition is -3: 1. 5. The average particle size ratio of (1) and (2) is 1: 5.
The cleaning composition according to any one of claims 1 to 4, which is 1: 1.