JP6541756B2 - Scrub agents and scrub-containing cleaners - Google Patents

Description

The present invention relates to a scrub agent in which the irritation to the skin and the like is reduced by the particles absorbing and swelling appropriately by contact with water and the surface becoming soft and smooth. More particularly, it relates to particulate scrubs and scrub-containing cleaners containing gelatinized starch.

With regard to micro plastic beads (beads such as polyethylene, polypropylene, nylon, etc.) that are used as scrubs for industrial hand-washing agents, face-washing agents and tooth powders, adverse effects on the environment and ecosystem have been reported. Demand is rising. With regard to this problem, in recent years, development of scrub agents using biodegradable natural materials has progressed.

The manufacturing methods of the scrub agent which uses a natural raw material as a raw material are roughly classified into three types.
(1) A method of obtaining a scrubbing agent by crushing the crushed method material with a mill or a hammer. Typical examples include crushed materials of plant materials such as walnut shells and corn cobs.
(2) Granulation method A method of obtaining a scrub agent by granulating the material by spraying an aqueous solution of a water-soluble binder using a stirring granulator or a fluidized bed granulator. Patent Document 1 and Patent Document 2 describe scrub particles having a good feeling of use that is broken by pressure or water at the time of use by granulating a powdery substance such as starch or cellulose.
(3) Liquid phase method A method of obtaining a scrub agent by dissolving a material once and insolubilizing the produced solution in the presence of a specific solvent or a crosslinking agent. Patent Document 3 discloses scrub particles having low irritation to teeth and skin using glucomannan gel. In Patent Document 4, a water-soluble polymer that forms a thermoreversible gel such as gelatin and agar is solidified with a water-soluble polymer that is crosslinked and thickened by polyvalent metal ions such as alginate and pectin. Spherical granules obtained by

Japanese Patent Application Laid-Open No. 2002-053459 JP 2000-302630 A JP, 2006-169300, A JP-A-9-143046

However, the scrub agents produced by the conventional method have the following problems.
(1) Although the scrub agent obtained by the pulverization method shows sufficient massage effect and dirt removal effect, the shape of the surface of the scrub agent is not smooth and the strength is too hard to give excessive irritation to the skin. .
(2) The scrub agent obtained by the granulation method has high disintegrability and low irritation to the skin, but on the other hand, a sufficient scrub feeling can be obtained only at the initial stage of use due to the disintegrability, and a water-soluble bond Since the agent is used, there is a problem that the granulation is broken by the water contained in the detergent when blended with the detergent.
(3) Scrub agents obtained by the liquid phase method have improved particle shape and hardness, and good scrub feeling is obtained, but since an organic solvent such as ethanol or liquid paraffin is required at the time of production, There are problems such as the need for recovery equipment and an increase in manufacturing costs.

Therefore, in the present invention, it is an object of the present invention to provide a scrub agent having excellent scrub feeling and having low irritation, formulation stability to a detergent, and easy manufacturability.

As a result of various studies to achieve the above-mentioned purpose, the present inventor uses a particulate scrub agent containing gelatinized starch and having a gelatinization degree of 10 to 90%, and absorbs moisture at the time of use. It has been found that it swells and has an appropriate hardness and an excellent feeling in use can be obtained, and the present invention has been completed.

That is, the present invention is as follows.
1. Particulate scrubbing agent containing gelatinized starch and having a gelatinization degree of 10 to 90%.
2. The scrub agent according to 1, wherein the swelling disintegration rate is 1.0 to 5.0.
3. The scrub agent according to any one of 1 to 2, wherein the median diameter is 50 to 1000 μm.
4. The method for using a scrub agent according to any one of 1 to 3, characterized in that the scrub agent is brought into contact with water at the time of blending the scrub agent with the detergent or at the time of use.
The detergent containing the scrub agent in any one of 5.1-3.

The scrub agent obtained by the present invention has high hardness in the dry state, but the particles absorb and swell to a suitable degree at the time of blending with the detergent and at the time of use, and the surface becomes smooth, and as a scrub agent as a whole. The soft surface can reduce irritation to the skin etc while maintaining the peeling function and the massage effect. Moreover, since it can manufacture without using an organic solvent etc., the scrub agent which can be manufactured with a water solvent can be provided.

Hereinafter, the present invention will be described in detail. The scrub agent in the present invention is characterized by containing gelatinized starch and having a gelatinization degree of 10 to 90%.

Examples of starch that can be used in the scrub agent of the present invention include potato starch, corn starch, high amylose corn starch, waxy corn starch, green bean starch, green bean starch, sweet potato starch, tapioca starch, waxi tapioca starch, sago starch, rice starch, mochi rice starch, Natural starches such as amaranth starch, mulberry starch and wheat starch, and modified starches thereof (acid-degraded starch, oxidized starch, starch derivatives such as etherification, esterification, crosslinking, etc.) can be mentioned. The starch may be used alone or in combination of two or more. Among them, potato starch, corn starch, green bean starch, green bean starch and sweet potato starch are suitably used in the present invention.

(1) Gelatinization When ungelatinized starch in a crystalline state is heated in the presence of water, the starch granules gradually start to swell and develop viscosity. This phenomenon is an example of gelatinization, and starch molecular chains having a crystal structure due to hydrogen bonds break due to heating, hydrogen bonds are broken, crystal structure is loosened, and water molecules enter between molecular chains and caused by hydration. . The temperature at which this gelatinization starts is called gelatinization start temperature, and is defined as a point at which an endothermic peak of differential scanning calorimetry (DSC) appears. The gelatinized starch confirms partial / complete disappearance of the birefringence of the starch observed under a polarizing microscope as compared to ungelatinized starch. Moreover, the powder obtained by rapidly drying the starch in such a gelatinized state in a high temperature state with a dryer such as a drum dryer or an extruder can reproduce the gelatinized state with cold water, so that it can be used in various applications. It is used by

(2) Aging On the other hand, when gelatinized starch is cooled, white turbidity and syneresis occur with the passage of time. This phenomenon is called aging, and is caused by recomposition and aggregation of hydrogen bonds between starch molecular chains again. The starch in such a state is called aged starch and has a crystal structure different from that of ungelatinized starch, and changes in crystallinity and disappearance of birefringence are confirmed as compared with ungelatinized starch. You can do it. Aging hardly occurs at high temperature (70 ° C. or higher), but the aging progresses accelerate as the temperature decreases and reaches a maximum at 2 to 4 ° C. just before water is frozen. Due to the characteristics described above, aged starch is resistant to reduced solubility in water and enzymatic degradation, and vermicelli and cold rice, which are typical examples, are recognized as foods containing resistant starch (RS). .

The gelatinized starch in the present invention refers to partially or completely gelatinized starch, and more specifically, to a state in which the gelatinization degree is 10% or more. Examples of the gelatinization method include a heating gelatinization method, an alkali gelatinization method, a gelatinization method using pressure and shear force, and the like, and are not particularly limited. One preferable gelatinization method is a heat gelatinization method, and as a gelatinization means in the case of using a heat gelatinization method, a method using a heating device such as a drum dryer, an extruder, a jet cooker, a hanging type or an extrusion type The method of putting into a hot water in the shape of a noodle by this, the method of shape | molding in a sheet shape, and heating with a metal plate top, a vapor | steam, etc., etc. are mentioned. Next, an example of a gelatinization process is given. First, starch and water are mixed to obtain a starch slurry (or dough). The moisture content of this mixture is adjusted according to the type of starch and the blending amount of other thickeners, but in consideration of moldability and production efficiency, a moisture content of about 25% to 75% is preferable. In addition, a part of starch or one in which a polysaccharide thickener such as carboxymethylcellulose or xanthan gum is dissolved may be mixed as a carrier paste to improve formability. Subsequently, heating is performed at a temperature higher than the gelatinization start temperature to gelatinize the starch slurry (or dough). It is preferable that the heating temperature and the heating time be appropriately adjusted according to the physical properties of the scrubbing agent to be obtained.

The water content of the scrub agent of the present invention is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, in consideration of the storability of the scrub agent and the workability at the time of use. As a drying method, in addition to sun drying and air drying, drying devices such as drum dryer, extruder, spray dryer, freeze dryer, tray dryer, belt dryer, fluid bed dryer, microwave dryer and the like Can be used.

It is preferable to grind | pulverize the scrub agent of this invention as needed. The pulverizing method is not particularly limited, and examples thereof include a hammer mill, a roller mill, a pin mill, a jet mill, a ball mill, a bead mill, a cutter mill and the like, and a granulator or classifier may be used if necessary. Grinding may be carried out in water, before or after drying.

The shape of the scrub agent of the present invention is not particularly limited as long as it is in the form of particles, but from the viewpoint of skin and eye irritation, it is preferable that the shape is more spherical.

The scrub agent in the present invention is characterized in that the degree of gelatinization measured by the method described in the examples is 10 to 90%. Furthermore, it is more preferable that the gelatinization degree is 20 to 50% from the viewpoint of achieving a better feeling in use, durability during use, and formulation stability to a detergent. If the gelatinization degree is 90% or more, the solubility in water is high, and if the gelatinization degree is less than 10%, the starch is not sufficiently gelatinized and the water absorption is poor, so the effect of the present invention is sufficient. Can not get

As a method for obtaining a desired gelatinization degree, (1) a method of stopping gelatinization at a desired gelatinization degree after the gelatinization degree reaches 10% or more (partial gelatinization method), (2) desired After gelatinizing to a gelatinization degree or more, two methods of cooling to a desired gelatinization degree (cooling method) may be mentioned. These methods may be performed alone or in combination. A preferred method is a cooling method, which includes a method of cooling to 70 ° C. or less after setting the gelatinization degree to a desired gelatinization degree or more. The cooling method is not particularly limited, and examples thereof include natural cooling and cooling in cold water, etc., and if necessary, it may be subjected to a refrigeration or freezing step. The cooling step may be performed before or after drying. As temperature at the time of cooling, -20-70 ° C is preferred, -10-30 ° C is still more preferred, and -5 ° C-10 ° C are especially preferred. The degree of gelatinization can also be controlled by adjusting the cooling time.

The effect of the scrub agent of the present invention can be judged by the swelling and disintegration rate. The scrub agent having a swelling and disintegration ratio of 1.0 or more, which is measured by the method described in the examples, indicates that it absorbs water and swells by contact with water, and the skin irritation is reduced. . On the other hand, a scrub agent having a swelling / disintegration rate of less than 1.0 causes the particle to be disintegrated, so that the durability of the scrub feeling during use and the compounding stability to a detergent are inferior. It is preferable that the swelling degradation rate of the scrub agent in this invention is 1.0-5.0. Among these, 1.0 to 1.3 is preferable in applications that require a strong scrub feeling. On the other hand, in the application which requests | requires a soft scrub feeling, 1.3-5.0 are preferable, 1.3-3.0 are more preferable, and 1.3-2.1 are especially preferable.

Although the particle size of the scrub agent in the present invention varies depending on the use application and the required scrub feeling, it is preferable that the median diameter in ethanol measured by the method described in the examples be 50 μm to 1000 μm. In particular, from the viewpoint of touch and feel, 100 μm to 500 μm is more preferable. On the other hand, if the median diameter is less than 50 μm, sufficient scrub feeling and massage effect can not be obtained.

The scrub agent of the present invention can obtain the scrub feeling and the compounding stability to the detergent characteristic of the present invention even with starch alone, but components other than starch may be added, and the effect of the present embodiment If necessary, add thickeners, surfactants, pigments, perfumes, oils, preservatives, and moisturizers, functional ingredients such as vitamins, etc., to the extent that they do not affect It is also good. For example, by adding polysaccharides such as carboxymethyl cellulose and xanthan gum, and alum, biodegradable plastics such as polylactic acid and cellulose acetate, etc., the workability at the time of production can be improved, the strength and swelling of the scrub agent, and washing The formulation stability to the agent can be improved. Moreover, it can also be set as a functional scrub agent by setting it as a coloring scrub agent using organic / inorganic pigments and pigment | dyes, such as iron oxide, and adding various agents, such as surfactant and a cosmetic liquid.

The scrub agent of the present invention is used by being added to a detergent. The cleaning agent of the present invention can be used not only for cosmetic applications but also for industrial applications. For cosmetic use, it can be used for face wash, hand wash detergent, cleansing agent, soap, shampoo, body soap, rinse, massage agent, pack agent, dentifrice, nail remover, bath agent and the like. Industrial (industrial) applications include cleaning agents used by workers in factories, cleaning agents for human hands and skin, cleaning agents for machine parts, and the like. Examples of the product form include cream, paste, gel, gel, liquid, solid or powder.

The scrub agent of the present invention can be used by absorbing and swelling the scrub agent, since it can reduce irritation to the skin and the like. The time of water absorption and swelling is not particularly limited, but may be at the time of formulation or storage of the scrub agent-containing product, at the time of use of the product, or the like.

When the scrub agent of the present invention is used as a detergent, the compounding amount can be appropriately changed depending on the product, but the amount of the scrub agent is 0.03 to 20% by mass based on 100% by mass of the entire detergent. Is preferably 0.3 to 10% by mass. The method of blending the scrub agent into the detergent can be carried out using a known blending method, and the scrub agent of the present invention is previously impregnated in water to adjust to the desired hardness and swelling degree You may mix | blend after.

The detergent of the present invention preferably contains water. The water is not particularly limited as long as it is water used for a detergent, and may be water previously included in components used for a detergent such as a surfactant. The content of water is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 8% by mass or more, based on 100% by mass of the total amount of the cleaning agent. By containing water, the scrub agent absorbs and swells moderately, and the surface becomes soft and smooth, thereby reducing the irritation to the skin and the like.

In the detergent of the present invention, components used in the detergent, anionic surfactant, amphoteric surfactant, nonionic surfactant, cationic surfactant, polyhydric alcohol, water-soluble polymer, water-soluble acid or Its salts, hydrocarbons, liquid oils and fats, solid fats and oils, waxes, higher alcohols, synthetic ester oils, silicone resins, silicone oils, lower alcohols, sequestering agents, powder components, ultraviolet absorbers, antioxidants, pH adjusters Organic amine, preservative, disinfectant, anti-inflammatory agent, astringent, skin-whitening agent, vitamins, amino acid, blood circulation promoter, activator, excipient, refreshing agent, various extracts, flavors, etc. It can be used in the range which does not lose

 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Production Example 1
4 parts by mass (hereinafter referred to as a part) of potato starch was dispersed in 50 parts of water and gelatinized in a boiling bath to obtain a carrier paste. After 96 parts of potato starch and 70 parts of water were added to the carrier paste, the mixture was thoroughly kneaded to form a starch slurry (water content: about 62%). The starch slurry was poured into a stainless steel tray to a thickness of about 1 cm, gelatinized in a steamer at 90 ° C. for 15 minutes, and then crude heat was taken in cold water to obtain gelatinized starch. Furthermore, after cooling the gelatinized starch at 4 ° C. to obtain a desired gelatinization degree, it is dried by a tray dryer (50 ° C.) until the water content becomes 20% by mass or less, and then a small pulverizer (Shibata science The mixture was crushed and classified by a sieve according to Kikuchi Kogyo Co., Ltd. (SCM-40A type) to obtain particulate scrub agents (A1 to A3) having different particle sizes.

Production Example 2
Production was carried out in the same manner as in Production Example 1 except that 4 ° C. was changed to -20 ° C. for cooling, to obtain particulate scrub agents (A4, A5) having different particle sizes.

Production Example 3 The procedure of Production Example 1 was repeated except that potato starch was changed to soybean starch to obtain particulate scrub agents (A6 to A9) having different particle sizes.

Production Example 4 The procedure of Production Example 1 was repeated except that potato starch was changed to mung bean starch, to obtain particulate scrub agents (A10, A11) having different particle sizes.

Production Example 5
0.5 parts of carboxymethylcellulose and 0.5 parts of alum were dispersed in 50 parts of water and dissolved by heating to form a carrier paste. After 70 parts of potato starch, 30 parts of sweet potato starch and 120 parts of water were added to this carrier paste, the mixture was sufficiently kneaded to form a starch slurry. The starch slurry was poured into a stainless steel tray to a thickness of about 1 cm and gelatinized in a steamer at 90 ° C. for 15 minutes, and then crude heat was taken in cold water to obtain a gelatinized starch-containing composition. Furthermore, the gelatinized starch-containing composition is cooled at 4 ° C. to obtain a desired gelatinization degree, and then dried by a tray dryer (50 ° C.) to a water content of 20% by mass or less, and then a small pulverizer The resultant was pulverized and classified by a sieve to obtain particulate scrub agents (A12, A13) having different particle sizes. The gelatinization degree of the gelatinized starch obtained by using the same method only with 70 parts of potato starch and 30 parts of sweet potato starch without adding carboxymethylcellulose and alum was 10% or more.

Production Example 6
0.5 parts of carboxymethylcellulose and 0.5 parts of xanthan gum were dispersed in 50 parts of water and dissolved by heating to form a carrier paste. After 70 parts of potato starch, 30 parts of corn starch and 120 parts of water were added to this carrier paste, the mixture was sufficiently kneaded to form a starch slurry. The starch slurry was poured into a stainless steel tray to a thickness of about 1 cm and gelatinized in a steamer at 90 ° C. for 15 minutes, and then crude heat was taken in cold water to obtain a gelatinized starch-containing composition. Furthermore, the gelatinized starch-containing composition is cooled at 4 ° C. to obtain a desired gelatinization degree, and then dried by a tray dryer (50 ° C.) to a water content of 20% by mass or less, and then a small pulverizer The resultant was pulverized and classified by a sieve to obtain particulate scrub agents (A14, A15) having different particle sizes. The gelatinization degree of gelatinized starch obtained by using the same method using only 70 parts of potato starch and 30 parts of corn starch without adding carboxymethylcellulose and xanthan gum was 10% or more.

Production Example 7
Four parts of waxy corn starch were dispersed in 50 parts of water and gelatinized in a boiling bath to form a carrier paste. After 96 parts of waxy corn starch and 70 parts of water were added to this carrier paste, the mixture was thoroughly kneaded to form a starch slurry. The starch slurry was poured into a stainless steel tray to a thickness of about 1 cm, and gelatinization was performed for 15 minutes in a steamer at 90 ° C. to obtain gelatinized starch. Furthermore, the gelatinized starch is allowed to cool at ordinary temperature to obtain a desired gelatinization degree, and then dried with a shelf dryer (50 ° C.) to a water content of 20% by mass or less, and then crushed with a small crusher, The resultant was classified by a sieve to obtain particulate scrub agents (A16, A17) having different particle sizes.

Production Example 8
Twenty parts of high amylose corn starch was dispersed in 50 parts of water and gelatinized in a boiling bath to form a carrier paste. After 80 parts of high amylose corn starch and 70 parts of water were added to this carrier paste, the mixture was thoroughly kneaded to form a starch slurry. The starch slurry was poured into a stainless steel tray to a thickness of about 1 cm, gelatinized in a steamer at 90 ° C. for 15 minutes, and then crude heat was taken in cold water to obtain gelatinized starch. Furthermore, after cooling the gelatinized starch at -5 ° C to obtain a desired gelatinization degree, it is dried by a tray dryer (50 ° C) until the water content is 20% by mass or less, and then crushed by a small crusher The resultant was classified by sieve to obtain particulate scrub agents (A18, A19) having different particle sizes.

[Comparative Production Example 1]
120 parts of water was added to 100 parts of potato starch to prepare a starch slurry. The obtained starch slurry was subjected to gelatinization and rapid drying using a double drum dryer (internal pressure of steam: 6.0 kg / cm ² , drum diameter φ 0.4 m, drum length 0.5 m, rotation speed 1.2 rpm) according to a conventional method. Conducted to obtain gelatinized starch. The obtained gelatinized starch was ground with a small grinder and classified with a sieve to obtain a film-like scrub agent (B1).

[Comparative production example 2]
The soybean starch is continuously fed at a feed rate of 22.0 g / min to a twin-screw extruder, and water is introduced at 3 to 5 g / min, barrel temperature 150 ° C, die outlet temperature 130 to 140 ° C, pressure By extruding at 60 to 80 kgf / cm ² , gelatinization and rapid drying were performed to obtain gelatinized starch. The obtained gelatinized starch was ground with a small grinder and classified with a sieve to obtain a particulate scrub agent (B2, B3).

[Comparative production example 3]
Using a fluid bed granulation coating apparatus, according to a conventional method, a solution of 5 parts of polyvinyl alcohol dispersed in 200 parts of water with respect to 100 parts of corn starch is granulated using a binder solution, classified by a sieve, and a granular scrub An agent (C1) was obtained.

[Comparative production example 4]
Using a fluid bed granulation coating apparatus, a solution of 3 parts of sodium alginate dispersed in 100 parts of water with respect to 100 parts of spherical fine granular starch "Graflaw M" (manufactured by Sun Seri Co., Ltd.) is coated on the surface of spherical fine granular starch did. Subsequently, a solution of 3 parts of calcium chloride dispersed in 100 parts of water was coated to perform water resistance. The obtained water-resistant granulated material was classified by a sieve to obtain a granular scrub agent (C2).

Table 1 shows particle sizes, swelling and disintegration rates and gelatinization degrees of the scrub agents A1 to A19. In addition, as a comparative example, non-gelatinized potato starch raw material (N1), scrub agents B1 to B3 and C1 to C2 prepared in the comparative production example, commercially available corn cob ground product (D1), glucomannan scrub (E1) The particle size, the swelling and disintegration rate and the degree of gelatinization of each are shown in Table 2. Each physical property value described in Tables 1 and 2 was measured by the following method.

[Measurement of particle size]
Measure using a laser diffraction particle size distribution analyzer (SALD-2200: manufactured by Shimadzu Corporation, using a batch cell), disperse the scrub agent in ethanol and in water, and measure the median diameter after 1 minute It is a value.

[Swelling disintegration rate]
The swelling and disintegration rate of the scrubbing agent in water was calculated according to the following equation.
Swelling disintegration rate = (median diameter of scrub agent in water) ÷ (median diameter of scrub agent in ethanol)

[Measurement of gelatinization degree]
The scrub agents A1, A4, A6, A10, A12, A14, A16, A18 and N1, B1, B2 are scrubbed with a small crusher, if necessary, after passing through a 100 mesh sieve Let it be a measurement sample. The gelatinization degree was measured by the following method.

(reagent)
0.8 M acetate buffer (pH 6.0)
・ 2M acetic acid solution
・ Enzyme solution (containing 3.4 units of pullulanase and 0.8 units of β-amylase in 1 mL)
Pullulanase and β-amylase were dissolved in 0.8 mol / L acetate buffer (pH 6.0), and the insoluble portion was dissolved in no. Filter with 2 filter paper.
・ Copper test solution
Solution A: 15% copper sulfate solution (CuSO ₄ · 5 H ₂ O 15 g / 100 mL)
Solution B: 25 g of anhydrous sodium carbonate, 25 g of Russel salt, 20 g of sodium hydrogen carbonate and 200 g of anhydrous sodium sulfate are made 1 L with ion-exchanged water.
Use as a copper reagent mixed with 1.0 mL of solution A and 25 mL of solution B.
Nelson's test solution 25 g of ammonium molybdate is dissolved in 900 mL of deionized water, to which 42 g of concentrated sulfuric acid and 3 g of disodium hydrogen arsenate heptahydrate are added. Further, ion exchange water is added to make the total amount 1 liter.

(Measuring method)
1. 100 mg of a sample is placed in a glass homogenizer (with Teflon® pestle), 10 mL of ion exchange water is added, and the homogenizer is moved up and down to achieve sufficient dispersion. After this, take 4 mL each into two 50 mL volumetric flasks.
2. Make a volume of 0.8M acetate buffer (pH 6.0), and use this as the sample for (A) sample. Add 0.4 mL of 10 M aqueous sodium hydroxide solution (NaOH) to the other and allow to gelatinize completely in a 50 ° C water bath for 3 to 5 minutes. Then neutralize by adding 2 mL of 2 M acetic acid. Make volume with 0.8 M acetate buffer (pH 6.0) (B) to make a completely gelatinized sample.
3. 4 mL of each of (A) and (B) is collected in a test tube, 1 mL of an enzyme solution is added, and the reaction is performed in a shaking thermostat at 40 ° C. for 30 minutes. At the same time, for (a) blank test, make a section to which 4 mL of sample for sample and 1 mL of inactivated enzyme (boiled for 10 minutes, filter precipitate with No. 2 filter paper) are added.
4. After completion of the reaction, inactivate the enzyme in a boiling bath for 5 minutes and dilute 5 times. From this, 1 mL is collected, and the reducing power is measured according to Somogyi-Nelson (Somogyi-Nelson method).
<Method based on Somogyi-Nelson method>
5. Add 1 mL of sample and 1 mL of copper reagent to a threaded test tube, stopper and heat in a boiling bath for 10 minutes.
6. After quenching, 1 mL of Nelson's reagent is added and mixed to dissolve copper (I) oxide (Cu ₂ O) and develop color. Add 20 mL of deionized water to dilute.
7. Measure absorbance at 500 nm after 15 minutes.
8. The degree of gelatinization is measured according to the following equation.
Degree of gelatinization (%) = ((A) absorbance of sample for sample-(a) absorbance of blank)) ((B) absorbance of completely gelatinized sample-(a) absorbance of blank) x 100

[Examples 1 to 19]
Five parts of the scrub agent A1 to A19 were added to 95 parts of a commercially available facial cleansing foam (manufactured by Kao Corporation: Biole skin care face cleanser rich moisture, the ingredients contain water), and thoroughly mixed and dispersed. A sensory evaluation was conducted using the scrub agent alone and the resulting scrub agent-containing facial wash foam. Evaluation items and evaluation methods are as follows, and the results are shown in Table 3.

(Evaluation of feeling of use)
(Test area A) 1 g of dry scrubbing agent, (Test area B) 1 g of scrub agent-containing face wash foam, (Test area C), 1 g of scrub agent-containing face wash foam with 10 g of water added The scrub feeling (graininess) when rubbed together was evaluated.
+3: Scrub feeling is quite strong +2: Scrub feeling is strong +1: Moderate scrub feeling (slightly stronger than 0)
0: Moderate scrub feeling -1: Moderate scrub feeling (somewhat weaker than 0)
-2: Scrub feeling is weak -3: Scrub feeling is very weak or does not feel scrub feeling

(Evaluation of sustainability)
In test area B, continue rubbing with palm for 1 minute. The durability was evaluated with respect to the sense of scrub after 1 minute (graininess).
: 1: Scrub feeling equal to that immediately after use even after 1 minute ○: Scrub feel after 1 minute ×: No scrub feeling

(Evaluation of irritation)
In the test zone C, the irritant ability when rubbing with a palm was evaluated.
:: no sensation of irritant such as pain ○: hardly irritant such as sensation of pain x: irritant such as sensation of pain, and discomfort

(Evaluation of formulation stability)
The adjusted scrubbing face wash foam was stored in a thermostat at 50 ° C. for one week. After one week, a test was conducted in the same manner as in Test Area B to evaluate the compounding stability.
◎: Scrub feeling similar to that immediately after preparation after 1 week ○: Scrub feeling after 1 week (slightly inferior to よ り)
X: After 1 week, the feeling of scrub decreased significantly or disappeared immediately after preparation

(Comprehensive evaluation)
S: Evaluation of feeling in use (test area B, C) is ± 1 or 0, and out of durability, irritation and compounding stability, x is not included and 以上 is 2 or more A: use When the evaluation of feeling (test area B, C) is ± 1 or 0, and 持 続 is one out of sustained, irritating, and compounding stability B: feeling of use (test area B, when the evaluation of C) is ± 1 or 0, and all of the persistence, irritation and compounding stability are C C: Evaluation of feeling in use (test area B, C) is ± 2 or ± 3 or in the case of x being 1 or more among durability, irritation and compounding stability

[Comparative Examples 1 to 8]
A scrub agent-containing cleansing foam was prepared and sensory evaluation was performed in the same manner as in Example 1 except that the scrub agent A1 was changed to the scrub agents N1, B1 to B3, C1 to C2, D1 and E1. The results are shown in Table 4.

As can be seen from the results in Tables 1 to 4, the scrub agents (A1 to A19) having a degree of gelatinization of 10 to 90% have high hardness in the dry particle state, and thus have a strong scrub feeling, I feel irritating. However, when incorporated into detergents and used, swelling of the particles and softening of the surface occur by absorbing moisture, and as a result, the irritation during use decreases. Furthermore, dissolution or disintegration does not occur even in the presence of water, and the particle shape is maintained, so that good durability and formulation stability to a detergent can be obtained.
On the other hand, when a scrubbing agent (B1 to B3) having a degree of gelatinization of 90% or more is used, swelling of particles occurs as in the above A1 to A19, but the scrub feeling and the cleaning agent which are the features of the present invention Compounding stability can not be obtained.

(Prescription Examples 1 to 7)
Although the formulation example of the cleaning agent containing the scrub agent of this invention is shown below, a formulation example is what was manufactured by the usual method in manufacture of each product, and showed only the content in an agent. Also, the present invention is not limited to these formulations. In addition, the numerical value described in each table is mass% when the whole composition is set to 100.

All the scrub-containing cleansing agents described in Formulation Examples 1 to 7 have no discomfort such as a feeling of pain when used, and have a good feeling of use even after long-term storage, and further the cleansing property and / or the massage effect Was excellent.

The scrub agent of the present invention is characterized by containing gelatinized starch. The above-mentioned scrubbing agents have an excellent scrubbing feeling, and also have low irritation such as not to feel pain on the skin and formulation stability to detergents.

Claims (4)

Particulate scrubbing agent containing gelatinized starch, having a gelatinization degree of 10 to 90%, and a swelling and disintegration ratio of 1.3 to 5.0 Median diameter of 50 to 1000 [mu] m, scrubbing agent according to claim 1. The method for using a scrub agent according to any one of claims 1 to 2 , characterized in that the scrub agent is brought into contact with water at the time of blending the scrub agent with the detergent or at the time of use. The cleaning agent containing the scrub agent in any one of Claims 1-2 .