JP6879999B2 - Cellulose granules, a method for producing the same, and a cleaning composition containing the granules. - Google Patents

Description

The present invention relates to cellulose granules and a method for producing the same. The present invention also relates to a composition containing the granules.

In recent years, it has removed aged keratinocytes and promoted metabolism by giving an appropriate stimulus to the skin, and it has entered the pores and dirt (extra keratin) that is difficult to remove with ordinary skin cleansers in physical cleaning. For the purpose of washing off dirt and the like, wash-off type facial cleansers, skin cleansers such as body soaps and bar soaps, and cosmetics containing particles in massage creams and the like are provided as scrub cleansers. These scrub cleaners are in widespread and persistent demand because they give an appropriate feeling of use (scrub feeling) when washing the skin with particles.

The particles (scrub particles) contained in such a scrub cleaning agent include particles of about 50 to 1000 μm made of crushed plant inner skin or seeds or seed nuclei, and synthetic resin-based polymers such as nylon powder and polyethylene powder. Can be mentioned.

Japanese Unexamined Patent Publication No. 10-226621 JP-A-2002-053459

In recent years, there is concern that scrub particles made of synthetic polymers that have been washed away after use will have an adverse effect on the environment by accumulating in the natural world without being decomposed after flowing into rivers and the ocean, and improvement is required. .. On the other hand, the crushed product of the inner pericarp or seed or seed nucleus of a plant is a naturally derived product and is environmentally friendly, but since it is obtained by crushing, the shape is distorted, so that it cannot be said that the slipperiness as particles is good. There is a concern that the sharp part may damage the skin.

Therefore, an object of the present invention is to provide granules that give an appropriate scrubbing feeling when used and have a small risk of adversely affecting the environment even if they flow into a river or the sea after being washed and rinsed.

In view of this situation, the present inventors have diligently studied the material, manufacturing method, characteristics, etc. of the particles to be used, and found that particles containing powdered cellulose and a water-soluble polymer are suitable, and further studies have been carried out. The present invention has been reached.

The present invention includes, for example, the subjects described in the following sections.
Item 1.
Contains powdered cellulose and water-soluble polymers
Powdered cellulose
1) The average value of the maximum aspect ratio is 1.5 to 3
2) Powdered cellulose with an average maximum diameter of 80 μm or less.
The content of the water-soluble polymer is 1 to 100 parts by mass with respect to 100 parts by mass of powdered cellulose.
Cellulose granules having an average particle size of 100 to 1400 μm.
Item 2.
Item 2. Cellulose granules according to Item 1, wherein the water-soluble polymer is polyvinyl alcohol or a modified product thereof.
Item 3.
Item 2. The cellulose granule according to Item 2, wherein the degree of saponification of polyvinyl alcohol or a modified product thereof is 80 to 99%.
Item 4.
Item 3. The cellulose granule according to any one of Items 1 to 3, which has an average circularity of 80 to 90.
Item 5.
Item 2. The cellulose granule according to any one of Items 1 to 4, wherein the 10% displacement compression strength is 1 MPa or more.
Item 6.
Item 2. The cellulose granule according to any one of Items 1 to 5, further containing a drug.
Item 7.
Item 2. The method for producing cellulose granules according to any one of Items 1 to 6.
(B) A method comprising a step of drying an aqueous solution of a water-soluble polymer (preferably polyvinyl alcohol or a modified product thereof) in which powdered cellulose is dispersed.
Item 8.
Item 7. The method according to Item 7, further comprising (A) a step of heating and stirring powdered cellulose, a water-soluble polymer, and water to obtain a water-soluble polymer aqueous solution in which powdered cellulose is dispersed before the step (B).
Item 9.
Item 7. The method according to Item 7 or 8, wherein the step (B) is a step of heating and stirring a water-soluble polymer aqueous solution in which powdered cellulose is dispersed to evaporate water to dry and granulate.
Item 10.
A cleaning composition containing the cellulose granules according to any one of Items 1 to 6.

The cellulose granules of the present invention can give an appropriate scrubbing feeling at the time of use, and even if they flow into a river or the sea by washing and rinsing, there is little possibility of adversely affecting the environment. Further, the cellulose granules of the present invention preferably have high storage stability even when blended in an aqueous or oil-in-water composition, and maintain a state of giving an appropriate scrubbing feeling for a long period of time.

The cellulose granules of the present invention are granules containing powdered cellulose and a water-soluble polymer.

[Powdered cellulose]
As the powdered cellulose contained in the cellulose granules of the present invention, known powdered cellulose can be used, and for example, powdered cellulose such as linter, pulp, and regenerated fiber can be used.

The powdered cellulose is a powdered cellulose having an average maximum aspect ratio of 1.5 to 3 and an average maximum diameter of 80 μm or less. By using the powdered cellulose as a raw material for the cellulose granules of the present invention, the cellulose granules of the present invention having an appropriate strength and a feeling of use can be obtained. Since powdered cellulose having an average maximum aspect ratio of more than 3 or an average maximum diameter of more than 80 μm is relatively long or relatively large as a cellulose fiber, it can be obtained by using such powdered cellulose. In the resulting cellulose granules, the cellulose fibers may protrude on the surface of the granules and the shape may be distorted. Even if the cellulose granules having a distorted shape are used as scrub particles, a cotton-like soft touch (feeling of use) is obtained, and a scrubbing feeling cannot be obtained. The average value of the maximum aspect ratio of the powdered cellulose is preferably 1.5 to 2.5. The average maximum diameter of the powdered cellulose is preferably 10 to 80 μm, more preferably 10 to 50 μm. The method of measuring the average value of the maximum aspect ratio and the average maximum diameter will be described later.

The average particle size of the powdered cellulose is preferably 10 to 60 μm, more preferably 10 to 50 μm. By setting the average particle size to 60 μm or less, fluffing due to the cellulose fibers on the surface of the obtained granule particles is suppressed, and there is a tendency to develop a better grain feeling and usability as scrub particles. Further, since the granule particles have a dense structure, an appropriate scrubbing feeling tends to be maintained for a longer period of time even when the granules are blended in an aqueous or oil-in-water composition. The method for measuring the average particle size will be described later.

As the particle shape of the powdered cellulose, fibrous or spherical powdered cellulose or the like can be used. The average circularity of the powdered cellulose is preferably 70 to 95, more preferably 80 to 95. By setting the average circularity to 70 or more, the number of long fibrous cellulose particles is reduced, and the surface of the obtained granule particles is smoothed, so that granules having a good usability tend to be formed. The method for measuring the average circularity will be described later.

As the powdered cellulose, those that have been mechanically dispersed and pulverized may be used. By this treatment, the average value, the average maximum diameter, the average particle size, etc. of the maximum aspect ratio of the powdered cellulose can be adjusted.

Examples of the equipment for performing the above-mentioned dispersion and crushing treatment include a dry crusher (for example, a hammer mill, a pin mill, a jet mill, etc.) or a wet crusher (for example, a bead mill, a disc mill, a high-pressure homogenizer). ..

[Water-soluble polymer]
Examples of the water-soluble polymer contained in the cellulose granules of the present invention include hydroxypropyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and modified products thereof. The water-soluble polymer may be used alone or in combination of two or more. Above all, powdered cellulose can be strongly bonded, and the storage stability in an oil-water solution (composition of an aqueous component and an oil-based component; particularly an oil-in-water type composition) in an aqueous solution of the obtained cellulose granules is high, and Since the environmental load when washed away by washing is small, a biodegradable water-soluble polymer is preferable, and polyvinyl alcohol or a modified product thereof is particularly preferable.

The average degree of polymerization of the polyvinyl alcohol or its modified product is preferably 100 to 3000, more preferably 300 to 2600. It is desirable to use polyvinyl alcohol having a relatively high average degree of polymerization or a modified product thereof because the adhesive strength is increased and the mechanical strength of the resulting cellulose granules is also increased. Since polyvinyl alcohol having a low average degree of polymerization or a modified product thereof has high heat meltability and water solubility, it is difficult to maintain stable particle strength when the obtained cellulose granules are blended in an aqueous or oil-in-water composition. By using polyvinyl alcohol having an average degree of polymerization in the above range or a modified product thereof, cellulose granules capable of preferably maintaining an appropriate scrubbing feeling for a long period of time can be obtained. The average degree of polymerization is calculated from the molecular weight measured by the GPC method.

The degree of saponification of the polyvinyl alcohol or a modified product thereof is preferably 80 to 99 mol%, more preferably 90 to 99 mol%, still more preferably 95 to 99 mol%. When the degree of saponification is less than 80 mol%, when the obtained cellulose granules are blended as scrub particles in an aqueous or oil-in-water composition, they are easily dissolved in water, the particle shape and strength cannot be maintained, and they are stable for a long period of time. May not exist. By using polyvinyl alcohol having a saponification degree in the above range or a modified product thereof, cellulose granules capable of preferably maintaining an appropriate scrubbing feeling for a long period of time can be obtained.

Examples of polyvinyl alcohol (PVA) modified products include anion-modified PVA derivatives and cationic-modified PVA derivatives. Examples of the anion-modified PVA derivative include carboxylic acid-modified PVA, undecylene-modified PVA, and sulfonic acid-modified PVA. Examples of the cation-modified PVA derivative include ammonium-modified PVA, sulfonium-modified PVA, and amino group-modified PVA.

An anion-modified PVA derivative, for example, a carboxylic acid-modified PVA can be produced by introducing a compound having a carboxy group into polyvinyl alcohol by a conventionally known method. Examples of the compound containing a carboxy group include fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, trimetic anhydride, acrylic acid and salts thereof. Further, the sulfonic acid-modified PVA can be produced by introducing a compound having a sulfonic acid group into polyvinyl alcohol by a conventionally known method. Examples of the compound having a sulfonic acid group include ethylene sulfonic acid, allyl sulfonic acid, metaallyl sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, p-sulfonic acid benzaldehyde and salts thereof.

The total content (ratio) of the powdered cellulose and the water-soluble polymer in the cellulose granules of the present invention is preferably 60 to 100% by mass, more preferably 80 to 100% by mass. By setting the total amount to 60% by mass or more, there is a tendency that an appropriate scrubbing feeling and excellent environmental compatibility are compatible with each other in a good balance.

The content ratio of the powdered cellulose and the water-soluble polymer in the cellulose granules of the present invention is 1 to 100 parts by mass of the water-soluble polymer with respect to 100 parts by mass of the powdered cellulose. The water-soluble polymer is preferably 2 to 80 parts by mass, more preferably 3 to 70 parts by mass, further preferably 4 to 60 parts by mass, and further preferably 5 to 50 parts by mass with respect to 100 parts by mass of powdered cellulose.

The cellulose granules preferably have a structure in which powdered celluloses are bonded to each other by a water-soluble polymer.

As the material constituting the cellulose granules of the present invention, a material other than powdered cellulose and a water-soluble polymer (sometimes referred to as “other components”) can also be used. Other components include, for example, film coating agents (eg, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, ethylcellulose aqueous dispersion, aminoalkylmethacrylate copolymer E, methacrylic acid copolymer L, Metaacrylic acid copolymer S, Metaacrylic acid copolymer LD, Aminoalkyl methacrylate copolymer RS, Hardened oil, etc.), Surfactants (For example, sucrose fatty acid ester, polyoxyethylene polyoxypropylene glycol, polysorbate, sodium lauryl sulfate, etc.) , Excipients (eg corn starch, potato starch, rice starch, powdered sugar, lactose, D-mannitol, trehalose, crystalline cellulose carmellose sodium, etc.), disintegrants (eg, low substitution hydroxypropyl cellulose, carmellose, etc.) Ingredients that can be generally used in preparations such as calcium, croscarmellose sodium, partially pregelatinized starch, etc. can be mentioned.

In addition, the cellulose granules of the present invention may contain a drug. In this case, the cellulose granules of the present invention can exert a drug-derived effect. Drugs include, for example, moisturizers, tactile improvers, reducing agents, oxidizing agents, preservatives, antibacterial agents, chelating agents, pH adjusters, UV absorbers, whitening agents, vitamins and their derivatives, anti-inflammatory agents, antifungal agents. Inflammatory agents, hair growth agents, blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging agents, tightening agents, cold sensitizers, warming agents, wound healing promoters, stimulant relievers, analgesics, cell activation Agents, plant / animal / microbial extracts, antipruritic agents, keratin exfoliating / dissolving agents, antiperspirants, refreshing agents, astringents, anti-inflammatory analgesics, antifungal agents, antihistamines, hypnotic sedatives, tranquilizers, antihypertensive agents, Antihypertensive diuretics, antibiotics, anesthetics, antibacterial substances, antiepileptic agents, coronary vasodilators, crude drugs, moisturizers, antipruritic agents, keratin softening release agents, UV blockers, antiseptic agents, antioxidants, etc. Can be mentioned. The method of including these drugs in the cellulose granules is a method of immersing the cellulose granules in a drug solution in which the drug is dissolved in an appropriate solvent (for example, water, alcohol, etc.), or a method of applying the drug solution to the cellulose granules (for example, application by spraying). The method of doing this can be exemplified. Cellulose granules may be dried after immersion or application.

The cellulose granules of the present invention can be produced, for example, by drying an aqueous solution of a water-soluble polymer in which powdered cellulose is dispersed (hereinafter, may be referred to as “powdered cellulose dispersion”).

The powdered cellulose dispersion can be produced, for example, by heating and mixing powdered cellulose such as linter, pulp, and regenerated fiber, polyvinyl alcohol, and water. As a result, a slurry-like dispersion liquid in which cellulose particles are dispersed in polyvinyl alcohol water is produced. The powdered cellulose used is a powdered cellulose having an average maximum aspect ratio of 1.5 to 3 and an average maximum diameter of 80 μm or less.

Heat mixing can be performed, for example, by mechanical treatment. A known method can be used as the mechanical treatment, and for example, heating and mixing can be performed using a reaction vessel with a stirring function, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, or the like. The powdered cellulose dispersion preferably contains, for example, 5 to 50% of solid content (total of powdered cellulose and water-soluble polymer), and more preferably 20 to 50%.

The higher the solid content concentration, the smaller the load for evaporation to dryness in the drying step, but if the solid content is too high, the liquid fluidity of the dispersion will be lost and uniform mixing will be difficult, so the fluidity will be reduced. It is desirable to disperse with a solid content that maintains.

Further, the drying can be carried out by evaporating the water by heating the cellulose powder dispersion liquid while standing or stirring. In particular, if drying is carried out under stirring and mixing, it is possible to produce cellulose granules having rounded corners (that is, granulated) and having high density and strength, which is preferable. Stirring and mixing in the drying step can be performed using, for example, a kneader with a jacket, a multi-screw dryer, or the like. After drying, the water content of the cellulose granules is preferably 2% or less.

Further, the obtained cellulose granules can be used as they are in the present invention, or may be pulverized if necessary. For example, granule crushed particles (crushed product) can be obtained by a pulverization treatment using a dry crusher (for example, a hammer mill, a pin mill, a jet mill, etc.) and a classification treatment (for example, wind power classification, sieving classification). The pulverized product can also be preferably used as the cellulose granules of the present invention.

The cellulose granules of the present invention preferably have an average circularity of 80 to 90. When the average circularity is 80 or more, the particle shape is not too distorted and a smooth feeling of use can be preferably obtained.

The cellulose granules of the present invention have an average particle size of 100 to 1400 μm, preferably 150 to 800 μm. If the average particle size is less than 100 μm, it may be difficult to feel the graininess when used as a scrubbing agent. Further, if the particle size exceeds 1400 μm, the grain size is strong at the time of use and the skin irritation becomes large, which may not be preferred.

The 10% displacement compression strength of the cellulose granules of the present invention is preferably 1 MPa or more, more preferably 2 to 15 MPa. When the 10% displacement compression strength is less than 1 MPa, the particle strength is weak and there is a tendency that a grainy feeling of moderate hardness cannot be felt.

Of the shape coefficients of powdered cellulose and cellulose granules, the average values of average circularity, average maximum diameter, average minimum diameter, and maximum aspect ratio are determined by an image analysis type particle size distribution measuring device (for example, Microtrac Bell Co., Ltd.). Measured using a Microtrack PartAn SI). It is also possible to use another image analysis type particle size distribution measuring device that can measure by the same principle (dynamic image analysis method). Each shape coefficient will be described below.

Circularity: A typical index showing how close the projected image is to a circle (circle equivalent diameter / peripheral major axis)
Circle equivalent diameter: Diameter of a circle with the same area as the particle projection image Peripheral major axis: Diameter of a circle with the same peripheral length as the projected image Average value of maximum aspect ratio: Maximum aspect calculated by minimum diameter / maximum diameter Average value of ratio Average maximum diameter: Average value of the diameter (maximum diameter) at which the distance between the two parallel lines sandwiching the particle image is maximum Average minimum diameter: The distance between the two parallel lines sandwiching the particle image is the minimum Average value of diameter (minimum diameter) The maximum diameter and the minimum diameter here are also referred to as the maximum ferret diameter and the minimum ferret diameter, respectively.

For the average particle size of the cellulose granules, 30 g of a sample is sieved for 15 minutes using a JIS standard sieve (Z8801-1987) using a low-tap sieve shaker (for example, Sheave Shaker A type manufactured by Heiko Seisakusho Co., Ltd.). Therefore, the particle size distribution is measured, and the cumulative particle size of 50% by weight is expressed as the average particle size. The number of repetitions is 3, and the average value is taken.

Further, the 10% displacement compression strength of the cellulose granules is 10 with respect to the particle shape by applying a load to the granulated particles (cellulose granules) using a microcompression tester (for example, a microcompression tester MCT-510 manufactured by Shimadzu Corporation). It is a value measured as the compressive strength at the time of% displacement.

The present invention also includes a cleaning composition containing the cellulose granules of the present invention. The cleansing composition is suitable as a composition (skin cleansing composition) used for washing the skin. More specifically, for example, it can be suitably used for washing pigments, body soaps, body shampoos, shower gels, hand soaps, hair shampoos, dish detergents, liquid laundry detergents and the like. The cleaning composition is preferably an aqueous composition or an oil-in-water composition.

In addition to the cellulose granules, the cleaning composition may contain any components (base material, carrier, active ingredient, etc.) usually used as long as the effects of the present invention are not impaired, depending on the use and purpose of the cleaning composition. May contain. These ingredients include, for example, surfactants, oils, thickeners, moisturizers, wetting agents, coloring agents, preservatives, astringents, fragrances, anti-inflammatory agents, bactericides, UV absorbers, antioxidants, etc. Examples include agents such as astringents, whitening agents and anti-inflammatory agents, water, alcohol and the like.

Examples of the content of cellulose granules in the cleaning composition include 0.5 to 30% by mass, 1 to 20% by mass, 2 to 10% by mass, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples. Hereinafter, the average circularity, the average maximum diameter, the average minimum diameter, and the average value of the maximum aspect ratio of the powdered cellulose and the cellulose granules are determined by an image analysis type particle size distribution measuring device (Microtrac PartAn manufactured by Microtrac Bell Co., Ltd.). Measured using SI). Regarding the average particle size of the cellulose granules, 30 g of the sample is sieved for 15 minutes using a JIS standard sieve (Z8801-1987) with a low-tap type sieve shaker (manufactured by Heiko Seisakusho Co., Ltd., sheave shaker A type). Therefore, the particle size distribution was measured, and the cumulative particle size of 50% by weight was taken as the average particle size. The 10% displacement compressive strength of the cellulose granules was determined by applying a load to the cellulose granules using a microcompression tester MCT-510 manufactured by Shimadzu Corporation and measuring the compressive strength at 10% displacement with respect to the particle shape. It was.

[Example 1]
Powdered cellulose "KC Flock W-400" (manufactured by Nippon Paper Co., Ltd., average value of maximum aspect ratio 2.1, average maximum diameter 35 μm) 100 parts by mass and polyvinyl alcohol "PVA124" (Kurare Co., Ltd., degree of polymerization 99%, An average degree of polymerization of 2400) 20 parts by mass and 300 parts by mass of water were put into a desktop kneader "PBV-06S" (manufactured by Irie Shokai Co., Ltd.), and the mixture was stirred at 90 ° C. for 1 hour to obtain powdered cellulose. A dispersed slurry-like dispersion was prepared.

Subsequently, while stirring and dispersing the slurry-like dispersion in the tabletop kneader, the jacket was heated to 98 ° C. and water was evaporated to produce cellulose granules.

The obtained cellulose granules had an average particle size of 550 μm and an average circularity of 87. The 10% displacement compression strength of the obtained cellulose granules was as high as 9.5 MPa, which was sufficient strength as scrub particles.

In addition, the tactile sensation of the cellulose granules was evaluated by five male panelists on a five-point scale based on the following criteria, and the average score was 5, which was smooth and able to give moderate irritation to the skin. The evaluation criteria were also used in the tactile evaluation of the following cellulose granules.

<Evaluation criteria for tactile sensation of cellulose granules>
5 points: It is slippery and has a strong graininess.

4 points: There is slipperiness and a grainy feeling is felt.

3 points: A grainy feeling is felt, but it is a little weak.

2 points: A grainy feeling is felt, but it is weak.

1 point: No graininess is felt.

[Example 2]
Same as in Example 1 except that the powdered cellulose "KC Flock W-400" was changed to "KC Flock W-100" (manufactured by Nippon Paper Industries, average value of maximum aspect ratio 2.8, average maximum diameter 62 μm). , Cellulose granules having an average particle diameter of 680 μm were produced. The cellulose granules had an average circularity of 82 and a high 10% displacement compression strength of 5.0 MPa, which was sufficient strength as scrub particles.

Moreover, when the tactile sensation of the cellulose granules was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and the slipperiness was smooth and moderate irritation could be given to the skin.

[Example 3]
Cellulose granules having an average particle size of 260 μm were prepared in the same manner as in Example 1 except that the amount of polyvinyl alcohol “PVA124” (Kuraray Co., Ltd., saponification degree 99%, average degree of polymerization 2400) was 10 parts by mass. Manufactured. The cellulose granules had an average circularity of 88 and a high 10% displacement compression strength of 12.6 MPa, and had sufficient strength as scrub particles. Moreover, when the tactile sensation of the cellulose granules was evaluated on a 5-point scale by 5 male panelists, the average score was 5 points, and the slipperiness was smooth and moderate irritation could be given to the skin.

[Example 4]
Instead of evaporating the water in the slurry-like dispersion using a tabletop kneader, the water is evaporated by static drying, and the recovered dry matter is used as a high-speed mill "Rotor Speed Mill vulvisette 14" (Fritsch Japan). Cellulose granules having an average particle size of 300 μm were produced in the same manner as in Example 1 except that the pulverization treatment was carried out using (manufactured by Co., Ltd.). The cellulose granules had an average circularity of 84 and a high 10% displacement compression strength of 1.4 MPa, and had sufficient strength as scrub particles.

Moreover, when the tactile sensation of the cellulose granules was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and the slipperiness was smooth and moderate irritation could be given to the skin.

[Example 5]
The average particle size was the same as in Example 1 except that the polyvinyl alcohol "PVA124" was changed to "AH-26" (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree 97-99%, average degree of polymerization 2600). 260 μm cellulose granules were produced. The cellulose granules had an average circularity of 88 and a high 10% compressive strength of 10 MPa, and had sufficient strength as scrub particles.

Moreover, when the tactile sensation of the cellulose granules was evaluated on a 5-point scale by 5 male panelists, the average score was 5 points, and the slipperiness was smooth and moderate irritation could be given to the skin.

[Example 6]
A pseudo scrub detergent was prepared by blending 5 parts by mass of the cellulose granules obtained in Example 1 with 100 parts by mass of a commercially available cleaning agent (without scrubbing agent added). When the feeling of use of this pseudo-scrub detergent was evaluated by 5 male panelists, the average score was 5, and it was found that a smooth and good grain feeling was felt in the detergent.

In addition, when the feeling of use after leaving the above-mentioned pseudo-scrub detergent at 60 ° C. for 6 months was evaluated on a 5-point scale by 5 male panelists, the average score was 5 points, and a good grain feeling could be felt without discomfort. there were. The evaluation criteria were also used in the evaluation of the usability of the following scrub cleaners. In addition, the commercially available cleaning agents (without scrubbing agent added) used below are all the same.

<Evaluation criteria for usability of scrub cleaner>
5 points: It is slippery and has a strong graininess.
4 points: There is slipperiness and a grainy feeling is felt.
3 points: A grainy feeling is felt, but it is a little weak.
2 points: A grainy feeling is felt, but it is weak.
1 point: No graininess is felt.

[Example 7]
A pseudo scrub detergent was prepared by blending 5 parts by mass of the cellulose granules obtained in Example 2 with 100 parts by mass of a commercially available cleaning agent (without scrubbing agent). When the feeling of use of this pseudo-scrub detergent was evaluated by 5 male panelists, the average score was 4, and it was found that a smooth and good grain feeling was felt in the detergent.

In addition, when the feeling of use after leaving the above-mentioned pseudo-scrub detergent at 60 ° C. for 6 months was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and a good grain feeling could be felt without discomfort. there were.

[Example 8]
A pseudo scrub detergent was prepared by blending 5 parts by mass of the cellulose granules obtained in Example 3 with 100 parts by mass of a commercially available cleaning agent (without scrubbing agent). When the feeling of use of this pseudo-scrub detergent was evaluated by 5 male panelists, the average score was 5, and it was found that a smooth and good grain feeling was felt in the detergent.

In addition, when the feeling of use after leaving the above-mentioned pseudo-scrub detergent at 60 ° C. for 6 months was evaluated on a 5-point scale by 5 male panelists, the average score was 5 points, and a good grain feeling could be felt without discomfort. there were.

[Example 9]
A pseudo scrub detergent was prepared by blending 5 parts by mass of the cellulose granules obtained in Example 4 with 100 parts by mass of a commercially available cleaning agent (without scrubbing agent). When the feeling of use of this pseudo-scrub detergent was evaluated by five male panelists, the average score was 4, and it was found that a smooth and good grain feeling was felt in the detergent.

In addition, when the feeling of use after leaving the above-mentioned pseudo-scrub detergent at 60 ° C. for 6 months was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and a good grain feeling could be felt without discomfort. there were.

[Example 10]
A pseudo scrub detergent was prepared by blending 5 parts by mass of the cellulose granules obtained in Example 5 with 100 parts by mass of a commercially available cleaning agent (without scrubbing agent added). When the feeling of use of this pseudo-scrub detergent was evaluated by 5 male panelists, the average score was 5, and it was found that a smooth and good grain feeling was felt in the detergent.

In addition, when the feeling of use after leaving the above-mentioned pseudo-scrub detergent at 60 ° C. for 6 months was evaluated on a 5-point scale by 5 male panelists, the average score was 5 points, and a good grain feeling could be felt without discomfort. there were.

[Example 11]
Similar to Example 1, except that "PVA224" (manufactured by Kuraray Co., Ltd .: saponification degree 86 to 89%, average degree of polymerization 2400) was used instead of the polyvinyl alcohol "PVA124", the average particle size was 350 μm. Cellulose granules were produced. The average circularity of the cellulose granules was 84, and the 10% compressive strength was as high as 4.0 MPa, which was sufficient strength as scrub particles.

In addition, when the tactile sensation of the cellulose granules was evaluated on a 5-point scale by 5 male panelists, an average of 5 points was obtained, and the slipperiness was smooth and moderate irritation could be given to the skin.

Further, using the cellulose granules, a cleaning agent was produced in the same manner as in Example 6. When the feeling of use of this pseudo-scrub detergent was evaluated on a 5-point scale by 5 male panelists, the average score was 5, and a smooth and good grain feeling was felt in the detergent.

Further, when the feeling of use of the pseudo-scrub cleaning agent after being left at 60 ° C. for 6 months was evaluated on a 5-point scale in the same manner, the average score was 3 points, and although it is considered that the change with time occurred in the cleaning agent, the graininess was felt. Was felt.

[Example 12]
Cellulose granules having an average particle size of 700 μm were prepared in the same manner as in Example 1 except that the amount of polyvinyl alcohol “PVA124” (Kuraray Co., Ltd., saponification degree 99%, average degree of polymerization 2400) was 100 parts by mass. Manufactured. The cellulose granules had an average circularity of 80 and a high 10% displacement compression strength of 14.5 MPa, and had sufficient strength as scrub particles.

Moreover, when the tactile sensation of the cellulose granules was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and the slipperiness was smooth and moderate irritation could be given to the skin.

Further, using the cellulose granules, a cleaning agent was produced in the same manner as in Example 6. When the feeling of use of this pseudo-scrub detergent was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and a smooth and good grain feeling was felt in the detergent.

Further, when the feeling of use of the pseudo-scrub detergent after being left at 60 ° C. for 6 months was similarly evaluated on a 5-point scale, the average score was 4 points, and a good grain feeling could be felt without discomfort.

[Comparative Example 1]
Examples except that the powdered cellulose "KC Flock W-400" was changed to "KC Flock W-50" (manufactured by Nippon Paper Co., Ltd., average maximum aspect ratio 3.5, average maximum diameter 94 μm, average minimum diameter 27 μm). Cellulose granules having an average particle size of 460 μm were produced in the same manner as in 1. The average circularity of the cellulose granules was 75, the cellulose fibers were protruding from the surface of the granule particles and fluffed, the slipperiness was poor, and the 10% compression strength was as low as 0.8 MPa. When the tactile sensation of the cellulose granules was evaluated on a 5-point scale by five male panelists, the average score was 2 points, and the particles did not have a grainy feel as scrub particles.

Further, using the cellulose granules, a cleaning agent was produced in the same manner as in Example 6. When the feeling of use of this pseudo-scrub cleaning agent was evaluated on a 5-point scale by 5 male panelists, the average score was 2 points, and the feeling of use was insufficient because no smooth grain feeling was felt in the cleaning agent.

Further, when the feeling of use of the pseudo-scrub detergent after being left at 60 ° C. for 6 months was similarly evaluated on a 5-point scale, the average score was 2 points, and a good grain feeling could not be felt.

[Comparative Example 2]
Cellulose having an average particle diameter of 250 μm in the same manner as in Example 1 except that the powdered cellulose “KC Flock W-400” was changed to “Linter pulp” (average value of maximum aspect ratio 4.0, average maximum diameter 105 μm). Granules were produced. The average circularity of the cellulose granules was 70, the cellulose fibers protruded from the surface of the particles (granule) and became fluffy, the slipperiness was poor, and the 10% compression strength was as low as 0.6. When the tactile sensation of the cellulose granules was evaluated on a 5-point scale by five male panelists, the average score was 2 points, and the particles did not have a grainy feel as scrub particles.

Further, using the cellulose granules, a cleaning agent was produced in the same manner as in Example 6. When the feeling of use of this pseudo-scrub cleaning agent was evaluated on a 5-point scale by five male panelists, the average score was 2 points, and the feeling of use was insufficient because no smooth grain feeling was felt in the cleaning agent.

Further, when the feeling of use of the pseudo-scrub detergent after being left at 60 ° C. for 6 months was similarly evaluated on a 5-point scale, the average score was 2 points, and a good grain feeling could not be felt.

[Example 13]
Similar to Example 1, except that "PVA505" (manufactured by Kuraray Co., Ltd .: saponification degree 73 to 75%, average degree of polymerization 2000) was used instead of the polyvinyl alcohol "PVA124", the average particle size was 250 μm. Cellulose granules were produced. The average circularity of the cellulose granules was 85, and the 10% compressive strength was 2.0 MPa. When the tactile sensation of the obtained cellulose granules was evaluated on a 5-point scale by 5 male panelists, the average score was 5 points, and the slipperiness was smooth and moderate irritation could be given to the skin.

Further, using the cellulose granules, a cleaning agent was produced in the same manner as in Example 6. When the feeling of use of this pseudo-scrub detergent was evaluated on a 5-point scale by 5 male panelists, the average score was 5, and a smooth and good grain feeling was felt in the detergent.

However, when the feeling of use of the pseudo-scrub detergent after being left at 60 ° C. for 6 months was similarly evaluated on a 5-point scale, the average score was 1, suggesting that the shape of the particles could not be maintained.

This suggests that the degree of saponification of the polyvinyl alcohol used affects the stability of the cellulose granules.

[Comparative Example 4]
100 parts by mass of powdered cellulose "KC Flock W-400" (manufactured by Nippon Paper Co., Ltd., average value of maximum aspect ratio 2.1, average maximum diameter 35 μm) and 30 parts by mass of hydroxyethyl cellulose "HEC" (manufactured by Sumitomo Seika Co., Ltd.) And 300 parts by mass of water were put into a tabletop kneader "PBV-06S" (manufactured by Irie Shokai Co., Ltd.), and the mixture was stirred for 1 hour to prepare a slurry-like dispersion in which powdered cellulose was dispersed.

Instead of evaporating the water in the slurry-like dispersion using a tabletop kneader, the water is evaporated by static drying, and the recovered dry matter is used as a high-speed mill "Rotor Speed Mill granulesette 14" (Fritsch Japan). The same procedure as in Example 1 was carried out except that the pulverization treatment was carried out using (manufactured by Co., Ltd.), but cotton-like lumps were obtained and granules could not be obtained.

[Comparative Example 5]
Powdered cellulose "KC Flock W-400" (manufactured by Nippon Paper Co., Ltd., average value of maximum aspect ratio 2.1, average maximum diameter 35 μm) 100 parts by mass and polyvinyl alcohol "PVA124" (Kurare Co., Ltd., degree of polymerization 99%, Average degree of polymerization 2400) 150 parts by mass and 100 parts by mass of water were put into a desktop kneader "PBV-06S" (manufactured by Irie Shokai Co., Ltd.), stirred for 1 hour and mixed to form a slurry in which powdered cellulose was dispersed. A dispersion was prepared.

Subsequently, the jacket was heated to 98 ° C. while stirring and dispersing the slurry-like dispersion in the tabletop kneader, and water was evaporated to obtain a dry matter. , The slipperiness was poor, and it did not have a moderate tactile sensation.

[Example 14]
Powdered cellulose "Linter pulp" (average value of maximum aspect ratio 4.0, average maximum diameter 105 μm) 100 parts by mass dispersed in 300 parts by mass of water is used in a high-pressure dispersion treatment device (NIRO-SOAVI TYPE NS100IL2K, 150 MPa). The treatment was performed once to obtain a powdered cellulose dispersion. The average value of the maximum aspect ratio of the powdered cellulose in this powdered cellulose dispersion was 2.5, and the average maximum diameter was 48 μm.

Using this powdered cellulose dispersion (100 parts by mass in terms of powdered cellulose) and 20 parts by mass of polyvinyl alcohol "PVA124" (Kurare Co., Ltd., saponification degree 99%, average degree of polymerization 2400), the same as in Example 1. To produce cellulose granules having an average particle size of 320 μm.

The cellulose granules had an average circularity of 81 and a high 10% displacement compression strength of 11.0 MPa. Moreover, when the tactile sensation of the cellulose granules was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and the slipperiness was smooth and moderate irritation could be given to the skin.

Further, using the cellulose granules, a cleaning agent was produced in the same manner as in Example 6. When the feeling of use of this pseudo-scrub detergent was evaluated on a 5-point scale by 5 male panelists, the average score was 4 points, and a smooth and good grain feeling was felt in the detergent.

Further, when the feeling of use of the pseudo-scrub detergent after being left at 60 ° C. for 6 months was similarly evaluated on a 5-point scale, the average score was 4 points, and a good grain feeling could be felt without discomfort.

Claims (9)

Contains powdered cellulose and water-soluble polymers
Powdered cellulose
1) The average value of the maximum aspect ratio is 1.5 to 3
2) Powdered cellulose with an average maximum diameter of 80 μm or less.
The content of the water-soluble polymer is 1 to 100 parts by mass with respect to 100 parts by mass of powdered cellulose.
The average particle diameter of Ri 100~1400μm der,
10% displacement compressive strength 1MPa or more der Ru cellulose granules. The cellulose granule according to claim 1, wherein the water-soluble polymer is polyvinyl alcohol or a modified product thereof. The cellulose granule according to claim 2, wherein the degree of saponification of polyvinyl alcohol or a modified product thereof is 80 to 99%. The cellulose granule according to any one of claims 1 to 3, wherein the average circularity is 80 to 90. The cellulose granule according to any one of claims 1 to 4 , further containing a drug. The method for producing cellulose granules according to any one of claims 1 to 5.
(B) A method comprising a step of drying a water-soluble polymer aqueous solution in which powdered cellulose is dispersed. The method according to claim 6 , further comprising (A) a step of heating and stirring powdered cellulose, a water-soluble polymer, and water to obtain a water-soluble polymer aqueous solution in which powdered cellulose is dispersed before the step (B). .. The method according to claim 6 or 7 , wherein the step (B) is a step of heating and stirring a water-soluble polymer aqueous solution in which powdered cellulose is dispersed to evaporate water to dry and granulate. A cleaning composition containing the cellulose granules according to any one of claims 1 to 5.