JP6063725B2 - Pigment granules - Google Patents

Description

  The present invention relates to pigment granules useful for detergents such as whole body cleansers and facial cleansers, a method for producing the pigment granules, a detergent containing the pigment granules, and a method for coloring bubbles during washing.

Conventionally, cosmetics, pharmaceuticals and the like containing granules containing pigments are known.
Patent Document 1 discloses a primary composition having a water-insoluble average particle size of 50 μm or less as a cosmetic composition having an appropriate massage / cleaning effect by disintegrating granules when applied to hands and skin during use. A cosmetic composition is disclosed in which granules granulated using a water-soluble binder are blended with disintegrable granules having a specific particle size coated with a water-insoluble coating agent.
Patent Document 2 includes a solid particulate pigment that dissolves quickly in water, and includes an outer water-soluble shell and organic and / or inorganic pigments as pigments suitable for paints, coating agents, printing inks, and cosmetics. An encapsulated pigment comprising a core is disclosed.

JP 2000-169338 A JP 2005-120368 A

Patent Document 1 is a cosmetic composition that imparts a massage effect and the like, and is a technique that requires disintegrating granules with physical force.
Patent Document 2 is a solid particulate pigment intended to be mixed and dissolved in various compositions and colored, and is not a technique for stably presenting granules in the composition.
Usually, the foam of the detergent contains a large amount of bubbles, and the liquid film of the foam is very thin. Therefore, in order to color the foam, a large amount of pigment must be blended with the cleaning agent. As a result, the liquid color of the cleaning agent becomes dark, and the satisfaction of the user cannot be obtained.
The present invention relates to a pigment granule capable of suppressing coloration during storage of a cleaning agent and capable of quickly developing foam during cleaning, a method for producing the pigment granule, a cleaning agent containing the pigment granule, and a method for coloring foam during cleaning. The issue is to provide.

The inventors of the present invention have disclosed that the core-shell pigment granules granulated using two specific water-soluble binders retain their granular form during storage of the detergent containing the granules, thereby It was found that coloring was suppressed, and when the detergent was bubbled, the granule rapidly disintegrated and dispersed, and the foam could be developed quickly.
That is, the present invention relates to the following [1] to [4].
[1] A pigment granule containing a pigment, polyvinyl pyrrolidone and polyvinyl alcohol, having a pigment and polyvinyl pyrrolidone in the core portion and having polyvinyl alcohol in the shell portion.
[2] A cleaning agent containing the pigment granule according to [1].
[3] A method for producing pigment granules, comprising the following steps A and B.
Step A: (a) Step of adding and granulating (b) a polyvinylpyrrolidone solution to the powder containing the pigment Step B: (c) Adding and granulating the polyvinyl alcohol solution to the granulated product obtained in Step A Step [4] A method for coloring bubbles during washing, using the pigment granules according to [1].

  The detergent containing the pigment granules of the present invention suppresses the coloring of the detergent by maintaining the granular form during storage, and the pigment granules rapidly disintegrate and disperse during use and quickly foam. Can develop color.

It is a figure which shows the film solubility test method of polyvinyl alcohol.

[Dye granules]
The pigment granule of the present invention is a pigment granule containing a pigment, polyvinyl pyrrolidone, and polyvinyl alcohol, and is a pigment granule having a core-shell structure that contains a pigment and polyvinyl pyrrolidone in the core portion and polyvinyl alcohol in the shell portion.
The reason why the pigment granule of the present invention can improve the pigment granule stability in the cleaning agent and the color development property of the foam at the time of washing is not clear, but is considered as follows.
The pigment granule of the present invention has polyvinyl alcohol in the shell part, but this polyvinyl alcohol acts as a binder, imparts stability to the granule so as to maintain the granular form in the cleaning agent, and is contained in the core part. To prevent the release of pigments. On the other hand, since the core portion contains polyvinylpyrrolidone that can quickly disperse the dye during washing (foaming), coloring of the washing agent is suppressed during storage of the washing agent, but quickly during washing. It is thought that bubbles can be developed.
Hereinafter, the pigment granules of the present invention (hereinafter also simply referred to as “granules”) will be described.

<Dye>
The pigment used in the pigment granules of the invention is preferably used in cosmetics and the like, and any pigment selected from organic pigments and inorganic pigments can be used.
The pigment is preferably an organic pigment from the viewpoint of coloring bubbles, and the organic pigment is selected from an azo pigment, a phthalocyanine pigment, and a condensed polycyclic pigment from the viewpoint of stabilizing the granules in a detergent. Two or more species are preferred, and condensed polycyclic pigments are more preferred.
Examples of azo pigments include azo lake pigments, insoluble azo pigments, and condensed azo pigments. Examples of phthalocyanine pigments include phthalocyanine blue and phthalocyanine green. Examples of condensed polycyclic pigments include anthraquinone, quinacridone, and diazo pigments. One or more kinds selected from ketopyrrolopyrrole, perylene, perinone, and indigoid (Red No. 226) are preferably mentioned, diketopyrrolopyrrole or indigoid is more preferred, and indigoid is more preferred. These can be used alone or in combination of two or more.
The dye is preferably insoluble in water from the viewpoint of stably existing in the granules in the detergent. “Water-insoluble” means that the amount dissolved in 100 g of water at 20 ° C. is preferably 1 g or less, more preferably 0.1 g or less.
The content of the dye is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more in the pigment granule, from the viewpoint of promptly coloring the foam during washing. From the viewpoint of property, it is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

<Polyvinylpyrrolidone>
In the present invention, polyvinyl pyrrolidone is used not only as a water-soluble binder for granulating granules, but also from the viewpoint of rapidly dispersing a dye when foaming and using a detergent to quickly develop bubbles. .
The mass ratio of polyvinyl pyrrolidone to the pigment (polyvinyl pyrrolidone / dye) is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0, from the viewpoint of disintegrating the granule at the time of use and rapidly developing the foam. 0.03 or more, more preferably 0.035 or more, and from the viewpoint of the storage stability of the pigment granules in the cleaning agent, preferably 0.12 or less, more preferably 0.08 or less, still more preferably 0.06. It is as follows.
The content of polyvinylpyrrolidone in the granule is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% from the viewpoint of improving the dispersibility of the dye in the cleaning agent. From the viewpoint of rapidly disintegrating the granule at the time of use, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less. More preferably, it is 5 mass% or less.
The viscosity characteristic value (K value) of polyvinyl pyrrolidone is preferably 25 or less, more preferably 20 or less, from the viewpoint of rapidly disintegrating the granules at the time of use, rapidly dispersing the pigment and quickly developing the foam, From the viewpoint of granulation property of the granule, it is preferably 5 or more, more preferably 10 or more.

The K value of polyvinylpyrrolidone is a well-known viscosity characteristic value that correlates with the molecular weight, and can be calculated by applying a relative viscosity value (25 ° C.) measured by a capillary viscometer to the following Fikentscher equation. (H.Fikentscher, Cellulosechemie 13 (1932) 58-64 und 71-74)
_{K = (1.5 logη rel -1)} / (0.15 + 0.003c) + (300clogη rel + (c + 1.5c logη rel) 2) 1/2 /0.15c + 0.003c 2)
_ηrel : Relative viscosity of polyvinylpyrrolidone aqueous solution with respect to water (25 ° C)
c: Polyvinylpyrrolidone concentration (1%) in an aqueous polyvinylpyrrolidone solution

<Polyvinyl alcohol>
In the present invention, polyvinyl alcohol is not only used as a water-soluble binder for granulation, but also improves the stability of the granules so as to maintain the granular form in the cleaning agent during storage, and is contained in the core part. Used to prevent dye release.
As an embodiment of polyvinyl alcohol that is preferably used, from the viewpoint of the stability of granules in the cleaning agent, in the “polyvinyl alcohol film solubility test” described in the examples, when the sodium chloride concentration is 6% by mass, The film dissolution time is preferably 400 seconds or more, more preferably 500 seconds or more, still more preferably 600 seconds or more, and there is no particular upper limit, and it may be insoluble.
In addition, from the viewpoint of causing the granules to disintegrate during use and quickly developing bubbles, when the sodium chloride concentration is 1% by mass, the polyvinyl alcohol film dissolution time is preferably 250 seconds or less, preferably 200 seconds or less. Some are more preferable, more preferably 100 seconds or less, and there is no particular lower limit, but it may be 5 seconds or more.

As the polyvinyl alcohol, unmodified polyvinyl alcohol (hereinafter also referred to as “unmodified PVA”), acid-modified polyvinyl alcohol (hereinafter also referred to as “acid-modified PVA”), and the like can be used. The acid-modified PVA is a vinyl alcohol polymer containing a predetermined amount of carboxy group or sulfonic acid group, the former being called carboxylic acid-modified PVA and the latter being called sulfonic acid-modified PVA.
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.
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, methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, P-sulfonic acid benzaldehyde, and salts thereof.
The acid-modified degree of the acid-modified PVA is preferably 0.5 mol% or more, more preferably 1 mol% or more, from the viewpoint of quickly disintegrating the granules during use and improving the color development of the foam. From the viewpoint of the stability of the granules, it is preferably at most 10 mol%, more preferably at most 5 mol%.
Among polyvinyl alcohols, acid-modified PVA is preferable from the viewpoint of controlling salt sensitivity, and one or more selected from maleic acid-modified PVA, itaconic acid-modified PVA and sulfonic acid-modified PVA are more preferable. Modified PVA is more preferred.

The saponification degree of polyvinyl alcohol (unmodified PVA and acid-modified PVA) is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more, from the viewpoint of granule stability in the detergent. From the viewpoint of causing the granules to collapse during use and developing the bubbles quickly, it is preferably 99.5% or less, more preferably 99% or less.
The molecular weight of polyvinyl alcohol (unmodified PVA and acid-modified PVA) is preferably 5,000 or more, more preferably 30,000 or more, still more preferably 50,000 or more, from the viewpoint of granule stability in the cleaning agent. From the viewpoint of easiness, it is preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less.
The molecular weight of polyvinyl alcohol can be calculated from the degree of polymerization.
The degree of polymerization can be calculated from the relative viscosity between a completely saponified aqueous polyvinyl alcohol solution and water (see JIS K6726: 1994).
Polyvinyl alcohol can be used alone or in combination of two or more.

The content of polyvinyl alcohol in the granules is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, from the viewpoint of granule stability in the cleaning agent. More preferably, it is 0.2% by mass or more, and from the viewpoint of disintegrating the granule during use, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and still more preferably. 1% by mass or less.
The mass ratio of polyvinyl alcohol to polyvinyl pyrrolidone in the granules (polyvinyl alcohol / polyvinyl pyrrolidone) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably from the viewpoint of granule stability in the detergent. From the viewpoint of foam color developability, it is preferably 1 or less, more preferably 0.5 or less, and still more preferably 0.3 or less.
When adding polyvinylpyrrolidone and / or polyvinyl alcohol, it is preferable to use it in the state of an aqueous solution previously dissolved in water from the viewpoint of facilitating storage, weighing, and addition operation.

<Polyhydric alcohol>
In the present invention, a polyhydric alcohol can be used from the viewpoint of improving the solubility of the pigment granules and improving the color developability of the foam.
The polyhydric alcohol is preferably a polyhydric alcohol having 2 to 6 hydroxyl groups, preferably 3 to 6 hydroxyl groups. Specific examples thereof include glycols such as diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol and 1,4-butylene glycol; glycerols such as glycerin and diglycerin; sorbitol, mannitol, Examples thereof include sugar alcohols such as xylitol and maltitol. Among these, one or more selected from ethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, xylitol, and maltitol are preferable, and one or two selected from ethylene glycol, propylene glycol, glycerin, and sorbitol. The above is more preferable, and glycerin is still more preferable.

The polyhydric alcohol is preferably used in the shell part together with polyvinyl alcohol from the viewpoint of improving the solubility of the pigment granules.
The content of the polyhydric alcohol in the pigment granules is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably from the viewpoint of improving the solubility of the pigment granules. From the viewpoint of the granulation property of the pigment granules, it is preferably 30% by mass or less, more preferably 10% by mass or less, and further preferably 1% by mass or less.
The mass ratio of (polyhydric alcohol / polyvinyl alcohol) is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.1 or more, from the viewpoint of improving the solubility of the pigment granules. From the viewpoint of storage stability of the pigment granules in the cleaning agent, it is preferably 10 or less, more preferably 2 or less, and still more preferably 1 or less.

<Other ingredients>
In addition to the above-mentioned components, the pigment granules of the present invention preferably contain water-insoluble particles from the viewpoint of the stability and granulation properties of the granules in the cleaning agent. From the viewpoint of improving the color developability, it is preferable to contain water-soluble particles.
Here, “water-insoluble” means that when 1 part by mass of the target particles is dissolved in 99 parts by mass of water at 25 ° C., the solubility of the particles is less than 50% by mass (that is, the amount of dissolution of the target particles in 99 parts by mass of water is Less than 0.5 parts by mass), preferably 20% by mass or less, more preferably 10% by mass or less. “Water-soluble” means that the solubility under the same conditions is 50% by mass or more (that is, the amount of dissolution of target particles in 99 parts by mass of water is 0.5 parts by mass or more), preferably 90% by mass or more, more preferably 100% by mass. The solubility is calculated from the solid content in the filtrate by filtering the aqueous solution through a filter paper (No. 2 manufactured by ADVANTEC).

(Water-insoluble particles)
Examples of water-insoluble particles include water-insoluble organic particles and water-insoluble inorganic particles.
Examples of water-insoluble organic particles include (i) polyethylene, polypropylene, polyamide, polyethylene terephthalate, polystyrene, polyurethane and their crosslinked products, sodium poly (meth) acrylate, poly (meth) acrylate and their crosslinked products, ethylene Synthetic polymers such as rubber, propylene rubber, styrene-butadiene rubber, butadiene rubber, silicone rubber, and their crosslinked products, (ii) cellulose and its derivatives, chitosan and its derivatives, starch such as corn starch, fruit Examples thereof include natural polymers such as shells and derivatives thereof. Among these, from polyethylene, polyamide, polystyrene, sodium poly (meth) acrylate and cross-linked products thereof, poly (meth) acrylic acid ester and cross-linked product thereof, cellulose and derivatives thereof, starch such as corn starch, and derivatives thereof 1 type or 2 types or more selected are preferable, and 1 type or 2 types or more selected from starches, such as cellulose and corn starch, and derivatives thereof are more preferable.
Examples of water-insoluble inorganic particles include bentonite, talc, mica, kaolin, sepiolite, silica, calcium carbonate, titanium oxide, anhydrous silicic acid, hydroxy-calcium-apatite, and pearl. Among these, one or more selected from bentonite, talc, mica, kaolin, silica and the like are preferably used.

(Water-soluble particles)
Examples of the water-soluble particles include water-soluble organic particles and water-soluble inorganic particles.
Examples of water-soluble organic particles include (i) alkali salt of poly (meth) acrylic acid, alkali salt of (meth) acrylic acid / (meth) acrylic acid ester copolymer, alkali salt of acrylic acid / maleic acid copolymer, etc. (Ii) natural polymers such as methyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, hydroxyalkyl cellulose, modified starch (hydroxyalkyl-modified starch, phosphate ester-modified starch, etc.), sugars such as sucrose, lactose and glucose Is mentioned.
In addition, as water-soluble inorganic particles, chlorides such as sodium chloride (commercially available salt, high-purity purified salt, natural salt, etc.), potassium chloride, magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, aluminum sulfate Carbonates such as sodium carbonate and sodium hydrogen carbonate are listed. Among these, one or more water-soluble inorganic particles selected from sodium chloride, potassium chloride, magnesium chloride, sodium carbonate and the like are preferable.
The shape of the water-insoluble particles and the water-soluble particles is not particularly limited, and may be a spherical shape, a substantially spherical shape, a flat plate shape, a rod shape, or an irregular shape by pulverization, or a hollow or porous particle. Can be used. Moreover, said water-insoluble particle | grains and water-soluble particle | grains can be used individually or in combination of 2 or more types.

The average particle diameter of the water-insoluble particles or water-soluble particles is preferably 5 to 70 μm, more preferably 10 to 70 μm, from the viewpoints of ease of granulation and a sense of discomfort and washability when the particles are disintegrated. The average particle diameter is determined by the number average of 100 random particles observed with an optical microscope. When the particle has a major axis and a minor axis, the major axis is used.
The content of the water-insoluble particles in the pigment granules is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass from the viewpoint of the stability and granulation properties of the granules in the detergent. From the viewpoint of disintegrating the granules during use, it is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.
The mass ratio of the dye and the water-insoluble particles (dye / water-insoluble particles) is preferably 0.3 to 10, more preferably 0.5 to 5, and still more preferably 1 to 3.
The content of the water-soluble particles in the pigment granules is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more from the viewpoint of causing the granules to collapse during use. From the viewpoint of the stability of the granules, it is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

[Method for producing pigment granules]
Although the manufacturing method of the pigment granule of this invention is not specifically limited, According to the following manufacturing method, the pigment granule of the core shell structure of this invention can be manufactured efficiently.
Step A: (a) Step of obtaining a granulated product by adding (b) a polyvinylpyrrolidone solution (hereinafter also referred to as “PVP solution”) to the powder containing the pigment. Step B: Granulated product obtained in Step A (C) Step of adding a polyvinyl alcohol solution (hereinafter also referred to as “PVA solution”) and granulating

<Process A>
Step A is a step in which (a) the PVP solution is added to the powder containing the pigment (b) and granulated to obtain a granulated product that becomes a core part.
(A) As the powder containing the pigment, the above water-insoluble particles and water-soluble particles can be used in addition to the pigment. From the viewpoint of granulation, the water-insoluble particles are used in advance as a powder. It is preferable to prepare a granulated product by adding it to a granulator and premixing it to obtain (a) a dye-containing powder and then (b) adding a PVP solution.
(A) The content of the pigment in the powder containing the pigment is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less. It is.
The mass ratio of the pigment to the powder, particularly the water-insoluble particles (dye / water-insoluble particles) is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 1 or more, and preferably 10 or less. The following is more preferable, and 3 or less is still more preferable.

(B) The PVP solution is preferably an aqueous solution from the viewpoint of facilitating addition and granulation operation, but may contain a water-soluble organic solvent such as ethanol.
From the viewpoint of the granulation property of the pigment granules, (b) the PVP solution is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30 parts by mass with respect to 100 parts by mass of the powder containing the pigment. The above is more preferable. In addition, from the viewpoint of foam color development, (b) the PVP solution is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less.
Further, (b) the PVP concentration (solid content) of the PVP solution is preferably 3% by mass or more, more preferably 5% by mass or more, from the viewpoint of uniformly mixing the polyvinylpyrrolidone and the pigment. From the viewpoint of handling properties, it is preferably 30% by mass or less, more preferably 20% by mass or less.
In addition, the mass ratio of (polyvinylpyrrolidone / dye) is as described above.

(B) The viscosity of the PVP solution is preferably 1 mPa · s or more, more preferably 3 mPa · s, under measurement conditions at a temperature of 25 ° C. using a B-type viscometer, from the viewpoint of uniformly mixing polyvinylpyrrolidone and the dye. s or more, more preferably 5 mPa · s or more. From the viewpoint of the handleability of the granulated product, it is preferably 1000 mPa · s or less, more preferably 500 mPa · s or less, still more preferably 100 mPa · s or less, and even more preferably. 50 mPa · s or less.
(B) By adjusting the viscosity of the PVP solution to the above range and stirring granulation, granulation control, (b) uniform dispersion and handling of the PVP solution are facilitated, and properties such as hardness and disintegration are uniform. Pigment granules can be easily and stably produced.

(Granulation)
As a stirring granulator used for the pigment granule of the present invention, a stirring blade is provided inside the stirring tank, and is usually 30 mm or less, preferably 0.1 mm to between the stirring blade and the inner wall surface of the stirring tank. Preferable examples include an internal stirring granulator having a clearance of about 5 mm. Specific examples of internal agitation granulators include Henschel mixers, high speed mixers, vertical granulators, super mixers, vertical mixers such as GRAL-Gral, horizontal mixers such as Redige mixers, Spartan Luzers, pin mixers, etc. Is mentioned. Among these, from the viewpoint of granulation operation, a vertical stirring and rolling granulator such as a Henschel mixer and a high speed mixer is preferable, and a high speed stirring and rolling granulator such as a Henschel mixer is more preferable.
The tip peripheral speed of the stirring blade of the stirring granulator is preferably 5 to 40 m / s, more preferably 10 to 30 m / s, from the viewpoints of agglomeration and sizing properties.
The temperature of the jacket of the stirring granulator is preferably 5 to 50 ° C, more preferably 7 to 35 ° C, and still more preferably 10 to 25 ° C.
The addition time of the (b) PVP solution for granulation is preferably 1 to 100 minutes, more preferably 2 from the viewpoint of granulation and productivity, although it depends on the capacity of the stirring tank of the stirring granulator. It is about ~ 60 minutes.
(B) From the viewpoint of forming the granule of the core part after adding the PVP solution, preferably 10 seconds or more, more preferably 20 seconds or more, still more preferably 30 seconds or more, stirring and granulating, From the viewpoint of preventing the core portion from becoming too strong and reducing the color developability of bubbles during washing, the stirring is preferably performed for 60 minutes or less, more preferably 30 minutes or less, and even more preferably 10 minutes or less. It is preferable to granulate.

<Process B>
Step B is a step of obtaining pigment granules having a core-shell structure by adding (c) the PVA solution to the granulated product to be the core portion obtained in Step A and granulating. Further, from the viewpoint of improving the solubility of the pigment granules, (c) before, after or simultaneously with the addition of the PVA solution, the above-mentioned polyhydric alcohol is added to the granulated product to be the core part obtained in step A. be able to. It is preferable to add the polyhydric alcohol by mixing with the (C) PVA solution because the polyhydric alcohol can be uniformly applied to the core portion.
(C) The PVA solution is preferably an aqueous solution from the viewpoint of facilitating the addition and granulation operation, but may contain a water-soluble organic solvent such as ethanol.
(C) The viscosity of the PVA solution is preferably 10 mPa · s or more, more preferably 50 mPa · s, under measurement conditions at a temperature of 25 ° C. using a B-type viscometer from the viewpoint of uniformly mixing the polyvinyl alcohol and the dye. s or more, more preferably 100 mPa · s or more, and preferably 5000 mPa · s or less, more preferably 2000 mPa · s or less, and still more preferably 800 mPa · s or less, from the viewpoint of the handleability of the granulated product.

The amount of the (C) PVA solution added during granulation is preferably 1 with respect to 100 parts by mass of the powder containing the (a) pigment from the viewpoint of storage stability of the pigment granule in the detergent. More than 2 parts by mass, more preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and preferably from 50 parts by mass or less, more preferably 30 parts by mass or less, from the viewpoint of disintegration of the pigment granules during washing. Preferably it is 10 mass parts or less.
In addition, (c) the PVA concentration (solid content) of the PVA solution is preferably 3% by mass or more, more preferably 5% by mass or more from the viewpoint of obtaining a uniform shell portion of polyvinyl alcohol. From a viewpoint of property, Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less.
The addition time of the (C) PVA solution for granulation is preferably 0.5 to 60 minutes, more preferably from the viewpoint of granulation and productivity, although it depends on the capacity of the stirring tank of the stirring granulator. Is about 0.5 to 30 minutes.
Preferable conditions such as the type of the stirring granulator, the temperature of the jacket of the stirring granulator, the tip peripheral speed of the stirring blade of the stirring granulator, and the like are the same as those in step A.
(C) After adding the PVA solution, a shell portion is formed, and from the viewpoint of maintaining the granular form when blended into a cleaning agent or the like and stored in the cleaning agent, preferably 10 seconds or more, more preferably 20 seconds or more. Further, it is preferable to stir and granulate for 30 seconds or more, preferably 60 minutes or less, more preferably 30 minutes or less, still more preferably 10 minutes or less, and granulate.
The mass ratio of (polyvinylpyrrolidone / dye) and (polyvinyl alcohol / polyvinylpyrrolidone) is as described above.
The tip peripheral speed of the agitation blade of the granulator, the agitation granulator, and the temperature of the jacket of the agitation granulator are the same as the conditions of step A.

(Dry)
The pigment granules having a core-shell structure obtained in step B are preferably dried. By drying, the hardness can be adjusted to a good handleability.
The drying method is not particularly limited, and can be performed by a known method using, for example, a stationary type, a rotary type, a fluidized bed type, a vacuum drying type or the like. In particular, the hot air fluidized bed dryer is suitably used because it has advantages such as high productivity and low force applied to the granulated particles.
This drying step is performed by setting the temperature of the pigment granules to preferably 100 ° C. or less, more preferably 80 ° C. or less, from the viewpoint of the quality of the granulated product, in particular, the prevention of deterioration of solubility accompanying crystallization of the water-soluble binder. Is desirable. Further, from the viewpoint of productivity, it is preferable to carry out at 60 ° C. or higher, more preferably 70 ° C. or higher.

[Core-shell structured pigment granules]
The pigment granule of the present invention has a core-shell structure containing a pigment and polyvinylpyrrolidone in the core portion and polyvinyl alcohol in the shell portion. The shell portion preferably covers the entire core portion, but the core portion may be partially exposed as long as the effects of the present invention are not impaired.
The average particle diameter of the pigment granules of the present invention is preferably 50 μm or more, more preferably 75 μm or more, still more preferably 100 μm or more, and even more preferably 150 μm or more, from the viewpoint of the appearance of the cleaning agent. From the viewpoint of decreasing, it is more preferably 2000 μm or less, more preferably 1500 μm or less, and still more preferably 1000 μm or less.
The average particle diameter of the pigment granules can be measured by the method described in the examples.
The content of each component in the pigment granule is as described above.
The shape of the pigment granule is not particularly limited, and may be a spherical shape, a substantially spherical shape, a flat plate shape, a rod shape, or an irregular shape by pulverization.
The core part preferably contains water-insoluble particles from the viewpoint of granulation of the granules, and the shell part contains the above-mentioned polyhydric alcohol and / or water-soluble particles from the viewpoint of the disintegration characteristics of the granules. It is preferable to include. The content and mass ratio of each component are as described above.
In the pigment granules, the core / shell (mass ratio) is preferably 50/50 or more, more preferably 80/20 or more, still more preferably 90/10 or more, from the viewpoint of foam color development. From the viewpoint of the storage stability of the pigment granules, it is preferably 99.99 / 0.01 or less, more preferably 99.95 / 0.05 or less, still more preferably 99.9 / 0.1 or less.

[Washing soap]
The cleaning agent of the present invention contains the pigment granule from the viewpoint of the stability of the pigment granules in the cleaning agent and from the viewpoint of causing the granules to disintegrate during use and rapidly developing the foam.
The content of the pigment granules in the cleaning agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0, from the viewpoint of causing the granules to collapse during use and quickly developing bubbles. From the viewpoint of reducing the feel of the pigment granules of the cleaning agent, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
The content of the dye in the cleaning agent is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, and still more preferably 0.01% by mass or more from the viewpoint of foam color development. From the viewpoint of suppressing coloring of the agent, it is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less.
The method of blending the pigment granules into the cleaning agent is not particularly limited, but it can be easily prepared by directly adding the pigment granule into the cleaning agent and then performing a homomixer or stirring.

<Water-soluble salts>
The cleaning agent of the present invention preferably contains a water-soluble salt from the viewpoint of the stability of the pigment granules in the cleaning agent. Examples of the water-soluble salts include water-soluble inorganic salts and water-soluble organic salts, and these may be used alone or in combination of two or more. The water-soluble salts are salts that dissolve 10 g or more in 100 g of water (at 25 ° C.).
Examples of the water-soluble inorganic salt include chlorides such as sodium chloride, potassium chloride and magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate; carbonates such as sodium carbonate and sodium hydrogen carbonate. . In the case of sodium chloride, commercially available salt, highly purified salt, natural salt and the like are also used.
Examples of the water-soluble organic salt include citrate, succinate, maleate, fumarate, malate, phosphate, sulfate, and amino acid salt. These water-soluble inorganic salts and water-soluble organic salts can be used in combination, but water-soluble inorganic salts are preferred from the viewpoint of the stability of pigment granules in the detergent.
In the detergent, the total content of the water-soluble inorganic salt and the water-soluble organic salt is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of the stability of the pigment granules in the detergent. Yes, it is preferably 10% by mass or less, more preferably 8% by mass or less, from the viewpoint of disintegrating during use and causing the foam to develop a color quickly and from the viewpoint of foam performance of the cleaning agent.

<Surfactant>
The cleaning agent of the present invention preferably contains a surfactant. Surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants.
Anionic surfactants include fatty acid soaps, phosphate ester activators, sulfate ester activators, sulfonic acid activators, carboxylic acid activators, amino acid activators, sulfosuccinate activators, taurate activators, Examples of the nonionic surfactant include nonionic surfactants such as ester type, ether type, ether ester type, alkanolamide type, and alkylene glycol type, and amphoteric surfactants. Examples thereof include amphoteric surfactants such as imidazoline type, betaine type, and acylamino acid type. Among these, it is possible to use one or more selected from anionic surfactants, nonionic surfactants, and amphoteric surfactants from the viewpoints of stability and foamability of the detergent composition and detergency. preferable.
Although content of surfactant is not specifically limited, From a viewpoint of sufficient foaming property and detergency, Preferably it is 5-90 mass%, More preferably, it is 8-70 mass%, More preferably, it is 10-50 mass%, More preferably, it is 10-30 mass%.

In addition to the above components, components usually used for cleaning agents, such as oil agents, thickeners, moisturizers, wetting agents, coloring agents, preservatives, feel improvers, fragrances, flame retardants, bactericides, UV absorbers, astringents , Whitening agents, anti-inflammatory agents and the like can be used as long as the effects of the present invention are not impaired.
For example, as a moisturizing agent, amino acids such as L-arginine, alanine and glycine, lipids having moisturizing properties such as betaine, pyrrolidone carboxylic acid, ceramide, phospholipid, and plant extracts having moisturizing effects such as aloe, hypericum and okra Products, natural products such as yogurt and honey, and extracts and fractions thereof.
Examples of the disinfectant include trichlorohydroxydiphenyl ether (triclosan), isopropylmethylphenol, trichlorocarbanilide, sanizole, hexachlorophene, resorcin, crystal violet, benzethonium chloride, benzalkonium chloride, chlorhexidine gluconate, and derivatives thereof. .
Examples of UV absorbers include benzoic acid UV absorbers such as paraaminobenzoic acid and glyceryl paraaminobenzoic acid, salicylic acid UV absorbers such as menthyl salicylate, octyl salicylate, and phenyl salicylate, octyl cinnamate, ethyl Cinnamic acid-based ultraviolet absorbers such as -4-isopropyl cinnamate and diethanolamine p-methoxycinnamate, and animal and plant extracts having ultraviolet absorbing action such as yarrow, aloe, bellows, burdock, and salvia.
Examples of whitening agents include L-ascorbic acid and derivatives thereof, hydroquinone derivatives, placenta extract and ellagic acid and derivatives thereof, chamomile, tea, earthen ground, kakkon, clove, licorice, aloe, altea, rosemary and other plants. There are extracts, etc.
The cleaning agent of the present invention is preferably a liquid cleaning agent from the viewpoint of exhibiting the effect of the pigment granule of the present invention.
The cleaning agent of the present invention is, for example, a facial cleanser, body wash such as body soap and shower gel, cosmetics such as hand soap and shampoo, hard wash such as dishwashing detergent, or liquid laundry detergent. It can be used for washing clothes.

[Foam coloring method]
The coloring method of the foam of the present invention uses the pigment granules of the present invention. The pigment granules are contained in the cleaning agent, and when diluted with water, the pigment granules are disintegrated, the pigments are rapidly dissolved or dispersed, and the bubbles are rapidly colored. Physical force such as a hand or a cleaning tool may be applied to the disintegration of the pigment granules and the dissolution and dispersion of the pigments.
In the foam coloring method of the present invention, the detergent used is preferably diluted 2 to 10 times with water, more preferably 3 to 8 times.

In relation to the above-described embodiments, the present invention discloses the following pigment granules, a production method thereof, a cleaning agent containing pigment granules, and a method of coloring bubbles during washing.
<1> A pigment granule containing a pigment, polyvinyl pyrrolidone and polyvinyl alcohol, having a pigment and polyvinyl pyrrolidone in a core part and having polyvinyl alcohol in a shell part.

<2> The average particle size is preferably 50 μm or more, more preferably 75 μm or more, further preferably 100 μm or more, still more preferably 150 μm or more, and preferably 2000 μm or less, more preferably 1500 μm or less, and even more preferably 1000 μm. The pigment granule according to <1>, wherein:
<3> The pigment content is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less. The pigment granule according to <1> or <2>, more preferably 60% by mass or less.
<4> The dye is one or more selected from azo pigments, phthalocyanine pigments and condensed polycyclic pigments, preferably condensed polycyclic pigments, more preferably anthraquinone, quinacridone, di One or more selected from ketopyrrolopyrrole, perylene, perinone, and indigoid (Red No. 226), more preferably diketopyrrolopyrrole or indigoid, and even more preferably indigoid, <1 >-<3> The pigment granule in any one of.
<5> The mass ratio of polyvinylpyrrolidone to the dye (polyvinylpyrrolidone / dye) is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, and still more preferably 0.035 or more. The pigment granules according to any one of <1> to <4>, preferably 0.12 or less, more preferably 0.08 or less, and still more preferably 0.06 or less.

<6> The mass ratio of polyvinyl alcohol to polyvinyl pyrrolidone (polyvinyl alcohol / polyvinyl pyrrolidone) is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and preferably 1 or less. The pigment granules according to any one of <1> to <5>, more preferably 0.5 or less, still more preferably 0.3 or less.
<7> The content of polyvinyl alcohol is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more. And preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and still more preferably 1% by mass or less, according to any one of <1> to <6>. Pigment granules.
<8> The viscosity characteristic value (K value) of polyvinylpyrrolidone is preferably 25 or less, more preferably 20 or less, and preferably 5 or more, more preferably 10 or more, <1> to <7> The pigment granule according to any one of the above.
<9> Polyvinyl alcohol is acid-modified polyvinyl alcohol, preferably one or more selected from maleic acid-modified polyvinyl alcohol, itaconic acid-modified polyvinyl alcohol and sulfonic acid-modified polyvinyl alcohol, more preferably maleic acid. The pigment granule according to any one of <1> to <8>, which is a modified polyvinyl alcohol.

<10> In the “polyvinyl alcohol film solubility test” described in the examples, the film dissolution time of polyvinyl alcohol at a sodium chloride concentration of 6% by mass is preferably 400 seconds or more, more preferably 500 seconds or more, and still more preferably. The pigment granule according to any one of <1> to <9>, which is 600 seconds or longer.
<11> In the “polyvinyl alcohol film solubility test” described in the examples, the film dissolution time of polyvinyl alcohol at a sodium chloride concentration of 1% by mass is preferably 250 seconds or less, more preferably 200 seconds or less, and still more preferably. The pigment granule according to any one of <1> to <10>, which is 100 seconds or shorter, preferably 5 seconds or longer.
<12> The pigment granule according to any one of <1> to <11>, which contains a polyhydric alcohol, and preferably contains a polyhydric alcohol in the shell portion.
<13> The polyhydric alcohol is one or more selected from ethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, xylitol, and maltitol, preferably selected from ethylene glycol, propylene glycol, glycerin, and sorbitol. The pigment granule according to the above <112>, which is one type or two or more types, more preferably glycerin.
<14> The content of the polyhydric alcohol in the pigment granule is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably. The pigment granule according to <12> or <13>, which is 0.07% by mass or more, preferably 30% by mass or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less.
<15> The mass ratio of (polyhydric alcohol / polyvinyl alcohol) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 10 or less, more preferably 2 Hereinafter, the pigment granule according to any one of <12> to <14>, more preferably 1 or less.

<16> The pigment granule according to any one of <1> to <15>, further including water-insoluble particles, and preferably including water-insoluble particles in the core.
<17> The water-insoluble particles are one or more selected from water-insoluble organic particles and water-insoluble inorganic particles, preferably polyethylene, polyamide, polystyrene, sodium poly (meth) acrylate, and cross-linked products thereof. Poly (meth) acrylic acid esters and cross-linked products thereof, cellulose and derivatives thereof, starch and derivatives thereof such as corn starch, bentonite, talc, mica, kaolin, sepiolite, silica, calcium carbonate, titanium oxide, silicic anhydride, hydroxy 1 type or 2 types or more selected from pearls such as calcium and apatite, more preferably 1 type or 2 selected from starches such as cellulose and corn starch and derivatives thereof, bentonite, talc, mica, kaolin, silica, etc. It is more than a seed, described in the above <16> The pigment granules listed.
<18> The pigment granule according to <16> or <17>, wherein the water-insoluble particles have an average particle size of preferably 5 to 70 μm, more preferably 10 to 70 μm.
<19> The content of water-insoluble particles in the pigment granules is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, preferably 70% by mass or less, more preferably. The pigment granule according to any one of <16> to <18>, which is 60% by mass or less, more preferably 50% by mass or less.
<20> The mass ratio of the dye to the water-insoluble particles (dye / water-insoluble particles) is preferably 0.3 to 10, more preferably 0.5 to 5, and still more preferably 1 to 3. >-<19> The pigment granule in any one of.
<21> In the pigment granules, the core / shell (mass ratio) is preferably 50/50 or more, more preferably 80/20 or more, still more preferably 90/10 or more, and preferably 99.99 / 0.01. The pigment granule according to any one of <1> to <20>, more preferably 99.95 / 0.05 or less, and still more preferably 99.9 / 0.1 or less.

<22> A cleaning agent containing the pigment granule according to any one of <1> to <21>.
<23> The content of the pigment granules in the cleaning agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and preferably 10% by mass. Hereinafter, the cleaning agent according to <22>, more preferably 5% by mass or less, and further preferably 2% by mass or less.
<24> The content of the pigment in the cleaning agent is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, and preferably 3% by mass or less. The cleaning agent according to <22>, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less.
<25> The content of the surfactant in the cleaning agent is preferably 5 to 90% by mass, more preferably 8 to 70% by mass, still more preferably 10 to 50% by mass, and still more preferably 10 to 30% by mass. The cleaning agent according to any one of <22> to <24>, wherein
<26> For face washing, body wash such as body soap and shower gel, cosmetics such as hand soap and shampoo, hard washing such as dishwashing detergent, or washing clothes such as liquid laundry detergent The cleaning agent according to any one of <22> to <25>.

<27> The method for producing a pigment granule according to any one of <1> to <21>, which includes the following steps A and B.
Step A: (a) Step of adding and granulating (b) a polyvinylpyrrolidone solution to the powder containing the pigment Step B: (c) Adding and granulating the polyvinyl alcohol solution to the granulated product obtained in Step A <28> The method for producing a pigment granule according to <27>, wherein granulation is performed using a stirring tumbling granulator.
<29> The method for producing a pigment granule according to <28>, wherein the tip peripheral speed of the stirring blade of the stirring tumbling granulator is preferably 5 to 40 m / s, more preferably 10 to 30 m / s.
<30> After step (A) adding the (b) polyvinylpyrrolidone solution to the powder containing the pigment, preferably 10 seconds or more, more preferably 20 seconds or more, and even more preferably 30 seconds or more, preferably The method for producing pigment granules according to any one of <27> to <29>, wherein the mixture is stirred and granulated for 60 minutes or less, more preferably 30 minutes or less, and even more preferably 10 minutes or less.
<31> After adding the polyvinyl alcohol solution (c) to the granulated product obtained in step A, the step B is preferably 10 seconds or longer, more preferably 20 seconds or longer, still more preferably 30 seconds or longer, preferably The method for producing pigment granules according to any one of <27> to <30>, wherein stirring and granulation are performed for 60 minutes or less, more preferably 30 minutes or less, and even more preferably 10 minutes or less.
<32> A method for coloring bubbles during washing, using the pigment granule according to any one of <1> to <21>.

In the following examples and comparative examples, unless otherwise specified, “%” means “% by mass” and “parts” means “parts by mass”.
(1) Measurement of viscosity Viscosity was measured at 25 ° C using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVB-10M).
Rotor No. 2 (500 mPa · s or more) or 3 is used, and the measurement time is 1 minute.

(2) Measurement of average particle diameter of pigment granules 2000, 1400, 1000, 710, 500, 355, 250 of JIS Z8801-1 (established on May 20, 2000, final revised on November 20, 2006) Using a 12-stage sieve of 180, 125, 90, 63, 45 μm and a saucer, stack them in order from a sieve with a small opening on the saucer, add 100 g of particles from the top of the top 2000 μm sieve, and cover the lid. And attached to a low-tap type sieve shaker (manufactured by HEIKO MFG, tapping 156 times / minute, rolling: 290 times / minute), and after vibrating for 5 minutes, the mass of the particles remaining on the respective sieves and trays is measured. Measure and calculate the mass percentage (%) of the particles on each sieve. The mass ratio of the particles on the sieve having a small mesh size was accumulated in order from the saucer, and the particle size at which the total was 50% was defined as the average particle size.

(3) Polyvinyl alcohol film solubility test A casting film (film thickness: 15 ± 1 µm) was prepared from a defoamed aqueous solution (25 ° C) containing 15% by mass of polyvinyl alcohol using a table coater. Next, the PVA casting film obtained above is pasted between two 50 mm square mounts (with 30 mmΦ cutout windows), and as shown in FIG. 1, 1 L of water with each salt concentration is put into a 1 L beaker, and the mount Fix the mount with a clip so that the upper end of the casting film (the upper end of the casting film is 2 cm from the liquid level) is 1 cm from the liquid level, and both ends of the mount are equidistant from the side of the beaker and positioned at the center of the beaker. While stirring with a tic stirrer (CT-1A manufactured by AS ONE Corporation, rotation speed: 600 rpm, stirrer diameter: 40 mm), the time required for the film to completely dissolve was measured.

Example 1
Mixing granulator, FM-20 type Henschel mixer (Nippon Coke Kogyo Co., Ltd., capacity 20L, upper blade: Y1 type, lower blade: S0 type, jacket temperature 10-15 ° C.), corn starch (average particle size 17 μm) , Trade name: Japanese Pharmacopoeia Corn Starch, Matsutani Chemical Industry Co., Ltd.) 0.8 kg and pigment (trade name: Red No. 226, Hatake Kasei Co., Ltd.) 1.2 kg, stirring blade (upper blade and lower blade) ) At a rotation speed of 900 rpm (tip blade peripheral speed: 14 m / s) for 5 minutes. Here, a 10% aqueous solution (viscosity: 10 parts by mass of polyvinylpyrrolidone (trade name: K-15, PVP manufactured by International Specialty Products, Inc., molecular weight 8000, K value: 16.6) in 90 parts by mass of purified water. (10 mPa · s, 25 ° C.) 705.7 g (temperature 40 ° C.) was added in 4 minutes, followed by stirring for 1 minute.
Subsequently, 10 parts by mass of polyvinyl alcohol (trade name: KM-118, manufactured by Kuraray Co., Ltd., maleic acid 2 mol% modified PVA, molecular weight 80,000, polymerization degree 1800, saponification degree 95.5 to 98.5%) are purified. 54.3 g (temperature: 40 ° C.) of a 10% aqueous solution (viscosity: 400 mPa · s, 25 ° C.) dissolved in 90 parts by mass of water was added in 1 minute and stirred for 1 minute to obtain pigment granules.
The obtained pigment granules were dried with hot air at 100 ° C. for 30 minutes using a hot air dryer, and the average particle size was measured. As a result, it was 813 μm. Moreover, content of the pigment | dye in this pigment | dye granule was 57.8 mass%. The core / shell mass ratio was 99.7 / 0.3.
The film dissolution time of the modified PVA when the sodium chloride concentration was 6% by mass was 600 seconds or more, and the film dissolution time when the sodium chloride concentration was 1% by mass was 44 seconds.
The results are shown in Table 1.

Example 2
624.3 g of polyvinyl pyrrolidone aqueous solution was added in 3 minutes and stirred for 1 minute, then 135.7 g of polyvinyl alcohol aqueous solution was added in 1 minute and stirred for 2 minutes. Pigment granules were produced. The core / shell mass ratio was 99.3 / 0.7. The results are shown in Table 1.
Example 3
Pigment granules were produced in the same manner as in Example 1 except that 2.7 g of glycerin solution (Japanese Pharmacopoeia glycerin, solid content 86%) was added after being uniformly mixed with 51.6 g of an aqueous polyvinyl alcohol solution. The core / shell mass ratio was 99.7 / 0.3. The results are shown in Table 1.

Comparative Example 1
Pigment granules were produced in the same manner as in Example 1 except that 760.0 g of an aqueous polyvinyl alcohol solution was added and stirring was performed for 6 minutes. The results are shown in Table 1.
Comparative Example 2
Pigment granules were produced in the same manner as in Example 1 except that only 760.0 g of the polyvinylpyrrolidone aqueous solution was added and stirred for 6 minutes. The results are shown in Table 1.

[Test evaluation]
The pigment granules obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were blended into the whole body detergent as follows and evaluated according to the following evaluation criteria. The results are shown in Table 1.
The composition of the whole body cleaning agent is 8% by mass of lauric acid (trade name: NAA-122, manufactured by NOF Corporation), 5% by mass of myristic acid (trade name: NAA-142, manufactured by NOF Corporation), palmitic acid ( Product name: NAA-171, manufactured by Nippon Oil & Fats Co., Ltd. 5% by mass, glycerin (product name: RG, Co., manufactured by Nippon Oils & Fats Co., Ltd.) 10% by mass, sodium laureth sulfate (trade name: Synoline 1300, Shin Nippon Rika 5% by mass), 1% by mass of palm kernel fatty acid amidopropyl betaine (trade name: Nissan Anon BDC-S, manufactured by Nippon Oil & Fats Co., Ltd.), glycol distearate (trade name: KUTINA EGMS, manufactured by Cognis Japan) 2% by weight, potassium hydroxide (trade name: white caustic, manufactured by Nippon Soda Co., Ltd.) 4.5% by weight, mixed and added together with the remaining water After hot dissolution and cooling, the pigment granules were added to 0.17% by mass. Each facial cleanser was allowed to stand for 2 weeks after production in order to stabilize the granular state. The content of the pigment in the cleaning agent was 0.1% by mass.
After that, the detergent panel (researcher engaged in the technical field for more than 5 years) gently mixed the appearance (color density) of the detergent with 1 g of the obtained detergent and 5 g of warm water (40 ° C.). The color developability of the foamed foam was evaluated according to the following evaluation criteria.
As a whole body cleaning agent for the following evaluation criteria, a pigment that is directly mixed in place of pigment granules and stirred at 20 ° C. for 1 hour and uniformly dispersed is used. It was.

<Evaluation criteria for appearance color of detergent>
6: Same as the appearance color of the detergent when no pigment granules are blended (0% by weight of pigment) 5: The pigment is directly applied so that the concentration is 1/100 of the pigment blended with granules (0.001% by weight of pigment) Same as the appearance color of the cleaning agent when blended 4: Same as the appearance color of the cleaning agent when the pigment is directly blended so that the concentration is 1/20 of the pigment blended in granules (0.005% by mass) 3: Same as the appearance color of the detergent when the pigment is directly blended so as to be 1/10 the concentration of the pigment blended in the granule (0.01% by weight) 2: Half the concentration of the pigment blended in the granule Same as the appearance color of the cleaning agent when the pigment is directly blended so that the pigment is 0.05% by mass 1: The pigment is adjusted to the same concentration as the pigment blended in the granules (0.1% by mass of the pigment) Same as the appearance color of the detergent when blended directly

<Evaluation criteria for foam color development>
6: Same color as when a detergent containing a pigment is foamed directly so as to have the same concentration as the pigment blended in granules (0.1% by weight of pigment) 5: Half the concentration of pigment blended in granules (Dye 0) .05% by mass) The same color as when a detergent directly formulated with a dye so as to be foamed 4: 4: 1% of the color of the dye compounded in granules (0.01% by mass of the dye) The same color as when foaming the directly formulated detergent 3: Same color as when foaming the detergent directly blended so that the pigment concentration in the granules is 1/20 (0.005% by mass) 2: The same color as the appearance color of the cleaning agent when the pigment is directly blended so that the concentration is 1/100 of the pigment blended with the granule (0.001% by mass of the pigment) 1: When pigment granules are not blended (pigment) 0% by weight) same color as the detergent foam color

From Table 1, it can be seen that the whole body detergent using the pigment granules obtained in Examples 1 to 3 is excellent in both the appearance color of the detergent and the color development of the foam. In particular, the whole body detergent of Example 3 was excellent in practical use because the appearance color of the detergent and the color development of the foam were highly balanced.
On the other hand, the whole body cleaning agents of Comparative Examples 1 and 2 that do not use any one of polyvinyl pyrrolidone and polyvinyl alcohol are remarkably inferior in either the appearance color or the foam color development.

  The detergent containing the pigment granule of the present invention is suppressed in coloring during storage, but when used, the pigment granule disintegrates and disperses quickly, and bubbles can be quickly colored. In particular, it is useful as an attractive cleaning agent such as a whole body cleaning agent and a facial cleanser.

Claims (14)

A pigment granule containing a pigment, polyvinyl pyrrolidone and acid-modified polyvinyl alcohol, wherein the core portion contains a pigment and polyvinyl pyrrolidone, and the shell portion has acid-modified polyvinyl alcohol.   The pigment granule according to claim 1, wherein the average particle size is 50 to 2000 µm.   The pigment granule according to claim 1 or 2, wherein the pigment content is 30% by mass or more.   The pigment granule according to any one of claims 1 to 3, wherein the mass ratio of polyvinyl pyrrolidone to the pigment (polyvinyl pyrrolidone / dye) is 0.01 to 0.12. The weight ratio of the acid-modified polyvinyl alcohol to polyvinylpyrrolidone is (acid-modified polyvinyl alcohol / polyvinyl pyrrolidone) 0.01-1, pigment granules according to claim 1. The pigment granule according to any one of claims 1 to 5, wherein the content of the acid-modified polyvinyl alcohol is 0.01 to 10% by mass.   The pigment granule according to any one of claims 1 to 6, wherein the polyvinylpyrrolidone has a viscosity characteristic value (K value) of 25 or less. The pigment granule according to any one of claims 1 to 7, wherein the acid-modified polyvinyl alcohol has an acid modification degree of 0.5 mol% or more and 10 mol% or less .   The pigment granule according to any one of claims 1 to 8, wherein the shell part contains a polyhydric alcohol.   The pigment granule according to any one of claims 1 to 9, further comprising water-insoluble particles.   The cleaning agent containing the pigment granule in any one of Claims 1-10. The manufacturing method of the pigment granule in any one of Claims 1-10 which has the following process A and B.
Step A: (a) Step of adding and granulating (b) polyvinylpyrrolidone solution to powder containing pigment Step B: (c) Adding acid-modified polyvinyl alcohol solution to the granulated product obtained in Step A Granulation process   The manufacturing method of the pigment granule of Claim 12 granulated using a stirring rolling granulator.   The coloring method of the foam at the time of washing | cleaning using the pigment granule in any one of Claims 1-10.