JPH07242532A - Bathing agent - Google Patents

Abstract

PURPOSE:To obtain a bathing agent producible by a simple production process and enabling sufficient enjoyment of the color change of the bath water during bathing by a single use of the bathing agent by coating a carrier holding a colorant with a specific polymeric substance and compounding the obtained coloring agent with a pH-varying agent. CONSTITUTION:This bathing agent is produced by compounding (A) a coloring agent produced by coating a carrier holding a colorant such as amaranth, tartrazine and brilliant blue FCF with a polymeric substance varying the dissolution rate by the pH variation of hot water in a bathtub (e.g. an enteric polymer such as cellulose acetate phthalate and polyvinyl alcohol phthalate or a polymeric substance soluble in the stomach such as carboxymethylethylcellulose) with (B) a pH-varying agent capable of varying the pH of hot water by dissolution (e.g. an acidic substance such as dl-malic acid and an alkaline substance such as sodium carbonate).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bathing agent, and more particularly to a bathing agent which controls the diffusion of a dye in hot water in a bath by varying the pH value.

[0002]

2. Description of Related Art Conventionally, hot water in a bathtub (hereinafter referred to as "bathwater")
Various types of bathing agent compositions are known which are put into and used in. Of these, there have been various studies on how to change the color of the bath water while bathing and to enjoy the bath with a richer sense. For example, Japanese Examined Patent Publication No. 50-27846 discloses that a color-changing agent having a property of discoloring in an aqueous solution having a pH value of 6 or more is adsorbed with an alcohol in an organic or inorganic adsorbent of neutral fine powder, and then the alcohol is A color-changing substance is prepared by volatilization, and the color-changing substance is coated with a water-soluble synthetic surfactant or with a moisture-proof substance having a melting point of 30 ° C. or lower selected from wax, wax and petrolatum, and powdered. A color-changing composition characterized by being mixed with a detergent or a powdery bath agent is shown. In addition to this, JP-A-62-252715 discloses that a bath agent component is coated with a water-soluble capsule film, and JP-A-62-2
In No. 83916, when a bath agent component is encapsulated with a water-soluble capsule coating, one in which the solubility of the base material of the capsule is temperature-dependent is studied. In addition to the above, as a substance which is affected by the hydrogen ion concentration in the bath water, a bathing agent containing an inorganic substance coated with a polymer substance that reacts with an alkali in order to improve the dispersibility of the inorganic substance in the bath water. Are being considered.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Conventionally, most of bathing agents have a definite color when used in a single bath. Also, if you change the color of the bath water with multiple pigments, you can use capsules for about 15 seconds to 20 seconds.
Since it changed after a second and changed immediately after the bathing agent was put into the bath, it was not possible to enjoy the change in the bath while taking a bath. Therefore, the present invention provides a bathing agent which is easy to manufacture and which allows the user to fully enjoy the change in the color of the bathing water during bathing by using the bathing agent once.

[0004]

[Means for Solving the Problems] The present inventors have completed the present invention by examining a bathing agent that changes the color of the bath water during bathing. That is, the present invention comprises the following (1) and (2). (1) A dye agent coated with a carrier holding a dye with a polymer substance having a different dissolution rate depending on the change in the pH value of the bath water, and a pH modifier that changes the pH of the hot water when dissolved Bath salt characterized by (2) A composition in which a bathing agent composed of a dye and other bath components is coated with a polymer substance having a different dissolution rate due to a change in pH value of the bath water, and the pH of the hot water in the bath is changed by dissolving A bathing agent, characterized in that a pH changing agent is mixed.

In the present invention, the pH of the bath water can be dissolved to dissolve it.
The pH-changing agent that changes pH can be selected from at least one or more of acidic substances such as acids or salts thereof, or alkaline substances such as bases or salts thereof, and does not mix acidic substances and alkaline substances. Is not limited in any way.

Examples of the acidic substance include straight chain fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, oleic acid, palmitic acid and valeric acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, Pimelic acid,
Dicarboxylic acids such as maleic acid, phthalic acid, isophthalic acid and terephthalic acid; acidic amino acids such as glutamic acid and aspartic acid; adipic acid, glycolic acid,
Oxyacids such as lactic acid, hydroxyacrylic acid, α-oxybutyric acid, glyceric acid, tartronic acid, citric acid or dl-malic acid, tartaric acid, salicylic acid, gallic acid, mandelic acid, trobaic acid, ascorbic acid and gluconic acid; cinnamic acid Examples thereof include benzoic acid, phenylacetic acid, nicotinic acid, kainic acid, sorbic acid, pyrrolidecarboxylic acid, trimellitic acid, benzesulfonic acid and toluenesulfonic acid, and salts thereof.

In the present invention, the compounding amount of the acidic substance in the bathing agent depends on the magnitude of the change in pH of the agent, but for example, the pH of 200 l of bath water (almost neutral)
When dl-malic acid is used to adjust the value of 5.5 to 5.0, dl-malic acid is added to the bath water in an amount of 10 to 20 g, preferably 12 to 15 g, and more preferably about 13 g. do it.

Examples of alkaline substances include sodium hydroxide, potassium hydroxide, calcium hydroxide,
Sodium carbonate, potassium carbonate, sodium hydrogen carbonate,
Examples include potassium hydrogen carbonate, sodium sulfide, sodium thiosulfate, sodium phosphate, and sodium hydrogen phosphate. The amount of the drug that adjusts the pH to alkaline depends on the magnitude of the change in the pH that the drug adjusts. For example, the pH of 200 l of bath water (almost neutral)
When sodium carbonate is used for adjusting the value of 8.0 to 8.5, sodium carbonate may be added to the bath water in an amount of 3 to 8 g, preferably 4 to 6 g, and more preferably about 5 g.

[0009] Even with the above-mentioned acidic substance or alkaline substance, if the width of the change in pH of the bath water is small, the amount of input is small, and the change in pH is strong alkaline to weak alkaline, such as pH 10 to 7.5, and pH 7. .5 to 7.0
Weakly alkaline to neutral, pH 7.0 to 6.0
Neutral to weakly acidic, such as pH 6.0 to 4.5
From weakly acidic to strongly acidic or vice versa
There are various changes in pH in the bath, such as changes in
In addition to the properties of a polymer substance (hereinafter referred to as "coating polymer") whose dissolution rate varies depending on the pH value of the bath water, various factors such as the thickness of the coating layer of the coating polymer and the time until discoloration are involved However, the compounding amount in the bath agent of the present invention can be 0.1 to 10 parts by weight of the pH modifier with respect to 1 part by weight of the coating polymer.

In the present invention, the polymer substance having a different dissolution rate depending on the pH value of the bath water has a different dissolution rate when the pH in the bath water is changed by the above-mentioned pH modifier, and a pigment carrier or There is no limitation as long as it can coat other bathing agent components. Examples thereof include gastric-soluble polymer substances and enteric-coated polymer substances used in pharmaceuticals. At the time of use, at least one kind of gastric-soluble polymer substance or enteric-soluble polymer substance can be used, but it is not preferable to mix the gastric-soluble substance and the enteric-soluble substance.

Examples of the enteric polymer include dibasic acid monoesters of hydrocarbon derivatives and dibasic acid monoesters of polyvinyl compounds. The dibasic acids constituting each are phthalic acid and amber. Acid, maleic acid, etc. are present, and one of the carboxyl groups of this dibasic acid is bound to a carbohydrate derivative or a polyvinyl compound by an ester bond, and the other one carboxyl group is in a free form. The free carboxyl group reacts with the hydroxyl group to obtain water solubility.

The dibasic acid monoesters of carbohydrate derivatives include cellulose acetate phthalate, cellulose acetate succinate, cellulose acetate maleate, cellulose benzyl phthalate, methyl cellulose phthalate, hydroxypropylmethyl cellulose phthalate 200731 (pH
Dissolved at 5.5 or higher; pH values in parentheses below indicate the pH at which it dissolves), hydroxypropylmethylcellulose phthalate 220824 (pH 5.0 or higher), ethyl hydroxyethyl cellulose phthalate, cellulose such as hydroxypropylmethylcellulose acetate phthalate Dibasic acid monoesters of derivatives; Dibasic acid monoesters of starch such as starch phthalate starch and amylose acetate phthalate; Other phthalate monoesters of dextrin; Polymers of sugars such as glucose, galactose and sorbitol Phthalic acid monoesters are preferred.

The dibasic acid monoesters of polyvinyl compounds include phthalic acid monoesters or succinic acid monoesters of polyvinyl alcohol such as phthalic acid polyvinyl alcohol, polyvinyl acetate phthalate, polyvinyl butyl phthalate and the like. Is preferred.

Other similar properties, that is, a polymer substance capable of reacting with a hydroxyl group to obtain solubility in water, include a copolymer of maleic anhydride and a vinyl monomer, acrylic acid, methacrylic acid and a vinyl monomer. There are copolymers such as methacrylic acid copolymer L (pH
6.0 or more), methacrylic acid copolymer LD (pH
5.5 or more), methacrylic acid copolymer S (pH
7.0 or more) and the like.

Many compounds have been investigated as gastric soluble polymer substances, such as vinyl pyridine copolymers, cellulose derivatives obtained by introducing amino groups into cellulose ethers,
There is also a product called HA Sankyo (manufactured by Sankyo Co., Ltd.), which is a mixture of vinyl alcohol copolymer or polyvinyl acetal diethylaminoacetate and hydroxypropylmethylcellulose modified for water-based coating.
Generally, carboxymethyl ethyl cellulose, hydroxypropyl methyl cellulose 2910, polyvinyl acetal diethyl amino acetate (pH 5.8 or less), aminoalkyl methacrylate copolymer E
(PH 5.0), hydroxypropylmethyl cellulose acetate (pH 5.0 or less), hydroxypropyl cellulose and the like can be exemplified.

The amount of the coating polymer compounded in the bath agent of the present invention depends on the amount of the carrier or other bath component coated with the coating polymer, and 1 volume of the carrier or other bath component to be coated. 1 to 50 parts by volume of the coating polymer per part, for example talc as the carrier and polyvinyl acetal diethylaminoacetate as the coating polymer,
When the color of the bath water is changed in about 7 minutes, 1 to 3 parts by volume of the coating polymer can be added to 1 part by volume of talc.

The dye in the present invention is a water-soluble substance, or is water-soluble and does not deteriorate due to air oxidation,
And at a concentration of 100 ppm or less, the ocular mucosal irritation is moderate or less, and there is no limitation.
More than one species can be used. For example, they are described in Appendices Nos. 1, 2 and 3 of the Ministry of Health and Welfare Example No. 30 dated August 31, 1941. Amaranth (red No. 2) is attached to the attached table No. 1,
Erythrosin (red 3), new coccin (red 10)
2), Phloxine B (Red No. 104 (1)), Rose Bengal (Red No. 105 (1)), Acid Red (Red No. 106), Tartrudine (Yellow No. 4), Sunset Yellow FCF (Yellow 5). No.), Brilliant Blue FCF (Blue No. 1), Indigo Carmine (Blue No. 2),
And Red No. 2, Red No. 3, Red No. 102, Red No. 104
No. 1 (1), Red No. 105 (1), Red No. 106 or Yellow No. 5 aluminum lakes are described.

In the second table of the attached table, Resor Rubin B (red 20
1), Resor Rubin BCA (Red No. 202), Laked C (Red No. 203), Laked CBA (Red No. 2)
04), Resole Red (Red No. 205), Resole Red CA (Red No. 206), Resole Red BA (Red No. 207), Resole Red SR (No. 208 Red),
Rhodamine B (Red No. 213), Rhodamine B Acetate (Red No. 214), Rhodamine B Stearate (Red No. 215), Tetrachlortetrabrom Fluorescein (Red No. 218), Brilliant Trail Kit R (Red No. 2).
19), Deep Maroon (Red No. 220), Toluidine Red (Red No. 221), Tetrabromofluorescein (Red No. 223), Sudan III (Red No. 225).
No.), Herringdon Pink CN (Red 226), Fast Acitud Magenta (Red 227), Permaton Red (Red 228), Eosin YS (Red 230 (1)), Eosin YSK (Red 230). (2)), Phloxine BK (red No. 231), Rose Bengal K (red No. 232), dibrom fluorescein (daidai 2)
01), permanent orange (daily color 203)
No.), Bench Chijin Orange G (daidai 204
No.), orange II (daidai 205), jodhfluorescein (daily 206), erythrosine yellow NA (daily 207), fluorescein (yellow 201), uranine (yellow 202 (1)), uranine. K (Yellow No. 202 (2)), Quinoline Yellow WS
(Yellow No. 203), Quinoline Yellow SS (Yellow 204)
No.), Benzijin Yellow G (Yellow No. 205), Alizarin Cyanine Green F (Green No. 201), Kinizarin Green SS (Green No. 202), Pyranine Conc (Green No. 2).
04), light green SF yellow (green 205), indigo (blue 201), patent blue NA (blue 2)
02), Patent Blue CA (Blue No. 203), Carbanslen Blue (Blue No. 204), Alphazurin F
G (blue No. 205), resorcin brown (and color 20
No. 1), Alizurin purple SS (purple No. 201), and red 227, red 230 (1), red 230
No. (2), Red 231, Red 232, Day 205, Day 207, Yellow 202 (1), Yellow 202 (2), Yellow 203, Green 201, Aluminum lake compound of Green No. 204, Green No. 205, Blue No. 205 or Color No. 201, Daidai No. 205, Yellow No. 203, Blue No. 202, Red No. 104 (1), Yellow No. 4, Yellow No. 5 or Blue 1
Barium Lake compound of No. 205, and No. 205
Yellow No. 203, Green No. 205, Yellow No. 4, Yellow No. 5 or Blue No. 1 zirconium lake compounds are described.

And, in Appendix 3, Violamine R (Red No. 401), Brilliant Fast Scarlet (Red No. 404), Permanent Red F5R (Red 405).
No.), medicinal scarlet (red 501), Ponceau 3
R (Red No. 502), Ponceau R (Red No. 503), Ponceau SX (Red No. 504), Oil Red XO (Red No. 505), Huast Red S (Red No. 506), Hansa Orange (Daidai No. 401), Orange I (daidai 402), Orange SS (dai 403)
No.), Ensaello (Yellow No. 401), Paula Yellow 5
G (Yellow No. 402), Naphthol Yellow S (Yellow 403)
(1)), Yellow AB (Yellow 404), Yellow O
B (Yellow 404), Etanyl Yellow (Yellow 406)
No.), Huastrite Yellow 3G (Yellow 407), Naphthol Green B (Green No. 401), Guinea Green B (Green No. 402), Sudan Blue B (Blue No. 403)
No.), phthalicyanine blue (blue No. 404), alizrole purple (purple No. 401), naphthol blue black (black No. 401), and red No. 401, red No. 50.
No. 2, Red 503, Red 504, Red 506, Daidai 402, Yellow 402, Yellow 403, Yellow 406, Yellow 407, Green 402, Purple 401 or Black 401 Aluminum Lake Compounds and the barium lake compounds of Daidai No. 402 or Green No. 402.

Further, as a pigment which is not deteriorated by air oxidation or the like and has a concentration of 100 ppm or less and a moderate or lower eye mucosal irritation, chlorophyll, riboflavin, annatto, canthaxanthin, crocin, cochineal, safflower, paprika pigment , Natural pigments recognized as food additives such as anthraquinone. The amount of these dyes to be added may be 0.05 to 1 part by weight, preferably 0.1 to 0.5 part by weight, based on the total bath agent. This indicates the total amount of the dye coated with the coating polymer or the dye not coated, and when each of the dyes is blended, an appropriate amount depending on the hue may be used.

The carrier for holding the dye in the present invention is solid at room temperature and can be dissolved in the bath water or sufficiently dispersed in the bath water when placed in the bath water. Is not limited as long as it does not affect the color of the bath water, and may be selected from at least one of these. It suffices that this carrier be able to hold the solution of the above dye dissolved in the solvent until it is coated with the coating polymer. In addition, the fact that the carrier retains the dye in this case means that the product in which the dye and the carrier are mixed and further kneaded while adding the solvent uniformly contains the dye. That is, the highly viscous dye solution is not attached to the surface of the carrier. Such carriers include, for example, talc (acidic magnesium metasilicate), light silicic acid anhydride, metasilicic acid and silicic acid anhydride (silicon oxide), silica (including those having a special structure such as petals), activated clay, Diatomaceous earth,
At least one selected from titanium mica, kaolin, magnesium aluminum silicate, calcium silicate, synthetic aluminum silicate, chromium oxide, titanium oxide, natural aluminum silicate, nylon powder, bentonite is blended, and the blending amount is retained. 200 to 300 parts by weight of the carrier is mixed with 1 part by weight of the dye.

The other bath component in the present invention has the same properties as the above-mentioned carrier, that is, it is a solid at room temperature, and the carrier itself can be dissolved in the bath water or sufficiently dispersed in the bath water when added to the bath water. The color of the other bath component itself does not affect the color of the bath water, and is not particularly limited as long as it is at least one selected from organic salts and / or inorganic salts. For example, inorganic salts include sodium chloride, sodium sulfate, potassium nitrate, sodium nitrate, calcium nitrate, aluminum sulfate, sodium polyphosphate, ammonium chloride, iron sulfate, sodium carbonate, magnesium sulfate, sodium thiosulfate, sodium alkanesulfonate, aluminum chloride. , Potassium chloride, calcium chloride, stearyldimethylbenzylammonium chloride, cetyltrimethylammonium chloride, ferric chloride, magnesium chloride, pyridoxine hydrochloride, iron oxide yellow, seawater dried product, potassium hydroxide, calcium hydroxide, hydrogenated soybean phospholipid , Sodium sesquicarbonate, sodium cetyl sulfate, potassium cetyl sulfate, sodium hydrogen carbonate, sodium carbonate, light magnesium carbonate, sodium thiosulfate, sodium lactate, lactic acid Risuchiru, sodium sulfite, sodium thiosulfate anhydrous sulfate, anhydrous sodium sulfate, magnesium aluminometasilicate, sodium metaphosphate, potassium sulfate, and barium sulfate and magnesium sulfate.

The organic salts include, for example, sodium ascorbate, sodium alginate, sodium benzoate, sodium oleoyl methyl taurine, sodium guaizulene sulfonate, sodium citrate, disodium succinate, calcium palmitate, and the like.
Examples include monosodium fumarate and sodium monohydrogen phosphate. The amount of these other bath components is at least the same as that of the above-mentioned carrier, that is, 200 to 300 parts by weight of the other bath components per 1 part by weight of the dye.

The amount of the above-mentioned carrier or other bath component is the amount for holding the pigment, and is not limited to the total amount of the bath agent of the present invention. For example, one kind of carrier and Looking at the blending amount of the other bath components in the total bathing agent, one coated with the coating polymer is 1
In some cases, 50 parts by weight of uncoated material may be used.

Further, as the raw material added to the bath additive of the present invention, depending on the intended effect of the bath additive,
If one or more raw materials selected from inorganic acids or organic acids and salts thereof, crude drugs, fats and oils, alcohols, surfactants, binders, compounds having an antibacterial action, etc. are appropriately selected and used, Good. The following are mentioned as these raw materials.

Examples of the inorganic or organic acids and salts thereof include sulfur, mineral sand, yunohana, sulfuric acid, stearyldimethylbenzylammonium chloride, cetyltrimethylammonium chloride, diisopropyl adipate, dioctyl adipate, disodium adenosine triphosphate, Arginine, sodium edetate, cetyl octanoate, cetostearyl octanoate, diglyceryl oleate, propylene glycol oleate, guaiazulene, glyceryl glycyrrhetinate, methyl salicylate, ascorbyl dipalmitate, serine, ceresin, isopropyl palmitate, octyl palmitate. , Retinol palmitate, proline, decaglyceryl pentaoleate, etc.

As the organic substance, acetylpantothenyl ethyl ether, 2-amino-2-methyl-1,3-propanediol, allantoin, allantoin chlorohydroxyaluminum, ergocalciferol, oxybenzone, xylit, glycine, glycerin, cinnamon bark Aldehydes, cholesterol, mixed fatty acid diethanolamide, tocopherol acetate, dipropylene glycol, stearic acid, ascorbyl stearate, octyl stearate, dextran, pentaerythriet tetraisostearate, natural vitamin E, copper chlorophyllin sodium, tocopherol, triethanolamine, Glyceryl trioctanoate, tri (capryl / carulinic acid) glyceryl, lactose, urea, sorbit solution, sucrose, biotin, pi Sodium Ridonkarubon acid, sodium pyrophosphate, butylhydroxyanisole, t-
Butylmethoxydibenzoylmethane, glucose, maltitol, mannitol, isopropyl myristate, octyldodecyl myristate, anhydrous maltose, isopropyl lanolate, etc.

[0028] Examples of crude drugs include, butterbur, beetle, valerian, oyster, pearl oyster, senkyu, orange peel, Japanese perch, ginger powder, carrot, cinnamon, peony, mint, sardine, sardine, butterbur,
Dokukatsu, Shobu, Gayou, Matsuba, Beetle,
Shuyaku, Ryunohafun, Oataku extract, Chinpi, Fennel, Campi powder, Chamomile powder, Almond kernel powder, Aloe powder, Seaweed powder, Hydrolyzed elastin powder, Hydrolyzed keratin powder, Hydrolyzed collagen powder, Sage powder, Degreased rice bran, Chimpi Powder, powdered tosaka extract, red iron oxide, lavender powder, rosemary powder, etc.

Animal extracts include albumin, yeast powder, skim milk powder, hydrolyzed keratin solution, hydrolyzed collagen solution, hydrolyzed collagen ethyl solution, hydrolyzed conchiolin solution, hydrolyzed silk, sodium caseinate, milk sugar protein, White beeswax, lactic acid bacterium fermentation broth, honey, mica, beeswax, rutin, egg yolk powder, etc.

Examples of the plant extract include aloe extract, age extract, sardine extract, sage extract, Hypericum extract, orange extract, seaweed extract, brown alga extract, chamomile extract, licorice extract powder, raspberry extract, kiwi extract, cucumber extract, gardenia. Extract, clara extract, grapefruit extract, brown sugar extract powder, mulberry extract, black tea extract, burdock extract, pomegranate extract, hawthorn extract, hawthorn extract, dio extract, konjac extract, linden extract, peony extract, ginger extract, birch extract, honeysuckle extract, Water-soluble Arnica extract, water-soluble Yokuinin extract, horsetail extract, Ivy extract, Achillea millefolium extract, sage extract, senkyu extract, assembly extract, Isophyte extract, tea extract, clove extract, chimpanzee extract, dwarf extract, dwarf extract, spruce extract, Dokudami extract, carrot extract, Novara extract, Hamamelis water, Hamamelis extract, Hikiokoshi extract, loquat leaf extract, Bukuryo extract, loofah extract, safflower extract , Bodaiju extract, hop extract, Matsukasa extract, horse chestnut extract,
Saprose extract, peach extract, peach leaf extract, cornflower extract, oil-soluble Arnica extract, oil-soluble Hypericum extract, oil-soluble chamomile extract, oil-soluble shikon extract, oil-soluble birch extract, oil-soluble horsetail extract, oil-soluble sage extract, oil-soluble carrot extract , Oil-soluble horse chestnut extract, oil-soluble yokuinin extract, oil-soluble rosemary extract, lily extract, mugwort extract, apple extract, lemon extract, rose water, rosemary extract, oleander extract.

Examples of fats and oils are bran oil, rice bran extract, olive oil, jojoba oil, soybean oil, liquid paraffin, white petrolatum, avocado oil, almond oil, liquid lanolin, orange laffy oil, carrot oil, reduced lanolin, and light liquid paraffin. , Wheat germ oil, rice bran oil, rice germ oil, safflower oil, vegetable squalane, squalane, soybean oil, camellia oil, spruce oil, corn oil, lavender oil, jasmine oil, lemon oil, rose oil, orange oil, γ -Oryzanol, pine oil, peppermint oil, paraffin, vitamin A oil, castor oil, sunflower oil, jojoba oil, macadamian nut oil, mink oil, cottonseed oil, coconut oil, eucalyptus oil,
Peanut oil, lanolin, egg yolk oil, ethyl linoleate,
Liquid isoparaffin, liquid paraffin, petrolatum, etc.

Examples of the fragrances include synthetic fragrances such as geraniol, citronellol, phenylethyl alcohol, linalool, benzyl acetate, camphor, borneol and menthol.

The alcohols include ethanol, stearyl alcohol, isopropanol, cetyl alcohol, hexadecyl alcohol, glycerin, propylene glycol, sorbitol, geraniol modified alcohol, octaacetylated sucrose modified alcohol, phenylethyl alcohol modified alcohol, brucine modified alcohol, Linalool modified alcohol, diethylphthalate modified alcohol, linalyl acetate modified alcohol,
Benzyl acetate denatured alcohol, 10% desodium benzoate alcohol solution denatured alcohol, flavor H-No14 denatured alcohol, isopropylmethylphenol, octyldodecanol, oleyl alcohol,
Cetanol, concentrated glycerin, bisabolol, phenylethyl alcohol, phenoxyethanol, 1,3-butylenebricol, propylene glycol, hexyldecanol, behenyl alcohol, benzyl alcohol, jojoba alcohol, absolute ethanol, lanolin alcohol and the like.

As the surfactant, hydrogenated soybean phospholipid, disodium lauryl sulfosuccinate, sodium lauryl sulfate, sodium polyoxyethylene urilyl ether sulfate, diethanolamide urinate, polyethylene glycol monostearate, 2-alkyl-N
-Carboxymethyl-N-hydroxyethyl imidazolinim betaine, polyoxyethylene glyceryl isostearate (hereinafter "polyoxyethylene" is referred to as POE), POE isostearate (20 to 30) hydrogenated castor oil, potassium potash, carboxylated Polyoxyethylene (3) tridecyl ether sodium salt, glycerin fatty acid ester, diglyceryl diisostearyl acid, polyoxyethylene glycol diisostearyl acid, neopentyl glycol dioctanoate, ethylene glycol dioleate, polyethylene glycol dioleate,
Neopentyl glycol dicaprate, propylene glycol dicaprate, self-emulsifying glyceryl monostearate, ethylene glycol distearate, polyethylene glycol distearate, dihydroxydimethoxybenzophenone, dihydroxybenzophenone, dibutylhydroxytoluene, diventaerythritol fatty acid ester, dimethyloctanoic acid Hexyldecyl, dimethyl siloxane-methyl (POE) siloxane copolymer,
Sucrose fatty acid ester, polyethylene glycol dilaurate, lipophilic glyceryl monooleate, lipophilic glyceryl monostearate, sorbitan sesquioleate, sodium dextran sulfate, tetraoleate P
OE sorbit, sodium tetradecene sulfonate,
Sodium dodecylbenzene sulfonate, POE glyceryl triisostearate, PO triisostearate
E hydrogenated castor oil, sorbitan trioctanoate, POE (20) sorbitan trioctanoate, POE glyceryl isostearate pyroglutamate, POE hydrogenated castor oil isostearate pyroglutamate, POE dinonyl phenyl ether, POE stearyl ether, POE cetyl ether, POE cetostearyl Ether, POE
Nonyl phenyl ether, POE castor oil, POE (1
6 to 160) POP (17 to 30) glycol, P
OE-POP decyl tetradecyl ether, POE (3
To 5) POP (5 to 6) lauryl ether, POE
(3) Myristyl ether sodium sulfate, polyoxyethylene methyl glucoside, POE lauryl ether, P
OE lauryl ether sulfate triethanolamine, PO
E Sodium lauryl ether sulfate, POE sodium lauryl ether phosphate, POE lanolin, POE (1
0) Lanolin alcohol, polyvinyl pyrrolidone, sodium polyphosphate, myristic acid POE myristyl ether (3), POE octyl phenyl ether, POE
Oleyl ether, POE glyceryl oleate, PO
E (6) Capryl / glyceryl caprate, POE / reduced lanolin, POE hydrogenated castor oil, methylphenyl polysiloxane, methyl polysiloxane, polyethylene glycol monooleate, POE (6 to 20) polyethylene sorbitan monooleate, monostearic acid Polyethylene glycol, sorbitan monostearate, POE glycerin monostearate, P monostearate
OE (20) sorbitan, polyethylene glycol monolaurate, POE (20) sorbitan monolaurate, N-coconut oil fatty acid acyl-glutamic acid triethanolamine, coconut oil fatty acid amidopropyl betaine, coconut oil fatty acid ethyl ester sulfonate sodium, coconut oil fatty acid Hydrolyzed collagen potassium, coconut oil fatty acid hydrolyzed collagen triethanolamine, coconut oil fatty acid diethanolamine, coconut oil fatty acid POE glyceryl,
Lauryl dimethylamino acetic acid betaine, lauryl dimethyl amine oxide solution, sodium lauryl sulfoacetate,
Lauryl sulfate diethanolamine, lauryl sulfate triethanolamine, sodium lauryl sulfate, lauric acid diethanolamide, lauric acid myristic acid diethanolamide, lauroyl glutamic acid POE octyldodecyl ether diester and the like.

Examples of the binder include sodium carboxymethyl cellulose, polyvinylpyrrolidone, gum arabic, carrageenan, carboxyvinyl polymer, carboxymethyl tincture, xanthan gum, gelatin, corn starch, hydroxyethyl cellulose, hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride, hydroxystearin. Cholesteryl acid, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose dimethyl diallyl ammonium chloride, sodium hydroxymethoxybenzophenone sulfonate, vinyl methyl ether / ethyl maleate copolymer, sodium polyacrylate, polyethylene glycol (200 to 60,000) , Such as chill cellulose.

Compounds having an antibacterial action include benzalkonium chloride, phenylphenol, dipotassium glycyrrhizinate, chlorhexidine gluconate solution, tetrahydroxybenzophenone, sodium dehydroacetate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, and paraoxybenzoic acid. Ethyl, butyl paraoxybenzoate, propyl paraoxybenzoate, methyl paraoxybenzoate, etc.

Further, in the present invention, as the raw material of the bathing agent, in addition to the above-mentioned ones, a bactericidal agent, a sequestering agent, and a wide range of other raw materials can be used if necessary. Further, among the above-mentioned various components, there are some that electrolyze to slightly change the pH of the bath when dissolved in the bath, and these can be used as an auxiliary agent of the above-mentioned pH modifier. .

Next, the method for producing the bath salt of the present invention will be described. First, the dye and the carrier and / or other bath components are added to the carrier and / or 1 part by weight of the dye as described above.
Alternatively, 250 to 300 parts by weight of another bath component is mixed, and 20 to 5 parts of the solvent is added to 100 parts by weight of the mixed powder.
It kneaded, adding 0 weight. Then, the pigment carrier is prepared by granulating with a basket type granulator and drying at about 80 ° C. for about 2 to 3 hours. At this time, the size of the dye carrier is preferably about 0.8 to 1.0 mm in diameter, and if it is in this range, even if the particle size is slightly increased in the next coating operation,
It can float in the bath until the coating polymer dissolves.

In some cases, it is preferable to perform a spheroidizing step between the granulating step in the basket type granulator and the subsequent drying step. This generally shows that most of the granulated particles in the basket-type granulator show a cylindrical shape, and when used in the coating step of the next coating polymer as it is,
The corners of the top or bottom that are in contact with the sides are not covered with the coating polymer, and when added to the bath water, the pigment agent or the pigment in the bath agent consisting of the pigment and other bath components elutes immediately. In many cases. In order to prevent this, it is preferable to perform a work of taking a columnar corner, that is, a spheroidizing process, before subjecting the dye carrier to the coating process of the simple substance-coated polymer.

Next, as a coating agent for the above dye carrier, 7 to 15 parts by weight of the coating polymer is added to 80 to 95 parts by weight of a suitable organic solvent such as acetone or ethanol, and the mixture is allowed to stand at room temperature for about 2 to 3 hours. A coating polymer solution is prepared by mixing and stirring the mixture to a degree. Further, at this time, the coating can be facilitated by adding a lubricant or the like.

The dye carrier is put in the drum of a coating machine, the drum is rotated while sending hot air, and the coating polymer solution is sprayed onto the dye carrier by an air spray to obtain a dye agent or other dyes. It is possible to prepare a bathing agent consisting of the bathing ingredient. As for the size of the bath agent composed of the dye agent or the dye or other bath components coated as described above, as long as the bath agent passes through 14 to 42 mesh, the coated polymer is dissolved. Can float in bath water.

On the other hand, when the coating polymer is a gastric-soluble polymer, an acidic substance is used as the pH-changing agent, and when it is an enteric-soluble polymer, an alkaline substance is used as the pH-changing agent. The bathing agent of the present invention can be prepared by granulating with a machine and mixing it with a bathing agent comprising the above-mentioned coloring agent and / or coloring matter and other bath components.

In some cases, the above-mentioned coloring agent or a bathing agent comprising a coloring agent and other bath components is mixed with the above-mentioned pH-changing agent, other raw materials and a binder, and then the gauge pressure is about 2
It can also be solidified by tableting at 50 to 450 kg / cm ² . In this case, if the gauge pressure is too high, the previously coated material may collapse.

In any case, the bathing agent of the present invention can adjust the time from the color immediately after being added to the time when the color changes, depending on the thickness of the layer formed of the coating polymer. That is, thickening the layer increases the time,
Although it can be shortened by making it thin, it is necessary for the layer to have a thickness that does not cause cracks during production and use.

In use, when the bathing agent of the present invention is put into the bath water, the color of the dye in the other raw materials initially remains colorless or colorless, but when the coating polymer is dissolved thereafter, the dye and / or other dyes are dissolved. The color changes to a mixture of the dyes retained in the bath agent consisting of the bath ingredients. Further, by using a coloring agent coated with a coating polymer of different thickness in the bath agent, by pouring one type of bath agent into the bath water once,
For example, the bath water can be discolored twice 15 minutes and 30 minutes after the addition. Furthermore, by using a coloring agent which is obtained by increasing the thickness of the coating polymer in the bathing agent, it is possible to change the color of the bathing water a plurality of times, for example, 10 minutes, 20 minutes, and 30 minutes after the addition.

[0046]

The bathing agent of the present invention changes the color of the bath water by changing the pH of the bath water. That is, when the bathing agent of the present invention is put into a bath water, other raw material dyes (in some cases, no dye is mixed) are dispersed, and the color of the dye changes the color of the bath water (colorless in the case of no compound). Then, the pH-changing agent that begins to diffuse upon addition changes the hydrogen ion concentration in the bath water and the coating polymer begins to dissolve, exposing the bath agent consisting of the coloring agent and / or other bath components, and gradually. The dye in the bath agent composed of the coloring agent and / or other bath components is dissolved to change the color of the bath water.

[0047]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

Example 1 First, 1 part by weight of Blue No. 1 as a pigment was mixed with 9 parts by weight of glucose as another bath component, and 4 parts per 100 g of the mixture were mixed.
0 ml of water was added and kneaded to hold it in glucose, and then a basket-type granulator (manufactured by Hata Tekko Co., Ltd.) having a diameter of about 0.
Granulated to 8 mm, further granulated about 500 ml
Spherical sizing machine Marumerizer Q-400 (using a 3 mm plate: manufactured by Fuji Paudal) was sized for about 15 to 20 seconds, then dried at about 80 ° C. for about 2 hours and bathed with other bath ingredients. Adjust the agent. Separately, 8 parts by weight of polyvinyl acetal diethylaminoacetate (trade name: AEA Sankyo Sankyo Co., Ltd.) and 5 parts by weight of talc were dissolved in 87 parts by weight of an acetone: ethanol mixed solvent (mixing ratio 4: 6) to obtain a solid content. A coating polymer solution was prepared so as to be 13%.

Fluidized bed granulator Marumerizer NQ-L
Into an ABO (Fuji Paudal Co., Ltd.) drum, 450 g of a bathing agent composed of other bath components prepared above was put, and the intake air temperature was 50 ° C., the exhaust air temperature was 40 ° C., and the spray rate was 6.2.
The above coating polymer solution was sprayed onto the bathing agent in the drum under the conditions of g / min, solution amount of 460 ml, and coating time of 75 minutes to prepare a coloring agent. On the other hand, 42 parts by weight of dl-malic acid as a pH modifier, and 56% of dried sodium sulfate as other raw materials.
By weight, 1 part by weight of Yellow No. 4 is granulated (14 to 42 mesh) at room temperature with a basket granulator and dried at about 80 ° C. for 2 hours to prepare a bathing agent containing a pH modifier. The bathing agent of the present invention was prepared by mixing 99.97 g of the bathing agent with 0.03 g of the above polymer coating.

Example 2 42 parts by weight of dl-phosphoric acid and 5 parts by weight of pyrrolidonecarboxylic acid as a pH modifier and 0.5 part by weight of hydroxypropyl cellulose (trade name: HPC-L, manufactured by Nippon Soda Co., Ltd.) Part and 0.1 part by weight of Blue No. 1 are put in a basket-type granulator, mixed and kneaded, then granulated to a diameter of about 0.8 mm, and dried at about 80 ° C. for about 2 hours to prepare a bath agent. To do. On the other hand, after 37 parts by weight of dry sodium sulfate, 10 parts by weight of magnesium sulfate trihydrate, 1 part by weight of hydroxypropyl cellulose and 0.04 part by weight of Red No. 106 were put in a basket type granulator and mixed and kneaded. Granulate to a diameter of about 0.8 mm and dry at about 80 ° C. for about 2 hours to prepare a bathing agent consisting of other bath components, and carry out the bathing agent with the coating polymer solution described in Example 1. A coating was prepared by coating the bath and the bath using the apparatus and conditions described in Example 1 and consisting of a dye and other bath components with the coating polymer. Then, the bath agent of the present invention was prepared by mixing 15 g of the bath agent containing dl-phosphoric acid and 10 g of the bath agent coated with a coating polymer.

Use test Each of the bath agents described in Examples 1 and 2 was bathed at 20 ° C.
The pH, the discoloration time and the color were observed by pouring the solution in 0 l and the results are shown in Table 1. However, 30 g of the bathing agent of Example 1 was used.

[0052]

[Table 1]

[0053]

When the bathing agent of the present invention is used by dissolving it in the bath water, in addition to the effect of the conventional bathing agent, the color of the bath water changes during bathing. You can enjoy. Further, the time until the color of the bath water changes can be adjusted by the thickness of the layer coated with the polymer coating.

Claims (2)

[Claims] 1. A dye agent in which a carrier holding a dye with a polymer substance having a different dissolution rate due to a change in pH value of hot water in a bath is coated, and a pH for changing the pH of the hot water by dissolution.
A bathing agent characterized by containing a modifier. 2. A composition in which a bathing agent comprising a dye and other bath components is coated with a polymer substance having a different dissolution rate depending on the change in the pH value of the hot water in the bath, and hot water in the bath when dissolved. A bathing agent, characterized in that a pH changing agent that changes the pH of the mixture is mixed.