JP2012131740A - Granular bath agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a granular bath agent composition which generates a great volume of fine carbon dioxide foams and brings a good warmed-up feeling after taking a bath.SOLUTION: The granular bath agent composition includes : (A) granulated material containing an organic acid, a water-soluble binder, and 4-30 mass% nonionic surfactant, and (B) carbonate.

Description

  The present invention relates to a granular bath agent composition.

  A bath agent containing a carbonate and an organic acid is widely known as an excellent bath agent because it generates bubbles of carbon dioxide gas in the bath water and the blood circulation promoting effect by the carbon dioxide gas is obtained. In such a bath preparation, as a means for increasing the concentration of carbon dioxide gas generated in the bath water, in order to dissolve the bath preparation in the vicinity of the bottom of the bathtub, the form is not granular but a relatively large tablet type. There are many cases.

  The granular foaming bath agent, which is another form of bath agent, does not require special manufacturing technology such as tableting, and generally has a short dissolution time, so it is used separately from the tablet type depending on the usage condition and preference. Various studies have been conducted. For example, a technique (Patent Document 1) has been reported in which an oil component is blended with a specific content for foamability and storage stability to form granules having a certain average particle size range.

JP 2009-62319 A

  However, in recent years, with the advancement of IT in offices, etc., the number of people suffering from poor cooling, etc. is increasing throughout the year, and even in the case of granular bath preparations, the feeling of warmth after bathing is further improved. Is expected.

  Therefore, in view of such circumstances, an object of the present invention is to provide a granular bath agent composition that provides an excellent warm feeling after bathing.

As a result of various studies to solve the above-mentioned problems, the present inventors made a granulated product by adding a specific amount of a nonionic surfactant to carbonate and an organic acid, and combined the granulated product and the carbonate. If used, the bubbles of carbon dioxide generated in the bath water can be made extremely fine, and a large amount of carbon dioxide dissolves in the bath water and an excellent warm feeling after bathing is obtained. completed.
That is, the present invention includes the following components (A) and (B):
(A) A granulated product containing an organic acid, a water-soluble binder and 4 to 30% by mass of a nonionic surfactant, and (B) a granular bath composition containing a carbonate.

  According to the granular bath agent composition of the present invention, a large amount of fine carbon dioxide gas bubbles are generated, so that a large amount of carbon dioxide gas dissolves in the bath water, and an excellent warm feeling can be provided after bathing. Moreover, since the granular bath agent composition of this invention shows the outstanding solubility immediately after throwing into bath water, it can fully suppress a melt | dissolution residue and its usability | use_condition is also suitable.

Hereinafter, the present invention will be described in detail.
The component (A) contained in the granular bath composition of the present invention comprises (a1) an organic acid, (a2) a water-soluble binder, and (a3) 4 to 30% by mass of a nonionic surfactant. (Hereinafter also referred to as granulated product (A)).

  Examples of the organic acid (a1) used in the present invention include malic acid, tartaric acid, citric acid, maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid, benzoic acid, salicylic acid, pyrrolidone carboxylic acid and oxalic acid. Organic acids that are solid at room temperature (25 ° C.) are preferred. These may be used alone or in combination of two or more. Of these, fumaric acid, succinic acid and tartaric acid are preferred from the viewpoints of solubility in bath water and handling during production and use. In particular, the content of fumaric acid when the total amount of (a1) organic acid is 100% by mass is preferably 40% by mass or more, more preferably 60 to 100% by mass, and particularly preferably 80 to 100% by mass.

  The content of the (a1) organic acid in the granulated product (A) is preferably 40 to 95% by mass, and more preferably 60 to 90% by mass from the viewpoint of the amount of carbon dioxide gas generated. In addition, (a1) the oil absorption capacity of the organic acid is, in particular, when the oil component is blended in the granulated product (A), from the viewpoint of stabilizing the oil component and favorably promoting fine foaming. The thing of 02 mL / g or more is preferable, and the thing of 0.05 mL / g or more is more preferable. The oil absorption capacity is a value determined by the method described in Examples described later. The upper limit of the oil absorption capacity is desirably 1.0 mL / g or less from the viewpoint of particle strength.

  The (a2) water-soluble binder used in the present invention is used together with the above-mentioned (a1) organic acid and a specific amount of (a3) nonionic surfactant to be described later, thereby controlling the solubility of the granulated product. This effectively acts on further refinement and foaming of the material and increases the strength of the granulated product. In addition, the organic acid is coated with a water-soluble binder to prevent the organic acid in the granulated product (A) from contacting and reacting with the carbonate present mainly outside the granulated product during storage. In addition, problems such as expansion of the packaging container due to the generation of carbon dioxide gas can be prevented and storage stability can be improved.

  The (a2) water-soluble binder is preferably a thermoplastic one, and the thermoplastic (a2) water-soluble binder is preferably polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, or polyoxyethylene phenol ether. Polyethylene glycol and polypropylene glycol are particularly preferable.

  In addition, the number average molecular weight of the (a2) water-soluble binder is preferably 4,000 to 20,000 by GPC method using polystyrene as a standard from the viewpoints of viscosity adjustment and handling properties when powdered, 000 to 13,000 are more preferable, and 7,000 to 9,000 are more preferable. When measuring the molecular weight of polyethylene glycol as a water-soluble binder, water / ethanol was used as a solvent.

  Moreover, when using said (a2) water-soluble binder, you may use in combination of 2 or more types of water-soluble binders from which a number average molecular weight differs.

  2-30 mass% is preferable and, as for content of the (a2) water-soluble binder in granulated material (A), 5-20 mass% is more preferable. When the amount is not less than the lower limit, the particle strength when granulated is increased, and the granulated product is hardly broken during the transport process during production. When the amount is not more than the upper limit, the solubility of the granulated product (A) in the bath water is improved, the fine foaming property is enhanced, and a sufficient amount of carbon dioxide gas dissolves in the bath water, so that a feeling of warming after bathing is obtained. Promoted.

  The nonionic surfactant (a3) used in the present invention is contained in the granulated product (A) in an amount of 2 to 30% by mass, preferably 3 to 27% by mass, more preferably 5 to 25% by mass. . (A3) By containing the nonionic surfactant in an amount within the above range, (a2) in combination with the water-soluble binder, while exhibiting good solubility of the granulated product (A) in the bath water, Generation of carbon dioxide bubbles can be improved. Therefore, a sufficient amount of carbon dioxide gas dissolves in the bath water, and the excellent warm feeling after bathing can be fully realized, and there is no undissolved residue of the granulated product.

  Examples of the (a3) nonionic surfactant include sucrose fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkenyl. Ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid ester Sorbitan fatty acid ester, polyoxypropylene alkyl ether, and the like. A nonionic surfactant may be used alone, but it is preferable to use two or more nonionic surfactants in combination since the above effects can be further improved.

  In particular, at least a nonionic surfactant of HLB6-20, more preferably a nonionic surfactant of HLB8-19, from the viewpoint that a large amount of fine carbon dioxide bubbles is generated and a sufficient amount of carbon dioxide dissolves in the bath water. In particular, it is preferable to use a nonionic surfactant of HLB 10-18. The content of the nonionic surfactant of HLB 6 to 20 when the total amount of the nonionic surfactant in the granulated product (A) is 100% by mass is preferably 30 to 100% by mass, and 40 to 100% by mass. More preferably, 50-100 mass% is further more preferable.

Here, HLB is a value usually used to represent the balance between the hydrophilicity and hydrophobicity of the surfactant, and can be obtained by several calculation formulas such as the Kawakami formula commonly used in this field. . In the present invention, the following Kawakami equation is adopted.
HLB = 7 + 11.7log (Mw / M0)
Mw: Molecular weight of hydrophilic group M0: Molecular weight of hydrophobic group

  Among the above (a3) nonionic surfactants, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, etc. Is preferred. In particular, at least one nonionic surfactant selected from polyoxyethylene alkyl ether and polyoxyethylene alkenyl ether, and at least one nonionic interface selected from polyoxyethylene sorbitol fatty acid ester and polyoxyethylene sorbitan fatty acid ester. It is particularly preferred to combine the activators. By doing so, among the above effects of the nonionic surfactant, particularly the generation of fine carbon dioxide bubbles is remarkably improved, so that the dissolution of carbon dioxide gas in the bath water is sufficiently promoted, and after bathing This is very preferable in that it provides a warming effect.

  The granulated product (A) in the present invention can be appropriately mixed with components other than those described above as long as the effects of the present invention are not impaired. Examples of such components include oily components, disintegration aids, skin feel improvers, antifoaming agents, antioxidants, dispersants, antibacterial / antifungal agents, pigments, herbal medicines, and the like.

  Specifically, the oil component is a fatty acid ester having a molecular weight of 100 or more and a ClogP value of 4 to 18, cetyl octanoate, cetyl isooctanoate, butyl laurate, isoamyl laurate, methyl myristate, Ethyl myristate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, ethyl stearate, butyl stearate, isotridecyl isononanoate, isononyl isononanoate, isopropyl linoleate, isostearyl isostearate, isopropyl isostearate, methyl oleate, Examples include ethyl oleate and oleyl oleate. In addition, fatty acid glycerides such as tri (caprylic acid / capric acid) glycerin and glyceryl tricaprylate having a fatty acid ester structure in the molecule; fatty acid polyglycerides such as polyglyceryl-2 isostearate and polyglyceryl-2 triisostearate; soybean oil , Nuka oil, jojoba oil, avocado oil, almond oil, olive oil, cacao butter, sesame oil, persic oil, castor oil, coconut oil, mink oil, beef tallow, pork fat, and other natural fats and oils. Examples of the resulting oil include glycerides such as glyceryl myristate and glyceryl 2-ethylhexanoate. Examples of oil components other than fatty acid esters having a molecular weight of 100 or more and a ClogP value of 4 to 18 include hydrocarbon oils such as liquid paraffin, petrolatum, paraffin, microcrystalline wax, ceresin, squalane, squalene, dioctylcyclohexane, and bristan; Higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, lanolinic acid, isostearic acid; lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cholesterol, 2 -Higher alcohols such as hexyl decanol; peppermint oil, jasmine oil, ginger brain oil, cypress oil, spruce oil, ryu oil, turpentine oil, cinnamon oil, bergamot oil, mandarin oil, ginger oil, pine oil Lavender oil, bay oil, clove oil, hiba oil, rose oil, eucalyptus oil, lemon oil, thyme oil, rosemint oil, sage oil, menthol, cineole, eugenol, citral, citronellal, borneol, linalool, gellerall, Essential oils such as camphor, thymol, spirantol, pinene, limonene, terpene compounds; silicone oils and the like.

  The oil component is less than 2.5% by mass in the granulated product (A), preferably less than 2% by mass, from the point of maintaining the shape-retaining property of the granulated product and problems such as bleeding. It is particularly preferably less than 1% by mass, more preferably less than 0.5% by mass. Most preferably, the oil component is not contained in the granulated product (A).

  In particular, the ratio of the content of (a3) nonionic surfactant to the content of oil component in the granulated product (A) (oil component / nonionic surfactant) is preferably 0 to 1. When it is 0, more preferably 0 to 0.5, it is very effective in that the effect of warming after bathing is brought about while suppressing problems during production.

  In particular, when (a3) a polyoxyethylene sorbitol fatty acid ester is contained as a nonionic surfactant, the ratio of the content of the polyoxyethylene sorbitol fatty acid ester and the oil component in the granulated product (A) (oil component / The polyoxyethylene sorbitol fatty acid ester) is preferably 0 to 4.0, more preferably 0 to 1.0, and particularly preferably 0 to 0.5, while suppressing problems during production and after bathing. It is very effective in that it has the effect of promoting warmth.

  By further adding a disintegration aid to the granulated product (A), the disintegration property of the granulated product (A) is improved and the solubility of the granulated product (A) in bath water is improved. Can do. As the disintegration aid, saccharides and inorganic salts which are solid at normal temperature (20 ° C.) are preferable.

  Examples of the saccharide include glucose, fructose, lactose, maltose, sucrose, dextrin, maltodextrin, cyclodextrin, maltose, fructose, and trehalose.

  Examples of the inorganic salt include sodium sulfate, magnesium sulfate, sodium chloride, potassium chloride, magnesium oxide, sodium polyphosphate, and sodium phosphate, and the inorganic salt may contain a carbonate. Less than 15% by mass in the granule (A), preferably less than 2% by mass, particularly preferably less than 1% by mass, more preferably less than 0.5% by mass from the viewpoint of storage stability. . In particular, the carbonate is most preferably not contained in the granulated product (A) from the viewpoint of storage stability.

  The average particle size of the disintegration aid is 1 μm to 100 μm from the viewpoint of granulation, finer foam, foamability, and solubility in bath water when the granulated product (A) is produced. It is preferable to use a certain one, and in particular, when granulating by extrusion granulation, it is more preferable to use one having an average particle size of 3 μm to 50 μm, and one having an average particle size of 5 μm to 30 μm is used. More preferably. When the particle size is larger than the above, it is preferable to disintegrate in advance until a suitable particle size is obtained. The average particle size of the disintegration aid is determined by the measurement method described in the examples.

  From the viewpoint of solubility, the content of the disintegration aid in the granulated product (A) is preferably 0.1% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.

  The bulk density of the granulated product (A) is 700 g / L or less and 400 to 700 g from the viewpoint of securing the foamability of fine carbon dioxide gas when the bath agent composition of the present invention is administered to bath water. / L is preferable, and 450 to 650 g / L is more preferable. It is considered that the bulk density of the present invention can be achieved by not being too compact during the production of the component (A) described later. In addition, the bulk density of the granulated product of the component (A) is determined by a method defined by JIS K 3362.

  Furthermore, the average particle diameter of the granulated product (A) is preferably 100 to 1500 μm, preferably 400 to 1200 μm, and preferably 600 to 900 μm from the viewpoints of powdering, solubility of the granulated product, and sedimentation. In addition, the average particle diameter of a granulated material (A) is determined by the measuring method as described in an Example.

  The content of the granulated product (A) in the bath agent composition of the present invention is 30 to 80 mass from the viewpoint of obtaining the amount of carbon dioxide dissolved in the bath water, the amount of carbon dioxide generated and the fine carbon dioxide bubbles. %, More preferably 35 to 75% by mass, and particularly preferably 40 to 70% by mass.

  Examples of the carbonate of the component (B) contained in the granular bath agent composition of the present invention include sodium carbonate and potassium carbonate which are dialkali metal carbonates; sodium hydrogen carbonate which is hydrogen carbonates; Examples thereof include calcium carbonate which is a carbonate. Among these, from the point of generating fine carbon dioxide gas bubbles, it is preferable to contain 50 to 100% by mass of a dialkali metal carbonate, more preferably 75 to 100% by mass, and further 80 to 100% by mass. It is preferable to contain, and it is preferable to contain especially 85-100 mass%. As the dialkali metal carbonate, sodium carbonate is particularly preferable, and as the hydrogen carbonate, sodium hydrogen carbonate is particularly preferable. These may be used alone or in combination of two or more. Further, a carbonate containing 50% by mass or less of hydrogen carbonate is preferable from the viewpoint of generating fine carbon dioxide bubbles. Furthermore, content of the hydrogen carbonate in the carbonate of a component (B) becomes like this. More preferably, it is 0-50 mass%, More preferably, it is 0.01-25 mass%.

  The average particle diameter of the carbonate of the component (B) is preferably 100 to 750 μm, more preferably 200 to 500 μm, particularly preferably 250 to 400 μm, from the viewpoints of finer foam, duration of foam, sedimentation and the like. . In addition, the average particle diameter of the carbonate of a component (B) is determined by the measuring method as described in an Example.

  The content of the carbonate which is the component (B) in the granular bath agent composition of the present invention is preferably 20 to 70% by mass, more preferably 25 to 25%, from the viewpoint of obtaining a carbon dioxide generation amount and fine carbon dioxide bubbles. 60% by mass, particularly 30 to 50% by mass is preferred.

  In the present invention, components usually used in bath preparations can be added as long as the effects of the present invention are not impaired.

  In the granular bath agent composition of the present invention, the component (A) and the component (B) are present in independent particle states. Here, “existing in an independent particle state” means that the component (A) and the component (B) in separate and independent particle states exist in a mixed state. Then, the component (A) and the component (B) are mixed and are generally called powder or granule.

  The granular bath agent composition of the present invention is prepared by appropriately granulating each component used in normal granulation means, that is, component (A), and then granulating with an extrusion granulator or a tumbling granulator. The granulated product (A) can be produced, and further it can be produced by mixing the granular (B) carbonate and the other bath agent composition raw material (C).

  The granular bath agent composition of the present invention preferably has a 0.01 mass% aqueous solution having a pH of 5 to 7, particularly 5.5 to 6.5 at 25 ° C. This is because, if the pH is 5 to 7, the generated carbon dioxide gas is easily dissolved in the bath water, and the effect of providing an excellent warm feeling after bathing is enhanced.

  The granular bath agent composition of the present invention generates a large amount of fine carbon dioxide bubbles when dissolved in bath water. The generation of fine bubbles can be confirmed from the fact that the bath water quickly becomes cloudy due to the generated bubbles of carbon dioxide gas when 40 to 60 g of the bath agent composition of the present invention is dissolved in 180 liters of bath water. The degree of fine foaming is measured by the method described in the examples described later.

  The granular bath agent composition of the present invention is used by dissolving in bath water and generating bubbles of carbon dioxide gas. It is particularly preferable to take a bath while carbon dioxide bubbles are generated. That is, a granule containing a component (A) organic acid, a water-soluble binder and 4 to 30% by mass of a nonionic surfactant, and a granular bath agent composition containing component (B) carbonate are added to bath water. Thus, the effect of the present invention is particularly prominent if it is a method in which foaming is started and at least a part of the body is immersed in the bath water in which bubbles remain in the bath water during foaming or after foaming. The bath agent composition of the present invention can be used not only for a whole body bath such as a bath, but also as a partial bath such as a foot bath and an arm bath.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

<Particle size>
The particle size was measured by the following two methods.
(1) The particle diameters of the granulated product (A) and carbonate are determined by the median from the weight fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve (mesh 2000 to 125 μm) of JIS K 8801. The diameter was calculated.
More specifically, using a 9-stage sieve and a tray with a mesh opening of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm, the top of the top is stacked in order from the small sieve. Add 100 g of particles from the top of a 2000 μm sieve, cover and attach to a low-tap type sieve shaker (manufactured by HEIKO, tapping 156 times / minute, rolling: 290 times / minute), and shake for 5 minutes. The mass of the particles remaining on each sieve and the tray was measured, and the mass ratio (%) of the particles on each sieve was calculated.

  (2) The average particle size of the disintegration aid was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.), and the median diameter measured by dispersing the particles in a solvent that did not dissolve them. Was the average particle size. In addition, acetone was used as a solvent for the average particle diameter measurement of the fumaric acid and disintegration aid used in the examples.

<Oil absorption capacity>
The oil absorption capacity of the organic acid was measured by the following method. 45 g of powder was put into an absorption measuring device (A410 manufactured by Asahi Research Institute) and rotated at a driving blade of 200 rpm. 50 ° C. mixed solution in which an oil component and a nonionic surfactant are dissolved (Exepal IPP 50% by mass, Kao Corp. Exepar O-DM 15% by mass, Lunac BA 5 manufactured by Kao Corp.) 10% by mass, 10% by mass of Emulgen 306P manufactured by Kao Corporation, and 20% by mass of Nikkor GO-440V manufactured by Nikko Chemicals Co., Ltd. were dropped at a liquid supply rate of 2 mL / min to determine the point at which the maximum torque was obtained. The liquid addition amount at the point where the torque becomes 70% of the point where the maximum torque is reached is divided by the amount of powder input to obtain the oil absorption capacity.

[Examples 1 to 10, Comparative Examples 1 to 3]
After mixing the components used for the component (A) shown in Tables 1-2, a granulated product having a bulk density (500 g / L to 600 g / L) and an average particle size (700 to 900 μm) is granulated with an extrusion granulator. , (B) component and other components were mixed to produce a granular foaming bath agent. Each obtained bath agent was evaluated according to the following method. The fumaric acid used had an oil absorption capacity of 0.082 mL / g, glucose had an average particle size of 20 μm, and carbonate had an average particle size of 290 μm. The results are shown in Tables 1-2.

《Degree of fine foaming (turbidity)》
Put hot water of 40L at 40 ° C into the bath, add the bath preparation composition, stir well, submerge a circular black rubber plate with a diameter of 5cm in bath water to a depth that makes it completely invisible to the naked eye (turbidity) Degree) and measured. It shows that the finer bubble has arisen, so that the numerical value (cm) of depth is small.

《Degree of warming after bathing》
Evaluation was made by a total of 10 panelists from 20 to 40 years old. After putting hot water of 40 L at 40 ° C. into the bathtub and introducing the bath agent composition, the paneler was quickly bathed, and the warmth feeling immediately after bathing was evaluated according to the following criteria, and the average value of 10 persons was used as the evaluation score.
5: Warm up.
4: Slightly warms up.
3: Equivalent to Sarayu.
2: It does not warm a little compared with Sarayu.
1: Not warm compared with Sarayu.

《Bath bottom unmelted》
Put hot water of 40L at 40 ° C into the bath, add the bath agent composition, stir well, and evaluate the undissolved residue at the bottom of the bath when 4 minutes have passed since the addition according to the following criteria. The average value was used as the evaluation score.
5: There is a large amount of unmelted residue.
4: There is a little unmelted and I am worried about the roughness.
3: There is a little undissolved, but not enough.
2: Almost no unmelted residue.
1: There is no undissolved residue.

  According to Tables 1 and 2, if the bath agent composition of the present invention is used, there is no undissolved residue at the bottom of the bath, and a large amount of fine carbon dioxide bubbles are generated, realizing an excellent warm feeling after bathing. be able to.

Claims (6)

The following components (A) and (B):
(A) A granulated product containing an organic acid, a water-soluble binder and 4 to 30% by mass of a nonionic surfactant, and (B) a granular bath composition containing a carbonate.   The granulated product (A) further contains an oil component, or does not contain an oil component, and the ratio of the content of the nonionic surfactant and the content of the oil component in the granule (A) (oil component) The granular bath agent composition according to claim 1, wherein (/ nonionic surfactant) is 0 to 4.0.   The granular bath agent composition according to claim 1 or 2, wherein the nonionic surfactant in component (A) contains at least a nonionic surfactant having an HLB of 6 to 20.   The nonionic surfactant is selected from sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene hydrogenated castor oil. The granular bath agent composition according to any one of -3.   The granular bath agent composition according to any one of claims 1 to 4, wherein the organic acid in component (A) is one or more selected from fumaric acid, succinic acid and tartaric acid.   The granular bath agent composition according to any one of claims 1 to 5, wherein the component (B) contains 50 mass% to 100 mass% of a dialkali metal carbonate.