JP6209079B2 - Method for producing foamable composition - Google Patents

Description

  The present invention relates to a method for producing a foamable composition and a foamable composition.

Conventionally, foamable compositions that can diffuse aroma by adding water to react an organic acid and a carbonate to generate carbon dioxide are known.
For example, Patent Document 1 discloses the following components (A) to (C):
(A) Fragrance 1.2-5.0% by mass,
(B) 15 to 70% by mass of sodium carbonate having a hard bulk density of less than 1.0 g / ml,
(C) It is disclosed that the foamable composition containing an organic acid can ensure good manufacturability and sufficient storage stability even when the content of the fragrance is increased.
Patent Document 2 discloses a bath agent composition containing particles obtained by granulating a fragrance with a water-soluble polymer that is solid or pasty at room temperature, in order to obtain a bath agent composition whose fragrance does not change during storage. Things are disclosed.

JP 2012-240921 A JP 2000-229843 A

However, in the said patent document 1, although storage stability is improved by using sodium carbonate of a specific bulk density, it cannot be said that it is still sufficient, and furthermore, the persistence of the fragrance is not considered.
In Patent Document 2, there is little change in the scent during storage, but the storage stability of the product itself is not sufficient, and the persistence of the scent is not considered.
This invention makes it a subject to provide the foamable composition obtained by the manufacturing method of the foamable composition which has sufficient fragrance and its persistence, and was excellent in storage stability, and the said manufacturing method.

  The inventors of the present invention use a compression-molded product obtained by mixing a mixture containing an organic acid, a fragrance, and a water-soluble binder with a carbonate after granulation and compressing the mixture. The present inventors have found that a foamable composition having a good property and excellent storage stability can be realized.

That is, the present invention provides the following [1] and [2].
[1] A method for producing a foamable composition having the following steps (1) and (2), wherein the content of the fragrance is 2% by mass or more.
Step (1): Step of mixing organic acid, perfume and water-soluble binder to obtain a granulated product Step (2): Step of mixing granulated product obtained in step (1) and carbonate and compression molding [2] A foamable composition containing a fragrance, an organic acid and a carbonate, comprising a granulated product containing an organic acid, a fragrance and a water-soluble binder, and a carbonate, and a fragrance content of 2 A foamable composition that is at least% by mass.

  The foamable composition obtained by the production method of the present invention has excellent scent retention and excellent storage stability.

[Method for producing foamable composition]
The method for producing a foamable composition of the present invention is a method for producing a foamable composition having the following steps (1) and (2), wherein the content of the fragrance is 2% by mass or more.
Step (1): Step of mixing organic acid, perfume and water-soluble binder to obtain a granulated product Step (2): Step of mixing granulated product obtained in step (1) and carbonate and compression molding

The foamable composition obtained by the production method of the present invention has excellent scent retention and excellent storage stability. The reason is not necessarily clear, but is considered as follows.
That is, the organic acid is a component for generating carbon dioxide gas by reacting with the carbonate. In the present invention, this organic acid is used as a perfume holding medium. For this reason, compared with the case where much oil-absorbing powders, such as dextrin conventionally used as the said medium, are used, the organic acid content in a foamable composition can be raised. As a result, it is considered that more carbon dioxide gas can be generated at the time of use, and good fragrance can be maintained.
Moreover, by granulating these organic acids and fragrances together with a water-soluble binder, the fragrances can be stably retained in the granulated material even if a large amount of fragrance is used. In addition, the granulated product in which the organic acid and the fragrance are firmly held by the water-soluble binder in this way is stained with the fragrance held by the granulated product even when compression molding is performed after mixing with the carbonate. It is possible to suppress the ejection. For this reason, it is thought that generation | occurrence | production of the carbon dioxide gas which the fragrance | flavor which oozed out becomes a reaction medium of an organic acid and carbonate and causes is prevented. As a result, the storage stability is improved, and a large amount of perfume is released together with a large amount of carbon dioxide gas during use, and the scent is considered to be maintained well.
Furthermore, since the organic acid and the fragrance are granulated using a water-soluble binder, it takes time to dissolve the granulated product at the time of use, thereby maintaining a good fragrance for a longer time. Conceivable.
Next, components used in each step will be described, and then each step of the method for producing a foamable composition will be described.

<Organic acid>
The organic acid used in the present invention retains a fragrance in the composition, and at the time of use, when the product of the present invention comes into contact with water or hot water (hereinafter simply referred to as water or the like), it neutralizes with the carbonate. This is a component that generates carbon dioxide gas, volatilizes the fragrance by spraying, and enhances the fragrance.
The organic acid used in the present invention is solid at room temperature (25 ° C.). The melting point of the organic acid is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and preferably 300 ° C. or lower, from the viewpoint of storage stability and sustainability of fragrance. Preferably it is 250 degrees C or less, More preferably, it is 230 degrees C or less.
This organic acid has a solubility in water at 20 ° C. of preferably 10 g / 100 g or less, more preferably 8 g / 100 g, from the viewpoints of handling properties, moderate solubility in water, sustainability of fragrance, and storage stability. Hereinafter, it is more preferably 5 g / 100 g or less.

  Such organic acids include fumaric acid, malic acid, tartaric acid, citric acid, maleic acid, succinic acid, phthalic acid, glutaric acid, adipic acid, benzoic acid, salicylic acid, oxalic acid and pyrrolidone carboxylic acid. Among these, it is preferable to use at least one selected from the group consisting of fumaric acid, succinic acid, malic acid, adipic acid, oxalic acid, and citric acid, and it is easy to handle (low hygroscopicity) and economical. From the viewpoint, it is more preferable to use at least one selected from the group consisting of fumaric acid, succinic acid, adipic acid and oxalic acid, and fumaric acid is particularly preferable. These organic acids can be used alone or in combination of two or more.

  Further, from the viewpoint of supporting a liquid fragrance in the step (1), the oil absorption capacity of the organic acid is preferably 0.02 ml / g or more, more preferably 0.05 ml / g or more, and 0.1 ml / g or more. Further preferred. The oil absorption capacity is a value determined by the method described in the examples. The upper limit of the oil absorption capacity is not particularly limited, but is preferably 1.0 ml / g or less, more preferably 0.8 ml / g or less, and still more preferably 0.5 ml / g or less.

  Furthermore, from the viewpoints of granulation properties, solubility, and oil absorption, the average particle size of the organic acid is preferably 250 μm or less, more preferably 200 μm or less, further preferably 150 μm or less, further preferably 100 μm or less, and particularly preferably 50 μm or less. preferable. The lower limit is preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more from the viewpoint of productivity. The average particle size of the organic acid is measured by the method described in the examples.

  When the particle size is larger than the above, it is preferable to disintegrate in advance until a suitable particle size is obtained. Examples of the crusher that can be used for crushing include impact crushers such as hammer crushers, impact crushers such as atomizers and pin mills, and shear crushers such as flash mills. These may be a single stage operation, or may be a multistage operation of the same kind or different kind of pulverizer.

  The content of the organic acid in the foamable composition is from the viewpoint of enhancing the retention of the fragrance in the composition, and enhances the foamability due to the generation of carbon dioxide gas. From the standpoint of maintaining standing, it is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and still more preferably 40% by mass or more, and suppresses the remaining undissolved organic acid. In view of the above, it is preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, and still more preferably 50% by mass or less.

In the foamed composition, the content of the organic acid in the granulated product (that is, the content of the organic acid brought in from the granulated product) is preferably from the viewpoint of enhancing foamability and maintaining the fragrance of the fragrance by foaming. 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, from the viewpoint of suppressing the remaining undissolved organic acid. More preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less.
Therefore, the content of the organic acid in the granulated product (that is, the content of the organic acid brought in from the granulated product) in the total organic acid content increases the foaming property and maintains the fragrance of the fragrance by foaming. From a viewpoint, Preferably it is 20 mass% or more, More preferably, it is 30 mass% or more, More preferably, it is 40 mass% or more, From a viewpoint of suppressing undissolved organic acid, Preferably it is 90 mass% or less, More preferably, 85 It is not more than mass%, more preferably not more than 80 mass%, still more preferably not more than 75 mass%.
In addition, the content of the organic acid in the granulated product is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, from the viewpoint of retaining a fragrance and improving storage stability. More preferably, it is 60% by mass or more, and from the viewpoint of granulation property, it is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.

<Fragrance>
The fragrance used in the present invention is not only that when the product of the present invention comes into contact with water or the like, while being well dissolved, the volatilization into the atmosphere is promoted by spraying with carbon dioxide gas, and the fragrance is not only rapidly imparted to the space. It is a component for maintaining excellent fragrance.

  As a fragrance | flavor, it can select suitably in order to make a desired fragrance drift. Specific examples include hydrocarbons such as terpenes, phenols, alcohols, ethers, aldehydes, ketones, esters, lactones, synthetic musks, nitrogen-containing / sulfur compounds, and the like. At least one of hydrogens and phenols is preferable, and at least one of terpenes and phenols is more preferable. Such a fragrance may be used alone or in combination of two or more.

The content of the fragrance in the foamed composition is 2% by mass or more, preferably 2.5% by mass or more, more preferably 3% by mass or more, from the viewpoint of perfume fragrance and sustainability, and storage stability. From the viewpoint of property, it is preferably 6% by mass or less, more preferably 5.5% by mass or less, still more preferably 5% by mass or less, and still more preferably 4.5% by mass or less.
The content of the fragrance in the granulated product is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and still more preferably 4%, from the viewpoint of fragrance formation and sustainability. From the viewpoint of storage stability, it is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, and still more preferably 10% by mass or less. .
The mass ratio of the fragrance to the organic acid in the granulated product (fragrance / organic acid) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably from the viewpoint of containing the fragrance in the granulated product. From the viewpoint of enhancing foamability and maintaining the fragrance of the fragrance by foaming and storage stability, it is preferably 0.3 or less, more preferably 0.2 or less, and still more preferably 0.15. It is as follows.

In the present invention, a fragrance may be further blended in the step (2).
From the viewpoint of the storage stability of the foamable composition, the mass ratio of the fragrance outside the granulated product and the fragrance inside the granulated product (outside / inside granulated product) in the foamable composition is preferably 1.0 or less, 0.5 or less is more preferable, 0.1 or less is more preferable, 0.05 or less is still more preferable, and 0 is still more preferable.

<Water-soluble binder>
The water-soluble binder used in the present invention is a component for increasing the strength of the granulated product. In addition, the organic acid and the fragrance are coated with the water-soluble binder, so that the fragrance exudation in the step (2) is suppressed, and the contact between the organic acid and the carbonate is avoided and stored in the packaging container. The reaction between the organic acid and the carbonate is suppressed by using the scented fragrance as a reaction medium. Thereby, it can prevent that a packaging container expand | swells by generation | occurrence | production of a carbon dioxide gas, and the foamable composition excellent in storage stability is obtained. The water-soluble binder is solid or pasty at 25 ° C., and the solubility in water at 20 ° C. is preferably 10 g / 100 g or more. The solubility can be judged visually.

The water-soluble binder is preferably thermoplastic from the viewpoint of granulation.
As such a water-soluble binder, polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol are preferable from the viewpoint of storage stability, polyethylene glycol and polypropylene glycol are more preferable, and polyethylene glycol is still more preferable from the viewpoint of storage stability and handling. .

The number average molecular weight of the water-soluble binder is preferably 4,000 or more, more preferably 6,000 or more, and still more preferably 7,000 or more, from the viewpoints of viscosity adjustment during granulation or compression molding and handling properties. Moreover, it is preferably 20,000 or less, more preferably 13,000 or less, and still more preferably 9,000 or less. The number average molecular weights of polypropylene glycol and polyethylene glycol can be determined from the hydroxyl value.
Here, when polyethylene glycol is used as the water-soluble binder, water / ethanol may be used as the solvent, but it is preferable not to use it.
When these water-soluble binders are used, two or more water-soluble binders having different number average molecular weights may be used in combination.

  The melting point of the water-soluble binder is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 50 ° C. or higher from the viewpoint of storage stability, and preferably 100 from the viewpoint of handling during granulation. ° C or lower, more preferably 90 ° C or lower, and still more preferably 80 ° C or lower. The melting point can be measured by a differential scanning calorimeter (DSC). Specifically, using a differential scanning calorimeter (for example, manufactured by Rigaku Corporation, trade name: Thermo plus DSC8230), measurement was performed under the conditions of 10 to 20 mg of sample and a heating rate of 5 ° C./min. The melting peak temperature of the curve is taken as the melting point.

  The content of the water-soluble binder in the foamable composition is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 8% by mass or more, from the viewpoint of the strength of the compression molded product. From the viewpoint of improving the solubility in bath water, improving foamability, and sustaining the fragrance by foaming, it is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 13% by mass or less. .

  The content of the water-soluble binder in the granulated product is preferably 8% by mass or more, more preferably from the viewpoint of enhancing the strength of the granulated product and preventing its collapse and the storage stability of the foamable composition. 12% by mass or more, more preferably 14% by mass or more, and the solubility in bath water is improved, the foaming property is improved, and from the viewpoint of the persistence of the scent by foaming, preferably 23% by mass or less, More preferably, it is 20 mass% or less, More preferably, it is 17 mass% or less.

<Carbonate>
The carbonate used in the present invention is a component for generating carbon dioxide gas by neutralization with an organic acid when the product of the present invention comes into contact with water and the like, volatilizing the fragrance by spraying, and enhancing the fragrance. .
Examples of the carbonate include a dialkali metal carbonate, a hydrogen carbonate and the like from the viewpoint of enhancing foamability and sustaining the scent by foaming. Among these, as the dialkali metal carbonate, sodium carbonate and potassium carbonate are preferable, and sodium carbonate is more preferable. As the hydrogen carbonate, sodium hydrogen carbonate is preferable. These may be used alone or in combination of two or more.

  The average particle diameter of the carbonate is preferably 50 μm or more, more preferably 60 μm or more, still more preferably 70 μm or more, from the viewpoint of the duration of foam, and preferably 350 μm or less from the viewpoint of enhancing the initial fragrance due to foaming. More preferably, it is 300 micrometers or less, More preferably, it is 250 micrometers or less. The average particle size of the carbonate is measured by the method described in the examples.

  The content of the carbonate in the foamable composition is preferably 15% by mass or more, from the viewpoint of enhancing foamability due to the generation of carbon dioxide gas and effectively evaporating the fragrance by foaming to express excellent fragrance. Preferably it is 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more, and from the viewpoint of maintaining the scent and suppressing the deterioration of the scent, preferably 64% by mass or less. More preferably, it is 57 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.

  Further, from the viewpoint of ensuring storage stability, the content of sodium carbonate in the carbonate is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. Moreover, from the same viewpoint, 100 mass% or less is preferable and 80 mass% or less is more preferable.

  In the foamable composition, the molar ratio of carbonate to organic acid (carbonate (mole) / organic acid (mole)) is preferable from the viewpoint of securing a proper amount of carbon dioxide gas generation and fragrance and sustainability. Is 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and from the same viewpoint, it is preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1. 1 or less.

<Other ingredients>
Even if it is a component other than the above, other components can be appropriately blended within the range in which the problems of the present invention can be solved.

(Oil-absorbing powder)
The foamable composition of the present invention can further contain an oil-absorbing powder. Examples of the oil-absorbing powder include polysaccharides, alkyl methacrylate methacrylate copolymers, and inorganic powders.
Polysaccharides modified with dextrin, alkyl glyceryl ether having a linear or branched alkyl group having 10 to 40 carbon atoms and / or a sulfoalkyl having 1 to 5 carbon atoms which may be substituted with a hydroxyl group. Water-soluble nonionic cellulose ethers such as sugars, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, ionic celluloses such as cationized cellulose, carboxymethylcellulose, and cationized hydroxyethylcellulose, guar gum, hydroxy Ethyl guar gum, methyl guar gum, ethyl guar gum, hydroxypropyl guar gum, hydroxyethyl methyl guar gum, hydroxypropi Guar gum, starch, hydroxyethyl starch, methyl starch, ethyl starch, hydroxypropyl starch, hydroxyethyl starch and hydroxypropyl starch and the like.
Examples of the inorganic powder include calcium silicate and silica.
These various oil-absorbing powders may be used alone or in combination of two or more. Among these, dextrin is preferable from the viewpoint of storage stability of the foamable composition and high fragrance.

  The number average molecular weight of the dextrin is preferably 1500 or more, more preferably 2000 or more, further preferably 2500 or more, preferably 10,000 or less, more preferably 9000 or less, and still more preferably 8000 or less.

The content of the oil-absorbent powder in the granulated product is preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 8% by mass or less, from the viewpoint of undissolved residue and scent persistence. % Or less is still more preferable, and it is still more preferable not to contain.
The content of the oil-absorbing powder in the foamable composition is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, from the viewpoint of undissolved and scent sustainability. The mass% or less is still more preferable, and it is especially preferable not to contain.

(Nonionic surfactant)
The foamable composition of the present invention may contain a nonionic surfactant from the viewpoint of solubility of the fragrance component in water.
Examples of the 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 Examples include fatty acid esters and polyoxypropylene alkyl ethers. These may be used singly or in combination of two or more, since the above effects can be further improved.
Among these, sucrose fatty acid esters are preferable, and HLB is more preferably 10 to 16 in that the foamable composition of the present invention exhibits the above-described effects. Specific examples of the sucrose fatty acid ester include sucrose behenic acid ester, sucrose stearic acid ester, sucrose palmitic acid ester, sucrose myristic acid ester, sucrose lauric acid ester, and sucrose oleic acid ester.

Here, HLB is a value usually used to represent the balance between the hydrophilicity and hydrophobicity of a 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 + 11.7 log ₁₀ (M _w / M ₀ )
M _w : Sum of formula weight of hydrophilic part M ₀ : Sum of formula weight of lipophilic part

  The content of these nonionic surfactants is preferably 0.001% by mass or more, more preferably 0.005 in the total amount of the foamable composition, from the viewpoint of storage stability of the foamable composition and high fragrance. It is at least mass%, preferably at most 0.1 mass%, more preferably at most 0.05 mass%.

(Stabilizer)
The foamable composition of the present invention may contain a stabilizer from the viewpoint of improving the storage stability of the granulated product or compression-molded product. As the stabilizer, a poorly water-soluble metal oxide is preferable. As the water-insoluble metal oxide, alkaline earth metal oxides such as magnesium oxide, calcium oxide, and zinc oxide are particularly preferable.

  The average particle diameter of the stabilizer is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less, from the viewpoint of expressing the effect as a stabilizer. In the case of granulation by granulation, it is preferable to use one having an average particle diameter of 50 μm or less, and more preferably one having an average particle diameter of 30 μm or less. The average particle diameter of the stabilizer is measured by the method described in the examples.

  The content of the stabilizer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the foamable composition from the viewpoint of improving the solubility of the granulated product or the compression molded product. 1 mass% or more is still more preferable. On the other hand, the upper limit of the content of the disintegration aid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less from the viewpoint of cost.

In the foamable composition obtained by the method of the present invention, the content of the essential component and the optional component, that is, an organic acid, a fragrance, a water-soluble binder, a carbonate, an oil-absorbing powder, a nonionic surfactant, and The total content of the stabilizer is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, More preferably, it is 100 mass%.
However, in the foamable composition used in the present invention, components other than those described above can be appropriately blended within a range that does not impair the effects of the present invention. Such ingredients include inorganic salts such as sodium metaphosphate, sodium chloride, calcium chloride, magnesium chloride, sugars such as glucose, fructose, lactose, maltose, sucrose, maltose, fructose, trehalose, oily ingredients, and excipients. Agents, antifoaming agents, antioxidants, antibacterial / antifungal agents, pigments, herbal medicines and the like.

<Method for producing foamable composition>
As above-mentioned, the manufacturing method of the foamable composition of this invention has the following process.
Step (1): Step of mixing an organic acid, a fragrance and a water-soluble binder and granulating to obtain a granulated product Step (2): Mixing the granulated product obtained in Step (1) and carbonate. In addition, as long as there exists an effect of this invention, you may add a part of carbonate in a process (1). Next, each step will be specifically described.

(Process (1))
Step (1) is a step in which an organic acid, a fragrance, and a water-soluble binder are mixed to obtain a granulated product.
In step (1), it is preferable to drop-mix the fragrance into the organic acid and then drop-mix the water-soluble binder.
The water-soluble binder may be mixed after melting part or all of it in advance, or may be blended as a solid and heated and melted inside the mixer, but it is preferably used after being melted in advance.
In the step (1), when the oil-absorbing powder is added, it is preferable to mix the organic acid and the oil-absorbing powder in advance and then drop and mix the fragrance.

When extruding and granulating in the above step (1), the mixer for mixing the components may be any device that does not give a large amount of compaction by applying strong shear during mixing. For example, a drum mixer, a ribbon mixer, a nauter mixer, and the like can be given.
However, in the case of Shugi mixer, Henschel mixer, or a vertical type or horizontal type mixing machine equipped with main wings and crushing blades, high speed mixer etc. It can be used by setting the number low and suppressing consolidation.

It is preferable to set the fluid number of the granulator defined by the following formula to 60 or less from the viewpoint of suppressing compaction during mixing, increasing foamability, and sustaining fragrance by foaming, and to 50 or less. More preferably, it is more preferably set to 40 or less. From the viewpoint of storage stability, it is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more.
Fluid number: Fr = V ² / (R × g)
V: Circumferential speed [m / s]
R: Radius from the center of rotation to the circumference of the rotating object [m]
g: Gravity acceleration [m / s ² ]
In a vertical or horizontal granulator equipped with main wings and crushing wings, V and R use the values of the main shaft, and in a Nauter mixer where the agitator draws a rotation and revolution orbit, V and R are rotation agitation shafts. The value of is used.

  In the step (1), the temperature at which the components are mixed is more preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and more preferably 40 ° C. or higher from the viewpoint of efficiently mixing. More preferably, from the viewpoint of suppressing sublimation of the organic acid, 150 ° C. or lower is more preferable, 100 ° C. or lower is further preferable, and 80 ° C. or lower is even more preferable.

  When extruding and granulating the mixture obtained above, multi-gran, pelleter double, dome gran, twin dome gran, disc pelleter (all manufactured by Dalton Co., Ltd.), basket type granulator ( A well-known extrusion granulator such as Kikusui Seisakusho) can be used.

When using an extrusion granulator, the hole diameter of the screen is preferably 0.3 mm or more, more preferably 0.4 mm or more, still more preferably 0.5 mm or more, and preferably 2.0 mm or less, more preferably. Is 1.5 mm or less, more preferably 1.0 mm or less.
By using such a screen, a cylindrical or noodle-shaped granulated product can be obtained.

  The obtained extruded granulated product can be cooled in order to suppress coalescence and agglomeration, and then can be sized as necessary. As a machine to be used for sizing, a pulverizer (or a pulverizer) equipped with a screen having a well-known desired hole diameter can be used. For example, a Fitzmill (Dalton Co., Ltd.), a power mill ( All include Dalton Co., Ltd., Comil (Paulec Co., Ltd.), and the like.

When rolling granulation in the above step (1), Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.), high speed mixer (manufactured by Earth Technica Co., Ltd.), vertical granulator (manufactured by Paulek Co., Ltd.), Ready Ge mixer (manufactured by Matsuzaka Giken Co., Ltd.), Broshear mixer (manufactured by Taiheiyo Kiko Co., Ltd.), V-type mixer (manufactured by Fuji Powder Co., Ltd.), ribbon mixer (manufactured by Hosokawa Micron Co., Ltd.), Nauter mixer ( Hosokawa Micron Co., Ltd.) and SV mixer (Shinko Bantec Co., Ltd.) can be used.
From the viewpoint of the storage stability of the foamable composition, an extrusion granulator is preferred.
The average particle size of the granulated product is preferably 100 μm or more, more preferably 300 μm or more, still more preferably 400 μm or more, still more preferably 500 μm or more, and preferably 2000 μm or less, more preferably 1500 μm or less, even more preferably. Is 1000 μm or less, more preferably 800 μm or less.

(Process (2))
Step (2) is a step in which the granulated product obtained in step (1) and carbonate are mixed and compression molded.
In the step (2), an organic acid may be further mixed and compression molded. As a result, the scenting in the initial stage of use becomes better, and the dissolution time of the obtained compression-molded product is prevented from becoming excessively long and undissolved.

  When mixing each component in the step (2), any method may be used as long as the granulated product and the carbonate can be mixed substantially uniformly. For example, you may mix using the mixer demonstrated regarding process (1), a V-type blender (made by Paulex Co., Ltd.), a double cone mixer (made by Tokuju Kosakusho Co., Ltd.), and a ribbon blender. (Hosokawa Micron Co., Ltd.), SV mixer (Shinko Bantec Co., Ltd.), etc. may be used for mixing.

The compression molding is not limited as long as a tablet or briquette can be obtained, and a known tableting machine and briquetting machine can be used.
The tableting machine is an apparatus that fills a granule in a mortar and compresses it between a lower punch and an upper punch to form. A tableting machine is a single-punch tableting machine in which a pair of upper and lower punches move up and down within a single die, and a die is embedded in the outer periphery of a horizontally rotating turntable at equal intervals. There is a rotary tableting machine in which a series of operations of filling, compression, and discharging are continuously performed while rotating. As a known tableting machine, a tableting machine manufactured by Riken Kikai Co., Ltd. can be used as a single tableting machine, and a tableting machine manufactured by Kikusui Chemical Co., Ltd. can be used as a rotary tableting machine.

  The tablet size when using a tableting machine is preferably 70 mm or less, more preferably 65 mm or less, and more preferably 10 mm or more in the case of a columnar shape (in the case of a polygon, the length of one side). Is preferably 30 mm or more. The thickness of the tablet is preferably 20 mm or less, more preferably 15 mm or less, more preferably 2 mm or more, more preferably 5 mm or more, and still more preferably 8 mm or more. The shape of the tablet is not particularly limited, but a columnar shape and a polygonal shape are preferable.

The briquetting machine continuously compresses and molds the two rolls that have pockets that become the matrix of the desired compressed product on the outer periphery and feeds the granules between the rolls rotating at the same speed. Device. As a known briquetting machine, a briquetting machine (manufactured by Shinto Kogyo Co., Ltd.) or the like can be used.
The briquette particle size when using a briquetting machine is preferably 25 mm or less, more preferably 20 mm or less, still more preferably 15 mm or less, and even more preferably 10 mm or less from the viewpoint of briquette solubility. The briquette shape is not particularly limited, but a briquette shape, an almond shape, a pillow shape, a finger shape, a lens shape and the like are preferable.

In the step (2), other components such as a water-soluble binder, a nonionic surfactant, a disintegration aid, a fragrance and the like can be appropriately blended within the range in which the problem of the present invention can be solved.
From the viewpoint of solubility, the content of the granulated product in the foamable composition obtained in the step (2) is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 62% by mass or less, 55 mass% or less is still more preferable. Moreover, from a viewpoint of containing a fragrance | flavor and improving storage stability, 10 mass% or more is preferable, 15 mass% or more is more preferable, 20 mass% or more is further more preferable, and 25 mass% or more is still more preferable.

[Foaming composition according to the first embodiment]
The foamable composition which concerns on the 1st aspect of this invention can be manufactured with the manufacturing method of the above-mentioned foamable composition. The kind and content of each component in this foamable composition are also as described above.

[Foaming composition according to second embodiment]
The foamable composition according to the second aspect of the present invention is a foamable composition containing a fragrance, an organic acid and a carbonate, and a granulated product containing an organic acid, a fragrance and a water-soluble binder, It is a foamable composition that contains salt and has a perfume content of 2% by mass or more.
The granulated product in the foamable composition can be produced by the above-mentioned step (1), and the type and content of each component in the granulated product are determined in the above-described method for producing a foamable composition. As explained.
Moreover, this foamable composition can be manufactured by the above-mentioned steps (1) and (2), and the kind and content of each component in this granulated product are also the method for manufacturing the above-mentioned foamable composition. As described above.

[Usage]
The foamable composition obtained by the production method of the present invention can be used, for example, in a bathroom with water or the like in a container such as a cup. There is no restriction on the order of placing in this container, and after pouring water or the like into the container, these foamable compositions may be put in, or after putting these foamable compositions into the container, water or the like may be poured in, You may put these in a container simultaneously.
Moreover, you may use these foamable compositions in a bathtub as a bath agent.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, an Example describes the illustration of this invention and does not limit this invention.

<Method for measuring various physical properties of powder and granulated product>
1. Average particle diameter The average particle diameter was measured by the following two methods.
(1) The average particle size of the granulated product was obtained by oscillating for 5 minutes using a standard sieve of JIS K 8801 (mesh opening 2000 to 125 μm), and then calculating the median diameter from the weight fraction according to the size of the sieve mesh.
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 granulated material 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 vibrate for 5 minutes. After that, 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.
The average particle size of the granulated product was determined by accumulating the mass ratio of the particles on the sieve having a small mesh size in order from the saucer to give a total particle size of 50%.
The average particle size of the carbonate was measured in the same manner as above except that a 12-stage sieve having a mesh size of 45 μm, 63 μm, 90 μm, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm was used. .

(2) Measurement of average particle diameter of organic acid, oil-absorbing powder, and stabilizer The average particle diameter of organic acid, oil-absorbing powder, and stabilizer is determined by the laser diffraction / scattering particle size distribution analyzer LA-920. The median diameter measured by dispersing each powder in a non-dissolving dispersion medium (made by HORIBA, Ltd.) was taken as the average particle diameter.
Specifically, when measuring an organic acid, acetone was used as a dispersion medium. In the case of measuring a water-soluble polymer among the oil-absorbing powders, acetone was used as a dispersion medium, and in the case of measuring an inorganic powder, ion-exchanged water was used as a dispersion medium. Similarly, when measuring the stabilizer, ion-exchanged water was used as a dispersion medium.

2. Bulk density The bulk density of each powder was measured by a method defined by JIS K 3362.

3. Oil absorption capacity The oil absorption capacity of each powder was measured by the following method.
In the oil absorption capacity measurement, first, approximately 80 ml of powder was put into an absorption measuring device (S410, manufactured by Asahi Research Institute) and rotated at a driving blade of 200 rpm. The amount of powder charged was calculated from the bulk density. Nonionic surfactant (Nikko Chemicals Co., Ltd. product Nikkor GO-440V HLB = 12.6) was dripped here at a liquid supply rate of 2 ml / min to determine the point at which the maximum torque was obtained. The amount of liquid (nonionic surfactant) added at a point at which the torque becomes 70% of the point at which the maximum torque is reached was divided by the amount of powder input to obtain the oil absorption capacity of each powder.

4). Storage stability Each of the 10 tablets obtained was sealed in a bag-shaped aluminum pillow (aluminum pillow inner volume / foamable composition volume = 2) and stored at 50 ° C. for 1 month. The presence or absence of blistering was confirmed visually and evaluated according to the following evaluation criteria.
4: No change in the appearance of the aluminum pillow. 3: A slight bulge in the appearance of the aluminum pillow. 2: A slight bulge in the aluminum pillow. 1: A bulge in the aluminum pillow.

5. Evaluation of fragrance The obtained tablet (mass 20 g) was poured into 200 ml of hot water at 40 ° C., and one skilled evaluator in accordance with the following evaluation criteria for fragrance 2 minutes, 6 minutes, and 10 minutes after injection. evaluated.
A: good scent B: good scent C: bad scent

6). Dissolution time The obtained tablets (mass 20 g) were put into 200 ml of hot water at 40 ° C., it was visually confirmed that the whole amount was dissolved, and the time after the addition was measured.

<Manufacture of extruded granules>
In the following production examples and comparative production examples, extruded granules were produced using the following raw materials.
(Organic acid)
・ Fumaric acid-1: prepared by pulverizing fumaric acid manufactured by Nippon Shokubai Co., Ltd., oil absorption capacity 0.220 ml / g, bulk density 809 g / l, average particle size 35 μm
(Fragrance)
-Kao Co., Ltd. compounding fragrance | flavor: 30-50 mass% of terpenes and 20 mass% of phenols are included.
(Water-soluble binder)
Polyethylene glycol: manufactured by Kao Corporation, number average molecular weight 8500, 66 ° C
(Oil-absorbing powder)
Dextrin: manufactured by Nippon Star Chemical Co., Ltd., oil absorption 1.507 ml / g, bulk density 142 g / l, average particle size 455 μm
・ Calcium silicate: Abuta Pharmaceutical Co., Ltd., oil absorption 4.517 ml / g, bulk density 74 g / l, average particle size 28 μm

Production Example 1
2L high speed mixer (Fukae Powtech Co., Ltd .: LFS-2, agitator rotation speed 600 rpm / chopper rotation speed 1000 rpm / fluid number 34.0 / jacket hot water temperature 60 ° C.), fumaric acid-1: 253.2 g, dextrin : 46.8 g was added and mixed for 1 minute.
Next, the fragrance | flavor: 31.2g was dripped and mixed in 2 minutes, and it mixed for 1 minute after the whole quantity addition.
Further, 58.4 g of polyethylene glycol was added in 1 minute 40 seconds, followed by mixing for 1 minute, and the mixture was extracted.
The obtained mixture was extruded and granulated using Multigran (manufactured by Dalton Co., Ltd .: MG-55, φ0.5 mm dome die screen, rotation speed 30 rpm) to obtain an extruded granulated product.
The extruded granulated product is received in a bat and cooled at 25 ° C., and then granulated with a comil (manufactured by POWREC Co., Ltd .: QC-U5, φ2.1 mm screen, rotation speed 504 rpm) to produce an average particle size of 560 μm. An extruded granulated product 1 was obtained.

Production Example 2
To a 2 L high speed mixer (Fukae Powtech Co., Ltd .: LFS-2, agitator rotation speed 600 rpm / chopper rotation 1000 rpm / fluid number 34.0 / jacket hot water temperature 60 ° C.), fumaric acid-1: 300.0 g was added 30 Mixed for 2 seconds.
Next, the fragrance | flavor: 31.2g was dripped and mixed in 1 minute and 10 second, and it mixed for 1 minute after the whole quantity addition.
Further, 58.4 g of polyethylene glycol was added in 1 minute, and then mixed for 40 seconds to extract the mixture.
The obtained mixture was extruded and granulated using Multigran (manufactured by Dalton Co., Ltd .: MG-55, φ0.5 mm dome die screen, rotation speed 30 rpm) to obtain an extruded granulated product.
The extruded granulated product is received in a bat and cooled at 25 ° C., and then granulated with a comil (manufactured by POWREC Co., Ltd .: QC-U5, φ2.1 mm screen, rotation speed 504 rpm) to produce an average particle size of 554 μm An extruded granulated product of 2 was obtained.

Production Example 3
To a 2 L high speed mixer (Fukae Powtech Co., Ltd .: LFS-2, agitator rotation speed 600 rpm / chopper rotation 1000 rpm / fluid number 34.0 / jacket hot water temperature 60 ° C.), fumaric acid-1: 271.9 g, dextrin: 28.1 g was added and mixed for 1 minute.
Next, 18.8 g of fragrance was added dropwise and mixed in 1 minute and 10 seconds, and the whole amount was added and mixed for 1 minute.
Further, 62.3 g of polyethylene glycol was added in 2 minutes, mixed for 1 minute, and the mixture was extracted.
The obtained mixture was extruded and granulated using Multigran (manufactured by Dalton Co., Ltd .: MG-55, φ0.5 mm dome die screen, rotation speed 30 rpm) to obtain an extruded granulated product.
The extruded granulated product is received in a bat and cooled at 25 ° C., and then granulated with a comil (manufactured by POWREC Co., Ltd .: QC-U5, φ2.1 mm screen, rotation speed 504 rpm) to produce an average particle size of 573 μm 3 was obtained.

Comparative production example 1
Dextrin: 50.0 g is added to 2.5 L Nauter mixer (manufactured by Hosokawa Micron Co., Ltd .: LABOMIXER LV-1 / rotation speed setting scale: MAX / without jacket), and fragrance: 33.3 g is added dropwise over 3 minutes 30 seconds. Mixed. After the entire amount was added, the mixture was mixed for 5 minutes to obtain a fragrance powder of Comparative Production Example 1.

Comparative production example 2
2L high speed mixer (Fukae Powtech Co., Ltd .: LFS-2, agitator rotation speed 600 rpm / chopper rotation 1000 rpm / fluid number 34.0 / jacket hot water temperature 60 ° C.), dextrin: 157.5 g, calcium silicate: 17. 5 g was added and mixed for 1 minute.
Next, the fragrance | flavor: 35.0g was dripped and mixed in 1 minute and 10 second, and it mixed for 1 minute after the whole quantity addition.
Further, 140.0 g of polyethylene glycol was added in 1 minute and 40 seconds, followed by mixing for 40 seconds, and the mixture was extracted.
The obtained mixture was extruded and granulated using Multigran (manufactured by Dalton Co., Ltd .: MG-55, φ0.5 mm dome die screen, rotation speed 30 rpm) to obtain an extruded granulated product.
The extruded granulated product is received in a bat and cooled at 25 ° C., and then granulated with a comil (manufactured by POWREC Co., Ltd .: QC-U5, φ2.1 mm screen, rotation speed 504 rpm), and a comparative production with an average particle size of 592 μm. The extruded granulated product of Example 2 was obtained.

Example 1
Extrusion of Production Example 1 with 2.5 L Nauter mixer (manufactured by Hosokawa Micron Corporation: LABOMIXER LV-1 / rotation speed setting scale: MAX / without jacket) sodium bicarbonate: 28.6 g, sodium carbonate: 50.6 g Granules: 68.8 g, magnesium oxide: 4.4 g, polyethylene glycol: 16.6 g, sucrose fatty acid ester: 0.038 g, fumaric acid-2: 51.0 g were added and mixed for 5 minutes to obtain a mixture. . The resulting mixture: 20.0 g of a tableting cell having a diameter of 40 mm was filled and compression-molded at 10 MPa using a tableting machine manufactured by Riken Kikai Co., Ltd., and a foam-like foaming composition having a diameter of 40 mm and a thickness of 12.1 mm I got a thing.
The results are listed in Table 2. The results are also shown in Table 2 in the examples and comparative examples described later.

Examples 2 to 4, Comparative Examples 1 to 4 , and Reference Example 1
A foamable composition was obtained in the same manner as in Example 1 except that the formulation shown in Table 2 was used. The evaluation results are shown in Table 2.

In the examples and comparative examples, the following raw materials were used.
(Organic acid)
-Fumaric acid-2: Nippon Shokubai Co., Ltd. fumaric acid, oil absorption capacity 0.131 ml / g, bulk density 809 g / l, average particle size 140 μm
(Carbonate)
・ Sodium bicarbonate: manufactured by Tosoh Corporation, average particle size of 234 μm
・ Sodium carbonate: manufactured by Central Glass Co., Ltd., average particle size 93 μm
(Water-soluble binder)
Polyethylene glycol: manufactured by Kao Corporation, number average molecular weight 8500, melting point 66 ° C.
(Disintegration aid)
Magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 8 μm
(Nonionic surfactant)
-Sucrose fatty acid ester: Mitsubishi Chemical Foods Co., Ltd., sucrose stearate, HLB11

In Examples 1 to 4 , all were excellent in storage stability and excellent in scent sustainability (6 minutes).
From the comparison between Example 2 and Example 4, in Example 4, since the oil-absorbing powder (dextrin) was not used in the step (1), the scent persistence (10 minutes) may be more excellent. Conceivable.
Moreover, in Reference Example 1 , since all of the organic acid was used in step (1), the fragrance persistence (10 minutes) was excellent, but there was undissolved organic acid.
From the comparison between Example 1 and Comparative Examples 1 to 3, it can be seen that when the fragrance powder is used without using the granulated product, it is inferior in both storage stability and scent sustainability.
From the comparison between Example 2 and Comparative Example 4, it can be seen that when the extruded granule does not contain an organic acid, it is inferior in any of storage stability, initial fragrance formation and fragrance persistence.

Claims (6)

A method for producing a foamable composition having the following steps (1) and (2):
Der content of the perfume of the foamable composition is more than 2 wt% is,
The content of the organic acid to be mixed in the following step (1) is, Ru der 20 to 90 mass% of the total content of organic acids in the foamable composition, method for producing the foamable composition.
Step (1): Step of mixing organic acid, perfume and water-soluble binder to obtain a granulated product Step (2): Step of mixing granulated product obtained in step (1) and carbonate and compression molding   Production of the foamable composition according to claim 1, wherein a mass ratio of the fragrance to the organic acid (fragrance / organic acid) is 0.01 to 0.3 in the granulated product obtained in the step (1). Method.   The manufacturing method of the foamable composition of Claim 1 or 2 whose content of the organic acid in a foamable composition is 25 mass% or more and 65 mass% or less.   The mass ratio (outside the granule / inside the granule) of the fragrance outside the granule and the fragrance inside the granule in the foamable composition is 0.05 or less. The manufacturing method of the foamable composition of description.   The manufacturing method of the foamable composition in any one of Claims 1-4 whose content of the granulated material in a foamable composition is 10 mass% or more and 70 mass% or less. A foamable composition containing a granulated product and a carbonate,
The granulated product contains an organic acid, a fragrance and a water-soluble binder ,
Der content of the perfume of the foamable composition is more than 2 wt% is,
The foamable composition whose content of the organic acid of a granulated material is 20 to 90 mass% of content of all the organic acids in a foamable composition.