JP7168347B2 - Method for improving shape retention of solid preparation and solid preparation - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for improving the shape retention of solid preparations and solid preparations, and more particularly, to a method for improving the shape retention of solid preparations that may lose their shape upon contact with water, and the shape retention thereof. The present invention relates to solid formulations with improved properties.

BACKGROUND ART Conventionally, solid formulations have been used which, upon contact with water, elute their ingredients together with the water to obtain desired effects. For example, soaps and solid toilet cleaners are known. Solid formulations used as detergents are solid at room temperature, and generally contain a water-soluble surfactant as a main ingredient and contain aromatic components, pigments, etc., and are molded.

Such solid preparations can be stored in a container and removed from the container at the time of use and brought into contact with water for use. It is used by contacting it with water (specifically, running water), but if it is in contact with water for a long time, it loses its shape due to the ingredients in the product. Sometimes. A solid preparation that has lost its shape may spread to the bottom of the container or leak (drip) from a hole in the container. The solid preparation loses its shape and runs off from the adhered surface, and in either case, the intended effect cannot be obtained.

In particular, solid toilet cleaners are put into the water storage tank of the flush toilet (in-tank method); placed in the water inlet of the upper lid of the water storage tank (on-tank method); directly attached to the bowl of the toilet bowl; However, if the shape retention is not sufficiently maintained due to deformation, the expected service life and cleaning effect cannot be obtained, and improvement is required.

Therefore, various studies have been made to improve the shape retention of solid detergents. For example, Patent Literature 1 proposes a toilet solid detergent containing an esterified polyoxyethylene/polyoxypropylene copolymer and a fatty acid alkanolamide.
Further, in Patent Document 2, an N-acylamino acid salt is the main component, and 0.5 to 3% by mass of a specific polyoxyalkylene alkyl ether is contained therein, and the counter ion for the N-acylamino acid is ethanolamine. A solid washing characterized by containing 40 to 60% of counter ions and 40 to 60% of counter ions consisting of potassium ions, and having a degree of neutralization of N-acyl amino acids with the counter ions of 1.6 to 2.0. A composition is proposed.

Japanese Patent Application Laid-Open No. 2004-156007 JP 2011-153274 A

Here, Patent Document 1 aims to improve the shape retention of a composition based on an esterified polyoxyethylene/polyoxypropylene copolymer, and Patent Document 2 uses an N-acylamino acid salt as a main component. It is intended to improve the shape retention of the composition to be used. As can be seen from these examples, it is necessary to examine means for solving the cause of shape loss for each causative component in solid preparations.

On the other hand, when cationic surfactants and anionic surfactants are blended into solid formulations such as solid detergents, water is taken into the formulation due to contact with water, and the shape retention is lost and the shape is lost. may occur, but there is no known effective means for resolving it.
Therefore, the present invention is a new method that suppresses the deformation of the formulation when it comes into contact with water caused by blending a cationic surfactant or an anionic surfactant in the solid formulation, and improves the shape retention of the solid formulation. The challenge is to provide a means to

As a result of extensive studies, the present inventors identified a polyethylene glycol fatty acid ester having specific properties in a solid preparation containing at least one surfactant selected from a cationic surfactant and an anionic surfactant. The inventors have found that the shape retention of the formulation is improved by using it in an amount, and have completed the present invention.

That is, the present invention is characterized by the following (1) to (6).
(1) A solid preparation containing at least one surfactant selected from a cationic surfactant and an anionic surfactant is added with a polyethylene glycol fatty acid ester having an HLB value of 10 or less in a mass ratio of the surfactant A method for improving the shape retention of a solid preparation, characterized in that it is contained in an amount of 0.3 or more with respect to 1 of the agent.
(2) The method for improving shape retention of a solid preparation according to (1) above, wherein the surfactant is a quaternary ammonium salt-type cationic surfactant.
(3) The above (1) or (2), wherein the polyethylene glycol fatty acid ester having an HLB value of 10 or less is a diester-type polyethylene glycol fatty acid ester represented by the following general formula (A). A method for improving shape retention of solid preparations.

(In formula (A), R ¹ and R ² each independently represent a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms, and n is represents an integer from 1 to 15.)
(4) A solid preparation for use in a place in contact with water, comprising at least one surfactant selected from cationic surfactants and anionic surfactants and a polyethylene glycol fatty acid having an HLB value of 10 or less. A solid preparation characterized by containing 0.3 or more of the polyethylene glycol fatty acid ester having an HLB value of 10 or less relative to 1 of the surfactant in a mass ratio.
(5) The solid preparation according to (4) above, wherein the surfactant is a quaternary ammonium salt-type cationic surfactant.
(6) The above-mentioned (4) or (5), wherein the polyethylene glycol fatty acid ester having an HLB value of 10 or less is a diester-type polyethylene glycol fatty acid ester represented by the following general formula (A). Solid formulation.

(In formula (A), R ¹ and R ² each independently represent a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms, and n is represents an integer from 1 to 15.)

According to the present invention, when the solid preparation contains at least one surfactant selected from a cationic surfactant and an anionic surfactant, a specific amount of polyethylene glycol fatty acid ester having an HLB value of 10 or less is included. As a result, deformation and dripping of the solid preparation after contact with water can be suppressed, the shape can be maintained for a sufficient period of time, and the desired effect can be obtained from the expected period of use.

It is a photograph view showing the state of the solid formulation attached to the bowl portion surface of the toilet bowl, (a) is the state after the running water contact test of Reference Example 1, and (b) is after the running water contact test of Reference Example 2. It is a figure which shows a state. FIG. 2 is a diagram illustrating evaluation criteria for shape retention of solid preparations in Test Examples 2 to 4. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
The method for improving the shape retention of a solid preparation of the present invention comprises adding polyethylene glycol fatty acid having an HLB value of 10 or less to a solid preparation containing at least one surfactant selected from a cationic surfactant and an anionic surfactant. It is characterized in that the ester is contained in a mass ratio of 0.3 or more with respect to 1 of the surfactant. Hereinafter, "at least one surfactant selected from cationic surfactants and anionic surfactants" is also referred to as a "target surfactant" in the sense of a causative component that causes deformation of solid preparations.

A polyethylene glycol with an HLB value of 10 or less is obtained by including a polyethylene glycol fatty acid ester with an HLB value of 10 or less in the solid preparation so that the mass ratio is 0.3 or more with respect to 1 of the target surfactant. The fatty acid ester has the effect of suppressing the contact of the target surfactant with water, suppressing the solid formulation from becoming too soft when it comes into contact with water, suppressing excessive deformation, and improving the solid formulation. We think that shape retention can be maintained.

The solid preparation of the present invention comprises a main agent, at least one surfactant selected from cationic surfactants and anionic surfactants (target surfactant), and a polyethylene glycol fatty acid ester having an HLB value of 10 or less. contains

The polyethylene glycol fatty acid ester having an HLB value of 10 or less contained in the solid preparation of the present invention suppresses the subject surfactant from coming into contact with water, and acts to moderate the dissolution into water. If the HLB value of the polyethylene glycol fatty acid ester is 10 or less, the desired effect of the present invention can be obtained, but 5 or less is more preferable.

In this specification, the HLB value is a value determined by the so-called "Griffin method", which is the formula shown below based on the formula weight and molecular weight of the hydrophilic group.
HLB = 20 x (sum of formula weights of hydrophilic groups/molecular weight)

The polyethylene glycol fatty acid ester having an HLB value of 10 or less used in the present invention is preferably a diester-type polyethylene glycol fatty acid ester represented by the following general formula (A).

(In formula (A), R ¹ and R ² each independently represent a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms, and n is represents an integer from 1 to 15.)

Examples of linear or branched alkyl groups having 11 to 21 carbon atoms include undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl and heptadecyl groups.
The linear or branched alkenyl group having 11 to 21 carbon atoms includes, for example, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group and the like.
Among them, a linear or branched alkyl group having 13 to 19 carbon atoms or a linear or branched alkenyl group having 13 to 19 carbon atoms is preferable, and a linear alkyl group having 13 to 19 carbon atoms is more preferable. R ¹ and R ² may be the same or different, but are preferably the same.

Specific examples of the diester-type polyethylene glycol fatty acid ester represented by formula (A) include, for example, glycol distearate (alkyl group having 17 carbon atoms, n=1, HLB calculated by Griffin method=about 3.9 ), glycol dilaurate (alkyl group with 11 carbon atoms, n = 1, HLB calculated by the Griffin method = about 5.4), PEG-4 distearate (alkyl group with 17 carbon atoms, n = 4 (average) , HLB calculated by the Griffin method = about 6.8), PEG-8 distearate (alkyl group carbon number 17, n = 8 (average), HLB calculated by the Griffin method = about 9.4), poly Glycol oxyethylenedioleate (alkyl group having 17 carbon atoms, n=4, HLB=about 6.9 calculated by Griffin's method), and the like. Among these, glycol distearate, glycol dilaurate, PEG-4 distearate, and PEG-8 distearate are preferable from the viewpoint of improving the effects of the present invention.
These HLB values are calculated by defining carboxyl groups, carbonyl groups, and glycol moieties or PEG (polyethylene glycol) moieties as hydrophilic groups, and other hydrocarbon group moieties as hydrophobic groups.

Polyethylene glycol fatty acid esters having an HLB value of 10 or less may be used singly or in combination of two or more.

The polyethylene glycol fatty acid ester having an HLB value of 10 or less is contained in the solid preparation in a mass ratio of 0.3 or more to 1 part of the target surfactant. If the content of the polyethylene glycol fatty acid ester with an HLB value of 10 or less is less than 0.3 in mass ratio with respect to the content of the target surfactant, the effects of the present invention may not be obtained.
The weight ratio of the polyethylene glycol fatty acid ester having an HLB value of 10 or less to 1 part of the target surfactant is preferably 0.5 or more.
The upper limit of the content ratio of the polyethylene glycol fatty acid ester having an HLB value of 10 or less relative to the target surfactant is not particularly limited, but if the content is too large, the target surfactant may not be eluted and may remain undissolved. . Therefore, it is preferable to adjust the total amount of the target surfactant and the polyethylene glycol fatty acid ester having an HLB value of 10 or less to 50% by mass or less in the solid preparation.

As the cationic surfactant, conventionally known various cationic surfactants can be used without particular limitation. Cationic surfactants include, for example, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, dimyristyldimethylammonium chloride, stearylbenzyldimethylammonium chloride, dimyristyldimethylammonium methyl Sulfate, didecyldimethylammonium methosulfate, 1,4-bis(3,3'-(1-decylpyridinium)methyloxy)butane dibromide, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propio and quaternary ammonium salts such as didecylethylmethylammonium ethosulfate.

Various conventionally known anionic surfactants can be used as the anionic surfactant, and there is no particular limitation. Examples of anionic surfactants include potassium, sodium, monoethanolamine, diethanolamine, triethanolamine, and aminomethylpropanol of higher fatty acids such as myristic acid, stearic acid, palmitic acid, behenic acid, instearic acid, and oleic acid. Salts such as amine acids; alkali salts of ether carboxylic acids; linear alkylbenzene sulfonate (LAS); lauryl sulfate (SLS); sodium α-olefin sulfonate (AOS) and the like.

The cationic surfactants and/or anionic surfactants (target surfactants) may be contained alone or in combination of two or more in the solid preparation.

Among these, quaternary ammonium salts are highly water-soluble and easily dissolved upon contact with water, but the effect of suppressing dissolution by polyethylene glycol fatty acid esters having an HLB value of 10 or less is likely to be obtained. Excessive outflow of ingredients can be suppressed when the solid preparation comes into contact with water.
Therefore, the method for improving the shape retention of solid preparations of the present invention is particularly effective for solid preparations containing quaternary ammonium salt-type cationic surfactants.

In the solid preparation of the present invention, the content of the target surfactant is preferably 35% by mass or less, more preferably 0.1 to 25% by mass, even more preferably 0.1 to 10% by mass. If the target surfactant content exceeds 35% by mass, the content of polyethylene glycol fatty acid esters with an HLB value of 10 or less must be increased accordingly, and the content of these will increase. If it is too low, the content of the main ingredient in the solid preparation becomes too small, and the original effect of the solid preparation may not be obtained.

The main agent is not particularly limited as long as it contains 40% by mass or more of the solid preparation and exhibits the desired effects of the solid preparation, and examples thereof include detergents and fragrances.

Examples of detergents include polyoxyethylene (POE)/polyoxypropylene (POP) copolymers, polyoxyalkylene alkyl ethers, POE hydrogenated castor oil, POE branched alkyl ethers, sorbitan esters, POE sorbitan fatty acid esters, glycerin fatty acids. Nonionic surfactants such as esters, POE glycerin fatty acid esters, POE hydrogenated castor oil fatty acid esters, POE alkylphenyl ethers, glyceryl ethers, POE glyceryl ethers, polyglycerin fatty acid esters; alkyldimethylaminoacetic acid betaine, alkylcarboxymethylhydroxyethylimidazo amphoteric surfactants such as lium betaine, alkylamidopropyl betaine, alkyldimethylamine oxide; fluorine-based amphiphilic substances;

Examples of POE/POP copolymers include those in which polyoxyethylene (POE) units and polyoxypropylene (POP) units form block copolymers. It is preferable that the POE unit and the POP unit are connected to each other, and the Pluronic type is preferable. Further, the POE/POP copolymer preferably has a number average molecular weight of 1,000 to 30,000.
The POE/POP copolymer can also be obtained by esterifying one end or both ends of the POE/POP copolymer with a fatty acid. Suitable fatty acids include stearic acid, isostearic acid, behenic acid and the like.
Further, the POE/POP copolymer may be urethaned.

Examples of polyoxyalkylene alkyl ethers include polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene tridecyl ether.

Examples of aromatic agents include natural fragrances composed of essential oil components extracted from lemon, orange, bergamot, grapefruit, lavender, rosemary, jasmine, rose, peppermint, eucalyptus, camphor, etc.; limonene, linalool, linalool acetate, borneol, citral. , citronellal, menthol, cineole, and the like; and compounded fragrances obtained by mixing these natural and artificial fragrances.

In the present invention, when the main component is a liquid component, water-soluble solid bases (for example, higher alcohols such as cetyl alcohol, stearyl alcohol, and oleyl alcohol; higher fatty acids such as stearic acid and oleic acid; It can be used by kneading it into a gel base).

The main ingredient is contained in the solid preparation in an amount of 40% by mass or more, more preferably 40 to 90% by mass, even more preferably 50 to 70% by mass.

In addition, the solid preparation of the present invention can also contain various known additives other than those described above, if necessary. Known additives include, for example, antioxidants, pigments, cleaning aids, solvents and the like.

Antioxidants include, for example, anhydrous citric acid, dibutylhydroxytoluene, vitamin C, vitamin E, butylhydroxyanisole and the like.

Examples of dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Yellow No. 4, Yellow No. 5, Blue No. 1, Blue No. 2, Green No. 3, Red No. 201, Red No. 205, Red No. 213, Red No. 214, Red No. 219, Red No. 227, Red No. 230 (1), Red No. 230 (2), Red No. 231, Red No. 232, Orange 207 Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Green No. 205, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Red No. 401, Red No. 502, Red No. 503, Red No. 504, Red No. 506, Orange No. 402, Yellow No. 402, Yellow No. 403 (1), Yellow No. 406, Yellow No. 407, Green No. 401, Green No. 402, Purple No. 401, Black 401 No. etc. can be mentioned.

Cleaning aids include, for example, EDTA salts; enzymes such as protease, lipase, amylase, pectinase, cellulase, lysozyme, and the like.

Examples of the solvent include glycols such as ethylene glycol, propylene glycol and dipropylene glycol, alcohols such as ethanol and isopropanol, hydrocarbons such as normal paraffin and isoparaffin, esters such as isopropyl myristate, and water. .

Furthermore, if necessary, a bactericide, an antifungal agent, a disinfectant, an insecticide, an insect repellent, a film-forming agent, and the like can be contained.
Bactericides, antifungal agents, and disinfectants include, for example, imidazole fungicides such as enilconazole and thiabendazole; Examples include phenolic fungicides such as triclosan.

Examples of insecticides/insect repellents include pyrethroid insect repellents such as metofruthrin, transfluthrin, profluthrin, allethrin, permethrin, phenothrin, cyphenothrin, empentrin, and imiprothrin.

Film-forming agents include, for example, silicones and fluorine-based solvents.

These additives can be appropriately contained in a desired content within a range that does not impair the effects of the present invention.

The solid preparation of the present invention can be produced by conventionally known production methods, for example, known methods such as melt molding, tabletting molding, and extrusion molding can be applied. Among them, it is preferable to manufacture by melt molding in order to uniformly mix and disperse each compounding component.

For example, in melt molding, the main agent, target surfactant, polyethylene glycol fatty acid ester with an HLB value of 10 or less, and other additives are heated and melted, uniformly mixed, and poured into a mold to form a desired shape. Then, it can be produced by cooling and solidifying. Heating and mixing may be carried out for all the components at once, or may be carried out by separating the easily soluble components and the less soluble components and then heating and mixing them while adjusting the temperature.

The solid formulation of the present invention is particularly useful as a solid detergent for toilets, and can be suitably used, for example, as a solid detergent to be directly attached to the bowl of a toilet bowl. When the solid preparation of the present invention is attached to the surface of the bowl of the toilet bowl and used, it is gradually dissolved after each flushing. Since it can be maintained for a sufficient period of time, a desired effect can be obtained within a period of time expected from the design point of view.

Thus, the present invention can provide a method for improving shape retention of a solid preparation and a solid preparation that can maintain its shape for a sufficient period of time even when in contact with water.

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
In addition, the HLB value of the polyethylene glycol fatty acid ester used in the following examples or comparative examples defines the carboxyl group, carbonyl group, and glycol moiety or PEG moiety as hydrophilic groups, and other hydrocarbon group moieties as hydrophobic groups. As a base, it was calculated by Griffin's method using the following formula.
HLB = 20 x (sum of formula weights of hydrophilic groups/molecular weight)

<Test Example 1>
(Reference examples 1 and 2)
Solid preparations of Reference Examples 1 and 2 were prepared according to the formulations shown in Table 1.
First, a POE/POP copolymer, POE behenyl ether, POE (15) tridecyl ether, and benzalkonium chloride were melted by heating and uniformly stirred. After that, the soap-based perfume was added and the whole composition was uniformly stirred.
The mixed composition was poured into a mold, cooled and solidified to produce a cylindrical solid preparation (3 g) with a diameter of 27 mm and a thickness of 8 mm.

On the bottom of each solid preparation, 0.1 g of paste (trade name “Polygrip”, manufactured by GlaxoSmithKline Consumer Healthcare Japan Co., Ltd.) was spread and spread at room temperature of 25 to 35 ° C. and humidity. Affixed to the inner wall of the bowl of a toilet installed in a test room under conditions of 65 to 85% RH. After that, from 8:00 am to 10:00 pm, the inner wall of the bowl portion was flushed with water at a rate of once every hour (flushing of about 2 L was performed 15 times). After flushing, it was allowed to stand overnight, and the appearance of a solid preparation was observed the next morning. The results are shown in FIG.

In FIG. 1, (a) is a photograph showing the state after the running water contact test of Reference Example 1, and (b) is a photograph showing the state after the running water contact test of Reference Example 2. As can be seen from FIG. 1, in Reference Example 1, the shape retention of the solid preparation was maintained after the test, and liquid dripping did not occur, whereas in Reference Example 2, liquid dripping occurred. From these results, it was found that the inclusion of benzalkonium chloride (cationic surfactant) in the solid preparation reduces the shape retention when the solid preparation comes into contact with water, and the solid preparation loses its shape and flows out, so-called liquid dripping. was found to occur.

<Test Example 2>
(Example 1)
A solid preparation was prepared according to the formulation shown in Table 2.
First, a POE/POP copolymer, POE (50) stearyl ether, POE (15) tridecyl ether, benzalkonium chloride and glycol distearate were melted by heating and stirred uniformly. After that, the soap-based perfume was added and the whole composition was uniformly stirred.
The mixed composition was poured into a mold, cooled and solidified to produce a cylindrical solid preparation (3 g) with a diameter of 27 mm and a thickness of 8 mm.

(Comparative Examples 1 to 3)
Solid formulations of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that glycol distearate in Example 1 was replaced with montan wax, monoglyceride or oleic acid amide.

On the bottom of each solid preparation, 0.1 g of paste (trade name “Polygrip”, manufactured by GlaxoSmithKline Consumer Healthcare Japan Co., Ltd.) was spread and spread at room temperature of 25 to 35 ° C. and humidity. Affixed to the inner wall of the bowl of a toilet installed in a test room under conditions of 65 to 85% RH. After that, from 8:00 am to 10:00 pm, the inner wall of the bowl portion was flushed with water at a rate of once every hour (flushing of about 2 L was performed 15 times).
After flushing, it was allowed to stand overnight, and the state of the solid preparation was visually checked the next morning. The code|symbol 1 of FIG. 2 represents a solid formulation, and the code|symbol 2 represents a liquid drip. Specifically, "5" indicates that there is almost no liquid dripping and the area around the solid preparation is slightly soft, and "5" indicates that liquid dripping occurs but is 1/4 or less of the adhesion area of the solid preparation. 4", when liquid dripping occurs, but it is more than 1/4 or less than 1/2 of the adhesion area of the solid preparation, "3", liquid dripping is more than half of the adhesion area of the solid preparation A case where it was less than the same level as that was evaluated as "2", and a case where liquid dripping occurred in a range larger than the adhesion area of the solid preparation was evaluated as "1". The results are also shown in Table 2.

<Test Example 3>
(Examples 2-7, Comparative Examples 4-5)
Solid formulations of Examples 2 to 7 and Comparative Examples 4 and 5 were produced in the same manner as in Example 1 according to the formulations shown in Table 3.

In the same test method as in Test Example 2, each solid preparation was subjected to a running water contact test. The results are also shown in Table 3.

From the results of Tables 2 and 3, benzalkonium chloride (cationic surfactant) is contained by containing glycol distearate at a mass ratio of 0.3 or more to benzalkonium chloride. It was found that the solid preparation can be prevented from losing its shape and dripping when it comes into contact with water, and can maintain sufficient shape retention.

<Test Example 4>
(Examples 8-12, Comparative Examples 6-10)
According to the formulation shown in Table 4, POE POP copolymer, POE (50) stearyl ether, POE (15) tridecyl ether, anionic surfactants (sodium α-olefin sulfonate, sodium linear alkylbenzene sulfonate, lauryl sulfate sodium) or cationic surfactants (cetylpyridinium chloride, benzethonium chloride) and glycol distearate were melted by heating and stirred uniformly. After that, the soap-based perfume was added and the whole composition was uniformly stirred.
The mixed composition was poured into a mold, cooled and solidified to prepare various cylindrical solid preparations (3 g) having a diameter of 27 mm and a thickness of 8 mm.

In the same test method as in Test Example 2, each solid preparation was subjected to a running water contact test. The results are also shown in Table 4.

Examples 8 to 12 are examples in which glycol distearate was contained at a mass ratio of 0.5 to the cationic surfactant or anionic surfactant, and all contained glycol distearate. It was found that the shape retention of the solid preparation was improved as compared with Comparative Examples 6 to 10 in which the solid preparation was not treated, and that it was possible to suppress deformation and dripping of the solid preparation upon contact with water.

<Test Example 5>
(Examples 13-20)
According to the formulation shown in Table 5, POE POP copolymer, POE (50) stearyl ether, POE (15) tridecyl ether, cationic surfactants (didecyldimethylammonium methosulfate, 1,4-bis(3, 3′-(1-decylpyridinium)methyloxy)butane dibromide, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate, didecylethylmethylammonium ethosulfate), solvent (propylene glycol, ethylene Glycol, water) and glycol distearate were melted by heating and stirred uniformly. After that, the soap-based perfume was added and the whole composition was uniformly stirred.
The mixed composition was poured into a mold, cooled and solidified to prepare various cylindrical solid preparations (3 g) having a diameter of 27 mm and a thickness of 8 mm.

In the same test method as in Test Example 2, each solid preparation was subjected to a running water contact test. The results are also shown in Table 5.

All of Examples 13 to 20 can suppress the deformation and dripping of the solid preparation when it comes into contact with water, and the shape retention of the solid preparation can be improved even when other cationic surfactants are contained. We found that it could be improved.

<Test Example 6>
(Examples 21-24, Comparative Examples 11-12)
According to the formulation shown in Table 6, POE POP copolymer, POE (50) stearyl ether, POE (15) tridecyl ether, cationic surfactant (benzalkonium chloride, didecyldimethylammonium methosulfate), solvent ( Propylene glycol, water) and polyethylene glycol distearate (PEG-4 distearate, PEG-8 distearate, PEG-250 distearate) were heated and melted and stirred uniformly. After that, a soap-based perfume was added, and the entire composition was uniformly stirred.
The mixed composition was poured into a mold, cooled and solidified to prepare various cylindrical solid preparations (3 g) having a diameter of 27 mm and a thickness of 8 mm.

In the same test method as in Test Example 2, each solid preparation was subjected to a running water contact test. The results are also shown in Table 6.

From the results in Table 6, Examples 21 to 24 containing PEG-4 distearate and PEG-8 distearate having an HLB value of 10 or less were able to suppress the deformation and dripping of solid preparations. Comparative Examples 11 and 12 containing PEG-250 distearate with an HLB value of more than 10 could not suppress the deformation and dripping of the solid preparation. From these results, it was found that the inclusion of a polyethylene glycol fatty acid ester with an HLB value of 10 or less improved the shape retention of solid preparations.

<Test Example 7>
(Examples 25-27)
According to the formulation shown in Table 7, POE POP copolymer, POE (50) stearyl ether, POE (15) tridecyl ether, cationic surfactant (benzalkonium chloride, didecyldimethylammonium methosulfate, N, N -didecyl-N-methyl-poly(oxyethyl)ammonium propionate), solvents (propylene glycol, ethylene glycol, water) and glycol dilaurate were melted by heating and stirred uniformly. After that, a soap-based perfume was added, and the entire composition was uniformly stirred.
The mixed composition was poured into a mold, cooled and solidified to prepare various cylindrical solid preparations (3 g) having a diameter of 27 mm and a thickness of 8 mm.

In the same test method as in Test Example 2, each solid preparation was subjected to a running water contact test. The results are also shown in Table 7.

From the results in Table 7, even when glycol dilaurate is contained as a polyethylene glycol fatty acid ester with an HLB value of 10 or less, it was found that the shape loss and liquid dripping of the solid preparation due to the presence of the cationic surfactant can be suppressed. .

1 solid formulation 2 liquid drip

Claims (6)

A solid preparation containing a cationic surfactant contains a polyethylene glycol fatty acid ester having an HLB value of 10 or less in a mass ratio of 0.3 or more to 1 of the cationic surfactant. A method for improving shape retention of a solid preparation characterized by: 2. The method for improving shape retention of solid preparations according to claim 1, wherein the cationic surfactant is a quaternary ammonium salt type cationic surfactant. 3. The shape retention of the solid preparation according to claim 1 or 2, wherein the polyethylene glycol fatty acid ester having an HLB value of 10 or less is a diester-type polyethylene glycol fatty acid ester represented by the following general formula (A): How to improve.

(In formula (A), R ¹ and R ² each independently represent a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms, and n is represents an integer from 1 to 15.) A solid preparation for use in a place in contact with water, containing a cationic surfactant and a polyethylene glycol fatty acid ester having an HLB value of 10 or less, in a mass ratio of 1 to the cationic surfactant A solid preparation characterized by containing 0.3 or more of a polyethylene glycol fatty acid ester having an HLB value of 10 or less. 5. The solid preparation according to claim 4, wherein the cationic surfactant is a quaternary ammonium salt type cationic surfactant. 6. The solid preparation according to claim 4, wherein the polyethylene glycol fatty acid ester having an HLB value of 10 or less is a diester-type polyethylene glycol fatty acid ester represented by the following general formula (A).

(In formula (A), R ¹ and R ² each independently represent a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms, and n is represents an integer from 1 to 15.)

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