JP5948153B2 - Cosmetics-containing articles - Google Patents

Description

  The present invention relates to a cosmetic-containing article in which a cosmetic containing piroctone olamine is filled in a container.

Conventionally, cosmetics such as hair growth agents, hair growth shampoos, and conditioners containing active ingredients such as piroctone olamine and 6-benzylaminopurine are filled in containers made of glass or polyethylene terephthalate (PET) as cosmetic-containing articles. It is in circulation.
However, in a glass or PET container, a texture such as a degree of freedom in shape and a high-quality feeling cannot be obtained sufficiently, and there is room for improvement in terms of cost. Furthermore, when a cosmetic material containing 6-benzylaminopurine was filled in a PET container, 6-benzylaminopurine was easily adsorbed to the container over time. Moreover, since PET containers tend to have a high moisture permeability, there is also a problem that the moisture in the cosmetic material volatilizes over time.

Therefore, the moisture in the cosmetics is less likely to evaporate, and even when filling cosmetics containing 6-benzylaminopurine, 6-benzylaminopurine is difficult to be adsorbed to the container, and can be manufactured at a low cost. A container capable of obtaining a texture such as the above has been desired.
For these reasons, containers made of polyolefin resins such as polyethylene and polypropylene have recently attracted attention.
For example, Patent Documents 1 and 2 disclose cosmetics containing an active ingredient such as piroctone olamine filled in a polyethylene container.

JP-A-9-48708 JP 2001-354514 A

  However, when a cosmetic material containing piroctone olamine is filled in a polyolefin resin container, there is a new problem that piroctone olamine is adsorbed on the container. In particular, when stored at a high temperature of 40 ° C. or higher, adsorption of piroctone olamine to a container and decomposition of piroctone olamine occurred easily, and storage stability could not be satisfied.

By the way, cosmetics containing piroctone olamine are mainly used as hair restorers, but since they are applied directly to the scalp and rubbed with fingers, stickiness during use leads to user discomfort.
In addition, since piroctone olamine is difficult to dissolve in water, pirocton olamine sometimes precipitated when stored at a low temperature.

  As described above, cosmetic-containing articles containing piroctone olamine are unlikely to adsorb piroctone olamine into containers or decompose piroctone olamine even when stored at high temperatures, and store at low temperatures. However, it is required to have excellent storage stability such that piroctone olamine does not easily precipitate, and excellent usability.

  The present invention has been made in view of the above circumstances, and a cosmetic material containing piroctone olamine is filled in a polyolefin resin container and is excellent in storage stability of piroctone olamine even when stored at high or low temperatures. At the same time, it is an object to provide a cosmetic-containing article that is excellent in usability.

  As a result of intensive studies, the present inventors have focused on the fact that an antistatic agent is generally contained in a polyolefin resin container. And when the nitrogen-containing antistatic agent was contained in the container made from polyolefin resin among antistatic agents, it discovered that it became the cause of adsorption | suction to the container of piroctone olamine. Furthermore, the present inventors have found that the composition of cosmetics leads to the precipitation and decomposition of piroctone olamine and the improvement of the feeling of use, and has completed the present invention.

That is, this invention has the following aspects.
[1] A cosmetic-containing article in which a cosmetic material containing piroctone olamine, a nonionic surfactant, and ethanol is filled in a resin container, wherein the resin is a polyolefin resin, and the container is A cosmetic-containing article characterized by substantially not containing a nitrogen-containing antistatic agent.
[2] The light transmittance of the container at a wavelength of 200 to 400 nm is 0 to 2%, and the light transmittance of the container at a wavelength of 500 nm is 5 to 40% [1] Cosmetic-containing articles as described in 1.
[3] The cosmetic-containing article according to [1] or [2], wherein the cosmetic is a hair restorer.

  According to the present invention, a cosmetic material containing piroctone olamine is filled in a polyolefin resin container, and even if stored at high or low temperatures, the piroctone olamine has excellent storage stability and excellent use feeling. A material-containing article can be provided.

It is a front view which shows an example of the container used for the cosmetics containing article of this invention.

Hereinafter, the present invention will be described in detail.
The cosmetic-containing article of the present invention is a cosmetic containing a piroctone olamine, a nonionic surfactant, and ethanol filled in a specific container.

<Cosmetics>
(Piroctone olamine)
Piroctone olamine has an antibacterial and antioxidant action and is an active ingredient that suppresses excessive secretion of scalp fat. By containing piroctone olamine, the scalp can be kept clean and unpleasant odors such as dandruff, kayumi and sweat can be prevented.

  The content of piroctone olamine is preferably 0.001 to 3% by mass, more preferably 0.01 to 1.0% by mass in 100% by mass of the cosmetic, and is particularly a type that does not wash away hair restorer or hair tonic. In the case of this cosmetic, 0.01 to 0.5% by mass is more preferable. If the content of piroctone olamine is 0.001% by mass or more, sufficient antibacterial / antioxidant action can be obtained. On the other hand, if the content of piroctone olamine is 3% by mass or less, piroctone olamine is less likely to precipitate even when stored at a low temperature, and the storage stability is further improved.

(Other active ingredients)
The cosmetic may contain other active ingredients other than piroctone olamine. Other active ingredients include 6-benzylaminopurine having hair growth promoting action, β-glycyrrhetinic acid having anti-inflammatory action, nicotinic acid amide having blood flow promoting action, t-flavanone which suppresses apoptosis, cell proliferation action And adenosine, paulownia leaf extract, assembly, minoxidil with vasodilatory action, carpronium chloride, pentadecanoic acid glyceride with energy supply action, and the like.
The content of these other active ingredients is about 0.1 to 5% by mass in 100% by mass of the cosmetic, and particularly 6-benzylaminopurine is preferably 0.1 to 2.0% by mass, β-glycyrrhetinic acid is preferably 0.001 to 0.2% by mass, and nicotinamide is preferably 0.001 to 1.0% by mass. If the content of these other active ingredients is less than 0.1% by mass, the hair-growth effect may not be sufficiently obtained, and if it exceeds 5% by mass, the low-temperature stability may be lowered.
In particular, when the cosmetic is a hair restorer, it preferably contains 6-benzylaminopurine.

(Nonionic surfactant)
A nonionic surfactant is a component that aims at low-temperature storage stability so that pyroctonolamine is less likely to precipitate even when stored at low temperatures.
Examples of nonionic surfactants include ether type surfactants, ester type surfactants, ether / ester type surfactants, and the like.

  Examples of ether type surfactants include polyoxyethylene (2-30) cetyl ether, polyoxyethylene (2-50) oleyl ether, polyoxyethylene (2-40) stearyl ether, polyoxyethylene (10-50). Lauryl ether, polyoxyethylene (15-30) isocetyl ether, polyoxyethylene (10-30) isostearyl ether, polyoxyethylene (5-30) octyldodecyl ether, polyoxyethylene (5-30) behenyl ether, Polyoxyethylene (2-20) oleyl ether, polyoxyethylene (5-30) decyl tetradecyl ether, polyoxyethylene (12-30) polyoxypropylene (6) decyl tetradecyl ether, polyoxyethylene (5-30 ) Such as Steri ether, and the like. The numbers in parentheses after “ethylene” and “propylene” are the average added mole numbers of ethylene oxide and propylene oxide.

  Examples of the ester type surfactant include sorbitan fatty acid esters such as sorbitan palmitate, sorbitan stearate, sorbitan sesquistearate, sorbitan tristearate; monofatty acid glycerin such as glyceryl stearate, glyceryl palmitate, glyceryl myristate; stearin Examples include propylene glycol fatty acid esters such as propylene glycol acid and propylene glycol distearate; ethylene glycol fatty acid esters such as glycol stearate and glycol dilaurate.

  Examples of ether ester type surfactants include polyethylene glycol stearate (2-40), polyoxyethylene (30-100) hydrogenated castor oil, polyethylene glycol monostearate (5-40), polyoxyethylene (20-50). ) Castor oil, polyoxyethylene stearate (3-10) cetyl ether, polyoxyethylene stearate (4-12) stearyl ether, polyoxyethylene stearate (3-15) lauryl ether, polyethylene glycol distearate (2- 150), polyoxyethylene (3-20) glyceryl tristearate, polyoxyethylene (40-60) triisostearate hydrogenated castor oil, polyoxyethylene (3-10) trimethylolpropane tristearate Shi sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, tetra-oleate polyoxyethylene (6 to 60) sorbitol, polyoxyethylene - polyoxypropylene alkyl glyceryl ether and the like. The numerical value in parentheses after “polyethylene glycol” is the average added mole number of ethylene oxide.

Among the nonionic surfactants, among the above-mentioned, from the viewpoint of the stability of piroctone olamine, polyoxyethylene (40) sorbite tetraoleate, polyoxyethylene (2) oleyl ether, polyoxyethylene (30) polyoxypropylene (6) Decyl tetradecyl ether is preferred.
These nonionic surfactants may be used alone or in combination of two or more.

  The content of the nonionic surfactant is preferably 0.01 to 5% by mass in 100% by mass of the cosmetic, and 0.05 to 3% by mass from the viewpoint of storage stability and usability of pyroctonolamine at low temperatures. % Is more preferable, and 0.05 to 2% by mass is more preferable. If the content of the nonionic surfactant is 0.01% by mass or more, the effect of storage stability of pyroctonolamine at a low temperature can be sufficiently obtained even when the content of ethanol described later is small. . On the other hand, if the content of the nonionic surfactant is 5% by mass or less, it is difficult to feel stickiness during use, and the usability can be maintained well.

(ethanol)
Ethanol is a component that gives excellent feeling of use and is intended to improve the storage stability of piroctone olamine. Accordingly, piroctone olamine is hardly precipitated even when stored at a low temperature, and piroctone olamine is hardly decomposed even when stored at a high temperature.

  The content of ethanol is preferably 50 to 96% by mass and more preferably 75 to 96% by mass in 100% by mass of the cosmetic. If the content of ethanol is 50% by mass or more, the effect of storage stability of pyroctone olamine at low and high temperatures can be sufficiently obtained. Moreover, an antibacterial effect is also obtained. On the other hand, even if the ethanol content exceeds 96% by mass, the effect of storage stability of piroctone olamine reaches its peak, and when the ethanol content increases, alcohol odor and irritation tend to increase. Therefore, the ethanol content is preferably 96% by mass or less.

(Other ingredients)
In addition to the above-described piroctone olamine, nonionic surfactant, ethanol, and other active ingredients, the cosmetic may contain other ingredients as necessary.
Other ingredients include transdermal absorption enhancers, fresheners, fragrances, surfactants (excluding nonionic surfactants), polymer compounds, amino acids, protein hydrolysates, sequestering agents, thickeners. Polyols, oils, ultraviolet absorbers, pH adjusters, antioxidants, oxidants, reducing agents, alkali agents, dyes, and the like.

Examples of the transdermal absorption enhancer include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and fatty acid esters such as ethyl oleate and octyldodecyl lactate.
The content of the transdermal absorption enhancer is preferably 0.5 to 10.0% by mass and more preferably 0.5 to 5.0% by mass in 100% by mass of the cosmetic.

Examples of the refreshing agent include menthol, menthyl glyceryl ether, menthyl carboxamide, vanillyl butyl ether, menthone, camphor, borneol, cineole menthone, methyl salicylate, menthyl malonate, glycosyl-monomenthyl-O-acetate, 3-l-menthoxypropane. -1,2-diol, l-menthyl-3-hydroxybutyrate, spearmint oil, peppermint oil, peppermint oil, eucalyptus oil and the like. Among these, menthol, menthyl glyceryl ether, menthyl carboxamide, vanillyl butyl ether, camphor, spearmint oil, peppermint oil, peppermint oil, and eucalyptus oil are preferable.
0.01-5 mass% is preferable in 100 mass% of cosmetics, and, as for content of a refreshing agent, 0.1-2 mass% is more preferable.

As a fragrance | flavor, the fragrance | flavor and fragrance | flavor composition which are described in Unexamined-Japanese-Patent No. 2003-95895 can be illustrated.
0.00001-2 mass% is preferable in 100 mass% of cosmetics, and, as for content of a fragrance | flavor, 0.0001-1 mass% is more preferable.

Examples of surfactants other than nonionic surfactants include amphoteric surfactants, and specific examples include betaines such as imidazoline betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and alkylhydroxysulfobetaines. Surfactant is mentioned. In particular, alkylcarboxymethylhydroxyethyl imidazolium betaine, fatty acid amidopropyl betaine and alkylhydroxysulfobetaine are preferred. The fatty acid amidopropyl betaine and the alkylhydroxysulfobetaine are preferably those having an alkyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and particularly amide propyl betaine laurate, palm kernel oil fatty acid amidopropyl betaine, and coconut oil fatty acid. Amidopropyl betaine, lauryl hydroxysulfobetaine and the like are preferred.
The content of the surfactant other than the nonionic surfactant is preferably 0.1 to 5.0% by mass and more preferably 0.1 to 3.0% by mass in 100% by mass.

(Physical properties of cosmetics)
Although the pH of cosmetics is not specifically limited, 2.5-10.0 are preferable and 3.0-7.0 are more preferable.
The pH of the cosmetic (controlled to 25 ° C.) is a value measured by a pH meter or the like.

(Cosmetics production method)
The method for producing the cosmetic is not particularly limited, and can be produced according to a conventional method.
For example, piroctone olamine, other active ingredients, nonionic surfactant, ethanol, and other ingredients as needed, with water (for example, purified) It can be produced by mixing and dissolving in a solvent such as water) and adjusting to a predetermined pH using a pH adjuster.

(Use)
Cosmetics are used as hair restorers such as hair restorers, hair tonics, hair creams, set agents, treatment agents, hair dyes, hair gels, hair cleansing agents such as hair-growth shampoos, hair-growth rinses, etc. Suitable as agent and hair tonic.

<Container>
The container filled with the cosmetic described above is made of resin and does not substantially contain a nitrogen-containing antistatic agent.
The resin is a polyolefin resin, and specific examples include polyethylene, polypropylene, and polybutylene. Among these, polyethylene is preferable, and high-density polyethylene (density 0.92 to 0.97 g / cm ⁻³ ) is particularly preferable from the viewpoint of strength and cost.
These polyolefin resins may be used individually by 1 type, and may use 2 or more types together.
In the cosmetic-containing article of the present invention, the container for filling the cosmetic is made of a polyolefin resin, so that the cost is lower than that of a glass or PET container, the degree of freedom of the shape is high, and a high-class feeling, etc. A texture is also obtained. In addition, moisture in the cosmetic is less likely to volatilize, and even if the cosmetic contains 6-benzylaminopurine, 6-benzylaminopurine is less likely to be adsorbed to the container.

As described above, when a cosmetic material containing piroctone olamine is filled in a polyolefin resin container, there is a problem that piroctone olamine is adsorbed on the container. In particular, when stored at a high temperature of 40 ° C. or higher, piroctone olamine was easily adsorbed to the container, and storage stability could not be satisfied.
However, according to the present invention, cosmetics are filled in a polyolefin resin container that does not substantially contain a nitrogen-containing antistatic agent. Therefore, even if stored at a high temperature, piroctone olamine is difficult to adsorb on the container and is stored. Satisfactory stability. The reason why piroctone olamine is difficult to adsorb in the container is not clear, but is considered as follows.

  In general, a container made of polyolefin resin contains an antistatic agent. Among the antistatic agents, when a nitrogen-containing antistatic agent is contained in a polyolefin resin container, the nitrogen of the nitrogen-containing antistatic agent interacts with piroctone olamine in the cosmetic, and the nitrogen-containing antistatic agent It is considered that piroctone olamine is adsorbed to the container by taking piroctone olamine. Therefore, if it is a container made from polyolefin resin which does not contain a nitrogen-containing antistatic agent substantially, it is thought that adsorption of piroctone olamine to a container can be suppressed.

Examples of the nitrogen-containing antistatic agent include alkyldiethanolamine and polyoxyethylene alkylamine.
Examples of the alkyldiethanolamine include lauryl diethanolamine, stearyl diethanolamine, and oleyl diethanolamine.
Examples of the polyoxyethylene alkylamine include “Amate 102”, “Amate 105”, “Amate 302”, and “Amate 320” manufactured by Kao Corporation.

  In the present invention, “substantially does not contain” means that the nitrogen-containing antistatic agent may be contained to the extent that it does not affect. Specifically, the content of the nitrogen-containing antistatic agent is preferably 0.2 mass ppm or less, more preferably 0.1 mass ppm or less with respect to 100 parts by mass of the polyolefin resin. More preferably not.

By the way, piroctone olamine may be decomposed by exposure to ultraviolet light or visible light (sun exposure). Therefore, the container preferably contains an ultraviolet absorber and a pigment.
Examples of the ultraviolet absorber include benzotriazole, hydroxyphenyl triazine (HPT), benzophenone, benzoate, triazine, cyanoacrylate, organic nickel, hindered piperidine and the like. Among these, a benzotriazole type is preferable in terms of good compatibility with the polyolefin resin.
Examples of the benzotriazole ultraviolet absorber include tinuvin P (2- (5-methyl-2-hydroxyphenyl) benzotriazole) and tinuvin 234 (2- [2-hydroxy-3,5-bis (α, α-dimethyl). Benzyl) phenyl] -2H-benzotriazole), tinuvin 326 (2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole), tinuvin 329 (2- (2′-hydroxy) -5′-t-octylphenyl) benzotriazole), tinuvin 213 (methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol ( Condensate with a molecular weight of about 300)), Tinuvin 571 (hydroxyphenylbenzotriazo) Le derivative) and the like. Among these, tinuvin 326 is particularly preferable in terms of excellent compatibility with the polyolefin resin.

  0.01-0.5 mass part is preferable with respect to 100 mass parts of polyolefin resin, and, as for content of a ultraviolet absorber, 0.03-0.3 mass part is more preferable. If the content of the ultraviolet absorber is 0.01 parts by mass or more, an ultraviolet absorption effect in the ultraviolet region of 400 nm or less can be sufficiently obtained. Therefore, even if the cosmetic is exposed to light (particularly, ultraviolet light), piroctone ola Mining is not easily decomposed and storage stability is further improved. On the other hand, even if the content of the ultraviolet absorber exceeds 0.5 parts by mass, not only the ultraviolet absorption effect reaches its peak, but also the transparency of the container tends to decrease, and the remaining amount of the contents (cosmetics) remains. It may be difficult to confirm. Therefore, the content of the ultraviolet absorber is preferably 0.5 parts by mass or less.

By containing the pigment in the container, toning of the container and a shielding effect such as ultraviolet rays can be obtained.
Examples of the pigment include organic pigments and inorganic pigments.
Organic pigments include red permanent red, yellow first yellow, and green phthalocyanine green.
Examples of organic pigments include azo pigments and polycyclic pigments.
Examples of the azo pigments include yellow, such as benzidine yellow (; Pigment Yellow 14); blue, such as brilliant carmine 6B (; Pigment Red 57: 1), according to color tone.
As the polycyclic pigment, yellow such as isoindolinone, quinophthalone, isoindoline, anthraquinone, anthrone, xanthene; orange such as diketopyrrolopyrrole, perylene, anthraquinone (anthrone), perinone, quinacridone, indigoid; anthraquinone Red, such as quinacridone, diketopyrrolopyrrole, perylene, perinone, indigoid; purple such as dioxazine, quinacridone, perylene, indigoid, anthraquinone, anthrone, xanthene; blue such as phthalocyanine, anthraquinone, indigoid; phthalocyanine, azomethine, perylene, etc. Examples include green.

On the other hand, the color tone of the inorganic pigment includes white titanium dioxide, black carbon black, brown bengara, vermilion chrome vermilion, blue bitumen, yellow yellow lead and red iron oxide.
Inorganic pigments are classified according to color, white such as zinc white, lead white, lithopone, titanium dioxide, precipitated barium sulfate, barite powder, etc .; red such as red lead, iron oxide red; yellow such as yellow lead, zinc yellow; ultra Blue such as marine blue and prussian blue (potassium ferrocyanide); black such as carbon black and the like.

The color of the container may be adjusted using only an inorganic pigment or only an organic pigment, or a combination of an inorganic pigment and an organic pigment.
Furthermore, a pearl pigment may be used in combination with the above-described inorganic pigment or organic pigment for the purpose of imparting a beautiful appearance.

  The content of the pigment is preferably 0.03 to 0.4 parts by mass and more preferably 0.04 to 0.2 parts by mass with respect to 100 parts by mass of the polyolefin resin. If the pigment content is 0.03 parts by mass or more, a sufficient shielding effect in the visible region of 400 nm or more can be obtained, so that pyroctone olamine is decomposed even when the cosmetic is exposed to light (particularly visible light). Storage stability can be further improved. As the content of the pigment increases, the decomposition of the piroctone olamine due to exposure to sunlight is suppressed, while the contents (cosmetics) become less visible. If the pigment content is 0.4 parts by mass or less, the contents (cosmetics) can be visualized while suppressing the decomposition of piroctone olamine, and the remaining amount can be easily confirmed. Therefore, it is possible to easily measure the timing of refilling the contents (cosmetics) and purchasing the product according to the remaining amount.

The container may contain other components as necessary in addition to the ultraviolet absorbent and the pigment described above.
Examples of other components include tourmaline, titanium and other minerals, antibacterial agents, fragrances, antistatic agents (excluding nitrogen-containing antistatic agents), and the like.
Examples of antistatic agents other than nitrogen-containing antistatic agents (that is, antistatic agents that do not contain nitrogen) include glycerin fatty acid esters.
Specific examples of the glycerin fatty acid ester include monoglycerides such as glycerin monostearate and glycerin monopalmitate; acetylated monoglycerides such as glycerin diacetomonolaurate, and the like from the viewpoint of compatibility with polyolefin resins. Glycerol monostearate is preferred. The content is preferably 0.05 to 1 part by mass and more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the polyolefin resin.

As described above, since pyroctone olamine is decomposed by both ultraviolet light and visible light, in order to obtain the effect of suppressing the decomposition of piroctone olamine by exposure to sunlight, light having a wavelength of 200 to 600 nm is used in a container. Is desirable to absorb. If the container contains an ultraviolet absorber, the light shielding effect in the ultraviolet region of 400 nm or less can be sufficiently obtained, but if the container only contains the ultraviolet absorber, the light shielding effect in the visible region of 400 to 600 nm can be obtained. Absent.
Therefore, it is preferable to use a container having a light transmittance of 5 to 40% at a wavelength of 500 nm. If the light transmittance is 5% or more, the contents (cosmetics) can be well visualized. On the other hand, if the light transmittance is 40% or less, even if the cosmetic is exposed to light (particularly visible light), pyroctone olamine is hardly decomposed, and the storage stability is further improved.
The light transmittance of the container in the visible region of 400 to 600 nm is also preferably 5 to 40%. Here, “the light transmittance in the visible region of 400 to 600 nm is 5 to 40%” means that the value at which the light transmittance is minimum at the wavelength of 400 to 600 nm (minimum light transmittance) is 5% or more, It means that the value at which the light transmittance is maximum (maximum light transmittance) is 40% or less.
The light transmittance of the container at a wavelength of 400 to 600 nm can be adjusted by a combination of the pigment content in the container and the average thickness of the container described later.

On the other hand, the light transmittance of the container in the ultraviolet region of 200 to 400 nm is preferably 0 to 2% from the viewpoint of suppressing decomposition of pyroctone olamine. This value can be adjusted by the content of the ultraviolet absorber in the container. Here, “the light transmittance in the ultraviolet region of 200 to 400 nm is 0 to 2%” means that the light transmittance is maximum at a wavelength of 200 to 400 nm (maximum light transmittance) is 2% or less. It means that there is.
Thus, in order to suppress decomposition regardless of whether pyroctone olamine is exposed to ultraviolet light or visible light, the light transmittance at a wavelength of 200 to 400 nm is 0 to 2% and a wavelength of 500 nm. It is preferable to use a container having a light transmittance of 5 to 40%, and it is particularly preferable to use a container containing both an ultraviolet absorber and a pigment.
The light transmittance of the container at each wavelength can be measured using a spectrophotometer with an integrating sphere.

The container may have a single layer structure or a multilayer structure, but a single layer is preferable in consideration of cost and moldability.
The average thickness of the container is preferably 500 to 1200 μm, more preferably 700 to 1000 μm. When the average thickness of the container is 500 μm or more, even if the cosmetic is exposed to light, piroctone olamine is hardly decomposed, and the storage stability is further improved. On the other hand, if the average thickness of the container is 1200 μm or less, the contents (cosmetics) can be well visualized.
Here, the “average thickness of the container” refers to the average thickness of the container body portion in which the cosmetic is filled.

The shape of the container is not particularly limited, and a general container shape filled with a hair composition such as a hair-growth agent or a hair cleaning agent such as a hair-growth shampoo can be employed. Here, FIG. 1 shows an example of a container filled with cosmetics.
A container 1 shown in FIG. 1 includes a bottomed cylindrical container body 10 filled with cosmetics and a covered cylindrical cap part 20, and a screw part is formed on the outer periphery of a mouth part 10 a of the container body 10. The cylinder bottle is formed with a screw portion that is screwed with a screw portion formed on the outer periphery of the mouth portion 10a of the container body 10 on the inner surface of the side wall of the cap portion 20.

In the case of the container 1 shown in FIG. 1, at least the container main body 10 is made of a polyolefin resin and does not substantially contain a nitrogen-containing antistatic agent. 20 is preferably the same material as the container body 10. In addition, if at least the light transmittance and the average thickness of the container body 10 are within the above ranges, it is possible to prevent pyroctonolamine from being decomposed even when the cosmetic is exposed to light. The physical properties are preferably the same as those of the main body 10.
In the container 1 shown in FIG. 1, the container body 10 has a bottomed cylindrical shape and the cap portion 20 has a covered cylindrical shape. For example, the container body 10 may have a bottomed rectangular tube shape, or the cap portion. 20 may be a covered rectangular tube shape, and the shape of the container is not limited.

<Effect>
Since the cosmetic-containing article of the present invention described above is filled with a cosmetic in a polyolefin resin container, it is less expensive than a glass or PET container and has a texture such as a high-class feeling. . In addition, moisture in the cosmetic is less likely to volatilize, and even if the cosmetic contains 6-benzylaminopurine, 6-benzylaminopurine is less likely to be adsorbed to the container.
Further, in the cosmetic-containing article of the present invention, since the container does not substantially contain a nitrogen-containing antistatic agent, piroctone olamine in the cosmetic is hardly adsorbed to the container even when stored at a high temperature.
In addition, since the cosmetic-containing article of the present invention contains a nonionic surfactant and ethanol in the cosmetic, piroctone olamine is hardly decomposed even when stored at high temperatures, and pirocton even when stored at low temperatures. Olamin is difficult to precipitate. In addition, it has excellent usability.

  In particular, if the light transmittance of the container at a wavelength of 200 to 400 nm is 0 to 2% and the light transmittance at a wavelength of 500 nm is 5 to 40%, the cosmetic is exposed to light such as ultraviolet light and visible light. However, the contents (cosmetics) can be visualized while suppressing the decomposition of piroctone olamine.

<Other embodiments>
The cosmetic-containing article of the present invention is not limited to those described above. In the cosmetic-containing article described above, in order to suppress decomposition of piroctone olamine due to exposure to sunlight, a container filled with the cosmetic contains an ultraviolet absorber or a pigment, and the light transmittance of the container at a specific wavelength or Although the average thickness of the container is specified, for example, covering the outer surface of the container with a blocking film that can block light with a wavelength of 200 to 600 nm also suppresses the decomposition of piroctone olamine by sun exposure. it can. In this case, since light having a wavelength of 200 to 600 nm does not reach the cosmetic filled in the container by the shielding film, even if the container does not contain an ultraviolet absorber or a pigment, Even if the light transmittance and the average wall thickness of the container are out of the above-described ranges, the decomposition of piroctone olamine by exposure to sunlight can be suppressed.

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

[Examples 1-1 to 1-31 and Comparative Examples 1-1 to 1-3]
According to the composition shown in Tables 1 to 4, cosmetics of Examples and Comparative Examples were prepared by the production methods shown below. Moreover, according to the compounding composition shown to Tables 1-4, the container of each Example and the comparative example was manufactured with the manufacturing method shown below. The cosmetic material prepared in each example was filled in a container to obtain a cosmetic-containing article. The obtained cosmetic-containing article was evaluated by the following method. The results are shown in Tables 1-4.
In addition, the unit of the compounding quantity of the cosmetics in Tables 1-4 is "mass%", and all components show pure amount conversion amount. Moreover, the unit of the compounding quantity of the container in Tables 1-4 is a "mass part."
Moreover, the cosmetics of each example were prepared by balancing with purified water so that the total of each component described in the table was 100% by mass.

<Preparation of cosmetics>
In a beaker, add ethanol, piroctone olamine, other active ingredients, a nonionic surfactant, and a transdermal absorbent according to the descriptions in Tables 1 to 4, and thoroughly stir with a magnetic stirrer. After dissolution, purified water as a balance component was added, and the mixture was sufficiently stirred with a magnetic stirrer. Thereafter, an appropriate amount of citric acid was added to adjust the pH to 5, and the remaining purified water was added and balanced so that the total amount was 100% by mass to prepare cosmetics of each example.
The pH was measured by adjusting the cosmetic to 25 ° C. and using a pH meter (“HM-30G” manufactured by Toa DKK Co., Ltd.). The measuring method was performed based on JIS K3362-1998.
The “balance” indicating the blending amount of purified water means the balance added so that the total blending amount (mass%) of all the blending ingredients contained in the cosmetic is 100 mass%.

The active ingredients, nonionic surfactants, ethanol, percutaneous absorption agents, and citric acid in Tables 1 to 4 are as follows.
・ Pirocton Olamine: “Octopirox” manufactured by Clariant Japan
・ 6-Benzylaminopurine: Sansho Pharmaceutical Co., Ltd., “CTP”
Β-glycyrrhetinic acid: manufactured by Maruzen Pharmaceutical Co., Ltd., “β-glycyrrhetinic acid”
・ Nicotinamide: DSM Nutri Japan, “Nicotinamide”
-GO-440V: Polyoxyethylene (40) sorbitol tetraoleate (manufactured by Nikko Chemicals Co., Ltd., “NIKKOL GO-440V”)
E-202S: polyoxyethylene (2) oleyl ether (manufactured by NOF Corporation, “Nonion E-202S”)
PEN 4630: polyoxyethylene (30) polyoxypropylene (6) decyl tetradecyl ether (manufactured by Nikko Chemicals Co., Ltd., “NIKKOL PEN 4630”)
・ Ethanol: Nippon Alcohol Sales Co., Ltd., “95% synthetic alcohol”
・ PEG300K: Polyethylene glycol having an average molecular weight of 300 (manufactured by Lion Corporation)
・ Citric acid: manufactured by Fuso Chemical Industry Co., Ltd., “Crystal citric acid”

<Manufacture of containers>
(Preparation of resin composition)
A high-density polyethylene containing no pigment (density: 0.956) and high-density polyethylene in which an arbitrary pigment was dispersed in advance were mixed to prepare a masterbatch colored in each color.
Next, the wavelength of 500 nm when the content of the pigment and the antistatic agent in the resin composition is the amount described in Tables 1 to 4 with respect to 100 parts by mass of the high-density polyethylene, and when the container is formed. The master batch was diluted with high-density polyethylene (density: 0.956) so that the light transmittance in Table 1 became the values described in Tables 1 to 4 to prepare a resin composition.

(Molding)
The container main body 10 shown in FIG. 1 was manufactured with the blow molding machine using the obtained resin composition. About the obtained container main body 10, the average thickness and the light transmittance in the wavelength of 500 nm were calculated | required as follows. The results are shown in Tables 1-4.
The shape of the container body 10 has an outer diameter of 31 mm, a height (excluding the mouth portion 10a) of 84 mm, an outer diameter of the mouth portion 10a of 20 mm, an inner diameter of the mouth portion 10a of 15 mm, and a height of the mouth portion 10a. It was 15 mm.
Further, a cap part 20 having an outer diameter of 31 mm, an inner diameter of 24 mm, and a height of 15 mm was separately prepared.

The antistatic agents in Tables 1 to 4 are as follows.
・ Glycerin monostearate: Antistatic agent containing no nitrogen ・ Lauryldiethanolamine: Antistatic agent containing nitrogen

(Measurement of average wall thickness)
About 10 points | pieces of the container main body 10, it measured using the handy ultrasonic thickness meter (The Olympus company make, "35DL"), and calculated | required the average value.

(Measurement of light transmittance)
The light transmittance of the container body 10 at an arbitrary wavelength was measured using a spectrophotometer with an integrating sphere (manufactured by Shimadzu Corporation).
In addition, when the light transmittance in the wavelength of 200-400 nm is measured, the maximum light transmittance in the wavelength of 200-400 nm is shown in a table | surface.

[Evaluation]
<Evaluation of storage stability>
(1) Low temperature storage 50 mL of cosmetic material is filled into the container body 10, the cap portion 20 is screwed into the mouth portion 10 a and sealed, and the cosmetic-containing article is not exposed to light in a thermostatic bath at −5 ° C. Stored for 1 month. Thereafter, the appearance of the cosmetic when it was returned to room temperature was visually observed and evaluated according to the following evaluation criteria. In addition, it means that even if the score is higher, the piroctone olamine in the cosmetic is less likely to precipitate even if the cosmetic is stored at a low temperature.
5 points: Precipitates cannot be confirmed even at −5 ° C. or even at room temperature.
4 points: At -5 ° C., a slight amount of precipitate is confirmed, but dissolves when returned to room temperature.
3 points: Precipitates are confirmed at −5 ° C., but dissolves when returned to room temperature.
2 points: Precipitates were confirmed at −5 ° C., and some did not dissolve even when the temperature was returned to room temperature.
1 point: Precipitates were confirmed at −5 ° C. and did not dissolve even when returned to room temperature.

(2) High temperature storage 50 mL of cosmetic material is filled into the container body, the cap portion 20 is screwed into the mouth portion 10a and sealed, and the cosmetic-containing article is not exposed to light, and is kept in a constant temperature bath at 40 ° C. for 6 months. Saved for a while. The content of piroctone olamine in the cosmetic after storage was measured as follows.
First, about 0.2 g of the cosmetic after storage was accurately weighed, and 5 mL of the internal standard solution was accurately added and dispersed. Thereafter, 15 mL of the mobile phase was further added and dispersed, and the sample solution was filtered through a liquid chromatograph filter (0.45 μm).
Separately, about 0.1 g of standard piroctone olamine was accurately weighed and methanol was added to make exactly 50 mL. 5 mL of this liquid was accurately weighed, and methanol was further added to make exactly 50 mL. 5 mL of this solution was accurately measured, and 5 mL of the internal standard solution was accurately added. Thereafter, 10 mL of mobile phase was further added and mixed to obtain a standard solution.
As an internal standard solution, a methanol solution of methyl paraben was used.

The sample solution and 10 μL of the sample solution were tested by liquid chromatography under the following conditions. The ratio Q _T of the peak area of piroctone olamine to the internal standard substance in the sample solution and the piroctone to the internal standard substance in the standard solution determine the specific Q _S of the peak area of olamine was calculated piroctone olamine content in cosmetics from the following equation.
Piroctone olamine content (%)
= Amount of standard piroctone olamine (g) × (5/50) × (5/50) × (Q _T / Q _S ) × (1 / sample amount (g)) × 100
= Amount of standard piroctone olamine (g) × (Q _T / Q _S ) × (1 / Amount of sample (g))

measuring equipment;
Electronic balance: Mettler AJ-180 (Mettler)
・ Pump: LC-20AD (manufactured by Shimadzu Corporation)
Degasser: DGU-20A ₃ (manufactured by Shimadzu Corporation)
Autosampler: SIL-20A (manufactured by Shimadzu Corporation)
-Column oven: CO630 (manufactured by Shimadzu Corporation)
・ Detector: SPD-M20A (manufactured by Shimadzu Corporation)
Data processing device: Lab Solutions (manufactured by Shimadzu Corporation)

Liquid chromatography measurement conditions;
・ Injection volume: 10 μL
Photodiode array detector (monitor wavelength: 270 nm, measurement wavelength: 220 to 300 nm)
Column: Inertsil ODS-2 (φ4.6 mm × 150 mm, manufactured by GL Sciences Inc.)
-Column temperature: 40 ° C
Mobile phase: methanol / water / ethylenediaminetetraacetic acid disodium dihydrogen acetate dihydrate solution / phosphoric acid mixture (40: 8: 1: 1)

For the cosmetic before storage, the piroctone olamine content in the cosmetic was calculated in the same manner, and this was used as the initial value. It calculated | required what% of the piroctone olamine content in the cosmetics after a preservation | save corresponded to an initial value, and evaluated it with the following evaluation criteria. In addition, it means that even if the cosmetic is stored at a high temperature, the higher the score is, the more difficult it is for the piroctone olamine in the cosmetic to be adsorbed on the container, and the pirocton olamine is difficult to decompose.
5 points: Initial value 90% or more 4 points: Initial value 80% or more and less than 90% 3 points: Initial value 50% or more and less than 80% 2 points: Initial value 30% or more and less than 50% 1 point: Initial value Less than 30%

<Evaluation of feeling of use>
A sticky feeling when 1 mL of cosmetic was extended with a palm was subjected to sensory evaluation. Specifically, the average score was calculated using a monitor of 10 men and women, based on the following five-point absolute evaluation.
5 points: No stickiness at all.
4 points: Not sticky.
3 points: Slightly sticky.
2 points: Sticky.
1 point: very sticky.

  As apparent from Tables 1 to 4, the cosmetic-containing articles obtained in Examples 1-1 to 1-31 are difficult to adsorb piroctone olamine in the cosmetics to the container even when stored at high temperatures. It is difficult to disassemble. Moreover, even when stored at a low temperature, piroctone olamine was hardly precipitated, and the storage stability was excellent. Moreover, the feeling of use was excellent.

On the other hand, the cosmetic-containing article of Comparative Example 1-1 in which a container containing a nitrogen-containing antistatic agent was filled with the cosmetic was easy to adsorb piroctone olamine in the cosmetic on the container when stored at a high temperature. In addition, in the case of Example 1-22 in which cosmetics were filled in a container containing an antistatic agent other than the nitrogen-containing antistatic agent, no adsorption of piroctone olamine to the container was observed. Therefore, it was shown that the nitrogen-containing antistatic agent contained in the container is the cause of the adsorption of piroctone olamine to the container.
The cosmetic-containing article of Comparative Example 1-2 in which a cosmetic not containing ethanol is filled in a container is easy to decompose piroctone olamine in the cosmetic when stored at a high temperature, and piroctone olamine when stored at a low temperature. Was likely to precipitate and the storage stability was poor. Moreover, the cosmetics of Examples 1-1, 1-7 to 1-15, 1-19 to 1-22, and 1-27 to 1-31 having the same composition except for the cosmetic of Comparative Example 1-2 and ethanol It was inferior to the feeling of use compared to the fee.
In the cosmetic-containing article of Comparative Example 1-3 in which a container containing a cosmetic that does not contain a nonionic surfactant was stored at a low temperature, piroctone olamine was likely to precipitate, and the storage stability was poor.

[Examples 2-1 to 2-19]
According to the composition shown in Tables 5 to 7, cosmetics of each example were prepared by the production methods shown below. Moreover, the container of each Example was manufactured with the manufacturing method shown below according to the compounding composition shown to Tables 5-7. The cosmetic material prepared in each example was filled in a container to obtain a cosmetic-containing article. About the obtained cosmetics containing article, the storage stability and usability in low temperature storage and high temperature storage were evaluated in the same manner as in Example 1-1. Furthermore, the storage stability by exposure to sunlight and the appearance of cosmetics were evaluated by the following methods. These results are shown in Tables 5-7.
In addition, the unit of the compounding quantity of the cosmetics in Tables 5-7 is "mass%", and all components show the amount equivalent to a pure part. Moreover, the unit of the compounding quantity of the container in Tables 5-7 is a "mass part."
Moreover, the cosmetics of each example were prepared by balancing with purified water so that the total of each component described in the table was 100% by mass.

<Preparation of cosmetics>
Except having changed into the compounding composition shown to Tables 5-7, cosmetics of each example were prepared like Example 1-1.

<Manufacture of containers>
When the content of the pigment, ultraviolet absorber, and antistatic agent in the resin composition is as shown in Tables 5 to 7 with respect to 100 parts by mass of high-density polyethylene, The master batch was diluted with high-density polyethylene (density: 0.956) so that the light transmittance at a wavelength of 500 nm was a value described in Tables 5 to 7, and a resin composition was prepared.
A container body was produced in the same manner as in Example 1-1 except that the obtained resin composition was used, and the average wall thickness, the light transmittance at a wavelength of 200 to 400 nm, and the light transmittance at a wavelength of 500 nm were determined. Asked. The results are shown in Tables 5-7.
In addition, the ultraviolet absorbers in Tables 5 to 7 are as follows.
Tinuvin 326: 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole

[Evaluation]
<Evaluation of storage stability>
(3) Sun exposure The high temperature of (2) except that the cosmetic-containing article was stored while irradiating it with sunlight until the cumulative amount of sun exposure reached 15 MJ / sm ² instead of the storage conditions of 40 ° C. × 6 months. The piroctone olamine content before and after storage was measured and evaluated in the same manner as in the case of storage. In addition, a higher score means that pyroctonolamine is less likely to be decomposed even when the cosmetic is exposed to light.

<Evaluation of appearance of cosmetics>
50 mL of cosmetic material was filled in the container body, the cap part 20 was screwed into the mouth part 10a and sealed, and the appearance of the contents (cosmetics) was evaluated under a fluorescent lamp. Specifically, the average score was calculated using a monitor of 10 men and women, based on the following five-point absolute evaluation.
5 points: The liquid level of the cosmetic is clearly visible.
4 points: The liquid level of the cosmetic is visible.
3 points: The cosmetic liquid level is slightly visible.
2 points: The liquid level of the cosmetic is slightly visible.
1 point: The liquid level of the cosmetic is not visible at all.

As is apparent from Tables 5 to 7, the cosmetic-containing articles obtained in Examples 2-1 to 2-19 were less likely to adsorb piroctone olamine in the cosmetics to the container even when stored at a high temperature. It is difficult to disassemble. Moreover, even when stored at a low temperature, piroctone olamine was hardly precipitated, and the storage stability was excellent. Moreover, the feeling of use was excellent.
The cosmetic-containing articles obtained in Examples 2-1 to 2-19 have a light transmittance of 0 to 2% at a wavelength of 200 to 400 nm and a light transmittance of 5 to 40% at a wavelength of 500 nm. Since the container was filled with cosmetics, the decomposition of piroctone olamine could be suppressed even when the cosmetics were exposed to light, the storage stability was further improved, and the contents (cosmetics) could be visualized.

  1: Container, 10: Container body, 10a: Mouth, 20: Cap.

Claims (4)

A cosmetic-containing article in which a cosmetic material containing piroctone olamine, a nonionic surfactant, and ethanol is filled in a resin container,
The resin is a polyolefin resin;
And the content of the nitrogen-containing antistatic agent in the said container is 0.2 mass ppm or less with respect to 100 mass parts of said polyolefin resins, The cosmetics containing article characterized by the above-mentioned . A cosmetic-containing article in which a cosmetic material containing piroctone olamine, a nonionic surfactant, and ethanol is filled in a resin container,
The resin is a polyolefin resin;
A cosmetic-containing article characterized in that the total content of alkyldiethanolamine and polyoxyethylenealkylamine in the container is 0.2 mass ppm or less with respect to 100 parts by mass of the polyolefin resin. Light transmittance of the container at a wavelength of 200~400nm a is 0 to 2%, and, to claim 1 or 2 light transmittance of the container at a wavelength of 500nm is characterized in that it is a 5-40% The cosmetic-containing article as described. The cosmetic-containing article according to any one of claims 1 to 3, wherein the cosmetic is a hair restorer.

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