JP2009113838A - Container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a container in which there is no possibility that a filling solid oily composition is rotated or released in the container when it is used. <P>SOLUTION: In the container, the inner face is coated with a polymer with a glass transition temperature (Tg) in a range of -150°C to 10°C. A cosmetic article is obtained by filling the container with a solid oily cosmetic article. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a container for filling a solid oily composition.

  When a solid oily composition is filled in a container such as glass, metal, plastic, etc., a method of thermally melting and filling the container is performed. However, the heat-melted solid oily composition undergoes volume shrinkage in the process of being cooled after being filled in the container. For this reason, the solid oily composition cannot be sufficiently adhered to the container, and there is a problem that the solidified composition rotates in the container during use or can be peeled off.

In order to solve this, a method of providing a protrusion in the container and fixing the contents can be considered, but there is a problem that the protrusion becomes an obstacle during use.
Further, in Patent Document 1, in order to prevent the occurrence of a gap between the solid filling and the inner wall of the container, when filling a container having a freezing point of room temperature or higher into the container, the container at the time of filling is designated as the freezing point of the filling. There is described a filling method of a solid filling in which the temperature is maintained and the filling is heated to fill the container in a liquid state, and then a lid is attached to solidify the filling.
However, even when filled by this method, the generation of a gap between the solid filler and the container inner wall cannot be sufficiently prevented, and the filler peels off from the container inner wall during use and rotates over time.
JP 2002-173101 A

  An object of the present invention is to provide a container in which the filled solid oily composition does not rotate or peel off in use.

  The present inventors have found that if the inner surface is coated with a polymer having a specific glass transition temperature, the above problems can be solved and a container having excellent usability can be obtained.

The present invention provides a container whose inner surface is coated with a polymer having a glass transition temperature (Tg) in the range of −150 ° C. to 10 ° C.
Moreover, this invention provides the cosmetics formed by filling the said container with solid oily cosmetics.

  The container of the present invention is excellent in usability because the filled solid oily composition is sufficiently adhered to the container, so that it does not rotate or peel off in use during use.

The polymer used in the present invention has a glass transition temperature (Tg) in the range of −150 ° C. to 10 ° C. If the glass transition temperature is within this range, the solid oily composition can be sufficiently adhered to the polymer film formed on the inner surface of the container.
In the present invention, the glass transition temperature is a value measured by a differential scanning calorimeter (DSC). Specifically, when measurement is performed under the conditions of the following continuous temperature programs 1 to 4, the value measured by the temperature program 3 is set as the glass transition temperature.
(1) 30 to 100 ° C .: Temperature rising rate 30 ° C./min, holding temperature 1 min.
(2) 100 to -170 ° C .: cooling rate 200 ° C./min, holding temperature 10 min.
(3) -170 to 100 ° C .: temperature rising rate 10 ° C./min, holding temperature 1 min.
(4) 100-30 ° C .: Cooling rate 30 ° C./min.

  Examples of such polymers include natural rubber or synthetic rubber, such as natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, butyl rubber, ethylene propylene rubber, urethane rubber, acrylic rubber, epichlorohydrin rubber. , Polysulfide rubber, nitrile rubber, hydrogenated nitrile rubber, chlorosulfonated polyethylene rubber, fluorine rubber and the like.

  In addition, examples of the polymer include acrylic acid-based or vinyl-based polymers having one or more types selected from monomers represented by the general formulas (1) to (3) as structural units. In particular, those having at least one monomer represented by the general formula (1) as a structural unit are preferred.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with an amino group, a perfluoroalkyl group, a cyano group or a hydroxyl group. Showing).

  Such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, lauryl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, benzyl (meth) acrylate, 3-methoxyethyl (meth) acrylate, hexyl (meth) acrylate, isostearyl (meth) Acrylate, tetradecyl (meth) acrylate, octyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, stearyl (meth) acrylate Relate and the like.

(In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with an amino group, a cyano group or a hydroxyl group. )

  Examples of such monomers include acrylamide, N, N-dimethylacrylamide, isopropylacrylamide, t-butylacrylamide, Nn-butoxymethylacrylamide, diacetone acrylamide, N- (3-dimethylaminopropyl) acrylamide, N- ( 3-dimethylaminopropyl) methacrylamide and the like.

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, and Z represents a phenyl group optionally substituted with an alkyl group, a perfluoroalkyl group, an alkyloxy group, an amino group, a carboxyl group, an acetoxy group, a hydroxyl group, or a halogen atom. A group; an amino group, a carboxyl group, a hydroxyl group or a halogen atom, an alkyl group optionally substituted with an oxygen atom; a perfluoroalkyl group, a perfluoroalkoxyalkyl group, an alkyloxy group, a halogen atom or a nitrogen atom; A good alkenyl group; pyridine; pyrrolidone; cyano group)

  Examples of such monomers include vinyl acetate, acrylonitrile, propylene, butene, isobutene, isoprene, butadiene, chloroprene, styrene, α-methylstyrene, vinyl pyridine, vinyl pyrrolidone, vinyl alkyl silicone, and the like.

  As the polymer used in the present invention, (meth) acrylic acid alkyl polymer, (meth) acrylic acid / (meth) alkyl acrylate copolymer, (meth) alkyl acrylate / styrene copolymer, vinyl acetate polymer, Vinylpyrrolidone / styrene copolymer (INCI: STYRENE / VP COPOLYMER), silicone-containing polymer, and the like can be mentioned, and these emulsions can be preferably used. Specifically, iodosol GH34F (INCI: American Acrylates Copolymer) (Japan NS Co., Ltd., solid content: 45 to 47% by mass, Tg: −16 ° C.), Ditozol 5000SJ (INCI: Acrylates Copolymer) (Daito Kasei Kogyo Co., Ltd.) Solid content: 48-52% by mass, Tg: -14 ° C), Jurimer ET-416 (INCI: Ammonium Acrylates Copolymer) (Nippon Pure Chemicals Co., Ltd., solid content: 56-58% by mass, Tg: 0 ° C) Product can be used.

  Among these, iodosol GH34F, ditozole 5000SJ, and dirimer ET-416 are preferable, and iodosol GH34F is more preferable.

  In the present invention, the container whose inner surface is coated with a polymer is not particularly limited as a material, and for example, glass, metal, polypropylene, polyethylene terephthalate, acrylonitrile-butadiene-styrene resin, ethylene-vinyl acetate resin, ethylene-vinyl. Examples include alcohol resin, polyamide, polycarbonate, polybutylene terephthalate, polyethylene, polymethylpentene, polystyrene, polyvinyl chloride, polyvinylidene chloride, styrene-acrylonitrile resin, and paper. Moreover, the shape will not be restrict | limited especially if a solid oil-based composition can be filled, A jar container, a container for sticks, a wide mouth bottle, a tray, etc. can be used. In particular, a jar container is preferable.

  In the present invention, the inner surface of the container is coated with the polymer as described above. What is necessary is just to coat | cover at least one part with an inner surface, It is preferable that the bottom inner surface of a container is coat | covered, and it is preferable that at least one part of a bottom inner surface is coat | covered.

  The method for coating the inner surface of the container with the polymer is not particularly limited, for example, a method of applying a polymer solution or an aqueous dispersion with a brush, a spatula, or a brush, a method of spraying, a polymer solution is dropped on the container, and the container is rotated at a high speed. Or the method etc. which produce | generate a membrane | film | coat by drying after spreading on the inner surface by blowing air to the dropped polymer solution are mentioned. Thereafter, the container of the present invention can be obtained by drying to form a film. In addition, after the monomer is applied to or sprayed on the inner surface of the container with a brush, a spatula, a brush, or the like, a film is formed by polymerization with light or heat, whereby the container of the present invention can be obtained.

Coating weight of the polymer as the polymer solids, 0.001~0.03g / cm ^2, especially in the range of 0.003~0.01g / cm ^2, preferably it is possible to thinly coat the entire inner surface of the container.

  The container of the present invention thus obtained is suitable for filling a solid oily composition. Solid oil-based compositions include lipsticks, foundations, solid hair conditioners, whitening, wrinkles, firmness, pores, acne and other skin oil cosmetics and other solid oil-based cosmetics; car wax; floor and furniture wax Etc.

The solid oily composition used in the present invention can be composed of a solid or semi-solid oily component at 25 ° C., an oily component liquid at 25 ° C., and a mixture thereof. Examples of oily components that are solid or semisolid at 25 ° C. include hydrocarbons, fatty acid esters, triglycerides, fatty acids, higher alcohols, and derivatives thereof. Specifically, hydrocarbon waxes such as solid paraffin, ceresin, microcrystalline wax, low molecular weight polyethylene, low molecular weight polyolefin, petrolatum; natural waxes such as lanolin, beeswax, carnauba wax, candelilla wax; lauric acid Long chain fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid; synthetic and modified waxes such as lanolin fatty acid, hydrogenated castor oil, 12-hydroxystearic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, and behenyl alcohol Can be mentioned. In particular, candelilla wax, carnauba wax, ceresin, microcrystalline wax, low molecular polyethylene, low molecular polyolefin, solid paraffin, and petroleum jelly are preferred.
The solid or semi-solid oily component at 25 ° C. can be used alone or in combination of two or more, and is 5 to 90% by mass, particularly 2 to 60% by mass, and more preferably 5 to 50% by mass in the solid oily composition. % Content is preferable.

Examples of oily components that are liquid at 25 ° C. include hydrocarbon oils such as liquid paraffin and heavy liquid isoparaffin; diisostearyl malate, dioctyldodecyl malate, isodecyl isononanoate, triglyceride isostearate, isododecyl isononanoate, dion Glyceryl myristate, glyceryl diisostearate, myristic acid / isostearic acid triglyceride, dicapric acid neopentyl glycol, castor oil, macadamian nut oil, jojoba oil, olive oil and other esters and triglycerides; ethers such as alkyl 1,3-dimethylbutyl ether And the like: silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, dimethylcyclopolysiloxane, methylhydrogenpolysiloxane, etc. That. In particular, liquid paraffin, isostearic acid triglyceride, isonondecyl isononanoate, neopentyl glycol dicaprate, olive oil, and alkyl 1,3-dimethylbutyl ether are preferable.
The oily component that is liquid at 25 ° C. can be used alone or in combination of two or more, and is contained in the solid oily composition in an amount of 10 to 95% by mass, particularly 10 to 80% by mass, and further 20 to 60% by mass. It is preferable.

The solid oily composition may contain a powder, and examples of the powder include a silicone resin, an acrylic resin, a urethane resin, a polyethylene resin, a nylon resin, and a styrene-divinylbenzene copolymer. Nylon resin and silicone resin are particularly preferable.
Further, the solid oily composition may contain a preservative, and examples of the preservative include paraben, phenoxyethanol, sorbic acid, dibutylhydroxytoluene and the like. In particular, dibutylhydroxytoluene is preferable.

  The solid oily composition refers to those having a penetration hardness at 30 ° C. of 65 or more, particularly 80 or more. Here, the penetration hardness refers to the load (g) applied when a 2 mm diameter cylindrical rod is inserted at a moving speed of 2 cm / min, and the composition to be measured is placed at 30 ° C. for 1 day or more. Is measured from The penetration hardness was measured using a FUDOH RHEOMETER RT-2010J-CW manufactured by RHETECH.

  The method for filling the container with the solid oil-based composition is not particularly limited, and the solid oil-based composition can be heated and dissolved in a container according to a normal method.

Production Example 1 (Production of polymer emulsion 1)
A glass reaction vessel was charged with 0.6 g of sodium N-stearoyl-N-methyltaurine (Nikko Chemical Co., Nikkor SMT) and 875 g of ion-exchanged water. Until heated. After adding a solution prepared by dissolving 2.5 g of ammonium persulfate in 25 g of ion-exchanged water, a solution prepared by mixing 80 g of methyl methacrylate, 405 g of butyl acrylate, and 15 g of acrylic acid was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 1 hour, then heated to 75 ° C., further reacted for 3 hours, cooled, and 73 g of 1N sodium hydroxide aqueous solution was added. Concentration was performed using an evaporator to obtain a polymer latex. When measured with a particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.), the particle size of the polymer latex was 0.1 μm. The polymer latex had a pH of 6.5 and a solid content of 50%.

Production Example 2 (Production of polymer emulsion 2)
The monomer of Production Example 1 was replaced with 70 g of methyl methacrylate, 405 g of butyl acrylate, and 25 g of methacrylic acid, and produced in the same manner. The solid content was 50%.

Production Example 3 (Production of polymer emulsion 3)
The monomer of Production Example 1 was replaced with 200 g of methyl methacrylate, 285 g of butyl acrylate, and 15 g of methacrylic acid, and produced in the same manner. The solid content was 50%.

Production Example 4 (Production of polymer emulsion 4)
The monomer of Production Example 1 was replaced with 165 g of methyl methacrylate, 270 g of butyl acrylate, 15 g of acrylic acid, and 50 g of perfluorodecyl methacrylate, and produced in the same manner. The solid content was 50%.

Production Example 5
The components shown in Table 1 were heated and dissolved at 85 ° C. and mixed by stirring to produce a solid oily composition. The penetration hardness of the obtained solid oily composition was 90.

Examples 1-6 and Comparative Examples 1-2
Using the polymer shown in Table 2, the inner surface of the glass jar was coated.
That is, an aqueous solution or water of each polymer is formed on the bottom inner surface (10 cm ² ) of a glass jar (made by Kodai Glass Co., Ltd .; a cylinder with a diameter of 3.7 cm, a height of 2.3 cm, with a screw cap, and the inner surface is hemispherical). 0.1 g of the dispersion was applied to the inner surface by rotating the container and dried to form a film to obtain a jar container.

  In addition, the measurement of the glass transition point (Tg) of a polymer was performed using the differential scanning calorimeter (the Seiko Instruments company make, DSC6200).

The obtained jar container was melt-filled with a solid oily composition (Production Example 5) to half of the container. After cold storage, the usability when the solid oily composition in the container was scraped off with a spatula was evaluated according to the following criteria.
◯: The solid oily composition did not peel off and could be scraped off with a spatula, and the usability was good.
X: The solid oily composition was peeled off and rotated, and it was difficult to scrape off with a spatula, resulting in poor usability.

Example 7
0.03 g of isoprene rubber (Kraton IR307, manufactured by Kraton Polymer Japan; glass transition temperature -73 ° C.) was dissolved in 1.5 mL of hexane to coat the inner surface of the glass jar.
That is, 0.1 g of the polymer solution was applied to the bottom inner surface (10 cm ² ) of a glass jar (made by Kodai Glass Co., Ltd .; a cylinder with a diameter of 3.7 cm, a height of 2.3 cm, with a screw cap, and the inner surface is hemispherical). It was applied to the inner surface by rotation of the container and dried to form a film to obtain a jar container.

  The obtained jar container was melt-filled with a solid oily composition (Production Example 5) to half of the container. After cooling storage, the usability when the solid oily composition in the container was scraped off with a spatula was evaluated. As a result, it was confirmed that the solid oily composition was not peeled off and could be scraped off with a spatula, and the usability was good.

Claims (6)

  A container whose inner surface is coated with a polymer having a glass transition temperature in the range of −150 ° C. to 10 ° C.   The container according to claim 1, wherein the polymer is selected from natural rubber and synthetic rubber. The polymer is represented by the general formulas (1) to (3):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with an amino group, a perfluoroalkyl group, a cyano group or a hydroxyl group. Indicate)

(In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with an amino group, a cyano group or a hydroxyl group. )

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, Z represents an alkyl group, a perfluoroalkyl group, an alkyloxy group, an amino group, a carboxyl group, a hydroxyl group, or a phenyl group optionally substituted with a halogen atom; Group, carboxyl group, hydroxyl group or halogen atom, alkyl group optionally substituted by oxygen atom; perfluoroalkyl group, perfluoroalkoxyalkyl group, alkyloxy group, alkenyl optionally substituted by halogen atom or nitrogen atom Group; represents a cyano group)
The container according to claim 1, wherein one or more selected from monomers represented by formula (1) is used as a structural unit.   The container according to any one of claims 1 to 3, wherein the solid oily composition is melt-filled.   The container according to any one of claims 1 to 3, wherein the solid oily cosmetic is melt-filled.   Cosmetics formed by filling the solid oil-based composition into the container according to any one of claims 1 to 3.