JPH0636814B2 - External composition having film-forming ability - Google Patents

Description

TECHNICAL FIELD The present invention relates to an external composition for use in cosmetics, quasi-drugs, external medicines, skin products, etc., in which a limited polyamide resin is used in a water and / or alcohol system. The present invention relates to a composition for external use which has a film-forming ability when dissolved in a solvent. Specific examples will be described below. As cosmetics, it is used for peel-off, eyeliner, peelable nail products, packs, film-forming perfumes, hair sprays and the like.

As quasi-drugs, for example, antiperspirants, insect repellents, armpit odor inhibitors, etc. are used.

As an external medicine, for example, it is used in plastic dressings, plasters, poultices, skin disinfectants, etc. Deserve.

As the outer skin product, for example, a moisture evaporation protective film agent for fruits and vegetables, a strippable protective film agent for protecting from contamination and the like, a strippable rust preventive agent and the like are used.

Of further interest is the application to occlusive dressing (ODT). For example, it can be used in a method of increasing the transdermal absorbability of a drug by applying a drug such as an ointment to the skin and then overcoating the composition for external use of the present invention with a spray, a liquid agent or the like.

As described above, various applications can be considered by utilizing the film forming ability of the polyamide resin, and its usefulness as an external composition is shown. Further, it can be used as a base for external use when an active ingredient such as an agricultural chemical or a pharmaceutical is administered.

The composition for external use of the present invention is a composition for external use that can be used by appropriately adding additives such as active ingredients according to the fields and applications to be used.

2. Description of the Related Art A film-forming external composition has been applied to various types or for various purposes depending on the type of polymer (base polymer) that forms a film, or has been applied for a patent.

As the solvent used, ethanol or hydrous ethanol is often used because it does not affect the human body and requires drying property. As base polymers for cosmetics which are soluble in these solvents and have film-forming ability, for example, ethyl cellulose; hydroxypropyl cellulose; polyvinyl alcohol; polyvinyl acetate; vinylpyrrolidone / vinyl acetate copolymer; polyvinylpyrrolidone; methoxyethylene maleic anhydride copolymer Examples thereof include polymers.

Polyvinyl butyral as other base polymer,
There are examples of alcohol-soluble nylon and the like, and in particular, alcohol-soluble nylon is said to be suitable as a base polymer due to its excellent tensile strength and elongation in a film state, water vapor permeability, etc. (see JP-A-58-69249). , JP-A-58-6981
1, JP-A-54-140713).

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, from the practical point of view, any of the base polymers have poor solution stability in an alcohol solution or a hydroalcoholic solution, and may gel or solidify when left for a long time. It was Especially, when it is left at a temperature below freezing, the number of days to gel or solidify becomes short, and it is impossible to store it in a solution state, so it has to be adjusted and the handling is very troublesome. It was an upper problem.

In order to improve the stability in this solution state, a method of adding an additive has been conventionally used.

That is, (i) in JP-A-54-150459, a method of adding an inorganic or organic metal salt such as sodium chloride, zinc sulfate, calcium chloride or calcium pantothenate,
(Ii) In JP-A-55-16019, a method in which a surfactant is added is implemented and the improvement effect is obtained to some extent. However, there is no case where it exists stably for about one year at low temperature. In addition, it is desirable not to include metal salts and surfactants that are added to promote stabilization because they may cause problems such as adversely affecting adherends.

As described above, the conventional composition for external use having film-forming ability has a problem of solution stability, and it is the current situation that an ideal composition for external use has not been obtained yet.

Needless to say again, regarding the external composition used in cosmetics, quasi drugs, external medicines, skin products, etc., the solution stability is the most important than other physical properties in terms of practical use. It is clear that it is a necessary and indispensable condition as a thing.

Means and Actions for Solving Problems In view of such a situation, the inventors of the present invention have an unprecedented stability, that is, a composition for external use having a solution stability of one year or more at a low temperature (-20 ° C). In order to develop the above, among the above-mentioned base polymers, the structure of mylon having the most excellent film properties is focused on. That is, the following two points were found as a result of earnestly studying a method of achieving sufficient stabilization only with nylon without adding additives.

First, the crystal structure of nylon is as small as possible,
That is, it was found that the heat of fusion (ΔHm) of nylon is as small as possible, and when expressed numerically, it is in the range of 0 to 5 mcal / mg, and amorphous nylon with no melting point is ideal.

That is, in the conventional nylon, alcohol and water systems, it is presumed that gelation or solidification was caused as a result of the gradual progress of various hydrogen bonds mainly of each amide group, but the heat of fusion (ΔHm ) Is in the range 0-5 mcal / mg,
Since the conformation of the amide group is likely to be disturbed, it is presumed that the above hydrogen bonding property is weakened, which makes it difficult to shift to a metastable gel state.

The second is to improve the solubility in an alcohol solution, which can be presumed to be related to the type and average molecular weight of the constituent monomers of the polymer, and further to the first crystallinity. It can be summarized that stability can be maintained by reducing the heat of fusion as much as possible and incidentally improving the solubility in alcohol. As a method for reducing the heat of fusion of the polyamide resin, (1) multi-component copolymerization method, (2) introduction of bulky monomer, (3) hydrogen substitution at N-position and the like are considered. By adopting these techniques, it was possible to solve the solution stability by producing an alkali-soluble nylon satisfying the above-mentioned necessary conditions or by using a polyamide resin made completely water-soluble nylon. Moreover, there is a merit that it can be easily sprayed, probably because the solubility in the alcohol solvent is increased.

Further, when the influence of the average molecular weight on the solution stability and the physical properties of the film was examined, it was surprisingly found that the optimum average molecular weight exists. The optimum average molecular weight is indicated by the number average molecular weight, and the range is 8,000 to 30,000.

Hereinafter, the relationship between the configuration of the present invention and the function and effect will be described in more detail.

The present invention has a heat of fusion of 0 to 5 mc as a film-forming resin.
The composition for external use is obtained by dissolving al / mg of a polyamide resin in water and / or an alcohol solvent. Heat of fusion (hereinafter, ΔHm
Say. It can be clearly seen from FIG. 1 that the solution stability is poor in the case of a polyamide resin having a) of more than 5 mcal / mg.

That is, the heat of fusion is preferably 0 to 5 mcal / mg, preferably 0 to 4 m
Cal / mg, more preferably 0 to 3 mcal / mg is desirable.

The average molecular weight is shown by the number average molecular weight, 8,000 to 30,000 is good, preferably 9,000 to 30,000, more preferably,
9,000 to 25,000 is desirable.

The crystallinity and the solubility in a solvent are larger for the low molecular weight compounds, and the viscosity stability as a solution is excellent, but conversely, as far as the film forming property is concerned, the low molecular weight molecules have a negative effect. That is, when the number average molecular weight is less than 8,000, the film-forming property is poor, and when the number average molecular weight is more than 30,000, the viscosity stability as a solution is poor.

The polyamide resin may be commercially available water-soluble nylon and / or alcohol-soluble nylon,
It may be modified by the method described above. As water-soluble nylon, AQ-Nylon manufactured by Toray Industries, Inc., A-90
(ΔHm≈0 mcal / mg); P-70 (ΔHm≈0 mcal / mg) is exemplified, and alcohol-soluble nylon is manufactured by Toray Industries, Inc.
AQ-Nylon A-70 (ΔHm ≒ 0mcal / mg); Plate-Bonn P
LATAMID M 1372 (ΔHm ≒ 0mcal / mg), PLATABOND MX16
02 (ΔHm ≒ 2.3mcal / mg), MX1603 (ΔHm ≒ 0mcal / m)
g) etc. are illustrated. It should be noted that these nylons have been newly manufactured recently, and are conventionally used as hot-melt adhesives, adhesives, fiber treatment agents, dyeing agents, ink modifiers, base materials for water-based paints, and photosensitizers. It is used for the purpose of additives, binders, resin modifiers, etc. However, there has been no case where the composition has been used as an external composition until now, and there is no known material or the like that suggests it. That is, the use of these nylons as a composition for external use is a novel finding first made by the present inventors.

The method for modifying the polyamide resin is not limited,
The modified polyamide resin obtained by the above-mentioned method or the like can also be used.

The content of the polyamide resin is preferably 1 to 60% by weight, preferably 1 to 45% by weight, more preferably 1 to 60% by weight of the entire composition.
25% by weight is desirable. If it is less than 1%, the film obtained from the composition for external use is thin and it is difficult to peel off the film. On the contrary, if the compounding amount exceeds 60% by weight, the solution stability is poor and gelation or solidification may occur. Wake up.

Ethanol is most preferable as the alcohol solvent, but alcohols such as isopropanol, butanol, benzyl alcohol, and cresol described in the cosmetic original group can be used, and two or more kinds can be used in combination.

The composition for external use of the present invention is a uniform solution and, in addition to being excellent in solution stability, particularly at low temperatures, has the following performance.

(i) It can be uniformly applied to the object to be coated as a liquid agent and a spray agent.

(ii) A film is formed quickly with a short drying time.

(iii) The film is transparent and can be easily colored.

(iv) The dried film is not sticky and adheres well to the object to be coated.

(v) Even if the film is left for a long period of time, no cracking or appearance deterioration due to deterioration is observed.

(vi) When peeling the film, it peels off in a single sheet.

(vii) It can be easily removed by washing with water. Etc. have excellent performance.

Furthermore, when applying the composition for external use for various purposes, the solution stability and the above-mentioned characteristics are not impaired even if an appropriate amount of various additives, fragrances, bactericides, pigments and the like are blended,
Moreover, it does not affect those additives.

Due to these features, this external preparation composition can be positively used and applied to cosmetics, quasi drugs, external medicines, film-forming products and the like. The present invention will be specifically described below with reference to examples. The present invention is not limited to this.

Example (Including Test Example) (Measurement Method of Number Average Molecular Weight) The end groups were quantitatively determined by conductivity titration using hydrochloric acid. The number of moles of —NH ₂ [NH ₂ ] per 1 g of the polymer was determined, and the number average molecular weight (▲ ▼) was calculated from ▲ ▼ = 1 / [NH ₂ ].

Example-1 Strippable protective film agent PLATAMID M-1372 (▲ ▼ ≒ 17,400) 20 parts [Plate-Bonn company] Ethanol / water (90/10; wt / wt) 76 Benzine alcohol 3 Silicon oil (Toray company) , Silicon SH200) 1 total 100 Modified nylon A was dissolved in ethanol / water and benzyl alcohol in the above mixing ratio by heating, and after cooling, silicone oil was added to prepare a strippable protective film agent. Even when the protective film agent was allowed to stand at a low temperature of -20 ° C for 8 months, no change in appearance such as gelation or solidification was observed. After applying this strippable protective film agent to a ventilation fan to form a protective film, after actually using it for 3 months, it can be easily and neatly peeled off when peeled off, and the protective surface is discolored. , Was not contaminated.

Example-2 Sealed dressing method (ODT agent) A sealed dressing solution was prepared according to the following formulation.

PLATAMID M-1372 (▲ ▼ ≒ 17,400) 20 parts [Plate-Bonn] ethanol / water (80/20; wt / wt) 77 glycerin 3 total 100 50 parts of the above-mentioned prescription sealed dressing method and freon 12 50 parts Was mixed and the occlusive dressing aerosol was also adjusted.

The external anti-inflammatory analgesic ointment was applied to the upper back, and then the present closed dressing solution or the closed dressing aerosol was applied or spray-applied. After application, it became a transparent film without stickiness and could be easily removed at the time of peeling. In addition, both the liquid agent and the aerosol agent in the sealed dressing method should be stored at a low temperature of -20 ° C.
Even after being left for 12 months, no change in appearance such as gelation or solidification was observed.

Example-3 Spray type plastic dressing PLATABOND MX 1603 (▲ ▼ ≈18,200) 4 (part) [Plate-Bonn] tetramethylthiuram disulfide 0.02 (bactericide) ethanol / water (95/5; wt / wt) 46 CFC-12 50 Total 100.02 A spray type plastic dressing was prepared according to the above formulation. Even when left as a spray agent at low temperature (-20 ° C) for 12 months, no change in appearance such as gelation or solidification was observed.

Further, as a plastic dressing, it was possible to spray-apply evenly on the cut site and protect the cut site. In addition, since the solvent contained in this drug is ethanol, it causes less irritation to the affected area and is extremely safe in terms of toxicity.

Example-4 Oil pack agent PLATABOND MX 1602 (▲ ▼ ≈17,000) 10 (parts) [Plate-Bonn] Liquid paraffin 10 Olive oil 20 Ethanol / water (80/20; wt / wt) 50 Castor oil 10 Perfume proper amount 0.02 Total 100.02 When a film-forming oil pack was prepared according to the above formulation, no change in appearance such as gelation or solidification was observed even when left for 12 months at low temperature (-20 ° C). Also, when not in use, it could be peeled and removed unlike the conventional oil pack.

Example-5 Deodorant Spray AQ Nylon A70 (▲ ▼ ≈18,000) 6 (part) [Toray Industries, Inc.] Aluminum hydroxychloride 4 Halocarban 0.03 Isopropyl myristate ester 0.6 Trioleyl acid glycerin ester 0.9 Ethanol 26 Fragrance 0.03 Freon 12 62.44 Total 100 A deodorant spray was prepared according to the above formulation. This spray, even if left at low temperature (-20 ℃) for 12 months,
No change in appearance such as gelation or solidification was observed. Also,
The deodorant effect lasted for a long time due to the formation of a film. Moreover, when not in use, it could be easily peeled and removed.

Comparative Example-1 A strippable protective film agent was prepared by replacing PLATAMID M-1372 in Example-1 only with Ultraamide 1C manufactured by BASF. This protective agent is unstable, especially at low temperatures (-20
(° C) solidifies on the second day, which is not preferable in terms of performance. By the way, the heat of fusion of Ultraamide 1C is 7.8 mca.
It was l / mg and Mn was 15,900.

Comparative Example-2 In Example-2, PLATAMID M-1372 was replaced with Elponamide 8023 manufactured by DuPont to prepare a sealed dressing method. Both the liquid agent for the sealed dressing method and the aerosol agent for the sealed dressing method are unstable, and both are solidified in one day at a low temperature of -20 ° C, which is not preferable for the product. Elbamide 8023 (▲
The heat of fusion of ▼ ≒ 12,000) was 9.0 mcal / mg.

Comparative Example-3 In Example-2, PLATAMID M-1372 (manufactured by Plate-Bonn Co.) has the same composition but a low prototype B (▲ ▼
Approximately 7,500) was used instead to adjust the occlusive dressing.

Both sealed dressing method liquid agent and sealed bandage method aerosol-
It was stable at low temperature of 20 ℃ for more than 1 year. However,
No film was formed and the film could not be peeled off as a single film, which was not preferable as a product.

Comparative Example-4 In Example-1, PLATAMID M-1372 was used as Daiamide (ΔHm≅8.2 mcal / mg, manufactured by Daicel Chemical Industries, Ltd.)
▼ ≒ 35,100) and adjusted the strippable protective film agent. This protective agent is unstable and solidifies when left at room temperature for 30 minutes, which is not preferable in terms of performance.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the heat of fusion (ΔHm) of various alcohol-soluble nylons and water-soluble nylons and the number of days of gelation of the solution at −20 ° C. 20% by weight (20% by weight of ethanol
Is. ) Nylon concentration 15% by weight in hydrous ethanol
It can be said that the low temperature stability of the solution is high when ΔHm is in the range of 0 to 5 mcal / mg. If the polymer concentration becomes low,
Furthermore, the low temperature stability of the solution is good.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C09D 177/00 PLS 9286-4J (72) Inventor Misao Miyamoto 11-11 Goi Minamikaigan, Ichihara City, Chiba Prefecture Nissan Kagaku Kogyo Co., Ltd. Polymer Research Laboratory (72) Inventor Tomomitsu Kawasaki 11 Iiminamikaigan 11, Ichihara-shi, Chiba 1 Nissan Kagaku Kogyo Co., Ltd.

Claims (3)

[Claims] 1. A resin capable of forming a film, which has a heat of fusion (ΔHm) of 0 to 5 mcal / mg and a number average molecular weight of 8,000.
A composition for external use in which a polyamide resin of 30,000 is dissolved in water and / or an alcohol solvent. 2. The polyamide resin according to claim 1, which is water-soluble nylon and / or alcohol-soluble nylon.
External composition according to the item. 3. The composition for external use according to claim 1 or 2, wherein the content of the polyamide resin is 1 to 25% by weight of the whole.