JPS6232963A - Surgical composition having film forming capacity - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention Industrial Benefits 1 The present invention relates to external compositions used in cosmetics, quasi-drugs, external medicines, skin care products, etc. The present invention relates to a composition for external use that is dissolved in an alcoholic solvent and has a film-forming ability. To give an example, the cosmetics are used in peel-off products, eyeliners, removable beauty nail products, packs, film-forming perfumes, hair sprays, and the like.

As quasi-drugs, it is used, for example, as antiperspirants, insect repellents, and armpit odor inhibitors.

As external medicines, it is used for example in plastic bandages, plaster preparations, poultices, skin disinfectants, etc., and it is attracting attention because there has never been an example of an alcohol solvent-based spray set of plastic bandages. Worth it.

As skin products, it is used, for example, as a moisture evaporation protective coating agent for fruits and vegetables, a strippable protective coating agent for protecting against contamination, a strippable rust preventive agent, and the like.

Of further interest is its application to occlusive dressing techniques (ODT). For example, after applying medicines such as ointments to the skin,
The external composition of the present invention can be applied as a top coat with a spray, liquid, etc., and can be used in a method of increasing transdermal absorption of a drug.
′′：Using the film-forming ability of polyamide resin,
Various uses are considered, and its usefulness as an external composition is demonstrated. Furthermore, it can also be used as an external base for administering active ingredients such as agricultural chemicals or pharmaceuticals.

The external composition of the present invention can be used by adding additives such as active ingredients as appropriate depending on the fields and uses mentioned above.

External compositions of the iΦ-technical film-forming type are used in a wide variety of applications, and patent applications have been filed, depending on the type of polymer (pace polymer) used to form the film.

Ethanol or aqueous ethanol is often used as the solvent because it has no effect on the human body and needs to dry quickly. Examples of base polymers for cosmetics that are soluble in these solvents and have film-forming properties include ethyl cellulose; hydroxypropyl cellulose; polyvinyl alcohol; polyvinyl acetate; vinylpyrrolidone/vinyl acetate copolymer; polyvinylpyrrolidone; methoxyethylene maleic anhydride copolymer; Examples include polymers.

Other base polymers include polyvinyl butyral,
Examples include alcohol-soluble nylon, and alcohol-soluble nylon in particular has excellent tensile strength and elongation in film form, water vapor permeability, etc., and has been said to be suitable as a pace polymer (Reference: JP-A-58-69249). , JP-A-58-69811, JP-A-54-14071.3).

Clear light-ga solution-L [try-61? However, from a practical standpoint, all of the pace polymers have poor solution stability in alcoholic solutions or hydroalcoholic solutions, and may gel or solidify if left for a long period of time. In particular, if it is left at a low temperature below freezing, the number of days it will gel or solidify will be shortened, and it will not be possible to store it in a solution state, so it will have to be adjusted and the handling will be very troublesome. This was a problem.

In order to improve the stability in the solution state, a method of adding additives has conventionally been adopted.

Namely, (i) JP-A-54-150459 discloses a method of adding an inorganic or organic metal salt such as sodium chloride, zinc sulfate, calcium chloride, calcium pantothenate, etc., and Ni) JP-A-55-16019 discloses a method of adding a surfactant. A method of adding it has been implemented, and some improvement has been obtained, but there have been no examples of it remaining stable for about a year at low temperatures. In addition, metal salts and surfactants that are added to promote stabilization may have problems such as having an adverse effect on the adhered materials, so it is preferable not to include them as much as possible.

As mentioned above, conventional compositions for external use having film-forming ability have problems with solution stability, and the current situation is that an ideal composition for external use has not yet been obtained.

It goes without saying that for external compositions used in cosmetics, quasi-drugs, external medicines, skin products, etc., the solution stability is more important than other physical properties in terms of practical application. It is clear that this is an indispensable condition for being a thing.

In view of this situation, the inventors of the present application have demonstrated unprecedented stability, that is, at low temperatures (-20°C) for more than - years. In order to develop an external composition with solution stability, we focused on the structure of nylon, which has the best film properties among the base polymers mentioned above.

That is, as a result of intensive study on a method for achieving sufficient stabilization using only nylon without adding additives, the following two points were discovered.

Firstly, the crystal structure of nylon is as small as possible,
That is, the heat of fusion of nylon (61 m) is as small as possible, and expressed numerically as 0 to 5 mca1. /mg range, and found that a non-grade nylon with no melting point is ideal.

In other words, in the conventional nylon, alcohol, and water system, it is presumed that various hydrogen bonds mainly in each amide group gradually progressed, resulting in gelation or solidification, but the heat of fusion (611 m ) is in the range of O to 5 mcal/mg, the conformation of the amide group is likely to be disordered, so the above hydrogen bonding is weakened, and it is presumed that this makes it difficult to transition to a metastable gelled state. .

The second purpose is to improve the solubility in an alcohol solution, and it is presumed that this is 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 concomitantly improving the solubility in alcohol.

As a method to reduce the heat of fusion of polyamide resin, (
1) Multi-component copolymerization method, (2) Introduction of bulky monomers,
(3) Hydrogen substitution at the N position, etc. can be considered. By taking these approaches, we were able to produce an alkali-soluble nylon that satisfies the above-mentioned requirements, and solve the problem of solution stability by using a polyamide resin that has been made completely water-soluble nylon.

Moreover, perhaps due to increased solubility in alcoholic solvents,
It has the advantage that it can be easily made into a spray.

Furthermore, when the influence of average molecular weight on solution stability and film physical properties was investigated, it was surprisingly found that an optimum average molecular weight exists. This optimum average molecular weight is expressed as a number average molecular weight, which ranges from 8,000 to 30,000.

Hereinafter, the relationship between the structure and the effects of the present invention will be explained in more detail.

The present invention has a heat of fusion of 0 to 5 as a resin with film forming ability.
This is a composition for external use in which mcal/mg of polyamide resin is dissolved in water and/or an alcoholic solvent. Heat of fusion (
Hereinafter, it will be referred to as 61m. ) is 5mca1. In the case of polyamide resins larger than /mg, the first problem is poor solution stability.
It can be seen clearly from the figure.

That is, the heat of fusion is preferably O~5 mcal/mg, preferably O~4 mcal/mg, and more preferably O~5 mcal/mg.
311 cal/log is desirable.

The average molecular weight is expressed as a number average molecular weight, and is 8,000 to 30.
000 is good, preferably 9,000 to 30,000
, more preferably 9,000 to 25,000.

Low molecules have greater crystallinity and solubility in solvents, and are superior in viscosity stability as a solution, but conversely, low molecules have a negative effect on film-forming properties.

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 greater than 30,000, the viscosity stability as a solution is poor.

The polyamide resin may be a commercially available water-soluble nylon and/or alcohol-soluble nylon,
It may be modified by the method described above. As water-soluble nylon, AO-nylon manufactured by Toshisha Co., Ltd.
-90 (8Hn+; Omcal/mg); P-70
(ΔHm#Omcal/mg) is exemplified, and alcohol-soluble nylons include AO-Nylon A-70 manufactured by Toshi Co., Ltd. (ΔHm: Omcal/mg); Pla
PLATAMTD M 1.372 manufactured by te-Bonn
(Δl(+11':r Omcal/mg), PLA
TABOND MX1602 (Δl1m# 2,3mc
al/II+g), MX1603 (ΔHm# Omca
l/mg) and the like. Note that these nylons have recently been newly manufactured, and have traditionally been used in hot melt adhesives, fixing agents, fiber treatment agents, dye-facilitating agents, ink modifiers, base materials for water-based paints, and photosensitizers. It is used for purposes such as additives, binders, and resin modifiers. However, there have been no examples of its use as an external composition, and there are no publicly known materials that suggest this. That is, the use of these nylons as a composition for external use is a novel finding first made by the inventors of the present application.

Although there are no limitations on the method of modifying polyamide resin,
Modified polyamide resins obtained by the methods described above can also be used in the same manner.

The amount of polyamide resin blended is 1 to 60% by weight of the entire composition.
The content is preferably 1 to 45% by weight, more preferably 1 to 25% by weight. If the amount is less than 1%, the film obtained from the external composition will be thin and it will be difficult to remove the film.On the other hand, if the amount exceeds 60%, the solution stability will be poor and phenomena such as gelation or solidification may occur. wake up

Ethanol is most preferred as the alcoholic solvent, but alcohols such as isopropanol, butanol, benzyl alcohol, cresol, etc. described in Shohara 1 can also be used, and two or more types can also be used in combination.

The external composition of the present invention is a homogeneous solution and not only has excellent solution stability, especially solution stability at low temperatures, but also has the following properties.

(i) Can be applied uniformly to the object to be coated as a liquid or spray.

(ij) Drying time is short and a film is formed quickly.

(iiD film is transparent and can be easily colored.

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

(v) Even if the film is left for a long time, no cracks or deterioration in appearance due to deterioration etc. are observed.

(vi) When the film is peeled off, it comes off in one piece.

(vii) Easy QL can be obtained by washing with water.

It has excellent performance such as.

Furthermore, when applying this external composition for various purposes, even if appropriate amounts of various additives, fragrances, disinfectants, pigments, etc. are added, the solution stability and the above-mentioned characteristics may be impaired.
Moreover, it does not affect those additives.

Due to these characteristics, this external preparation composition can be actively used and applied to cosmetics, quasi-drugs, external medicines, film-forming products, and the like. The present invention will be specifically explained below with reference to Examples. Note that the present invention is not limited to this.

Examples (including test examples) (Method for measuring number average molecular weight) The terminal groups were determined by conductivity titration using hydrochloric acid. The number of moles of -N112 (NO3) per gram of polymer is determined, and the number average molecular weight (salmon) is Mn = 1 / [Nl + □
] Calculated from.

Example-1 Strippable protective film agent PLATAMTD M-1372 (stripe 417,400)
20 parts (manufactured by Plate-Bonn) Ethanol/water (90/10; νt/wt)
76 benzyl alcohol
3 Silicone oil (manufactured by Toshisha, silicone 5t)
(200) 1. - Total 100 Modified nylon A with the above blending ratio ethanol/water = 11
= A strippable protective film agent was prepared by heating and dissolving in benzyl alcohol and adding silicone oil after cooling. Even when this protective film agent was left at a low temperature of -20° C. for 8 months, changes in appearance such as gelation and assimilation were not tolerated. After applying this strippable protective film agent to a ventilation fan to form a protective film and using it for 3 months, it can be easily peeled off in one piece, and there is no discoloration of the protective surface. , it was not contaminated.

Example-2 Occlusive dressing agent (ODT agent) An occlusive bandage solution was prepared according to the following formulation.

PLAYAMTD M-1372 (Envy # 17,400
) 20 (copies) [Plate-Bo
manufactured by nn] Ethanol/water (80/20; wt/wt)
77 glycerin
-''-Total 100 50 parts of the occlusive bandage liquid of the above formulation and 1250 parts of Freon were mixed to prepare an occlusive bandage aerosol.

A topical anti-inflammatory and analgesic ointment was applied to the upper back, and then a 12-piece occlusive bandage solution or an occlusive bandage aerosol was applied or sprayed. After application, it became a transparent film with no stickiness, and was easily removable when peeled. In addition, both these occlusive bandage liquids and aerosols are kept at -20°C.
No changes in appearance such as gelation or assimilation were observed even when the sample was left at a low temperature for 12 months.

Example-3 Spray type PLATABOND MX 1603 (Mn418,2
00) 4 (Part) [Plate-B
onn] Tetramethylthiuram disulfide 0.
02 (Bactericide) Ethanol/Water (9515; wt/wt)
46 Freon - 1250 Total 100.02 A spray-type plastic dressing was prepared according to the above recipe. Even when it was left as a spray agent at a low temperature (-20°C) for 12 months, no changes in appearance such as gelation or assimilation were observed.

In addition, as a plastic dressing, it could be sprayed uniformly onto the cut site, protecting the cut site. Furthermore, since the solvent contained in the solution is ethanol, there is little irritation to the affected area, and it can be said to be extremely safe in terms of toxicity.

Example-4 Oil pack agent Pl, ATABOND MX 1602 (Mn'=17
,000) 10 (copies) [Plate-B
onn] Liquid paraffin 10 Olive oil 20 Ethanol/Water (80/20; wt/wt) 50 Castor oil 10 Fragrance
Amount: 0.02 Total: 100.02 When a film-forming oil pack was prepared using the above formulation, no changes in appearance such as gelation or solidification were observed even after it was left at low temperatures (-20°C) for 12 months. There wasn't. Also, when not in use, it can be peeled off and removed, unlike conventional oil packs.

Example-5 Deodorant spray AQ nylon A70 (Mr + grade 1g, 000)
6 (part) [manufactured by Toshisha] Aluminum hydroxychloride 4-halocarpane 0.0
3 Isopropyl myristate ester 0.
6 trioleyl acid glycerin ester 0.
9 ethanol 2
6 Fragrance 0.03 Freon 12 □β? □U
A total of 100 deodorant sprays were prepared according to the above formulation. Even when this spray was left at low temperature (-20°C) for 12 months, no changes in appearance such as gelation or assimilation were observed. Furthermore, since it forms a film, the deodorizing effect lasted for a long time. Furthermore, it could be easily peeled off and removed when not in use.

Comparative Example-1 A strippable protective film agent was prepared by replacing PLATAMID M-1372 with BASF's -15=Ultraamide IC in Example-1. This protective agent is unstable and solidifies on the second day, especially at low temperatures (-20°C), which is unfavorable in terms of performance. By the way, the heat of fusion of Ultraamide IC is 7.8 mcal/mg, and the Mn is 15.900.
Met.

Comparative Example-2 In Example-2, PLATAMID M-1372
An occlusive dressing was prepared by replacing the sample with Elbamide 8023 manufactured by DuPont. Both the occlusive bandage liquid and the occlusive bandage aerosol are unstable, and both solidify in one day at low temperatures of -20°C, which is not desirable in terms of products. The heat of fusion of Elbamide 8023 (Mn # 12,000) was 9, kcal/mg.

Comparative Example-3 In Example-2, PLATAMID M-1372 (
An occlusive dressing was prepared by replacing Prototype B (manufactured by Plate-Bonn) with the same composition but a lower molecular weight (Mr+; 7,500).

Both occlusive bandage liquid and occlusive bandage aerosol are -
It was stable for more than one year at a low temperature of 20°C.

However, a film was not formed and could not be peeled off as a single film, making it undesirable as a product.

Comparative Example-4 In Example-1, PLATAMID M-1372 was replaced with DIAMID (68m') manufactured by Daicel Chemical Industries, Ltd.
F 8.2IIcal/+eg, Mn~35,10
A strippable protective film agent was prepared by replacing only 0). This protective agent is unstable and solidifies when left at room temperature for 30 minutes, which is unfavorable in terms of performance.

[Brief explanation 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 for gelation of a solution at -20°C. 20% by weight (ethanol is 2%
It is 0% by weight. ) At a nylon concentration of 15% by weight in aqueous ethanol, Δt1m is O ~ 5 mcal, /
If it is in the mg range, it can be said that the solution has high low temperature stability. The lower the polymer concentration, the better the low temperature stability of the solution. Agent Patent attorney Door 1) Parent Male 1 Heat of fusion Hm (r+ynQ/mn1

Claims (1)

[Claims] 1) As a resin having film-forming ability, heat of fusion (ΔHm)
is 0 to 5 mcal/mg, and the number average molecular weight is 8,
000~30,000 polyamide resin with water and/or
Or a composition for external use dissolved in an alcoholic solvent. 2) The external composition according to claim 1, wherein the polyamide resin is water-soluble nylon and/or alcohol-soluble nylon. 3) The composition for external use according to claim 1 or 2, wherein the amount of polyamide resin blended is 1 to 25% by weight of the total amount.