JP2018203739A - Skin external composition - Google Patents

Abstract

To provide an absorbent article which maintains the surface condition of the skin after absorbing a liquid and suppresses inflammation of the skin.SOLUTION: There is provided a skin external composition which comprises a polyurethane resin or a polyurea resin (P) containing an active hydrogen-containing compound (A) containing an active hydrogen-containing compound (a) containing a tertiary amine group (salt) and/or an active hydrogen-containing compound (b) containing a quaternary ammonium salt group and a polyisocyanate compound (B) as constituent units, wherein the content of the tertiary amine group (salt) and/or the quaternary ammonium salt group is preferably 0.01 to 3 mmol/g.SELECTED DRAWING: None

Description

The present invention relates to an external preparation for skin.

Conventional skin external preparations containing amphoteric urethane resins are known as external preparations for skin (Patent Document 1). In addition, an amphoteric urethane resin in which a polysiloxane compound having a functional group containing active hydrogen at both ends or one end of a siloxane chain is introduced into a skeleton of an amphoteric urethane resin is known (patent document). 2).

JP 11-228363 A JP 2000-191476 A

However, the conventional method has a problem that it is inferior in followability to the skin when the skin is moved, and is easy to drop off because of its low adsorptivity to the skin. Accordingly, an object of the present invention is to provide an external preparation for skin that coats the skin surface by achieving both the following and adsorbability to the skin, protects the skin from irritation such as friction and stuffiness, and suppresses / improves rough skin. And

The present invention relates to an active hydrogen-containing compound (A) containing an active hydrogen-containing compound (a) containing a tertiary amine group (salt) and / or an active hydrogen-containing compound (b) containing a quaternary ammonium base. And a polyisocyanate compound (B) as a constitutional unit is a skin external preparation containing a polyurethane resin or a polyurea resin (P). The present invention is also a skin coating method for treating skin with the above-mentioned external preparation for skin.

  The external preparation for skin of the present invention coats the skin surface by making both followability to the skin and adsorptivity compatible, protects the skin from irritation such as friction and stuffiness, and can suppress and improve rough skin.

The present invention relates to an active hydrogen-containing compound (A) containing an active hydrogen-containing compound (a) containing a tertiary amine group (salt) and / or an active hydrogen-containing compound (b) containing a quaternary ammonium base. And an active hydrogen-containing compound (a) containing a tertiary amine (salt) group as at least a part of (A) and a polyurethane resin and / or a polyurea resin containing the polyisocyanate compound (B) as structural units A skin external preparation characterized by using an active hydrogen-containing compound (b) containing a quaternary ammonium base.

In the present invention, examples of the active hydrogen-containing group in the active hydrogen-containing compound (a) containing a tertiary amine (salt) group include a hydroxyl group, a mercapto group, and an amino group. Although it does not specifically limit as a compound containing a tertiary amine group and having an active hydrogen containing group, The compound (a1) shown by the following general formula (1), its alkylene oxide adduct (a2), and Examples thereof include polyester diols, polyamide diamines, and polythioester dimercaptans (a3) obtained by condensation reaction with them and dicarboxylic acids.

In the formula, R ¹ , R ² and R ³ may be the same or different, and are a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyalkyl group, a mercaptoalkyl group, a carboxylalkyl group or an aminoalkyl group; ^At least one of ¹ , R ² and R ³ is a hydroxyalkyl group, a mercaptoalkyl group or an aminoalkyl group. Specific examples of the compound (a1-1) containing a tertiary amine group and having a hydroxyl group include N, N-diethylethanolamine, N, N-dibutylethanolamine, N, N-dimethylethanolamine, N -Methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-lauryldiethanolamine, N-methyl-N-hydroxyethylaniline, N-ethyl-N-hydroxyethylaniline, N, N-dioxyethylaniline, N, N-dioxyethyl toluidine, N-cyclohexyl diethanolamine, triethanolamine and the like can be mentioned.

Specific examples of the compound (a1-2) containing a tertiary amine group and containing an amino group include N, N-dimethylhydrazine, N, N-dimethylethylenediamine, bis- (aminopropyl) -methylamine. Bis- (aminoethyl) -methylamine, bis- (aminomethyl) -methylamine, bis- (aminoethyl) -ethylamine, bis- (aminoethyl) -cyclohexylamine, N-methyl-N-aminoethyltoluidine, And bis-aminopropylaniline.

Specific examples of the compound (a1-3) containing a tertiary amine group and containing a mercapto group include N, N, N-diethylmercaptoethylamine, N, N, N-dibutylmercaptoethylamine, N, N , N-dimethylmercaptoethylamine, N, N, N-dimercaptoethylmethylamine, N, N, N-dimercaptoethylmethylamine, N, N, N-dimercaptopropylmethylamine, N, N, N-di Mercaptoethylstearylamine, N-methyl-N-mercaptoethylaniline, N-ethyl-N-mercaptoethylaniline, N, N-dimercaptoethylaniline, N, N-dimercaptoethyltoluidine, N, N, N-di And mercaptoethylcyclohexylamine.

Specific examples of the compound (a1-4) containing a tertiary amine group and containing a hydroxyl group and an amino group include N-methyl-N- (aminoethyl) ethanolamine, N-ethyl-N- (amino Propyl) ethanolamine, N-hydroxyethyl-N-aminoethylaniline and the like.

Specific examples of the compound (a1-5) containing a tertiary amine group and containing a hydroxyl group and a mercapto group include N-methyl-N- (mercaptoethyl) ethanolamine, N-ethyl-N- (mercapto). Ethyl) ethanolamine, N-methyl-N- (mercaptomethyl) ethanolamine, N-methyl-N- (mercaptopropyl) ethanolamine, N-methyl-N- (mercaptoethyl) propanolamine and the like.

Specific examples of the compound (a1-6) containing a tertiary amine group and containing an amino group and a mercapto group include N-methyl-N- (aminoethyl) mercaptoethylamine, N-methyl-N- ( Aminobutyl) mercaptoethylamine, N-methyl-N- (aminoethyl) mercaptolaurylamine, N-methyl-N- (aminoethyl) mercaptostearylamine, N-methyl-N- (aminobutyl) mercaptoethylamine and the like. .

In the alkylene oxide adduct (a2) of the compound (a1) represented by the general formula (1), the alkylene oxide may be ethylene oxide (EO), propylene oxide (PO), 1,2-, 2, 3- or 1 , 3-butylene oxide, tetrahydrofuran (THF), epichlorohydrin and the like. Alkylene oxides may be used alone or in combination of two or more. In the latter case, block addition, random addition or a mixture of both may be used.

Polyester diol, polyamide diamine, and polythioester dimercaptans (a3) obtained by condensation reaction of the compound (a1) represented by the general formula (1) or an alkylene oxide adduct (a2) thereof with a dicarboxylic acid are represented by the general formula ( The compound represented by 1) or an alkylene oxide adduct thereof is a compound obtained by condensation reaction of a compound having 2 or 3 active hydrogens with a dicarboxylic acid, and has at least two active hydrogen-containing groups. Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (such as succinic acid, adipic acid, azelaic acid, and sebacic acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid, and phthalic acid), and mixtures of two or more thereof. It is done.

Other than the above, any compound having an active hydrogen-containing group containing a tertiary amine group described in JP-B-43-9076 can be carried out.

Among these compounds (a) having a tertiary amine group and having an active hydrogen-containing group, preferably a compound having a tertiary amine group and having a hydroxyl group, more preferably N-methyldiethanolamine. It is.

In the present invention, examples of the active hydrogen-containing compound (a) containing a tertiary amine base include those obtained by neutralizing the above compound with an inorganic acid, an organic acid, or a mixture of two or more thereof. Specific examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and the like. Examples of the organic acid include at least one organic acid selected from the group consisting of carboxylic acids, sulfonic acids, and organic phosphorus compounds.

As carboxylic acid, what has a carboxyl group in a molecule | numerator can be used. Specific examples include formic acid, acetic acid, propionic acid, lauric acid, stearic acid, behenic acid, isostearic acid, lactic acid, hydroxylauric acid, hydroxystearic acid, polyoxyethylene lauryl ether acetic acid, polyoxyethylene octyl ether acetic acid, poly Examples thereof include oxyethylene stearyl ether acetic acid, polyoxypropylene lauryl ether acetic acid and polyoxypropylene octyl ether acetic acid.

As the sulfonic acid, one having a sulfonic acid group or a sulfate ester group in the molecule can be used. Specific examples include methyl sulfuric acid, ethyl sulfuric acid, isopropyl sulfuric acid, propyl sulfuric acid, octyl sulfuric acid, lauryl sulfuric acid, stearyl sulfuric acid, isostearyl sulfuric acid, benzene sulfonic acid, alkyl benzene sulfonic acid and the like.

As the organic phosphorus compound, one having a phosphate group in the molecule can be used. Specific examples include dimethyl phosphoric acid, diethyl phosphoric acid, methyl ethyl phosphoric acid, methyl phosphorous acid, diisopropyl phosphoric acid, dilauryl phosphoric acid, distearyl phosphoric acid and the like.

In the present invention, the active hydrogen-containing compound (b) containing a quaternary ammonium base is not particularly limited, and examples thereof include compounds represented by the general formula (2). Quaternized and amphoteric compounds of the secondary amino (salt) group-containing active hydrogen-containing compound (a) can be mentioned. The quaternization or amphotericization (modification) of the active hydrogen-containing compound containing a tertiary amino (salt) group includes a method of modifying in advance before polymerization and a method of modifying after polymerization, preferably polymerization. This is a method of post-modification.

In the formula, R ¹ , R ² and R ³ may be the same or different, and are a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyalkyl group, a mercaptoalkyl group, a carboxylalkyl group or an aminoalkyl group; ^At least one of ¹ , R ² and R ³ is a hydroxyalkyl group, a mercaptoalkyl group or an aminoalkyl group. R ⁴ is a hydrocarbon group having 1 to 24 carbon atoms or a carboxyalkyl group. X is a halogen atom, monoalkyl carbonic acid or monoalkyl sulfuric acid. In the present invention, the compound for quaternizing the tertiary amine (salt) group is not particularly limited, and examples thereof include aliphatic monohalogenated alkyl, aromatic monohalogenated alkyl, dialkyl carbonate, and dialkyl sulfate. It is done. Examples of the aromatic monohalogenated alkyl include benzyl chloride, benzyl bromide, benzyl iodide and the like. Of these, benzyl chloride is preferred. Examples of the aliphatic monohalogenated alkyl include methyl chloride, ethyl chloride, butyl bromide, methyl iodide, lauryl bromide, stearyl chloride, isopropyl iodide and the like. Of these, methyl chloride and ethyl chloride are preferred.

Examples of the dialkyl sulfate include, but are not limited to, dimethyl sulfate, diethyl sulfate, dibutyl sulfate, diisopropyl sulfate, dilauryl sulfate, distearyl sulfate, dibehenyl sulfate, and the like. Of these, dimethyl sulfate and diethyl sulfate are preferable.

In the present invention, the compound for amphotericizing the tertiary amine (salt) group is not particularly limited, and examples thereof include monohalogenated acetic acid (monochloroacetic acid and the like) and salts thereof. As salts of monohalogenated acetic acid, alkali metal salts, alkaline earth metal salts, amine salts and ammonium salts are used. Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. Examples of alkaline earth metal salts include magnesium salts and calcium salts. Examples of the amine salt include trimethylamine, triethylamine, triethanolamine, dimethylaminoethanol, aminomethylpropanol, pyridine, and ethylenediamine.

In the present invention, the content of the tertiary amine (salt) group and / or the quaternary ammonium base in the polyurethane resin or polyurea resin is the same as that of the polyurethane resin or polyurea resin from the viewpoint of film water resistance and skin affinity. Based on the weight, it is 0.01 to 3 mmol / g, preferably 0.02 to 2.5 mmol / g.

In the present invention, the compound having an active hydrogen-containing group other than the above-mentioned compound (a) or (b) that may be contained in the active hydrogen-containing compound (A) is not particularly limited. And low molecular active hydrogen-containing compounds. Examples of the polymer polyol include polyether polyol, polyester polyol, and silicone polyol. Examples of the polyether polyol include a compound having a structure in which an alkylene oxide is added to an active hydrogen-containing polyfunctional compound and a mixture of two or more of these.
Of these, polyether polyols and low molecular weight active hydrogen-containing compounds are preferred from the viewpoint of affinity with the skin, and polyether polyols and dihydric alcohols are more preferred. Most preferred are 2-3 trihydric alcohols.

Examples of the active hydrogen-containing polyfunctional compound include polyhydric alcohols, polyhydric phenols, amines, and polycarboxylic acids. Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, bis (hydroxymethyl) cyclohexane, bis Dihydric alcohols such as (hydroxyethyl) benzene; 3-8 such as glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose Valent polyhydric alcohol and the like.

Specific examples of the polyhydric phenol include polyphenols such as pyrogallol, catechol, and hydroquinone, and bisphenols such as bisphenol A, bisphenol F, and bisphenol S.

Specific examples of amines include ammonia, monoamines such as alkylamines having 1 to 20 carbon atoms (such as butylamine) and aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine and diethylenetriamine; piperazine, N-aminoethyl Piperazine and other heterocyclic polyamines described in JP-B No. 55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, Aromatic polyamines such as diphenyl ether diamine and polyphenylmethane polyamine; and monoethanolamine, diethanolamine, triethanolamine, triiso Ropanoruamin like alkanolamines such.

Specific examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid and adipic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid. Two or more kinds of the above active hydrogen-containing polyfunctional compounds can be used.

Examples of the alkylene oxide added to the active hydrogen-containing polyfunctional compound include the same ones as described above.

Alkylene oxides may be used alone or in combination of two or more. In the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixture of both may be used. Among these, preferred are EO alone, PO alone, THF alone, combined use of PO and EO, combined use of PO and / or EO and THF (in the case of combination, random, block and mixed system of both), and particularly preferred. Is THF alone.

The addition of the alkylene oxide to the active hydrogen-containing polyfunctional compound can be carried out in the usual manner, in the presence of no catalyst or a catalyst (alkali catalyst, amine catalyst, acidic catalyst) (particularly the latter half of the alkylene oxide addition). In a single step or multiple steps under normal pressure or under pressure.

Further, the polyether polyol may be one having a higher molecular weight by reacting with a small proportion of polyisocyanate (described later) (polyalkylene ether polyol / polyisocyanate equivalent ratio: 1.2 to 10, preferably 1.5-2).

The equivalent of the polyether polyol (molecular weight per hydroxyl group) is 100 to 10,000, preferably 250 to 5,000, more preferably 500 to 1,500. The functionality of the polyether polyol is 2 to 8, preferably 2 to 3, particularly preferably 2.

Of these polyether polyols, an alkylene oxide adduct of a polyhydric alcohol is preferable, and polypropylene glycol and polytetramethylene glycol are more preferable.

Polyamines include aliphatic polyamines (specifically ethylenediamine, diethylenetriamine, hexamethylenediamine, etc.) aromatic polyamines (phenylenediamine, diaminotoluene, xylenediamine, methylenediamine, diphenyl ether, etc.), alicyclic polyamines (isophoronediamine and other) Alicyclic polyamines, etc.), heterocyclic polyamines (piperazine and other heterocyclic polyamines described in JP-B No. 55-21044) and the like. Of these polyamines, aliphatic polyamines are preferred.

As the low-molecular active hydrogen-containing compound, at least two, preferably 2 to 5 compounds having an active hydrogen equivalent of less than 200, which are called crosslinking agents and chain extenders, can be used. Specific examples thereof include 2- to 3-hydric alcohols (ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, etc.), amines (diethanolamine). , Triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine, isophoronediamine, diaminotoluene, diethyltoluenediamine, methylenedianiline, methylenebisorthochloroaniline, etc.) and the aforementioned bivalent alcohol, tetravalent to octavalent alcohol ( Pentaerythritol, methyl glucoside, sorbitol, saccharose, etc.), polyphenols (bisphenol A, hydroquinone, etc.), the above amines, and other amines (aminoethyl pyridine). Rajin, aniline), and the like minor amounts of ethylene oxide and / or polyhydroxy compounds and water equivalent of less than 200 obtained by adding an alkylene oxide such as propylene oxide and the like. Of these, preferred are 2 to 3 alcohols, amines and water, and more preferred are 2 to 3 alcohols.

In addition, as a low molecular weight active hydrogen-containing compound, it is called an end-capping material, and monoalcohol (hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane diallyl ether, etc.); amine ( Ptylamine, diallylamine, etc.). Of these, hydroxyethyl acrylate and hydroxypropyl acrylate are preferred.

The said active hydrogen containing compound can be used individually or in mixture of 2 or more types.

In the present invention, as the polyisocyanate compound (B), those conventionally used for polyurethane production can be used. Such a polyisocyanate compound is not particularly limited, but is an aromatic polyisocyanate having 6 to 20 carbon atoms (for example, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2 , 4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane {condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof: diaminophenylmethane and a small amount (for example, 5-20% by weight) of a mixture with a trifunctional or higher polyamine}: polyallyl polyisocyanate (PAPI), etc.]: aliphatic polyisocyanate having 2 to 18 carbon atoms (for example, hexamethylene diisocyanate, lysine diisocyanate, etc.) ): C4-C15 alicyclic polyi Cyanate (for example, isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc.): C8-15 aromatic aliphatic polyisocyanate (for example, xylene diisocyanate): and modified products of these isocyanates (urethane group, carbodiimide group, allophanate group, urea group, Buret group, uretdione group, uretonimine group, isocyanurate group, modified product containing oxazolidone group): and a mixture of two or more thereof.

In producing the polyurethane resin or polyurea resin of the present invention, the ratio of the active hydrogen-containing compound (A) and the polyisocyanate compound (B) can be variously changed, but the equivalent ratio of isocyanate group to active hydrogen is (0 0.5-2): 1, preferably (1.05-1.5): 1.

The method for producing the polyurethane resin or polyurea resin of the present invention includes, for example, a method in which compounds (A) and (B) are divided and subjected to a multistage reaction (prepolymer method), and compounds (A) and (B) in a lump. A reaction method (one-shot method) and the like can be mentioned, and a prepolymer method is preferred. As an example of the prepolymer method, the compounds (A) and (B) are reacted in advance and the reaction is completed with a low molecular diamine or the like, and then the tertiary amine group is partially or completely neutralized, quaternized and And / or a method of amphotericizing.

In the present invention, the reaction can be carried out using a solvent inert to the isocyanate group. Solvents include amide solvents (N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.): ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) aromatic hydrocarbon solvents (toluene, xylene, etc.): ether System solvents (dioxane, tetrahydrofuran, etc.): Sulfoxide solvents (dimethyl sulfoxide, etc.) and these may be two or more types of mixed solvents. The amount of solvent is 0 to 400% with respect to the amount of polyurethane. The reaction temperature is 20 to 150 ° C, preferably 20 to 100 ° C. The reaction time is 3 to 20 hours. The reaction pressure is also performed under normal pressure, but may be performed under pressure. In order to accelerate the reaction, a catalyst such as an amine catalyst (such as triethylrangeamine, N-methylmorpholine, or triethylamine), a tin catalyst (such as dibutyltin dilaurate), or a lead catalyst (such as lead octylate) is used. Also good.

In the present invention, the molecular weight of the polyurethane resin or polyurea resin is 1000 or more in terms of weight average molecular weight, preferably 5000 to 2 million, more preferably 10,000 to 1 million.

The polyurethane resin or polyurea resin obtained in the present invention can be made into a dispersion by an ordinary method (for example, the method described in JP-B-42-24192). For example, an aqueous dispersion (concentration of about 45%) is obtained by adding water with stirring to an acetone solvent (concentration of about 60%) of the polyurethane resin or polyurea resin obtained in the present invention and then distilling off acetone under heating. ) Can be obtained.

The method for measuring the 100% modulus of the resin film is performed under the following conditions.
(1) Production of resin film (resin film having a thickness of 0.2 ± 0.05 mm) Examples of the production of the film include the following method. A resin solution prepared by diluting the solid content to about 20% with water (although a low-boiling organic solvent such as alcohol or ketone may be used in combination if necessary) is used for a horizontal release substrate (for example, a polypropylene plate, if necessary) A release agent or release paper may be used), a frame is provided, and the resulting mixture is flowed to a thickness of 1 mm and left to stand at room temperature for about 12 hours to be naturally dried. Next, after drying for about 12 hours in a circulating drier at about 60 ° C., peeling is performed to obtain a resin film having a thickness of 0.2 ± 0.05 mm.

(2) Preparation of measurement test piece The above resin film was processed into a test piece using No. 3 dumbbell (JIS K6723), and after accurately measuring the thickness, 30 ± 2 ° C., 80 ± 5% R.D. H. Condition the test piece with a constant temperature and humidity chamber. Since the 100% modulus varies depending on the moisture absorption state, a sample absorbed for 24 hours or more and 48 hours or less is used for measurement.
(3) Measurement room temperature 25 ± 2 ° C., humidity 65 ± 5% R.D. H. Measurement is performed under the following conditions using an autograph (for example, Shimadzu Autograph AGS-500D) installed in the environment of In addition, the humidity-controlled test piece is taken out from the thermo-hygrostat and measured within 5 minutes.
Load cell: 0.5 MPa Tensile speed: 50 mm / min Thin resin film, and measurement of a small 100% modulus varies depending on the tensile speed.

In the present invention, the loss tangent (tan δ) of the resin film is preferably 0.3 or less, more preferably 0.2. When tan δ is 0.3 or less, the viscosity of the resin is small, so that the followability when in close contact with the skin is good. The measurement method of tan δ of the resin film is performed under the following conditions.
(1) Preparation of resin film The resin film is prepared by the method described in the above-mentioned 100% modulus measurement method.
(2) Preparation of measurement test piece The above film is cut into a size of 45 mm in length and 5 mm in width using a cutter or the like, and a test piece is prepared, and the thickness is measured accurately.
(3) Measurement Using a commercially available viscoelasticity measuring device (for example, ORIENTEC's MODEL DDV-25FP), measurement is performed under the following conditions, and tan δ at 25 ± 1 ° C. is taken as a measurement value.
Load: 2.0 MPa (displacement 0.3-3%)
Excitation frequency: 30 Hz

The external preparation for skin of the present invention has a liquid form, an aerosol, a cream, a gel (jelly), a powder, an ointment and the like. Among these dosage forms, a liquid agent, an aerosol agent, a cream agent or a gel agent is preferable from the viewpoint of ease of use.
In addition, the content of the polyurethane resin or polyurea resin in the external preparation for skin of the present invention is not particularly limited as long as it is 0.1% by weight or more based on the weight of the external preparation for skin. In the case of an agent, cream or gel, it is preferably 0.1 to 5% (in the following, unless otherwise specified,% represents% by weight), more preferably 0.3 to 3%, particularly preferably 0. 5 to 1%.

Other components that can be contained other than the polyurethane resin or polyurea resin in the external preparation for skin of the present invention include the following additives, for example, oily components, hydrophilic components, surfactants, thickeners, gelling agents, powdered inorganics Examples include substances, preservatives, antioxidants, pH adjusters, and flavoring agents. These other components are appropriately selected according to the dosage form at the time of use.

Examples of the oil component include petroleum jelly, liquid paraffin, paraffin wax, silicone oil, triglyceride, squalene, beeswax, white beeswax, microcrystalline wax, paraffin wax, whale wax, purified lanolin and the like.
Examples of hydrophilic components include hydrophilic fatty acid esters, polyethylene glycol, monohydric alcohols (ethanol, isopropanol, etc.), polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-tetramethylene. Glycol, glycerin, sorbitol, etc.) and alkanolamines (diethanolamine, triethanolamine, etc.).

Surfactants include anionic surfactants (such as sodium alkyl sulfate), nonionic surfactants [polyoxyethylene sorbitan fatty acid esters (such as monooleyl polyoxyethylene sorbitan), polyoxyethylene castor oil derivatives, polyoxyethylene Hydrogenated castor oil, glycerin fatty acid ester (such as glycerin monostearate and sorbitan monooleate), sorbitan fatty acid ester (such as sorbitan monostearate and sorbitan sesquiolate), polyoxyethylene higher alcohol ether (such as polyoxyethylene cetyl ether), poly Oxyethylene alkylphenol and polyoxyethyleneoxypropylene copolymers (pluronics, etc.)], cationic surfactants (cetyltrimethylammonium chloride) Ride, etc.), and the like ampholytic surface active agents.

As thickeners and gelling agents, polysaccharides (such as colloidally dispersed starch, tragacanth, alginate, gum arabic, pullulan, locust bin gum, bing gum, pectin, xanthan gum and guar gum), cellulose derivatives (eg methyl cellulose, carboxymethyl cellulose) , Sodium carboxymethyl cellulose), colloidal clay (for example, silicates such as bentonite and bee gum), vinyl polymers (polyvinyl alcohol, polyvinyl pyrrolidone, acrylic acid copolymers, etc.) and colloidal microcrystalline cellulose.
Examples of the particulate inorganic substance include talc, silicic anhydride, calcium carbonate, magnesium carbonate, colloidal silica, bentonite and the like.

Examples of the preservative include paraoxybenzoic acid esters such as methyl paraoxybenzoate and propyl paraoxybenzoate.
Examples of the antioxidant include dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), α-tocopherol, erythorbic acid, sodium pyrosulfite and the like.
Examples of the pH adjuster include citric acid, sodium hydroxide, and organic amines such as diisopropanolamine.

When the skin external preparation of the present invention is a liquid preparation, a surfactant, a higher fatty acid ester, a higher alcohol, a thickener, a polyhydric alcohol, a preservative and the like are preferably used.

In the case of an aerosol agent, a propellant is preferably used together with the components of the liquid agent, and a solvent such as ethanol, glycerin and propylene glycol, a higher fatty acid ester, a surfactant and the like can be used as necessary.

As the propellant, low-boiling fluorocarbons (for example, Freon 22) and aliphatic hydrocarbons (for example, propane, butane, etc.) can be used.

When it is a gel, it contains a gelling agent, and as the base for creams and ointments, the oily components, surfactants, hydrophilic components and the like can be used.

Although the method of using the external preparation for skin of the present invention varies depending on the dosage form, it can be applied to the skin to form a coating film on the skin surface and improve skin irritation caused by excreta etc. It becomes.

Moreover, the skin external preparation of this invention can also be apply | coated etc. to the members (for example, pulp etc.) which contact skin. When applied to the surface of a member in contact with the skin, it can be expected that the skin external preparation of the present invention is transferred from the member to the skin to form a coating film on the surface of the skin and improve skin irritation.

The external preparation for skin of the present invention is obtained by blending each of the above components.
When the skin external preparation of the present invention is a liquid, for example, 1 to 60 parts by weight of polyurethane resin or polyurea resin in the present invention, 1 to 60 parts by weight such as ethylene glycol or propylene glycol, preferably 5 to 50 parts by weight, and Anionic surfactant, amphoteric surfactant or nonionic surfactant is added in an amount of 1 to 60 parts by weight, preferably 5 to 50 parts by weight, uniformly mixed and dissolved, and if necessary, other additives are added, Examples thereof include a method in which water is added with sufficient stirring to obtain an aqueous emulsion or aqueous suspension [the concentration of the polyurethane resin or polyurea resin is 1 to 30%, preferably 5 to 20%].

The external preparation for skin of the present invention can be used as a medicine, a quasi-drug, a cosmetic, or a toiletry product. Moreover, it is applicable as what is used as a processing agent of the member which contacts skin.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the following, parts and% indicate parts by weight and% by weight, respectively.

<Production Example 1>
In a closed reactor equipped with a thermometer and a stirrer, 180.0 parts of polyester diol composed of 1,4-butanediol and adipic acid having a molecular weight of about 2000, 6.3 parts of 1,4-butanediol, N-methyldiethanolamine 14.4 parts, 89.3 parts of isophorone diisocyanate and 122 parts of acetone were charged, the reaction system was replaced with nitrogen gas, and then reacted at 80 ° C. for 5 hours with stirring. 15.2 parts of dimethyl sulfuric acid was added to the obtained acetone solution, and quaternization was performed at 45 to 55 ° C. The obtained quaternized product was cooled to 30 ° C., 700 parts of water was added, acetone was distilled off at 50 to 60 ° C. under reduced pressure, and a urethane resin aqueous dispersion solution having a solid content of 30% and a viscosity of 510 mPa · s (P -1) 1000 parts were obtained. The obtained resin had a quaternary ammonium salt content of 0.40 mmol / g.

<Production Example 2>
In a closed reactor equipped with a thermometer and a stirrer, 94.7 parts of polytetramethylene glycol having a molecular weight of about 2000, 90.7 parts of polyester diol composed of 3-methylpentanediol having a molecular weight of about 2000 and adipic acid, 1, 4 -Butanediol (6.6 parts), N-methyldiethanolamine (15.0 parts), isophorone diisocyanate (83.3 parts) and acetone (122 parts) were charged, and the reaction system was replaced with nitrogen gas, followed by reaction at 80 ° C for 5 hours with stirring. 14.7 parts of sodium monochloroacetate was added to the obtained acetone solution, and the mixture was amphoteric at 80 ° C. The obtained amphoteric product was cooled to 30 ° C., 700 parts of water was added, acetone was distilled off at 50 to 60 ° C. under reduced pressure, and an aqueous urethane resin dispersion (P) having a solid content of 30% and a viscosity of 350 mPa · s. -2) 1000 parts were obtained. The resin obtained had a quaternary ammonium salt content of 0.42 mmol / g.

<Production Example 3>
A closed reactor equipped with a thermometer and a stirrer was charged with 85.0 parts of N-methyldiethanolamine, 140.0 parts of hexamethylene diisocyanate and 122 parts of acetone, and the reaction system was replaced with nitrogen gas. For 5 hours. 30.0 parts of absolute ethanol was added to the obtained acetone solution, and the reaction was further performed at 50 ° C. for 4 hours. 65.0 parts of lactic acid was added to the obtained urethane resin solution, and neutralized at 45 to 55 ° C. The obtained neutralized product was cooled to 30 ° C., 700 parts of water was added, acetone was distilled off at 50-60 ° C. under reduced pressure, and an aqueous urethane resin dispersion (P = 30 m) and a viscosity of 2000 mPa · s (P -3) 1000 parts were obtained. The resulting resin had a tertiary amine salt content of 2.37 mmol / g.

<Production Example 4>
A closed reactor equipped with a thermometer and a stirrer was charged with 256.2 parts of polytetramethylene glycol having a molecular weight of about 2000, 0.7 parts of N-methyldiethanolamine, 42.2 parts of isophorone diisocyanate and 122 parts of acetone, and the reaction system Was replaced with nitrogen gas and reacted at 80 ° C. for 5 hours with stirring. Methyl chloride 0.3 part was added to the obtained acetone solution, and quaternization was performed at 45-55 degreeC. The obtained quaternized product was cooled to 30 ° C., 700 parts of water was added, acetone was distilled off at 50 to 60 ° C. under reduced pressure, and a urethane resin aqueous dispersion (P) with a solid content of 30% and a viscosity of 380 mPa · s. -4) 1000 parts were obtained. The resulting resin had a quaternary ammonium salt content of 0.02 mmol / g.

<Production Example 5>
A closed reactor equipped with a thermometer and a stirrer is charged with 229.3 parts of polypropylene glycol having a molecular weight of about 2000, 5.6 parts of N-methyldiethanolamine, 57.6 parts of 4,4′-diphenylmethane diisocyanate and 122 parts of acetone. The reaction system was replaced with nitrogen gas, and reacted at 80 ° C. for 5 hours with stirring. To the obtained acetone solution, 6.4 parts of ammonium monochloroacetate was added, and amphotericization was performed at 80 ° C. The obtained amphoteric product was cooled to 30 ° C., 700 parts of water was added, acetone was distilled off at 50-60 ° C. under reduced pressure, and a urethane resin water dispersion solution (P−) having a solid content of 31% and a viscosity of 450 mPa · s was obtained. 5) 1000 parts were obtained. The resulting resin had a quaternary ammonium salt content of 0.16 mmol / g.

<Production Example 6>
In a closed reactor equipped with a thermometer and a stirrer, 189.0 parts of polypropylene glycol having a molecular weight of about 2000, 40.3 parts of modified silicone polyol X-21-5841 (manufactured by Shin-Etsu Silicone Co., Ltd.), N-methyldiethanolamine, 5. 6 parts, 4,4′-diphenylmethane diisocyanate (57.6 parts) and acetone (122 parts) were added, and the reaction system was replaced with nitrogen gas, followed by reaction at 80 ° C. with stirring for 5 hours. To the obtained acetone solution, 6.4 parts of ammonium monochloroacetate was added, and amphotericization was performed at 80 ° C. The obtained amphoteric product was cooled to 30 ° C., 700 parts of water was added, acetone was distilled off at 50-60 ° C. under reduced pressure, and a urethane resin water dispersion solution (P−) having a solid content of 31% and a viscosity of 450 mPa · s was obtained. 6) 1000 parts were obtained. The resulting resin had a quaternary ammonium salt content of 0.16 mmol / g.

<Comparative Production Example 1>
In a closed reactor equipped with a thermometer and a stirrer, 180.2 parts of polyester diol consisting of 1,4-butanediol and adipic acid having a molecular weight of about 2000, 6.2 parts of 1,4-butanediol, dimethylolpropionic acid 19.6 parts, 94.0 parts of isophorone diisocyanate and 122 parts of acetone were charged, and the reaction system was replaced with nitrogen gas, and then reacted at 80 ° C. for 5 hours with stirring. 140 parts of 1N sodium hydroxide was added to the obtained acetone solution, and neutralized at 45 to 55 ° C. The obtained neutralized product was cooled to 30 ° C., 560 parts of water was added, acetone was distilled off at 50 to 60 ° C. under reduced pressure, and a urethane resin aqueous dispersion (X) having a solid content of 30% and a viscosity of 320 mPa · s (X '-1) 1000 parts were obtained.

<Comparative Production Example 2>
In a closed reactor equipped with a thermometer and a stirrer, 91.6 parts of polytetramethylene glycol having a molecular weight of about 2000, 91.6 parts of polyester diol composed of 3-methylpentanediol and adipic acid having a molecular weight of about 2000, 1, 4 -6.6 parts of butanediol, 20.8 parts of dimethylolpropionic acid, 78.8 parts of isophorone diisocyanate, and 122 parts of acetone were substituted with nitrogen gas, and the reaction was carried out at 80 ° C for 5 hours with stirring. 30.0 parts of absolute ethanol was added to the obtained acetone solution, and the reaction was further performed at 50 ° C. for 4 hours. To the obtained urethane resin solution, 13.8 parts of dimethylethanolamine was added and neutralized at 45 to 55 ° C. The obtained neutralization was cooled to 30 ° C., 700 parts of water was added, acetone was distilled off at 50-60 ° C. under reduced pressure, and a urethane resin water dispersion solution (X: 30% solids, viscosity: 380 mPa · s) '-2) 1000 parts were obtained.

A skin external preparation in the form of a liquid agent and an aerosol agent was prepared using the above urethane resin aqueous dispersion. The preparation formulation is shown below.

Examples 1 to 6 and Comparative Examples 1 and 2 (liquid formulation);
Emulsions (P-1) to (P-6), (X′-1) or (X′-2) 100 g
330 g of polyoxyethylene glycol (Macrogol 400)
Methyl ethyl ketone 100mL
450 mL of ethanol
Purified water Total 1000mL
(Preparation method)
Each component was mixed and dissolved, and purified water was added to adjust the total amount to 1000 ml to prepare a liquid.

Examples 7 to 12 and Comparative Examples 3 and 4 (aerosol formulation);
Emulsions (P-1) to (P-6), (X'-1) or (X'-2) 30 g
50g ethanol
Purified water 100mL
Propellant: 100 mL dimethyl ether
(Preparation method)
The emulsion was mixed and dissolved in a base containing ethanol and purified water, filled into a container, then fitted with a valve, filled with a spray, to produce an aerosol.
It summarizes in Table 1 about the rough skin improvement evaluation of Examples 1-12 and Comparative Examples 1-4.

<Improves rough skin 1>
A test was conducted using 8 female employees (age 25-45 years old) using a rough skin model induced with an aqueous 5% by mass sodium lauryl sulfate (SLS) solution. Two 1.5 cmφ sites were provided on the inner side of the forearm, and the transcutaneously dissipated moisture (TEWL) was measured with “Tevameter TM300” manufactured by Integral. 0.05 g of TEWL prepared in Examples 1 to 6 and Comparative Examples 1 and 2 was applied to the inner side of the measured forearm so as to be 1.5 cmφ. Cosmetic cotton (for example, Silcot (Unicharm Co., Ltd.)) impregnated with 3.0 mL of 5% SLS aqueous solution was affixed to the inner side of the forearm. After 4 hours, the same operation was performed for 4 consecutive days (4 hours / day), and after 4 days, the cotton was peeled off and the skin surface was fixed with ion-exchanged water. After washing the surface, the skin surface was dried for 30 minutes in a room with an air temperature of 24 to 26 ° C. and a relative humidity of 62%, and TEWL was measured, and the difference between TEWL measured before the test and TEWL measured after the test was expressed as “ΔTEWL. The higher the “ΔTEWL”, the greater the progress of the rough skin. From the results of Table 1, the present invention has an effect of preventing or improving the rough skin. Rukoto is found.

<Rough skin improvement 2>
A test was conducted using 8 male employees (age 25 to 50 years old) using a rough skin model induced with an aqueous 5% by mass sodium lauryl sulfate (SLS) solution. Two 1.5 cmφ sites were provided on the inner side of the forearm, and the transcutaneously dissipated moisture (TEWL) was measured with “Tevameter TM300” manufactured by Integral. Cosmetic cotton (for example, Silcot (Uni./Uni) was sprayed for 3 seconds on the inner side of the forearm where the TEWL of the aerosol agents produced in Examples 7 to 12 and Comparative Examples 3 and 4 was measured, and impregnated with 3.0 mL of 5% SLS aqueous solution. (Made by Charm Co., Ltd.) was applied to the inner part of the forearm where TEWL was measured, and the applied cosmetic cotton was fixed with a medical tape (for example, 3M baby skin surgical tape 50 mm), and the tape was removed after 4 hours. 4 days later (4 hours / day) After 4 days, the cotton was peeled off, the skin surface that had been fixed was washed with ion exchange water, and then the skin surface was dried indoors for 30 minutes, TEWL was measured, and the difference between TEWL measured before the test and TEWL measured after the test was defined as “ΔTEWL”, which was used as an index of rough skin. There than. Table 1 results showing that in progress, the present invention is seen to have a rough skin preventing or ameliorating effect.

From the results in Table 1, it can be seen that the external preparations for skin obtained in Examples 1 to 12 of the present invention are excellent in rough skin improvement.

  The external preparation for skin of the present invention can be used as a medicine, a quasi-drug, a cosmetic, and a toiletry product, and as a member that can be transferred to the skin, a children's paper diaper, an adult paper diaper, a napkin, a pet sheet, panties It is useful for liners, incontinence pads, sweat-absorbing sheets, medical blood-absorbing articles, wound protection materials, wound healing agents, surgical waste liquid treatment agents, and the like.

Claims (5)

  Active hydrogen-containing compound (A) containing active amine-containing compound (a) containing tertiary amine group (salt) and / or active hydrogen-containing compound (b) containing quaternary ammonium base and polyisocyanate compound A skin external preparation containing a polyurethane resin and / or a polyurea resin (P) containing (B) as a structural unit. The skin external preparation according to claim 1, wherein the content of the tertiary amine group (salt) and / or the quaternary ammonium base is 0.01 to 3 mmol / g based on the weight of the polyurethane resin and the polyurea resin. The skin external preparation according to claim 1 or 2, wherein (a) is a compound represented by the general formula (1) or a salt thereof.

(Wherein R ¹ , R ² and R ³ may be the same or different and each represents a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyalkyl group, a mercaptoalkyl group, a carboxylalkyl group or an aminoalkyl group; (At least one of R ¹ , R ² and R ³ is a hydroxyalkyl group, a mercaptoalkyl group or an aminoalkyl group.) (B) is a compound represented by General formula (2), The skin external preparation of any one of Claims 1-3.

(Wherein R ¹ , R ² and R ³ may be the same or different and each represents a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyalkyl group, a mercaptoalkyl group, a carboxylalkyl group or an aminoalkyl group; At least one of R ¹ , R ² and R ³ is a hydroxyalkyl group, a mercaptoalkyl group or an aminoalkyl group, R ⁴ is a hydrocarbon group or carboxyalkyl group having 1 to 24 carbon atoms, X is a halogen atom, Monoalkyl carbonic acid or monoalkyl sulfuric acid.)   The skin external preparation according to any one of claims 1 to 4, wherein the active hydrogen-containing compound (A) further contains a dihydric alcohol.