JP2007039340A - Antiseptic disinfectant and external composition for skin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiseptic microbicide in place of paraben conventionally used as the antiseptic microbicide and to provide compositions of an external preparation for skin and a hair cosmetic characterized as formulating the antiseptic microbicide. <P>SOLUTION: The use of a tyrosol derivative as the antiseptic microbicide composed thereof is provided. Furthermore, the external preparation for skin and cosmetic are characterized as formulating the tyrosol derivative as an essential ingredient. The tyrosol derivative is further preferably used in combination with phenoxyethanol. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antiseptic disinfectant comprising a tyrosol derivative, and an external preparation for skin and cosmetics comprising the same, and more specifically, the amount of tyrosol derivative, which is an antiseptic disinfectant having excellent antibacterial activity, and parabens The present invention relates to a highly safe external skin preparation and cosmetics.

  Tyrosol is produced from tyrosine by the action of yeast during alcoholic fermentation of sugar. For example, it is included as a bitter ingredient in brewed sake such as sake and wine. Hydroxytyrosol has been proposed as an applied technology as an inhibitor of melanin production and as an antioxidant. (See Patent Document 1)

  On the other hand, conventionally, parabens such as methylparaben, ethylparaben, propylparaben, butylparaben and the like are frequently used as antiseptic fungicides in cosmetics, quasi drugs, and pharmaceuticals. In recent years, parabens have been considered to be a risk of breast cancer and effects on reproductive tissues as skin irritation and estrogen biological activity (Non-Patent Documents 1 and 2), and an alternative is desired from the viewpoint of safety. .

Therefore, various methods such as blending of plant extracts and blending of alkanediols such as 1,2-pentanediol and 1,2-pexanediol have been proposed as weight reduction and alternatives for parabens (Patent Documents 3 to 6). . In recent years, the application of phenoxyethanol on the positive list is also increasing. However, these ingredients affect the texture and stability of the preparation, and the amount of use may be limited due to the problem of odor preference.
Japanese Patent Laid-Open No. 8-119855 JP 11-310506 A JP-A-8-73364 JP-A-8-73368 Japanese Patent Laid-Open No. 10-182333 JP-A-10-203955 JP 2005-15361 A P. D. Darbre, A .; Aljarrah et al., J. MoI. Appl. Toxicol. 24,5-13,2004 Cristina Lemini et al., Toxicology and Industrial Health 2003, 19, 69-79

In the above circumstances, there has been a demand for an antiseptic and bactericidal agent that is easy to be blended into a preparation, has no unique odor, has a wide antibacterial spectrum, and is stable in the preparation. That is, the object of the present invention is to provide an antiseptic and bactericidal agent in place of parabens and to prepare an external preparation for skin and cosmetics characterized by blending the components.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the tyrosol derivative represented by the following general formula (1) has antiseptic sterilizing power and is formulated with this component. The present inventors have found that compositions and cosmetic compositions possess effective preservative power and have completed the present invention. That is, the present invention relates to an excellent antiseptic disinfectant comprising a tyrosol derivative. The present invention also relates to an external preparation for skin and a cosmetic comprising the tyrosol derivative as an antiseptic disinfectant.

式中、Ｒは水素原子又は炭素数２〜１０のアシル基である。

In the formula, R is a hydrogen atom or an acyl group having 2 to 10 carbon atoms.

  The tyrosol derivative of the present invention has antibacterial activity against bacteria, yeasts and sputum. In addition, parabens are used in the external composition for skin and cosmetics containing 0.01 to 1% by mass (hereinafter simply referred to as%) of the tyrosol derivative of the present invention, preferably 0.05% or more as an essential component. The effective antiseptic sterilization power can be possessed.

  Among the compounds represented by the general formula (1) used in the present invention, those in which R is an acyl group having 2 to 10 carbon atoms can be obtained by a method already known as acylation of a phenol compound. For example, it can be easily obtained by reacting 2- (4-hydroxyphenyl) ethyl alcohol and acid chloride in pyridine. In addition, as an acyl group, even if it has an unsaturated bond inside, there is no problem and you may have an aromatic ring. Moreover, you may have functional groups, such as an amino group. Specific examples include acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, lauroyl, palmitoyl, oleoyl and the like. Among these, acetyltyrosol and propionyltyrosol are preferable from the viewpoint of effects, and propionyltyrosol is particularly preferable.

  The tyrosol derivative according to the present invention has an excellent antiseptic effect equivalent to paraben, but in combination with a chelating agent such as alcohol, phenoxyethanol, dipropylene glycol or butylene glycol, alkanediol, sodium edetate, The synergistic effect can increase the antiseptic effect. In particular, the combined use with phenoxyethanol is preferable from the viewpoint of the effect. In addition, tyrosol derivatives, particularly monoacetyltyrosol, do not have a specific odor, and can be easily and stably blended into skin external preparations and cosmetics.

The tyrosol derivative according to the present invention has an excellent antiseptic effect, and can be used for various products for which antiseptics or bactericides such as parabens have been conventionally used. For example, pharmaceuticals, quasi drugs, cosmetics It can be used for various skin external preparations such as a preparation.

  Cosmetics using the tyrosol derivative of the present invention can be used for various cosmetics without any limitation. For example, basic cosmetics such as skin lotion, cream, milky lotion, sunscreen cream, sunscreen milky lotion, sunscreen lotion, foundation Makeup cosmetics such as oils, packs, facial cleansers, body soaps, shaving lotions, nail cosmetics, eyebrow cosmetics, perfumes, oral products, deodorant preparations, bath preparations, shampoos, rinses, hair Hair cosmetics such as tonics, hair styling agents, hair dyes and hair coloring agents can be used. Moreover, what is necessary is just to mix | blend by a conventional method in the case of a mixing | blending.

  Furthermore, the tyrosol derivative according to the present invention can be blended in fiber products, cotton yarn products, nonwoven fabric impregnated products, and aerosol products.

  Various components generally used in cosmetics, quasi drugs, etc. within a range not impairing the effects of the present invention, such as animal and vegetable oils, mineral oils, ester oils, wax oils, silicone oils, higher alcohols, lower alcohols, Phospholipids, fatty acids, anionic surfactants, cationic surfactants, amphoteric surfactants or nonionic surfactants, vitamins, UV absorbers, antioxidants, glycerin, 1,3-butylene glycol, propylene glycol , Dipropylene glycol, polypropylene glycol, ethylin glycol, diethylene glycol, polyethylene glycol, diglycerin, maltitol, xylitol, sucrose, glucose, raffinose, hyaluronic acid and its salts, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, Arabic , Alginic acid (salt), carrageenan, agar, guar gum, quince seed, tamarind gum, dextrin, dextran, starch, locust bean gum, caraya gum, tragacanth gum, pectin, quince, chitosan, xanthan gum, gellan gum, hyaluronic acid (salt), pullulan , Methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, cationized cellulose, polyacrylic acid amide, polyvinyl alcohol, polyvinylpyrrolidone, hyaluronic acid, chondroitin 4 sulfate, chondroitin 6 sulfate, dermatan sulfate, chondroitin 4 , 6 disulfate, dermatan 4,6 disulfate, keratan sulfate, hevalan sulfate Examples of salts thereof include potassium salts and sodium salts of these mucopolysaccharides, water-soluble polymers, pH adjusters, coloring agents, fragrances, animal and plant proteins and their degradation products, animal and plant polysaccharides and their salts. Degradation products, microorganism culture metabolic components, blood flow promoters, anti-inflammatory agents, anti-inflammatory agents, emulsifiers, anti-allergic agents, cell activators, amino acids and their salts, keratolytic agents, astringents, foam enhancers, oral preparations, It can be blended with a deodorant / deodorant.

・ Production Example 1
(Production of acetyltyrosol)
Tyrosol (5.0 g) was placed in a 200 mL eggplant-shaped flask, 100 mL of anhydrous ether was added, and the mixture was stirred under ice cooling. Further, 1.0 mL of pyridine and 4.0 g of acetyl chloride were sequentially added, and after 4 hours, post-treatment was performed according to a conventional method to obtain 4.3 g of a crude product.

  The obtained product was fractionated by silica gel chromatography (mobile phase: ethyl acetate / n-hexane = 1: 4) using silica gel 60N (100-210 μm) manufactured by Kanto Chemical Co., and 4.2 g of acetyltyrosol was obtained. Obtained

(Identification of acetyltyrosol)
The purified acetyltyrosol was confirmed by ¹ H, ¹³ C-NMR (100 MHz, CDCl ₃ ), and the following results were obtained.

^{By 1} H-NMR (400 MHz, CDCl ₃ ), the following signals [δ (ppm); 2.04 (s, 3H), 2.86 (t, J = 4.0 Hz, 2H), 4.24 (t, J = 4.0 Hz, 2H), 6.78 (d, J = 8.0 Hz, 2H), 7.04 (d, J = 8.0 Hz, 2H)].

^{By 13} C-NMR (100 MHz, CDCl ₃ ), the following signal [δ (ppm); 21.0, 34.1, 65.6, 115.5, 129.3, 129.9, 154.7, 172. 1] was detected.

Test example 1
The antibacterial activity test results of tyrosol derivatives and parabens against various microorganisms are shown. In addition, the thing manufactured according to the manufacture example 1 was used for the acetyltyrosol according to the manufacture example 1, and the other samples were used.

(Test method for antibacterial activity) Disperse the test bacteria cultured by the method shown in the Japanese Pharmacopoeia in 0.1% peptone salt solution to prepare a bacterial solution containing about 10 ⁶ cells / mL viable bacteria or spores. did. Next, the sample was dissolved in dimethyl sulfoxide (hereinafter referred to as DMSO) to prepare a sample. The prepared bacterial solution is streaked on a plate agar medium in which 5% sample and 1.5% agar are added to the medium used for culturing the test bacteria, and stored at the optimum temperature for each bacterial species. It was measured.

Test example 2
In the same manner as in Test Example 1, the growth inhibitory concentration when phenoxyethanol and monoacetyltyrosol were used in combination was measured. The results are shown below.

Test example 3
The results of the antiseptic sterilization effect confirmation test using the above-mentioned bacterial species in the cream formulation shown in the below-mentioned Formulation Example 1 are shown below. The test was conducted according to the preservation efficacy test listed in the Japanese Pharmacopoeia reference information. Judgment was made as “preservative” if a decrease in the number of bacteria of 99.9% or more was observed 7 days after the inoculation and the level was maintained after 4 weeks. Furthermore, also in the prescription examples 2-48, all showed sufficient antiseptic effect in the range of 0.01 to 1% of compounding amounts.

Preservative Formulation Example 1 Formulation Example 2 Formulation Example 3
Monoacetyltyrosol 0.2% 0% 0%
Methylparaben 0% 0% 0.15%
Ethylparaben 0% 0% 0.05%
---------------------------------
Antiseptic Yes No Yes

・ Cream (A) Stearic acid 1
Glycerol monoisostearate 2
Behenyl alcohol 2
Sarah Beeswax 1
Isocetyl myristate 1
Sorbitan isostearate 1
Retinyl palmitate 0.1
Hydrogenated lecithin 0.1
Ubidecarenone 0.03
Phytosterol 0.1
Plant Squalane 5
Dicapryl carbonate 5
(B) Preservatives
1,3-butylene glycol 5
Concentrated glycerin 5
N-acetylglucosamine 0.1
Ascorbic acid sulfate disodium salt 0.2
γ-aminobutyric acid 0.1
Sodium N-stearoyl glutamate 0.2
Monoammonium glycyrrhizinate 0.1
Edelweiss Extract 0.2
Yeast extract (Note 1) 0.2
Alkyl-modified carboxyvinyl polymer 0.05
Nicotinamide 0.1
Creatine 0.2
Carnitine chloride 0.1
Ascorbic acid phosphate magnesium 0.1
Purified water balance
Note 1) Dismutin BTJ (Penta Farm)

・ Prescription Example 2 (Cream)
(A) Isostearic acid 1
Glycerol monoisostearate 2
Behenyl alcohol 2
Sarah Beeswax 1
Isocetyl myristate 1
Sorbitan isostearate 1
Retinyl palmitate 0.1
Hydrogenated lecithin 0.1
Ubidecarenone 0.03
Phytosterol 0.1
Plant Squalane 5
Dicapryl carbonate 5
(B) Propionyltyrosol 0.2
Methyl paraoxybenzoate 0.2
1,3-butylene glycol 10
Concentrated glycerin 5
N-acetylglucosamine 0.1
Ascorbic acid sulfate disodium salt 0.2
γ-aminobutyric acid 0.1
Sodium N-stearoyl glutamate 0.2
Monoammonium glycyrrhizinate 0.1
Edelweiss Extract 0.2
Yeast extract (Note 1) 0.2
Alkyl-modified carboxyvinyl polymer 0.05
Nicotinamide 0.1
Creatine 0.2
Carnitine chloride 0.1
Ascorbic acid phosphate magnesium 0.1
Purified water balance
Note 1) Dismutin BTJ (Penta Farm)

・ Prescription Examples 3-5 (Sunscreen)
Formulation Example 3 4 5
---------------------------------------
Dioctyl ether 22 15 10
Co-modified silicon (Note 2) 2 2 2
Glyceryl tri-2-ethylhexanoate 0 0 0.5
Hardened oil 0 0 0.1
Methylphenylpolysiloxane 0 3 0
Macadamia nut fatty acid phytosteryl 0 0 2
Titanium oxide 5 0 4
Zinc oxide 5 0 4
Acetyltyrosol 0.1 0.1 0.1
Phenoxyethanol 0.3 0.3 0.3
Magnesium chloride 1 1 1
1,3-butylene glycol 5 5 5
Royal Jelly Extract 1 1 1
Aloe extract 0.1 0.1 0.1
Oat extract 0.5 0.5 0.5
Yeast extract (Note 1) 1 1 1
Purified water remaining amount remaining amount remaining amount

Note 1) Dismutin BTJ (Penta Farm)
Note 2) ABIL EM90 manufactured by Goldschmidt

・ Prescription Examples 6-8 (Cosmetics)
Formulation Example 6 7 8 --------------------------------------
Co-modified silicon (Note 2) 2 2 2
POE-modified silicon dispersion (Note 3) 0 2 0
Squalane 0 0 10
Decamethylcyclopentasiloxane 15 20 10
Methyl polysiloxane 5 2 3
Long-chain branched fatty acid cholesteryl (Note 4) 0 0 2
Silicon elastomer dispersion (Note 5) 5 2 0
Propionyltyrosol 0.05 0.05 0.05
P-Hydroxybenzoic acid butyl ester 0.05 0.05 0.05
Sodium chloride 1 1 1
Dipropylene glycol 5 5 5
Concentrated glycerin 5 5 5
Raffinose 1 1 1
Mixed isomerized sugar 1 1 1
Licorice extract 0.1 0.1 0.1
N-methyl-L-serine 0.5 0.5 0.5
Purified water remaining amount remaining amount remaining amount
Note 2) ABIL EM90 manufactured by Goldschmidt
Note 3) Silicon BY22-008 manufactured by Toray Dow Corning Silicone
Note 4) YOFCO CLE-NH manufactured by Nippon Seika Co., Ltd.
Note 5) Toray Fill made by Toray Dow Corning Silicone

・ Prescription examples 9 to 11 (lotion)
Formulation Example 9 10 11 ---------------------------------------
Acetyltyrosol 0.2 0.1 0.5
Phenoxyethanol 0.2 0.2 0.2
1,3-butylene glycol 0.1 0.3 0.3
Dipropylene glycol 5 0 5
Raffinose 0 5 5
Hyaluronic acid dimethylsilanol solution (Note 6) 0.1 0.1 0.1
MPC polymer (Note 7) 0.1 0.1 0.1
Niga mint extract 0.1 0.1 0.1
Ethanol 0 0 1
Pectin 0 0 0.05
Xanthan gum 0 0 0.01
Sodium citrate 0.05 0.05 0.05
Horsetail extract 0.1 0.1 0.1
Diisopropylamine dichloroacetate 0.2 0.2 0.2
γ-amino-β-hydroxybutyric acid 0.2 0.2 0.2
Sodium hyaluronate 0.001 0.001 0.001
Dipotassium glycyrrhizinate 0.2 0.2 0.2
Pentapeptide-3 (Note 8) 0.05 0.05 0.05
Decarboxycarnosine hydrochloride 0.05 0.05 0.05
Perfume 0.02 0.02 0.02
Purified water remaining amount remaining amount remaining amount
Note 6) DSHC-N (manufactured by EXYMOL)
Note 7) Lipidur PMB (Nippon Yushi Co., Ltd.)
Note 8) MATRIXYL (manufactured by Croda Japan)

Formulation examples 12-14 (aqueous mascara)
Formulation example 12 13 14
----------------------------------------
Polyvinyl alcohol 10.0 5.0 10.0 Carboxyvinyl polymer (Note 9) 0.5 0 0.5 Hydroxypropylcellulose 0 2 0 Alkyl acrylate copolymer emulsion (2)
(Note 10) 0 10 20 1,3-butylene glycol 5.00 5.0 propylene glycol 0 5.00 triethanolamine 0.6 0 0.6 ethanol 5.00 5.0 purified water remaining amount remaining Amount Residual amount Acetyltyrosol 0.2 0.2 0.2 Methylparaben 0.1 0.1 0.1 Blue No. 1 0.1% aqueous solution 0 0.1 0.1 Nylon powder 0 1.0 1.0 Fluorescence PET / Al / epoxy laminated powder (Note 11) 0 0 2 Fluorescent PET / Polymethylmethacrylate
Laminated powder (Note 12) 1.0 3.0 5.0 PET / Polymethylmethacrylate
Laminated powder (Note 13) 0 5.0 2.0
Note 9) Carbopol 941 (manufactured by BF Goodrich)
Note 10) Iodosol (NSC Japan)
Note 11) Diamond hologram HG701-10EP (manufactured by Dia Kogyo Co., Ltd.)
Note 12) Rainbow Flake II No. 501-S Fluorescent type (Diamond Industry Co., Ltd.)
Note 13) Crystal color X-701-10 (Diamond Industry Co., Ltd.)

・ Prescription examples 15 to 17 (lip gloss)
Formulation Example 15 16 17
----------------------------------------
Dextrin palmitate 3.0 3.0 3.0
Heavy liquid isoparaffin Residual amount Residual amount Residual amount Isononyl isooctanoate 10.0 10.0 10.0
Squalane 5.0 5.0 5.0
Red No. 201 0 0.2 0.2
Gunjo Pink 0 0.5 0.5
Barium sulfate 0.1 2.0 2.0
Titanium oxide 0.5 0.5 0.5
Mica titanium 3.0 3.0 3.0
Fluorescent PET / Polymethylmethacrylate
Laminated powder (Note 14) 1.0 3.0 5.0
PET / Al / epoxy laminated powder (Note 15) 0 0 2.0
Acetyltyrosol 0.01 0.01 0.01 Phenoxyethanol 0.05 0.05 0.05
Note 14) Rainbow Flake II No. 501-S Fluorescent type (Diamond Industry Co., Ltd.)
Note 15) Diamond hologram HG5EP (manufactured by Diamond Industrial Co., Ltd.)

・ Prescription examples 18 to 21 (oil-based foundation)
Formulation Example 18 19 20 21
----------------------------------------
Carnauba wax 3.0 3.0 3.0 3.0 Candelilla wax 4.0 4.0 4.0 4.0 Microcrystalline wax 3.0 3.0 3.0 3.0 Hydrogenated polybutene 0 8.0 8.0 8.0 Tri (Capryl / Capric acid)
Glycerin remaining amount remaining amount remaining amount remaining amount isononyl isononanoate 20.0 20.0 20.0 20.0 zinc stearate 3.0 3.0 3.0 3.0 titanium oxide 12.0 12.0 12.0 12.0 Bengala 0.5 0.5 0.5 0.5 Yellow iron oxide 1.5 1.5 1.5 1.5 Black iron oxide 0.2 0.2 0.2 0.2 Nylon powder 5. 0 5.0 5.0 5.0 Sericite 15.0 15.0 15.0 15.0 Talc 5.0 5.0 5.0 5.0 Cellulose phosphor (Note 16) 1.0 5.0 0 0
Cellulose phosphor (Note 17) 0 3.0 0 0 Alkyl acrylate 0 0 5.0 0 Calcium tungstate phosphor 0 0 0 10.0 Acetyltyrosol 0.01 0.01 0.01 0.01 Methyl paraben 0 .1 0.1 0.05 0.05
Note 16) ILLUMI YARN No. 13-03 White (Diamond Industry Co., Ltd.)
Note 17) ILLUMI YARN No. 25-05 White (Diamond Industry Co., Ltd.)

・ Prescription examples 22-25 (powder eye shadow)
Formulation Example 22 23 24 25
----------------------------------------
Talc 15.0 15.0 15.0 15.0 Mica Remaining amount Remaining amount Remaining amount Remaining amount Nylon powder 5.0 5.0 5.0 5.0 Barium sulfate 10.0 10.0 10.0 10.0 Gun 3.0 3.0 3.0 3.0 3.0 Red 226 0.5 0.5 0.5 0.5 Yellow iron oxide 5.0 5.0 5.0 5.0 Titanium oxide 1.0 0 1.0 1.0 Titanium mica 5.0 5.0 5.0 5.0 5.0 Methylphenylpolysiloxane 3.0 3.0 3.0 3.0 Octyldodecanol 5.0 5.0 5.0 5 0.0 Petrolatum 2.0 2.0 2.0 2.0 Fluorescent PET / Al / Epoxy laminated powder (Note 18) 1.0 0 3.0 0 Fluorescent PET / Polymethylmethacrylate
Laminated powder (Note 19) 0 3.0 3.0 0 PET / Al / Epoxy laminated powder (Note 20) 0 0 2.0 3.0 Zinc oxide phosphor 0 0 0 3.0 Acetyltyrosol 0.1 0 .1 0.1 0.1 Butylparaben 0.05 0.05 0.05 0.05
Note 18) Diamond beads CO-3EP Silver Fluorescent type (Diamond Industry Co., Ltd.)
Note 19) Rainbow Flake II No.501-S No. 7 Fluorescent type (Diamond Industry Co., Ltd.)
Note 20) DC Glitter Silver C (0.001) (Diachemco)

・ Prescription examples 26 to 29 (emulsification type eye shadow)
Formulation Example 26 27 28 29
------------------------------------ Stearic acid 3.0 3.03. 0 3.0
Cetyl alcohol 2.5 2.5 2.5 2.5
Isononyl isooctanoate 3.0 3.0 3.0 3.0
Acetyltyrosol 0.5 0.5 0.5 0.5
Methylparaben 0.05 0.1 0.05 0.1
Propylene glycol 3.0 3.0 3.0 3.0
Triethanolamine 1.5 1.5 1.5 1.5
Hydroxyethyl cellulose 0.5 0.5 0.5 0.5
Purified water remaining amount remaining amount remaining amount remaining
Titanium oxide 1.0 1.0 1.0 1.0
Gun 1.0 1.0 1.0 1.0 1.0
Mica titanium 8.0 8.0 8.0 8.0
Talc 2.0 2.0 2.0 2.0
Fluorescent PET / Polymethylmethacrylate
Laminated powder (Note 21) 1.0 0 5.0 0
Cellulose phosphor (Note 22) 0 5.0 2.0 0
PET / Polymethylmethacrylate
Laminated powder (Note 23) 0 3.0 1.0 3.0
1-hydroxy-3,6,8-pyrene
Trisodium trisulphonate
Phosphor 0 0 0 0.01

Note 21) Rainbow Flake II No.501-S No. 7 Fluorescent type (Diamond Industry Co., Ltd.)
Note 22) ILLUMI YARN No. 13-03 White (Diamond Industry Co., Ltd.)
Note 23) Crystal color X-701-10 (Diamond Industry Co., Ltd.)

Formulation examples 30 to 32 (water-in-oil mascara)
Formulation Example 30 31 32
--------------------------------------- Light liquid isoparaffin Remaining amount Remaining amount Remaining amount
Decamethylcyclopentasiloxane 5.0 5.0 5.0
Trimethylsiloxysilicic acid 5.0 5.0 5.0
Beeswax 10.0 10.0 10.0
Carnauba wax 5.0 5.0 5.0
Rosin acid pentaerythrit 0 0 0.5
Eicosene vinylpyrrolidone copolymer 3.0 1.0 5.0
Hexadecene / vinylpyrrolidone copolymer 0 1.5 0
Vinyl acetate / allyl stearate copolymer 3.0 0 1.0
Dextrin palmitate 3.0 5.0 5.0
Dimethyl distearyl ammonium
Hectorite 1.0 1.0 1.0
Sorbitan monoisostearate 1.0 1.0 1.0
Polyoxyethylene methylpolysiloxane
Copolymer 0 1.0 0
Lecithin 0.5 0.5 0.5
Polyglyceryl diisostearate 1.0 0 3.0
Purified water 15.0 5.0 20.0
Alkyl acrylate copolymer emulsion 0 0 3.0
Polyvinyl acetate emulsion 1.0 1.0 1.0
Polyvinyl alcohol 1.0 1.0 1.0
1,3-butylene glycol 1.0 1.0 1.0
Sodium citrate 0.5 0.5 0.5
Hydroxyethyl cellulose 0.5 0.5 0.5
Talc 1.0 1.0 1.0
Black iron oxide 5.0 5.0 5.0
Nylon powder (1mm, 5 denier) 0 0 1.0
Silicic acid 0 0 1.0
Mica titanium 1.0 1.0 1.0
Acetyltyrosol 0.4 0.4 0.4
Methylparaben 0.1 0.1 0.1

・ Prescription Example 33 (Powder Foundation)
Dimethylpolysiloxane 4.0
Isononyl isononanoate 2.0
3-ethylhexyl hydroxystearate 2.0
2-Ethylhexyl paramethoxycinnamate 2.0
Acetyltyrosol 0.1
Methylparaben 0.1
Nε-lauroyl-L-lysine-treated Bengala 0.5
Nε-lauroyl-L-lysine-treated yellow iron oxide 2.0
Nε-lauroyl-L-lysine-treated black iron oxide 0.3
Titanium oxide treated with ferrous myristate 20.0
Silicon treated fine particle titanium oxide 5.0
Silicone hemp cellulose powder 10.0
Silicon-treated synthetic phlogopite 20.0
Zinc myristate-treated sericite 27.0
Polyalkyl acrylate 5.0

Formulation example 34 (emulsification foundation)
Sorbitan monoisostearate 1.0
Polyether-modified silicone 1.0
Decamethylcyclopentasiloxane 20.0
Liquid paraffin 5.0
Propylene glycol dicaprylate 2.0
Glycerin 3.0
Acetyltyrosol 0.2
Methylparaben 0.1
Purified water remaining amount Titanium oxide 10.0
Bengala 0.2
Yellow iron oxide 0.8
Black iron oxide 0.1
Talc 0.9
Cross-linked silicone powder 2.0

・ Prescription Example 35 (Loose Powder)
Liquid paraffin 3.0
Acetyltyrosol 0.2
Methylparaben 0.1
Bengala 0.2
Yellow iron oxide 0.2
Talc 50.0
Mica 26.3
Plate-like barium sulfate 10.0
Spherical silica 5.0
Nylon powder 5.0

・ Prescription Example 36 (Setting Lotion)
Highly polymerized polyethylene glycol (Note 24) 0.2
Polyethylene glycol (Note 25) 10.0
Polyoxyethylene / methylpolysiloxane copolymer (Note 26) 1.0
Ethanol 15.0
Polyvinylpyrrolidone 0.1
Acetyltyrosol 0.1
Methylparaben 0.1
Remaining pure water Note 24) POLYOXWSR-303 (manufactured by Union Carbide)
Note 25) PEG # 200 (manufactured by NOF Corporation)
Note 26) Silicon SS-2804 (manufactured by Toray Dow Corning Silicone)

・ Prescription Example 37 (hair cream)
Polyoxyethylene cetyl ether (7EO) 2.0
Polyoxyethylene hydrogenated castor oil (60 EO) 1.5
2-palmitoyloxystearic acid isopropyl ester 1.0
Diglyceryl adipate mixed fatty acid ester (Note 27) 0.5
Liquid paraffin 20.0
Stearyl alcohol 3.0
Propylene glycol 2.5
Methylphenylpolysiloxane 2.0
(100,000 mm ₂ / s; 25 ° C.)
Guar gum 0.5
Acetyltyrosol 0.2
Phenoxyethanol 0.1
Perfume proper amount Purified water remaining amount

Note 27) SOFTISAN 649 (manufactured by SASOL Germany)

・ Prescription example 38 (hair foam)
(Stock solution composition) (mass%)
・ Ethanol 10.0
Stearyl trimethyl ammonium chloride 1.0
・ Triethyl citrate 3.0
・ Polyoxyethylene hydrogenated castor oil (80 EO) 0.5
・ Methylphenyl polysiloxane 2.0
(100,000 mm ₂ / s; 25 ° C.)
・ Quaternized polyvinylpyrrolidone derivative 2.0
(Product name: GAFQUAT755N [manufactured by ISP])
・ Undecylenic acid trehalose 0.5
Acetyltyrosol 0.1
・ Methylparaben 0.1
・ Purified water balance

(Gas composition ratio)
Stock solution 90.0
LPG 7.0
DME 3.0

・ Prescription example 39 (styling form)
(Stock solution composition) (mass%)
・ Highly polymerized polyethylene glycol 0.02
(POLYOX WSR-308 (manufactured by Union Carbide))
1,3-butylene glycol 0.5
・ Stearic acid 1.5
・ Ethanol 10.0
・ Triethanolamine 0.5
・ Cetanol 0.3
・ Propylene glycol 3.5
・ Polyoxyethylene cetyl ether 1.0
(BC-15TX (Nikko Chemicals))
・ Polyoxyethylene hydrogenated castor oil 0.5
(HCO-80 (Nikko Chemicals))
・ Polymethylsiloxane 2.0
(Silicon L-45 (Toray Dow Corning Silicone))
・ Methylphenyl polysiloxane 5.0
(Silicon KF-56 (Shin-Etsu Chemical Co., Ltd.))
Castor oil 1.0
・ Ethylglucoside solution 0.1
・ Fragrance 0.3
Acetyltyrosol 0.2
・ Butylparaben 0.1
・ Pure water balance

(Gas composition ratio)
Stock solution 90.0
LPG 7.0
DME 3.0

・ Prescription Example 40 (styling gel)
(Composition) (Component)
(mass%)
・ Highly polymerized polyethylene glycol 0.3
(RITA PEO-27 (manufactured by RITA))
・ Polyoxyethylene ・ methylpolysiloxane copolymer 0.2
(Silicon KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.))
・ Ethanol 20.0
・ Polyvinylpyrrolidone 1.0
・ N-methacryloylethyl N, N-dimethyl
Ammonium α-N-methylcarboxybetaine
・ Alkyl methacrylate copolymer 2.0
(Yuka Former 301 (Mitsubishi Chemical Corporation))
・ Sorbitol 3.0
・ Carboxyvinyl polymer 0.5
・ Triethanolamine 0.4
・ Polyoxyethylene hydrogenated castor oil 0.3
(HCO-60 (Nikko Chemicals))
・ Hydrolyzed wheat powder 0.1
(GLUADIN W20 (manufactured by Cognis Japan))
・ Perfume 0.1
Acetyltyrosol 0.1
・ Phenoxyethanol 0.1
・ Pure water

・ Prescription Example 41 (styling wax)
(Composition) (Component)
(mass%)
・ Highly polymerized polyethylene glycol 0.2
(POLYOX WSR-303 (manufactured by Union Carbide))
・ Stearic acid 2.0
-Liquid paraffin 35.0
・ Potassium hydroxide 0.1
・ Cetanol 2.8
・ Propylene glycol 6.0
・ Salah beeswax 4.0
・ Microcrystalline wax 1.0
Self-emulsifying glyceryl monostearate 3.8
(MGS-BSE (manufactured by Nikko Chemicals))
・ Polyoxyethylene cetyl ether 3.0
(BC-30TX (Nikko Chemicals))
・ Polyoxyethylene oleyl ether 1.2
(BO-2 (Nikko Chemicals))
・ Polyethylene glycol monostearate 0.2
(MYS-10 (Nikko Chemicals))
・ Polymethylsiloxane 2.0
(Silicon KF-96A (100cs) (manufactured by Shin-Etsu Chemical Co., Ltd.))
・ Sorbitol 0.1
・ Fragrance 0.3
Acetyltyrosol 0.2
・ Phenoxyethanol 0.2
・ Pure water balance

・ Prescription Example 42 (styling wax)
(Composition) (Ingredient; Mass%)
・ Oil-swelling clay mineral 5.0
(BENTONE 38V (manufactured by NL CHEMICAL))
・ Octildodecanol 35.0
・ Methylpolysiloxane network polymer 5.0
(Tospearl 2000 (GE Toshiba Silicone))
・ Stearic acid 2.0
・ Vaseline 20.0
・ Salah beeswax 8.0
・ Potassium hydroxide 0.1
・ Cetanol 2.0
・ Microcrystalline wax 1.0
・ Self-emulsifying glyceryl monostearate 3.0
(MGS-BSE (manufactured by Nikko Chemicals))
・ Polyoxyethylene cetyl ether 2.5
(BC-15TX (Nikko Chemicals))
・ Polyoxyethylene lauryl ether 1.5
(BL-2 (Nikko Chemicals))
・ Polyethylene glycol monostearate 0.3
(MYS-10 (Nikko Chemicals))
・ Polymethylsiloxane 1.0
(Silicon KF-96A (100cs) (manufactured by Shin-Etsu Chemical Co., Ltd.))
・ Sage extract 0.1
・ Fragrance 0.3
・ Paraoxybenzoic acid ester 0.2
Acetyltyrosol 0.2
・ Pure water

・ Prescription example 43 (hair shampoo)
(mass%)
-POE (3) sodium lauryl ether sulfate 8.0
-Lauryl sulfate triethanolamine 10.0
・ Lamidate amidopropyl betaine 5.0
・ Lauric acid isopropanolamide 3.0
・ Dimethylpolysiloxane 2.0
(100,000 mm ₂ / s; 25 ° C.)
-Cationized cellulose derivative 0.1
(Kachinar HC-200 [manufactured by Toho Chemical Industry Co., Ltd.])
・ Undecylenic acid trehalose 1.0
・ Hydrolyzed conchiolin solution 1.0
(Pearl protein extract [Maruzen Pharmaceutical Co., Ltd.])
・ Hydrolysis silk solution 1.0
(Promoise Silk-1000 [Nariwa Kasei Co., Ltd.])
Acetyltyrosol 0.2
・ Sodium benzoate 0.1
・ Perfume proper amount ・ Purified water balance

・ Prescription Example 44 (Full body (both hair and body) shampoo)
(mass%)
-POE (2) sodium lauryl ether sulfate 5.0
・ Ammonium lauryl sulfate 5.0
・ N-coconut oil fatty acid acyl-L-guru
Triethanolamine tamate 4.0
2-alkyl-N-carboxymethyl-N-hydroxyethyl
Imidazolinium betaine 3.0
・ Lauric acid isopropanolamide 1.0
・ Ethylene glycol distearate 1.0
-Lauric acid polyoxyethylene glycerin 1.0
(Cetiol HE [manufactured by Cognis])
-Cationized cellulose derivative 0.1
(Kachinar HC-200 [manufactured by Toho Chemical Industry Co., Ltd.])
・ Wheat hydrolyzate 1.0
(GLUADIN W20 [made by Henkel])
・ Hydrolyzed conchiolin solution 1.0
(Pearl protein extract [Maruzen Pharmaceutical Co., Ltd.])
・ Hydrolysis silk solution 1.0
(Promoise Silk-1000 [Nariwa Kasei Co., Ltd.])
Acetyltyrosol 0.3
・ Methylparaben 0.1
・ Perfume proper amount ・ Purified water balance

・ Prescription example 45 (body shampoo)
(mass%)
・ Potassium laurate 5.0
-Potassium palmitate 3.0
・ Potassium stearate 2.0
・ Sodium lauryl sulfate 5.0
2-lauroyl-N-carboxymethyl-N-
Hydroxyethyl imidazolinium betaine 7.0
-POE (1) Palm oil fatty acid isopropanolamide 2.0
Coconut oil fatty acid polyoxyethylene glycerin (7EO) 1.0
(Product name: Cethiol HE [manufactured by Cognis)]
-Cationized cellulose derivative 0.1
(Product name: Kachinar HC-200 [manufactured by Toho Chemical Industry Co., Ltd.])
・ Propylene glycol 2.5
Acetyltyrosol 0.2
・ Phenoxyethanol 0.2
・ Dye amount, perfume amount, purified water balance

・ Prescription example 46 (hair conditioner)
(mass%)
・ Alkyltrimethylammonium chloride 3.0
・ Cetyl alcohol 2.0
Arginine derivative 2.0
(Amisafe LMA-60 [Ajinomoto Co., Inc.])
・ Glycerin 5.0
・ Dimethylpolysiloxane 2.0
(1,000,000 mm ₂ / s; 25 ° C.)
・ Undecylenic acid trehalose 1.0
・ Propylene glycol 2.0
-Liquid paraffin 1.0
・ Wheat hydrolyzate 1.0
(GLUADIN W20 [made by Henkel])
Acetyltyrosol 0.2
・ Phenoxyethanol 0.2
・ Dye amount, perfume amount, purified water balance

・ Prescription example 47 (hair treatment)
(mass%)
・ Stearyl alcohol 10.0
・ Alkyltrimethylammonium chloride 2.0
・ Stearyltrimethylammonium chloride 2.0
・ Glycerin 2.0
・ Diglyceryl adipate mixed fatty acid ester 5.0
(SOFTISAN 649 [manufactured by SASOL Germany))
・ Vaseline 2.0
・ Methylphenyl polysiloxane 5.0
Dimethylpolysiloxane (500,000 mPa · s; 25 ° C.) 1.0
・ Arginine 0.5
・ Wheat hydrolyzate 1.0
(GLUADIN W40 [manufactured by Cognis)]
・ Soy protein hydrolyzate 1.0
(Hydro Soi 2000 [made by Croda Japan Co., Ltd.])
Acetyltyrosol 0.2
・ Sodium benzoate 0.1
・ Dye amount, perfume amount, purified water balance

・ Prescription example 48 (milky lotion)
(mass%)
Methylphenylpolysiloxane 3.0
Dicapryl carbonate 1.0
Olive oil 1.0
Medfoam oil 0.1
Monolauric acid polyoxyethylene (20) sorbitan 0.5
Nicotinic acid dlα tocopherol 0.01
Polyoxyethylene 100 hydrogenated castor oil 2.0
Shea fat (Croda Japan cropure SB) 0.01
Ascorbyl tetraisopalmitate 0.1
N-acetylglucosamine 0.02
Superoxide dismutase solution 3.0
(Dismutin BTJ-5000 manufactured by Penta Farm)
1,3-butylene glycol 3.0
Sorbitol solution 3.0
Polyethylene glycol 1000 1.0
Carboxyvinyl polymer 0.1
Japanese evening primrose extract 0.1
Methyl paraoxybenzoate 0.2
White jellyfish polysaccharide (Tremoisut-TP manufactured by Nippon Seika Co., Ltd.) 0.05
Edetate 0.02
Potassium hydroxide 0.05
Xanthan gum 0.05
Polyacrylic amide (Cosmedia SP manufactured by Cognis) 0.01
Kawara mugwort extract 0.3
Butyltyrosol 0.1
Green tea extract 0.1
Purified water balance

The fragrance | flavor used by said each prescription is the following.

  INDUSTRIAL APPLICABILITY According to the present invention, an external preparation for skin and a hair cosmetic that retains the antiseptic sterilizing effect with an antiseptic sterilizing agent that replaces parabens can be provided.

Claims (4)

An antiseptic fungicide comprising a tyrosol derivative represented by the following formula (1).

In the formula, R is a hydrogen atom or an acyl group having 2 to 10 carbon atoms. A skin external preparation comprising the tyrosol derivative according to claim 1. A cosmetic comprising the tyrosol derivative according to claim 1. The cosmetic according to claim 3, further comprising phenoxyethanol.