• 专利附录
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    • 专利摘要:
    When used on the skin as a detergent, it has a moist feeling and compares the concentration of the solubilizer, the emulsion or the dispersion in the solvent containing water with the concentration of the solubility, the emulsion or the dispersion. Solubilizers, emulsifiers and dispersants which have a property of improving the above-mentioned concentration in appearance and can be homogenized in an emulsified state or a dispersed state, and are represented by the general formula (R 1 , R 2 , R 3 : H, C in the side chain). A polymer formed by polymerizing a monomer composition containing a hydrophilic monomer (a) having a group represented by 1 to 4 alkyl groups) is contained as an active ingredient. (Formula 1)
    公开号:KR20000029452A
    申请号:KR1019997000416
    申请日:1997-07-30
    公开日:2000-05-25
    发明作者:시이노다이지로；와키가즈노리；나카바야시노부오；이시하라가즈히코
    申请人:우노 마사야스；닛폰 유시 가부시키가이샤；가와사키 마사히로；가가쿠 기쥬츠 신코 지교단；이시하라 가즈히코；나카바야시 노부오；
    IPC主号:
    专利说明:

    Solubilizers, emulsifiers and dispersants {SOLUBILIZERS, EMULSIFIERS AND DISPERSANTS}
    Various surfactants are widely used in various fields as detergents, solubilizers, emulsifiers, and dispersants. Examples of the solubilizer, the emulsion, and the dispersion include the contamination to be cleaned, fats and oils in the pharmaceutical field, drugs, and processed products.
    Conventionally, as the polymer surfactant, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene monolauryl ether, polyvinyl py Rollidone, carboxymethylcellulose, hydroxypropylcellulose, gelatin, gum arabic and the like are known. However, when these polymer surfactants are used on the skin as a detergent, they do not necessarily have a good effect on the skin, and in particular, they cannot give a moist feeling to the skin.
    In the pharmaceutical field, it is known that the various polymer surfactants are used as suspending agents or emulsifiers ("13th Edition Revised Japan Pharmacy Defense", Tokyo Hirokawa Bookstore, 1996).
    In addition, it is known that albumin, gelatin, starch or agar, which are bio-derived surfactants, may be used as drug carriers to enhance the apparent solubility of the drug. (Drug Development, Volume 13, Drug Delivery Method, Sesakijin Edit, Dora Published by Kawa Bookstore (1995) pp. 216-331). It is also known that polyethylene glycol polyamino acid block copolymers, which are non-biologically derived surfactants, can be used as drug carriers (see Japanese Patent Application Laid-Open No. 6-107565).
    The bio-derived surfactants have a problem that the safety is reduced by the admixture. The abiotic-derived surfactants have a problem of insufficient solubilizing power, emulsifying power, and dispersing power depending on the properties of the solubilized substance, the fluoride, and the dispersed product.
    However, homopolymers of 2-methacryloyloxyethylphosphorylcholine and copolymers of 2-methacryloyloxyethylphosphorylcholine with hydrophilic monomers and / or hydrophobic monomers moisturize the skin and improve rough skin. It is known to show an effect and to be used as a cosmetic (Japanese Patent Application Laid-Open No. 5-70321, Japanese Patent Application Laid-Open No. 6-157269, Japanese Patent Application Laid-Open No. 6-157270, Japanese Patent Application Laid-Open No. 6-157271). However, it is not known that these polymers exhibit solubilization, emulsification and dispersion.
    Disclosure of the Invention
    It is an object of the present invention to have a moist feeling when used on the skin as a detergent, and to determine the concentration of the solubilizer, the emulsion or the dispersion in the solvent containing water, the solubilizer, the emulsion or the dispersion. The present invention provides a solubilizer, an emulsifier, and a dispersant which have a property of increasing the concentration or making it uniform in an emulsified state or a dispersed state and improving the concentration in appearance.
    The present inventors have made a thorough review in view of the above problems and found that the polymer obtained by polymerizing a polymer of a hydrophilic monomer and a monomer composition containing a specific hydrophilic monomer and a hydrophobic monomer becomes an excellent solubilizer, emulsifier and dispersant. Completed.
    That is, according to the present invention, a hydrophilic monomer having a group represented by the formula (1) wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different groups (a). There is provided a solubilizer, emulsifier or dispersant containing a polymer obtained by polymerizing a monomer composition containing a) as an active ingredient.
    In addition, according to the present invention, 2- represented by the formula (2) wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different group as the hydrophilic monomer (a). 100 to 20% by weight of (methacryloyloxy) ethyl-2 '-(alkyl substituted or unsubstituted ammonio) ethyl phosphate, and formula 3 as a hydrophobic monomer (b) (wherein R 4 represents a hydrogen atom or a methyl group, A solubilizer, an emulsifier or a dispersant is provided which contains, as an active ingredient, a polymer obtained by polymerizing a monomer composition composed of 0 to 80% by weight of (meth) acrylate represented by R 5 represents an alkyl group having 4 to 8 carbon atoms.
    The present invention has a function of solubilizing, emulsifying or dispersing various compounds or materials, and relates to solubilizers, emulsifiers and dispersants that can be used in the fields of detergents, paints, chemicals, pharmaceuticals and the like.
    BRIEF DESCRIPTION OF THE DRAWINGS The graph which shows the measurement result of the critical micelle concentration of the polymer A performed by the reference example 1.
    In the present invention, solubilization means that a transparent or semitransparent homogeneous solution is obtained when the solubility is dissolved in a solvent. In the present invention, emulsification means that the emulsion is dispersed uniformly when the liquid emulsion and the solvent are emulsified to obtain an emulsion. In this invention, dispersion means that the to-be-dispersed solid substance is disperse | distributed uniformly in a solvent.
    The solubilizers, emulsifiers and dispersants of the present invention can further improve the solubility, emulsification or dispersion state as compared with the case where the resin, drug, etc. are dissolved, emulsified or dispersed in a solvent alone. The monomer composition containing a hydrophilic monomer (a) which has a group, and a hydrophobic monomer (b) is polymerized as needed, and a polymer is used as an active ingredient.
    In the monomer composition serving as a raw material of the solubilizer, the emulsifier and the dispersing agent of the present invention, the hydrophilic monomer (a) having a group represented by the formula (1) has a polymerizable double bond in the molecule, and the side chain is represented by the formula (1). The monomer etc. which have a group are mentioned preferably.
    As the hydrophilic monomer (a), 2- (meth) acryloyloxyethyl-2 '-(trimethylammonio) ethyl phosphate and 3- (meth) acryloyloxypropyl-2'-(trimethylammonio) ethyl phosphate , 4- (meth) acryloyloxybutyl-2 '-(trimethylammonio) ethyl phosphate, 5- (meth) acryloyloxypentyl-2'-(trimethylammonio) ethyl phosphate, 6- (meth) Acryloyloxyhexyl-2 '-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2'-(triethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl -2 '-(tripropylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2'-(tributylammonio) ethyl phosphate, 2- (meth) acryloyloxypropyl-2'- (Trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxybutyl-2 '-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxypentyl-2'-(trimethylammon 5) ethylphosphate, 2- (meth) acryloyloxyhexyl-2 '-(trimethylammonio) ethylphosphate, 2- (vinyloxy) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (allyl Oxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyloxy) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (p-vinylbenzoyloxy) ethyl-2 ' -(Trimethylammonio) ethyl phosphate, 2- (steeloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyl) ethyl-2'-(trimethylammonio) ethylphosphate, 2 -(Vinyloxycarbonyl) ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (allyloxycarbonyl) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (acryloylamino) ethyl -2 '-(trimethylammonio) ethylphosphate, 2- (vinylcarbonylamino) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (allyloxycarbonylamino) ethyl-2 '-(trime Ammonio) ethyl phosphate, 2- (buteroyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (crotosoyloxy) ethyl-2'-(trimethylammonio) ethyl phosphate, ethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, butyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, hydroxyethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate , Ethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, butyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, hydroxyethyl- (2'-trimethylammonioethylphosphorylethyl ) Fumarate and the like. Preferably, the compound represented by the said Formula (2) is mentioned by availability etc. Especially, 2- (methacryloyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate ((it is MPC hereafter)). Abbreviation) = 2-methacryloyloxyethylphosphorylcholine). These may be used alone or as a mixture in use.
    In the monomer composition which becomes a raw material of the solubilizer, an emulsifier, and a dispersing agent of this invention, a hydrophobic monomer (b) can be contained as needed. As the hydrophobic monomer (b), for example, (meth) acrylic acid, aconic acid, itaconic acid, metaconic acid, citraconic acid, fumaric acid, maleic acid, vinylsulfonic acid, acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid and these Various metal salts; N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and various quaternary salts thereof; 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, N-methyl-2-vinylimidazole, N-vinylimidazole, (meth) acrylamide, N-methyl ( Meta) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, 2-hydroxyethyl ( Meta) acrylate, (meth) acrylic acid monoglycerol, N- (tris (hydroxymethyl) methyl) acrylamide, vinyl methyl ether, polyethylene glycol (meth) acrylate, N-vinylpyrrolidone, N- (meth) Acryloylpyrrolidone, acryloyl morpholine, imide maleic acid, vinyl acetate, maleic anhydride; Styrene monomers such as styrene, methyl styrene, chloromethyl styrene and amino styrene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylic Various monoalkyl (meth) acrylates such as acrylate and 2-ethylhexyl (meth) acrylate; Reactive functional group-containing (meth) acrylates such as glycidyl (meth) acrylate and (meth) acryloyloxyethyltrimethoxysilane; Urethane modified (meth) acrylates such as 2- (meth) acryloyloxyethylbutylurethane, 2- (meth) acryloyloxyethylbenzylurethane and 2- (meth) acryloyloxyethylphenylurethane; Ethyl vinyl ether, butyl vinyl ether, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, isobutylene, diethyl fumarate, diethyl maleate, acrylonitrile, vinyl benzylamine and the like. Especially, the hydrophobic monomer (b) represented by the said Formula (3) is preferable.
    As the combination of the hydrophilic monomer (a) and the hydrophobic monomer (b), a combination of butyl methacrylate or 2-ethylhexyl methacrylate and the above MPC is most preferred. Among these, when vinyl acetate, maleic anhydride and glycidyl (meth) acrylate are used, the ring-opening reaction in which hydrolysis or hydrophilicity is imparted after the polymerization can be performed to improve hydrophilicity. Moreover, when glycidyl (meth) acrylate and (meth) acryloyloxyethyl trimethoxysilane are used, hydrophobicity can also be improved by performing reaction to which hydrophobicity is provided after superposition | polymerization.
    The content ratio of the hydrophilic monomer (a) in the monomer composition is preferably in the range of 100 to 20% by weight, in particular 100 to 30% by weight, of the totally unsaturated monomer in the monomer composition. Less than 20% by weight is not preferable because the solubility of the polymer obtained in water is low. On the other hand, the content ratio of the hydrophobic monomer (b) in the monomer composition is preferably in the range of 0 to 80% by weight, particularly 0 to 70% by weight, of all the unsaturated monomers in the monomer composition. When it exceeds 80 weight%, the solubility of the polymer obtained in water is low and it is not preferable.
    The active ingredient of the solubilizer of the present invention is a polymer obtained by polymerizing the monomer composition. The weight average molecular weight of the polymer is not particularly limited, and is preferably 500 to 5000000, more preferably 1000 to 150000.
    In the polymer, the monomer composition is replaced with an inert gas such as nitrogen, carbon dioxide, helium or the like, using a known solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, or the like, if necessary. It can prepare by the method of radically polymerizing on conditions of polymerization temperature 0-100 degreeC, and polymerization time 10 minutes-48 hours. In the polymerization, a polymerization initiator can be used, and as the polymerization initiator, 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanogilacetic acid), 2,2 '-Azobis (2- (5-methyl-2-imidazolin-2-yl) propane) dihydrochloride, 2,2'-azobis (2- (2-imidazolin-2-yl) propane) Dihydrochloride, 2,2'-azobisisobutylamide dihydrate, ammonium persulfate, potassium persulfate, benzoyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butyl Peroxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, azobisisobutyronitrile (abbreviated as AIBN), 2,2'-azobis (2,4-dimethylvaleronyltrile) and t-butyl peroxy neodecanoate (trade name "pabutyl ND", manufactured by Nippon Oil Holding Co., Ltd., hereinafter abbreviated as P-ND) or a mixture thereof. As the polymerization initiator, various redox-based accelerators may be used. As for the usage-amount of a polymerization initiator, 0.01-5.0 weight part is preferable with respect to 100 weight part of monomer compositions.
    Polymer purification can be carried out by general purification methods such as reprecipitation, dialysis and ultrafiltration.
    Examples of the solubilized or emulsified solubilized or emulsified by the solubilizing agent or emulsifying agent of the present invention include indomethacin, siconin, hydrocortisone, erythromycin, adremycin, and ethyl eicosaptanate (EPA- E), drugs such as α-tocopherol, prostaglandins, bioactive peptides, vitamins, tetracycline, hexamethazone, dichlorophenamide, helene, calcium diyodostearate and metazoramid; Fats and oils such as soybean oil, olive oil, safflower oil, sesame oil, hardened oil, and rapeseed oil.
    As a to-be-dispersed product disperse | distributed by the dispersing agent of this invention, For example, organic powders, such as a phthalocyanine; Inorganic powders, such as carbon black and a titanium oxide, etc. are mentioned.
    The solubilizers, emulsifiers and dispersants of the present invention may be used in combination with the polymer as the active ingredient, other solubilizers added to dissolve compounds or drugs which are difficult to dissolve in water, in water-soluble solvents mainly comprising water, and various surfactants. .
    The solubilizers, emulsifiers and dispersants of the present invention can solubilize, emulsify, or disperse a solubilizer that is difficult to dissolve, a emulsion that is difficult to emulsify, and a dispersion that is difficult to disperse in a large amount. Therefore, the solubilizers, emulsifiers and dispersants of the present invention can be used in a wide range of medicines, blended products, paints and the like, and are particularly useful as cleaning components such as shampoos, face washes and detergents.
    Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
    Example 1-1
    MPC is used as the hydrophilic monomer (a) and butyl methacrylate (hereinafter abbreviated as BMA) is used as the hydrophobic monomer (b), and these monomers are prepared so as to have concentrations of 0.473 mol / L and 1.10 mol / L, respectively. It was dissolved and mixed in ethanol. Nitrogen was sprayed on this solution for 2 hours, and the temperature of the system was set to 60 ° C, and P-ND was added so as to be 0.055 mol / L as a polymerization initiator. Then, it stirred at 60 degreeC for 3 hours, stirred at 70 degreeC for 1 hour, and cooled to room temperature. This solution was inserted into a dialysis membrane (Spectrum Medical Industries, Ltd., trade name "Spectra / por. 6, Mw CO.8000") and 10 times the volume of ethanol: water = 7: 3 (V / V) of the polymerization solution was used. The dialysis operation was carried out to carry out the dialysis operation by continuing the solvent exchange once a day for 7 days to prepare a solution containing a polymer (hereinafter referred to as polymer A) which can be an active ingredient of a solubilizer. The molecular weight, viscosity, MPC content measurement and solubilization, emulsification and dispersion tests of the obtained polymer A were carried out according to the following method.
    Molecular Weight Measurement (GPC)
    The resulting solution containing Polymer A was dissolved and diluted to 3% by weight with respect to chloroform: methanol = 6: 4 (V / V) containing 0.5% by weight of lithium chloride, and the solution was diluted with a 0.5 μm membrane filter. It filtered and used as the sample solution.
    Analytical conditions of GPC were eluent: 0.5 wt% of lithium chloride, chloroform: methanol = 6: 4 (V / V), flow rate: 1 ml / min, sample solution used: 100 μl, column temperature: 40 ° C., column: polymer It was set as MIXED-C (two pieces) by Lavora TRIZ company, a detector: a differential refractometer, and a standard substance: polymethyl methacrylate (10 kinds of material of molecular weight known between 1.00x10 <3> -1.58 * 10 <6> were used). 100 μl of the sample solution was injected. The average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were calculated using a molecular weight calculation program (GPC program for SC-8020) built by Tosoh Inc .. The results are shown in Table 1 and Table 2.
    Viscosity measurement
    The solution containing Polymer A thus obtained was adjusted to ethanol: water = 7: 3 (V / V) to a final concentration of 10% by weight (the solution after purification by dialysis was solvent-diluted as it is, and in the case of dried product, it was Dissolved), and left overnight. Next, this solution was measured with the rotation speed shown in Table 1 and Table 2 using the E-type viscosity meter. The measurement was continued five times and the average value and the deviation were calculated. The results are shown in Table 1 and Table 2.
    MPC content measurement (composition ratio measurement (phosphorus quantitative moisture measurement))
    Phosphorus determination: The solution containing the obtained polymer A was air-dried, and it vacuum-dried at 70 degreeC to make a sample. 6 mg of this sample was diluted in 10 ml with distilled ethanol using a 10 ml volumetric flask. Next, 50 microliters of this solution were accurately measured using a micro syringe, and it put into a washing test tube, removed the solvent using 100 degreeC block heater, and returned to room temperature. 0.25 ml of perchloric acid solution (70%) was added to the test tube, and the tube was capped with glass beads. Next, the sample was transferred to a block heater and heated at 180 ° C. for 20 minutes to decompose the polymer and return to room temperature. 1.90 ml of distilled water, 0.40 ml of 1.25% (wt / wt) ammonium molybdate solution and 0.40 ml of 5% (wt / wt) ascorbic acid solution were added and stirred and mixed with a vortex mixer, followed by heating for several minutes with a boiling water bath. I was. The absorbance of this solution was measured at the maximum absorption wavelength (about 817.8 nm), and the phosphorus concentration of the subject was quantified on a calibration curve using separately produced phosphoric acid.
    Moisture Determination: The test sample obtained by air drying the solution containing the obtained polymer A and then vacuum dried at 70 ° C. was subjected to the determination of moisture by a separate Karl Fischer method.
    From this water quantitative value and the said phosphorus quantitative value, the composition ratio of the polymer A after refinement | purification was calculated | required, and the content rate of MPC was computed. The results are shown in Table 1 and Table 2.
    Solubilization, Emulsification, Dispersion Test
    To 0.11 g of the obtained polymer A, 1.2 g of water was added to dissolve it, and it was set as the sample aqueous solution. After placing 0.1 g of powdered activated carbon on the back of the hand, the vibration was dropped, and the aqueous solution of the sample was placed on the back of the hand with the activated carbon, rubbed for 10 seconds, and washed with running water. On the other hand, after placing 0.1 g of powdered activated carbon on the back of the hand, it was vibrated and washed with running water after rubbing the back of the activated carbon for 10 seconds without using the sample aqueous solution. These two tests evaluated the cleaning effect of Polymer A on activated carbon attached to the back of the hand and the moist feeling after drying the back of the hand. The same test was conducted when 0.1 g of silicon oil was used instead of powdered activated carbon. In addition, the same test was done also when the 10-weight% aqueous solution of 1.2 g polyoxyethylene (20 mol) sorbitan monooleate which is surfactant instead of the aqueous solution containing the said polymer A was used. The results are shown in Table 3.
    Examples 1-2 to 1-19
    The monomer having the composition shown in Table 1 and Table 2 was polymerized as the active ingredient of the solubilizer by using any one of the following purification methods as in Example 1-1 by the polymerization conditions shown in Table 1 and Table 2. Each solution was prepared. The obtained solution and the polymer were subjected to various measurements and tests as in Example 1-1. The results are shown in Tables 1 to 3. In addition, EHMA in a table | surface represents 2-ethylhexyl methacrylate.
    Purification method;
    1) Purification was performed by dialysis 7 times for ethanol: water = 7: 3 using a dialysis membrane (Spectrum Medical Industries, Ltd., trade name "Spectra / por. 6, Mw Co. 8000").
    2) Dialysis was carried out 7 times with respect to ethanol: water = 7: 3 using a dialysis membrane (Spectra / por. 6, Mw Co. 8000) manufactured by Spectrum Medical Industries, Inc. after reprecipitation and drying with diethyl ether. After purification, reprecipitation with acetonitrile was performed twice.
    3) Dialysis was performed 7 times for ethanol: water = 7: 3 using a dialysis membrane (Spectrum Medical Industries Co., Ltd., trade name "Spectra / por. 6, Mw Co. 8000"), followed by reprecipitation with acetonitrile. Purification was performed once.
    4) Dialysis was carried out 7 times for ethanol: water = 7: 3 using a dialysis membrane (Spectra / por.6, Mw Co.8000) manufactured by Spectrum Medical Industries, Inc. after reprecipitation and drying with diethyl ether. Purification was carried out.
    5) Purification was carried out twice by reprecipitation with acetonitrile.

    Example 2-1; (Solubilization by Polymer A of Example 1-1)
    0.5 g of the polymer A prepared in Example 1-1 was dissolved in 1 g of ethanol, and 0.01 g of indomethacin was dissolved therein, followed by dissolution, followed by dialysis membrane (Spectrum Medical Industries, Ltd., trade name "Spectra / por. 6, Mw Co. 8000"). Dialysis was carried out by exchanging 666 ml of purified water 20 times with The dialysis solution was then filtered through a membrane filter (0.45 μm) made of acetylcellulose. At this time, the state of the liquid was visually observed. The results are shown in Table 4.
    Example 2-2; (Solubilization by Polymer A of Example 1-1)
    0.5 g of the polymer A prepared in Example 1-1 was dissolved in 1 g of water, and 0.01 g of siconin was added again, using a probe-type ultrasonic irradiator (manufactured by Spectrum Medical Industries, trade name "ASTRASON, XL2020, Heart Systems"). The liquid obtained by ultrasonic irradiation for 10 minutes was filtered by the membrane filter (0.45 micrometer) made from acetylcellulose. At this time, the state of the liquid was visually observed. The results are shown in Table 4.
    Examples 2-3-2-14
    The method (dialysis method) or Example 2 of Example 2-1 using the composition of the solubilizer, emulsifier, and dispersing agent which become a polymer of Table 4, and the solvate, the emulsion, and the dispersoid which are the drugs of Table 4 are used. The liquid was prepared by the method of -2 (ultrasonic method).
    However, Examples 2-5 and 2-6, in which the description of the additive solvent is shown in Table 4, were added to ethanol to add pyridine (Example 2-5) and toluene (Example 2-6) as shown in Table 4, The liquid was prepared. Again, in Example 2-5, no filtration by the membrane filter was performed. At this time, the state of the liquid was visually observed. The results are shown in Table 4.
    The results of Table 4 show that the solubilizers, emulsifiers and dispersants of the present invention exhibit excellent solubilization, emulsification and dispersing.
    Example 3-1
    The washing test was performed by the washing test machine (Terg-O-tometer; Ueshima Co., Ltd. product) using the aqueous solution (concentration; 10 g / liter) of the polymer A prepared in Example 1-1 as a washing | cleaning liquid. The results are shown in Table 5.
    <Cleaning test>
    The washing solution prepared at the above concentration was added to the washing tank of the washing tester, and then two artificial stain cloths described later and two untreated cotton cloths (10 × 10 cm) for recontamination test were placed, and the cleaning solution temperature was 40 ° C. at 150 rpm and 30 degrees. Washing was performed for 30 minutes under inverting conditions once per second. Subsequently, the test cloth was taken out of the washing | cleaning liquid, and it rinsed twice for 5 minutes with a 40 degreeC hot water at 150 rpm and once in 30 second, and the test cloth was dried and it was set as the test cloth for measurement.
    The measurement of the cleaning test was performed by measuring the reflectance of each of four cloths for four types of cleaning cloth, re-contamination test cloth, contaminated cloth by artificial tools described later, and untreated cotton cloth (raw cloth) for re-contamination test. It measured by (The Suga Test Machine Co., Ltd. product), and calculated | required by calculating | requiring the reflectance (%) with respect to the contaminated cloth or a raw cloth according to following Formula. The reflectance was made into the measured average of four cloths. The results are shown in Table 6.
    Cleaning rate (%) = (((reflectance after staining cloth)-(reflectivity of cloth)) / ((reflectance of cloth)-(reflectance of cloth)) × 100
    Recontamination rate (%) = (((reflectance of gun)-(reflectance after recontamination test of gun)) / ((reflectance of gun)-(reflectance of gun)) × 100
    <Preparation of contaminated fabric by artificial ward>
    1.5 g oleic acid, 0.75 g palmitic acid, 0.75 g myristic acid, 3.0 g rapeseed oil, 1.0 g cholesterol, 0.5 g squalane, 1.0 g cetyl alcohol, 1.5 g liquid paraffin, 1.75 g and 1,1,1- Two sheets of cotton cloth (10 × 10 cm) were put in an artificial globule dispersion made up of 800 ml of trichloroethylene, immersed for 1 minute, taken out, adjusted to 100% of throttling ratio using a roller, and dried to prepare a contaminated cloth.
    Comparative Example 1
    A washing test was carried out in the same manner as in Example 3-1, except that 1 liter of purified water containing no Polymer A prepared in Example 1-1 was used as the washing liquid. The results are shown in Table 5.
    The results of Example 3-1 and Comparative Example 1 show that the cleaning agent containing the solubilizer, the emulsifier and the dispersant of the present invention has a high cleaning rate. Moreover, it turns out that Example 3-1 has a low recontamination rate.
    Examples 4-1 to 4-3
    The shampoo composition of Table 6 was prepared, and performance was evaluated by the following evaluation methods. The results are shown in Table 6.
    <Creamy evaluation of bubble>
    Twenty women (ages 20 to 60 years) were used as panels to evaluate the creaminess of the foam when hair was washed using 5 ml of the shampoo composition. Evaluation was made into 2 points when the foam felt creamy, 1 point when the cream felt somewhat creamy, and 0 points when the foam felt rough and creamy. Was evaluated.
    <Finger Feeling Evaluation at Tricycle>
    Twenty women (ages 20 to 60 years) were assessed as a finger passing feeling (hereinafter referred to as a notice feeling) when hair was washed using 5 ml of the shampoo composition as a panel. The evaluation was performed with 2 points where the fingers passed smoothly and did not catch the head, 1 point when the fingers passed smoothly and the head felt slightly caught by the finger, and 0 points when the fingers felt very bad. Was obtained and the average score was 1.5 or more, indicating that the feeling of notification was good.
    <Comb Penetration Evaluation After Tricycle>
    Twenty women (ages 20 to 60 years) were used as a panel to wash hair using 5 ml of the shampoo composition, and the comb penetrability (hereinafter, referred to as “tongsheng”) when dried was evaluated. In the evaluation, the average value is calculated by 2 points when the comb feels smoothly passing through, 1 point when the head feels slightly caught by the comb, and 0 when the comb feels very bad through the comb. It evaluated that this was favorable.
    <Evaluation of conditioning effect after tricycle>
    Twenty women (ages 20 to 60 years) were used as panels to wash hair using 5 ml of the shampoo composition, and the conditioning effect when dried was evaluated. The evaluation was carried out to obtain an average value of 2 points for feeling that the conditioning effect was excellent, 1 point for feeling that the conditioning effect was obtained somewhat, and 0 point for feeling that the conditioning effect was not obtained. It was evaluated that the conditioning effect was excellent.
    <Evaluation of Setability of Hair after Tribal Drying>
    Twenty women (ages 20 to 60 years) were used as panels to wash hair using 5 ml of the shampoo composition, and the setability of hair when dried was evaluated. The evaluation was performed by 2 points for the case where the feeling of setability of the hair was excellent, 1 point for the case where the feeling of setability of the hair was somewhat excellent, and 0 points for the case where the feeling of the setability of the hair was bad, and the average score was 1.5 points. The above was evaluated that the setability of the hair was excellent.
    <Evaluation of moist feeling of hair after hair-drying>
    Twenty women (ages 20 to 60 years) were used as panels to wash hair using 5 ml of shampoo composition and to evaluate the moist feeling of hair when dried. The average of the evaluations is 2 points for feeling that the hair feels excellent, 1 point for feeling that the hair feels slightly superior, 0 points for feeling that the hair feels not good, and an average score of 1.5. Above the point, the moist feeling of hair was evaluated as being excellent.
    〈Stability of Composition>
    After the shampoo composition shown in Table 6 was filtered and sterilized, the shampoo composition was stored at -5 ° C, 25 ° C, and 45 ° C for 1 month, and then the visual appearance was visually evaluated in three steps of ○, Δ, and ×.
    (Circle): Stability is good, external appearance is a transparent or turbid state, (triangle | delta): The state is somewhat poor stability, the appearance is a muddy or colored state, x: The stability is poor, and an appearance has a precipitate and remarkable coloring.
    Comparative Example 2
    It evaluated like Example 4-1-4-3 except having used the shampoo composition of Table 6 shown. The results are shown in Table 7.
    As a result of Table 6, the solubilizer, emulsifier or dispersing agent of the present invention, when used as a cleaning agent of the shampoo composition, evaluation of the noticeability at the time of hair triangulation, evaluation of the painfulness after hair treatment, evaluation of the conditioning effect after hair washing, and a set of hair after hair drying It can be seen that all the evaluations of the sexual evaluation and the moist feeling evaluation of the hair after hair-drying are excellent. Moreover, it turns out that a composition has good stability with time.
    Examples 5-1 to 5-3
    The face-wash composition of Table 7 was prepared, and performance evaluation was performed by the following evaluation method. The results are shown in Table 7.
    <Creamy evaluation of bubble>
    Twenty women (ages 20 to 60 years) were used as panels to evaluate the creaminess of the foam when the face was washed using 5 ml of the face-wash composition. The evaluation was made with 2 points for the case where the foam felt creamy, 1 point for the case where the cream felt somewhat creamy, and 0 for the case where the foam felt rough and creamy, and the average score was 1.5 points or more. It evaluated good.
    <Smooth feeling evaluation after rinsing>
    Twenty women (age 20-60 years old) were used as a panel to wash face with 5 ml of face-wash compositions, and it washed with three liters of warm water of about 40 degreeC, and washed three times, and evaluated the smooth feeling. The evaluation is based on four points for feeling that there is no smooth feeling, three points for feeling that there is little smooth feeling, two points for feeling that there is some smooth feeling, and one point for feeling that there is a smooth feeling. The average score of 3.0 or more was evaluated as having no smooth feeling.
    <Fresh feeling evaluation after rinsing>
    Twenty women (ages 20 to 60 years) were used as a panel to wash with 5 ml of face-washing composition, and 1 liter of warm water of about 40 ° C was used to wash and washed three times while washing. The evaluation is based on 4 points for feeling fresh and 3 points for feeling fresh, 2 points for feeling fresh, and 1 point for feeling fresh. The average score evaluated 3.0 points or more as having a fresh feeling.
    <Moist feeling evaluation of skin after washing and drying>
    Twenty women (ages 20 to 60 years) were used as panels to wash the face using 5 ml of the face-washing composition, and the moist feeling of the skin after rinsing was evaluated. The evaluation was performed by calculating the average of 2 points for feeling that the skin feels excellent, 1 point for feeling that the skin feels excellent, and 0 for feeling that the skin is not moist, with an average score of 1.5. The above point was evaluated as having a moist feeling of skin.
    〈Time and Abundance of Compositions〉
    Evaluation was carried out in the same manner as the aging stability of the shampoo compositions of Examples 4-1 to 4-3.
    Comparative Example 3
    It evaluated similarly to Examples 5-1 to 5-3 except having used the face-wash composition shown in Table 7. The results are shown in Table 7.
    In the results of Table 7, the solubilizers, emulsifiers or dispersants of the present invention, when used as a detergent for washing face, all of the evaluation of the smooth feeling after rinsing, the evaluation of the fresh sense after rinsing, and the evaluation of the moist feeling after washing face is excellent. Able to know. Moreover, it turns out that a time-lapse stability is favorable for a composition.
    Reference Example 1 (Measurement of Critical Micelle Concentration)
    Using the polymer A prepared in Example 1-1, an aqueous solution having a concentration of 0.255 to 255 mg / liter was prepared, and an aqueous solution of ethylene prepared at a concentration of 6.0 × 10 −7 mol / liter in advance was added to each of the same amounts and mixed. Em (350-400 nm) was measured for the fluorescence intensity of these solutions on Ex = 384 nm, and the peak ratio ((P-3) of peak 1 (P-1) of 372-376 nm and peak 3 (P-3) of 383-385 nm was measured. P-1) / (P-3)) were obtained and plotted against the concentration of polymer A of Example 1-1. The results are shown in FIG. In FIG. 1, the numerical value on the vertical axis represents the value of the peak ratio ((P-1) / (P-3)), and the horizontal axis value represents the concentration of the polymer A (mg / l).
    It is known that the fluorescence intensity peak ratio ((P-1) / (P-3)) of the ethylene becomes about 1.8 in the hydrophilic state and lower than 1.8 in the hydrophobic state. 1 shows that the aqueous solution of Polymer A of Example 1-1 has an inflection point at a concentration of about 3 mg / liter and a peak ratio ((P-1) / (P-3)) <1.8 at a concentration higher than that. Able to know. In other words, it can be seen that the polymer A of Example 1-1 forms micelles at a concentration of about 3 mg / liter or more, and the polymer has surfactant performance available as a solubilizer, emulsifier or dispersant.
    Reference Example 2 (Biochemical Safety Test)
    Bacterial reverse mutation test
    The polymer A prepared in Example 1-1 was used as a sample, and the test was carried out according to the displacement originality test method of JP 24 (September 11, Heisei Co., Ltd.). That is, a reverse mutation test containing metabolic activation using four strains of Esherichia coli WP2 uvr A strain and Salmonella typhimurium TA strain was carried out at a concentration of 156 to 5000 µg / plate for the polymer A prepared in Example 1-1. As a result, no increase in the number of return displacement colonies was observed in either case. In view of the above, the mutant organicity of polymer A was negatively confirmed.
    Colony Formation Inhibition Test Using Cultured Bacteria
    Using the polymer A prepared in Example 1-1 as a sample, colony formation inhibitory tests were performed according to "Guidelines for Basic Biological Testing of Medical Equipment and Medical Materials" (Annex 7, 1999). . That is, a sample was prepared in such a manner that the polymer A prepared in Example 1-1 was 0.5 to 2 mg / ml in MO5 medium, and the colony count of 50 or more cells was measured using the 21st generation of Chinese hamster fibroblast V79 strain. As a result, the colony formation rate in the sample and the negative control test solution was not particularly reduced with respect to the untreated test solution. Therefore, the inhibition of colony formation of the sample containing Polymer A was confirmed negatively.
    Pyrogenic test
    Using the polymer A prepared in Example 1-1 as a sample, a pyrogenic substance test was conducted in accordance with the twelfth revised Japanese Pharmacy Room General Test Method. In other words, a 56 μg / ml physiological saline solution prepared in Example 1-1 was used as a sample and administered to a Japanese white male hare at a dose of 10 ml per 1 kg of body weight in the ear vein, and then subjected to temperature measurement three times at 1 hour intervals. Compared to control body temperature. As a result, it was not confirmed that the body temperature rise was 0.6 deg. C or higher than the control body temperature. As a result, it was confirmed that Polymer A was exothermic test negative.
    Intradermal Reaction Test
    Using the polymer A prepared in Example 1-1 as a sample, an intradermal reaction test was conducted in accordance with the Twelfth Revised Japanese Pharmacy Room General Test Method. That is, 10 microliters of 0.2 ml each of the physiological saline solution of the polymer A prepared in Example 1-1 was used as a sample, and the axial ring of the Japanese white male rabbit. 24 hours after administration, 48 hours after, 72 hours after the administration site was observed. As a result, changes in local erythema, edema, bleeding, and necrosis were not confirmed. In the above fact, it is confirmed that polymer A is negative in the intradermal reaction test.
    Acute Toxicity Test
    Using the polymer A prepared in Example 1-1 as a sample, an acute toxicity test was conducted in accordance with the twelfth revised Japanese Pharmacopoeia General Test Method. That is, a physiological saline solution of 56 μg / ml of polymer A prepared in Example 1-1 was used as a sample and administered once into the tail vein at a dose of 50 ml per 1 kg of body weight of the ddy male mouse. Observations were made for 5 days after administration, and no abnormalities or deaths were observed in the mice. This result confirms that the sample is negative for acute toxicity test.
    Hemolytic test
    Using the polymer A prepared in Example 1-1 as a sample, a hemolytic test was carried out in accordance with the twelfth revised Japanese Pharmacopoeia General Test Method. That is, 0.1 ml of defibrated blood prepared by collecting blood from a Japanese white rabbit was added to 10 ml of the physiological saline solution of 5 μg / ml of the polymer A prepared in Example 1-1, and left for 24 hours at 37 ° C. Investigate. As a result, the fact that hemolysis was not confirmed, Polymer A confirms that the hemolytic test is negative.
    Acute Toxicity Test (Intravenous Administration)
    The acute toxicity test (intravenous administration) in mice was performed using the polymer prepared in Example 1-18 as a sample. That is, when the polymer prepared in Example 1-18 was administered once in a male and female mouse vein at a dose of 200 mg / kg, no abnormalities or deaths were found in the test animals. Therefore, it is confirmed that the amount of lethality by intravenous single administration in the mouse, which is a specimen, is 200 mg / kg or more in both sexes.
    Skin sensitization test
    Using the polymer prepared in Example 1-6 as a sample, a skin sensitization test was carried out using molar montone according to the Maximization method. In other words, a 5%, 0.5% or 0.05% ethanol solution of the polymer prepared in Example 1-6 was applied to the skin of Mormont, which had been subjected to sensitization induction by intradermal injection and closed application, after 24 hours, after 48 hours and 72 hours. The subsequent application site | part was scored of skin reaction according to the evaluation criteria of the Draize method, and the sensitization positive rate at each observation was calculated | required. As a result, the sensitization positive rate was 0% at any observation time and at any concentration. From the above facts, it is confirmed that the specimen does not have skin sensitization.
    Skin Primary Irritation Test
    A skin primary irritation test was conducted using the polymer prepared in Example 1-18 as a sample. In other words, 2.5 × of healthy white rabbits (12-16 weeks old, 2.50-3.11 kg) were shaved and dropped with 0.5 ml of the polymer solution (40% aqueous solution) prepared in Example 1-18. A 2.5 cm gauze was affixed and the rabbits were then fixed in a corset and scored for erythema and edema formation after 1 hour, after 24 hours, after 48 hours and after 72 hours. As a result, the rating average is 0.0 and it is confirmed that a sample is a non-irritating substance.
    Acute Toxicity (Oral)
    The acute toxicity test (oral administration) in mice was performed using the polymer prepared in Example 1-18 as a sample. That is, the polymer prepared in Example 1-18 was administered orally once orally in male and female mice fasted at a dose of 5000 mg / kg. No abnormalities or deaths of test animals were observed during the 14-day observation period. Therefore, it is thought that the lethal dose by oral single administration in the mouse of a sample is 5000 mg / kg or more in both male and female.
    The above test results show that the polymer used as an active ingredient of the solubilizer, emulsifier and dispersant of the present invention has high biological stability.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] A monomer composition containing a hydrophilic monomer (a) having a group represented by the formula (1 in which R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different group) in a side chain thereof; A solubilizer characterized by containing a polymer obtained by polymerization as an active ingredient.
    (Formula 1)

    [2" claim-type="Currently amended] The hydrophilic monomer (a) according to claim 1, wherein the hydrophilic monomer (a) is represented by the formula (2) wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different groups. A solubilizer characterized in that it is methacryloyloxy) ethyl-2 '-(alkyl substituted or unsubstituted ammonio) ethylphosphate.
    (Formula 2)

    [3" claim-type="Currently amended] 2- (methacryloyloxy) represented by Chemical Formula 2 (wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different group) as the hydrophilic monomer (a). 100-20% by weight of ethyl-2 '-(alkyl substituted or unsubstituted ammonio) ethylphosphate, and formula (3) as a hydrophobic monomer (b) (wherein R 4 represents a hydrogen atom or a methyl group, and R 5 represents 4 to 8 carbon atoms) A solubilizer characterized by containing a polymer obtained by polymerizing a monomer composition composed of 0 to 80% by weight of (meth) acrylate represented by the alkyl group).
    (Formula 2)

    (Formula 3)

    [4" claim-type="Currently amended] A monomer composition containing a hydrophilic monomer (a) having a group represented by the formula (1 in which R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different group) in a side chain thereof; An emulsifier comprising a polymer obtained by polymerization as an active ingredient.
    (Formula 1)

    [5" claim-type="Currently amended] The method according to claim 4, wherein the hydrophilic monomer (a) is represented by the formula (2) wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different groups. Emulsifier, characterized in that the methacryloyloxy) ethyl-2'- (alkyl substituted or unsubstituted ammonio) ethyl phosphate.
    (Formula 2)

    [6" claim-type="Currently amended] 2- (methacryloyloxy) represented by Chemical Formula 2 (wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different group) as the hydrophilic monomer (a). 100 to 20% by weight of ethyl-2 '-(alkyl substituted or unsubstituted ammonio) ethylphosphate, and formula 3 as a hydrophobic monomer (b), wherein R 4 represents a hydrogen atom or a methyl group, and R 5 represents 4 to 8 carbon atoms The polymer formed by superposing | polymerizing the monomer composition which consists of 0-80 weight% of (meth) acrylates represented by the alkyl group of) is contained as an active ingredient, The emulsifier characterized by the above-mentioned.
    (Formula 2)

    (Formula 3)

    [7" claim-type="Currently amended] A monomer composition containing a hydrophilic monomer (a) having a group represented by the formula (1 in which R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different group) in a side chain thereof; A dispersant comprising a polymer obtained by polymerization as an active ingredient.
    (Formula 1)

    [8" claim-type="Currently amended] 8. The hydrophilic monomer (a) according to claim 7, wherein the hydrophilic monomer (a) is represented by the formula (2) wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different groups. Dispersing agent, characterized in that the methacryloyloxy) ethyl-2'- (alkyl substituted or unsubstituted ammioio) ethyl phosphate.
    (Formula 2)

    [9" claim-type="Currently amended] 2- (methacryloyloxy) represented by Chemical Formula 2 (wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different group) as the hydrophilic monomer (a). 100 to 20% by weight of ethyl-2 '-(alkyl substituted or unsubstituted ammonio) ethylphosphate, and formula 3 as a hydrophobic monomer (b), wherein R 4 represents a hydrogen atom or a methyl group, and R 5 represents 4 to 8 carbon atoms A polymer formed by polymerizing a monomer composition composed of 0 to 80% by weight of (meth) acrylate represented by the alkyl group of) is contained as an active ingredient.
    (Formula 2)

    (Formula 3)
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    同族专利:
    公开号 | 公开日
    EP0947244A1|1999-10-06|
    DE69732139D1|2005-02-03|
    EP0947244B1|2004-12-29|
    KR100307132B1|2001-09-24|
    DE69732139T2|2005-12-15|
    WO1998004341A1|1998-02-05|
    EP0947244A4|2000-07-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-07-31|Priority to JP20262096
    1996-07-31|Priority to JP96-202620
    1999-01-20|Application filed by 우노 마사야스, 닛폰 유시 가부시키가이샤, 가와사키 마사히로, 가가쿠 기쥬츠 신코 지교단, 이시하라 가즈히코, 나카바야시 노부오
    2000-05-25|Publication of KR20000029452A
    2001-09-24|Application granted
    2001-09-24|Publication of KR100307132B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP20262096|1996-07-31|
    JP96-202620|1996-07-31|
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