JPS58105907A - Emulsified cosmetic - Google Patents

Abstract

PURPOSE:A cosmetic, containing a water-insoluble water absorbing polymer consisting of fibroin, a crosslinking monomer, an anionic monomer or further a nonionic monomer as an emulsifying agent, having improved emulsion stability, etc. without irritant action on the skin, and capable of giving improved properties to hair. CONSTITUTION:A cosmetic containing 0.05-5.0wt% water-insoluble water absorbing polymer consisting of 1-40wt% fibroin (regenerated), 0.1-5wt% crosslinking monomer, e.g. ethylene glycol dimethacrylate, 60-95wt% anionic monomer, e.g. acrylic acid, and 0-20wt% nonionic monomer, e.g. an acrylic ester, as an emulsifying agent. The cosmetic has improved emulsion stability, viscosity stability, humectant property in use, water resistance, touch, make-up durability, etc. without irritant action on the skin and is capable of giving softness, smoothness and gloss to the hair. The water absorption of the polymer is at least 60ml/g, and the cosmetic may further contain ethanol.

Description

Detailed Description of the Invention The present invention uses a water-insoluble water-absorbing polymer as an emulsifier, which contains fibroin, a crosslinkable monomer, a 7-ionic monomer, or a nonionic monomer as polymer components. O Concerning emulsion cosmetics in the form of creams or emulsions.More details: BL - Emulsion cosmetics that are non-irritating, have excellent emulsion quality, viscosity stability, moisturizing properties during use, water resistance, feel, and makeup retention. The requirements for emulsified cosmetics such as creams and milky lotions are as follows: (1) Ji M
t-High safety without irritation. (2) Emulsion stability life [(mt) Stability is suitable. (5) Supply and retain an appropriate amount of moisture to the skin, etc. (high moisturizing properties).

(4) Water. It does not leak (re-emulsify) due to sweat, etc., and has good cosmetic properties. (5) It has a good feel when used.

However, in order to satisfy the following conditions.

Selection and combination of emulsifying agents. Careful compositional design has been carried out, such as using special base materials, but it is difficult to determine the purpose. Nonionic surfactants such as ethereal surfactants have poor emulsifying power; emulsified cosmetics made with these surfactants as emulsifiers also have poor water resistance (easily washed away by water, sweat, etc.);
Emulsion stability and viscosity stability are significantly reduced by adding a small amount of ethyl alcohol. Therefore, emulsified cosmetics with good water resistance and containing ethyl alcohol (with a refreshing feeling) are not yet known.

On the other hand, emulsified cosmetics using anionic molecular electrolytes (carboxyvinyl polymers and carboxymethyl cellulose mats) as emulsifiers give the sticky feeling characteristic of poly 1-, and also cause the polymer to evaporate when blending pigments or when in contact with seawater. It has the disadvantage that it causes agglomeration and agglomeration of pigments, thickens over time, and agglomerates during application, making it impossible to apply it uniformly.

In view of the current situation, the present inventors conducted extensive research and found that (1) the following polymer components were fibroin, a crosslinkable monomer, and an anionic hood-shaped lid or a nonionic monomer. Polymers (especially fibroin-graft polymers) are water-insoluble water-absorbing (water-retaining) polymers, which are insoluble in water but absorb (rehydrate) a large amount of water, and have extremely high While enveloping the oily substance as a microgel, it is emulsified homogeneously and stably in an aqueous system to form an oil-in-water m1 (0/Wm) emulsion.

(2) This emulsion soda produced (emulsion cosmetic)
is stable even when a large amount of ethanol (25% or less) is added without affecting the emulsifying properties or viscosity.

(3) First, the membrane has unique properties such as being able to retain an appropriate amount of moisture on the surface of the skin and fur, and being highly water resistant without causing emulsification or run-off even when it comes in contact with large amounts of water or sweat. The present invention has been achieved based on the discovery that

The purpose of the agl of the present invention is to improve skin M#L (emulsion stability,
We provide emulsion cosmetics that are excellent in viscosity stability, moisturizing properties during use, water resistance (water repellency), feel, and cosmetics.

An object of the present invention is to provide an emulsified cosmetic that can soften and cleanse hair and add shine to the hair.

That is, 1 the present invention provides a bridge-to-top type polymer (B) containing fibroin (ethylenically unsaturated or glycidyl 1k at both ends) and a monomer having an anionic property 1, or further at one end,・1 A water-insoluble water-absorbing polymer made of a nonionic monomer having ethylenically unsaturated material and a kn combined component is used as an emulsifier,
It is a cream-like or emulsion-like emulsion cosmetic made by blending an oily substance and water. The water-insoluble water-absorbing polymer in the present invention has a polymer component of 1 to 401% fibroin, cross-linking Single lid body α1-5j1 lid 2. Anion hood type lid body 60~95Jt
It is preferable that the composition consists of violet% and nonionic hood-type polymer 0 to 20%. Examples of cross-linkable monomers include divinylpene (n, i, 6-hexanediol diacrylate, ethylene glycol dimethacrylate).

Polyethylene glycol diacrylate, propylene glycol dimethacrylate, methylene bisacrylamide, ethylene glycol diglycidyl ether, glycidyl acrylate.

It is possible to extract glycidyl methacrylate, etc.

□ Examples of the anionic monomer include acrylic resin, methacrylic resin, and alkali metal salts, alkaline earth metal salts, aluminum salts, and ammonium salts thereof.

Examples of the nonionic canopy-shaped carrier include acrylamide, methacrylamide, vinyl acetate, acrylonitrile, styrene, acrylic ester, and methacrylic ester.

The water-insoluble water-absorbing polymer of the present invention is a novel polymer, which is usually combined with the above-mentioned anionic monomer and cross-monomer or even non-monomer in an aqueous solution or fraction of fibroin. It is obtained by polymerizing the ionic monomers in the presence of a gold-producing initiator, and then subjecting the resulting polymer (mainly 71 protein graft polymer) to VC, drying, and pulverizing.

Kono 41#, anionic monomer is Yue's carvone 1L
In the case of a polymer whose polymer component is a monomer having a sulfone group, it is converted into a salt by neutralization with an alkali, if necessary.

In the case of a polymer in which the polymer component bound to fibroin contains acrylamide, the polymer having acrylonitrile as a polymer component is post-treated (with acid or alkali for km
) to selectively hydrolyze only the -ON group to produce -■
It may also be one converted to NH2 group.

In the polymerization reaction, the W-holes in the reaction system are removed using an inert gas such as M gas, and radiation and electron beams are removed.

Polymerization is carried out by irradiating with ultraviolet rays or by adding a radical 1 polymerization catalyst. As a radical polymerization catalyst, water peroxide,
It may be appropriately selected from those commonly used such as benzoyl peroxide, potassium persulfate, ammonium peroxide, ceric salt, and azobisbutyronitrile.

At the same time, it is also possible to polymerize in a redox system using a subfa#It salt, a primary salt, and an adenate.

However, when a persulfate is used as a polymerization agent, a product with a high degree of polymerization can be obtained, and it is easy to manufacture, so it is preferable (tDI).

I go! The temperature is usually 10-110℃, preferably 20-8℃
hbx on/off time 0-600 minutes at 0°C, preferably 30 minutes
〜jSOO minutes.

Although the combination of fibroin, *bridging monomer (chest and anionic hood), or non-ionic monomer (D) is not particularly limited, (Q
(The weight ratio of the monument is % (A) for 100 K (B)
it(L001~10.(C)ii50-doo o o o
, (D) is between 0 and 1, preferably (B) a o
-~5, (o) is 1oo-2DO#, (In is 0~
50/It will be done if necessary. Hydrolysis of the polymerization reaction product obtained above may be carried out by any conventionally known method, but usually in an aqueous solvent or a mixed solvent of water and alcohol. It is carried out at a temperature of 10 to 150°C using potassium hydroxide or the like.

Subsequently, one reaction product is washed with a mixed solvent of water and alcohol to remove unreacted monomers and cross-linking agents, dried, and pulverized.

The water-insoluble water-absorbent 1 composite of the present invention thus obtained has a high water absorption (water retention) performance, i.e. at least 60 times its own weight (C60wm dish/y), preferably L<ti10G~50
It exhibits a ridge water rate of 0 times (100 waQ/p to 500 ynQ/y), does not lose its main line retention properties under pressure, and stably maintains a water-containing (hydrated) gel foreground for a long time. Furthermore, although this water-insoluble water-absorbing polymer is insoluble in water, it retains a large amount of water and becomes an extremely swollen homogeneous microgel, enveloping oily substances in the aqueous system.

Emulsifies uniformly and stably to form cream-like or milky lotion-like cosmetics, coexists with multi-leaf ethyl alcohol, does not reduce emulsion stability even when added, and improves emulsion stability at 20% by weight or less. The specificity of its action and effect is remarkable.

Furthermore, when applying and using this emulsified cosmetic, please use a paste.

The water-insoluble water-absorbent material that can be used in the present invention can provide a soft feel, a light but moist feeling after spreading, and supply and retain an appropriate amount of moisture to the skin. Regarding skin irritation caused by polymers, see D below.
The animal skin irritation score and human skin irritation score were both substantially KO.
It is recognized that all of them are substantially non-irritating.
of Food and [hugoffic
ials of the TJinited
Appraisal of the
fkf*ty of Ohmicals i
n Foods, Drugs and Ootrms
a%1cm, 46 (1959).

Texas, 8%at*Department
of Heartn, Augustin, ] Amount (amount used) of the water-insoluble water-absorbing polymer in the present invention
is 105 to 50% by weight, preferably 112 to 50% by weight based on the total amount of the formulation.The blending amount is α05ffif
less than i%.

Emulsification becomes difficult when the amount exceeds 5% by weight.

Liquidity decreases.

What is the particle size of the water-insoluble water-absorbing polymer when dried?

Oily substances of 100 microns or less are preferred for use in the present invention. Oily substances that can be used in the present invention include known oily substances for skin cosmetics, such as high-grade oils, oils and fats, vegetable oils and fats. , waxes.

-grade alcohols, higher fatty acids, ester oils, and silicone oils and fats. Examples of hydrocarbons include liquid paraffin, squalane, and lycerin.

Examples of vegetable oils and fats include ceresin, olive oil, castor oil, cacao sushi, and wheat oil; examples of animal fats and oils include:
Examples of waxes include cod liver oil, beef tallow, and butter fat, such as beeswax and carnauba wax, and examples of higher fatty acids include lauric acid, myristic acid, valmitic acid, stearic acid, oleic acid, behenic acid, and thunorin. fatty acids, etc.
Examples of higher alcohols include lauryl alcohol,
Stearyl alcohol, cetyl alcohol, oleyl alcohol, etc., ester oils, such as butyl stearate, hexyl turate, octyldodecyl myristate, diisofurovir adipate, diisopropyl sepacate, straight chain ester, KM ester, etc. You can fight.

These oil-based #IIJIX are used alone or in combination of two or more, and the amount used (compounded amount) is usually 5 to 40%.

The amount of water used is usually 50 to 95 Ji violet %. The cream or emulsion cosmetic of the present invention may contain ethyl alcohol.

In addition, when the amount is less than 20j11%, the emulsion stability improves as the amount is increased, and a good cooling sensation can be imparted to the skin.

Such effects are unique and not seen in emulsified cosmetics emulsified with ordinary surfactants. What is the amount of ethyl alcohol used (mixed amount)?

It is easily 25J14jit%, preferably 2 to 20%. Historically, in the present invention, pigments (for example, talc, kaolin, titanium oxide) are blended into the makeup base, and the pigment is at most 5% by weight, preferably LL5~AM!
◇ Other ingredients that are blended include fragrances, coloring agents, etc., as well as astringents, skin nutrients, anti-inflammatory agents, auxiliary chains, ultraviolet absorbers, solubilizers, etc. pH - The emulsified cosmetic material of the present invention in the form of an emulsion or emulsion containing a sanitary agent, etc.
Skin jIl11 No stinging, blends well into the skin, emulsion stability a%
Sleeves have good (hardness) stability, moisture retention during use, water resistance,
M water-based, M bottle (moist feeling, smooth feeling, f# coolness, excellent in makeup book 1st class).

It also has 41Illl properties such as making hair soft, smooth, and shiny. Therefore.

Skin debris cosmetics (e.g. skin cream, skin ζlux, makeup paste, sunscreen%).

Hair Cosmetics (Hunger & -r Hair Cream, Hair Examples will be described below.

In the examples, % means % by weight, and 1 part means part by weight.

In addition, the feel, moisturizing properties, viscosity stability, emulsion stability, water resistance, and water repellency were determined using the methods described below. The results are shown as an average value.The higher the score, the better the product.Feel after application (light feeling, moist feeling) (2)
Heat retention 1, B, impedance meter manufactured by 8 companies (In2-3
545). The measurement was carried out in a thermostatic room at 20° C. after applying the sample to the upper arm of an adult male at a constant Ca29/4 od), and then keeping the conductance (unit: micromho) constant over time. When the conductance value is high, the electrical resistance of the skin is generally low, and its moisturizing properties are excellent.

(3) Viscosity stability (45 & degree of qualityification due to Salmon H) A sample was placed at a melting temperature of 45° C. and changes in viscosity were examined. The viscosity was measured at 30°C with a Bffi rotary needle. (4) Emulsion stability: Place the sample in a constant temperature oven at 45°C and observe the emulsified state and appearance after leaving it for 3 months. No abnormalities were observed. If the emulsion was uniform (the emulsion state was uniform and a homogeneous emulsion was formed), it was evaluated as good, and if any abnormalities were observed (such as when oil separated or one particle became coarse), it was evaluated as poor.

(5) Water resistance test myristic octyldodecyl (MOD) (oil-based substance)
A uniform amount of blood was applied to certain areas of the backs and chests of 10 panelists, and immediately after mourning, the blood was wiped off from each location with absorbent cotton containing chloroform. Then swimming (
After 1 hour of water bathing, another coated area was wiped in the same manner as above to prepare a sample for immobilization after swimming for 1 hour.

Wipe-) Good, after immersing each sample (with oil sealed in absorbent cotton) in chloroform (extractant) at 50 V and stirring under constant conditions for 10 minutes to extract.

Repeat this operation with fresh chloroform.O About 100 m74 of the chloroform extract obtained is (
Fill up to a certain amount (if any insoluble matter is present), and then quantify MOD from the calibration curve by gas chromatography under the following conditions: Column 0V-1, stainless steel column: 1 m.

Column temperature = 270°C, Indie carbon temperature = 500
℃.

In addition, the tIk of 9 MOD obtained by wiping the blood directly on him is 1
00 and wipe it from another area after 1 hour of swimming! The residual rate of MOD leaves obtained by coffining was determined, and the average value of 10 people was shown. , while rubbing both hands together under running water for 1 minute, we examined the phlegm of the skin of the violet-covered fingers.A 5-point system was used for evaluation, and the results were expressed as an average value.The higher the score, the higher the score. The higher the temperature, the better the water resistance.

Example 1 (1) Production of fibroin-sodium acrylate polyethylene glycol diacrylate graft polymer 900 parts of provisional fibroin obtained by scouring raw silk waste in a soapy water bath to remove sericin and oil was mixed with 2000 parts of a 65% calcium nitrate aqueous solution. A fibroin bath liquid was obtained by immersing the fibroin in the fibroin solution and heating and stirring at 70 to 75°C. Next, this fibroin feed solution was diluted by adding 2000 parts of water and dialyzed using an fC monkey, holofiber type dialyzer to obtain fibroin water it (5% neuproin hydration).

For each 1 Mk of fibroin and fibroin in the fibroin aqueous solution, acrylic acid and polyethylene glycol ether diacrylate (50 times higher, 20 times higher, 5 times higher, 2 times higher, 1.6 times higher) and the same amount of each acrylic acid and polyethylene glycol ether diacrylate ( PKODA)
(CH2= (JIO('IQ (cn2ca2o)1
4 UOOH = OH2] to Fufibron, respectively 1/40 i14y1, 2 parts of 1 violet equivalent, 1/20 1/20 electric power @, 1/20 mass equivalent, 20
10% including 100% of the violet, diluted water to make 100 parts of total water, charged separately to a polymerization machine, and added 0.2 parts of ammonium persulfate/(hl for polymerization initiation) under a four-element stream. After adding O and carrying out a graft polymerization reaction for 2 hours at a humidity of 80°C, the resulting 10 L of each reaction (a fractional solution of fibroin-acrylic acid 22-tom combination) was neutralized with an aqueous sodium hydroxide solution. 100 parts of ethyl alcohol
Then, the fibroin-sodium acrylate-polyethylene glycol diacrylate graft polymer was separated by precipitation and purified by thorough washing with 40% alcohol.

Thereafter, it was dried under reduced pressure at 60 DEG C. for 8 hours, and ground into powder (grains & 10 to 50 microns).

As a short note, the obtained Gufufuto Aiai Stick Water has the property of absorbing multiple amounts of water.
Carboxyl groups were quantified and calculated by pk determination.

■Water absorption capacity (water absorption performance) was determined by dispersing the graft polymer powder in water and dispersing free water with a wire mesh of 300 meth 7 ≧.

Calculated from the weight of the insoluble gel. Next, dissolve 1 part each of the graft polymer (water-absorbing polymer) and disodium edteate [Lt part] in 8 parts and 9 parts of water to obtain the Creams were prepared by adding 5.0 parts of olive oil and 50 parts of octyl tosyl myristate to each of the aqueous solutions and emulsifying and dispersing them.Table 2 shows the characteristics of each cream obtained.

Iris 2 As is clear from Table 2, %2 ibroin is 1-40% sodium acrylate is 60-9.5 parts 1% by weight polyethylene glycol diacrylate is α1-531. amount%
A fibruin-sodium acrylate graft polymer consisting of the following is preferred.

Example 2 The blending amount of the fibouin-sodium acrylate-polyethylene glycol diacrylate graft polymer (F-GP) of Mu3 of Example 1, which was produced and used in Example 1, was varied as shown in Table 5 below. In addition, each cream was prepared in the same manner as in Example 1, and the relationship between the amount of the cream and the product properties was determined as shown in Table 3. The amount of polymer added is

[105 to 5%, particularly α2 to 50% is preferred.

Example 3 (1) Fibroin graph used) 1 combination Postscript 4th! l! The graft polymer of A1 was prepared as follows. Using the fibroin aqueous solution produced in Example 1,
After mixing fibroin (t), ethyl acrylate, divinylbenzene (DVB), and styrene (at) at a weight ratio of 20 parts, 75 parts, and 15 parts to 5 parts, potassium persulfate (
2 parts of polymerization initiator) and 2 parts of sodium sulfite (11 base agent) and 15s of sodium lauryl sulfate (emulsifier)
The procedure was the same as in Example 1 except for the use. After the polymerization reaction,
The produced neuproine-ethyl divinyl acrylate benzene sulfate copolymer was separated and purified, and then mixed with 50% methanol and 5N aqueous sodium hydroxide solution.
0% and hydrolyzed for 2 hours under methanol flow conditions to obtain 17% fibroin, 746% sodium acrylate, and divinylben(L6).
Fibroin with a composition of 8% and 8%
A sodium acrylate (AANa)-divinylbenzene (OVB)-styrene (St) graft copolymer was obtained. The water absorption capacity of this graft copolymer was 195 times.

Incidentally, the graft polymer of Mo2 in Table 4 is produced by copolymerizing acrylic acid, methylene bis acrylamide, and acryland as halfmers, and is produced by copolymerizing nine fibroin-acrylic acid (AA)-methylene bis acrylamide (MBAA).
II) -Acrylamide graft copolymer was produced in the same manner as in Example 1 by neutralizing the acrylic region of one integrated component with sodium hydroxide.

The graft polymer of No. 3 is fibroin-methacrylic acid under-2 ethylene glycol dimethacrylate (TK
GDMA)-graft polymer.

A4 Granod Polymer uses acrylic acid, vinyl acetate (VAO), and 1,6-hequinanediol diacrylate (t6 HDODA) as the leather cover, and produces fibroin-acrylic acid-produced through a copolymerization reaction. t6-
The graft polymer of Om5, which is produced by neutralizing the Sandiol diacrylate-vinyl acetate craft copolymer in the same manner as JI&2, contains acrylic acid and methylene bisacrylamide (MBAAm) as monomers. ), the produced fibroin-acrylic acid-methylenebisacrylamide (MBAAIll) graft copolymer was
It is produced by neutralization in the same manner as 2.

Muro's graft polymer is fibroin-acrylic acid-ethylene glycol dimethacrylate (KODMA), which is produced by copolymerizing acrylic acid, ethylene glycol dimethacrylate, and methyl acrylate as monomers.
)-methyl acrylate (AM) graft copolymer is produced by neutralizing acrylic acid, one of the combined components, with sodium hydroxide in the same manner as Nol1lI2.

As a graft combination of Mu7, acrylic acid (AA)
2-human p-xyethyl methacrylate) (EEMA
) and ethylene glycol dimethacrylate (KOD
The fibroin-acrylic acid-2-hydroxyethyl methacrylate-ethylene glycol dimethacrylate graft copolymer produced by copolymerization using MA) was neutralized in the same manner as Mu2.

The graft copolymer of Mome 8 contains acrylic acid and polyethylene glycol diacrylate as monomers [cu2=o
aaoo(oH2an2o)14ooa1(=ca2
) (PgGDA).

Each of the above-mentioned graft polymers was thoroughly washed with 60X ethanol, dried with MM, and filtered with a fine powder pulverized with a jet mill. Fibroin-acrylic aged sodium-tetraethylene glycol diacrylate graft polymer (ML composition is 1 layer ratio and 2 layers)
Except that α5 part of powder of 0:79.5 pairs (L5) was used in place of the fibroin-grafted poly 1- of Example 1.
The same procedure as in Example 1 was carried out.

The relationship between the performance of the obtained cream and the dead diameter is shown below.

M 6 Table As is clear from this result, the particle size when the fibroin graft polymer is continuously used is at most 100 μm, preferably 50 μm.
It is less than μ.

Example 5 Fibroin-acrylic soda polyethylene glycol diacrylate graft combination (a=5 in Example 1)
)(y-C)P), carboxymethyl cellulose (OM
O), carboxyvinyl polymer (Carboball)
4BA using polyvinyl alcohol (PVA) and polyvinyl alcohol (PVA) as emulsifiers was blended in the same manner as in Example 1. It is outstanding in terms of performance, such as stability, water resistance, moisture retention, and feel.

Example 6 (Cream) 1.0 part of the fibroin-graft polymer (water-insoluble water-absorbing polymer) of A3 in Example 1 (particle size 60 to 60 μm), and 11 parts of edetom disodium.

Example 1, except that ethyl alcohol and ethyl alcohol were changed as shown in Table 8, and water was adjusted to the amount necessary to bring the total concentration of the ingredients to 100.
Creams with different ethyl alcohol contents were prepared in the same manner as above. Its characteristic rudder is shown in Table 8.

As is clear from the results, even when ethyl alcohol is mixed with LIJ/Jt (25X or higher), a cream with good properties can be obtained in the emulsion, it has a refreshing feeling and is crushed, and has excellent water resistance and water resistance. In addition, in the range of 20% or less of ethyl alcohol content, ethyl alcohol 1-lua 7''l Add 15 parts of ethyl alcohol f, add each amount of pigment (titanium oxide) shown in the dX8 table, and adjust the amount of water to the required m (balance amount) to make the total wrinkles of the prescription ingredients 100 parts.
-The performance of the makeup base obtained is shown in Table 9.The performance of the makeup base obtained is shown in Table 9.

(Note) In Comparative 2, a carboxyvinyl polymer (carbopolymer) was used as an emulsifier in the fibroin-graft polymer No. 9.

As is clear from these results, the fibroin-graft polymer of the present invention exhibits unique and remarkable effects even in the coexistence of #I@.Example 8 (skin milk) - Graft polymer) 16 parts of water-insoluble water-absorbing polymer, 15 parts of ethyl alcohol, 40 parts of olive oil, 79.9 parts of water, 11 parts of edetate disodium, fragrance (always use skin milk consisting of L5 Zheng). It was prepared by the method.

The obtained skin milk is a smooth, glossy, homogeneous, and stable O/W tM emulsion with a viscosity f (50°C) of 4.
50000F! 3 (45℃, 420℃ after 5 months)
ps). Although it contained 15% ethyl alcohol, it was stable even after 3 months at 45°C, and no abnormality was noticed in 1 m of emulsion (extremely stable). Further, the water resistance (MOD' residual rate) was as high as 92% after 10 minutes, 89X after 50 minutes, and 81% in 1 hour, and the water repellency evaluation was also good at 4. Furthermore, panelists confirmed that when used, it not only gives a good feel such as a refreshing and moisturizing feeling to the skin, but also that makeup lasts well.

Example 9 (hair cream) 1.0 parts of the fibroin-gloss polymer (water-insoluble water-absorbing polymer) of Example 1, 8 parts of white petrolatum, 10 parts of beeswax, 15 parts of liquid paraffin, water 746 parts of edetate disodium, 11 parts of edetate disodium, and 5 parts of fragrance α were prepared in a conventional manner.

This hair cream is a homogeneous, stable 0/W emulsion with good texture and gloss, and the viscosity is 1.
5000CP8.45℃, 12110000 after 3 months
It was P8. The water repellency evaluation (as described in i11) was high with a rating of 1 to 5, and the emulsion stability after 5 months at 45°C was also good. In addition, when used, it was easy to remove and spread, gave hair a nice luster, and had good hair styling ability.

Example 10 (Sunscreen cream) Fibroin-grafted polymer of Mu3 of Example 1 (Suigun-soluble water-absorbing polymer) α8 parts, olive oil 10 parts, M
OEl 1.11 parts, ft, IdJ Puffin 9.0
1 part, 40 parts of ultraviolet ti1 absorber, 6 parts of water, 8 parts of water, 11 g of disodium edetate, and 3 parts of fragrance α.

The obtained sunscreen cream was a homogeneous and stable wax emulsion, and was found to have good emulsion stability, stable viscosity, and good quality after 6 months at 45°C. tIL's water repellency rating is 5,
The survival rate of MOD in terms of water resistance is 91 seconds after 10 minutes of swimming.
90% after 5As'' minutes and 8.6X after 1 hour.

Example 11 (Sunscreen cream) A sunscreen cream #IA was prepared in the same manner as in Example 10, except that MOD was not blended and 668 parts of water was used. The obtained sunscreen cream was a homogeneously stable 0/W emulsion, and had good emulsion stability at 45° C. for 3 months and good viscosity stability. In addition, the panelists (females = 19 out of 20) reported that the water repellency plan was 5, and the makeup retention during the iL period was as good as the sunscreen cream in Example 110. There is.

Example 12 (Cream hair treatment) Water 8
8 parts and 5 parts of Inpropyl Myristate.

Add 3 parts of fragrance a, and while stirring gently, proceed to step 4 of Example 1.
2 parts of Fibroin-Gunft polymer (water-insoluble water-absorbing polymer) of No. 5 was added as an emulsifier, and 1.
Stir for 0 minutes and apply the creamy hair treatment of the present invention (hereinafter referred to as treatment A for convenience)ttA&l
did.

This treatment A is stable even after 6 months at 45℃.
There was no abnormality in the emulsified embroidery, and no change was observed in the hardness (hardness was 6 by card meter). Also, for comparison, carboxyvinyl polymer (trade name, Carbo The first method using a hair ball (ball) is similar to that of the present invention described above.
Treatment (Treatment)
B) was ceramic-covered.

It was noted that when the hair treatment b kia was left at 5°C for 6 months, the emulsion stability deteriorated due to oil content, and the W degree also changed.

Next, the hair that has been thoroughly washed with shampoo is evenly coated with @tian treatment men (A and B), massaged, rinsed off with warm water, dried, and treated with 1. 11 hair 1°9"1 movement length *b measurement (hair smoothness, comb notification evaluation), basic 6 force measurement when folding (hair softness evaluation), The luster of the hair was rated according to the Wf rating. Those results are shown in the 10th
Table] J Eye Treatmen) A)
Treatment B (invention) (comparison) Dynamic ridge Ll, 156 0.206-
[Sirange stress -4, b6 b, 12 glossy iPF
m (points) 55 ffil) jlib Manatsu ridges are measured by radar method Masatsu measuring machine. (2) Bending stress is 1111 constant 0 (5) Gloss is 5! it place (5
9 based on the sensory evaluation (the best quality is set as i and the lowest as 1).

As is clear from this result, the tin-layered t-tail with hair treatment of the present invention is smooth and slips easily due to the small M-masatsu ridges, and is flexible because the stress when folded by 9 m is small. It was also confirmed that the 'i-6 needle price and the planned luster were good.

On the other hand, hair treated with Treatment B, which uses -C carboxypinyl polymer as an emulsifier, had a slightly larger stress when bent, and the hair tended to become slightly harder. I don't like it.

Example 19 (Skin Cream) Jill! as an emulsifier! 11 parts of A5 fibro (water-insoluble dazzling pentamer), 1 part of olive oil [10 parts,
1.0 parts of MOD, 19 parts of liquid paraffin.

Water 67, 6 Seagull, 11 parts of edetoid disodium, fragrance a
A skin cream consisting of 3 parts was prepared by a conventional method.The obtained skin cream had a 0/w d emulsion.The MOD residual rate in the water resistance mentioned above after 10 minutes was 9.
8 demons, 92% after 50 minutes and 85% after 1 hour, and the water repellency rating is 5 and 9.

Comparative Example 1 As an emulsifier, polyoxyethylene cetyl ether (WQ-=
An O/W type skin cream was prepared in the same manner as in Example 19 except that 0.5 parts of tristearin (gQm 20 mol) and 5 parts of tristearic polyoxyethylene sorbitan (gQm 20 mol) LL were used. In the aforementioned water resistance trial of this skin cream, the MOD cooking rate was 48 demons after 10 minutes.
It is 21% after 60 minutes and 8% after 1 hour wave, which is extremely low. In addition, as a result of the above-mentioned water rupture test conducted by a panel of panelists, the evaluation score was 0, and it was recognized that the skin cream applied to one finger turned white and dispersed in water with no water repellency.

Implementation v1114 In Example 1, the fc fibroin water bath solution was used.

Neuproin, acrylic acid, sodium acrylate, I
s2 Next, 20 parts and 14 parts of the pot-shaped mass are respectively
．． 5 parts, 65 parts, and 15 parts were mixed, and the mixture was diluted to 55% by volume on the surface. Next is the overtit
u5muj121LI, t for all monotonous bodies
7t4f7) Against 100ffllK? ◎The obtained washed carpet I4J was dried with hexane and methanol. ◎Each of the obtained fibroin-kraft weight Each cream was prepared in the same manner as in Example 1, except that the polymer (k-insoluble water-absorbing polymer) ft was used in place of the fibroin-craft polymer in Example 1. The characteristics of each ream made by A are shown in Table 11. 0 Procedural amendment (self-motivated) April 5, 1980, Japan Patent Office, Haruki Shimada, Patent of the 1956 patent Trial No. 20425"l @ 2 Name of the invention Emulsified cosmetics 5, Supplementary + E Minister with whom the patent applicant address 17-4 Sumida 5-chome, Tsuda-ku, Tokyo 554 Tomo, Korishima-ku, Osaka-shi Contents of Supplementary IE in Column 6 of “Detailed Description of the Invention” of 805j Fuchimachi 1-3 Non-ionic activators such as molds and ethers have poor emulsifying power." is deleted.

(2) Mei LAIEwJ+ sj (th + a row KeacD
Correct ruJ to C defense j.

(5) f (llI
Using J as a marker for 10 panelists and r (oily substance) as a marker, sample the sample on a panel of 1.
Corrected to 1 out of 0.

(4) “M from the calibration curve” stated on page 19, line 9 of the specification.
OD is corrected to j, and MOD in the sample is corrected to j from the calibration curve.

Claims (5)

[Claims] (1) Fibroin (A) 1 A crosslinkable monomer having an ethylenically unsaturated group or a glycidyl group at both ends (monomer (0) having an anionic group or an ethylene group at one end) A cream-like product made by blending an oil-based substance and water with a water-unbathable water-absorbing polymer as an emulsifier, which contains a nonionic capacitor (D) that is attached to a sexually unsaturated group 1 as a polymer component. Or emulsified cosmetics. (2) Fibroin is regenerated fibroin
Wt Mt The emulsified cosmetic according to item (1). (3) The molded lid body is made of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1.
6-hequinanediol diacrylate, methylene bis(
meth)acrylic ide, divinylbenzene, ethylene glycol diglycidyl ether, or glycidyl acrylate, the emulsified cosmetic according to item α) 0 (4) A single substance that emits anionic i is an acrylic compound,
Methacrylic acupuncture or acrylic sulfonic acid, or their alkali metal salts. It is an ammonium salt. Special 1'Fii^ Search range number (1
) Emulsified cosmetics described in section 0 (5) Non-ionic, acrylic late ester. Claims 1i1 Broom (1) Emulsified cosmetics made of methacrylic ester, acrylide, 2-hydroxy(meth)acrylate, ethylene, or acrylonitrile The polymer components include 1 to 40 μm of fibroin, 1 to 5% of monomer alpha, 60 to 95% of anionic monomer, and 0 to 0 to 95% of nonionic monomer. It consists of the composition of 20 electric 1iIL birds. Emulsified cosmetic according to claim (1), wherein the water-absorbing polymer (71ml/ml) is blended in an amount of 105 to 5.0ml based on the prescription ingredients. !f The emulsified cosmetic according to claim 1 (1) ◎ (mu) The pre-water distribution intolerant water-absorbing polymer has a water-absorbing capacity of at least 6 QtmQ/no,
%r1fI'# Desired range M (1) The emulsified cosmetic according to item 1. 19) [stl The water aqua regia-insoluble aqueous polymer contains 2 ibroin in water fa1tL, a crosslinkable monomer and a monomer having an anionic group, or a nonionic monocapsule in the dispersion. Scope of patent thIX (1): It is obtained by polymerizing and neutralizing if necessary. The emulsified cosmetics described in jl. ([) Preceding 1 Water-insoluble water-absorbing polymer is obtained by hydrolyzing 1 polymer produced by polymerizing a crosslinkable monomer and a nonionic monomer in an aqueous solution or dispersion of fibroia. The emulsified cosmetic according to claim (1), which is a water-absorbing water-absorbing polymer, is
1%a with a dry particle size of at most 100 microns
ff l# *Range No. 11 (Emulsified cosmetics described in dust)
(12) K-methyl alcohol or emulsified cosmetics as described in item (1) within the range of 2 seconds for the total amount of prescribed ingredients 0 (15) *
To. The emulsified cosmetic according to item (1), in which the amount of ingredient M is blended in an amount of at most 5% based on the total amount of prescription ingredients.