HK1116669B - Cosmetic - Google Patents
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- HK1116669B HK1116669B HK08107300.2A HK08107300A HK1116669B HK 1116669 B HK1116669 B HK 1116669B HK 08107300 A HK08107300 A HK 08107300A HK 1116669 B HK1116669 B HK 1116669B
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Description
Technical Field
The present invention relates to a cosmetic containing glycerin having a specific structure and modified at both ends with silicone.
Background
Silicone oil is blended in many cosmetics as an oil component having a refreshing feeling. For example, an alkyl-modified silicone (patent document 1), a fluorine-modified silicone (patent document 2), a cholesterol-modified silicone (patent document 3), an acylalkylimine-modified silicone (patent document 4), a glyceryl-modified silicone (patent document 5), an alkyl glyceryl ether-modified silicone (patent document 6), and an alkyl monoglycidyl ether/fluorine co-modified silicone (patent document 7) are blended in a cosmetic.
However, silicone oils have a strong refreshing feel and leave a rough skin feel (きしみ feel), and therefore silicone oil components having a good skin-friendly feel are strongly desired.
On the other hand, water-in-oil emulsion compositions containing an oil phase as an external phase and an aqueous phase as an internal phase are used in various cosmetics. The water-in-oil emulsion composition is excellent in protecting skin, imparting skin softness, suppressing skin moisture evaporation, and the like, as compared with the oil-in-water emulsion composition, and is a suitable formulation for use as an external preparation for skin.
Conventionally, as an emulsifier for a water-in-oil emulsion composition, a lipophilic surfactant having HLB of about 1 to 12, for example, a polyol fatty acid ester surfactant such as a glycerin fatty acid ester and a sorbitan fatty acid ester, and a polyoxyalkylene-modified polyorganosiloxane surfactant have been used (non-patent document 1).
However, water-in-oil emulsion compositions using these emulsifiers are poor in emulsion stability, and the aqueous phase and the oil phase separate under high temperature conditions or with time, and it is extremely difficult to stabilize the formulation.
In addition, a method of stabilizing a dosage form by blending a wax in an oil phase as an external phase has also been employed. However, the wax melts or softens under high temperature conditions, and thus the stability of the preparation is insufficient. And has new problems in use such as hard extension and adhesive feeling in coating.
Since many cosmetics containing powders such as sunscreens and foundations require water resistance and perspiration resistance, hydrophobic powders are often incorporated in W/O type preparations.
However, when a large amount of powder is blended in a W/O type preparation, the viscosity of the preparation increases due to aggregation of the powder, and the preparation is difficult to spread during use and the skin becomes too white after application. Therefore, a technique of dispersing the powder in the oil agent more stably has been developed.
The technique of primary dispersion of powder is further developed by a micronizing apparatus such as a roll mill, a sand mill, a high-pressure homogenizer, etc., but it is an important problem to disperse the finely dispersed powder without agglomeration for a long time. Many cosmetic compositions contain silicone oil as an oil component, and thus, a patent relating to a powder dispersant using a modified silicone has been filed. For example, patent document 8 discloses a powder-in-oil dispersion obtained by copolymerizing (a) a polyorganosiloxane monomer and (B) a monomer having a polylactone-containing group, a hydroxyl group, or an anionic group. Patent document 9 discloses dispersing ultraviolet-blocking fine particles with a silicone-based dispersant containing a modified silicone or a reactive silicone.
Patent document 10 discloses a dispersant of inorganic powder in oil, which contains a fatty acid to which an alkylene oxide is added, and examples thereof include POE (4.5) lauryl ether acetic acid, POE (4) stearyl ether acetic acid, POE (10) lauryl ether acetic acid, POE (12) stearyl ether acetic acid, and POE (10) sodium lauryl ether acetate, and the dispersibility and stability thereof were confirmed.
Patent document 1: japanese patent laid-open No. 5-262616
Patent document 2: japanese patent laid-open No. 5-247214
Patent document 3: japanese patent laid-open No. 5-25280
Patent document 4: japanese patent laid-open No. 5-112423
Patent document 5: japanese unexamined patent publication No. 6-157236
Patent document 6: japanese patent laid-open No. 5-112424
Patent document 7: japanese patent laid-open No. 9-249518
Patent document 8: japanese laid-open patent publication No. 11-263706
Patent document 9: re-published patent WO97/45097
Patent document 10: japanese patent laid-open No. 2000-262883
Non-patent document 1: "fourth edition oil chemistry toilet-lipid surfactant", 2001, edited by Nippon oil chemistry society, Takayao Kaisha
Disclosure of Invention
Problems to be solved by the invention
The present inventors have conducted intensive studies with respect to the above-mentioned viewpoints, and as a result, have found that: by blending glycerin having a specific structure and both ends modified with silicone as an oil component, a cosmetic, an oily cosmetic, a water-in-oil type emulsion cosmetic, and an oil-in-water type emulsion composition having a good refreshing feel and good skin suitability can be obtained, and a cosmetic having excellent powder dispersibility can be obtained, and the present invention has been completed.
The purpose of the present invention is to provide a cosmetic that is refreshing and has a good feeling of use with good skin compatibility.
Means for solving the problems
That is, the present invention provides a cosmetic characterized by: the cosmetic contains glycerin of which both ends are modified with silicone and which is represented by the following general formula (a).
(a)
[ chemical formula 1]
Wherein R1 is a C1-12 linear or branched alkyl group or a phenyl group, R2 is a C2-11 alkylene group, m is 10-120, and n is 1-11.
The present invention also provides the cosmetic described above, which is characterized in that: the cosmetic is oily cosmetic.
The present invention also provides the cosmetic described above, which is characterized in that: the cosmetic is water-in-oil type emulsion cosmetic.
The present invention also provides the cosmetic described above, which is characterized in that: the cosmetic is oil-in-water emulsion composition.
The present invention also provides the cosmetic described above, which is characterized in that: the cosmetic also contains powder.
Effects of the invention
(1) The cosmetic composition of the present invention contains glycerin having a specific structure and both ends modified with silicone as an oil component, and therefore has a refreshing feeling and excellent skin-friendly properties.
(2) The glycerin modified at both ends with silicone used in the present invention exerts an excellent emulsifying function for the water-in-oil type emulsion composition. As a result, a water-in-oil type emulsion cosmetic which is excellent in stability and feeling of use can be provided substantially without blending a surfactant.
(3) An emulsion composition having excellent stability and usability can be obtained by using an oil-in-water type emulsion cosmetic in combination with a known hydrophilic emulsifier.
(4) The cosmetic of the present invention has extremely high dispersion stability of the powder, and can provide a stable powder-dispersed cosmetic. In particular, in an oil containing silicone oil, the stability of the powder is remarkably high. Fig. 1 is a schematic diagram showing the dispersion stability of the powder. It can be considered that: since the glycerin having both ends modified with the siloxane functions as a powder dispersion stabilizer and has a dispersion site containing a siloxane chain at both ends, the powder can be held in an adsorption site containing a polyglycerol chain having a very high adsorbability, and the polymer can be diffused in a solvent of a dispersion medium, thereby exhibiting a very significant dispersion stability effect.
(5) The glycerin modified at both ends with silicone used in the present invention can exhibit various HLB and viscosity in cosmetics by appropriately selecting the molecular weight of the polydimethylsiloxane chain and the polyglycerol chain. As a result, a cosmetic having a desired feeling of use can be designed.
Brief Description of Drawings
FIG. 1 is a schematic diagram showing the powder dispersion stability of glycerin modified at both ends with silicone used in the present invention.
FIG. 2 is a diagram illustrating a scheme for synthesizing glycerin modified at both ends with silicone by an ether bond.
FIG. 3 is an IR spectrum of glycerin modified at both ends with silicone of Synthesis example 1.
Fig. 4 shows the results of rheological measurements of powder dispersion compositions obtained using glycerin modified at both ends with silicone of synthesis example 1, with the shear rate being varied.
Fig. 5 shows the results of rheological measurements of powder dispersion compositions obtained using glycerin modified at both ends with silicone of synthesis example 2, with the shear rate being varied.
Fig. 6 shows the results of rheological measurements obtained by changing the shear rate of the powder dispersion composition obtained using the polyether-modified glycerin of the comparative example sample.
Best Mode for Carrying Out The Invention
The basic structure of the glycerin modified at both ends with silicone used in the present invention is a BAB type triblock copolymer, and for B, for example, silicone having a hydrogen residue at one end as shown in the following structure (c) or the like can be used. In the general formula (a), R1 may be the same or different. Each R2 may be the same or different.
A is a glycerol residue.
The siloxane having a hydrogen at one terminal of the following structure (c) is a known compound. The BAB type triblock copolymer of arbitrary polymerization degree can be prepared by a known method.
(c)
[ chemical formula 2]
Wherein R1 is a straight chain or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, and m is a number of 10 to 120. R1 may be the same or different.
The bond between A and B is not an essential structure for the present invention, but glycerin modified at both ends with siloxane exemplified in the present invention is obtained by bonding a compound (c) and a compound represented by the following structural formula (d) through an ether bond using a platinum catalyst.
(d)
[ chemical formula 3]
Wherein n is a number of 1 to 11.
The BAB type triblock copolymer can be synthesized by a known method. The synthetic scheme is shown in FIG. 2.
As described above, glycerol having both ends modified with siloxane represented by the following structural formula (a) { preferably structural formula (b) } can be obtained.
(a)
[ chemical formula 4]
Wherein R1 is a C1-12 linear or branched alkyl group or a phenyl group, R2 is a C2-11 alkyl group, m is 10-120, and n is 1-11.
(b)
[ chemical formula 5]
Wherein R1 is a C1-12 linear or branched alkyl or phenyl, m is 10-120, and n is 1-11.
The polymerization degree m of the siloxane chain is preferably 10 to 120. The branched substituent is preferably a methyl group, and may be substituted with a phenyl group or other alkyl group.
The polymerization degree n of the glycerol chain is preferably 1 to 11.
As shown in fig. 1, in the functional expression of glycerin modified at both ends with siloxane, the solubility of the B block in a solvent and the high adsorption of the a block to the powder surface are important. That is, the hydrophilic/lipophilic balance (HLB) of the AB diblock is within a suitable range, which is necessary for functional expression. The HLB can be determined by a known method, and is calculated by, for example, Griffin's formula (HLB value ═ partial molecular weight of glycerin × 20/total molecular weight). In the present invention, the HLB is preferably 0.2 to 3.0.
The expansion of the a segment for preventing aggregation between powders is related to the molecular weight of the polymer, and the higher the molecular weight of the a segment is, the higher the effect of preventing aggregation is. On the other hand, adsorption to the powder is achieved by weak forces such as van der waals force and hydrogen bond of the B block. However, by using polyglycerol as the B block, a strong adsorbability can be obtained as compared with polyethylene glycol or the like, and therefore a sufficient adsorbability can be obtained with a low molecular weight. In addition, too high a molecular weight of the AB diblock makes the cosmetic difficult to spread and extend, and may feel less extensible. In view of the above, the molecular weight is also within an appropriate range, and the molecular weight is preferably 2000 to 20000.
The amount of glycerin modified at both ends with silicone used in the present invention can be determined as appropriate. The amount of the cosmetic is usually 0.1 to 50% by mass, preferably 0.1 to 30% by mass, based on the total amount of the cosmetic.
In a cosmetic containing a powder and a silicone oil, about 0.1 to 30% by mass of glycerin having both ends modified with silicone is generally blended with respect to the total amount of the powder, the silicone oil and the glycerin having both ends modified with silicone.
In the cosmetic of the present invention, other oil components may be blended in addition to glycerin modified at both ends with silicone as an oil component. The present invention is preferably an oily cosmetic.
Preferred are one or more kinds of oil components such as chain polysiloxanes such as polydimethylsiloxane and polymethylphenylsiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, modified siloxanes such as polyether-modified siloxanes, alkyl-modified siloxanes and epoxy-modified siloxanes, and silicone resins such as trimethylsiloxysilicacid and high-polymerized polymethylsiloxane.
Other oily components may be blended in the silicone dispersion medium within the range not impairing the effects of the present invention. For example, liquid paraffin, solid paraffin, vaseline, ceresin, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyl octanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyldiol monoisostearate, neopentyl glycol didecanoate, diisostearyl malate, glycerol di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, glycerol trioctanoate, etc. may be blended, Triisopalmitin, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, 2-ethylhexyl palmitate, glycerol trimyristate, glycerol tri-2-heptylundecanoate, methyl ricinoleate, oleyl oleate, acetin, 2-heptylundecyl palmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, cetyl 2-ethylhexylsebacate, glyceryl hexa-2-ethylhexoate, glyceryl hexa-2-hexylsebacate, glyceryl hexa-2, Diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, sesame oil, wheat germ oil, camellia oil, castor oil, linseed oil, safflower oil, cottonseed oil, soybean oil, peanut oil, grape seed oil, almond oil, tea seed oil, rice bran oil, jojoba oil, meadowfoam oil (meadowfoam), germ oil and other oil components.
The glycerin modified at both ends with silicone exerts an excellent emulsifier function for a water-in-oil type emulsion cosmetic. Therefore, the present invention can provide a water-in-oil type emulsion cosmetic excellent in emulsion stability and usability. The amount of glycerin modified with silicone at both ends, which functions as an emulsifier, is not particularly limited. Usually, the amount of the surfactant is 0.1 to 10.0% by mass based on the water-in-oil emulsion cosmetic. The amount of the additive is preferably 0.5 to 5.0% by mass. When the amount is less than 0.1% by mass, the emulsion stability is poor, and even when the amount is more than 10.0% by mass, the effect is not necessarily further improved. In the water-in-oil type emulsion cosmetic of the present invention, other emulsifiers may be used in combination, and a stable emulsion cosmetic can be obtained by substantially blending glycerin having both ends modified with silicone.
On the other hand, the glycerin modified at both ends with silicone can be used in combination with a known hydrophilic emulsifier in an oil-in-water type emulsion cosmetic to obtain an emulsion composition having excellent stability and usability. The amount of the silicone-modified glycerin blended at both ends is usually 0.1 to 30% by mass based on the total amount of the oil phase (the total amount of the powder dispersed in the oil phase and the oil component constituting the oil phase) in the oil-in-water emulsion cosmetic. The amount of the hydrophilic emulsifier to be blended is not particularly limited. The amount of the oil-in-water emulsion cosmetic is usually 0.1 to 10.0% by mass.
The present invention can improve the powder dispersibility or emulsion stability of glycerin obtained by blending glycerin having both ends modified with silicone into a cosmetic. In the cosmetic of the present invention, the ingredients used in usual cosmetics or pharmaceuticals may be prepared by a conventional method within a range not impairing the effects of the present invention.
The oil component to be blended in the water-in-oil type emulsion cosmetic and the oil-in-water type emulsion cosmetic is not limited. The amount of the oil component to be blended is not limited and can be determined appropriately, and in the case of a water-in-oil type emulsion cosmetic, the amount of the oil component to be blended is usually 10 to 95% by mass, preferably 20 to 80% by mass; in the case of an oil-in-water type emulsion cosmetic, the amount of the oil component is 5 to 70% by mass, preferably 10 to 30% by mass. The cosmetic of the present invention can be prepared by mixing the essential components according to a conventional method.
The cosmetic of the present invention is excellent in powder dispersibility, and therefore is preferably used as a cosmetic containing a powder. The dispersed powder is not particularly limited. Inorganic powders (particularly titanium oxide or zinc oxide) are preferred. The dispersion stability in the powder obtained by mixing the two powders is extremely high, which is also a feature of the present invention.
The average particle diameter of the powder is preferably 0.5 to 150 nm.
In this case, if a powder of titanium oxide or zinc oxide is blended as the ultraviolet scattering agent, fine particles having an average particle diameter of 1 to 50nm are preferable.
The powder incorporated in the cosmetic of the present invention can also improve the dispersion stability of the powder by surface-treating the powder.
The cosmetic of the present invention containing the powder can be prepared by subjecting the powder, glycerin modified at both ends with silicone, and a silicone-based dispersion medium to mechanical dispersion treatment.
The premixing or dispersion treatment may be carried out by using an appropriate dispersing machine while heating, if necessary. The dispersion may be carried out by using a roll mill, a high-pressure homogenizer, a sand mill or the like as appropriate depending on the viscosity of the slurry to be adjusted.
The powder dispersed in the cosmetic may preferably contain an ultraviolet scattering agent. Examples of the ultraviolet scattering agent include inorganic powders such as titanium oxide and zinc oxide, and inorganic powders having a surface coated with a fatty acid soap such as aluminum stearate and zinc palmitate, a fatty acid such as stearic acid, myristic acid and palmitic acid, a fatty acid ester such as dextrin palmitate, and the like.
One or more of the above-mentioned ultraviolet scattering agents may be selected and compounded. The amount of the ultraviolet scattering agent blended is 0.1 to 50.0% by mass, and more preferably 1.0 to 40.0% by mass in the cosmetic. When the amount of the uv scattering agent is too small, a sufficient uv protection effect cannot be obtained, and when it is too large, an emulsion may not be obtained. The cosmetic of the present invention has an excellent effect of extremely well dispersing the ultraviolet scattering agent powder.
The use of the cosmetic of the present invention is not particularly limited. For example, it can be applied to various products such as lotions, milky lotions, creams, foundations, lip glosses, cleansing foams, shampoos, conditioners, lip glosses, hair sprays, hair styling foams, sunscreens, skin creams, eyeliners, mascaras, nail creams, body makeup cosmetics, and the like.
Examples
The present invention will be described more specifically with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, the amount of the compound is% by mass based on the total amount. Synthesis example 1 Synthesis of glycerin modified at both ends with Silicone "
100g of a single-terminal hydrogenated polydimethylsiloxane of the formula (e) (Mw. apprxeq.4600), 3.5g of triglycerol diallyl ether and 100g of isopropanol were charged into a reaction vessel, and 0.05g of 3% chloroplatinic acid isopropanol solution was added and reacted at 80 ℃ for 5 hours. Then, 1.5g of 0.01N aqueous HCl solution was added, hydrolysis was performed at 60 ℃ for 3 hours, and then 0.2g of 1% aqueous sodium bicarbonate solution was added for neutralization. The reaction mixture was concentrated by evaporation to obtain the objective compound as a viscous liquid having fluidity.
(e)
[ chemical formula 6]
Synthesis example 2 Synthesis of Glycerol modified at both terminals with Silicone "
100g of single-ended hydrogenated polydimethylsiloxane of the formula (e) (Mw. apprxeq.4600), 4.3g of tetraglycerol diallyl ether and 100g of isopropanol were charged to a reaction vessel, and 0.05g of 3% chloroplatinic acid isopropanol solution was added and reacted at 80 ℃ for 5 hours. Then, 1.5g of 0.01N aqueous HCl solution was added, hydrolysis was performed at 60 ℃ for 3 hours, and then 0.2g of 1% aqueous sodium bicarbonate solution was added for neutralization. The reaction mixture was concentrated by evaporation to obtain the objective compound as a viscous liquid having fluidity.
(e)
[ chemical formula 7]
Synthesis example 3 Synthesis of glycerin modified at both ends with Silicone "
100g of single-ended hydrogenated polydimethylsiloxane of the formula (f) (Mw. apprxeq.7600), 2.6g of tetraglycerol diallyl ether and 100g of isopropanol were charged into a reaction vessel, and 0.05g of 3% chloroplatinic acid isopropanol solution was added and reacted at 80 ℃ for 5 hours. Then, 1.5g of 0.01N aqueous HCl solution was added, hydrolysis was performed at 60 ℃ for 3 hours, and then 0.2g of 1% aqueous sodium bicarbonate solution was added for neutralization. The reaction mixture was concentrated by evaporation to obtain the objective compound as a viscous liquid having fluidity.
(f)
[ chemical formula 8]
Synthesis example 4 Synthesis of glycerin modified at both ends with Silicone "
100g of single-terminal hydrogenated polymethylphenylsiloxane of the formula (g) (Mw. apprxeq.5600), 2.9g of triglycerol diallyl ether and 100g of isopropanol were charged into a reaction vessel, and 0.05g of 3% chloroplatinic acid isopropanol solution was added and reacted at 80 ℃ for 5 hours. Then, 1.5g of 0.01N aqueous HCl solution was added, hydrolysis was performed at 60 ℃ for 3 hours, and then 0.2g of 1% aqueous sodium bicarbonate solution was added for neutralization. The reaction mixture was concentrated by evaporation to obtain the objective compound as a viscous liquid having fluidity.
(g)
[ chemical formula 9]
In the formula, Ph represents a phenyl group.
Synthesis example 5 Synthesis of glycerin modified at both ends with Silicone "
100g of single-terminal hydrogenated polymethyldodecylsiloxane of the formula (h) (Mw. apprxeq.5900), 2.7g of triglycerol diallyl ether and 100g of isopropanol were charged into a reaction vessel, and 0.05g of 3% chloroplatinic acid isopropanol solution was added and reacted at 80 ℃ for 5 hours. Then, 1.5g of 0.01N aqueous HCl solution was added, hydrolysis was performed at 60 ℃ for 3 hours, and then 0.2g of 1% aqueous sodium bicarbonate solution was added for neutralization. The reaction mixture was concentrated by evaporation to obtain the objective compound as a viscous liquid having fluidity.
(h)
The above-mentioned compoundsThe synthetic schemes of examples 1-5 are shown in FIG. 2. Fig. 3 shows an IR spectrum of example 1. 800, 1000, 1260, 2960cm in spectrum-1The nearby peak is from dimethylpolysiloxane, 1400cm-1The vicinity is a peak derived from a secondary alcohol of polyglycerol, and it is found that the synthesis proceeds according to a synthetic scheme and the target compound can be obtained.
Evaluation of Dispersion stability "
< preparation of Dispersion >
38g of fine particle powder, 5g of the dispersant prepared by the methods of Synthesis examples 1 and 2, and a comparative sample were added to 57g of a silicone-based dispersion medium so that the weight ratio to the fine particle powder was 1:1, glass beads (1 mm. phi.) were added, and the mixture was mixed with a paint shaker mixer (ペィントシェィカ -) for 1 hour to prepare a slurry-like dispersion. In addition, a dispersion was also prepared in the same manner by using 5g of the dispersant prepared by the method of comparative example 1 instead of the dispersant prepared in synthesis example 1. The dispersed powder was a mixed powder obtained by mixing half amounts of P1 and P2, respectively.
The components used are shown below.
(1) Fine particle powder (P1): fatty acid soap treated particulate titanium dioxide
Trade name: 100TV (ティカ company)
Particle size: a long diameter of about 0.03 μm and a short diameter of about 0.005 μm
Aluminum myristate treatment amount: 10% by mass
(2) Fine particle powder (P2): silica-coated zinc oxide treated with siloxane
Trade name: SS-Activox C80 (Showa electrician)
Particle size: about 0.03 μm
Silica treatment amount: 20% by mass
(3) Comparison of samples: polyether modified siloxane
Trade name: siloxane KF6017 (preparation of Xinyue chemical industry)
Polyether modification rate: 20 percent of
Molecular weight: about 6000
HLB value: 4.0
(4) Dispersion medium: decamethylcyclopentasiloxane
Trade name: KF-995 (Xinyue chemical industry preparation)
< evaluation of Dispersion Property >
The dispersion was subjected to rheological measurement to evaluate the dispersion stability of the glycerin powder modified at both ends with silicone.
(evaluation method)
An evaluation device: TA ィンスツルメンツ Cone plate viscometer AR1000-N
The measurement conditions were as follows: 4cm4 DEG steel geometry
Shear rate 0.1s-1～500s-125℃
(results)
The evaluation results of the dispersion prepared using glycerin of synthesis example 1, both ends of which were modified with silicone, are shown in fig. 4.
The evaluation results of the dispersion prepared using glycerin of synthesis example 2, both ends of which were modified with silicone, are shown in fig. 5.
The evaluation results of the dispersion prepared using the comparative sample, polyether-modified siloxane, are shown in fig. 6.
When the dispersion stability of the powder in the dispersion is good, the flow characteristics of the dispersion medium siloxane reflect the flow characteristics of the dispersion medium siloxane, and the viscosity shows a newtonian dynamic state in which the viscosity is almost constant at any shear rate.
In fig. 6 showing the dynamic behavior of the dispersion obtained using the dispersant of the comparative sample, a significant increase in viscosity was observed in the low shear rate region of the dispersion obtained by mixing titanium oxide (P1) and zinc oxide (P2), indicating that the powder was aggregated.
On the other hand, in fig. 4 showing the dynamic behavior of the dispersion obtained by using the dispersants synthesized in synthesis examples 1 and 2, the dispersion obtained by mixing titanium oxide (P1) and zinc oxide (P2) showed almost newtonian flow characteristics, and the dispersion stability was very good. At present, no report has been found on a dispersant which exhibits almost newtonian dynamics in a dispersion when mixed powders (P1 and P2) are used, and the effect of improving dispersion stability is very remarkable.
As is clear from the evaluation and measurement, the compounds of Synthesis examples 1 to 2 exhibited excellent dispersion stabilizer action. The compound of Synthesis example 3 also exhibited the same dispersion stability as that of Synthesis examples 1 to 2.
"evaluation of dispersion stability: relationship between HLB and molecular weight "
Powder dispersion characteristics of glycerin and polyether-modified silicone modified at both ends, which were synthesized in the same manner as in synthesis examples 1 to 3 and comparative samples, were evaluated by rheological measurements in the same manner as described above, and the results are shown below. As is clear from the tables below, glycerin modified at both ends with silicone used in the present invention has excellent dispersion characteristics.
[ Table 1]
< evaluation results of powder Dispersion stabilizer having molecular weight of 11000 >
| Glycerol HLB value modified at both ends by siloxane | Dispersion characteristics |
| 0.10.150.20.481.41.82.02.52.83.2 | ××○○○○○○○△ |
| 4.8 | × |
| Polyether modified siloxane HLB value | Dispersion characteristics |
| 0.51.84.0 | ××× |
Dispersion characteristics
O: good, Δ: substantially good, x: failure of the product
[ Table 2]
< evaluation result of powder Dispersion stabilizer having HLB value of 0.5 >
| Glycerol modified at both ends by siloxane | Dispersion characteristics |
| 1000150020003000500090001200015000200002500031000 | ×△○○○○○○○×× |
| Polyether modified siloxane molecular weight | Dispersion characteristics |
| 6000 | × |
| 1100015000 | ×× |
Dispersion characteristics
O: good, Δ: substantially good, x: failure of the product
Next, an emulsion stability test was performed on a water-in-oil cream containing glycerin modified at both ends with silicone as an emulsifier and a water-in-oil cream containing a conventional emulsifier. The formulation composition of the water-in-oil cream and the results thereof are shown in the following "table 3". In comparative example 1, diglycerol diisostearate was used as a typical conventional water-in-oil emulsifier, and in comparative example 2, POE (3) hardened castor oil was used. 2-ethylhexyl p-methoxycinnamate (IOB0.28) and di-2-ethylhexyl succinate (IOB0.32) are blended as polar oily components.
(1) Long term stability (after 1 month)
The water-in-oil creams of examples and comparative examples were kept at room temperature for one month, and then the morphology of the emulsion was observed visually (or under an optical microscope).
< evaluation criteria >
Very good: the particles are uniform and the emulsion state is good.
O: the particles were slightly uneven, but the emulsified state was good.
And (delta): coarse particles, separation of the water phase and the oil phase can be seen.
X: the aqueous and oil phases were completely separated.
(2) Temperature stability (50 ℃ C.)
The water-in-oil creams of examples and comparative examples were stored at 50 ℃ for one month, and then the morphology of the emulsion was observed visually (or under an optical microscope). The evaluation criteria are as follows.
< evaluation criteria >
Very good: the particles are uniform and the emulsified state is very good.
O: the particles are substantially uniform and the emulsion state is good.
And (delta): slight unevenness was observed in the particles, and slight separation of the aqueous phase and the oil phase was observed.
X: the aqueous and oil phases were completely separated.
[ Table 3]
| Example A | Comparative example 1 | Comparative example 2 | |
| Synthesis example 1 polyglycerin modified at both ends with Silicone | 2.5 | — | — |
| Diglycerol diisostearate | — | 2.5 | — |
| POE (3) hardened Castor oil | — | — | 2.5 |
| Ion exchange water | Balance of | Balance of | Balance of |
| Polyethylene glycol | 1.0 | 1.0 | 1.0 |
| 1, 3-butanediol | 5.0 | 5.0 | 5.0 |
| Preservative | Proper amount of | Proper amount of | Proper amount of |
| Decamethylcyclopentasiloxane | 12.0 | 12.0 | 12.0 |
| 2-ethylhexyl p-methoxycinnamate | 10.0 | 10.0 | 10.0 |
| Succinic acid di (2-ethylhexyl) ester | 2.0 | 2.0 | 2.0 |
| Long term stability (1 month) | ◎ | △ | △ |
| Temperature stability (50 ℃ C.) | ◎ | △ | △ |
From the results of "table 3" above, it is understood that example a of the present invention is extremely superior in long-term stability and temperature stability of the emulsion composition to comparative examples 1 and 2 using the conventional water-in-oil emulsifier.
The following is a cosmetic containing glycerin modified at both ends with silicone.
Example 1< Mascara >
(evaluation)
The obtained mascara had good gloss and excellent color development.
Example 2< Mascara >
(evaluation)
The obtained mascara had good gloss and excellent color development.
Example 3< Mascara >
(evaluation)
The obtained mascara had good gloss and excellent color development.
Example 4< Mascara >
(evaluation)
The obtained mascara had good gloss and excellent color development.
Example 5< lip gloss >
(*) 15% of a methyl methacrylate monomer, 25% of an ethyl acrylate monomer, 0.1% of a polymerization initiator, and 5% of a dispersion stabilizer, a polydimethylsiloxane graft polymer (molecular weight: about 15 ten thousand) were added to 54.9% of decamethylcyclopentasiloxane as a dispersion medium, and stirred at 120 ℃ for 10 hours to carry out polymerization, followed by a demonomerization treatment under reduced pressure, and then cooled to 25 ℃ to obtain a non-aqueous polymer dispersion having an opalescent appearance and a volatile siloxane of 1 μm average particle size of the dispersed polymer particles as a dispersion medium.
(evaluation)
The obtained lip gloss has moist feeling, less stickiness, and good feeling in use.
Example 6< lip gloss >
(evaluation)
The obtained lip gloss has good gloss, moist feeling, less stickiness, and good feeling in use.
Example 7< lip gloss >
(evaluation)
The obtained lip gloss has moist feeling, less stickiness, and good feeling in use.
Example 8< solid powdered foundation >
(evaluation)
The obtained solid powdery foundation was excellent in color development and very smooth to the touch of the skin.
Example 9< solid powdered Foundation >
Example 10< solid powdered foundation >
(production method and evaluation)
The powder component, oily component and mica titanium ground solution in the formulation were dispersed and mixed in ethanol using a sand-blasting grinder having zirconia beads with a diameter of 3mm incorporated therein. After ethanol was distilled, the mixture was pulverized once with パルペラィザ —, and the resulting powder was filled into a container (resin dish) and dry-molded by a known method to obtain a solid powder foundation. The obtained solid powdery foundation was excellent in smoothness.
Example 11< solid powdered foundation >
(production method and evaluation)
The cosmetic base is prepared by mixing the powder components with a Henschel high speed kneader or the like, adding the oil component, and uniformly mixing. Adding 60-70% by mass of ethanol, and uniformly mixing to prepare slurry. In this case, the ethanol is removed, and a part of the oily components is lost, so that the amount of the ethanol added is 120 to 160% in large amount, and the amount of the final product is adjusted to a prescribed amount in the formulation. This was filled into a dish, and compression molding was performed using a molding head (molding pressure 20kg) while sucking ethanol from the inside of the molding head. After the suction, the molded article was dried at 50 ℃ for 2 hours. The slurry obtained in the preparation step has high fluidity and improved yield.
Example 12< Foundation >
(production method and evaluation)
Heating the oily component and the aqueous component respectively to dissolve completely. Adding the water phase into the oil phase, and emulsifying by using an emulsifying machine. The obtained emulsion was cooled by a heat exchanger to obtain a foundation. The obtained foundation had excellent smoothness, no stickiness, and good feeling in use.
Example 13< Foundation >
(production method and evaluation)
Heating the oily component and the aqueous component respectively to dissolve completely. Adding the water phase into the oil phase, and emulsifying by using an emulsifying machine. The obtained emulsion was cooled by a heat exchanger to obtain a foundation. The obtained foundation had excellent smoothness, no stickiness, and good feeling in use.
Example 14< Hair conditioner >
(production method and evaluation)
Mixing the above components according to conventional method to obtain hair conditioner. The obtained hair conditioner has no sticky feeling, no roughness, and improved smoothness of hair.
Example 15< Hair conditioner >
(production method and evaluation)
Mixing the above components according to conventional method to obtain hair conditioner. The obtained hair conditioner has no sticky feeling, no roughness, and improved smoothness of hair.
Example 16< Hair conditioner >
(production method and evaluation)
Mixing the above components according to conventional method to obtain hair conditioner. The obtained hair conditioner has good feeling and improved smoothness of hair.
Example 17< shampoo >
(production method and evaluation)
Mixing the above components according to conventional method to obtain shampoo. When used, the hair washed with the resulting shampoo was excellent in feeling.
Example 18< shampoo >
(production method and evaluation)
Mixing the above components according to conventional method to obtain shampoo. When used, the hair washed with the obtained shampoo had excellent feeling, and the dried hair had luster.
Example 19 combination of shampoo and Hair conditioner
< production method and evaluation >
Mixing the above components according to conventional method to obtain two-in-one product of shampoo and hair conditioner. When used, the obtained shampoo and conditioner combination product has excellent hair feeling, especially smooth feeling, and the hair is still smooth after drying.
Example 20< cleaning oil >
(production method and evaluation)
Mixing and melting to obtain the clean oil. The obtained cleaning oil was smooth and free from a sticky feeling, no rough feeling after washing, and good in use feeling.
Example 21< cleaning oil >
(production method and evaluation)
Mixing and melting to obtain the clean oil. The obtained cleaning oil was smooth and free from a sticky feeling, no rough feeling after washing, and good in use feeling.
Example 22< hairspray >
Stock solution/propellant 40/60(lp.g.0.115mpa)
(production method and evaluation)
Mixing and melting, and making into aerosol spray according to the above composition ratio. The hair spray obtained as described above can be sprayed to reduce the sticky feeling after application and exhibit a smooth and good feeling.
Example 23< Hair cream >
(evaluation)
The hair cream gives a soft feeling to hair and exhibits excellent effects.
Example 24< Hair cream >
Example 25< Hair cream >
(evaluation)
The hair cream gives a soft feeling to hair and exhibits excellent effects.
Example 26< mousse >
Stock solution/propellant 40/60(lp.g.0.43mpa)
(production method and evaluation)
Mixing and dissolving the aqueous component and the oily component, adding the oil phase into the water phase, and emulsifying with a homogenizer. The obtained emulsion is made into aerosol preparation according to the above composition. The obtained mousse was smooth and free from sticky feeling, and showed good usability.
Example 27< Hair wax >
Stock solution/propellant 90/10(lp.g.0.43mpa)
(evaluation)
The hair wax had no sticky feeling, was smooth and glossy, and showed good feeling in use.
Example 28< wax >
(evaluation)
The hair wax had no sticky feeling and showed good feeling in use.
Example 29< Hair oil >
(production method and evaluation)
Mixing and melting to obtain hair oil. The obtained hair oil has no sticky feeling, and can give hair with good luster.
Example 30< emulsion >
(production method and evaluation)
The emulsion is prepared by conventional methods. The resulting emulsion was fresh and smooth with good feel.
Example 31< emulsion >
(production method and evaluation)
The emulsion is prepared by conventional methods. The resulting emulsion was fresh and smooth with good feel.
Example 32< protectant >
(production method and evaluation)
Mixing the oil phase part and the water phase part separately. The oil phase portion was sufficiently dispersed with the powder, the water phase portion was added, and emulsification was performed using a homogenizer. The obtained protective agent has high transparency and excellent refreshing feeling.
Example 33< protectant >
(production method and evaluation)
Mixing the oil phase part and the water phase part separately. The oil phase portion was added to the water phase portion, and emulsification was performed using a homogenizer. The obtained protective agent has high transparency and excellent refreshing feeling. Example 34< cosmetic lotion >
(evaluation)
The cosmetic lotion is smooth and shows good feeling.
Example 35< cream >
(production method and evaluation)
Mixing the oil phase part and the water phase part separately. The aqueous phase portion was added to the oil phase portion, and emulsification was performed using a homogenizer. The obtained cream was smooth and showed good feeling.
Example 36< cream >
(production method and evaluation)
The oil phase portion and the aqueous phase portion were each heated to 70 ℃ to completely dissolve them. Adding oil into the water phase, and emulsifying with an emulsifying machine. Cooling the emulsion with heat exchanger to obtain cream. The obtained cream was excellent in smoothness, had no sticky feeling, and showed good feeling in use.
Example 37< sunscreen >
(production method and evaluation)
Mixing the oil phase part and the water phase part separately. The oil phase part was sufficiently dispersed with the powder, and the water phase part was added and emulsified with a homogenizer. The obtained sunscreen cream has high transparency and excellent refreshing property.
Example 38< gel >
(production method and evaluation)
Preparing translucent emulsified composition by conventional method, cooling to below 30 deg.C for gelation, fully solidifying, crushing gel with disperser to obtain microgel (average particle size of 70 μm), and degassing to obtain gel product. The obtained gel-like product is refreshing, has no rough feeling, and shows smoothness and good usability.
Example 39< sunscreen emulsion >
(production method and evaluation)
Mixing the oil phase part and the water phase part separately. The oil phase part was sufficiently dispersed with the powder, and the water phase part was added and emulsified with a homogenizer. The obtained sunscreen preparation has excellent refreshing feeling.
Example 40< sunscreen emulsion >
(production method and evaluation)
Mixing the oil phase part and the water phase part separately. The oil phase part was sufficiently dispersed with the powder, and the water phase part was added and emulsified with a homogenizer. The obtained sunscreen preparation has low viscosity and good refreshing feeling.
Example 41W/O type Foundation
(preparation method)
Dispersing and crushing (7), (8) and (9) by a sand mill, adding (1) to (6), (10) and (11), and mixing to prepare an oil phase. Heating and dissolving (12) - (15) at 70 deg.C, adding into oil phase, and emulsifying. Then (16) is added and mixed, and the mixture is filled into a container.
Example 42< oil foundation >
(preparation method)
Heating and mixing (8) and (10) - (14) at 90 deg.C to obtain oil phase. Separately, (6), (7), (9) and (15) were mixed, and dispersed and crushed by a sand mill, and then the kneaded mixture and (1) to (5) were added to the oil phase and mixed by a disperser. Remixing (16), filling into a container and cooling.
Example 43 two-layer type W/O sunscreen cream
(preparation method)
Heating and mixing (5), (6) and (8) at 70 deg.C to obtain oil phase. Separately, (2) to (4) and (7) were mixed and kneaded by three-roll kneading. The kneaded mixture and (1) were added to an oil phase, and mixed by a disperser. Heating and dissolving (9) - (11) at 70 deg.C, adding the dissolved mixture into the above mixture, emulsifying, mixing (12), and filling into a container.
EXAMPLE 44 stick sunscreen cream (oil-based cosmetic)
(preparation method)
Heating and mixing (6) - (11) at 90 deg.C to obtain oil phase. Separately, (4), (5) and (12) were mixed and kneaded by three rolls. The kneaded mixture and (1) to (3) were added to an oil phase, and mixed by a disperser. Remixed (13), filled into a container and cooled.
Example 45 sunscreen oil-in-water emulsions
(preparation method)
The above (1) to (5) were mixed, dispersed and crushed by a sand mill, and then added to the aqueous phase in which the above (6) to (11) were dissolved, while using a homogenizer. The sunscreen oil-in-water emulsion is refreshing, has good skin adaptability, and has good use feeling.
Example 46 oil-in-water emulsion Foundation
(production method and evaluation)
The above (1) to (10) were mixed, dispersed and crushed by a sand mill, and then added to the aqueous phase in which the above (11) to (16) were dissolved, while using a homogenizer. The obtained foundation had no color difference, was easily spreadable, had no sticky feeling, and showed good feeling in use.
Example 47: ultraviolet-proof whitening beauty lotion (oil-in-water type emulsion cosmetics)
(production method and evaluation)
The above (1) to (5) were mixed, dispersed and crushed by a sand mill, and then added to the aqueous phase in which the above (6) to (15) were dissolved, while using a homogenizer. The obtained cosmetic liquid is excellent in spreadability, smooth, free from stickiness, and exhibits excellent feeling in use.
Industrial applicability
The present invention can provide a cosmetic which is refreshing and has excellent skin adaptability. Also disclosed is an oil-based cosmetic, a water-in-oil emulsion cosmetic or an oil-in-water emulsion composition which is excellent in feeling of use and stability. Further, a powder-dispersed cosmetic having extremely high dispersion stability of the powder and excellent stability can be provided.
Claims (5)
1. A cosmetic characterized by: the cosmetic contains glycerin modified by siloxane at both ends, represented by the following general formula (a), having HLB of 0.2-3.0 and molecular weight of 2000-20000, wherein the content of the glycerin modified by siloxane at both ends is 0.1-30% by mass relative to the total amount of the cosmetic,
(a)
[ chemical formula 1]
Wherein R1 is a C1-12 linear or branched alkyl group or a phenyl group, R2 is a C2-11 alkylene group, m is 10-120, and n is 1-11.
2. Cosmetic product according to claim 1, characterized in that: the cosmetic is oily cosmetic.
3. Cosmetic product according to claim 1, characterized in that: the cosmetic is water-in-oil type emulsion cosmetic.
4. Cosmetic product according to claim 1, characterized in that: the cosmetic is oil-in-water emulsion composition.
5. The cosmetic of claim 1, 2, 3 or 4, characterized in that: the cosmetic also contains powder.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005009013 | 2005-01-17 | ||
| JP009013/2005 | 2005-01-17 | ||
| JP2005160799 | 2005-06-01 | ||
| JP160799/2005 | 2005-06-01 | ||
| PCT/JP2006/300329 WO2006075679A1 (en) | 2005-01-17 | 2006-01-13 | Cosmetic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1116669A1 HK1116669A1 (en) | 2009-01-02 |
| HK1116669B true HK1116669B (en) | 2011-10-14 |
Family
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