JP2876160B2 - Non-aqueous emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a non-aqueous emulsion composition exhibiting a dispersion state of a perfluoro organic compound phase / oil phase type (hereinafter referred to as “F / O type”).

[Problems to be solved by conventional technology and invention]

Conventionally, as the emulsion, a water-in-oil type emulsion in which water droplets are dispersed in an oil phase and an oil-in-water type emulsion in which oil droplets are dispersed in an aqueous phase are known. These emulsions are widely used as cosmetics, pharmaceuticals, agricultural chemicals, daily necessities, and the like, depending on the purpose, in the form of emulsions, creams, solids, and the like.

Among these, the emulsions used in the field of cosmetics, oil-in-water emulsified cosmetics have been used in the past. The water-in-oil type emulsified cosmetic is inferior in makeup disintegration due to sweat and water, but is prone to makeup disintegration due to sebum, is inferior in persistence of makeup, is further elongated, and is not sticky. In addition, among cosmetics, oil-based cosmetics, like water-in-oil emulsified cosmetics, are resistant to cosmetic breakdown due to sweat and water, but are prone to cosmetic breakdown due to sebum, are inferior in persistence of makeup, and are further extended. It had the disadvantage of being heavy and sticky. For this reason, development of cosmetics using silicone oil and having a long lasting makeup has been conducted (Japanese Patent Laid-Open No.
61-40204, JP-A-61-65809, etc.).

However, even when silicone oil is used in combination with conventional emulsified cosmetics or oily cosmetics, there is a drawback that sebum secreted with time and the cosmetics are mixed to cause makeup collapse. For this reason, there is a strong need for the development of a highly durable cosmetic that is resistant to sweat and water and that is more immiscible with sebum.

In addition, for emulsion compositions used in industrial fields other than cosmetics, durability of the coating film after application of the emulsion to water and oil is required, and a highly persistent one is desired. .

Thus, development of an emulsified composition having good spreadability at the time of use, high persistence of makeup and other effects, and excellent storage stability has been desired.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies and as a result, by using a specific fluoropolymer, emulsifying a liquid perfluoro organic compound and an oily base, it has excellent spreadability and stability over time, and F / O with long lasting effect
The present inventors have found that a non-aqueous emulsion composition can be obtained, and have completed the present invention.

That is, the present invention provides (A), (B) and (C): (A) a fluoropolymer having a perfluoroalkyl group and an alkyl group in a molecule; (B) a liquid perfluoroorganic compound; and (C) an oily group. It is intended to provide a non-aqueous emulsified composition which contains a perfluoro organic compound in an oil-containing dispersion state.

The fluorine-based polymer of the component (A) used in the present invention includes:
It has a perfluoroalkyl group and an alkyl group in the molecule, and has a molecular weight of 500 to 2,000,000, particularly 5,000 to 50.
It is preferably one of 0,000. Also, the relationship between the total number of carbon atoms in the alkyl group present in the fluoropolymer (hereinafter, referred to as “N _H ”) and the total number of carbon atoms in the perfluoroalkyl group (hereinafter, referred to as “N _F ”) Preferably satisfy 1 ≦ N _H / N _F ≦ 30. As these fluoropolymers,
For example, JP-A-55-9619, JP-A-55-29501, JP-A-55-45756
No. 58-118882, No. 58-118883, No. 58-59277
Polymers described in JP-A-61-73712 and JP-A-61-289009 can be used.
A copolymer of a long-chain alkyl (meth) acrylate obtained by the method described in JP-A-289009 and a (meth) acrylate having a fluorinated alkyl group bonded thereto is preferred. Examples of the copolymer include a copolymer of a (meth) acrylate having an alkyl group having 16 to 22 carbon atoms and a (meth) acrylate having a perfluoroalkyl group or a polyfluoroalkyl group having 4 or more carbon atoms. . Carbon number
Examples of the alkyl (meth) acrylate having an alkyl group of 16 to 22 include an ester of an alcohol such as cetyl alcohol, stearyl alcohol, and behenyl alcohol with (meth) acrylic acid, and a perfluoroalkyl group or a polyfluoroalkyl. Examples of the (meth) acrylate having a group include the following compounds.

CH ₂ = CHCOOC ₂ H ₄ C ₆ F ₁₃ , CH ₂ = CHCOOC ₂ H ₄ C ₈ F ₁₇ , CH ₂ = CHCOOC ₂ H ₄ C ₁₀ F ₂₁ , CH ₂ = CHCOOC ₂ H ₄ C ₁₂ F ₂₅ , CH _{2 = C (CH 3) COOC 2} H 4 C 6 F 13, CH 2 = C (CH 3) COOC 2 H 4 C 8 F 17, CH 2 = C (CH 3) COOC 2 H 4 C 10 F 21, CH _{2 = C (CH 3) COOC} 2 H 4 C 12 F 25, CH 2 = CHCOOC 2 H 4 - (CF 2) 4 -H, CH 2 = CHCOOC 2 H 4 - (CF 2) 5 -H, CH 2 CC (CH ₃ ) COOC ₂ H ₄ — (CF ₂ ) ₄ —H, CH ₂ CC (CH ₃ ) COOC ₂ H ₄ — (CF ₂ ) ₅ —H These long-chain alkyl (meth) acrylates and The copolymerization ratio with the (meth) acrylate to which the functionalized alkyl group is bonded is preferably 10: 1 to 1: 5 (weight ratio), particularly preferably 7: 1 to 1: 1. The molecular weight of the copolymer is 1,000 to 2,000,000, particularly 10,000 to 50, from the viewpoints of friction resistance, stickiness and the like.
0,000 is preferred.

In addition, Surflon SC-101, SC-105, S-381 and S
Commercially available products such as -382 (all manufactured by Asahi Glass Co., Ltd.) can also be used.

These fluoropolymers can be used alone or in combination of two or more depending on the kind of emulsion, the purpose, etc., and 0.1 to 40% by weight (hereinafter simply referred to as “%”) in the total composition. It is particularly preferable to add 1.0 to 30%. If it is less than 0.1%, its effect cannot be sufficiently exhibited to form a stable non-aqueous emulsified composition, and if it exceeds 40%, the viscosity of the oil phase becomes high and the usability is remarkably impaired.

The perfluoro organic compound as the component (B) is a liquid at room temperature, and examples thereof include perfluoroalkane and perfluoropolyether.

Among them, the following general formula (I) Wherein R ¹ , R ³ , R ⁴ and R ⁵ may be the same or different,
Each of a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, R ² is a fluorine atom or a perfluoroalkyl group, and p, q and r have a molecular weight of 500 to 1
Indicates a number of 0 or more that becomes 00,000. Where p = q = r =
It cannot be zero. The perfluoropolyether represented by these is preferable. Here, the perfluoro groups shown in parentheses need not be arranged in this order, and may be random polymerization or block polymerization. As the perfluoropolyether, a liquid having a viscosity of 5 to 5,000 cSt is particularly preferable. For example, the following general formula (II) (In the formula, m and n are numbers each having a molecular weight of 500 to 10,000, and n / m is 0.2 to 2.) FOMBLIN HC-04 (average molecular weight 1,500) and H
C-25 (3,200) and HC-R (6,600) (both manufactured by Monteflors) and the following general formula (III): FCF ₂ CF ₂ CF ₂ O ₁ CF ₂ CF ₃ (III) l represents a number from 4 to 500.) Demnum S-20 (weight average molecular weight 25,000)
0), S-65 (4,500), S-100 (5,600), and S-200 (8,400) (all manufactured by Daikin Industries, Ltd.) can be used.

These perfluoro organic compounds can be used singly or in combination of two or more depending on the kind and purpose of the emulsion, and 10 to 95%, particularly 20 to 90%, is blended in the whole composition. preferable.

The oil base of the component (C) is not particularly limited as long as it is a commonly used industrial oil substance, and examples thereof include oils and fats, waxes, hydrocarbons, ester oils, higher alcohols, higher fatty acids, and silicone oils. Examples of fats and oils include castor oil, olive oil, avocado oil, palm oil, cacao oil and the like; waxes such as wood wax, lanolin, beeswax, carnauba wax, candelilla wax and the like; and hydrocarbons such as petrolatum, liquid paraffin,
Solid paraffin, ceresin, microcrystalline wax, squalane, etc .; ester oils include, for example, butyl stearate, octyl dodecyl myristate, isopropyl myristate, isopropyl lanolin fatty acid, butyl stearate, hexyl lanolinate, olein Oleyl acid ester, diisopropyl adipate,
Higher alcohols such as stearyl alcohol, oleyl alcohol, etc .; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, lanolin fatty acid, etc .; Examples thereof include dimethylpolysiloxane, methylphenylpolysiloxane, dimethylcyclopolysiloxane, methylhydrogenpolysiloxane, and the like.

These oily bases can be used alone or in combination of two or more, and 0.5 to 80%, particularly 10 to 80%
It is preferable to mix them.

The non-aqueous emulsion composition of the present invention, in addition to the essential components,
Components commonly used, for example, pigments, dyes, surfactants, antioxidants, fragrances, pigments, alcohols, polyhydric alcohols, antifouling agents, ultraviolet absorbers, humectants, water and the like can be appropriately compounded. In addition, as the pigment, organic pigments, inorganic pigments, insoluble ones such as dyes can be used, but these pigments may be used as fine particles,
Powders in which two or more kinds of pigments are compounded using mechanochemical means can also be used. Further, the pigment surface may be subjected to metal soap treatment, silicon treatment, dialkyl phosphoric acid treatment, treatment with a perfluorocarbon group-containing compound, amino acid treatment, lecithin treatment, collagen treatment, or the like.

The non-aqueous emulsified composition of the present invention can be produced according to the same method as a usual emulsified composition, and includes, for example, cosmetics such as emulsions, creams, foundations, blushes, eye shadows, lip balms, lipsticks, and pharmaceuticals. , Can be applied as agricultural chemicals, daily necessities and the like.

[Action and effect]

In the present invention, the liquid perfluoro organic compound contained in the non-aqueous emulsion composition is not miscible with oil present in nature and sweat and sebum secreted from humans, as compared with conventional oils. In the case of the paint, there is no outflow of the decorative coating film over time. Therefore, the non-aqueous emulsified composition of the present invention has a long lasting effect and is significantly improved as compared with the conventional emulsified composition. In addition, a stable F / O-type emulsified composition can be obtained by using a fluorine-based polymer, the stability over time is excellent, and the spread during use is good.

〔Example〕

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 Creamy foundation: A creamy foundation having the composition shown in Table 1 was produced and evaluated for emulsion stability and feeling upon use. The results are shown in Table 2.

(Preparation method) Add Component C to Component A, which was heated to 80 ° C and uniformly dissolved, and dispersed uniformly with a disper. Then, while stirring with a homomixer, Component B heated to 80 ° C was added dropwise and emulsified. And
Add component D. The emulsion was cooled with a heat exchanger to a final temperature of 30 ° C. to obtain a creamy foundation.

(Evaluation method) Emulsion stability: The emulsified state immediately after production and after storage for one month was evaluated according to the following criteria.

：: No separation / aggregation Δ: Slight separation / aggregation ×: Separation / aggregation used Feeling of use: Sensory evaluation was conducted by 10 specialized panels, and the spread at the time of application and the stickiness were evaluated according to the following criteria.

○: 7 or more of 10 respondents were good △: 4 to 6 of 10 respondents were good ×: 3 or less of 10 respondents were good As is clear from Table 2, the creamy foundation of the present invention was excellent in stability over time, had good spreadability when used, and was excellent in makeup.

Example 2 Lip Balm: (Preparation method) The component A heated to 80 ° C was added dropwise to the component A, which was heated to 80 ° C and uniformly dissolved, and the mixture was stirred with a homomixer, emulsified, and the component C was added. The emulsion was poured into a lip balm container, allowed to stand at room temperature, and cooled to a final temperature of 30 ° C. to obtain a lip balm (Product 2 of the present invention).

Example 3 Sunscreen: (Preparation method) The component A heated to 80 ° C was added dropwise to the component A, which had been uniformly dissolved and dispersed by heating at 80 ° C while stirring with a homomixer, and emulsified, followed by adding the component C. Final temperature of the emulsion in a heat exchanger 30
C. to obtain a sunscreen agent (Product 3 of the present invention).

Example 4 Face care cream: (Preparation method) The component A heated to 80 ° C was added dropwise to the component A, which had been uniformly dissolved and dispersed by heating at 80 ° C while stirring with a homomixer, and emulsified, followed by adding the component C. Final temperature of the emulsion in a heat exchanger 30
C. to obtain a face care cream (Product 4 of the present invention).

Example 5 Lipstick: (Production method) 1% of liquid paraffin, 1% of ceresin, and 1% of organic pigment were milled with a roll mill to prepare a pigment paste.

The remaining component A is heated to 80 ° C. and uniformly dissolved, and the remaining component D and the pigment paste are added and uniformly heated and mixed. Further, while stirring these mixtures with a homomixer, Component B heated to 80 ° C. was added dropwise to emulsify, and Component C was added. The emulsion was poured into a lipstick container and cooled in an ice bath to a final temperature of 30 ° C. to obtain a lipstick (Product 5 of the present invention).

All of the products of the present invention produced in Examples 2 to 5 exhibited high emulsion stability, had good spreadability to the skin during use, and were excellent in cosmetic persistence.

Claims (1)

(57) [Claims] (A), (B) and (C) (A) a fluoropolymer having a perfluoroalkyl group and an alkyl group in a molecule (B) a liquid perfluoroorganic compound (C) an oily base And a non-aqueous emulsified composition exhibiting a dispersion state of a perfluoro organic compound in oil.