WO2010110047A1 - 可溶化組成物 - Google Patents
可溶化組成物 Download PDFInfo
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- WO2010110047A1 WO2010110047A1 PCT/JP2010/053856 JP2010053856W WO2010110047A1 WO 2010110047 A1 WO2010110047 A1 WO 2010110047A1 JP 2010053856 W JP2010053856 W JP 2010053856W WO 2010110047 A1 WO2010110047 A1 WO 2010110047A1
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- WIPO (PCT)
- Prior art keywords
- modified silicone
- carboxy
- solubilized
- nonionic surfactant
- alkyl
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
Definitions
- the present invention relates to a solubilized composition, particularly an improvement in a large amount and stable aqueous solubilization of carboxy-modified silicone.
- a solubilization technique for transparently and uniformly dissolving a substance that does not dissolve in water (solvent) has been widely used in the fields of cosmetics, pharmaceuticals, foods and the like.
- a surfactant is used for solubilization of a hardly soluble substance.
- the surfactant concentration exceeds cmc, the poorly soluble substance is taken into the micelle and dissolved, thereby achieving solubilization.
- an oil agent such as a fragrance comprising an ester, an aldehyde, a ketone, an alcohol, an ether, a phenol, or a lactone is solubilized in an aqueous solvent when producing an aqueous base cosmetic such as a transparent lotion or cosmetic liquid.
- an appropriate amount of EO or PO addition type nonionic surfactant is blended as a solubilizer.
- silicone oils which have high thermal stability and safety, have various properties and are excellent in use feeling, are frequently used as cosmetics in cosmetics.
- the carboxy-modified silicone oil in which the dimethylpolysiloxane chain of the silicone oil is modified with a carboxyl group is expected to be used as a surfactant because of the high chemical reactivity and adsorption of the carboxyl group as a substituent. It is also known to be incorporated into hair cosmetics (Patent Document 1).
- modified silicones with other hydrophilic functional groups introduced polyether-modified silicones in which dimethylpolysiloxane chains are modified with polyoxyethylene groups have improved the emulsion stability of silicone oil and are used in cosmetics. (Patent Document 2).
- the amount of solubilization of the oil depends greatly on the structure and amount of the solubilizer according to the substance to be solubilized, and also on the HLB.
- no solubilizing agent capable of solubilizing it in water has been known yet.
- the polyether-modified silicone is nonionic, the particles tend to aggregate during solubilization, and the polyoxyethylene chain has a stickiness due to the stickiness.
- This invention is made
- the carboxy-modified silicone is solubilized in water in an extremely large amount, thereby improving the stability.
- the inventors have found that the aqueous solution is excellent in transparency to almost transparency, and have completed the present invention.
- the solubilized composition according to the present invention is selected from (a) a polyoxyethylene alkyl ether type nonionic surfactant represented by the following general formula (I) or (II), and the weighted average of HLB values is 1 to 2 or more nonionic surfactants to be 10 to 15, (b) carboxy-modified silicone, and (c) water, and the amount of (b) carboxy-modified silicone is (a) It is characterized by being not more than 3 times the weight of the nonionic surfactant.
- R 1 represents an alkyl group having a branched chain having 8 to 18 carbon atoms, and a represents an integer satisfying 3 ⁇ a ⁇ 40.
- R 2 , R 3 , and R 4 is an alkyl group having a branched chain having 8 to 18 carbon atoms, and the remaining is a hydroxyl group.
- B, c, and d are 3 ⁇ An integer satisfying b + c + d ⁇ 40 is indicated.
- the nonionic surfactant in the solubilized composition, (a) is an integer satisfying 8 ⁇ a ⁇ 30, and b, c, and d are integers satisfying 8 ⁇ b + c + d ⁇ 30. Is preferred.
- the nonionic surfactant is one or two selected from the group consisting of POE isotridecyl ether, POE isostearyl ether, POE isocetyl ether, and POE glyceryl isostearate. It is preferable to consist of more than seeds.
- the carboxy-modified silicone is obtained by substituting one or more of the side chains of polydimethylpolysiloxane or a methyl group at one end with the following substituents. . (Chemical formula 3) -R 5 -COOH (Wherein R 5 is a linear alkyl represented by — (CH 2 ) k —, and k is an integer of 10 to 30.)
- the solubilized composition according to the present invention comprises the components (a) to (c) and (d) an alkyl-modified silicone represented by the following general formula (V). .
- R 7 is an alkyl group having 1 to 12 carbon atoms, and p is an integer of 0 to 2230.
- the alkyl-modified silicone is dimethylpolysiloxane and / or caprylylmethicone.
- the material includes the solubilized composition.
- solubilized composition in which a hardly soluble carboxy-modified silicone is stably solubilized in water in a large amount.
- solubilized composition makes it possible to stably mix carboxy-modified silicones, and further alkyl-modified silicones, which have conventionally been difficult to mix into water-based cosmetics.
- the (a) polyoxyethylene alkyl ether type nonionic surfactant used in the present invention is selected from those represented by the following general formula (I) or (II).
- R 1 represents an alkyl group having a branched chain having 8 to 18 carbon atoms.
- any one of R 2 to R 4 is an alkyl group having a branched chain having 8 to 18 carbon atoms, and the remaining R that is not an alkyl group is a hydroxyl group.
- Specific examples of the alkyl group having a branched chain having 8 to 18 carbon atoms include groups such as isotridecyl, isocetyl and isostearyl.
- a and b + c + d are average addition moles of ethylene oxide (CH 2 CH 2 O), and are integers of 3 to 40, more preferably integers of 8 to 30.
- HLB value -Lipophilic balance
- the HLB value is generally known as a value indicating the affinity of a surfactant for water and oil (hydrophilic-lipophilic balance), and can be easily determined by a known calculation method such as the Griffin method.
- the polyoxyethylene alkyl ether is such that the average added mole number of ethylene oxide and the chain length of the alkyl group are within the above numerical ranges, and the weighted average of HLB values is 10 to 15. It is preferable to use one type or a combination of two or more type nonionic surfactants. If the weighted average HLB value is lower than 10, the lipophilicity may be too high and the surfactant may be difficult to dissolve in water, and if it exceeds 15, the hydrophilicity may be too high and sticky.
- the nonionic surfactant having an HLB value of 10 to 15 is used singly or in combination of two or more, and the nonionic surfactant having an HLB value of less than 10 is used as a weighted average of the same value. Is included in combination with other nonionic surfactants such that
- nonionic surfactant is, in particular, one or more polyoxyethylene alkyl ether type nonions selected from POE isotridecyl ether, POE isostearyl ether, POE isocetyl ether, POE glyceryl isostearate. It is preferable that it is comprised from an ionic surfactant.
- polyoxyethylene alkyl ether type nonionic surfactant examples include POE (8) isotridecyl ether [HLB13], POE (10) isostearyl ether [HLB11], POE (10) isocetyl ether [ HLB10], POE (15) isocetyl ether [HLB13], POE (15) glyceryl isostearate [HLB12], POE (20) glycerin triisostearate, and the like.
- POE (15) glyceryl isostearate [HLB8] is preferred from the viewpoint of the structure of the branched chain, the molecular weight, and the high solubilizing ability related to HLB.
- the nonionic surfactant is easily dissolved in water to form a transparent aqueous solution. Further, by adding carboxy-modified silicone to this solution, the component is solubilized, and the solubilized composition of the present invention can be obtained as a transparent to almost transparent aqueous solution. At this time, it is considered that the nonionic surfactant / carboxy-modified silicone / water three-component system forms a bicontinuous phase.
- the (b) carboxy-modified silicone that can be solubilized in the nonionic surfactant solution is a compound in which a functional group containing a carboxyl group is introduced into the side chain and / or terminal of polydimethylpolysiloxane (linear silicone). It is.
- the use of carboxy-modified silicone in which one or more of the side chains of polydimethylpolysiloxane or the methyl group at one end is substituted with the following substituent is preferable from the viewpoint of the solubilization amount.
- R 5 is a linear alkyl represented by — (CH 2 ) k —.
- K is an integer of 10 to 30.
- carboxy-modified silicone side chain type substituted with a methyl group on the side chain of polydimethylpolysiloxane
- one represented by the following general formula (III) is preferable, and a carboxy-modified silicone substituted with a methyl group at one end (
- the one-end type those represented by the following general formula (IV) are preferable.
- R 5 is a linear alkyl represented by — (CH 2 ) k —.
- K is an integer of 10 to 30.
- R 6 represents an alkyl group, alkenyl group, aryl group, aralkyl group or alkylaryl group having 18 or less carbon atoms which may be substituted with a halogen atom.
- L represents an integer of 30 to 600, m represents an integer of 1 to 20, and n represents an integer of 10 to 400.
- examples of the side chain carboxy-modified silicone represented by the general formula (III) include “X-22-3701E” manufactured by Shin-Etsu Chemical Co., Ltd., and a single-terminal carboxy-modified silicone represented by the general formula (IV).
- examples of the modified silicone include “X-22-3710” manufactured by the same company, and these can be preferably used.
- carboxy-modified silicone it is considered that the smaller the amount of added carboxyl groups, the higher the hydrophobicity and the solubilizing amount in the solubilizer aqueous solution changes.
- the addition amount of the carboxyl group is not particularly limited, but a carboxy-modified silicone having a carboxyl group functional group equivalent of 1000 to 5000 g / mol is preferable in terms of solubilization efficiency.
- the solubilized composition according to the present invention comprises the above essential components, that is, (a) a nonionic surfactant having an HLB value in a specific range, (b) carboxy-modified silicone, and (c) water. It can be prepared by mixing and dissolving the components a) to (c) under appropriate heating.
- a nonionic surfactant having an HLB value in a specific range
- carboxy-modified silicone and (c) water. It can be prepared by mixing and dissolving the components a) to (c) under appropriate heating.
- the amount of each component is 60% by weight or more based on the solubilized composition
- the amount of carboxy-modified silicone is 3 times or less the weight of (a) nonionic surfactant ( (B) / (a) ⁇ 3/1), more preferably 2 times or less ((b) / (a) ⁇ 2/1).
- the system May separate and may not be sufficiently solubilized.
- the solubilized composition according to the present invention can be solubilized by adding (d) an alkyl-modified silicone having a specific structure to the above components. That is, the form of the present invention includes a solubilized composition comprising the components (a) to (c) and (d) an alkyl-modified silicone having a specific structure.
- a solubilized composition comprising the components (a) to (c) and (d) an alkyl-modified silicone having a specific structure.
- an alkyl-modified silicone having no hydrophilic group is hardly dissolved in water or a nonionic surfactant aqueous solution alone.
- the alkyl-modified silicone is not modified. Silicone solubilization is significantly accelerated.
- the alkyl-modified silicone used as the component (d) of the present invention is a compound represented by the following general formula (V).
- R 7 is an alkyl group having 1 to 12 carbon atoms
- p is an integer of 0 to 2230.
- alkyl-modified silicones represented by the general formula (V) dimethylpolysiloxane and caprylylmethicone are particularly preferred.
- examples of such commercially available alkyl-modified silicone include “KF-96A-6T” and “KF-96-20cs” manufactured by Shin-Etsu Chemical Co., Ltd., and “Wacker-Belsil (registered trademark)” manufactured by Wacker Chemie AG. DM1 PLUS ”,“ SS-3408 ”manufactured by Toray Dow Corning Co., Ltd., and the like.
- the blending amount of the alkyl-modified silicone may be appropriately adjusted according to the constituents of the solubilized composition, but ((a) nonionic surfactant + (b) carboxy-modified silicone): (d It is preferable to blend the alkyl-modified silicone in a range of 1: 0.1 to 1:10 by weight.
- the alkyl-modified silicone exhibits excellent solubilization when combined with a one-terminal carboxy-modified silicone as a substance to be solubilized (component (b)).
- the above-described solubilized composition of the present invention can be used in combination with components that can be blended in normal cosmetics, quasi-drugs, pharmaceuticals, etc. within the range that does not impair the effects of the present invention.
- the cosmetic according to the present invention includes the solubilized composition.
- the components that can be combined with the solubilized composition of the present invention are exemplified below.
- Moisturizer polyethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, glycerin, diglycerin, xylitol, maltitol, maltose, D-mannitol and the like.
- Water-soluble polymers plant polymers such as gum arabic, carrageenan, pectin, agar, quince seed (quince), starch, and alge colloid (brown algae extract); microbial polymers such as dextran and pullulan; collagen, Animal polymers such as casein and gelatin; starch polymers such as carboxymethyl starch and methylhydroxypropyl starch; alginic polymers such as sodium alginate; vinyl polymers such as carboxyvinyl polymer (such as CARBOPOL); polyoxy Ethylene polymer; polyoxyethylene polyoxypropylene copolymer polymer; acrylic polymer such as sodium polyacrylate and polyacrylamide; inorganic water-soluble polymer such as bentonite, aluminum magnesium silicate and laponite.
- plant polymers such as gum arabic, carrageenan, pectin, agar, quince seed (quince), starch, and alge colloid (brown algae extract); microbial polymers such as dextran and pullulan;
- UV absorbers benzoic acid UV absorbers such as paraaminobenzoic acid; anthranilic UV absorbers such as methyl anthranilate; salicylic UV absorbers such as octyl salicylate and phenyl salicylate; isopropyl paramethoxycinnamate, paramethoxy Cinnamic acid-based UV absorbers such as octyl cinnamate and glyceryl di-2-methoxycinnamate mono-2-ethylhexanoate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -Benzophenone ultraviolet activator such as sulfonic acid; urocanic acid; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; 4-tert-butyl-4'-methoxybenzoylmethane.
- sequestering agent sodium edetate, sodium metaphosphate, phosphoric acid and the like.
- Antioxidants ascorbic acid, ⁇ -tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like.
- Hormones such as allantoin and azulene; whitening agents such as arbutin; astringents such as zinc oxide and tannin; refreshing agents such as L-menthol and camphor; sulfur; lysozyme chloride; pyridoxine chloride; And so on.
- solubilized composition of the present invention is excellent in stability, solubilization ability, and feeling of use, it is particularly useful as a cosmetic or pharmaceutical product.
- lotion, aftershave lotion, cosmetic liquid, body lotion, hair tonic, hair can be set as liquid preparations, such as a liquid, a hair restorer, and a fragrance.
- the solubilized composition of the present invention can be applied to other dosage forms as long as the effects of the present invention are not impaired.
- it can be made into a gel-form preparation using a known thickener or the like, impregnated into a non-woven fabric or the like to form a sheet-form preparation, or a spray, aerosol, or roll-on type preparation by a known method.
- cosmetics that are manufactured (used) by diluting the solubilized composition components of the present invention.
- the blending amount is expressed in weight%.
- the test methods used below are as follows. (Test method) In accordance with the formulation shown in Table 1 below, a nonionic surfactant, carboxy-modified silicone, and water were dissolved and mixed at 70 ° C. to obtain samples of each Example and Comparative Example. Each sample was evaluated for solubilization by the following transparency measurements. Measuring method The transparency of each sample was confirmed by measuring the L value. The L value was measured as a transparency with a distilled water value of 100 as a control using a spectrophotometer (UV-160) manufactured by Shimadzu Corporation. The evaluation standard of solubilization is as follows.
- Table 2 shows the test results using the side chain carboxy-modified silicone
- Table 3 shows the test results using the one-end carboxy-modified silicone.
- solubilized state of the composition blended with the following blending ratio (% by weight) when the polyoxyethylene alkyl ether type nonionic surfactant having different HLB was combined was evaluated in the same manner as described above. Further, a weighted average of POE (20) glyceryl isostearate and POE (20) triisostearate was calculated, and the solubilized state by the same value was also evaluated. The results are shown in Table 4.
- nonionic surfactant POE (8) isotridecyl ether and side chain type or one-end type carboxy-modified silicone (“X-22-3701E” and “X-22-3710” manufactured by Shin-Etsu Chemical Co., Ltd.) Further, solubilization of alkyl-modified silicone (dimethylpolysiloxane) was attempted with solubilized compositions having various blending ratios. The test results are shown in Table 5.
- Nonionic surfactant, carboxy-modified silicone, and water are dissolved and mixed at 70 ° C., and dimethylpolysiloxane (KF-96A-6cs, manufactured by Shin-Etsu Chemical Co., Ltd.) is added at various concentrations (1 to 6 with respect to the composition).
- the composition obtained was evaluated for the success or failure of solubilization according to the above criteria.
- dimethylpolysiloxane which is a poorly soluble component, was not solubilized in POE (8) isotridecyl ether alone (Test Examples 29 and 35), but was a system in which carboxy-modified silicone was solubilized. In (Test Examples 30 to 34, 36 to 40), solubilization was observed depending on the added concentration. In particular, in Test Example 39 in which the blending amount of the single-terminal carboxy-modified silicone was 1.5 times the weight of the nonionic surfactant, a high concentration of dimethylpolysiloxane was solubilized. From the above results, it is clear that the solubilized composition of the present invention can further solubilize dimethylpolysiloxane.
- Nonionic surfactant carboxy-modified silicone, dimethylpolysiloxane, and water were mixed at high temperature (70 ° C.), and then cooled.
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Abstract
Description
特に、化粧品においては、透明な化粧水や美容液といった水性ベースの化粧料の製造に際して、エステル、アルデヒド、ケトン、アルコール、エーテル、フェノール、ラクトン等からなる香料などの油剤を水性溶媒に可溶化させる目的で、EOまたはPO付加型ノニオン性界面活性剤が可溶化剤として適量配合されている。
一方、近年では、熱安定性や安全性が高く、性状が多様で使用感触にも優れたシリコーンオイルが油剤として化粧品に多用されている。その中でも、シリコーンオイルのジメチルポリシロキサン鎖にカルボキシル基を修飾したカルボキシ変性シリコーンオイルは、置換基であるカルボキシル基の化学反応性、吸着性の高さから、界面活性剤等としての使用が期待されており、毛髪化粧料への配合も知られている(特許文献1)。
また、他の親水性官能基を導入した変性シリコーンとして、ジメチルポリシロキサン鎖にポリオキシエチレン基が修飾されたポリエーテル変性シリコーンが、シリコーン油の乳化安定性を改善し、化粧料使用されている(特許文献2)。
また、ポリエーテル変性シリコーンはノニオン性であるため、可溶化の際に粒子の凝集が起こりやすく、ポリオキシエチレン鎖を有するためべたつくなど使用感触に問題があった。
本発明はこのような従来技術の課題に鑑みなされたものであり、その目的は、カルボキシ変性シリコーンを多量且つ安定に可溶化させた可溶化組成物を提供することにある。
すなわち、本発明に係る可溶化組成物は、(a)下記一般式(I)又は(II)で表されるポリオキシエチレンアルキルエーテル型ノニオン性界面活性剤から選択され、HLB値の加重平均が10~15となる1種又は2種以上のノニオン性界面活性剤と、(b)カルボキシ変性シリコーンと、(c)水と、からなり、(b)カルボキシ変性シリコーンの配合量が、(a)ノニオン性界面活性剤の重量の3倍以下であることを特徴とする。
また、前記可溶化組成物において、(a)ノニオン性界面活性剤が、POEイソトリデシルエーテル、POEイソステアリルエーテル、POEイソセチルエーテル、イソステアリン酸POEグリセリルからなる群より選択される1種又は2種以上からなることが好適である。
(化3)
-R5-COOH
(式中、R5は-(CH2)k-で示される直鎖アルキルであって、kは10~30の整数である。)
また、a及びb+c+dはエチレンオキシド(CH2CH2O)の平均付加モル数であり、3~40の整数、より好ましくは8~30の整数である。
すなわち、本発明には、HLB値が10~15である上記ノニオン性界面活性剤を単独又は2種以上で使用する他、HLB値が10に満たない上記ノニオン性界面活性剤を同値の加重平均が10~15となるような他のノニオン性界面活性剤と組み合わせて使用することが包含される。
このようなポリオキシエチレンアルキルエーテル型ノニオン性界面活性剤としては、例えば、POE(8)イソトリデシルエーテル[HLB13]、POE(10)イソステアリルエーテル[HLB11]、POE(10)イソセチルエーテル[HLB10]、POE(15)イソセチルエーテル[HLB13]、イソステアリン酸POE(15)グリセリル[HLB12]、トリイソステアリン酸POE(20)グリセリン等が挙げられる。中でも、分岐鎖の構造、分子量、HLBに関係する可溶化能の高さ点から、イソステアリン酸POE(15)グリセリル[HLB8]の使用が好適である。
上記ノニオン界面活性剤は、水に容易に溶解して透明の水溶液となる。さらに、この溶液にカルボキシ変性シリコーンを添加することにより、該成分が可溶化され、透明~ほぼ透明の水溶液として本発明の可溶化組成物を得ることができる。この際、ノニオン性界面活性剤/カルボキシ変性シリコーン/水の3成分系は、バイコンティニュアス相を形成していると考えられる。
特に、本発明においては、ポリジメチルポリシロキサンの側鎖の1以上、又は片末端のメチル基を下記置換基で置換したカルボキシ変性シリコーンの使用が可溶化量の点から好ましい。
(化7)
-R5-COOH
上記式中、R5は、-(CH2)k-で示される直鎖アルキルである。また、kは10~30の整数である。
R6は、ハロゲン原子で置換されていてもよい炭素数18以下のアルキル基、アルケニル基、アリール基、アラルキル基又はアルキルアリール基を表す。
また、lは30~600の整数、mは1~20の整数、nは10~400の整数を示す。
なお、カルボキシ変性シリコーンの場合、付加されるカルボキシル基の量が少ないほど疎水性が高くなり、可溶化剤水溶液に対する可溶化量が変化すると考えられる。本発明においてカルボキシル基の付加量は特に制限されないが、カルボキシル基の官能基当量が1000~5000g/molであるカルボキシ変性シリコーンが、可溶化の効率上好ましい。
各成分の配合量としては、(c)水を可溶化組成物に対し60重量%以上とし、(b)カルボキシ変性シリコーンの配合量を(a)ノニオン性界面活性剤の重量の3倍以下((b)/(a)≦3/1)、より好ましくは2倍以下((b)/(a)≦2/1)とする。
配合する水の量が少なすぎると、組成物におけるノニオン性界面活性剤の溶解が不十分となることがあり、ノニオン性界面活性剤に対するカルボキシ変性シリコーンの配合比が上記範囲外であると、系が分離して十分な可溶化が成らないことがある。
本発明の(d)成分として用いられるアルキル変性シリコーンは、下記一般式(V)で表される化合物である。下記式中、R7は炭素数1~12のアルキル基であり、pは0~2230の整数である。
このようなアルキル変性シリコーンの市販品としては、例えば、信越化学工業株式会社製の「KF-96A-6T」及び「KF-96-20cs」、Wacker Chemie AG製の「Wacker-Belsil(登録商標) DM1 PLUS」、東レ・ダウコーニング株式会社製の「SS-3408」などが挙げられる。
本発明の可溶化組成物と組み合わせることのできる成分を以下に例示する。
(1)保湿剤:ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ヘキシレングリコール、グリセリン、ジグリセリン、キシリトール、マルチトール、マルトース、D-マンニット等。
(5)酸化防止剤:アスコルビン酸、α-トコフェロール、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール等。
(6)薬剤:ビタミンA油、レチノール、パルミチン酸レチノール、イノシット、塩酸ピリドキシン、ニコチン酸ベンジル、ニコチン酸アミド、ニコチン酸DL-α-トコフェロール、アスコルビン酸リン酸マグネシウム、アスコルビン酸2-グルコシド、ビタミンD2(エルゴカシフェロール)、dl-α-トコフェロール2-L-アスコルビン酸リン酸ジエステルカリウム塩、dl-α-トコフェロール、酢酸dl-α-トコフェロール、パントテン酸、ビオチン等のビタミン類;エストラジオール、エチニルエストラジオール等のホルモン;アラントイン、アズレン等の抗炎症剤;アルブチン等の美白剤;酸化亜鉛、タンニン等の収斂剤;L-メントール、カンフル等の清涼剤;イオウ;塩化リゾチーム;塩化ピリドキシン;γ-オリザノール等。
(8)その他:粉体、色素、pH調整剤、防腐剤(フェノキシエタノールなど)等。
また、本発明の可溶化組成物成分を薄めて製造(使用)する化粧料もここに包含される。
(試験方法)
下記表1に示す処方に従い、ノニオン性界面活性剤、カルボキシ変性シリコーン、及び水を70℃にて溶解混合し、各実施例及び比較例のサンプルを得た。各サンプルは、次の透明度の測定によって可溶化を評価した。
測定方法
各サンプルの透明度をL値の計測によって確認した。L値は、島津製作所社製の分光光度計(UV-160)を用い、コントロールとして蒸留水の値を100としたときの透明度として測定した。可溶化の評価基準は以下の通りである。
評価基準
◎:L値(透明度)が95以上(サンプルは透明状態で、カルボキシ変性シリコーンは完全に可溶化している。)
○:L値(透明度)85~95未満(サンプルはほぼ透明で、カルボキシ変性シリコーンはほぼ可溶化している。)
×:L値(透明度)85未満(サンプルは白濁~半透明で、カルボキシ変性シリコーンはほとんど可溶化していない)
測定不能:分離物が認められる。
一方、直鎖アルキル型のノニオン性界面活性剤を用いた比較例1~4においては、いずれもカルボキシ変性シリコーンが可溶化せず、組成物が白濁するか完全に二層に分離した。
以上の結果から、本発明において特定構造のノニオン性界面活性剤を配合することにより、カルボキシ変性シリコーンが溶解した透明~ほぼ透明の可溶化組成物が得られることが明らかになった。
なお、前記特定構造のノニオン性界面活性剤についてさらに詳細な可溶化試験を行ったところ、イソステアリン酸POE(15)グリセリルが特に好適であった。
側鎖型カルボキシ変性シリコーンを用いた試験結果を表2に、片末端型カルボキシ変性シリコーンを用いた試験結果を表3に示す。
さらに、本発明に適用可能な他のノニオン性界面活性剤についても上記試験を行ったところ、上記表2、3に示す結果と同様の傾向が認められた。
したがって、カルボキシ変性シリコーンの配合量は、特定構造ノニオン性界面活性剤の重量の3倍以下、より好ましくは2倍以下である。
また、ノニオン性界面活性剤のHLB値については、ノニオン性界面活性剤のHLBの加重平均が10に満たない試験例27、28においては、前記重量比関係を満たしているものの、十分な可溶化が認められなかった。HLB値の加重平均の範囲をさらに詳細に検討したところ、10~15である場合に透明~ほぼ透明の可溶化組成物となることが明らかとなった。
(試験方法)
ノニオン性界面活性剤、カルボキシ変性シリコーン、及び水を70℃にて溶解混合し、さらに、ジメチルポリシロキサン(KF-96A-6cs、信越化学工業社製)を各種濃度(組成物に対し1~6重量%)で添加し、得られた組成物について可溶化の成否を上記基準で評価した。
以上の結果から、本発明の可溶化組成物は、さらにジメチルポリシロキサンを可溶化させ得るものであることが明らかである。
(試験方法)
ノニオン性界面活性剤、カルボキシ変性シリコーン、水及び各種アルキル変性シリコーンを70℃にて溶解混合し、その後冷却することによって得られた組成物について可溶化の可否を上記方法で評価した。
以上の結果から、本発明の可溶化組成物は、さらにアルキル変性シリコーンを可溶化することができるものであることが明らかである。
また、更なる検討の結果、(ノニオン性界面活性剤+カルボキシ変性シリコーン):アルキル変性シリコーンが、重量比で1:0.1~1:10であるときに安定した透明の可溶化組成物が得られることが分かった。
Claims (7)
- (a)下記一般式(I)又は(II)で表されるポリオキシエチレンアルキルエーテル型ノニオン性界面活性剤から選択され、HLB値の加重平均が10~15となる1種又は2種以上のノニオン性界面活性剤と、
(b)カルボキシ変性シリコーンと、
(c)水と、
からなり、(b)カルボキシ変性シリコーンの配合量が、(a)ノニオン性界面活性剤の重量の3倍以下であることを特徴とする可溶化組成物。
- (a)ノニオン性界面活性剤において、aが8≦a≦30を満たす整数であり、b、c、dが8≦b+c+d≦30を満たす整数であることを特徴とする請求項1に記載の可溶化組成物。
- (a)ノニオン性界面活性剤が、POEイソトリデシルエーテル、POEイソステアリルエーテル、POEイソセチルエーテル、イソステアリン酸POEグリセリルからなる群より選択される1種又は2種以上からなることを特徴とする請求項1又は2に記載の可溶化組成物。
- (b)カルボキシ変性シリコーンが、ポリジメチルポリシロキサンの側鎖の1以上または片末端のメチル基を下記置換基で置換してなるものであることを特徴とする請求項1~3のいずれかに記載の可溶化組成物。
(化3)
-R5-COOH
(式中、R5は-(CH2)k-で示される直鎖アルキルであって、kは10~30の整数である。) - (d)アルキル変性シリコーンが、ジメチルポリシロキサン及び/又はカプリリルメチコンであることを特徴とする請求項5に記載の可溶化組成物。
- 請求項1~6のいずれかに記載の可溶化組成物を含むことを特徴とする化粧料。
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JP2011505955A JPWO2010110047A1 (ja) | 2009-03-27 | 2010-03-09 | 可溶化組成物 |
CN2010800137803A CN102365080A (zh) | 2009-03-27 | 2010-03-09 | 增溶组合物 |
US13/257,691 US20120010169A1 (en) | 2009-03-27 | 2010-03-09 | Solubilized Composition |
EP10755848A EP2412364A4 (en) | 2009-03-27 | 2010-03-09 | SOLUBILIZED COMPOSITION |
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EP2514405A1 (en) | 2011-04-22 | 2012-10-24 | Shin-Etsu Chemical Co., Ltd. | Silicone Microemulsion Composition |
WO2021014654A1 (ja) * | 2019-07-25 | 2021-01-28 | 三好化成株式会社 | 親水化有機パウダー及び親水化有機パウダーを配合した化粧料 |
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JP6233609B2 (ja) | 2015-10-27 | 2017-11-22 | トヨタ自動車株式会社 | 車両の駆動力制御装置 |
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