JP6548866B2 - Thickener for weakly acidic cosmetic, and weakly acidic cosmetic containing the thickener - Google Patents
Thickener for weakly acidic cosmetic, and weakly acidic cosmetic containing the thickener Download PDFInfo
- Publication number
- JP6548866B2 JP6548866B2 JP2014023518A JP2014023518A JP6548866B2 JP 6548866 B2 JP6548866 B2 JP 6548866B2 JP 2014023518 A JP2014023518 A JP 2014023518A JP 2014023518 A JP2014023518 A JP 2014023518A JP 6548866 B2 JP6548866 B2 JP 6548866B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- acid
- weakly acidic
- thickener
- soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000002537 cosmetic Substances 0.000 title claims description 84
- 230000002378 acidificating effect Effects 0.000 title claims description 56
- 239000002562 thickening agent Substances 0.000 title claims description 43
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 239000002245 particle Substances 0.000 claims description 43
- 229930006000 Sucrose Natural products 0.000 claims description 31
- 239000005720 sucrose Substances 0.000 claims description 31
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 28
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 22
- 238000006386 neutralization reaction Methods 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
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- 239000000203 mixture Substances 0.000 claims description 14
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- 230000000379 polymerizing effect Effects 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
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- 150000004676 glycans Chemical class 0.000 claims description 5
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- 239000005017 polysaccharide Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
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- 239000000194 fatty acid Substances 0.000 description 9
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- 238000006266 etherification reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 8
- 238000010557 suspension polymerization reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- ASKIVFGGGGIGKH-UHFFFAOYSA-N 2,3-dihydroxypropyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(O)CO ASKIVFGGGGIGKH-UHFFFAOYSA-N 0.000 description 6
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- 239000008346 aqueous phase Substances 0.000 description 6
- 235000010323 ascorbic acid Nutrition 0.000 description 6
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- 229960005070 ascorbic acid Drugs 0.000 description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 239000000230 xanthan gum Substances 0.000 description 6
- 229920001285 xanthan gum Polymers 0.000 description 6
- 235000010493 xanthan gum Nutrition 0.000 description 6
- 229940082509 xanthan gum Drugs 0.000 description 6
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 230000003020 moisturizing effect Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- LVYLCBNXHHHPSB-UHFFFAOYSA-N 2-hydroxyethyl salicylate Chemical compound OCCOC(=O)C1=CC=CC=C1O LVYLCBNXHHHPSB-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229930182478 glucoside Natural products 0.000 description 4
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- 229940057995 liquid paraffin Drugs 0.000 description 4
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229940032094 squalane Drugs 0.000 description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004909 Moisturizer Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
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- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 3
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- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 3
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Landscapes
- Polymerisation Methods In General (AREA)
- Cosmetics (AREA)
Description
本発明は、弱酸性化粧料用増粘剤に関する。また、当該増粘剤を配合してなる弱酸性化粧料に関する。 The present invention relates to a thickener for weak acid cosmetics. The present invention also relates to a weakly acidic cosmetic composition obtained by blending the thickener.
薬用クリーム、美白クリーム、美白乳液、及び毛髪化粧料等では、酸性物質として、消炎剤、抗ニキビ剤（例えば、サリチル酸、サリチル酸誘導体、レチノイン酸、およびその誘導体）、酸性老化防止剤（例えば、アスコルビン酸（ビタミンＣ））、等を含有し、ｐH４〜６程度の弱酸性に調整されたものが多く製造されている。このような化粧料においても、さっぱりした触感が好まれるため、カルボキシルビニルポリマーやアルキル変性カルボキシビニルポリマー等の、カルボキシル基を有する親水性重合体が増粘剤、分散剤又は乳化安定剤等として使用されている。しかしながら、これらの親水性重合体は、少量の使用で優れた増粘性を示し、さっぱりしたみずみずしい使用感が得られるものの、酸性条件下では多量に使用しないと所用の増粘効果が得られず、その際、べたつき、ヨレ等の問題を生じる。また、耐塩増粘性の観点からやむを得ずヒドロキシエチルセルロース、キサンタンガム等の多糖類系水溶性高分子が使用される場合もあるが、さっぱりしたみずみずしい触感を得ることは出来ない。 In the case of medicinal creams, whitening creams, whitening emulsions and hair cosmetics etc., as an acidic substance, anti-inflammatory agents, anti-acne agents (eg salicylic acid, salicylic acid derivatives, retinoic acid and derivatives thereof), acid anti-aging agents (eg ascorbic acid) A large number of products containing an acid (vitamin C), etc. and adjusted to a weak acidity of about pH 4 to 6 have been produced. Even in such cosmetics, since a refreshing touch is preferred, a hydrophilic polymer having a carboxyl group such as a carboxyl vinyl polymer or an alkyl-modified carboxyvinyl polymer is used as a thickener, a dispersing agent, an emulsion stabilizer, etc. It is done. However, although these hydrophilic polymers exhibit excellent thickening properties with a small amount of use and provide a fresh and fresh feeling in use, the thickening effect required can not be obtained unless used in large amounts under acidic conditions, At that time, problems such as stickiness and yole occur. In addition, polysaccharide-based water-soluble polymers such as hydroxyethyl cellulose and xanthan gum may be used inevitably from the viewpoint of salt thickening resistance, but a refreshing and fresh touch can not be obtained.
特許文献１記載の親水性増粘剤は従来のカルボキシビニルポリマーよりも更にさっぱりした軽い触感の化粧料の調製を可能としたものであるが、酸性物質を配合し、弱酸性（例えばｐH４〜６）の化粧料を調製すると、減粘、べたつきを生じ、さっぱりしたみずみずしい使用感を得ることは出来ない。 Although the hydrophilic thickener described in Patent Document 1 enables preparation of a light touch cosmetic which is more refreshing than conventional carboxyvinyl polymers, it is compounded with an acidic substance and is weakly acidic (for example, pH 4 to 6). When the cosmetic composition of the present invention is prepared, it causes thinning and stickiness, and a fresh and fresh feeling of use can not be obtained.
特許文献２では、アルキル変性カルボキシビニルポリマーにトラネキサム酸を併用した乳化組成物を提案しているが、所用のクリームを得るにはアルキル変性カルボキシビニルポリマーの配合量を増量する必要があり、べたつき、ヨレなどの問題を生じる。 Patent Document 2 proposes an emulsion composition in which tranexamic acid is used in combination with an alkyl-modified carboxyvinyl polymer, but it is necessary to increase the blending amount of the alkyl-modified carboxyvinyl polymer in order to obtain a cream for use. It causes problems such as yole.
特許文献３には、アルコキシサリチル酸等のサリチル酸誘導体を塩類及び所定分子量を持つポリエチレングリコールとともに配合することにより安定な油中水型乳化組成物が得られることが記載されている。しかし、さっぱりした軽い使用感触という観点からは満足できるものではない。 Patent Document 3 describes that a stable water-in-oil emulsion composition can be obtained by blending a salicylic acid derivative such as alkoxysalicylic acid with a salt and polyethylene glycol having a predetermined molecular weight. However, it is not satisfactory from the viewpoint of refreshing and light use feeling.
本発明の目的は、従来のカルボキシビニルポリマーや特許文献１記載の親水性増粘剤では、べたつき、ヨレ等の問題を生じる、酸性物質を含有した酸性の化粧料においても、ヨレの発生がなく、さっぱりした軽い使用感を達成することができる親水性増粘剤を提供することにある。また、当該使用感を有する化粧料を提供することにある。 The object of the present invention is that conventional carboxyvinyl polymers and hydrophilic thickeners described in Patent Document 1 cause no problems even in an acidic cosmetic containing an acidic substance, which causes problems such as stickiness and twisting. An object of the present invention is to provide a hydrophilic thickener capable of achieving a refreshing and light feeling in use. Another object is to provide a cosmetic having the feeling of use.
本発明者らは、水溶性架橋剤の存在下に水溶性不飽和カルボン酸単量体を重合して得られる、中和度５０％以下で、且つ中位粒子径が５〜３０μmの樹脂粒子が、弱酸性条件下において優れた増粘効果を有することを見出し、さらに改良を重ねて本発明を完成させるに至った。 The present inventors have obtained a resin particle having a degree of neutralization of 50% or less and a median particle diameter of 5 to 30 μm, which is obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of a water-soluble crosslinking agent. However, they have found that they have excellent thickening effect under weakly acidic conditions, and further improvements have been made to complete the present invention.
すなわち、本発明は例えば以下の項に記載の主題を包含する。
項１．
水溶性架橋剤の存在下に水溶性不飽和カルボン酸単量体を重合して得られる、中和度５０％以下且つ中位粒子径が５〜３０μmの樹脂粒子を含有する弱酸性化粧料用増粘剤。
項２．
水溶性架橋剤が、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、Ｎ，Ｎ’−メチレンビスアクリルアミド、エチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート及び水溶性ショ糖アリルエーテルからなる群より選ばれる少なくとも１種である項１に記載の弱酸性化粧料用増粘剤。
項３．
水溶性架橋剤が、水溶性ショ糖アリルエーテルである項１に記載の弱酸性化粧料用増粘剤。
項４．
水溶性不飽和カルボン酸単量体が、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、及びイタコン酸からなる群より選択される少なくとも１種である、項１〜３のいずれかに記載の弱酸性化粧料用増粘剤。
項５．
項１〜４のいずれかに記載の増粘剤を配合してなる弱酸性化粧料。
項６．
さらに酸性物質を含有する、項５に記載の弱酸性化粧料。
項７．
さらに多糖類系水溶性高分子を含有する、項５又は６に記載の弱酸性化粧料。
That is, the present invention includes, for example, the subject matter described in the following section.
Item 1.
For weakly acidic cosmetics containing resin particles having a degree of neutralization of 50% or less and a median particle size of 5 to 30 μm, obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of a water-soluble crosslinking agent Thickener.
Item 2.
The water soluble crosslinking agent is at least one selected from the group consisting of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, N, N'-methylene bisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and water soluble sucrose allyl ether Item 1. The thickener for weakly acidic cosmetics according to item 1, which is one type.
Item 3.
Item 2. The thickener for a weakly acidic cosmetic according to item 1, wherein the water soluble crosslinking agent is a water soluble sucrose allyl ether.
Item 4.
The water-soluble unsaturated carboxylic acid monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid, The thickener for weakly acidic cosmetics according to any of the above.
Item 5.
Item 4. A weakly acidic cosmetic composition comprising the thickener according to any one of Items 1 to 4.
Item 6.
The weakly acidic cosmetic according to item 5, further containing an acidic substance.
Item 7.
7. The weakly acidic cosmetic according to item 5 or 6, further comprising a polysaccharide-based water-soluble polymer.
項Ａ．
水溶性架橋剤の存在下に水溶性不飽和カルボン酸単量体を重合して得られる、中和度５０％以下の樹脂粒子を含み、
当該樹脂粒子は膨潤しており、その中位粒子径は４０〜３００μmである、
弱酸性化粧料。
項Ｂ．
水溶性架橋剤が、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、Ｎ，Ｎ’−メチレンビスアクリルアミド、エチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート及び水溶性ショ糖アリルエーテルからなる群より選ばれる少なくとも１種である項Ａに記載の弱酸性化粧料。
項Ｃ．
水溶性架橋剤が、水溶性ショ糖アリルエーテルである項Ａに記載の弱酸性化粧料。
項Ｄ．
水溶性不飽和カルボン酸単量体が、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、及びイタコン酸からなる群より選択される少なくとも１種である、項Ａ〜Ｃのいずれかに記載の弱酸性化粧料。
Item A.
And resin particles having a degree of neutralization of 50% or less obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of a water-soluble crosslinking agent,
The resin particles are swollen, and their median particle diameter is 40 to 300 μm.
Weak acid cosmetic.
Item B.
The water soluble crosslinking agent is at least one selected from the group consisting of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, N, N'-methylene bisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and water soluble sucrose allyl ether The weakly acidic cosmetic composition according to item A, which is one type.
Item C.
The weakly acidic cosmetic according to Item A, wherein the water-soluble crosslinking agent is a water-soluble sucrose allyl ether.
Item D.
The item A to C, wherein the water-soluble unsaturated carboxylic acid monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid Weakly acidic cosmetic composition according to any one of the above.
本発明においては、水溶性不飽和カルボン酸単量体を、水溶性架橋剤の存在下に重合して得られる中和度５０％以下、中位粒子径５〜３０μmの樹脂粒子を増粘剤として用いることにより、弱酸性化粧料においても、当該増粘剤を少量添加することにより、べたつきのないさっぱりした触感の化粧料を提供することができる。 In the present invention, a resin particle having a degree of neutralization of 50% or less and a median particle diameter of 5 to 30 μm obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of a water-soluble crosslinking agent In the case of a weakly acidic cosmetic composition, the addition of a small amount of the thickening agent can provide a cosmetic product with a non-sticky and fresh feel.
以下、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
本発明の弱酸性化粧料用増粘剤は、水溶性不飽和カルボン酸単量体を、水溶性架橋剤の存在下に重合して得られる、中和度５０％以下で、且つ中位粒子径が５〜３０μmの樹脂粒子を含んでなる。また、当該樹脂粒子は親水性であることが好ましい。そして、本発明の増粘剤は親水性であることが好ましい。 The thickener for weakly acidic cosmetics of the present invention is obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of a water-soluble crosslinking agent, having a degree of neutralization of 50% or less, and medium particles It comprises resin particles having a diameter of 5 to 30 μm. Moreover, it is preferable that the said resin particle is hydrophilic. And it is preferable that the thickener of this invention is hydrophilic.
前述の通り、本発明の弱酸性化粧料用増粘剤は、水溶性架橋剤によって架橋された、水溶性不飽和カルボン酸単量体の重合体（樹脂）を含む。当該重合体は、例えば、水溶性不飽和カルボン酸単量体を、水溶性架橋剤の存在下で懸濁重合法により重合させる工程を含む方法により得ることができる。懸濁重合法のなかでも、水溶性不飽和カルボン酸単量体、水溶性架橋剤及び水を含む水相の液滴を疎水性溶媒中に分散させながら重合反応を行う逆相懸濁重合法が好ましい。 As mentioned above, the thickener for weakly acidic cosmetics of the present invention comprises a polymer (resin) of a water-soluble unsaturated carboxylic acid monomer crosslinked by a water-soluble crosslinking agent. The polymer can be obtained, for example, by a method including the step of polymerizing a water-soluble unsaturated carboxylic acid monomer by suspension polymerization in the presence of a water-soluble crosslinking agent. In the suspension polymerization method, a reverse phase suspension polymerization method in which a polymerization reaction is carried out while dispersing droplets of an aqueous phase containing a water-soluble unsaturated carboxylic acid monomer, a water-soluble crosslinking agent and water in a hydrophobic solvent Is preferred.
水溶性不飽和カルボン酸単量体としては、特に限定されるものではないが、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、イタコン酸などが挙げられる。中でも、アクリル酸、メタクリル酸が好ましい。水溶性不飽和カルボン酸単量体は、１種単独で又は２種以上を組み合わせて用いることができる。
本発明においては水溶性不飽和カルボン酸のカルボキシル基をアルカリにより中和することにより、得られる重合体の中和度を容易に調整することができる。本発明において、中和度とは水溶性不飽和カルボン酸のカルボキシル基の総モル数に対する中和された基のモル数の割合を言う。中和に用いられるアルカリとしては、水酸化ナトリウム、水酸化カリウム、トリエタノールアミン、ジイソプロピルアミン、等が挙げられる。中和の方法としては特に限定されず、例えば、予め水溶性不飽和カルボン酸単量体を中和する方法、重合により得られた重合体を中和する方法等が挙げられる。
The water-soluble unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid and the like. Among them, acrylic acid and methacrylic acid are preferable. The water-soluble unsaturated carboxylic acid monomers can be used singly or in combination of two or more.
In the present invention, the degree of neutralization of the resulting polymer can be easily adjusted by neutralizing the carboxyl group of the water-soluble unsaturated carboxylic acid with an alkali. In the present invention, the degree of neutralization refers to the ratio of the number of moles of neutralized groups to the total number of moles of carboxyl groups of the water-soluble unsaturated carboxylic acid. Examples of the alkali used for neutralization include sodium hydroxide, potassium hydroxide, triethanolamine, diisopropylamine and the like. The method of neutralization is not particularly limited, and examples thereof include a method of previously neutralizing a water-soluble unsaturated carboxylic acid monomer, a method of neutralizing a polymer obtained by polymerization, and the like.
水溶性不飽和カルボン酸単量体を、水溶性架橋剤の存在下に重合して得られる重合体（樹脂）の中和度は、弱酸性化粧料への適合性および耐塩性の観点から５０％以下であり、４５％以下が好ましく、４０％以下がさらに好ましい。中和度が５０％より大きい場合、当該重合体を配合してなる弱酸性化粧料の粘度が低くなり、実用性に劣る。 The degree of neutralization of a polymer (resin) obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of a water-soluble crosslinking agent is 50 from the viewpoint of compatibility with weakly acidic cosmetics and salt resistance. % Or less, 45% or less is preferable, and 40% or less is more preferable. If the degree of neutralization is greater than 50%, the viscosity of the weakly acidic cosmetic composition obtained by blending the polymer is low, and the practicability is poor.
水溶性架橋剤としては、好ましくは、重合性不飽和基及び／又は反応性官能基を２個以上有する化合物が挙げられる。反応性官能基は、水溶性不飽和カルボン酸単量体が有するカルボキシル基と反応して、架橋構造を形成し得る官能基である。その具体例としては、グリシジル基が挙げられる。２個以上のグリシジル基を有する水溶性架橋剤の例としては、エチレングリコールジグリシジルエーテル及びポリエチレングリコールジグリシジルエーテルが挙げられる。２個以上の重合性不飽和基を有する水溶性架橋剤の例としては、Ｎ，Ｎ’−メチレンビスアクリルアミド、エチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート及び水溶性ショ糖アリルエーテルが挙げられる。これらの中でも水溶性ショ糖アリルエーテルが好ましく用いられる。なお、水溶性架橋剤は、１種単独で又は２種以上を組み合わせて用いることができる。 As a water soluble crosslinking agent, Preferably, the compound which has a polymerizable unsaturated group and / or 2 or more of reactive functional groups is mentioned. The reactive functional group is a functional group capable of reacting with the carboxyl group possessed by the water-soluble unsaturated carboxylic acid monomer to form a crosslinked structure. A glycidyl group is mentioned as the specific example. Examples of water-soluble crosslinking agents having two or more glycidyl groups include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether. Examples of water-soluble crosslinking agents having two or more polymerizable unsaturated groups include N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and water soluble sucrose allyl ether. Among these, water-soluble sucrose allyl ether is preferably used. In addition, a water-soluble crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
水溶性ショ糖アリルエーテルのエーテル化度は、好ましくは２．０〜３．５、より好ましくは２．２〜３．２である。水溶性ショ糖アリルエーテルのエーテル化度が低いと、架橋反応に関わる官能基であるアリル基が不足して、架橋反応が効果的に進行し難くなる傾向が若干ある。水溶性ショ糖アリルエーテルのエーテル化度が高いと、水に対する溶解性が若干低下するため、水相中においてショ糖アリルエーテルと水溶性不飽和カルボン酸単量体との架橋反応が若干進行し難くなる傾向がある。このエーテル化度は、ショ糖に対するアリルエーテル基のモル比の平均値である。エーテル化度は、ショ糖アリルエーテル中に残存する水酸基を、ピリジン中で無水酢酸と反応させ、このとき消費される無水酢酸の量から算出することができる。 The degree of etherification of the water-soluble sucrose allyl ether is preferably 2.0 to 3.5, more preferably 2.2 to 3.2. If the degree of etherification of the water-soluble sucrose allyl ether is low, there is a tendency that the cross-linking reaction becomes difficult to progress effectively due to a shortage of allyl groups which are functional groups involved in the cross-linking reaction. When the degree of etherification of the water-soluble sucrose allyl ether is high, the solubility in water is slightly reduced, so that the crosslinking reaction between the sucrose allyl ether and the water-soluble unsaturated carboxylic acid monomer proceeds slightly in the aqueous phase. It tends to be difficult. The degree of etherification is the average value of the molar ratio of allyl ether group to sucrose. The degree of etherification can be calculated from the amount of acetic anhydride consumed by reacting the hydroxyl group remaining in sucrose allyl ether with acetic anhydride in pyridine.
水溶性ショ糖アリルエーテルは、例えば、ショ糖水性液に触媒の水酸化ナトリウムを加え、ショ糖をアルカリショ糖に転化した後、臭化アリルを滴下してエーテル化を行う方法により得ることができる。このとき、臭化アリルの量を、ショ糖に対して２〜６倍モル、好ましくは２〜５倍モルの範囲に調整することにより、効率的に水溶性ショ糖アリルエーテルを得ることができる。エーテル化の反応温度は、例えば８０℃程度である。通常、臭化アリルの滴下後３時間程度で反応が完結する。反応液から分離した水相にアルコールを添加し、析出する塩類を濾別した後、余分なアルコールと水分を留去させることにより、水溶性ショ糖アリルエーテルを回収することができる。 Water-soluble sucrose allyl ether can be obtained, for example, by adding sodium hydroxide as a catalyst to aqueous sucrose solution, converting sucrose to alkaline sucrose, and then dropping ether to conduct etherification. it can. At this time, by adjusting the amount of allyl bromide in a range of 2 to 6 moles, preferably 2 to 5 moles with respect to sucrose, water-soluble sucrose allyl ether can be efficiently obtained. . The reaction temperature of etherification is, for example, about 80.degree. Usually, the reaction is completed about 3 hours after dropping of allyl bromide. An alcohol is added to the aqueous phase separated from the reaction solution, and the precipitated salts are separated by filtration, and then excess alcohol and water are distilled off, whereby the water-soluble sucrose allyl ether can be recovered.
逆相懸濁重合に用いられる疎水性溶媒としては、例えば、脂肪族炭化水素、脂環式炭化水素及び芳香族炭化水素から選ばれる石油系炭化水素溶媒が用いられる。脂肪族炭化水素としては、ｎ−ペンタン、ｎ−ヘキサン及びｎ−ヘプタン等が挙げられる。脂環式炭化水素としては、シクロペンタン、メチルシクロペンタン、シクロヘキサン及びメチルシクロヘキサン等が挙げられる。芳香族炭化水素としては、ベンゼン、トルエン及びキシレン等が挙げられる。特に、ｎ−ヘキサン、ｎ−ヘプタン、シクロヘキサン及びトルエンから選ばれる少なくとも１種の疎水性溶媒が、工業的な汎用溶媒として好適に使用される。疎水性溶媒の比率は、水溶性不飽和カルボン酸単量体等を含む水相１００質量部に対して、例えば１００〜２００質量部である。 As a hydrophobic solvent used for reverse phase suspension polymerization, for example, a petroleum hydrocarbon solvent selected from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons is used. Examples of aliphatic hydrocarbons include n-pentane, n-hexane and n-heptane. Examples of alicyclic hydrocarbons include cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane. Examples of aromatic hydrocarbons include benzene, toluene and xylene. In particular, at least one hydrophobic solvent selected from n-hexane, n-heptane, cyclohexane and toluene is suitably used as a general-purpose industrial solvent. The ratio of the hydrophobic solvent is, for example, 100 to 200 parts by mass with respect to 100 parts by mass of the aqueous phase containing the water-soluble unsaturated carboxylic acid monomer and the like.
逆相懸濁重合の際、水溶性不飽和カルボン酸単量体等を含む水相、又は前記疎水性溶媒は、界面活性剤及びラジカル開始剤等の他の成分を含んでいてもよい。 In reverse phase suspension polymerization, an aqueous phase containing a water-soluble unsaturated carboxylic acid monomer or the like, or the hydrophobic solvent may contain other components such as a surfactant and a radical initiator.
界面活性剤は、主に重合中の懸濁状態を安定化させるために用いられる。界面活性剤は、逆相懸濁重合において通常用いられるものであれば特に限定されない。好ましくは、ソルビタン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ソルビトール脂肪酸エステル、変性ポリエチレンワックス、変性ポリプロピレンワックス、ポリビニルアルコール、ポリエチレンオキサイド、セルロースエーテル（ヒドロキシエチルセルロース、エチルセルロース等）、アルキルベンゼンスルホン酸ナトリウム、及びポリオキシエチレンアルキルフェニルエーテル硫酸塩から選ばれる１種又は２種以上の界面活性剤が用いられる。 Surfactants are mainly used to stabilize the suspension during polymerization. The surfactant is not particularly limited as long as it is generally used in reverse phase suspension polymerization. Preferably, sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitol fatty acid ester, modified polyethylene wax, modified polypropylene wax, polyvinyl alcohol, polyethylene oxide, cellulose ether (hydroxyethyl cellulose, ethyl cellulose etc.), sodium alkylbenzene sulfonate, And one or more surfactants selected from polyoxyethylene alkylphenyl ether sulfates.
界面活性剤の量は、水溶性不飽和カルボン酸単量体に対して好ましくは０．１〜１０質量％、より好ましくは０．５〜５質量％である。界面活性剤の量が少ないと重合の際の懸濁状態の安定性に問題が生じる可能性が若干あり、界面活性剤の量が多いと経済的に不利となる傾向がある。 The amount of surfactant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the water-soluble unsaturated carboxylic acid monomer. If the amount of surfactant is small, there may be some problems in the stability of the suspension state during polymerization, and if the amount of surfactant is large, it tends to be economically disadvantageous.
ラジカル開始剤は、通常のラジカル重合に用いられるものであれば特に限定されないが、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム及びアゾ系開始剤などが好適に使用される。例えば、２，２’−アゾビス（２−メチルプロピオンアミジン）２塩酸塩をラジカル開始剤として用いることができる。 The radical initiator is not particularly limited as long as it is used for ordinary radical polymerization, and potassium persulfate, ammonium persulfate, sodium persulfate and an azo initiator are suitably used. For example, 2,2'-azobis (2-methylpropionamidine) dihydrochloride can be used as a radical initiator.
ラジカル開始剤の量は、水溶性不飽和カルボン酸単量体に対して好ましくは０．０１〜０．５質量％、より好ましくは０．０２〜０．２質量％である。ラジカル開始剤の量がこの範囲内にあると、重合反応がより効率的に進行し得、また得られる重合体を親水性増粘剤として用いた際の増粘性により優れる。 The amount of the radical initiator is preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.2% by mass, based on the water-soluble unsaturated carboxylic acid monomer. When the amount of the radical initiator is in this range, the polymerization reaction can proceed more efficiently, and the obtained polymer is more excellent in thickening property when it is used as a hydrophilic thickener.
逆相懸濁重合の際、水溶性不飽和カルボン酸単量体等を含む液滴のサイズは、得られるポリマー粒子のサイズと密接な関係がある。反応容器及び製造スケール等の条件により異なるが、例えば２Ｌのフラスコを反応容器として用いた場合、撹拌速度８００〜１０００回転／分の条件で逆相懸濁重合を行うことにより、適当なサイズのポリマー粒子を得ることができる可能性が高い。このように、重合反応時の撹拌速度を調整し、ポリマー粒子（樹脂粒子）のサイズを制御することで、中位粒子径５〜３０μmの樹脂粒子を得ることができる。このようにして得られたポリマー粒子の形状は球状であり、化粧品等の水性液中においても保持されるためこれを用いた化粧料において、種々の特性や触感・使用感によい影響を及ぼすものと考えられる。 In reverse phase suspension polymerization, the size of droplets containing a water-soluble unsaturated carboxylic acid monomer etc. is closely related to the size of the resulting polymer particles. Depending on the conditions of the reaction vessel and production scale, for example, when a 2 L flask is used as the reaction vessel, a polymer of an appropriate size can be obtained by performing reverse phase suspension polymerization at a stirring speed of 800 to 1000 rpm. It is likely that particles can be obtained. Thus, by adjusting the stirring speed at the time of the polymerization reaction and controlling the size of the polymer particles (resin particles), resin particles having a median particle diameter of 5 to 30 μm can be obtained. The shape of the polymer particles thus obtained is spherical, and is maintained even in aqueous liquids such as cosmetics, and therefore, in cosmetics using this, it has a favorable effect on various properties, touch and feeling of use it is conceivable that.
なお、当該粒子の中位粒子径は、当該粒子をｎ−ヘキサン中に分散させ、レーザー回折法により測定した体積平均粒径の中位粒子径である。当該方法による測定装置（レーザー回折式粒度分布測定装置）として、例えばＳＡＬＤ−２０００Ａ（島津製作所製）を用いることができる。 In addition, the median particle diameter of the said particle | grain is a median particle diameter of the volume average particle diameter which disperse | distributed the said particle | grain in n-hexane and was measured by the laser diffraction method. For example, SALD-2000A (manufactured by Shimadzu Corporation) can be used as a measuring device (laser diffraction particle size distribution measuring device) according to the method.
本発明において、当該粒子の中位粒子径は、上述の通り５〜３０μｍであり、好ましくは５〜２５μｍであり、より好ましくは６〜２０μｍである。中位粒子径が当該範囲内にない場合、当該粒子を配合してなる弱酸性化粧料を皮膚に適用したときの触感（さっぱりとした軽い触感）に劣り、また、ヨレが出やすくなる。 In the present invention, the median particle diameter of the particles is 5 to 30 μm as described above, preferably 5 to 25 μm, and more preferably 6 to 20 μm. When the median particle size is not within the above range, it is inferior to the touch (fresh and light touch) when a weak acid cosmetic containing the particles is applied to the skin, and it becomes easy to take off.
重合反応のその他の諸条件、例えばラジカル開始剤の量、重合反応温度、反応時間等も適宜調整される。重合反応温度は、例えば５０〜８０℃であり、反応時間は、例えば３０分〜３時間である。例えば２Ｌのフラスコを反応容器として用いる場合、その浴温を６０℃に調整して重合反応を開始させることができる。この場合、重合反応の開始は、反応容器内の温度が重合熱で７０℃程度に上昇することから確認できる。その後、３０分〜３時間程度の熟成反応を行うことで、通常は重合反応が完結する。熟成時間が、それより短いと反応が充分に完了せず、残存する水溶性不飽和カルボン酸単量体が多くなることがある。熟成反応後、浴温を上昇させて反応容器内の水及び石油系炭化水素溶媒を留去させることで、生成物を取得することができる。 Other various conditions of the polymerization reaction, such as the amount of the radical initiator, the polymerization reaction temperature, the reaction time and the like are also appropriately adjusted. The polymerization reaction temperature is, for example, 50 to 80 ° C., and the reaction time is, for example, 30 minutes to 3 hours. For example, when a 2 L flask is used as a reaction vessel, the temperature of the bath can be adjusted to 60 ° C. to start the polymerization reaction. In this case, the start of the polymerization reaction can be confirmed from the temperature in the reaction vessel rising to about 70 ° C. due to the heat of polymerization. Then, the polymerization reaction is usually completed by carrying out an aging reaction for about 30 minutes to 3 hours. If the aging time is shorter, the reaction may not be sufficiently completed, and the amount of the remaining water-soluble unsaturated carboxylic acid monomer may increase. After the aging reaction, the product can be obtained by raising the bath temperature and distilling off the water and the petroleum hydrocarbon solvent in the reaction vessel.
本発明の弱酸性化粧料用増粘剤は、上記樹脂粒子以外にも、本発明の効果を損なわない範囲で、公知の水溶性増粘剤を含んでもよい。このような水溶性増粘剤としては、ヒドロキシエチルセルロース、キサンタンガム等の多糖類系水溶性高分子、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー等が例示できる。なお、本発明の弱酸性化粧料用増粘剤は、上記樹脂粒子からなることが好ましい。 The thickener for weakly acidic cosmetics of the present invention may contain a known water-soluble thickener other than the above resin particles, as long as the effects of the present invention are not impaired. Examples of such water-soluble thickeners include polysaccharide-based water-soluble polymers such as hydroxyethyl cellulose and xanthan gum, carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers, and the like. In addition, it is preferable that the thickener for weak acid cosmetics of this invention consists of the said resin particle.
本発明の弱酸性化粧料用増粘剤は、その０．５質量％水溶液のｐＨが４〜７であることが好ましく、４．５〜６．５であることがより好ましい。また、当該０．５質量％水溶液の粘度が、１０，０００〜２０，０００（ｍＰａ・ｓ）であることが好ましく、１２，０００〜１９，０００（ｍＰａ・ｓ）であることがより好ましい。 The pH of the 0.5% by mass aqueous solution of the thickener for weakly acidic cosmetics of the present invention is preferably 4 to 7, and more preferably 4.5 to 6.5. The viscosity of the 0.5 mass% aqueous solution is preferably 10,000 to 20,000 (mPa · s), and more preferably 12,000 to 19,000 (mPa · s).
また、上記の通り、本発明は、上記弱酸性化粧料用増粘剤を配合してなる弱酸性化粧料も包含する。当該弱酸性化粧料は、さらに酸性物質を含んでもよい。 In addition, as described above, the present invention also encompasses weakly acidic cosmetics obtained by blending the above-mentioned thickeners for weakly acidic cosmetics. The weakly acidic cosmetic may further contain an acidic substance.
本発明において、弱酸性化粧料はｐＨが４以上７未満の化粧料であり、好ましくはｐＨが４〜６．５の化粧料であり、より好ましくはｐＨが４〜６の化粧料である。また、本発明において、弱酸性化粧料の粘度は、１２，０００〜２０，０００（ｍＰａ・ｓ）であることが好ましい。 In the present invention, the weakly acidic cosmetic is a cosmetic having a pH of 4 or more and less than 7, preferably a cosmetic having a pH of 4 to 6.5, and more preferably a cosmetic having a pH of 4 to 6. Moreover, in the present invention, the viscosity of the weakly acidic cosmetic is preferably 12,000 to 20,000 (mPa · s).
なお、上記弱酸性化粧料用増粘剤の０．５質量％水溶液、及び本発明の弱酸性化粧料におけるｐＨ及び粘度は、いずれも、次の方法により測定される。 The pH and viscosity of the 0.5 mass% aqueous solution of the above-mentioned thickener for weak acid cosmetic and the weak acidic cosmetic of the present invention are both measured by the following method.
すなわち、ｐＨは、２５℃においてｐＨメーターを用いて測定した値である。ｐＨメーターとしては、例えばＨＯＲＩＢＡ Ｄ−５１（株式会社堀場製作所）を用いることができる。また、粘度は、２５℃においてＢＨ型回転粘度計（ローターＮｏ．６あるいは７を使用し、回転速度は毎分２０回転）を用いて、ローターの回転を開始してから１分後に測定された値である。 That is, pH is a value measured using a pH meter at 25 ° C. As a pH meter, HORIBA D-51 (Horiba, Ltd.) can be used, for example. In addition, the viscosity was measured one minute after starting the rotation of the rotor using a BH type rotational viscometer (rotor No. 6 or 7 and the rotation speed was 20 revolutions per minute) at 25 ° C. It is a value.
本発明の弱酸性化粧料用増粘剤に含有される上記樹脂粒子は、弱酸性化粧料に配合されると、吸水して膨潤するため、その中位粒子径が配合前に比べて好ましくは約８〜１０倍になる。吸水した当該樹脂粒子の中位粒子径は、４０〜３００μm程度であることが好ましく、５０〜２５０μｍ程度であることがより好ましい。なお、当該中位粒子径は、レーザー回折法により測定した体積平均粒径の中位粒子径である。当該方法による測定装置（レーザー回折式粒度分布測定装置）として、例えばＳＡＬＤ−２０００Ａ（島津製作所製）を用いることができる。 The above-mentioned resin particles contained in the thickener for weakly acidic cosmetics of the present invention absorb water and swell when blended in weakly acidic cosmetics, so the median particle diameter thereof is preferably smaller than before blending. Approximately eight to ten times. The median particle diameter of the resin particles having absorbed water is preferably about 40 to 300 μm, and more preferably about 50 to 250 μm. In addition, the said median particle diameter is a median particle diameter of the volume average particle diameter measured by the laser diffraction method. For example, SALD-2000A (manufactured by Shimadzu Corporation) can be used as a measuring device (laser diffraction particle size distribution measuring device) according to the method.
本発明に用いられる酸性物質としては、水溶液中で酸性を示す、化粧料に用いられることが公知の成分であればよい。例えば、水溶液中で酸性を示す、公知の消炎剤、保湿剤、角質溶解剤、収斂剤、酸性老化防止剤、抗脂肪沈着剤、美白剤および抗ニキビ剤等が挙げられる。 The acidic substance used in the present invention may be any component known to be used in cosmetics that exhibits acidity in an aqueous solution. For example, known anti-inflammatory agents, moisturizers, keratolytic agents, astringents, acidic anti-aging agents, anti-fat deposition agents, skin-whitening agents, anti-acne agents, etc. which show acidity in aqueous solution can be mentioned.
具体的には、乳酸、グリコール酸、リンゴ酸、クエン酸、酒石酸、グルコン酸、マンデル酸、ベンジル酸、アゼライン酸、α−リポ酸、サリチル酸、α−ヒドロキシ酪酸、β−ヒドロキシ酪酸、アスパラギン酸、グルタミン酸、アスコルビン酸（ビタミンＣ））、アスコルビン酸グルコシド、サリチル酸、サリチル酸グリコール、レチノイン酸等が挙げられる。 Specifically, lactic acid, glycolic acid, malic acid, citric acid, tartaric acid, gluconic acid, mandelic acid, benzylic acid, azelaic acid, α-lipoic acid, salicylic acid, α-hydroxybutyric acid, β-hydroxybutyric acid, aspartic acid, Glutamate, ascorbic acid (vitamin C)), ascorbic acid glucoside, salicylic acid, glycol salicylate, retinoic acid and the like can be mentioned.
本発明の弱酸性化粧料における酸性物質の含有量は、その含有される成分に応じて異なるが、概ね全成分に対して０．５〜５質量％含有することが好ましい。 Although the content of the acidic substance in the weakly acidic cosmetic composition of the present invention varies depending on the component contained, it is preferable that the content is generally 0.5 to 5% by mass with respect to all the components.
本実施形態に係る化粧料の種類は、特に限定されないが、例えば、薬用クリーム、化粧水、乳液、美容液、クリーム、クリームパック、マッサージクリーム、クレンジングクリーム、クレンジングジェル、ジェルクリーム、洗顔フォーム、保湿ジェル、ヘアーセッティングジェル、日焼け止め、スタイリングジェル、アイライナー、マスカラ、口紅及びファンデーション等が挙げられる。また、本発明の化粧料に含まれるその他の成分としては、本発明の効果を損なわない限り、化粧料に配合される公知の成分であれば特に制限はされないが、例えば、水、粉末成分、液体油脂、固体油脂、ロウ、炭化水素油、高級脂肪酸、高級アルコール、エステル油、シリコーン油、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤、保湿剤、水溶性高分子、皮膜剤、紫外線吸収剤、金属イオン封鎖剤、低級アルコール、多価アルコール、糖、アミノ酸、有機アミン、高分子エマルジョン、ｐＨ調整剤、皮膚栄養剤、ビタミン、酸化防止剤、酸化防止助剤、香料等が挙げられる。 The type of the cosmetic according to the present embodiment is not particularly limited, but, for example, medicated cream, lotion, milk, serum, cream, cream pack, massage cream, cleansing cream, cleansing gel, gel cream, facial cleansing foam, moisturizing cream Gel, hair setting gel, sunscreen, styling gel, eyeliner, mascara, lipstick, foundation and the like. The other components contained in the cosmetic of the present invention are not particularly limited as long as they do not impair the effects of the present invention, as long as they are known components to be blended in the cosmetic. Liquid oil, solid oil, wax, hydrocarbon oil, higher fatty acid, higher alcohol, ester oil, silicone oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, water soluble Polymers, film agents, UV absorbers, sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids Agents, perfumes and the like.
クリーム、クリームパック、マッサージクリーム及びクレンジングクリーム等のクリーム化粧料、又は、クレンジングジェル、ジェルクリーム、保湿ジェル、ヘアーセッティングジェル及びスタイリングジェル等のジェル系化粧料として本実施形態に係る化粧料を用いると、高濃度で配合してもヨレを生じることなく、さっぱり感及び軽さも付与され、メリットが特に大きい。 When the cosmetic according to the present embodiment is used as a cream cosmetic such as cream, cream pack, massage cream and cleansing cream or as a gel cosmetic such as cleansing gel, gel cream, moisturizing gel, hair setting gel and styling gel Even if blended in high concentration, it does not cause deflection, and a refreshing feeling and lightness are also imparted, and the merit is particularly great.
例えば水中油型乳化化粧料である乳液及びクリームは、油性成分と、水及び本発明の弱酸性化粧料用増粘剤に加え、必要に応じて、酸性物質や、植物エキス等の有効成分、界面活性剤、キレート剤（エデト酸ナトリウム等）、防腐剤、香料などの成分から構成され得る。一般的には、水中油型乳化化粧料は、水相と油相を７０℃前後に加熱溶解し、ホモミキサーで乳化した後、撹拌しながら冷却する工程で製造される。本発明の弱酸性化粧料用増粘剤はこれらの製品のレオロジーコントロール剤及び乳化安定剤として機能すると考えられる。 For example, emulsions and creams, which are oil-in-water type emulsified cosmetics, contain an oily component, water and the thickener for weakly acidic cosmetics of the present invention, and, if necessary, active ingredients such as acidic substances and plant extracts, It may be composed of components such as surfactants, chelating agents (sodium edetate etc.), preservatives, perfumes and the like. In general, the oil-in-water emulsion cosmetic is prepared by heating and dissolving the aqueous phase and the oil phase to about 70 ° C., emulsifying with a homomixer, and then cooling with stirring. It is believed that the weak acid cosmetic thickener of the present invention functions as a rheology control agent and emulsion stabilizer for these products.
本発明の弱酸性化粧料における弱酸性化粧料用増粘剤の配合量は、当該化粧料の種類や求められる粘度に応じて、適宜設定することができる。例えば、０．３〜２質量％であり得る。なお、弱酸性化粧料における弱酸性化粧料用増粘剤の配合量は、通常の化粧料における増粘剤の添加量は、例えば、一般的な乳液では全成分に対し０．１〜０．３質量％、一般的なクリームでは０．２〜２質量％程度である。一般的に１質量％以上配合すると、べたつき、ヨレを生じやすいからである。しかし、本発明の弱酸性化粧料においては、所望の粘性を得る観点から、弱酸性化粧料用増粘剤を１〜２質量％程度好ましく配合することもできる。 The compounding quantity of the thickener for weak acid cosmetics in the weak acid cosmetics of this invention can be suitably set according to the kind of the said cosmetics, and the viscosity calculated | required. For example, it may be 0.3 to 2% by mass. In addition, as for the compounding quantity of the thickener for weak acid cosmetics in weak acid cosmetics, the addition amount of the thickener in normal cosmetics, for example, is 0.1-0. It is about 3% by mass, and 0.2 to 2% by mass in general creams. In general, when 1% by mass or more is blended, it is likely to cause stickiness and deflection. However, in the weakly acidic cosmetic composition of the present invention, from the viewpoint of obtaining a desired viscosity, a thickener for a weakly acidic cosmetic composition can be preferably blended in an amount of about 1 to 2% by mass.
弱酸性化粧料のなかでも、水中油型乳化化粧料である乳液及びクリームについて、以下述べる。 Among weakly acidic cosmetics, emulsions and creams which are oil-in-water type emulsified cosmetics are described below.
油性成分は、特に限定されないが、肌への質感、馴染み、外観、滑り性等を考慮して、天然系オイル、シリコーン系オイル及びエステル油等であってもよい。 The oily component is not particularly limited, but may be a natural oil, silicone oil, ester oil or the like in consideration of texture to the skin, familiarity, appearance, slipperiness and the like.
天然系オイルとしては、例えば、流動パラフィン等のパラフィン系炭化水素、オリーブオイル、マカデミアナッツ油、ヒマシ油、ホホバ油、オレンジラフィー油、ミツロウ、ラノリン、ミネラルオイル、及びスクワラン等が挙げられる。 Examples of natural oils include paraffinic hydrocarbons such as liquid paraffin, olive oil, macadamia nut oil, castor oil, jojoba oil, orange ruffy oil, beeswax, lanolin, mineral oil, squalane and the like.
シリコーン系オイルとしては、例えば、メチルポリシロキサン、メチルフェニルポリシロキサン、環状メチルシロキサン、及びシリコーンポリエーテルコポリマー等の変性シリコーンオイル等が挙げられる。 Examples of silicone-based oils include modified silicone oils such as methylpolysiloxane, methylphenylpolysiloxane, cyclic methylsiloxane, and silicone polyether copolymer.
エステル油としては、各種脂肪酸エステルが挙げられる。例えば、オレイン酸、エルカ酸、ミリスチン酸、リシノレイン酸等の各脂肪酸のオクチルドデシルエステルが好適である。 As ester oil, various fatty acid ester is mentioned. For example, octyldodecyl ester of each fatty acid such as oleic acid, erucic acid, myristic acid, ricinoleic acid is preferable.
これらの油性成分は、それぞれ単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 These oil components may be used alone or in combination of two or more.
美白剤や保湿剤を配合してもよい。なお、美白剤や保湿剤のなかで、水溶液中で酸性を示す成分は、酸性物質である。 You may mix a whitening agent and a moisturizer. Among the skin lightening agents and moisturizing agents, the components that show acidity in an aqueous solution are acidic substances.
美白剤としては、アスコルビン酸ナトリウム、アスコルビン酸グルコシド、アスコルビン酸２グルコシドなどが使用させる。 As the whitening agent, sodium ascorbate, ascorbic acid glucoside, ascorbic acid 2 glucoside and the like are used.
保湿剤は、グリセリン、プロピレングリコール、ソルビット、ポリエチレングリコール、ジプロピレングリコール、１，３−ブチレングリコール、ジグリセリン、マンニトール及びＰＯＥメチルグリコシド等から適宣選ばれる。 The humectant is suitably selected from glycerin, propylene glycol, sorbit, polyethylene glycol, dipropylene glycol, 1,3-butylene glycol, diglycerin, mannitol, POE methyl glycoside and the like.
界面活性剤は、ノニオン性のモノステアリン酸グリセリン、ＰＯＥソルビタン脂肪酸エステル、及びソルビタン脂肪酸エステル等が使用されることが多い。ただし、アニオン性、カチオン性又は両性の界面活性剤を使用することもできる。 As the surfactant, nonionic glycerin monostearate, POE sorbitan fatty acid ester, sorbitan fatty acid ester and the like are often used. However, anionic, cationic or amphoteric surfactants can also be used.
また、弱酸性化粧料が保湿ジェル、及びヘアーセッティングジェル等のジェル系化粧料の場合は、例えば水、保湿剤、及び必要によりヘアーセッティング剤などの薬剤と、弱酸性化粧料用増粘剤とを含有する。当該増粘剤の量は、ジェル系化粧料の質量を基準として好ましくは０．３〜２質量％である。 When the weakly acidic cosmetic is a gel-based cosmetic such as a moisturizing gel and a hair setting gel, for example, water, a moisturizing agent, and an agent such as a hair setting agent if necessary, and a thickener for weakly acidic cosmetic Contains The amount of the thickener is preferably 0.3 to 2% by mass based on the mass of the gel cosmetic.
また、本発明の弱酸性化粧料は、本発明の効果を損なわない範囲において、さらに親水性増粘剤を含んでもよい。このような親水性増粘剤としては、ヒドロキシエチルセルロース、キサンタンガム等の多糖類系水溶性高分子、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー等が例示できる。これらのなかでも、キサンタンガムは、本発明の弱酸性化粧料用増粘剤と組み合わせて用いることにより増粘効果がより一層高まるため、特に好ましい。なお、弱酸性化粧料にさらに配合するこれら親水性増粘剤は、１種単独で又は２種以上を組み合わせて用いることができる。 The weakly acidic cosmetic composition of the present invention may further contain a hydrophilic thickener as long as the effects of the present invention are not impaired. Examples of such hydrophilic thickeners include polysaccharide-based water-soluble polymers such as hydroxyethyl cellulose and xanthan gum, carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers and the like. Among these, xanthan gum is particularly preferable because the thickening effect is further enhanced by using it in combination with the thickener for weak acid cosmetic of the present invention. In addition, these hydrophilic thickeners further mix | blended with weak acid cosmetics can be used individually by 1 type or in combination of 2 or more types.
以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these examples.
＜水溶性ショ糖アリルエーテルの合成＞
（製造例１）
１０００ｍＬのセパラブルフラスコに撹拌機、還流冷却管及び滴下ロートを取り付けた。このセパラブルフラスコの中で、水１４４ｇに水酸化ナトリウム４８ｇ（１．２モル）を溶解した。そこにショ糖１３６．８ｇ（０．４モル）を加え、７０〜８５℃で１２０分間撹拌して、アルカリショ糖水溶液を調製した。このアルカリショ糖水溶液に対して、臭化アリル１４５．２ｇ（１．２モル）を、７０〜８５℃で１．５時間かけて滴下し、その後、８０℃で３時間熟成して、ショ糖をアリルエーテル化した。冷却後、水４４０ｇを添加し、分液ロートで余分な油分を分離して、粗ショ糖アリルエーテル水溶液を得た。この粗ショ糖アリルエーテル水溶液に塩酸を加えてｐＨを６〜８に調整した後、ロータリーエバポレーターを用いて、水溶液の質量が４８０ｇになるまで水分を除去した。そして、エタノール２００ｇを添加して副生成物の臭化ナトリウム等の塩類を析出させ、析出物を濾別により水溶液から除去した。さらにエバポレーターを用いて水溶液から余分な水分を除去し、エーテル化度２．４の精製された水溶性ショ糖アリルエーテル１６６ｇを得た。
<Synthesis of water-soluble sucrose allyl ether>
(Production Example 1)
A stirrer, a reflux condenser and a dropping funnel were attached to a 1000 mL separable flask. In this separable flask, 48 g (1.2 mol) of sodium hydroxide was dissolved in 144 g of water. Sucrose 136.8g (0.4 mol) was added there, and it stirred at 70-85 degreeC for 120 minutes, and prepared alkaline sucrose aqueous solution. To this aqueous alkaline sucrose solution, 145.2 g (1.2 mol) of allyl bromide is added dropwise at 70 to 85 ° C. over 1.5 hours, and then aged at 80 ° C. for 3 hours to obtain sucrose Was allyletherified. After cooling, 440 g of water was added, and the excess oil was separated with a separatory funnel to obtain a crude sucrose allyl ether aqueous solution. Hydrochloric acid was added to the crude sucrose allyl ether aqueous solution to adjust the pH to 6 to 8, and then the water content was removed using a rotary evaporator until the weight of the aqueous solution became 480 g. Then, 200 g of ethanol was added to precipitate salts such as sodium bromide as a by-product, and the precipitate was removed by filtration from the aqueous solution. Further, excess water was removed from the aqueous solution using an evaporator to obtain 166 g of purified water-soluble sucrose allyl ether having an etherification degree of 2.4.
＜樹脂（水溶性架橋剤によって架橋された水溶性不飽和カルボン酸単量体の重合体）の合成＞
（製造例２）
５００ｍＬセパラブルフラスコに撹拌機、還流冷却管及び滴下ロートを取り付けた。このセパラブルフラスコの中にアクリル酸７２ｇ及び水を入れ、８０質量％のアクリル酸水溶液９０ｇを調製した。さらにイオン交換水５６ｇと、架橋剤として製造例１の水溶性ショ糖アリルエーテル０．０２３ｇ（アクリル酸水溶液に対して０．２５質量％）と、開始剤としての２，２’−アゾビス（２−メチルプロピオンアミジン）２塩酸塩（和光純薬工業株式会社製 Ｖ−５０）０．０４ｇとを加えて、水溶性不飽和カルボン酸単量体水溶液を調製した。
<Synthesis of Resin (Polymer of Water-Soluble Unsaturated Carboxylic Acid Monomer Cross-Linked by Water-Soluble Cross-Linking Agent)>
(Production Example 2)
A stirrer, a reflux condenser and a dropping funnel were attached to a 500 mL separable flask. 72 g of acrylic acid and water were placed in the separable flask to prepare 90 g of an aqueous 80% by weight acrylic acid solution. Furthermore, 56 g of ion-exchanged water, 0.023 g (0.25% by mass with respect to the aqueous solution of acrylic acid) of the water-soluble sucrose allyl ether of Production Example 1 as a crosslinking agent, and 2,2′-azobis (2 as an initiator -Methyl propionamidine) dihydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.) and 0.04 g were added to prepare a water-soluble unsaturated carboxylic acid monomer aqueous solution.
これとは別に、撹拌機、還流冷却管、滴下ロート及び窒素ガス導入管を取り付けた２Ｌのセパラブルフラスコにｎ−ヘプタン３３０ｇを入れ、さらに界面活性剤であるソルビタンモノステアレート（日油株式会社製、ノニオンSP-60R）２．７ｇを加え、これをｎ−ヘプタンに分散及び溶解させた。そこに、先に調製した水溶性不飽和カルボン酸単量体水溶液を加えた。反応容器内の雰囲気、原料および溶媒中に存在している酸素を除去するために溶液中に窒素ガスを吹き込んで系内を窒素置換しながら、浴温を６０℃に保持して、撹拌速度１０００回転／分で撹拌して、１時間かけて逆相懸濁重合法により重合を行った。重合終了後、水およびｎ−ヘプタンを留去して、アクリル酸及びそのナトリウム塩の重合体であって、水溶性ショ糖アリルエーテルによって架橋された重合体である中和度０％の樹脂の粉末６２ｇを得た（以下当該樹脂を樹脂Ａとよぶ）。 Separately from this, 330 g of n-heptane is placed in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet, and a sorbitan monostearate as a surfactant (Nippon Co., Ltd. (Nonion SP-60R), and dispersed and dissolved in n-heptane. Thereto, the aqueous solution of the water-soluble unsaturated carboxylic acid monomer prepared above was added. In order to remove oxygen present in the atmosphere in the reaction vessel, the raw materials and the solvent, nitrogen gas is blown into the solution to replace the inside of the system with nitrogen, and the bath temperature is maintained at 60 ° C., and the stirring speed 1000 The polymerization was carried out by reverse phase suspension polymerization for 1 hour while stirring at a rotation / minute. After completion of the polymerization, water and n-heptane are distilled off, and a polymer of acrylic acid and its sodium salt, which is a polymer crosslinked by water-soluble sucrose allyl ether, has a degree of neutralization of 0%. 62 g of powder was obtained (hereinafter, the resin is referred to as resin A).
（製造例３）
５００ｍＬセパラブルフラスコに撹拌機、還流冷却管及び滴下ロートを取り付けた。このセパラブルフラスコの中にアクリル酸７２ｇ及び水を入れ、８０質量％のアクリル酸水溶液９０ｇを調製した。アクリル酸水溶液を冷却しながら、３０質量％の水酸化ナトリウム水溶液２７ｇを滴下して、水溶液を中和した。さらにイオン交換水５６ｇと、架橋剤として製造例１の水溶性ショ糖アリルエーテル０．０２３ｇ（アクリル酸水溶液に対して０．２５質量％）と、開始剤としての２，２’−アゾビス（２−メチルプロピオンアミジン）２塩酸塩（和光純薬工業株式会社製 Ｖ−５０）０．０４ｇとを加えて、水溶性不飽和カルボン酸単量体水溶液を調製した。
(Production Example 3)
A stirrer, a reflux condenser and a dropping funnel were attached to a 500 mL separable flask. 72 g of acrylic acid and water were placed in the separable flask to prepare 90 g of an aqueous 80% by weight acrylic acid solution. While cooling the acrylic acid aqueous solution, 27 g of a 30% by mass sodium hydroxide aqueous solution was added dropwise to neutralize the aqueous solution. Furthermore, 56 g of ion-exchanged water, 0.023 g (0.25% by mass with respect to the aqueous solution of acrylic acid) of the water-soluble sucrose allyl ether of Production Example 1 as a crosslinking agent, and 2,2′-azobis (2 as an initiator -Methyl propionamidine) dihydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.) and 0.04 g were added to prepare a water-soluble unsaturated carboxylic acid monomer aqueous solution.
これとは別に、撹拌機、還流冷却管、滴下ロート及び窒素ガス導入管を取り付けた２Ｌのセパラブルフラスコにｎ−ヘプタン３３０ｇを入れ、さらに界面活性剤であるソルビタンモノステアレート（日油株式会社製、ノニオンSP-60R）２．７ｇを加え、これをｎ−ヘプタンに分散及び溶解させた。そこに、先に調製した水溶性エチレン不飽和単量体水溶液を加えた。反応容器内の雰囲気、原料および溶媒中に存在している酸素を除去するために溶液中に窒素ガスを吹き込んで系内を窒素置換しながら、浴温を６０℃に保持して、撹拌速度１０００回転／分で撹拌して、１時間かけて逆相懸濁重合法により重合を行った。重合終了後、水およびｎ−ヘプタンを留去して、アクリル酸及びそのナトリウム塩の重合体であって、水溶性ショ糖アリルエーテルによって架橋された重合体である中和度２０％の樹脂の粉末８０ｇを得た（以下当該樹脂を樹脂Ｂとよぶ）。 Separately from this, 330 g of n-heptane is placed in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet, and a sorbitan monostearate as a surfactant (Nippon Co., Ltd. (Nonion SP-60R), and dispersed and dissolved in n-heptane. Thereto, the previously prepared water-soluble aqueous solution of ethylenically unsaturated monomer was added. In order to remove oxygen present in the atmosphere in the reaction vessel, the raw materials and the solvent, nitrogen gas is blown into the solution to replace the inside of the system with nitrogen, and the bath temperature is maintained at 60 ° C., and the stirring speed 1000 The polymerization was carried out by reverse phase suspension polymerization for 1 hour while stirring at a rotation / minute. After completion of the polymerization, water and n-heptane are distilled off, and a polymer of acrylic acid and its sodium salt, which is a polymer crosslinked by water-soluble sucrose allyl ether, having a degree of neutralization of 20% 80 g of powder was obtained (hereinafter, the resin is referred to as resin B).
（製造例４）
３０質量％の水酸化ナトリウム水溶液を５４ｇに変更したこと以外は製造例３と同様の操作により、中和度４０％の樹脂の粉末９０ｇを得た（以下当該樹脂を樹脂Ｃとよぶ）。
(Production Example 4)
According to the same operation as in Production Example 3 except that the 30% by mass aqueous sodium hydroxide solution was changed to 54 g, 90 g of a powder of a resin having a degree of neutralization of 40% was obtained (hereinafter, the resin is referred to as resin C).
（製造例５）
撹拌回転数を８００回転に変更した以外は製造例４と同様の操作により、中和度４０％の樹脂の粉末９０ｇを得た（以下当該樹脂を樹脂Ｄとよぶ）。
(Production Example 5)
According to the same operation as in Production Example 4 except that the number of revolutions for stirring was changed to 800, 90 g of a powder of a resin having a degree of neutralization of 40% was obtained (hereinafter, the resin is referred to as resin D).
（製造例６）
撹拌回転数を６００回転に変更した以外は製造例４と同様の操作により、中和度４０％の樹脂の粉末９０ｇを得た（以下当該樹脂を樹脂Ｅとよぶ）。
(Production Example 6)
By the same operation as in Production Example 4 except that the number of revolutions for stirring was changed to 600, 90 g of a powder of a resin having a degree of neutralization of 40% was obtained (hereinafter, the resin is referred to as resin E).
（製造例７）
３０質量％の水酸化ナトリウム水溶液を９４ｇに変更したこと以外は製造例３と同様の操作により、中和度７０％の樹脂の粉末１０２ｇを得た（以下当該樹脂を樹脂Ｆとよぶ）。
(Production Example 7)
By the same operation as in Production Example 3 except that the 30% by mass aqueous sodium hydroxide solution was changed to 94 g, 102 g of a powder of a resin having a neutralization degree of 70% was obtained (hereinafter, the resin is referred to as resin F).
＜カルボキシビニルポリマーの合成＞
（製造例８）
撹拌機、温度計、窒素吹き込み管及び冷却管を取り付けた５００ｍＬ容の四つ口フラスコに、アクリル酸４５ｇ（０．６２５モル）、ペンタエリトリトールアリルエーテル０．２７ｇ、ノルマルヘキサン１５０ｇ及び２，２’−アゾビスメチルイソブチレート０．０８１ｇ（０．０００３５モル）を仕込んで、反応液を調製した。反応液を撹拌して各原料を均一に混合した後、反応容器の雰囲気、原料及び溶媒中に存在している酸素を除去するために溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、反応液を６０〜６５℃に保持して４時間反応させた。反応終了後、生成したスラリーを９０℃に加熱して、ｎ−ヘキサンを留去し、さらに、１１０℃、１０ｍｍＨｇにて８時間減圧乾燥することにより、白色微粉末状のカルボキシビニルポリマーの粉末４２ｇを得た。
<Synthesis of Carboxyvinyl Polymer>
Production Example 8
45 g (0.625 mol) of acrylic acid, 0.27 g of pentaerythritol allyl ether, 150 g of normal hexane and 150 g of 2,2 ′ in a 500 mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a cooling tube. -Azobis methyl isobutyrate 0.081g (0.00035 mol) was charged, and the reaction liquid was prepared. After stirring the reaction solution and uniformly mixing the respective raw materials, nitrogen gas was blown into the solution to remove oxygen present in the atmosphere of the reaction vessel, the raw materials and the solvent. Next, the reaction solution was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the resulting slurry is heated to 90 ° C. to distill off n-hexane and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain 42 g of carboxyvinyl polymer powder in the form of white fine powder. I got
＜樹脂及びカルボキシビニルポリマーの特性評価＞
〈中位粒子径の測定〉
製造例２〜７で得られた各樹脂および製造例８で得られたカルボキシビニルポリマーの粉末を、それぞれｎ−ヘキサン中に分散させ、島津製作所製レーザー粒子径測定装置（ＳＡＬＤ２０００ フローセル使用）により体積平均粒径の中位粒子径を測定した。結果を表１に示した。
<Characteristic evaluation of resin and carboxyvinyl polymer>
<Measurement of medium particle diameter>
Each resin obtained in Production Examples 2 to 7 and the powder of carboxyvinyl polymer obtained in Production Example 8 are dispersed in n-hexane, respectively, and the volume is measured by a laser particle diameter measurement apparatus (using SALD 2000 flow cell) manufactured by Shimadzu Corporation. The median particle size of the average particle size was measured. The results are shown in Table 1.
〈０．５質量％水性液粘度の測定〉
各樹脂及びカルボキルビニルポリマーを水と混合して、それぞれの水性液（濃度０．５質量％）を調製した。樹脂がアクリル酸ナトリウム塩をモノマー単位として含む場合、アクリル酸のモノマー単位の質量を基準として、樹脂の質量％を計算した。樹脂Ｂ〜Ｆを含む各水性液のｐＨは４．８〜７．０であった。樹脂Ａ及びカルボキルビニルポリマーを含む各水性液については、所定量の６質量％水酸化ナトリウム水溶液を中和剤として用いてｐＨを６．０に調整するとともに、樹脂濃度を０．５質量％とした。各０．５質量％水性液の粘度を、ＢＨ型回転粘度計を用いて測定した。スピンドルローターの回転速度を毎分２０回転として、２５℃において、ローターの回転を開始してから１分後の粘度の値を読み取った。樹脂Ａ〜ＦはローターＮｏ．６、カルボキシビニルポリマーはローターＮｏ．７を使用した。結果を表１に示した。
<Measurement of 0.5 mass% aqueous liquid viscosity>
Each resin and carboxyl vinyl polymer were mixed with water to prepare each aqueous liquid (concentration: 0.5% by mass). When the resin contains acrylic acid sodium salt as a monomer unit, the mass% of the resin was calculated based on the mass of the monomer unit of acrylic acid. The pH of each aqueous liquid containing resins B to F was 4.8 to 7.0. For each aqueous liquid containing resin A and carboxyl vinyl polymer, the pH is adjusted to 6.0 using a predetermined amount of 6 mass% aqueous sodium hydroxide solution as a neutralizing agent, and the resin concentration is 0.5 mass% And The viscosity of each 0.5 mass% aqueous liquid was measured using a BH type rotational viscometer. The rotational speed of the spindle rotor was 20 revolutions per minute, and at 25 ° C., the value of viscosity was read one minute after the start of the rotation of the rotor. Resins A to F have rotor no. 6, carboxy vinyl polymer is no. 7 was used. The results are shown in Table 1.
＜化粧料の調整＞
＜美白クリームＡ＞
（実施例１）
以下のオイル成分１〜４を混合し、そこに樹脂Ａを加えホモミキサーで分散させ、さらに成分６〜１０を水に溶解して得た均一混合液を加え、ホモミキサー（１３０００ｒｐｍ）により乳化し、美白クリームＡ−１を得た。
<Adjustment of cosmetics>
<Whitening cream A>
Example 1
The following oil components 1 to 4 were mixed, resin A was added thereto and dispersed with a homomixer, and then a homogeneous mixed solution obtained by dissolving components 6 to 10 in water was added and emulsified with a homomixer (13000 rpm) , Whitening cream A-1 was obtained.
油相
１．流動パラフィン ５％
２．スクワラン ５％
３．パルミチン酸イソプロピル ５％
４．トリ（カプリル／カプリン酸）グリセリル ５％
５．樹脂Ａ １．５％
水相
６．イソステアリン酸ポリオキシエチレングリセリル（２０Ｅ．Ｏ．） ３％
７．アスコルビン酸グルコシド １．５％
８．フェノキシエタノール ０．５％
９．６％水酸化ナトリウム 適量
１０．精製水 残余
Oil phase 1. Liquid paraffin 5%
2. Squalane 5%
3. Isopropyl palmitate 5%
4. Tri (Capryl / Capric Acid) Glyceryl 5%
5. Resin A 1.5%
Water phase 6. Polyoxyethylene glyceryl isostearate (20E.O.) 3%
7. Ascorbic acid glucoside 1.5%
8. Phenoxyethanol 0.5%
9.6% sodium hydroxide dosage 10. Purified water residual
（実施例２）
樹脂Ａを樹脂Ｂに変更したこと以外は実施例１と同様の操作により、美白クリームＡ−２を調製した。
(Example 2)
A whitening cream A-2 was prepared in the same manner as in Example 1 except that the resin A was changed to the resin B.
（実施例３）
樹脂Ａを樹脂Ｃに変更したこと以外は実施例１と同様の操作により、美白クリームＡ−３を調製した。
(Example 3)
A whitening cream A-3 was prepared in the same manner as in Example 1 except that the resin A was changed to the resin C.
（実施例４）
樹脂Ａを樹脂Ｄに変更したこと以外は実施例１と同様の操作により、美白クリームＡ−４を調製した
(Example 4)
A whitening cream A-4 was prepared in the same manner as in Example 1 except that resin A was changed to resin D.
（比較例１）
樹脂Ａを樹脂Ｅに変更したこと以外は実施例１と同様の操作により、美白クリームＡ−５を調製した
(Comparative example 1)
Whitening cream A-5 was prepared in the same manner as in Example 1 except that resin A was changed to resin E.
（比較例２）
樹脂Ａを樹脂Ｆに変更したこと以外は実施例１と同様の操作により、美白クリームＡ−６を調製した
(Comparative example 2)
Whitening cream A-6 was prepared in the same manner as in Example 1 except that resin A was changed to resin F.
（比較例３）
樹脂Ａをカルボキシビニルポリマーに変更したこと以外は実施例１と同様の操作により、美白クリームＡ−７を調製した
(Comparative example 3)
A whitening cream A-7 was prepared in the same manner as in Example 1 except that resin A was changed to a carboxyvinyl polymer.
＜美白クリームＢ＞
（実施例５）
以下のオイル成分１〜４を混合し、そこに樹脂Ｃを加えホモミキサーで分散させ、さらに成分６〜１１を水に溶解して得た均一混合液を加え、ホモミキサー（１３０００ｒｐｍ）により乳化し、美白クリームＢ−１を得た。
<Whitening cream B>
(Example 5)
The following oil components 1 to 4 are mixed, resin C is added thereto and dispersed by a homomixer, and then a homogeneous mixed solution obtained by dissolving components 6 to 11 in water is added and emulsified by a homomixer (13000 rpm) , Whitening cream B-1 was obtained.
油相
１．流動パラフィン ５％
２．スクワラン ５％
３．パルミチン酸イソプロピル ５％
４．トリ（カプリル／カプリン酸）グリセリル ５％
５．樹脂Ｃ １％
水相
６．イソステアリン酸ポリオキシエチレングリセリル（２０Ｅ．Ｏ．） ３％
７．アスコルビン酸グルコシド １．５％
８．キサンタンガム ０．５％
９．フェノキシエタノール ０．５％
１０．６％水酸化ナトリウム 適量
１１．精製水 残査
Oil phase 1. Liquid paraffin 5%
2. Squalane 5%
3. Isopropyl palmitate 5%
4. Tri (Capryl / Capric Acid) Glyceryl 5%
5. Resin C 1%
Water phase 6. Polyoxyethylene glyceryl isostearate (20E.O.) 3%
7. Ascorbic acid glucoside 1.5%
8. Xanthan gum 0.5%
9. Phenoxyethanol 0.5%
10.6% sodium hydroxide dosage 11. Purified water residue
（比較例４）
実施例５において、樹脂Ｃを用いなかった以外は実施例５と同様にして美白クリームＢ−２を得た。
(Comparative example 4)
A whitening cream B-2 was obtained in the same manner as in Example 5 except that resin C was not used in Example 5.
＜薬用クリーム＞
（実施例６）
以下のオイル成分１〜４を混合し、そこに樹脂Ｃを加えホモミキサーで分散させ、さらに成分６〜１０を水に溶解して得た均一混合液を加え、ホモミキサー（１３０００ｒｐｍ）により乳化し、薬用クリームを得た。
<Medicine cream>
(Example 6)
The following oil components 1 to 4 are mixed, resin C is added thereto and dispersed with a homomixer, and then a uniform mixed solution obtained by dissolving components 6 to 10 in water is added and emulsified with a homomixer (13000 rpm) , I got a medicinal cream.
油相
１．流動パラフィン ５％
２．スクワラン ５％
３．パルミチン酸イソプロピル ５％
４．トリ（カプリル／カプリン酸）グリセリル ５％
５．樹脂Ｃ １．５％
水相
６．グリセリン ５％
７．１，３−ブチレングリコール ５％
８．イソステアリン酸ポリオキシエチレングリセリル（２０Ｅ．Ｏ．） ３％
９．サリチル酸グリコール １．５％
１０．フェノキシエタノール ０．５％
１１．６％水酸化ナトリウム 適量
１２．精製水 残余
Oil phase 1. Liquid paraffin 5%
2. Squalane 5%
3. Isopropyl palmitate 5%
4. Tri (Capryl / Capric Acid) Glyceryl 5%
5. Resin C 1.5%
Water phase 6. Glycerin 5%
7. 1,3-butylene glycol 5%
8. Polyoxyethylene glyceryl isostearate (20E.O.) 3%
9. Glycol salicylate 1.5%
10. Phenoxyethanol 0.5%
11.6% sodium hydroxide dosage 12. Purified water residual
（比較例５）
実施例６において、樹脂Ｃを樹脂Ｆに変更したこと以外は実施例６と同様の操作により、薬用クリームを調製した。
(Comparative example 5)
A medicinal cream was prepared in the same manner as in Example 6, except that resin C was changed to resin F in Example 6.
（比較例６）
実施例６において、樹脂Ｃをカルボキシビニルポリマーに変更したこと以外は実施例６と同様の操作により、薬用クリームを調製した。
(Comparative example 6)
A medicinal cream was prepared in the same manner as in Example 6, except that resin C was changed to a carboxyvinyl polymer in Example 6.
＜化粧料の特性評価＞
実施例１〜６及び比較例１〜６で得られた化粧料について、ｐＨ、粘度、触感、ヨレ性を以下の方法により評価した。結果を表２に示した。
<Characteristic evaluation of cosmetics>
The pH, the viscosity, the touch, and the repelling property of the cosmetic obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were evaluated by the following methods. The results are shown in Table 2.
<ｐＨ>
２５℃においてｐＨメーターＨＯＲＩＢＡ Ｄ−５１（株式会社堀場製作所）を用いて測定した。
<pH>
It measured at 25 degreeC using pH meter HORIBA D-51 (Horiba, Ltd.).
〈粘度〉
ＢＨ型回転粘度計を用いて測定した。スピンドルローターの回転速度を毎分２０回転として、２５℃において、ローターの回転を開始してから１分後の粘度の値を読み取った。なお、粘度１０００（ｍＰａ・ｓ）以下はローターＮｏ．２、粘度 ８０００〜２００００（ｍＰａ・ｓ）はローターＮｏ．６を使用した。
<viscosity>
It measured using the BH type | mold rotational viscometer. The rotational speed of the spindle rotor was set to 20 revolutions per minute, and at 25 ° C., the value of the viscosity one minute after the start of the rotation of the rotor was read. In addition, viscosity 1000 (mPa · s) or less is rotor No. 2. The viscosity of 8,000 to 20,000 (mPa · s) 6 was used.
〈触感〉
男女各５人（計１０人）の試験者によって、触感を以下の通り評価した。適量の化粧料を手の甲に塗付し、指で伸ばした時のさっぱり感および軽さを質感として以下の基準で評価した。
Touch
The tactile sensation was evaluated as follows by 5 male and 5 female (10 in total) examiners. An appropriate amount of cosmetic was applied to the back of the hand, and the feeling of lightness and lightness when stretched with a finger were evaluated as the texture according to the following criteria.
評価基準
○：さっぱり感、軽さが良いと評価した試験者が８人以上いた。
×：さっぱり感、軽さが良いと評価した試験者が７人以下であった。
Evaluation criteria :: There were eight or more testers who evaluated that the feeling of lightness was good.
X: Less than 7 testers evaluated that refreshing feeling and lightness were good.
〈ヨレ性〉
男女各５人（計１０人）の試験者によって、触感を以下の通り評価した。化粧料０．５gを肌にとり、塗りこみ時間１分で前腕部に塗布した際のヨレ（凝集物）の発生状況を確認した。
<Yollet nature>
The tactile sensation was evaluated as follows by 5 male and 5 female (10 in total) examiners. 0.5 g of the cosmetic was applied to the skin, and the occurrence of sagging (aggregates) when applied to the forearm in 1 minute of coating time was confirmed.
評価基準
×：１０人中９人以上が多量の凝集物ありと評価した。
△：１０人中２人〜８人がわずかに凝集物ありと評価した。
○：１０人中９人以上がほとんど凝集物無しと評価した。
Evaluation criteria x: 9 or more out of 10 evaluated that a large amount of aggregates were present.
Δ: 2 to 8 out of 10 were evaluated as slightly aggregate.
○: 9 or more out of 10 evaluated as almost no aggregate.
表２に示すように、樹脂Ａ〜Ｄを用いた実施例１〜４および実施例６によれば、酸性物質を含有する化粧料においても、さっぱりした軽い触感とヨレの出ない良好な化粧料が得られた。これら特定の樹脂（水溶性架橋剤の存在下に重合して得られる中和度５０％以下、中位粒子径５〜３０μmの樹脂）が親水性増粘剤として、特に酸性の化粧料に用いるのに適していることが分かった。 As shown in Table 2, according to Examples 1 to 4 and Example 6 using resins A to D, even in cosmetics containing an acidic substance, good cosmetics with a refreshing light touch and no omission. was gotten. These specific resins (resins having a degree of neutralization of 50% or less and a median particle size of 5 to 30 μm obtained by polymerization in the presence of a water-soluble crosslinking agent) are used as hydrophilic thickeners, particularly in acidic cosmetics It turned out to be suitable for
またさらに、実施例５によれば、当該特定の樹脂とキサンタンガムを併用することによって、増粘相乗効果が認められた。 Furthermore, according to Example 5, by using the specific resin in combination with xanthan gum, a thickening and synergistic effect was observed.
Claims (5)
前記弱酸性化粧料はｐＨが４以上７未満であり、
水溶性ショ糖アリルエーテルの存在下に水溶性不飽和カルボン酸単量体を重合して得られる、中和度５０％以下且つ中位粒子径が５〜３０μmの樹脂粒子を含有する弱酸性化粧料用増粘剤。 In the thickener for weak acid cosmetics,
The weakly acidic cosmetic has a pH of 4 or more and less than 7;
Weakly acidic cosmetic containing resin particles having a degree of neutralization of 50% or less and a median particle size of 5 to 30 μm, obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of a water-soluble sucrose allyl ether Thickeners.
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