JP2016094358A - Cellulose nanofiber dispersoid and cosmetic composition using the same - Google Patents
Cellulose nanofiber dispersoid and cosmetic composition using the same Download PDFInfo
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- JP2016094358A JP2016094358A JP2014230345A JP2014230345A JP2016094358A JP 2016094358 A JP2016094358 A JP 2016094358A JP 2014230345 A JP2014230345 A JP 2014230345A JP 2014230345 A JP2014230345 A JP 2014230345A JP 2016094358 A JP2016094358 A JP 2016094358A
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- Prior art keywords
- pulp
- acid
- cellulose
- cellulose nanofiber
- dispersion
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- PMBRBOODEWULOI-UHFFFAOYSA-N trichloromethanide Chemical compound Cl[C-](Cl)Cl PMBRBOODEWULOI-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 1
- PVNIQBQSYATKKL-UHFFFAOYSA-N tripalmitin Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 210000003954 umbilical cord Anatomy 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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- 235000019156 vitamin B Nutrition 0.000 description 1
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- 150000003698 vitamin B derivatives Chemical class 0.000 description 1
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- 239000011735 vitamin B7 Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
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- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
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- 229940045997 vitamin a Drugs 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
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Landscapes
- Cosmetics (AREA)
Abstract
Description
本発明は、セルロースナノファイバー分散体およびこれを用いた化粧料組成物に関するものである。 The present invention relates to a cellulose nanofiber dispersion and a cosmetic composition using the same.
クリーム状、ゲル状、乳液状あるいは液体状の剤型を有する化粧料には、水やアルコール、油等の分散媒体に、高分子材料等を配合した組成物が用いられている。上記高分子材料としてはセルロース由来の高分子材料が提案されている。例として、パルプの水懸濁液を高圧ホモジナイザーで処理し、ミクロフィブリルレベルまで粉砕する微小繊維状セルロースの製法が提案されている(特許文献1)。また、ナノサイズに微粒子化したセルロースを用いた化粧料組成物が提案されている(特許文献2)。 For cosmetics having a cream, gel, emulsion, or liquid dosage form, a composition in which a polymer material or the like is mixed in a dispersion medium such as water, alcohol, or oil is used. As the polymer material, a polymer material derived from cellulose has been proposed. As an example, a method for producing a microfibrous cellulose in which an aqueous suspension of pulp is treated with a high-pressure homogenizer and pulverized to a microfibril level has been proposed (Patent Document 1). A cosmetic composition using cellulose finely divided into nano-sizes has been proposed (Patent Document 2).
上記特許文献2に記載の微粒子化したセルロースを使用した化粧料組成物は、一定の使用感を得ることができるものの、皮膚に塗布した際のべとつき感のない使用感を得ることは難しい。 Although the cosmetic composition using the finely divided cellulose described in Patent Document 2 can obtain a certain feeling of use, it is difficult to obtain a feeling of use without stickiness when applied to the skin.
本発明は、このような事情に鑑みてなされたもので、糸引き性(曳糸性)が無いセルロースナノファイバー分散体、及び皮膚に塗布した際にべとつき感が無く使用感に優れた化粧料組成物の提供をその目的とする。 The present invention has been made in view of such circumstances, and a cellulose nanofiber dispersion having no stringiness (stringiness), and a cosmetic material that has no stickiness when applied to the skin and has an excellent feeling of use. The purpose is to provide a composition.
すなわち、本発明は下記に掲げる発明に関する。
〔1〕パルプのセルロースの水酸基に置換基を導入した後、分散媒中で解繊処理する事により得られるセルロースナノファイバー分散体であって、上記パルプに非木材パルプを含有するセルロースナノファイバー分散体。
〔2〕好ましい実施形態として、上記非木材パルプが竹パルプ及び/またはケナフパルプであるセルロースナノファイバー分散体
〔3〕好ましい実施形態として、上記パルプが、上記非木材パルプを10質量%以上含有するセルロースナノファイバー分散体。
〔4〕上記セルロースナノファイバー分散体及び機能性添加剤を含有する化粧料組成物。
That is, this invention relates to the invention hung up below.
[1] A cellulose nanofiber dispersion obtained by introducing a substituent into a cellulose hydroxyl group of a pulp and then defibrating in a dispersion medium, wherein the cellulose nanofiber dispersion contains non-wood pulp in the pulp body.
[2] As a preferred embodiment, a cellulose nanofiber dispersion in which the non-wood pulp is bamboo pulp and / or kenaf pulp. [3] As a preferred embodiment, the pulp contains 10% by mass or more of the non-wood pulp. Nanofiber dispersion.
[4] A cosmetic composition containing the cellulose nanofiber dispersion and a functional additive.
本発明のセルロースナノファイバー分散体は、糸引き性(曳糸性)が無く、化粧料組成物に使用した場合、皮膚に塗布した際にべとつき感が無い化粧料組成物を得ることができる。 The cellulose nanofiber dispersion of the present invention does not have stringiness (stringiness), and when used in a cosmetic composition, a cosmetic composition that does not feel sticky when applied to the skin can be obtained.
次に、本発明の実施の形態を詳しく説明する。 Next, embodiments of the present invention will be described in detail.
本発明のセルロースナノファイバー分散体はパルプのセルロースの水酸基に置換基を導入した後、分散媒中で解繊処理する事により得られるセルロースナノファイバー分散体であって、上記パルプに非木材パルプを含有するものである。 The cellulose nanofiber dispersion of the present invention is a cellulose nanofiber dispersion obtained by introducing a substituent into a cellulose hydroxyl group of a pulp and then performing a fibrillation treatment in a dispersion medium. It contains.
上記非木材パルプは、特に制限はなく、目的に応じて適宜のものを選択できるが、具体的には、ケナフパルプ、竹パルプ、バガス、エスバルト草、サイザル麻、稲わら、小麦わら、カラス麦わら、大麦わら、ライ麦わら、サンヘンプ、パピルス、ガンピ、サバイ草、亜麻、マニラ麻などが挙げられ、これらの中でも、剛性が高く、きょう雑物が少ないことから、ケナフパルプ、竹パルプが特に好ましい。これらは、1種単独で用いてもよいし、2種以上を併用してもよい。 The non-wood pulp is not particularly limited and can be appropriately selected according to the purpose.Specifically, kenaf pulp, bamboo pulp, bagasse, esbalt grass, sisal hemp, rice straw, wheat straw, crow straw, Examples include barley straw, rye straw, sun hemp, papyrus, ganpi, sabai grass, flax, and Manila hemp. Among these, kenaf pulp and bamboo pulp are particularly preferred because of their high rigidity and little impurities. These may be used individually by 1 type and may use 2 or more types together.
上記竹パルプは、中国、タイ、スリランカ地方で多く使用されている。市販の竹パルプとしては、タイのフェニックス社などの販売している竹パルプがある。竹パルプの原料として使用される竹は、主に孟宗竹である。 The bamboo pulp is often used in China, Thailand and Sri Lanka. Commercially available bamboo pulp includes bamboo pulp sold by Phoenix, Thailand. Bamboo used as a raw material for bamboo pulp is mainly Miso bamboo.
上記ケナフパルプに使用されるケナフは、中国、東南アジア、南米などで、広く栽培されており、市販されている。市販のケナフとしては、タイのフェニックス社などが販売しているケナフがある。 Kenaf used for the kenaf pulp is widely cultivated and marketed in China, Southeast Asia, South America and the like. As a commercially available kenaf, there is a kenaf sold by Phoenix of Thailand.
上記非木材パルプ以外のセルロースとしては、特に制限無く、目的に適宜のものを選択できるが、具体的には、晒又は未晒木材パルプ、精製リンター、酢酸菌等の微生物によって生産されるセルロース等の天然セルロースや、セルロースを銅アンモニア溶液、モルホリン誘導体等、何らかの溶媒に溶解し、改めて紡糸された再生セルロース、及び上記セルロース系素材の加水分解、アルカリ加水分解、酵素分解、爆砕処理、振動ボールミル処理等によって解重合処理した微細セルロース又は機械的に処理した微細セルロースが例示される。これらは、1種単独で用いてもよいし、2種以上を併用してもよい。 The cellulose other than the non-wood pulp is not particularly limited and can be appropriately selected for the purpose. Specifically, cellulose produced by microorganisms such as bleached or unbleached wood pulp, refined linter, acetic acid bacteria, etc. Natural cellulose, regenerated cellulose dissolved in some solvent, such as copper ammonia solution and morpholine derivative, and re-spun, and hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, and vibration ball mill treatment of the above cellulose materials Examples thereof include fine cellulose subjected to depolymerization treatment or the like or mechanically treated fine cellulose. These may be used individually by 1 type and may use 2 or more types together.
上記非木材パルプの含有量は特に制限されないが、具体的にはセルロース100質量部に対し10質量%以上が好ましく、20質量%以上がより好ましく、30質量%以上が更に好ましい。また、90質量%以下が好ましく、80質量%以下がより好ましく、70質量%以下が更に好ましい。 Although content in particular of the said non-wood pulp is not restrict | limited, Specifically, 10 mass% or more is preferable with respect to 100 mass parts of cellulose, 20 mass% or more is more preferable, 30 mass% or more is still more preferable. Moreover, 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is still more preferable.
非木材パルプが上記範囲内ある場合、糸引き性(曳糸性)が低いセルロースナノファイバー分散体が得られる。 When the non-wood pulp is in the above range, a cellulose nanofiber dispersion having a low stringiness (spinnability) can be obtained.
上記置換基としては、セルロース分子中の水酸基との間にエーテル結合が生じる置換基であれば特に限定されない。例えば、アルキル基、カルボキシアルキル基、シアノアルキル基、ヒドロキシアルキル基、アルコキシアルキル基などが挙げられる。より好ましくは、カルボキシアルキル基、メチル基、エチル基、シアノエチル基、ヒドロキシエチル基、ヒドロキシプロピル基、エチルヒドロキシエチル基、ヒドロキシプロピルメチル基であり、カルボキシメチル基がさらに好ましい。置換基は一種であっても二種以上であっても良い。 The substituent is not particularly limited as long as it is a substituent that generates an ether bond with a hydroxyl group in the cellulose molecule. Examples thereof include an alkyl group, a carboxyalkyl group, a cyanoalkyl group, a hydroxyalkyl group, and an alkoxyalkyl group. More preferred are a carboxyalkyl group, a methyl group, an ethyl group, a cyanoethyl group, a hydroxyethyl group, a hydroxypropyl group, an ethylhydroxyethyl group, and a hydroxypropylmethyl group, and a carboxymethyl group is more preferred. The substituent may be one kind or two or more kinds.
本発明のセルロースナノファイバー分散体は、セルロースを公知の方法を用いてアニオン変性させることにより得ることができる。その一例として次のような製造方法をあげることができる。すなわち、セルロースを原料とし、溶媒に重量で3〜20倍の低級アルコール、具体的にはメタノール、エタノール、n−プロピルアルコール、イソプロピルアルコール、n−ブチルアルコール、イソブチルアルコール、t−ブチルアルコール等の単独、又は2種以上の混合物と水の混合媒体を使用する。なお、低級アルコールの混合割合は、60〜95質量%である。マーセル化剤としては、セルロースのグルコース残基当たり0.5〜20倍モルの水酸化アルカリ金属、具体的には水酸化ナトリウム、水酸化カリウムを使用する。セルロースと溶媒、マーセル化剤を混合してマーセル化処理を行う。このときの反応温度は0〜70℃、好ましくは10〜60℃であり、反応時間は15分〜8時間、好ましくは30分〜7時間である。その後、カルボキシメチル化剤をグルコース残基当たり0.05〜10.0倍モル添加してエーテル化反応を行う。このときの反応温度は30〜90℃、好ましくは40〜80℃であり、反応時間は30分〜10時間、好ましくは1時間〜4時間である。 The cellulose nanofiber dispersion of the present invention can be obtained by anionic modification of cellulose using a known method. The following manufacturing method can be mention | raise | lifted as the example. That is, cellulose is used as a raw material and the solvent is 3 to 20 times lower alcohol, specifically methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, etc. Or a mixture of two or more and water. In addition, the mixing ratio of a lower alcohol is 60-95 mass%. As the mercerizing agent, 0.5 to 20 times moles of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide is used per glucose residue of cellulose. Cellulose is formed by mixing cellulose, a solvent, and a mercerizing agent. The reaction temperature at this time is 0 to 70 ° C., preferably 10 to 60 ° C., and the reaction time is 15 minutes to 8 hours, preferably 30 minutes to 7 hours. Thereafter, the etherification reaction is carried out by adding 0.05 to 10.0 times mole of carboxymethylating agent per glucose residue. The reaction temperature at this time is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is 30 minutes to 10 hours, preferably 1 to 4 hours.
本発明のセルロースナノファイバー分散体は、アニオン変性したセルロースを高圧ホモジナイザー等によって解繊処理することで得ることができる。高圧ホモジナイザーとは、ポンプによって流体に加圧し、流路に設けた非常に繊細な間隙より噴出させる装置である。粒子間の衝突、圧力差による剪断力等の総合エネルギーによって乳化・分散・解繊・粉砕・超微細化を行うことができる。 The cellulose nanofiber dispersion of the present invention can be obtained by fibrillating anion-modified cellulose with a high-pressure homogenizer or the like. A high-pressure homogenizer is a device that pressurizes a fluid with a pump and ejects it from a very delicate gap provided in a flow path. It is possible to emulsify, disperse, defibrate, grind, and make ultrafine particles by using total energy such as collision between particles and shear force due to pressure difference.
上記ホモジナイザーによる処理条件としては、特に限定されるものではないが、圧力条件としては、30MPa以上、好ましくは100MPa以上、さらに好ましくは140MPa以上である。また、高圧ホモジナイザーでの解繊・分散処理に先立って、必要に応じて、高速せん断ミキサーなどの公知の混合、攪拌、乳化、分散装置を用いて、アニオン変性されたセルロースに予備処理を施すことも可能である。
本発明の化粧料組成物は、上記セルロースナノファイバー分散体、及び機能性添加剤を含有するものである。
The treatment condition by the homogenizer is not particularly limited, but the pressure condition is 30 MPa or more, preferably 100 MPa or more, more preferably 140 MPa or more. In addition, prior to defibration / dispersion treatment with a high-pressure homogenizer, if necessary, pretreatment of anion-modified cellulose is performed using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. Is also possible.
The cosmetic composition of the present invention contains the cellulose nanofiber dispersion and a functional additive.
上記機能性添加剤としては、例えば、下記に示す油性原料,界面活性剤,アルコール類,機能性成分等が用いられ、これらは単独でもしくは二種以上併せて用いられる。 As the functional additive, for example, the following oily raw materials, surfactants, alcohols, functional components and the like are used, and these are used alone or in combination of two or more.
〔油性原料〕
上記油性原料としては、例えば、ホホバ油、マカデミアナッツ油、アボガド油、月見草油、ミンク油、ナタネ油、ヒマシ油、ヒマワリ油、トウモロコシ油、カカオ油、ヤシ油、コメヌカ油、オリーブ油、アーモンド油、ごま油、サフラワー油、大豆油、椿油、パーシック油、綿花油、モクロウ、パーム油、パーム核油、卵黄油、ラノリン、スクワレン等の天然動植物油脂類;合成トリグリセライド、スクワラン、流動パラフィン、ワセリン、セレシン、マイクロクリスタリンワックス、イソパラフィン等の炭化水素類;カルナバウロウ、パラフィンワックス、鯨ロウ、ミツロウ、キヤンデリラワックス、ラノリン等のワックス類;セタノール、ステアリルアルコール、ラウリルアルコール、セトステアリルアルコール、オレイルアルコール、ベヘニルアルコール、ラノリンアルコール、水添ラノリンアルコール、ヘキシルデカノール、オクチルドデカノール等の高級アルコール類、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、イソステアリン酸、オレイン酸、リノレン酸、リノール酸、オキシステアリン酸、ウンデシレン酸、ラノリン脂肪酸、硬質ラノリン脂肪酸、軟質ラノリン脂肪酸等の高級脂肪酸類;コレステリル−オクチルドデシル−ベヘニル等のコレステロールおよびその誘導体;ミリスチン酸イソプロピル、パルミチン酸イソプロピル、ステアリン酸イソプロピル、2−エチルヘキサン酸グリセロール、ステアリン酸ブチル等のエステル類;ジエチレングリコールモノプロピルエーテル、ポリオキシエチレンポリオキシプロピレンペンタエリトリトールエーテル、ポリオキシプロピレンブチルエーテル、リノール酸エチル等の極性オイル等があげられる。また、上記油性原料としては、例えば、アミノ変性シリコーン、エポキシ変性シリコーン、カルボキシル変性シリコーン、カルビノール変性シリコーン、メタクリル変性シリコーン、メルカプト変性シリコーン、フェノール変性シリコーン、片末端反応性シリコーン、異種官能基変性シリコーン、ポリエーテル変性シリコーン、メチルスチリル変性シリコーン、アルキル変性シリコーン、高級脂肪酸変性シリコーン、親水性特殊変性シリコーン、高級アルコキシ変性シリコーン、高級脂肪酸含有シリコーン、フッ素変性シリコーン等があげられ、より具体的には、シリコーン樹脂、メチルフェニルポリシロキサン、メチルポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサンシロキサン、メチルシクロポリシロキサン、オクタンメチルトリシロキサン、デカメチルテトラシロキサン、ポリオキシエチレン−メチルポリシロキサン共重合体、ポリオキシプロピレン−メチルポリシロキサン共重合体、ポリ(オキシエチレン−オキシプロピレン)メチルポリシロキサン共重合体、メチルハイドロゲンポリシロキサン、テトラヒドロテトラメチルシクロテトラシロキサン、ステアロキシメチルポリシロキサン、セトキシメチルポリシロキサン、メチルポリシロキサンエマルジョン、高重合メチルポリシロキサン、トリメチルシロキシケイ酸、架橋型メチルポリシロキサン、架橋型メチルフェニルポリシロキサン、架橋型メチルフェニルポリシロキサン、架橋型メチルフェニルポリシロキサン等の各種誘導体を含むシリコーン類等があげられる。これらは単独でもしくは二種以上併せて用いられる。
[Oil raw material]
Examples of the oily materials include jojoba oil, macadamia nut oil, avocado oil, evening primrose oil, mink oil, rapeseed oil, castor oil, sunflower oil, corn oil, cacao oil, coconut oil, rice bran oil, olive oil, almond oil, sesame oil Natural animal and vegetable fats and oils such as safflower oil, soybean oil, cocoon oil, persic oil, cotton oil, molasses, palm oil, palm kernel oil, egg yolk oil, lanolin, squalene; synthetic triglyceride, squalane, liquid paraffin, petrolatum, ceresin, Hydrocarbons such as microcrystalline wax and isoparaffin; waxes such as carnauba wax, paraffin wax, whale wax, beeswax, chiyandelilla wax, lanolin; cetanol, stearyl alcohol, lauryl alcohol, cetostearyl alcohol, oleyl alcohol, Higher alcohols such as hexyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, octyldodecanol, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, oleic acid, linolenic acid, linoleic acid, oxy Higher fatty acids such as stearic acid, undecylenic acid, lanolin fatty acid, hard lanolin fatty acid, soft lanolin fatty acid; cholesterol and its derivatives such as cholesteryl-octyldodecyl-behenyl; isopropyl myristate, isopropyl palmitate, isopropyl stearate, 2-ethyl Esters such as glycerol hexanoate and butyl stearate; diethylene glycol monopropyl ether, polyoxyethylene polyoxypropylene pentaeli Rito ether, polyoxypropylene butyl ether, a polar oil such as ethyl linoleate and the like. Examples of the oily raw material include amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phenol-modified silicone, one-end reactive silicone, and different functional group-modified silicone. , Polyether modified silicone, methyl styryl modified silicone, alkyl modified silicone, higher fatty acid modified silicone, hydrophilic special modified silicone, higher alkoxy modified silicone, higher fatty acid-containing silicone, fluorine modified silicone, etc., more specifically, Silicone resin, methylphenylpolysiloxane, methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohex Siloxane, methylcyclopolysiloxane, octanemethyltrisiloxane, decamethyltetrasiloxane, polyoxyethylene-methylpolysiloxane copolymer, polyoxypropylene-methylpolysiloxane copolymer, poly (oxyethylene-oxypropylene) methylpoly Siloxane copolymer, methylhydrogenpolysiloxane, tetrahydrotetramethylcyclotetrasiloxane, stearoxymethylpolysiloxane, cetoxymethylpolysiloxane, methylpolysiloxane emulsion, highly polymerized methylpolysiloxane, trimethylsiloxysilicic acid, cross-linked methylpolysiloxane Silyls containing various derivatives such as cross-linked methylphenyl polysiloxane, cross-linked methylphenyl polysiloxane, cross-linked methylphenyl polysiloxane Over emissions, and the like, and the like. These may be used alone or in combination of two or more.
〔界面活性剤〕
上記界面活性剤としては、例えば、プロピレングリコール脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステルソルビタン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンひまし油、ポリオキシエチレン硬化ひまし油、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンフィトステロール、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンラノリン、ポリオキシエチレンラノリンアルコール、ポリオキシエチレンミツロウ誘導体、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンアルキルフェニルホルムアルデヒド縮合体、ポリオキシエチレンアルキルエーテルリン酸(塩)等の非イオン界面活性剤やアルキル硫酸エステル塩;ポリオキシエチレンアルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、α−オレフィンスルホン酸塩等のアニオン界面活性剤;塩化アルキルトリメチルアンモニウム、塩化ジアルキルジメチルアンモニウム、塩化ベンザルコニウム等のカチオン界面活性剤;レシチン、ラノリン、コレステロール、サポニン等の界面活性能を有する天然物;スルホコハク酸エステル類やエチレンオキシド−プロピレンオキシドブロック共重合体等のような低刺激性界面活性剤;ラウリルジメチルアミノ酢酸ベタイン等の両性界面活性剤等があげられる。これらは単独でもしくは二種以上併せて用いられる。
[Surfactant]
Examples of the surfactant include propylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyglycerin fatty acid ester sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxy Ethylene hardened castor oil, polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene beeswax derivative, polyoxy Ethylene alkylamine, polyoxyethylene fatty acid amide, polyoxy Nonionic surfactants such as ethylene alkylphenyl formaldehyde condensates and polyoxyethylene alkyl ether phosphates (salts) and alkyl sulfate salts; polyoxyethylene alkyl sulfate salts, alkylbenzene sulfonates, α-olefin sulfonates, etc. Anionic surfactants; cationic surfactants such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and benzalkonium chloride; natural products having surface-active ability such as lecithin, lanolin, cholesterol and saponin; sulfosuccinic acid esters and ethylene oxide -Hypoallergenic surfactants such as propylene oxide block copolymers; amphoteric surfactants such as lauryldimethylaminoacetic acid betaine. These may be used alone or in combination of two or more.
〔アルコール類〕
上記アルコールとしては、例えば、エタノール,イソプロピルアルコール等の水溶性アルコール、グリセリン,エチレングリコール,プロピレングリコール,ブタンジオール等の水溶性多価アルコール、およびこれらの混合物等があげられる。
[Alcohols]
Examples of the alcohol include water-soluble alcohols such as ethanol and isopropyl alcohol, water-soluble polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, and butanediol, and mixtures thereof.
〔機能性成分〕
上記機能性成分としては、例えば、パラアミノ安息香酸およびその誘導体、ブチルメトキシベンゾイルメタン、ジパラメトキシケイ皮酸モノ2−エチルへキサン酸グリセリル、オクチルシンナメート等のケイ皮酸誘導体、アミノサリシレート等のサリチル酸誘導体、2,4−ジヒドロキシベンゾフェノン等のベンゾフェノリン誘導体、ジメトキシベンジリデンジオキソイミダゾリンプロピオン酸エチルヘキシル、酢酸液状ラノリン、コガネバナ根抽出エキス、トリアニリノパラカルボエチルヘキシルオキシ−トリアジン等の紫外線吸収剤;アルブチン、コウジ酸、リン酸アスコルビン酸マグネシウム等のアスコルビン酸およびその誘導体、グルタチオン、甘草エキス、チョウジエキス、茶抽出物、アスタキサンチン、牛胎盤エキス、トコフェロールおよびその誘導体、トラネキサム酸およびその塩、アズレン、γ−ヒドロキシ酪酸等の美白成分;マルチトール、ソルビトール、グリセリン、プロピレングリコール、1,3−ブチレングリコール、ポリエチレングリコール、グリコール等の多価アルコール、ピロリドンカルボン酸ナトリウム、酪酸ナトリウム、クエン酸ナトリウム等の有機酸およびその塩、ヒアルロン酸ナトリウム等のヒアルロン酸およびその塩、酵母および酵母抽出液の加水分解物、酵母培養液、乳酸菌培養液等の醗酵代謝産物、コラーゲン、エラスチン、ケラチン、セリシン等の水溶性タンパク、コラーゲン加水分解物、カゼイン加水分解物、シルク加水分解物、ポリアスパラギン酸ナトリウム等のペプチド類およびその塩、トレハロース、キシロビオース、マルトース、ショ糖、ブドウ糖、植物性粘質多糖類等の糖類、多糖類およびその誘導体、水溶性キチン、キトサン、ペクチン、コンドロイチン硫酸およびその塩等のグリコサミノグリカンおよびその塩、グリシン、セリン、スレオニン、アラニン、アスパラギン酸、チロシン、バリン、ロイシン、アルギニン、グルタミン、プロリン等のアミノ酸、アミノカルボニル反応物等の糖アミノ酸化合物、アロエ、マロニエ等の植物抽出液、トリメチルグリシン、尿素、尿酸、アンモニア、レシチン、ラノリン、スクワラン、スクワレン、グルコサミン、クレアチニン、DNA、RNA等の核酸関連物質等の保湿剤;カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルトリメチルアンモニウムクロリドエーテル、エチルセルロース、ヒドロキシプロピルセルロース、メチルヒドロキシプロピルセルロース、可溶性デンプン、カルボキシメチルデンプン、メチルデンプン、アルギン酸プロピレングリコールエステル、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル、カルボキシビニルポリマー、ポリアクリル酸、メチルセルロース、ヒドロキシエチルセルロース、アラビアガム、キサンタンガム、カラギーナン、ガラクタン、ペクチン、マンナン、デンプン、デキストラン、サクシノグルカン、カードラン、ヒアルロン酸、ゼラチン、カゼイン、アルブミン、コラーゲン、メトキシエチレン無水マレイン酸共重合体、両性メタクリル酸エステル共重合体、ポリ塩化ジメチルメチレンピペリジニウム、ポリアクリル酸エステル共重合体、ポリビニルアルコール、ニトロセルロース、シリコーンレジン、ポリエチレングリコール脂肪酸エステル、ジステアリン酸ポリエチレングリコール等のポリオキシエチレン脂肪酸エステル、ポリオキシエチレンジオレイン酸メチルグルコシド等のポリオキシエチレン脂肪酸エステルメチルグリコシド、テトラデセンスルホン酸等の増粘剤;エチレンジアミン四酢酸およびその塩類、リン酸、アスコルビン酸、コハク酸、グルコン酸、ポリリン酸塩類、メタリン酸塩類等の金属イオン封鎖剤;エタノール、プロピレングリコール、1,3−ブチレングリコール等の有機溶剤、ブチルヒドロキシトルエン、トコフェロール、フィチン酸等の酸化防止剤;安息香酸およびその塩、パラオキシ安息香酸アルキルエステル(エチルパラベン、ブチルパラベン等)およびその塩、デヒドロ酢酸およびその塩類、パラクロルメタクレゾール、ヘキサクロロフェン、ホウ酸、レゾルシン、トリブロムサラン、オクトフェニルフェノール、グルコン酸クロルヘキシジン、チラム、感光素201号、フェノキシエタノール、塩化ベンザルコニウム、塩化ベンゾトニウム、ハロカルバン、塩化クロルヘキシジン、トリクロロカルバニド、酢酸トコフェロール、ジンクピリチオン、ヒノキチオール、フェノール、イソプロピルメチルフェノール、2,4,4−トリクロロ−2−ヒドロキシフェノール、ヘキサクロロフェン等の抗菌、防腐剤;クエン酸、リンゴ酸、酒石酸、乳酸、アジピン酸、グルタミン酸、アスパラギン酸、マレイン酸等の有機酸;ビタミンAおよびその誘導体;ビタミンB6 塩酸塩、ビタミンB6 トリパルミテート、ビタミンB6 ジオクタノエート、ビタミンB2 およびその誘導体等のビタミンB類;アスコルビン酸、アスコルビン酸硫酸エステル、アスコルビン酸リン酸エステル等のビタミンC類、α−トコフェロール、β−トコフェロール、γ−トコフェロール等のビタミンE類、ビタミンD類、ビタミンH、パントテン酸等のビタミン類、ニコチン酸アミド、ニコチン酸ベンジル、γ−オリザノール、アラントイン、グリチルチン酸(塩)グリチルレチン酸およびその誘導体、ヒノキチオール、ムシジン、ビサボロール、ユーカリプトール、チモールイソシトール、サポニン類(キラヤサポニン、アズキサポニン、ヘチマサポニン等)、トラネキサム酸、パントテルエチルエーテル、エチニルエストラジオール、セファランジン、プラセンタエキス、センブリエキス、セファランチン、ビタミンEおよびその誘導体、γ−オリザノール等の血行促進剤、トウガラシチンキ、ショオウキョウチンキ、カンタリスチンキ、ニコチン酸ベンジルエステル等の局所刺激剤、アミノ酸等の栄養剤、グリチルレチン酸、グリチルリチン酸誘導体、塩化カルプロニウム、ノニル酸ワニルアミド、アラントイン、アズレン、アミノカプロン酸、ヒドロコルチゾン等の抗炎症剤、酸化亜鉛、硫酸亜鉛、アラントインヒドロキシアルミニウム、塩化アルミニウム、スルホ石炭酸亜鉛、タンニン酸等の収斂剤、メントール、カンフル等の清涼剤、抗ヒスタミン剤、高分子シリコーン、環状シリコーン等のシリコン系物質、BHA、BHT、没食子酸、NDGA等の酸化防止剤等の各種薬剤;サッカロマイセス等の酵母、糸状菌、バクテリア、牛胎盤、人胎盤、人せい帯、酵母、コラーゲン、牛乳由来タンパク、小麦、大豆、牛血液、豚血液、鶏冠、カミツレ、きゅうり、米、シアバター、シラカバ、茶、トマト、にんにく、ハマメリス、バラ、ヘチマ、ホップ、桃、杏、レモン、キウイ、どくだみ、トウガラシ、クララ、ギシギシ、コウホネ、セージ、ノコギリ草、ゼニアオイ、センキュウ、センブリ、タイム、トウキ、トウヒ、バーチ、スギナ、マロニエ、ユキノシタ、アルニカ、ユリ、ヨモギ、シャクヤク、アロエ、アロエベラ、オウゴン、オウバク、コウカ、ベニバナ、サンシン、シコン、タイソウ、チンピ、ニンジン、ヨクイニン、ハトムギ、クチナシ、サワラ等の動植物、微生物およびその一部から有機溶媒、アルコール、多価アルコール、水、水性アルコール等で抽出して、またはこれらを加水分解して得た天然エキス;色素類;炭酸カルシウム、タルク、カオリン、マイカ、イオウ、ラウロイルリジン、微粒子シリカ、二酸化チタン、二酸化亜鉛、ベンガラ、黄酸化鉄、黒酸化鉄、ナイロン12粉末、ポリメチルメタクリレート粉末、ポリエチレン粉末、ポリスチレン粉末等の粉末成分;カチオン化セルロース、カルボキシビニルポリマー、カルボニルピロリドン、ポリビニルピロリドン−酢酸ビニル共重合体、キサンタンガム、ヒドロキシエチルセルロース等の高分子添加剤;香料類;キレート剤;トリエタノールアミンや水酸化カリウム、ホウ砂等のアルカリ;酸化防止剤等があげられる。これらは単独でもしくは二種以上併せて用いられる。
[Functional ingredients]
Examples of the functional component include paraaminobenzoic acid and derivatives thereof, cinnamate derivatives such as butylmethoxybenzoylmethane, diparamethoxycinnamate mono-2-ethylhexylate, octylcinnamate, and aminosalicylate. UV absorbers such as salicylic acid derivatives, benzophenoline derivatives such as 2,4-dihydroxybenzophenone, dimethoxybenzylidenedioxoimidazoline ethylhexylpropionate, acetic acid liquid lanolin, coganebana root extract, trianilinoparacarboethylhexyloxy-triazine; arbutin Ascorbic acid and its derivatives such as kojic acid and magnesium phosphate ascorbate, glutathione, licorice extract, clove extract, tea extract, astaxanthin, cow placenta extract, tocopher And its derivatives, whitening components such as tranexamic acid and salts thereof, azulene, γ-hydroxybutyric acid; polyhydric alcohols such as maltitol, sorbitol, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycol, Fermentation of organic acids such as sodium pyrrolidone carboxylate, sodium butyrate and sodium citrate and salts thereof, hyaluronic acid and salts thereof such as sodium hyaluronate, hydrolysates of yeast and yeast extract, yeast culture fluid, and lactic acid bacteria culture fluid Metabolites, water-soluble proteins such as collagen, elastin, keratin, sericin, collagen hydrolysates, casein hydrolysates, silk hydrolysates, peptides such as sodium polyaspartate and their salts, trehalose, xylobiose, mal Sugars such as toose, sucrose, glucose, vegetable mucus polysaccharides, polysaccharides and derivatives thereof, water-soluble chitin, chitosan, pectin, chondroitin sulfate and salts thereof, glycosaminoglycan and salts thereof, glycine, serine, Amino acids such as threonine, alanine, aspartic acid, tyrosine, valine, leucine, arginine, glutamine, proline, sugar amino acid compounds such as aminocarbonyl reactants, plant extracts such as aloe, maronier, trimethylglycine, urea, uric acid, ammonia, Moisturizing agents such as lecithin, lanolin, squalane, squalene, glucosamine, creatinine, nucleic acid-related substances such as DNA and RNA; carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyltrimethylammonium chloride ether, ethyl cell , Hydroxypropyl cellulose, methyl hydroxypropyl cellulose, soluble starch, carboxymethyl starch, methyl starch, propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, polyacrylic acid, methyl cellulose, hydroxyethyl cellulose, Gum arabic, xanthan gum, carrageenan, galactan, pectin, mannan, starch, dextran, succinoglucan, curdlan, hyaluronic acid, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer Polymer, polydimethylmethylenepiperidinium chloride, polyacrylate copolymer, Such as vinyl alcohol, nitrocellulose, silicone resin, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester such as polyethylene glycol distearate, polyoxyethylene fatty acid ester methyl glycoside such as polyoxyethylene dioleic acid methyl glucoside, tetradecene sulfonic acid, etc. Thickeners; sequestering agents such as ethylenediaminetetraacetic acid and its salts, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyphosphates, metaphosphates; ethanol, propylene glycol, 1,3-butylene glycol, etc. Antioxidants such as organic solvents, butylhydroxytoluene, tocopherol, phytic acid; benzoic acid and its salts, paraoxybenzoic acid alkyl esters (ethylparaben, butylparaben) Etc.) and salts thereof, dehydroacetic acid and salts thereof, parachloromethcresol, hexachlorophene, boric acid, resorcin, tribromsaran, octphenylphenol, chlorhexidine gluconate, thiram, photosensitizer 201, phenoxyethanol, benzalkonium chloride Antibacterial and antiseptics such as benzotonium chloride, halocarban, chlorhexidine chloride, trichlorocarbanide, tocopherol acetate, zinc pyrithione, hinokitiol, phenol, isopropylmethylphenol, 2,4,4-trichloro-2-hydroxyphenol, hexachlorophene; vitamin a and its derivatives; citric acid, malic acid, tartaric acid, lactic acid, adipic acid, glutamic acid, aspartic acid, organic acids such as maleic acid vitamin B 6 hydrochloride, vitamin 6 tripalmitate, vitamin B 6 dioctanoate, vitamin B such as vitamin B 2 and derivatives thereof; ascorbic acid, ascorbic acid sulfuric ester, vitamin C such as ascorbic acid phosphoric acid esters, alpha-tocopherol, beta-tocopherol, gamma -Vitamin E such as tocopherol, vitamin D, vitamin H, vitamins such as pantothenic acid, nicotinic acid amide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt) glycyrrhetinic acid and its derivatives, hinokitiol, mucidin , Bisabolol, eucalyptol, thymol isositol, saponins (Quillaja saponin, azoxaponin, hetimasaponin, etc.), tranexamic acid, pantothel ethyl ether, ethinyl estradiol, cephalandin, p Center extract, assembly extract, cephalanthin, vitamin E and its derivatives, blood circulation promoters such as γ-oryzanol, local stimulants such as chili pepper tincture, ginger tincture, cantalis tincture, nicotinic acid benzyl ester, nutrients such as amino acids, Glycyrrhetinic acid, glycyrrhizic acid derivatives, carpronium chloride, nonylic acid vanilamide, allantoin, azulene, aminocaproic acid, hydrocortisone and other anti-inflammatory agents, zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, sulfosulfoic acid zinc, tannic acid, etc. Agents, refreshing agents such as menthol and camphor, antihistamines, silicone materials such as polymeric silicones and cyclic silicones, various agents such as antioxidants such as BHA, BHT, gallic acid and NDGA; Yeasts such as Myces, filamentous fungi, bacteria, cow placenta, human placenta, human umbilical cord, yeast, collagen, milk-derived protein, wheat, soybeans, cow blood, pig blood, chicken crown, chamomile, cucumber, rice, shea butter, birch , Tea, tomato, garlic, hamamelis, rose, loofah, hop, peach, apricot, lemon, kiwi, dodge, capsicum, clara, scallop, kohone, sage, sawtooth grass, mallow Birch, Horsetail, Maronie, Yukinoshita, Arnica, Lily, Mugwort, Peonies, Aloe, Aloe Vera, Ogon, Prunus, Pepper, Safflower, Sanshin, Shikon, Tisoiso, Chimpi, Carrot, Yokuinin, Swan, Gardenia, Sawara, etc. Organic solvent, alcohol, polyvalent Natural extracts obtained by extraction with hydrocol, water, hydroalcohol, etc. or hydrolysis thereof; pigments; calcium carbonate, talc, kaolin, mica, sulfur, lauroyl lysine, fine particle silica, titanium dioxide, zinc dioxide, Powder components such as bengara, yellow iron oxide, black iron oxide, nylon 12 powder, polymethyl methacrylate powder, polyethylene powder, polystyrene powder; cationized cellulose, carboxyvinyl polymer, carbonylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer, xanthan gum Polymer additives such as hydroxyethyl cellulose; fragrances; chelating agents; alkalis such as triethanolamine, potassium hydroxide and borax; and antioxidants. These may be used alone or in combination of two or more.
本発明の化粧料組成物は、上記セルロースナノファイバー分散体に、化粧品用途として用いられる機能性添加剤、すなわち、油性原料,界面活性剤,アルコール類,機能性成分等の機能性添加剤を適宜に配合し、混合処理することにより調製することができる。
上記混合処理としては、例えば、真空ホモミキサー、ディスパー型ミキサー、プロペラミキサー、ニーダー等の各種混練器、コロイドミル、ペブルミル、ビーズミル等の各種粉砕機、ブレンダー、ホモジナイザー、超音波ホモジナイザー、高圧ホモジナイザーならびに超高圧ホモジナイザー等を用いた混合処理があげられる。
In the cosmetic composition of the present invention, functional additives such as oily raw materials, surfactants, alcohols, functional components and the like, which are used for cosmetic applications, are appropriately added to the cellulose nanofiber dispersion. It can be prepared by blending and mixing.
Examples of the mixing treatment include various kneaders such as a vacuum homomixer, a disperser mixer, a propeller mixer, and a kneader, various pulverizers such as a colloid mill, a pebble mill, and a bead mill, a blender, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, and an ultra-high homogenizer. Examples thereof include a mixing process using a high-pressure homogenizer.
本発明の化粧料組成物における上記セルロースナノファイバー分散体の配合量は、求める機能により異なるが、使用感の点からセルロースナノファイバーの固形分換算で0.05質量%以上が好ましく0.1質量%以上がより好ましい。また、5.0質量%以下が好ましく、2.0質量%以下がより好ましい。
また、上記油性原料、界面活性剤もしくは機能性成分の配合量は、化粧料の用途に応じて適量用いられる。なお、上記セルロースナノファイバーの濃度、各成分の配合量、混合時の分散化処理条件を変更することにより、所望の性状の化粧料組成物を調製することができる。
The blending amount of the cellulose nanofiber dispersion in the cosmetic composition of the present invention varies depending on the desired function, but is preferably 0.05% by mass or more in terms of solid content of the cellulose nanofiber from the viewpoint of usability, and is 0.1% by mass. % Or more is more preferable. Moreover, 5.0 mass% or less is preferable, and 2.0 mass% or less is more preferable.
Moreover, the compounding quantity of the said oil-based raw material, surfactant, or a functional component is used suitably according to the use of cosmetics. A cosmetic composition having a desired property can be prepared by changing the concentration of the cellulose nanofiber, the blending amount of each component, and the dispersion treatment conditions during mixing.
このようにして得られる本発明の化粧料組成物は、例えば、化粧水、乳液、コールドクリーム、バニシングクリーム、マッサージクリーム、エモリエントクリーム、クレンジングクリーム、美容液、パック、ファンデーション、サンスクリーン化粧料、サンタン化粧料、モイスチャークリーム、ハンドクリーム、美白乳液、各種ローション等の皮膚用化粧料、シャンプー、リンス、ヘアコンディショナー、リンスインシャンプー、ヘアスタイリング剤(ヘアフォーム,ジェル状整髪料等)、ヘアトリートメント剤(ヘアクリーム,トリートメントローション等)、染毛剤やローションタイプの育毛剤あるいは養毛剤等の毛髪用化粧料、さらにはハンドクリーナーのような洗浄剤、プレシェーブローション、アフターシェーブローション、芳香剤や歯磨剤、軟膏、貼布剤等の用途に用いることができる。 The cosmetic composition of the present invention thus obtained includes, for example, lotion, milky lotion, cold cream, burnishing cream, massage cream, emollient cream, cleansing cream, serum, pack, foundation, sunscreen cosmetic, suntan. Cosmetics, moisture cream, hand cream, whitening emulsion, various skin lotions, shampoos, rinses, hair conditioners, rinse-in shampoos, hair styling agents (hair foam, gel hair conditioners, etc.), hair treatment agents (hair Creams, treatment lotions, etc.), hair dyes and lotion type hair restorers or hair cosmetics such as hair nourishing agents, as well as detergents such as hand cleaners, pre-shave lotions, after-shave lotions, fragrances And dentifrices, ointments, can be used for applications such as plasters.
つぎに、実施例について比較例と併せて説明する。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。
<グルコース単位当たりの置換度の測定方法>
セルロース繊維を0.6質量%スラリーに調製し、0.1M塩酸水溶液を加えてpH2.4とした後、0.05Nの水酸化ナトリウム水溶液を滴下してpHが11になるまで電気伝導度を測定し、電気伝導度の変化が緩やかな弱酸の中和段階において消費された水酸化ナトリウム量からカルボキシル基量を測定し、下式を用いて算出した。ここで言う置換度とは、無水グルコース単位1モル当たりの置換基のモル数の平均値を表している。
Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.
<Measurement method of substitution degree per glucose unit>
Cellulose fiber is prepared in a slurry of 0.6% by mass, 0.1M hydrochloric acid aqueous solution is added to adjust the pH to 2.4, and 0.05N sodium hydroxide aqueous solution is added dropwise until the pH reaches 11. The amount of carboxyl groups was measured from the amount of sodium hydroxide consumed in the neutralization step of a weak acid with a gradual change in electrical conductivity, and calculated using the following formula. The degree of substitution referred to here represents the average value of the number of moles of substituents per mole of anhydroglucose unit.
撹拌機に、竹パルプを乾燥質量で50g、広葉樹晒クラフトパルプ(LBKP、日本製紙(株)製)を乾燥質量で150g、水酸化ナトリウムを乾燥質量で350g加え、パルプ固形分濃度が15%になるように水を加えた。その後、30℃で30分攪拌した後に70℃まで昇温し、モノクロロ酢酸ナトリウムを450g(有効成分換算)添加した。1時間反応した後に、反応物を取り出して中和、洗浄して、グルコース単位当たりの置換度0.29のアニオン変性されたセルロースを得た。その後、アニオン変性したパルプに水を添加して固形分濃度5%とし、高圧ホモジナイザーにより20℃、140MPaの圧力で5回処理し、セルロースナノファイバー1の分散液を得た。
Add 50 g dry weight of bamboo pulp, 150 g hardwood bleached kraft pulp (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) and 350 g sodium hydroxide by dry mass to the stirrer, and the solid content of the pulp is 15%. Water was added so that Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 450 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.29 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa to obtain a dispersion of cellulose nanofibers 1.
〔製造例2〕
竹パルプをケナフパルプに変更した以外、製造例1と同様にしてセルロースナノファイバー2の分散液を得た。なお、得られたセルロース繊維のグルコース単位当たりの置換度は0.33であった。
[Production Example 2]
A dispersion of cellulose nanofibers 2 was obtained in the same manner as in Production Example 1 except that bamboo pulp was changed to kenaf pulp. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.33.
〔製造例3〕
竹パルプを乾燥質量で100g、LBKPを乾燥質量で100gに変更した以外、製造例1と同様にしてセルロースナノファイバー3の分散液を得た。なお、得られたセルロース繊維のグルコース単位当たりの置換度は0.31であった。
[Production Example 3]
A dispersion of cellulose nanofiber 3 was obtained in the same manner as in Production Example 1, except that bamboo pulp was changed to 100 g in dry mass and LBKP was changed to 100 g in dry mass. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.31.
〔製造例4〕
ケナフパルプを乾燥質量で100g、LBKPを乾燥質量で100gに変更した以外、製造例1と同様にしてセルロースナノファイバー4の分散液を得た。なお、得られたセルロース繊維のグルコース単位当たりの置換度は0.30であった。
[Production Example 4]
A dispersion of cellulose nanofibers 4 was obtained in the same manner as in Production Example 1 except that kenaf pulp was changed to 100 g in dry mass and LBKP was changed to 100 g in dry mass. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.30.
〔製造例5〕
竹パルプおよびケナフパルプを使用せず、LBKPを乾燥質量で200gに変更した以外は製造例3と同様にしてセルロースナノファイバー5の分散液を得た。なお、得られたセルロースのグルコース単位当たりの置換度は0.31であった。
[Production Example 5]
A dispersion of cellulose nanofibers 5 was obtained in the same manner as in Production Example 3 except that bamboo pulp and kenaf pulp were not used and LBKP was changed to 200 g in terms of dry mass. In addition, the substitution degree per glucose unit of the obtained cellulose was 0.31.
〔製造例6〕
撹拌機に、竹パルプを乾燥質量で50g、LBKPを乾燥質量で150g、水酸化ナトリウムを乾燥質量で480g加え、パルプ固形分濃度が15%になるように水を加えた。その後、30℃で30分攪拌した後に70℃まで昇温し、モノクロロ酢酸ナトリウムを640g(有効成分換算)添加した。1時間反応した後に、反応物を取り出して中和、洗浄して、グルコース単位当たりの置換度0.57のアニオン変性されたセルロースを得た。その後、アニオン変性したパルプに水を添加して固形分濃度5%とし、高圧ホモジナイザーにより20℃、140MPaの圧力で5回処理し、セルロースナノファイバー6の分散液を得た。
[Production Example 6]
To the stirrer, 50 g of bamboo pulp by dry mass, 150 g of LBKP by dry mass, and 480 g of sodium hydroxide by dry mass were added, and water was added so that the pulp solid content concentration was 15%. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 640 g (in terms of active ingredient) of sodium monochloroacetate was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.57 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa to obtain a dispersion of cellulose nanofibers 6.
〔製造例7〕
ケナフパルプを乾燥質量で50g、LBKPを乾燥質量で150gに変更した以外は製造例6と同様に製造し、セルロースナノファイバー7の分散液を得た。なお、得られたセルロースのグルコース単位当たりの置換度は0.60であった。
[Production Example 7]
A cellulose nanofiber 7 dispersion was obtained in the same manner as in Production Example 6 except that kenaf pulp was changed to 50 g in dry mass and LBKP was changed to 150 g in dry mass. In addition, the substitution degree per glucose unit of the obtained cellulose was 0.60.
〔製造例8〕
竹パルプを乾燥質量で100g、LBKPを乾燥質量で100gに変更した以外は製造例6と同様に製造し、セルロースナノファイバー8の分散液を得た。なお、得られたセルロースのグルコース単位当たりの置換度は0.59であった。
[Production Example 8]
A dispersion of cellulose nanofibers 8 was obtained in the same manner as in Production Example 6 except that bamboo pulp was changed to 100 g in dry mass and LBKP was changed to 100 g in dry mass. In addition, the substitution degree per glucose unit of the obtained cellulose was 0.59.
〔製造例9〕
ケナフパルプを乾燥質量で100g、パルプLBKPを乾燥質量で200gに変更した以外は製造例6と同様に製造し、セルロースナノファイバー9の分散液を得た。なお、得られたセルロースのグルコース単位当たりの置換度は0.58であった。
[Production Example 9]
A cellulose nanofiber 9 dispersion was obtained in the same manner as in Production Example 6 except that kenaf pulp was changed to 100 g in dry mass and pulp LBKP was changed to 200 g in dry mass. In addition, the substitution degree per glucose unit of the obtained cellulose was 0.58.
〔製造例10〕
竹パルプおよびケナフパルプを使用せず、LBKPを乾燥質量で200gに変更した以外は製造例6と同様に製造し、セルロースナノファイバー10の分散液を得た。なお、得られたセルロースのグルコース単位当たりの置換度は0.58であった。
[Production Example 10]
A dispersion of cellulose nanofiber 10 was obtained in the same manner as in Production Example 6 except that bamboo pulp and kenaf pulp were not used and LBKP was changed to 200 g in terms of dry mass. In addition, the substitution degree per glucose unit of the obtained cellulose was 0.58.
<曳糸性の評価>
各セルロースナノファイバーを固形分濃度1%に調整し、サンプル瓶に移した。外形10mmのガラス棒を立て、その状態から引き抜いたときの曳糸の様子を目視で観察した。
○:曳糸、付着がみられない
×:曳糸または付着がみられる。
<Evaluation of stringiness>
Each cellulose nanofiber was adjusted to a solid content concentration of 1% and transferred to a sample bottle. A glass rod having an outer diameter of 10 mm was set up, and the state of the kite string when it was pulled out from the state was visually observed.
○: No string or adhesion is observed. ×: A string or adhesion is observed.
<べたつき>
上記の水分散体を腕に塗布したときのべたつき感を社内パネラー10人(男5人、女5人)による官能試験によって評価した。「べたつく、ややべたつく、べたつかない」で回答させてべたつきがないと答えた人の割合で評価した。
○:8人以上
△:7〜5人
×:4人以下
上記評価結果を下記表1に示す。
<Stickiness>
The stickiness when the above aqueous dispersion was applied to the arm was evaluated by a sensory test with 10 in-house panelists (5 men and 5 women). Evaluation was based on the percentage of respondents who answered “no stickiness”, “no stickiness” or “no stickiness”.
○: 8 or more Δ: 7 to 5 people x: 4 or less The above evaluation results are shown in Table 1 below.
本発明のセルロースナノファイバー分散体は、例えば、化粧水、乳液、コールドクリーム、バニシングクリーク、マッサージクリーム、エモリエントクリーム、クレンジングクリーム、美容液、パック、ファンデーション、サンスクリーン化粧料、サンタン化粧料、モイスチャークリーム、ハンドクリーム、美白乳液、各種ローション等の皮膚用化粧料、シャンプー、リンス、ヘアコンディショナー、リンスインシャンプー、ヘアスタイリング剤(ヘアフォーム,ジェル状整髪料等)、ヘアトリートメント剤(ヘアクリーム,トリートメントローション等)、染毛剤やローションタイプの育毛剤あるいは養毛剤等の毛髪用化粧料、さらにはハンドクリーナーのような洗浄剤、プレシェーブローション、アフターシェーブローション、芳香剤や歯磨剤、軟膏、貼布剤等の用途に用いることができる。
The cellulose nanofiber dispersion of the present invention includes, for example, lotion, emulsion, cold cream, burnishing creek, massage cream, emollient cream, cleansing cream, serum, pack, foundation, sunscreen cosmetic, suntan cosmetic, and moisture cream. , Skin creams such as hand creams, whitening emulsions, various lotions, shampoos, rinses, hair conditioners, rinse-in shampoos, hair styling agents (hair foam, gel-like hair conditioners, etc.), hair treatment agents (hair creams, treatment lotions, etc.) ), Hair cosmetics such as hair dyes or lotion type hair restorers or hair nourishing agents, as well as detergents such as hand cleaners, pre-shave lotions, after-shave lotions, fragrances and Migakuzai, ointments, can be used for applications such as plasters.
Claims (4)
A cosmetic composition comprising the cellulose nanofiber dispersion of claim 1 or 3 and a functional additive.
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JP2019064734A (en) * | 2017-10-05 | 2019-04-25 | 株式会社コーヨー化成 | Packaged body for cosmetic pack sheet |
CN110087633A (en) * | 2016-12-15 | 2019-08-02 | 芬欧汇川集团 | The method of the dry hydrogel comprising nanometer fibril cellulose and the hydrogel of the drying comprising nanometer fibril cellulose |
WO2019189362A1 (en) * | 2018-03-30 | 2019-10-03 | 大王製紙株式会社 | Gel-state detergent composition and detergent product |
KR20200076101A (en) * | 2018-12-19 | 2020-06-29 | 이충식 | Natural hair growth agent and manufacturing method thereof |
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2014
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