JP2006218472A - Powder dispersion stabilizer and powder dispersion composition with the powder dispersion stabilizer incorporated therein - Google Patents
Powder dispersion stabilizer and powder dispersion composition with the powder dispersion stabilizer incorporated therein Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/892—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
Abstract
Description
本発明は粉体分散安定剤及びこれを含有する粉体分散組成物に関するものである。本発明の粉体分散安定剤及びこれを含有する粉体分散組成物は、特にシリコーン油に粉体を分散させる技術に好ましく使用される。 The present invention relates to a powder dispersion stabilizer and a powder dispersion composition containing the same. The powder dispersion stabilizer of the present invention and the powder dispersion composition containing the same are particularly preferably used in a technique for dispersing powder in silicone oil.
粉体分散安定剤は種々の産業分野に応用されている。例えば、顔料や充填剤を樹脂溶液に分散させた塗料やインク；炭酸カルシウム、酸化チタン等充填剤をポリ塩化ビニル樹脂等とともに可塑剤に分散させた床材・壁紙・シーリング材用樹脂組成物；フィラードＰＰで代表される無機充填剤を分散させた樹脂組成物；無機系研磨剤を配合したスプレー洗浄剤等に使用される。このように、粉体を、有機溶剤、可塑剤、樹脂等の油中に分散させる場合、一般的に油中分散剤が使用されている。 Powder dispersion stabilizers are applied in various industrial fields. For example, paints and inks in which pigments and fillers are dispersed in a resin solution; resin compositions for flooring, wallpaper, and sealing materials in which fillers such as calcium carbonate and titanium oxide are dispersed in a plasticizer together with polyvinyl chloride resin and the like; Resin composition in which an inorganic filler typified by filled PP is dispersed; used as a spray cleaning agent containing an inorganic abrasive. Thus, when dispersing powder in oil, such as an organic solvent, a plasticizer, and resin, the dispersing agent in oil is generally used.
そして、特許文献１には、アルキレンオキサイドを付加した脂肪酸からなる無機粉体用油中分散剤が開示され、その実施例には、ＰＯＥ（４．５）ラウリルエーテル酢酸、ＰＯＥ（４）ステアリルエーテル酢酸、ＰＯＥ（１０）ラウリルエーテル酢酸、ＰＯＥ（１２）ステアリルエーテル酢酸、ＰＯＥ（１０）ラウリルエーテル酢酸ナトリウムの分散性、安定性が確認されている。
一方、特許文献２には、スラリーの粘度調整、潤滑油や液体燃料の改質など、ポリノルボルネン系分散剤が開示されている。
また、印刷インキの分野においては、環境負荷の観点から有機溶媒系から水系インキへと移行しつつある。しかし、水系インキでは速乾性、耐水性が不十分であり、揮発性シリコーン油を溶媒とするインキが検討され、顔料粉体の高分散性が求められている。
このように様々な分野において、優れた粉体分散剤の開発が期待されている。
On the other hand,
Moreover, in the field of printing ink, from the viewpoint of environmental load, it is shifting from organic solvent type to water type ink. However, water-based inks are insufficient in quick drying and water resistance, and inks using volatile silicone oil as a solvent have been studied, and high dispersibility of pigment powder is required.
Thus, development of an excellent powder dispersant is expected in various fields.
本発明者等は上述の観点に鑑みて鋭意研究した結果、特定構造のＢＡＢ型トリブロック共重合体で、さらに共重合体中Ｂ部分に相当する構造がある特定の化合物からなる物質が、粉体の分散安定性を著しく向上させることを見出して本発明を完成した。 As a result of diligent research in view of the above-mentioned viewpoints, the present inventors have found that a substance composed of a specific compound having a structure corresponding to the B portion in the copolymer is a BAB type triblock copolymer having a specific structure. The present invention has been completed by finding that the dispersion stability of the body is remarkably improved.
すなわち、本発明は、下記一般式（ａ）で表される両末端シリコーン変性グリセリンからなることを特徴とする粉体分散安定剤を提供するものである。
（ａ）
(A)
また、本発明は、下記一般式（ｂ）で表される両末端シリコーン変性グリセリンからなることを特徴とする粉体分散安定剤を提供するものである。
（ｂ）
(B)
さらに、本発明は、ＨＬＢ値が０．２〜３．０であり、かつ分子量が２０００〜２００００であることを特徴とする上記の粉体分散安定剤を提供するものである。 Furthermore, the present invention provides the above-mentioned powder dispersion stabilizer characterized by having an HLB value of 0.2 to 3.0 and a molecular weight of 2000 to 20000.
また、本発明は、上記の粉体分散安定剤と、粉体と、シリコーン油とを含有することを特徴とする粉体分散組成物を提供するものである。 The present invention also provides a powder dispersion composition comprising the above powder dispersion stabilizer, powder, and silicone oil.
本発明の粉体分散安定剤は粉体の分散安定性が極めて高く、安定した粉体分散組成物を提供出来る。特にシリコーン油を含有する油中においては粉体の安定性が著しく高い。
本発明の粉体分散安定剤は、ジメチルポリシロキサン鎖とポリグリセリン鎖の分子量を適宜選択することにより、分散組成物中にて様々なＨＬＢや粘度を発揮できる。
図１に粉体分散安定性の模式図を示す。本発明の粉体分散安定剤は、両末端にシリコーン鎖からなる分散サイトがあるため、粉体を、吸着性の非常に高いポリグリセリン鎖からなる吸着サイトに保持しつつ、分散媒の溶媒中にてポリマーが広がり、極めて顕著な分散安定性効果を発揮すると考えられる。
The powder dispersion stabilizer of the present invention has extremely high powder dispersion stability, and can provide a stable powder dispersion composition. In particular, the stability of the powder is remarkably high in oil containing silicone oil.
The powder dispersion stabilizer of the present invention can exhibit various HLB and viscosities in the dispersion composition by appropriately selecting the molecular weight of the dimethylpolysiloxane chain and the polyglycerin chain.
FIG. 1 shows a schematic diagram of powder dispersion stability. Since the powder dispersion stabilizer of the present invention has dispersion sites composed of silicone chains at both ends, the powder is retained in the adsorption sites composed of polyglycerin chains with extremely high adsorptive properties, while in the solvent of the dispersion medium. It is considered that the polymer spreads and exhibits a very remarkable dispersion stability effect.
本発明の粉体分散安定剤の基本構造はＢＡＢ型トリブロック共重合体であり、Ｂは、例えば下記構造（ｃ）で示される片末端水素残基シリコーンなどを用いることができる。
Ａはグリセリン残基である。
下記構造（ｃ）の片末端水素シリコーンは公知の化合物である。そして、任意の重合度のＢＡＢ型トリブロック共重合体が公知の方法により製造出来る。
（ｃ）
A is a glycerin residue.
One-terminal hydrogen silicone having the following structure (c) is a known compound. A BAB type triblock copolymer having an arbitrary degree of polymerization can be produced by a known method.
(C)
ＡとＢとの間の結合は本発明にとって本質的な構造ではないが、本発明に例示される粉体分散安定剤は、化合物（ｃ）と下記構造式（ｄ）で示す化合物を、白金触媒を用い、エーテル結合により結合させたものである。
（ｄ）
(D)
ＢＡＢ型トリブロック共重合体は公知の方法により合成することが出来る。合成スキームを図２に示す。 The BAB type triblock copolymer can be synthesized by a known method. A synthesis scheme is shown in FIG.
このようにして、下記構造式（ａ）、（ｂ）で表される粉体分散安定剤が得られる。
（ａ）
（ｂ）
(A)
(B)
シリコーン鎖の重合度のｍは１０〜１２０が好ましい。側鎖置換基はメチル基が好ましいが、フェニルや他のアルキルに置換されていても構わない。
グリセリン鎖の重合度のｎは１〜１１が好ましい。
本発明の粉体分散安定剤の機能発現には、図１に示すようにＢブロックの溶媒中への溶解性とＡブロック鎖の粉体表面への高い吸着性が重要である。すなわち、ＡＢ両ブロックの親水／親油性のバランス（ＨＬＢ）が適切な範囲にあることが機能発現に必須となる。ＨＬＢは公知の方法により求めることができるが、例えばＧｒｉｆｆｉｎの式（ＨＬＢ値＝グリセリン部分子量×２０／総分子量）により算出される。本発明の粉体分散安定剤においては、ＨＬＢが０．２〜３．０であることが好ましい。
また、粉体同士の凝集を防止するＡブロック鎖の広がりは、高分子の分子量に依存し、Ｂブロック鎖は高分子量であるほど凝集防止効果は高い。一方、粉体への吸着はＡブロック鎖のファンデルワールス力等の弱い力によると考えられる。しかし、Ａブロック鎖としてポリグリセリンを用いることにより、ポリエチレングリコール等に比較し強い吸着力が得られるため、比較的低い分子量で十分な吸着力が得られる。また、ＡＢ両ブロックの分子量が高くなりすぎると、粉体分散組成物の塗り伸ばしが難くなる場合があり、また伸びの重さを感じる場合がある。以上のことから、分子量についても適切な範囲があり、本発明の粉体分散安定剤においては、分子量は２０００〜２００００が好ましい。
The polymerization degree m of the silicone chain is preferably 10 to 120. The side chain substituent is preferably a methyl group, but may be substituted with phenyl or other alkyl.
As for n of the polymerization degree of a glycerol chain, 1-11 are preferable.
For the functional expression of the powder dispersion stabilizer of the present invention, as shown in FIG. 1, the solubility of the B block in a solvent and the high adsorbability of the A block chain on the powder surface are important. That is, the hydrophilic / lipophilic balance (HLB) of both AB blocks is in an appropriate range, which is essential for function expression. The HLB can be obtained by a known method, and is calculated, for example, by the Griffin equation (HLB value = glycerin molecular weight × 20 / total molecular weight). In the powder dispersion stabilizer of the present invention, HLB is preferably 0.2 to 3.0.
Further, the spread of the A block chain that prevents aggregation between powders depends on the molecular weight of the polymer, and the higher the molecular weight of the B block chain, the higher the effect of preventing aggregation. On the other hand, the adsorption to the powder is considered to be due to weak force such as van der Waals force of the A block chain. However, by using polyglycerin as the A block chain, a strong adsorption force can be obtained as compared with polyethylene glycol and the like, so that a sufficient adsorption force can be obtained with a relatively low molecular weight. If the molecular weights of both AB blocks are too high, it may be difficult to spread the powder dispersion composition, and the weight of the elongation may be felt. From the above, there is an appropriate range for the molecular weight, and in the powder dispersion stabilizer of the present invention, the molecular weight is preferably 2000 to 20000.
本発明の粉体分散安定剤により、粉体が分散される分散媒は油分である。例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン等の鎖状ポリシロキサン、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等の環状ポリシロキサン、ポリエーテル変性シリコーン、アルキル変性シリコーン、エポキシ変性シリコーン等の変性シリコーン、トリメチルシロキシケイ酸、高重合メチルポリシロキサン等のシリコーン系樹脂等の１種または二種以上の油分が好ましい。
また、シリコーン系分散媒には、本発明の効果を損なわない限り、他の油性成分を配合することも可能である。例えば、流動パラフィン、固形パラフィン、ワセリン、セレシン等の炭化水素油、ミリスチン酸イソプロピル等のエステル油、天然油脂、パーフルオロポリエーテル、ラノリン、カルナバロウ等のワックス、高級脂肪酸、高級アルコール、シリコーン樹脂、フッ素樹脂、アクリル樹脂、ビニルピロリド樹脂等の樹脂等が挙げられる。
本発明の粉体分散安定剤は粉体とシリコーン油とを含有する粉体分散組成物に好ましく使用される。
The dispersion medium in which the powder is dispersed by the powder dispersion stabilizer of the present invention is an oil. For example, chain polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, modified silicones such as polyether-modified silicone, alkyl-modified silicone and epoxy-modified silicone One or more oils such as silicone resins such as trimethylsiloxysilicic acid and highly polymerized methylpolysiloxane are preferred.
Moreover, other oil-based components can be blended with the silicone-based dispersion medium as long as the effects of the present invention are not impaired. For example, hydrocarbon oils such as liquid paraffin, solid paraffin, petrolatum, ceresin, ester oils such as isopropyl myristate, natural fats and oils, waxes such as perfluoropolyether, lanolin, carnauba wax, higher fatty acids, higher alcohols, silicone resins, fluorine Examples thereof include resins such as resins, acrylic resins and vinyl pyrrolide resins.
The powder dispersion stabilizer of the present invention is preferably used for a powder dispersion composition containing a powder and silicone oil.
分散させる粉体は特に限定されない。特に無機粉体（酸化チタン若しくは酸化亜鉛など）が好ましい。両者の混合粉体においても分散安定性が極めて高いことも本願発明の特質である。 The powder to be dispersed is not particularly limited. In particular, inorganic powder (such as titanium oxide or zinc oxide) is preferable. It is a feature of the present invention that the dispersion stability of both the mixed powders is extremely high.
粉体の平均粒子径は０．５〜１５０ｎｍが好ましい。
この場合、酸化チタン若しくは酸化亜鉛の粉体を紫外線散乱剤として配合する場合は、平均粒子径１〜５０ｎｍの微粒子が好ましい。
なお、粉体分散安定剤の配合量は適宜決定されるが、粉体分散組成物（粉体分散安定剤と粉体とシリコーン油からなる組成物であって、他に任意の公知成分を含まない組成物）
全量に対して通常０．１〜３０質量％である。
The average particle size of the powder is preferably 0.5 to 150 nm.
In this case, when blending titanium oxide or zinc oxide powder as an ultraviolet scattering agent, fine particles having an average particle diameter of 1 to 50 nm are preferable.
The blending amount of the powder dispersion stabilizer is appropriately determined, but it is a powder dispersion composition (a composition comprising a powder dispersion stabilizer, powder and silicone oil, including other known components). Not composition)
It is 0.1-30 mass% normally with respect to the whole quantity.
なお、本発明の粉体分散安定剤は、粉体を表面処理することにより、粉体の分散安定性を向上させることも可能である。 The powder dispersion stabilizer of the present invention can also improve the dispersion stability of the powder by subjecting the powder to a surface treatment.
本発明の粉体分散組成物、特に微粒子粉体分散物は、粉体と、両末端シリコーン変性グリセリンと、シリコーン系分散媒とを機械的に分散処理することにより製造することができる。
予備混練や分散処理には、必要に応じて加熱しながら、適当な分散機械を用いればよい。調整するスラリーの粘度に応じて、ローラーミル、高圧ホモジナイザー、ビーズミル等の分散機械を適宜選択して用いる。
The powder dispersion composition of the present invention, particularly the fine particle powder dispersion, can be produced by mechanically dispersing the powder, the two-end silicone-modified glycerin, and the silicone-based dispersion medium.
An appropriate dispersing machine may be used for pre-kneading and dispersion treatment while heating as necessary. Depending on the viscosity of the slurry to be adjusted, a dispersing machine such as a roller mill, a high-pressure homogenizer, or a bead mill is appropriately selected and used.
次に本発明を実施例によりさらに具体的に説明する。本発明は、これらの実施例によって限定されない。配合量は特に断りのない限り全量に対する質量％である。 Next, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples. A compounding quantity is the mass% with respect to the whole quantity unless there is particular notice.
「実施例１ 本発明の粉体分散安定剤である両末端シリコーン変性グリセリンの合成」
式（ｅ）の片末端水素化ジメチルポリシロキサン（Ｍｗ≒４６００）１００ｇ、トリグリセリンジアリルエーテル３．５ｇ、およびイソプロピルアルコール１００ｇを反応容器に仕込み、３％塩化白金酸イソプロピルアルコール溶液０．０５ｇを加えて８０℃で５時間反応させる。続いて０．０１ＮのＨＣｌ水溶液を１．５ｇ添加し、６０℃にて３時間加水分解を行った後、１％重曹水０．２ｇを添加して中和を行った。反応溶液をエバポレーションにより濃縮し、流動性のある粘性液体である目的化合物を得る。
（ｅ）
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (e) (Mw≈4600), 3.5 g of triglyceryl diallyl ether, and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(E)
「実施例２ 本発明の粉体分散安定剤である両末端シリコーン変性グリセリンの合成」
式（ｅ）の片末端水素化ジメチルポリシロキサン（Ｍｗ≒４６００）１００ｇ、テトラグリセリンジアリルエーテル４．３ｇ、およびイソプロピルアルコール１００ｇを反応容器に仕込み、３％塩化白金酸イソプロピルアルコール溶液０．０５ｇを加えて８０℃で５時間反応させる。続いて０．０１ＮのＨＣｌ水溶液を１．５ｇ添加し、６０℃にて３時間加水分解を行った後、１％重曹水０．２ｇを添加して中和を行った。反応溶液をエバポレーションにより濃縮し、流動性のある粘性液体である目的化合物を得る。
（ｅ）
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (e) (Mw≈4600), 4.3 g of tetraglyceryl diallyl ether, and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(E)
「実施例３ 本発明の粉体分散安定剤である両末端シリコーン変性グリセリンの合成」
式（ｆ）の片末端水素化ジメチルポリシロキサン（Ｍｗ≒７６００）１００ｇ、テトラグリセリンジアリルエーテル２．６ｇ、およびイソプロピルアルコール１００ｇを反応容器に仕込み、３％塩化白金酸イソプロピルアルコール溶液０．０５ｇを加えて８０℃で５時間反応させる。続いて０．０１ＮのＨＣｌ水溶液を１．５ｇ添加し、６０℃にて３時間加水分解を行った後、１％重曹水０．２ｇを添加して中和を行った。反応溶液をエバポレーションにより濃縮し、流動性のある粘性液体である目的化合物を得る。
（ｆ）
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (f) (Mw≈7600), 2.6 g of tetraglyceryl diallyl ether, and 100 g of isopropyl alcohol, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(F)
「実施例４ 本発明の粉体分散安定剤である両末端シリコーン変性グリセリンの合成」
式（ｇ）の末端水素化メチルフェニルポリシロキサン（Ｍｗ≒５６００）１００ｇ、トリグリセリンジアリルエーテル２．９ｇおよびイソプロピルアルコール１００ｇを反応容器に仕込み、３％塩化白金酸イソプロピルアルコール溶液０．０５ｇを加えて８０℃で５時間反応させる。続いて０．０１ＮのＨＣｌ水溶液を１．５ｇ添加し、６０℃にて３時間加水分解を行った後、１％重曹水０．２ｇを添加して中和を行った。反応溶液をエバポレーションにより濃縮し、流動性のある粘性液体である目的化合物を得る。
（ｇ）
100 g of terminal hydrogenated methylphenylpolysiloxane of formula (g) (Mw≈5600), 2.9 g of triglyceryl diallyl ether and 100 g of isopropyl alcohol are charged into a reaction vessel, and 0.05 g of 3% chloroplatinic acid isopropyl alcohol solution is added. React at 80 ° C. for 5 hours. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(G)
「実施例５ 本発明の粉体分散安定剤である両末端シリコーン変性グリセリンの合成」
式（ｈ）の片末端水素化メチルドデシルポリシロキサン（Ｍｗ≒５９００）１００ｇ、トリグリセリンジアリルエーテル２．７ｇおよびイソプロピルアルコール１００ｇを反応容器に仕込み、３％塩化白金酸イソプロピルアルコール溶液０．０５ｇを加えて８０℃で５時間反応させる。続いて０．０１ＮのＨＣｌ水溶液を１．５ｇ添加し、６０℃にて３時間加水分解を行った後、１％重曹水０．２ｇを添加して中和を行った。反応溶液をエバポレーションにより濃縮し、流動性のある粘性液体である目的化合物を得る。
（ｈ）
Charge 100 g of hydrogenated methyldodecyl polysiloxane (Mw≈5900) of formula (h), 2.7 g of triglyceryl diallyl ether and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(H)
上記実施例１〜５の合成スキームを図２に示す。図３に実施例１のＩＲスペクトルを示す。スペクトル中８００、１０００、１２６０、２９６０ｃｍ-1付近のピークよりポリジメチルシロキサンに、また１４００ｃｍ-1付近にポリグリセリン中の二級アルコールに由来するピークがそれぞれ認められることから、合成はスキーム通り進行し、目的化合物が得られていることが分かる。 The synthesis scheme of Examples 1 to 5 is shown in FIG. FIG. 3 shows the IR spectrum of Example 1. Polydimethylsiloxane than peak around in 800,1000,1260,2960Cm -1 spectrum, and from the peak derived from a secondary alcohol in the polyglycerol around 1400 cm -1 is observed each synthesis proceeds Scheme Street It can be seen that the target compound is obtained.
「分散安定性の評価」
＜分散体の作成＞
微粒子粉体３８ｇ、実施例１、実施例２、の方法で作成した分散剤および比較サンプル５ｇをシリコーン系分散媒５７ｇに添加し、微粒子粉体との重量比が１：１になるように、ガラスビーズ（１ｍｍΦ）を加え、ペイントシェイカーにて１時間混合してスラリー状の分散体を作成する。また、実施例１で製造した分散剤の代わりに、比較例１の方法で製造した分散剤５ｇを用いた分散体も同様に作成する。分散させる粉体には、Ｐ１とＰ２を半量ずつの混合粉体を用いる。
用いた各成分を以下に示す。
（１）微粒子粉体(Ｐ１)：脂肪酸石鹸処理微粒子二酸化チタン
商品名：１００ＴＶ（テイカ社製）
粒子径：長径約０．０３μｍ、短径約０．００５μｍ
ミリスチン酸アルミニウム処理量：１０質量％
（２）微粒子粉体（Ｐ２）：シリコーン処理シリカ被覆酸化亜鉛
商品名：ＳＳ-Ａｃｔｉｖｏｘ Ｃ８０（昭和電工製）
粒子径：約０．０３μｍ
シリカ処理量：２０質量％
（３）比較サンプル：ポリエーテル変性シリコーン
商品名：シリコーンＫＦ６０１７（信越化学工業製）
ポリエーテル変性率：２０％ 分子量：約６０００ ＨＬＢ値：４．０
（４）分散媒：デカメチルシクロペンタシロキサン
商品名：ＫＦ−９９５（信越化学工業製）
"Evaluation of dispersion stability"
<Creation of dispersion>
38 g of the fine particle powder, the dispersant prepared by the method of Example 1 and Example 2, and 5 g of the comparative sample are added to 57 g of the silicone-based dispersion medium so that the weight ratio with the fine particle powder becomes 1: 1. Add glass beads (1 mmΦ) and mix for 1 hour in a paint shaker to create a slurry dispersion. In addition, a dispersion using 5 g of the dispersant manufactured by the method of Comparative Example 1 instead of the dispersant manufactured in Example 1 is similarly prepared. As the powder to be dispersed, a mixed powder of P1 and P2 each in half is used.
Each component used is shown below.
(1) Fine particle powder (P1): Fatty acid soap-treated fine particle titanium dioxide Product name: 100TV (manufactured by Teika)
Particle size: major axis about 0.03 μm, minor axis about 0.005 μm
Aluminum myristate treatment amount: 10% by mass
(2) Fine particle powder (P2): Silicone-treated silica-coated zinc oxide Product name: SS-Activox C80 (manufactured by Showa Denko)
Particle size: about 0.03μm
Silica treatment amount: 20% by mass
(3) Comparative sample: polyether-modified silicone Product name: Silicone KF6017 (manufactured by Shin-Etsu Chemical)
Polyether modification rate: 20% Molecular weight: about 6000 HLB value: 4.0
(4) Dispersion medium: Decamethylcyclopentasiloxane Product name: KF-995 (manufactured by Shin-Etsu Chemical)
＜分散特性の評価＞
分散物のレオロジー測定を行い、各両末端シリコーン変性グリセリンの粉体の分散安定性を評価する。
（評価方法）
評価装置：ＴＡインスツルメンツ社製 コーンプレート型粘度計 ＡＲ１０００−Ｎ
測定条件：４ｃｍ４°スチール製ジオメトリー
せん断速度 ０．１s-1〜５００s-1 ２５℃
（結果）
実施例１の両末端シリコーン変性グリセリンを用いた分散体の評価結果を図４に示す。
実施例２の両末端シリコーン変性グリセリンを用いた分散体の評価結果を図５に示す。
比較サンプルであるポリエーテル変性シリコーンを用いた分散体の評価結果を図６に示す。
分散体中の粉体の分散安定性が良好な場合、その流動特性は分散媒であるシリコーンの流動特性を反映することになり、いかなるせん断速度でも粘度がほぼ一定であるニュートニアン的な挙動を示す。
比較サンプルの分散剤を用いた分散体の挙動を表す図６において、酸化チタン（Ｐ１）と酸化亜鉛（Ｐ２）を混合した分散体は、低せん断速度領域で粘度の大幅な上昇が確認され、粉体が凝集していることが示唆された。
これに対し、実施例１および実施例２で合成される分散剤を用いた分散体の挙動を表す図４においては、酸化チタン（Ｐ１）と酸化亜鉛（Ｐ２）を混合した分散体は、ほぼニュートニアン的な流動特性を示し、分散安定性が非常に良好であることが示唆された。混合した粉体（Ｐ１およびＰ２）を用いた際に分散体がほぼニュートニアン的な挙動を示す分散剤はこれまでほとんど報告されておらず、本発明の分散安定剤の分散安定性向上効果が非常に高いことを示している。
上記の評価測定から、実施例１〜２の粉体分散安定剤は優れた分散安定剤を発揮する。なお、実施例３〜５の化合物も、実施例１〜２と同様の分散安定性が発揮される。
<Evaluation of dispersion characteristics>
The rheology of the dispersion is measured, and the dispersion stability of each terminally-modified silicone-modified glycerin powder is evaluated.
(Evaluation methods)
Evaluation device: Corn Instruments viscometer AR1000-N manufactured by TA Instruments
Measurement conditions: 4cm4 ° steel geometry
Shear rate 0.1 s -1 to 500 s -1 25 ° C
(result)
The evaluation results of the dispersion using the both-end silicone-modified glycerin of Example 1 are shown in FIG.
The evaluation result of the dispersion using the both-end silicone-modified glycerin of Example 2 is shown in FIG.
The evaluation result of the dispersion using the polyether-modified silicone as a comparative sample is shown in FIG.
If the dispersion stability of the powder in the dispersion is good, its flow characteristics will reflect the flow characteristics of silicone as a dispersion medium, and it will have a Newtonian behavior with almost constant viscosity at any shear rate. Show.
In FIG. 6 showing the behavior of the dispersion using the dispersant of the comparative sample, the dispersion obtained by mixing titanium oxide (P1) and zinc oxide (P2) was confirmed to have a significant increase in viscosity in the low shear rate region. It was suggested that the powder was agglomerated.
On the other hand, in FIG. 4 showing the behavior of the dispersion using the dispersant synthesized in Example 1 and Example 2, the dispersion obtained by mixing titanium oxide (P1) and zinc oxide (P2) is almost the same. It showed Newtonian flow characteristics, suggesting very good dispersion stability. There have been few reports on dispersants in which the dispersion exhibits almost Newtonian behavior when the mixed powders (P1 and P2) are used, and the dispersion stability improvement effect of the dispersion stabilizer of the present invention has not been reported so far. It is very high.
From said evaluation measurement, the powder dispersion stabilizer of Examples 1-2 exhibits the outstanding dispersion stabilizer. In addition, the compound of Examples 3-5 exhibits the same dispersion stability as Examples 1-2.
「分散安定性の評価：ＨＬＢと分子量の関係」
実施例１〜３、比較サンプルと同様にして合成した両末端シリコーン変性グリセリンおよびポリエーテル変性シリコーンの粉体分散特性を、上記方法と同様にレオロジー測定により評価した結果を下記に示す。各表から、本発明の粉体分散安定剤は優れた分散特性を有することが分かる。
“Evaluation of dispersion stability: Relationship between HLB and molecular weight”
The results of evaluating rheological measurements of the powder dispersion characteristics of both-end silicone-modified glycerin and polyether-modified silicone synthesized in the same manner as in Examples 1 to 3 and the comparative sample are shown below. From each table, it can be seen that the powder dispersion stabilizer of the present invention has excellent dispersion characteristics.
○：良好、△：ほぼ良好、×：不良
○：良好、△：ほぼ良好、×：不良
本発明の粉体分散安定剤及び粉体分散組成物は、優れた粉体の分散安定性を示し、塗料、インキ、研磨剤等の各種工業用途に利用できる。特にシリコーン油に無機粉体を分散させる組成物に対して有用性が高い。 The powder dispersion stabilizer and powder dispersion composition of the present invention exhibit excellent powder dispersion stability and can be used in various industrial applications such as paints, inks, and abrasives. It is particularly useful for a composition in which inorganic powder is dispersed in silicone oil.
Claims (4)
（ａ）
(A)
（ｂ）
(B)
A powder dispersion composition comprising the powder dispersion stabilizer according to claim 1, a powder, and silicone oil.
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| EP3881899A4 (en) * | 2018-11-12 | 2022-09-07 | Shiseido Company, Ltd. | Cosmetic |
| EP3881820A4 (en) * | 2018-11-12 | 2022-09-07 | Shiseido Company, Ltd. | Powder dispersion composition and dispersing method thereof |
| JP7430644B2 (en) | 2018-11-12 | 2024-02-13 | 株式会社 資生堂 | Powder dispersion composition and its manufacturing method |
| JP7436382B2 (en) | 2018-11-12 | 2024-02-21 | 株式会社 資生堂 | Cosmetic manufacturing method |
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