JP4897289B2 - Hydrophobic cellulose powder and method for producing the same - Google Patents
Hydrophobic cellulose powder and method for producing the same Download PDFInfo
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- JP4897289B2 JP4897289B2 JP2005373002A JP2005373002A JP4897289B2 JP 4897289 B2 JP4897289 B2 JP 4897289B2 JP 2005373002 A JP2005373002 A JP 2005373002A JP 2005373002 A JP2005373002 A JP 2005373002A JP 4897289 B2 JP4897289 B2 JP 4897289B2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 70
- 230000002209 hydrophobic effect Effects 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 15
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000004627 regenerated cellulose Substances 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 239000002537 cosmetic Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- YAPKLBSSEAZLGL-UHFFFAOYSA-N ethoxy(propyl)silane Chemical compound CCC[SiH2]OCC YAPKLBSSEAZLGL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CHHVJOKDGAOHMJ-UHFFFAOYSA-N methoxy(propyl)silane Chemical compound CCC[SiH2]OC CHHVJOKDGAOHMJ-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 description 1
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Cosmetics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
本発明は、例えばファンデーション、アイシャドウ、ほほ紅、口紅等のメイクアップ化粧料や、ハンドクリーム、乳液、日焼け止めクリーム等の化粧料、更には油性系の化粧料に配合して好適な疎水性セルロース粉体およびその製造方法に関するものである。 The present invention is suitable for use in makeup cosmetics such as foundations, eye shadows, cheeks and lipsticks, cosmetics such as hand creams, emulsions and sunscreens, and oily cosmetics. The present invention relates to cellulose powder and a method for producing the same.
従来、化粧料の感触を改善するとともに化粧料に対し保湿効果を付与するための手段として、セルロース粉体それ自体を直接に化粧料に配合する技術が知られている。 Conventionally, as a means for improving the feel of a cosmetic and imparting a moisturizing effect to the cosmetic, a technique of directly blending cellulose powder itself into the cosmetic is known.
しかしながら、このようにセルロース粉体それ自体を直接に化粧料に配合するものでは、セルロース粉体が親水性のために、その化粧料を皮膚に塗布したときに撥水性が低下してラスティング効果が若干乏しくなるという問題点がある。また、セルロース粉体は油と馴染みにくいために、例えば油性クリームのような化粧料にはセルロース粉体を少量しか配合できず、また配合できても分離が起こったり、粘度が上昇したりするという問題点がある。 However, in the case where the cellulose powder itself is blended directly into the cosmetic, the cellulose powder is hydrophilic, so when the cosmetic is applied to the skin, the water repellency is lowered and the lasting effect is achieved. There is a problem that becomes slightly scarce. In addition, since cellulose powder is difficult to blend with oil, cosmetics such as oily cream can contain only a small amount of cellulose powder, and even if it can be mixed, separation occurs or viscosity increases. There is a problem.
本発明は、このような問題点を解消するためになされたもので、十分な疎水性を有するとともに、油との相溶性にも優れる疎水性セルロース粉体およびその製造方法を提供することを目的とするものである。 The present invention has been made to solve such problems, and an object thereof is to provide a hydrophobic cellulose powder having sufficient hydrophobicity and excellent compatibility with oil, and a method for producing the same. It is what.
前記目的を達成するために、第１発明による疎水性セルロース粉体は、
結晶構造がセルロースＩＩ型の再生セルロースよりなるセルロース粉体に下記一般式（１）にて示される化合物を０．５〜３０重量％の被覆量で表面被覆してなることを特徴とする疎水性セルロース粉体。
Ｒ１ＣＨ２ＣＨ２Ｓｉ（ＯＲ２）３ ・・・・・・・・（１）
（式中、Ｒ１は炭素数が１以上の飽和炭化水素基または炭素数が１以上の飽和炭化フッ素基であり、Ｒ２は炭素数が１以上の飽和炭化水素基である。）
In order to achieve the above object, the hydrophobic cellulose powder according to the first invention comprises:
Hydrophobicity crystal structure characterized by being surface-coated by the following general formula (1) Similar coverage of 0.5 to 30 wt% of a compound represented by cellulose powder consisting of regenerated cellulose of the cellulose II type Cellulose powder.
R 1 CH 2 CH 2 Si (OR 2 ) 3 (1)
(In the formula, R 1 is a saturated hydrocarbon group having 1 or more carbon atoms or a saturated hydrocarbon group having 1 or more carbon atoms, and R 2 is a saturated hydrocarbon group having 1 or more carbon atoms.)
また、第２発明による疎水性セルロース粉体は、
結晶構造がセルロースＩＩ型の再生セルロースよりなるセルロース粉体に下記一般式（２）にて示される化合物を０．５〜３０重量％の被覆量で表面被覆してなることを特徴とする疎水性セルロース粉体。
（Ｒ ３ ＣＯＯ） ３ Ｔｉ（ＯＲ ４ ） ・・・・・・・・（２）
（式中、Ｒ ３ は炭素数が４以上の飽和炭化水素基、Ｒ ４ は炭素数が１以上の飽和炭化水素基である。）
The hydrophobic cellulose powder according to the second invention is
Hydrophobic , characterized in that a cellulose powder having a crystal structure of cellulose II type regenerated cellulose is surface-coated with a compound represented by the following general formula (2) at a coating amount of 0.5 to 30% by weight . Cellulose powder.
(R 3 COO) 3 Ti (OR 4 ) (2)
(In the formula, R 3 is a saturated hydrocarbon group having 4 or more carbon atoms , and R 4 is a saturated hydrocarbon group having 1 or more carbon atoms.)
第１発明または第２発明において、前記セルロース粉体の粒子形状が球状であるのが好ましい（第３発明）。 In the first invention or the second invention, the cellulose powder preferably has a spherical particle shape (third invention).
第１発明および第２発明によれば、セルロース粉体に前記一般式（１）または（２）にて示される化合物が表面被覆されるので、十分な疎水性を有するとともに、油との相溶性にも優れる疎水性セルロース粉体を得ることができる。この疎水性セルロース粉体が配合された化粧料では、皮膚に塗布した際にも十分な撥水性を示して満足のいくラスティング効果が発揮されるという効果を奏する。また、この疎水性セルロース粉体が配合される化粧料が油性系の化粧料であっても、この油性系化粧料中にその疎水性セルロース粉体が容易に分散されるので、感触の良い油性系化粧料を提供することができる。 According to the first and second inventions , the cellulose powder is coated with the compound represented by the general formula (1) or (2), so that it has sufficient hydrophobicity and compatibility with oil. In addition, an excellent hydrophobic cellulose powder can be obtained. Cosmetics containing this hydrophobic cellulose powder exhibit an effect that a satisfactory lasting effect is exhibited by exhibiting sufficient water repellency even when applied to the skin. Even if the cosmetic compounded with the hydrophobic cellulose powder is an oily cosmetic, the hydrophobic cellulose powder is easily dispersed in the oily cosmetic, so that the oily feel is good. -Based cosmetics can be provided.
また、原料となるセルロース粉体として、安価な製法で得られ、しかも安定性に優れるセルロースＩＩ型の結晶構造を持つ再生セルロースが用いられるので、コストダウンと安定性の向上を図ることができる。 Further, as the cellulose powder used as a raw material, a regenerated cellulose having a cellulose II type crystal structure which is obtained by an inexpensive manufacturing method and has excellent stability is used, so that cost reduction and stability improvement can be achieved.
第３発明によれば、原料となるセルロース粉体として、その粒子形状が球状のものが用いられるので、化粧料に配合された際にその化粧料の感触をより向上させることができる。 According to the third aspect of the invention, since the spherical cellulose powder used as the raw material is used, the feel of the cosmetic can be further improved when blended into the cosmetic.
次に、本発明による疎水性セルロース粉体およびその製造方法の具体的な実施の形態について説明する。 Next, specific embodiments of the hydrophobic cellulose powder and the production method thereof according to the present invention will be described.
本発明による疎水性セルロース粉体は、セルロース粉体に下記一般式（１）または（２）にて示される化合物を表面被覆してなるものである。
Ｒ１ＣＨ２ＣＨ２Ｓｉ（ＯＲ２）３ ・・・・・・・・（１）
（式中、Ｒ１は炭素数が１以上の飽和炭化水素基または炭素数が１以上の飽和炭化フッ素基であり、Ｒ２は炭素数が１以上の飽和炭化水素基である。）
（Ｒ３ＣＯＯ）３Ｔｉ（ＯＲ４） ・・・・・・・・（２）
（式中、Ｒ３は炭素数が４以上の飽和炭化水素基、Ｒ４は炭素数が１以上の飽和炭化水素基である。）
The hydrophobic cellulose powder according to the present invention is obtained by coating a cellulose powder with a compound represented by the following general formula (1) or (2).
R 1 CH 2 CH 2 Si (OR 2 ) 3 (1)
(In the formula, R 1 is a saturated hydrocarbon group having 1 or more carbon atoms or a saturated hydrocarbon group having 1 or more carbon atoms, and R 2 is a saturated hydrocarbon group having 1 or more carbon atoms.)
(R 3 COO) 3 Ti (OR 4 ) (2)
(In the formula, R 3 is a saturated hydrocarbon group having 4 or more carbon atoms, and R 4 is a saturated hydrocarbon group having 1 or more carbon atoms.)
前記一般式（１）または（２）にて示される化合物をセルロース粉体（セルロース粒子）の表面に固着・被覆させる表面被覆処理は、シラン反応またはチタネート反応を利用することによって成される。すなわち、前記一般式（１）または（２）にて示される化合物とセルロース粉体の表面の水酸基とを反応させることにより、セルロース粉体の表面に前記一般式（１）または（２）にて示される化合物が固着・被覆される。この表面被覆処理の具体的な方法としては、適当なミキサーによって撹拌されているセルロース粉体中に前記一般式（１）または（２）にて示される化合物を液滴下もしくはスプレー噴霧にて加え、その後一定時間高速強撹拌し、次いで撹拌を続けながら８０〜２００℃で加熱熟成させるという方法が一般的である。その他の表面被覆処理の方法としては、前記一般式（１）または（２）にて示される化合物を例えばｎ−ヘキサン、イソプロピルアルコール、低分子量ナフサ、塩化メチレン等の不活発な有機溶剤に溶解させておき、この溶液を撹拌中のセルロース粉体に添加して更に撹拌した後に、有機溶剤を完全に加熱蒸発除去し、その後８０〜２００℃で加熱熟成させるという方法が挙げられる。 The surface coating treatment for fixing and coating the compound represented by the general formula (1) or (2) on the surface of the cellulose powder (cellulose particles) is performed by utilizing a silane reaction or a titanate reaction. That is, by reacting the compound represented by the general formula (1) or (2) with the hydroxyl group on the surface of the cellulose powder, the surface of the cellulose powder is represented by the general formula (1) or (2). The indicated compound is fixed and coated. As a specific method of this surface coating treatment, a compound represented by the above general formula (1) or (2) is added to a cellulose powder stirred by a suitable mixer under a droplet or by spraying, Thereafter, a general method is to stir at a high speed for a certain period of time and then heat and age at 80 to 200 ° C. while continuing stirring. As another surface coating treatment method, the compound represented by the general formula (1) or (2) is dissolved in an inert organic solvent such as n-hexane, isopropyl alcohol, low molecular weight naphtha or methylene chloride. In addition, there is a method in which this solution is added to the cellulose powder being stirred and further stirred, and then the organic solvent is completely removed by evaporation by heating, followed by heat aging at 80 to 200 ° C.
前記表面被覆処理において、前記一般式（１）または（２）にて示される化合物とセルロース粉体との撹拌中に金属塩化物の水溶液を微量添加することにより、セルロース粉体の表面全体でシラン反応またはチタネート反応を速やかにかつ均一に起こさせることができ、前記一般式（１）または（２）にて示される化合物をセルロース粉体の表面に均一に被覆することができる。ここで、前記金属塩化物としては、例えば塩化アルミニウム、塩化第１錫、塩化第２錫、塩化カルシウム、塩化亜鉛、塩化マグネシウム等が挙げられる。なお、塩化アルミニウム水溶液は、シラン反応時またはチタネート反応時における触媒としての作用が一段と優れている。 In the surface coating treatment, a small amount of an aqueous solution of metal chloride is added during the stirring of the compound represented by the general formula (1) or (2) and the cellulose powder, whereby silane is added to the entire surface of the cellulose powder. The reaction or titanate reaction can be caused promptly and uniformly, and the compound represented by the general formula (1) or (2) can be uniformly coated on the surface of the cellulose powder. Here, examples of the metal chloride include aluminum chloride, stannous chloride, stannic chloride, calcium chloride, zinc chloride, and magnesium chloride. In addition, the aluminum chloride aqueous solution is more excellent in the action as a catalyst at the time of silane reaction or titanate reaction.
本発明において用いられるセルロース粉体としては、一次粒子径が０．２〜３００μｍのものが望ましく、またアセテート法、ビスコース法のいずれの方法にて製造されたものでもよいが、ビスコース法により製造されたセルロースＩＩ型の結晶構造を持つ再生セルロース粉体がより安価で安定性に優れるので望ましい。より望ましくは、それ自体公知の製造方法（例えば、特開昭６１−２４１３３７号公報参照）によって製造された粒子形状が球状のセルロース粉体を用いるのが良い。この球状セルロース粉体を用いると、化粧料に配合されたときにその化粧料の感触をより向上させることができる。 The cellulose powder used in the present invention preferably has a primary particle size of 0.2 to 300 μm, and may be produced by any of the acetate method and the viscose method. The produced regenerated cellulose powder having a cellulose II type crystal structure is desirable because it is cheaper and more stable. More desirably, cellulose powder having a spherical particle shape produced by a production method known per se (for example, see JP-A No. 61-241337) may be used. When this spherical cellulose powder is used, the feel of the cosmetic can be further improved when blended in the cosmetic.
また、本発明において用いられる前記一般式（１）にて示される化合物の具体例としては、プロピルメトキシシラン、プロピルエトキシシラン、ｉ−ブチルトリメトキシシラン、ｉ−ブチルトリエトキシシラン、ｎ−オクチルトリメトキシシラン、ｎ−オクチルトリエトキシシラン、ｎ−ヘキサデシルトリメトキシシラン、ｎ−ヘキサデシルトリエトキシシラン、トリデカフルオロオクチルトリメトキシシラン、トリデカフルオロオクチルトリエトキシシラン、トリドデカフルオロデシルトリメトキシシラン、トリドデカフルオロデシルトリエトキシシラン等が挙げられる。 Specific examples of the compound represented by the general formula (1) used in the present invention include propylmethoxysilane, propylethoxysilane, i-butyltrimethoxysilane, i-butyltriethoxysilane, n-octyltril. Methoxysilane, n-octyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexadecyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridodecafluorodecyltrimethoxysilane, And tridodecafluorodecyltriethoxysilane.
また、本発明において用いられる前記一般式（２）にて示される化合物の具体例としては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリイソミリスチロイルチタネート、メチルトリイソステアロイルチタネート、メチルトリイソミリスチロイルチタネート、エチルトリイソステアロイルチタネート、エチルトリイソミリスチロイルチタネート等が挙げられる。 Specific examples of the compound represented by the general formula (2) used in the present invention include isopropyl triisostearoyl titanate, isopropyl triisomyristyroyl titanate, methyltriisostearoyl titanate, methyltriisomyristyroyl. Examples thereof include titanate, ethyl triisostearoyl titanate, and ethyl triisomyristyroyl titanate.
本発明の疎水性セルロース粉体において、前記一般式（１）または（２）にて示される化合物のセルロース粉体への被覆量は、用いられるセルロース粉体に対して０．５〜３０重量％であるのが好ましく、より好ましくは１〜１０重量％である。この被覆量が０．５重量％よりも少ない場合には、十分な疎水性を得ることができない。一方、この被覆量が３０重量％を超える場合には、粉体の感触が非常に油っぽく湿った感じとなって乾粉として存在しないばかりでなく、前記一般式（１）または（２）にて示される化合物がセルロース粉体表面に固着されずにそれ自体が析出してしまうので好ましくない。 In the hydrophobic cellulose powder of the present invention, the coating amount of the compound represented by the general formula (1) or (2) on the cellulose powder is 0.5 to 30% by weight based on the cellulose powder used. It is preferable that it is 1 to 10% by weight. When the coating amount is less than 0.5% by weight, sufficient hydrophobicity cannot be obtained. On the other hand, when the coating amount exceeds 30% by weight, not only does the powder feel very oily and moist but does not exist as a dry powder, the general formula (1) or (2) The compound shown below is not preferable because it is not fixed to the surface of the cellulose powder and precipitates itself.
次に、本発明による疎水性セルロース粉体およびその製造方法の具体的な実施例について以下に説明する。なお、本発明は、以下に述べる実施例に限定されるものではない。 Next, specific examples of the hydrophobic cellulose powder and the production method thereof according to the present invention will be described below. In addition, this invention is not limited to the Example described below.
本実施例において、原料となるセルロース粉体は、それ自体公知の製造方法（例えば、特開昭６１−２４１３３７号公報参照）によって製造されたものである。すなわち、この原料となるセルロース粉体（セルロース粒子）は、（１）ビスコースと水溶性のアニオン性高分子化合物とを混合してビスコースの微粒子分散液を生成し、（２）前記分散液を加熱するもしくは前記分散液を凝固剤と混合することによって当該分散液中のビスコースを凝固させて後に酸で中和してセルロースの微粒子を生成する、または前記分散液を酸で凝固および中和してセルロースの微粒子を生成し、（３）このセルロースの微粒子を母液から分離し、そして必要により脱硫、酸洗い、水洗あるいは乾燥する、ことによって製造されたものである。この原料セルロース粉体において、その粒子形状は球形で、平均粒子径は約１０μｍであり、Ｘ線回折法により区別されるその結晶形態はセルロースＩＩ型であった。 In this example, the cellulose powder used as a raw material is produced by a production method known per se (for example, see JP-A No. 61-241337). That is, cellulose powder (cellulose particles) as a raw material is produced by mixing (1) viscose and a water-soluble anionic polymer compound to produce a fine particle dispersion of viscose, and (2) the dispersion Or by mixing the dispersion with a coagulant to coagulate the viscose in the dispersion and then neutralize with acid to produce fine cellulose particles, or coagulate and medium the dispersion with acid. It is produced by (3) separating the cellulose fine particles from the mother liquor and, if necessary, desulfurizing, pickling, washing with water or drying. In this raw material cellulose powder, the particle shape was spherical, the average particle diameter was about 10 μm, and the crystal form distinguished by the X-ray diffraction method was cellulose type II.
（実施例１）
前記原料セルロース粉体をヘンシェルミキサーで高速撹拌中にｎ−オクチルトリエトキシシランを当該原料セルロース粉体に対してその重量比が２重量％となるように液滴下した。その後、原料セルロース粉体の重量に対して０．１重量％の塩化アルミニウムを２０倍の水で溶解してなる塩化アルミニウム水溶液を同様に液滴下した。ここで、反応速度のばらつきをなくすため、ヘンシェルミキサー内の温度を５０℃に設定した。また、滴下終了後も同じ温度（５０℃）で３０分間撹拌した。その後、ミキサー内温度を１１０℃として３時間反応熟成させた。こうして、原料セルロース粉体にｎ−オクチルトリエトキシシランが表面被覆された表面被覆セルロース粉体（本発明の「疎水性セルロース粉体」に相当する。）を得た。
Example 1
While the raw material cellulose powder was stirred at a high speed with a Henschel mixer, n-octyltriethoxysilane was dropped in such a manner that the weight ratio of the raw material cellulose powder was 2% by weight. Thereafter, an aqueous solution of aluminum chloride obtained by dissolving 0.1% by weight of aluminum chloride with 20 times water with respect to the weight of the raw material cellulose powder was similarly dropped. Here, the temperature in the Henschel mixer was set to 50 ° C. in order to eliminate variations in the reaction rate. Moreover, after completion | finish of dripping, it stirred for 30 minutes at the same temperature (50 degreeC). Thereafter, the temperature inside the mixer was set to 110 ° C., and the reaction was aged for 3 hours. In this way, a surface-coated cellulose powder (corresponding to the “hydrophobic cellulose powder” of the present invention) in which n-octyltriethoxysilane was coated on the raw material cellulose powder was obtained.
（実施例２）
前記実施例１と同様の方法で、ｎ−オクチルトリエトキシシランを使用する代わりにトリデカフルオロオクチルトリメトキシシランを用いることにより、原料セルロース粉体にトリデカフルオロオクチルトリメトキシシランが表面被覆された表面被覆セルロース粉体（本発明の「疎水性セルロース粉体」に相当する。）を得た。
(Example 2)
In the same manner as in Example 1, tridecafluorooctyltrimethoxysilane was surface-coated on the raw material cellulose powder by using tridecafluorooctyltrimethoxysilane instead of using n-octyltriethoxysilane. A surface-coated cellulose powder (corresponding to the “hydrophobic cellulose powder” of the present invention) was obtained.
（実施例３）
前記実施例１におけるｎ−オクチルトリエトキシシランに代えてイソプロピルトリイソステアロイルチタネートを使用し、このイソプロピルトリイソステアロイルチタネートを原料セルロース粉体に対してその重量比が３重量％となるように液滴下する以外は実施例１と同様の方法により、原料セルロース粉体にイソプロピルトリイソステアロイルチタネートが表面被覆された表面被覆セルロース粉体（本発明の「疎水性セルロース粉体」に相当する。）を得た。
(Example 3)
In place of n-octyltriethoxysilane in Example 1, isopropyl triisostearoyl titanate was used, and the isopropyl triisostearoyl titanate was added to the droplets so that the weight ratio thereof was 3% by weight with respect to the raw material cellulose powder. A surface-coated cellulose powder (corresponding to the “hydrophobic cellulose powder” of the present invention) obtained by coating the raw material cellulose powder with isopropyltriisostearoyl titanate was obtained by the same method as in Example 1 except that. It was.
（比較例１）
実施例１と同様の方法であるが、塩化アルミニウム水溶液を液滴下することなしに製造して表面被覆セルロース粉体を得た。
(Comparative Example 1)
Although it was the same method as Example 1, it manufactured without dropping aluminum chloride aqueous solution, and obtained the surface covering cellulose powder.
（比較例２）
実施例２と同様の方法であるが、トリデカフルオロオクチルトリメトキシシランを原料セルロース粉体に対してその重量比が０．１重量％となるように液滴下して表面被覆セルロース粉体を得た。
(Comparative Example 2)
The same method as in Example 2, except that tridecafluorooctyltrimethoxysilane was dropped in such a manner that the weight ratio of the raw cellulose powder was 0.1% by weight to obtain a surface-coated cellulose powder. It was.
（比較例３）
実施例３と同様の方法であるが、イソプロピルトリイソステアロイルチタネートを原料セルロース粉体に対してその重量比が３５重量％となるように液滴下して表面被覆セルロース粉体を得た。
(Comparative Example 3)
The method was the same as in Example 3, but isopropyl triisostearoyl titanate was dropped in such a manner that the weight ratio of the isopropyl triisostearoyl titanate to the raw material cellulose powder was 35% by weight to obtain a surface-coated cellulose powder.
これら実施例１〜３および比較例１，２で得られた各表面被覆セルロース粉体をプレス機によって２００ｋｇ／ｃｍ２の力でプレスして調製した粉体プレート上で、水との接触角を測定した。その結果が表１に示されている。なお、接触角の数値が高いほど、疎水性が高いことを示す。また、比較例３で調製されたものは乾粉とはならずにオイル状となり、接触角の測定が不可能であった。 On the powder plate prepared by pressing each surface-coated cellulose powder obtained in Examples 1 to 3 and Comparative Examples 1 and 2 with a press at a force of 200 kg / cm 2 , the contact angle with water was changed. It was measured. The results are shown in Table 1. In addition, it shows that hydrophobicity is so high that the numerical value of a contact angle is high. Moreover, what was prepared in the comparative example 3 became oily instead of dry powder, and measurement of the contact angle was impossible.
この表１から明らかなように、実施例１〜３の表面被覆セルロース粉体は、いずれも接触角が大きく１００°を超えており、良好な疎水性が得られることが分かる。 As is apparent from Table 1, the surface-coated cellulose powders of Examples 1 to 3 all have a large contact angle and exceed 100 °, indicating that good hydrophobicity can be obtained.
Claims (3)
Ｒ１ＣＨ２ＣＨ２Ｓｉ（ＯＲ２）３ ・・・・・・・・（１）
（式中、Ｒ１は炭素数が１以上の飽和炭化水素基または炭素数が１以上の飽和炭化フッ素基であり、Ｒ２は炭素数が１以上の飽和炭化水素基である。） Hydrophobicity crystal structure characterized by being surface-coated by the following general formula (1) Similar coverage of 0.5 to 30 wt% of a compound represented by cellulose powder consisting of regenerated cellulose of the cellulose II type Cellulose powder.
R 1 CH 2 CH 2 Si (OR 2 ) 3 (1)
(In the formula, R 1 is a saturated hydrocarbon group having 1 or more carbon atoms or a saturated hydrocarbon group having 1 or more carbon atoms, and R 2 is a saturated hydrocarbon group having 1 or more carbon atoms.)
（Ｒ ３ ＣＯＯ） ３ Ｔｉ（ＯＲ ４ ） ・・・・・・・・（２）
（式中、Ｒ ３ は炭素数が４以上の飽和炭化水素基、Ｒ ４ は炭素数が１以上の飽和炭化水素基である。） Hydrophobic , characterized in that a cellulose powder having a crystal structure of cellulose II type regenerated cellulose is surface-coated with a compound represented by the following general formula (2) at a coating amount of 0.5 to 30% by weight . Cellulose powder.
(R 3 COO) 3 Ti (OR 4 ) (2)
(In the formula, R 3 is a saturated hydrocarbon group having 4 or more carbon atoms , and R 4 is a saturated hydrocarbon group having 1 or more carbon atoms.)
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