JPH0440229A - Method for modifying surface of semiconductor minute particle - Google Patents
Method for modifying surface of semiconductor minute particleInfo
- Publication number
- JPH0440229A JPH0440229A JP2145768A JP14576890A JPH0440229A JP H0440229 A JPH0440229 A JP H0440229A JP 2145768 A JP2145768 A JP 2145768A JP 14576890 A JP14576890 A JP 14576890A JP H0440229 A JPH0440229 A JP H0440229A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- semiconductor
- minute particles
- semiconductor fine
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 title abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 239000010419 fine particle Substances 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 230000005484 gravity Effects 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 description 9
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011859 microparticle Substances 0.000 description 8
- 239000003125 aqueous solvent Substances 0.000 description 6
- -1 polydimethylsiloxane Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000000434 field desorption mass spectrometry Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野〕
本発明は、非水溶媒中で良好な分散安定性を示すシロキ
サン重合物で被覆された半導体微粒子の作製方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing semiconductor fine particles coated with a siloxane polymer that exhibits good dispersion stability in non-aqueous solvents.
この微粒子を分散させた非水系の懸濁液は、塗料、化粧
品の分野はいうに及ばず、長期にわたる分散安定性を要
求される電気泳動を利用した表示素子（例えば、特開昭
４８−３１０９６） および異方性双極子微粒子の懸
濁液からなる電気光学素子（ＤＰＳ素子）（例えば、Ａ
．Ｍ．Ｍａｒｋｓ， ＡｐｐｌｉｅｄＯｐｔｉｃｓ，
８， Ｎｏ．７ （１９５９））には、特に有効である
。This non-aqueous suspension in which fine particles are dispersed can be used not only in the fields of paints and cosmetics, but also in display elements using electrophoresis that require long-term dispersion stability (for example, in Japanese Patent Laid-Open No. 48-31096). ) and an electro-optical device (DPS device) consisting of a suspension of anisotropic dipole particles (for example, A
．． M. Marks, Applied Optics,
8, No. 7 (1959)).
［従来の技術］
非水溶媒中で安定な分散状態を得るためには、２つの因
子を考える必要がある。１つは、電気二重層間の静電反
発効果であり、もう１つは、吸着ポリマー層間の立体障
害効果である。[Prior Art] In order to obtain a stable dispersion state in a non-aqueous solvent, it is necessary to consider two factors. One is the electrostatic repulsion effect between the electric double layers, and the other is the steric hindrance effect between the adsorbed polymer layers.
しかしながら、比較的誘電率の小さな非水溶媒中ではイ
オン解離は起こりにくく、前者の効果は比較的小さいこ
とから、後者を利用することが重要になる。However, since ionic dissociation is difficult to occur in a nonaqueous solvent with a relatively small dielectric constant, and the effect of the former is relatively small, it is important to utilize the latter.
微粒子を非水溶媒中に分散させる場合の一般的な方法は
、界面活性剤、ポリマーを微粒子表面に吸着させる方法
である。これについては現在までに数え切れないほど多
くの研究があり、微粒子および分散媒の種類に応じて界
面活性剤、吸着ポリマーを選ぶことによって分散性はか
なり改善されることがわかっている。A common method for dispersing fine particles in a non-aqueous solvent is to adsorb a surfactant or polymer onto the surface of the fine particles. There have been countless studies on this topic to date, and it has been found that dispersibility can be significantly improved by selecting surfactants and adsorbing polymers depending on the type of fine particles and dispersion medium.
坪用らはポリアクリルアミドなどのポリマーを酸化物微
粒子表面にグラフト化させることにより、水中で安定な
分散系が得られることを報告してＩ、ｚる。 （第２回
コロイドおよび界面化学特別討論会、１９８７、要旨集
ｐ、１１１）
また、福井らはＣｈｅｍｉｃａｌ ＶａｐｏｒＤｅｐ
ｏｓｆ ｔｌｏｎ （ＣＶＤ）の手法を用いて金属酸
化物微粒子を網目構造を持つオルガノシロキサンポリマ
ーで被覆できることを報告しており、親水性である金属
酸化物微粒子の新しい疎水化方法として注目される。Tsubo et al. reported that a stable dispersion system in water can be obtained by grafting a polymer such as polyacrylamide onto the surface of oxide fine particles. (2nd Special Conference on Colloid and Surface Chemistry, 1987, Abstracts p. 111) In addition, Fukui et al.
It has been reported that metal oxide fine particles can be coated with an organosiloxane polymer having a network structure using the OSF TLON (CVD) method, and this is attracting attention as a new method for making hydrophilic metal oxide fine particles hydrophobic.
［発明が解決しようとする問題点］
従来、微粒子を非水溶媒中に分散させる場合には、各種
の界面活性剤、ポリマーが分散剤として用いられている
が、それらのほとんどすべては分散剤の微粒子への物理
吸着を利用したものである。[Problems to be Solved by the Invention] Conventionally, when dispersing fine particles in a non-aqueous solvent, various surfactants and polymers have been used as dispersants, but almost all of them have been used as dispersants. This method utilizes physical adsorption to fine particles.
従って、その吸着力は小さく、脱着しやすい。Therefore, its adsorption force is small and it is easy to desorb.
さらに、その分散安定性は温度の影響を受けやすい。Furthermore, its dispersion stability is sensitive to temperature.
これに対してグラフト化では、ポリマーは微粒子表面に
共有結合で結合するために、その結合力は非常に大きい
という特徴を有する。On the other hand, in grafting, since the polymer is covalently bonded to the surface of the fine particles, the bonding force thereof is extremely large.
通常の熱反応によるグラフト化においては、ポリマーを
微粒子表面のＯＨ基と反応させる０ この場合に微粒子
表面のｏＨＭｌが微粒子の作製方法および熱履歴によっ
て異なるために、グラフトポリマー量を制御することは
困難を伴う。In normal grafting by thermal reaction, the polymer is reacted with the OH groups on the surface of the microparticles. In this case, it is difficult to control the amount of grafted polymer because the oHMl on the surface of the microparticles varies depending on the preparation method and thermal history of the microparticles. accompanied by.
また、福井らの考案したＣＶＤによるポリマー被覆にお
いては、微粒子が乾燥状態にあり、強く凝集しているた
めに、１次粒子への被覆は不可能に近い。Furthermore, in the polymer coating by CVD devised by Fukui et al., since the fine particles are in a dry state and strongly aggregated, it is almost impossible to coat the primary particles.
ｃ問題点を解決するための手段］
熱力学的に言えば、全自由エネルギーを減少させる方向
に変化は起こるから、分散系において界面自由エネルギ
ーが一定の時は、界面の面積を減らす方向の変化、すな
わち粒子の凝集が起こる。Measures to solve problem C] Thermodynamically speaking, changes occur in the direction of decreasing the total free energy, so when the interfacial free energy is constant in a dispersed system, changes occur in the direction of decreasing the area of the interface. , that is, particle agglomeration occurs.
一方、吸着性のポリマーが存在する場合には、吸着によ
り界面自由エネルギーが減少することから、ある程度凝
集を抑制することが可能となる。On the other hand, when an adsorbent polymer is present, the interfacial free energy decreases due to adsorption, making it possible to suppress aggregation to some extent.
しかしながら、長期間にわたる分散安定性を得るために
は、界面活性剤、ポリマーを吸着させる方法では、微粒
子との結合力が弱いことから、おのずと限界がある。However, in order to obtain dispersion stability over a long period of time, the method of adsorbing surfactants and polymers naturally has a limit because the bonding force with fine particles is weak.
微粒子へのポリマーのグラフト化は微粒子との結合力が
大きいことから、微粒子の分散安定化において非常に有
効な手段となると考えられる。Grafting a polymer onto fine particles is considered to be a very effective means for stabilizing the dispersion of fine particles, since it has a strong binding force with the fine particles.
本発明者らは、環状オルガノシロキサン溶液に半導体微
粒子を分散させた分散液に、半導体のバンドギャップ以
上のエネルギーを有する波長の光を照射することにより
、微粒子表面がシロ牛サン重合物で被覆されること、お
よび半導体微粒子が疎水化され、非水溶媒中における分
散安定性が向上することを見いだした。The present inventors discovered that by irradiating a dispersion of semiconductor fine particles in a cyclic organosiloxane solution with light of a wavelength having an energy greater than the bandgap of the semiconductor, the surfaces of the fine particles were coated with a white-beef san polymer. We also found that the semiconductor fine particles were made hydrophobic and their dispersion stability in non-aqueous solvents was improved.
環状オルガノシロキサンとしては、一般式（１）で表さ
れるものを用いることができるが、反応性の点からは、
特に１． ３． ５． ７−チトラメチルシクロテトラ
シロキサンを好んで使用することができる。As the cyclic organosiloxane, those represented by general formula (1) can be used, but from the viewpoint of reactivity,
Especially 1. 3. 5. 7-titramethylcyclotetrasiloxane can be used with preference.
また、ＤＰＳ素子への応用などのように、１次粒子への
ポリマー被覆が必須条件となる場合には、本反応が液相
光反応であることから、超音波照射を光照射と並行して
行うことが有効である。In addition, in cases where polymer coating on primary particles is an essential condition, such as in applications to DPS devices, since this reaction is a liquid phase photoreaction, ultrasonic irradiation may be performed in parallel with light irradiation. It is effective to do so.
得られた微粒子は、用いた環状オルガノシロ牛サンに対
する良溶媒中で良好な分散安定性を示す。The obtained fine particles exhibit good dispersion stability in a good solvent for the cyclic organosiloxan used.
例えば、１． ３． ５． ７−チトラメチルシクロテ
トラシロキサンの場合には、ベンゼン、トルエン、クロ
ロホルム、特にグラフトポリマーと良く似た構造を有す
るポリジメチルシロキサン中において優れた分散性をえ
ることができる。For example, 1. 3. 5. In the case of 7-titramethylcyclotetrasiloxane, excellent dispersibility can be obtained in benzene, toluene, chloroform, and especially in polydimethylsiloxane, which has a structure very similar to that of the graft polymer.
反応機構の詳細については、明かではないが、環状オル
ガノシロキサンの吸収が無い範囲の波長の光照射を行っ
ていること、また光照射時間とともにポリマー被覆量が
増加していることから、この反応は半導体微粒子の光触
媒活性によって銹起されているものと考えられる。さら
に、環状オルガノシロキサンは酸またはアルカリ触媒下
で開環重合し、線状ポリマーを生成することを考慮する
と、半導体のバンドギャップ励起によって価電子帯に生
じた正孔が、環状オルガノシロキサンを酸化することに
より、半導体微粒子表面で開環重合が起きているものと
推定される。Although the details of the reaction mechanism are not clear, it is believed that this reaction is possible because the light irradiation is performed within a wavelength range in which the cyclic organosiloxane does not absorb, and the amount of polymer coating increases with the light irradiation time. It is thought that the rust is caused by the photocatalytic activity of the semiconductor fine particles. Furthermore, considering that cyclic organosiloxanes undergo ring-opening polymerization under acid or alkali catalysts to produce linear polymers, holes generated in the valence band due to bandgap excitation of semiconductors oxidize cyclic organosiloxanes. Therefore, it is presumed that ring-opening polymerization occurs on the surface of the semiconductor fine particles.
本方法は、塗料、化粧品、電気泳動素子などに広く用い
られているＴｌＯ２微粒子の疎水化に特に有効である。This method is particularly effective for making TlO2 fine particles, which are widely used in paints, cosmetics, electrophoretic elements, etc., hydrophobic.
また、着色塗料、導電性フィラーとしてそのニーズが高
まりつつあるＴｌＯ２の還元体（Ｔ１０ｘ、１≦ｘく２
）の疎水化にも好んで用いることができる。さらに、−
数的にはその価電子帯が、環状オルガノシロキサンの酸
化電位よりも責な電位を有するものであれば良い。この
条件を満足する半導体としては、ＴｌＯ２，Ｔｌ０Ｘ以
外にＺｎＯ，ＷＯａ、５ｎ０２がある。In addition, the reduced form of TlO2 (T10x, 1≦x2
) can also be preferably used for hydrophobizing. Furthermore, −
Numerically, it is sufficient if the valence band has a higher potential than the oxidation potential of the cyclic organosiloxane. In addition to TlO2 and Tl0X, semiconductors that satisfy this condition include ZnO, WOa, and 5n02.
［作用］
本発明による半導体微粒子の表面改質方法の作用を以下
に整理する。[Function] The function of the method for surface modification of semiconductor fine particles according to the present invention is summarized below.
（１）グラフトポリマーであるポリジメチルシロキサン
のエントロピー斥力により、分散状態が安定化される。(1) The entropic repulsion of polydimethylsiloxane, which is a graft polymer, stabilizes the dispersion state.
（２）ポリジメチルシロキサンで被覆されることにより
、微粒子表面が疎水化されエンタルピー的な斥力が得ら
れる。(2) By coating with polydimethylsiloxane, the surface of the fine particles becomes hydrophobic and enthalpic repulsion is obtained.
（３）微粒子の比重を見かけ上小さくすることができる
ので、比重の大きな微粒子の沈降を抑制することができ
る。(3) Since the apparent specific gravity of fine particles can be reduced, sedimentation of fine particles with high specific gravity can be suppressed.
［実施例］
実施例１
チタニア微粒子（平均粒径、０．２μｍ）２００ｍｇヲ
１． ３． ５＋ ７−チトラメチルシクロテトラシ
ロキサン （ＴＭＣＴＳ）５ｇに加えて、アルゴンで１
５分間バブリングすることによって、前記ＴＭＣＴＳ中
の酸素を除去した。マグネチックスターラーでかくはん
しながら、高圧水銀灯を光源に用いて光照射を行った。[Example] Example 1 200 mg of titania fine particles (average particle size, 0.2 μm) 1. 3. 5+ 5g of 7-titramethylcyclotetrasiloxane (TMCTS) plus 1
Oxygen in the TMCTS was removed by bubbling for 5 minutes. Light irradiation was performed using a high-pressure mercury lamp as a light source while stirring with a magnetic stirrer.
反応温度は、恒温水を循環させることによって３０．０
＋０．５℃に維持した。光照射後、吸着したＴＭＣＴＳ
を除去するために、微粒子を３５．３ｍｌのトルエンで
６回洗浄し、さらに真空乾燥機中において５０℃で乾燥
させた。The reaction temperature was adjusted to 30.0 by circulating constant temperature water.
It was maintained at +0.5°C. TMCTS adsorbed after light irradiation
To remove the microparticles, the microparticles were washed six times with 35.3 ml of toluene and further dried at 50° C. in a vacuum dryer.
表１に光照射時間を変えて作製した微粒子（■暗所で２
時間攪拌、■光照射時間＝０．２５ｈ、 ０表１ 光
照射時間の異なるサンプルにおけるＴＭＣＴＳ被覆量の
定量結果
光照射時間−０，５ｈ、 ■光照射時間−１ｈ、
■光照射時間−２ｈ）上のシリコン被覆量を拡散反射フ
ーリエ変換赤外分光法（ＦＴ−Ｉ Ｒ）を用いて定量し
た結果を示す。Table 1 shows microparticles prepared by changing the light irradiation time (■ 2 in the dark).
Stir for a time, ■ Light irradiation time = 0.25 h, 0 Table 1 Quantitative results of TMCTS coating amount in samples with different light irradiation times Light irradiation time - 0.5 h, ■ Light irradiation time - 1 h,
(2) The results of quantifying the silicon coating amount on the surface (light irradiation time - 2 h) using diffuse reflection Fourier transform infrared spectroscopy (FT-IR) are shown.
この結果は、光照射時間と共にシリコン被覆量が増加し
ていることを表している。This result shows that the amount of silicon coating increases with the light irradiation time.
表１は、１３ｍｇの各微粒子をポリジメチルシロキサン
（２０ｃｓ）ｓｏｇに添加した後に、ウルトラデスパー
サ−を用いて１５分間かくはんした後の濁度を合わせて
示している。この値が大きいほどポリジメチルシロキサ
ンに対する分散性が良いことを意味している。Table 1 also shows the turbidity after adding 13 mg of each fine particle to polydimethylsiloxane (20 cs) sog and stirring for 15 minutes using an ultra desperser. The larger this value is, the better the dispersibility in polydimethylsiloxane is.
この結果より、光照射時間の増加にともなって、分散性
が向上していることがわかる。This result shows that the dispersibility improves as the light irradiation time increases.
光照射時間の増加と共にシリコン被覆量が増加している
ことを考慮すると、この分散安定性の向上は、微粒子上
のシリコン同志の容積制限効果に起因するものと解釈す
ることができる。Considering that the amount of silicon coating increases with increasing light irradiation time, this improvement in dispersion stability can be interpreted as being due to the volume-limiting effect of silicon on the fine particles.
実施例２
チタニア微粒子（平均粒径、０．２μｍ）２００ｍｇを
ポリジメチルシロキサン（２０ｃｓ、ＰＤＭＳ）５ｇに
加えて、アルゴンで１６分間バブリングすることによっ
て、前記ＦＤＭＳ中の酸素を除去した。マグネチックス
ターラーでかくはんしながら、高圧水銀灯を光源に用い
て光照射を行った。反応温度は、恒温水を循環させるこ
とによって３０． ０＋０． ５℃に維持した。Example 2 Oxygen in the FDMS was removed by adding 200 mg of titania fine particles (average particle size, 0.2 μm) to 5 g of polydimethylsiloxane (20 cs, PDMS) and bubbling with argon for 16 minutes. Light irradiation was performed using a high-pressure mercury lamp as a light source while stirring with a magnetic stirrer. The reaction temperature can be adjusted to 30.0% by circulating constant temperature water. 0+0. It was maintained at 5°C.
光照射後、吸着したＦＤＭＳを除去するために、微粒子
を３５．３ｍｌのトルエンで６回洗浄し、さらに真空乾
燥機中において５０℃で乾燥させた。After light irradiation, the microparticles were washed six times with 35.3 ml of toluene to remove the adsorbed FDMS, and further dried at 50° C. in a vacuum dryer.
表２に光照射時間を変えて作製した微粒子（■光照射時
間子０．５ｈ、 ■光照射時間−１，３ｈ。Table 2 shows microparticles produced with different light irradiation times (1) Light irradiation time 0.5 h, 2) Light irradiation time -1.3 h.
■光照射時間＝２ｈ）上のシリコン被覆量を拡散反射Ｆ
Ｔ−Ｉ Ｒを用いて定量した結果を示す。■ Light irradiation time = 2h) Diffuse reflection F
The results of quantification using T-IR are shown.
この結果は、光照射時間にかかわらずポリマー被覆量は
ほとんど変化していないることを表している。また、こ
の被覆量は実施例１で示したＴＭＣＴＳ系よりもほぼ１
桁小さく、ＰＤＭＳ系の場合には単に吸着しているもの
と考えられる。This result shows that the amount of polymer coating hardly changes regardless of the light irradiation time. Moreover, this coating amount is approximately 1 more than that of the TMCTS system shown in Example 1.
It is considered to be an order of magnitude smaller, and in the case of a PDMS system, it is simply adsorbed.
このことから、線状シロキサンの光反応性は著しく小さ
いことがわかる。This shows that the photoreactivity of linear siloxane is extremely small.
表２ 光照射時間の異なるサンプルにおけるＰＤＭＳ被
覆量の定量結果
（２）室温において、２時間以下の比較的短時間で十分
に微粒子を疎水化することが可能である。Table 2 Quantitative results of PDMS coverage in samples subjected to different light irradiation times (2) At room temperature, it is possible to sufficiently hydrophobize fine particles in a relatively short time of 2 hours or less.
（３）液相反応であることから、ＣＶＤ法と比べて１次
粒子へのポリマー被覆が比較的容易である。(3) Since it is a liquid phase reaction, it is relatively easy to coat the primary particles with the polymer compared to the CVD method.
さらに本発明は、半導体微粒子の非水溶媒中における分
散安定性が向上することがら、顔料および塗料をはじめ
、長期間の分散安定性が要求される電気泳動素子、およ
びＤＰＳ素子における半導体微粒子の分散安定化方法と
して寄与するところ大である。Furthermore, the present invention improves the dispersion stability of semiconductor fine particles in non-aqueous solvents, so the dispersion of semiconductor fine particles in electrophoretic elements and DPS elements, which require long-term dispersion stability, as well as pigments and paints, is advantageous. It makes a great contribution as a stabilization method.
特許出願人 日本板硝子株式会社
［発明の効果］
本発明による半導体微粒子の疎水化方法の特徴を以下に
まとめて示す。Patent Applicant: Nippon Sheet Glass Co., Ltd. [Effects of the Invention] The characteristics of the method for hydrophobizing semiconductor fine particles according to the present invention are summarized below.
（１）通常の熱反応によるグラフト化と異なり、グラフ
トポリマー量の再現性が良い。(1) Unlike grafting by normal thermal reaction, the reproducibility of the amount of grafted polymer is good.
Claims (1)
液に半導体微粒子を分散させた分散液に、半導体のバン
ドギャップ以上のエネルギーを有する波長の光を照射す
ることにより、微粒子表面をシロキサン重合物で被覆す
る半導体微粒子の表面改質方法。 ▲数式、化学式、表等があります▼（１） 但し、ｎ＝３〜５であり、またＲ＿１およびＲ＿２は水
素、アルキル基、フェニル基、アルコキシル基、ビニル
基からなる群の中から選ばれる。 ２、前記環状オルガノシロキサンが、１、３、５、７−
テトラメチルシクロテトラシロキサンである請求項１記
載の半導体微粒子の表面改質方法。 ３、前記半導体微粒子が、化学式ＴｉＯ＿ｘ（１≦ｘ≦
２）で表されるチタン酸化物である請求項１記載の半導
体微粒子の表面改質方法。[Claims] 1. By irradiating a dispersion in which semiconductor fine particles are dispersed in a cyclic organosiloxane solution represented by general formula (1) with light of a wavelength having energy greater than the band gap of the semiconductor, A method for modifying the surface of semiconductor fine particles by coating the surface of the fine particles with a siloxane polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) However, n = 3 to 5, and R_1 and R_2 are selected from the group consisting of hydrogen, an alkyl group, a phenyl group, an alkoxyl group, and a vinyl group. 2. The cyclic organosiloxane is 1,3,5,7-
2. The method of surface modification of semiconductor fine particles according to claim 1, wherein the semiconductor fine particles are tetramethylcyclotetrasiloxane. 3. The semiconductor fine particles have the chemical formula TiO_x (1≦x≦
2) The method for surface modification of semiconductor fine particles according to claim 1, wherein the titanium oxide is a titanium oxide represented by the formula 2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2145768A JPH0440229A (en) | 1990-06-04 | 1990-06-04 | Method for modifying surface of semiconductor minute particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2145768A JPH0440229A (en) | 1990-06-04 | 1990-06-04 | Method for modifying surface of semiconductor minute particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0440229A true JPH0440229A (en) | 1992-02-10 |
Family
ID=15392716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2145768A Pending JPH0440229A (en) | 1990-06-04 | 1990-06-04 | Method for modifying surface of semiconductor minute particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0440229A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329948A (en) * | 1993-05-21 | 1994-11-29 | Nara Kikai Seisakusho:Kk | Surface modification of powder |
| JP2001329189A (en) * | 2000-05-24 | 2001-11-27 | Asahi Kasei Corp | Photocatalyst composition |
| JP2006159184A (en) * | 2004-11-11 | 2006-06-22 | Konica Minolta Medical & Graphic Inc | Micro-particle dispersion having hydrophobic protective colloid and method of manufacture thereof, and photothermographic dry imaging material |
-
1990
- 1990-06-04 JP JP2145768A patent/JPH0440229A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329948A (en) * | 1993-05-21 | 1994-11-29 | Nara Kikai Seisakusho:Kk | Surface modification of powder |
| JP2001329189A (en) * | 2000-05-24 | 2001-11-27 | Asahi Kasei Corp | Photocatalyst composition |
| JP2006159184A (en) * | 2004-11-11 | 2006-06-22 | Konica Minolta Medical & Graphic Inc | Micro-particle dispersion having hydrophobic protective colloid and method of manufacture thereof, and photothermographic dry imaging material |
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