JP3125023B2 - Hydrophilic solid particles having a hydrophilic group on the surface, method for producing the same, and flocculant - Google Patents
Hydrophilic solid particles having a hydrophilic group on the surface, method for producing the same, and flocculantInfo
- Publication number
- JP3125023B2 JP3125023B2 JP08008978A JP897896A JP3125023B2 JP 3125023 B2 JP3125023 B2 JP 3125023B2 JP 08008978 A JP08008978 A JP 08008978A JP 897896 A JP897896 A JP 897896A JP 3125023 B2 JP3125023 B2 JP 3125023B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- solid particles
- hydrophilic
- surfactant
- 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.)
- Expired - Lifetime
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、表面に親水基を有
する新規な親水性固体粒子及びその製造方法ならびに新
規な凝集剤に関するものである。The present invention relates to a novel hydrophilic solid particle having a hydrophilic group on the surface, a method for producing the same, and a novel flocculant.
【0002】[0002]
【従来の技術】従来から、懸濁液中の粒子の凝集には高
分子凝集剤、無機塩凝集剤、界面活性剤等が使われてき
た。しかし、これらの既存凝集剤は懸濁液に溶けること
から廃水中に凝集剤が流出し、そのため廃水処理が困難
になったり環境を汚染したりする場合がある。それゆ
え、このような問題のない凝集剤が望まれている。一
方、化粧品や食品の分野等においては、油性の固体粒子
を水中に乳化させた乳化液を基材とする製品が作られて
いるが、この場合、その固体粒子自体は親水基を有しな
いことから、固体粒子の乳化安定性の点で問題がある。2. Description of the Related Art Conventionally, a polymer coagulant, an inorganic salt coagulant, a surfactant and the like have been used for agglomeration of particles in a suspension. However, since these existing flocculants dissolve in the suspension, the flocculants flow out into the wastewater, which may make wastewater treatment difficult or pollute the environment. Therefore, a flocculant without such a problem is desired. On the other hand, in the fields of cosmetics and foods, products based on an emulsion obtained by emulsifying oily solid particles in water have been made.In this case, the solid particles themselves do not have a hydrophilic group. Therefore, there is a problem in terms of the emulsion stability of the solid particles.
【0003】[0003]
【発明が解決しようとする課題】本発明は、前記した廃
水処理困難や環境汚染等の問題を起さない新規凝集剤及
びその製造方法を提供するとともに、水を加えるだけで
安定性の良い水中油滴型エマルジョンを容易に形成する
ことができる表面に親水基を有する固体粒子及びその製
造方法を提供することをその課題とする。SUMMARY OF THE INVENTION The present invention provides a novel flocculant which does not cause the above-mentioned problems such as wastewater treatment difficulties and environmental pollution, and a method for producing the same. It is an object of the present invention to provide a solid particle having a hydrophilic group on the surface, on which an oil droplet type emulsion can be easily formed, and a method for producing the same.
【0004】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく検討を重ねた結果、本発明を完成するに至
った。すなわち、本発明によれば、熱溶融性の非水溶性
固体粒子と親水基及び疎水基を有する界面活性剤とから
成り、該界面活性剤が該疎水基を介して該固体粒子と結
合しており、かつ該界面活性剤の結合量は前記非水溶性
固体粒子の0.01〜0.6重量%であることを特徴と
する表面に親水基を有する親水性固体粒子が提供され
る。また、本発明によれば、非水溶性物質の溶融液を界
面活性剤の存在下に水中で粒子化して水中油滴型エマル
ジョンを形成する工程と、該エマルジョンを冷却して該
非水溶性物質の溶融液粒子を固体粒子化する工程と、該
固体粒子を水中から分離する工程から成ることを特徴と
する前記親水基を有する親水性固体粒子の製造方法が提
供される。さらに、本発明によれば、界面活性剤が溶解
している非水溶性物質の溶融液を水中で液滴化して水中
油滴型エマルジョンを形成する工程と、該エマルジョン
を冷却して該非水溶性物質の溶融液粒子を固体粒子化す
る工程と、該固体粒子を水中から分離する工程からなる
ことを特徴とする親水基を有する前記親水性固体粒子の
製造方法が提供される。さらにまた、本発明によれば、
熱溶融性の非水溶性固体粒子と陰イオン性親水基及び疎
水基を有する陰イオン界面活性剤とからなり、該界面活
性剤が該疎水基を介して該固体粒子と結合しており、か
つ該界面活性剤の結合量は前記非水溶性固体粒子の0.
01〜0.6重量%である表面に陰イオン性親水基を有
する親水性固体粒子からなることを特徴とする懸濁粒子
の凝集剤が提供される。そしてまた、本発明によれば、
熱溶融性の非水溶性固体粒子と陽イオン性親水基及び疎
水基を有する陽イオン界面活性剤とからなり、該界面活
性剤が該疎水基を介して該固体粒子と結合しており、か
つ該界面活性剤の結合量は前記非水溶性固体粒子の0.
01〜0.6重量%である表面に陽イオン性親水基を有
する親水性固体粒子からなることを特徴とする懸濁粒子
の凝集剤が提供される。Means for Solving the Problems The inventors of the present invention have repeatedly studied to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, the water-soluble solid particles and the surfactant having a hydrophilic group and a hydrophobic group are composed of the heat-fusible water-insoluble solid particles, and the surfactant is bonded to the solid particles through the hydrophobic group. And the amount of the surfactant bound is the water-insoluble
The present invention provides hydrophilic solid particles having a hydrophilic group on a surface, which is 0.01 to 0.6% by weight of the solid particles. Further, according to the present invention, a step of forming an oil-in-water emulsion by granulating a melt of a water-insoluble substance in water in the presence of a surfactant, and cooling the emulsion to form the water-insoluble substance a step of solid particles of the melt particles, the method for producing a hydrophilic solid particles having a hydrophilic group, characterized by comprising the step of separating the solid particles from the water is provided. Furthermore, according to the present invention, a step of forming an oil-in-water emulsion by dropping a melt of a water-insoluble substance in which a surfactant is dissolved in water, and cooling the emulsion to form the water-insoluble A method for producing the hydrophilic solid particles having a hydrophilic group is provided, which comprises a step of converting the melt particles of the substance into solid particles, and a step of separating the solid particles from water. Furthermore, according to the present invention,
It is composed of heat-meltable non-water-soluble solid particles and an anionic surfactant having an anionic hydrophilic group and a hydrophobic group, and the surfactant is bonded to the solid particles through the hydrophobic group .
The binding amount of the surfactant is 0.1% of the water-insoluble solid particles.
The present invention provides a flocculant for suspended particles, comprising hydrophilic solid particles having an anionic hydrophilic group on the surface in an amount of from 0.01 to 0.6% by weight . And also according to the invention,
It comprises a heat-meltable water-insoluble solid particle and a cationic surfactant having a cationic hydrophilic group and a hydrophobic group, and the surfactant is bonded to the solid particle through the hydrophobic group .
The binding amount of the surfactant is 0.1% of the water-insoluble solid particles.
There is provided a flocculant for suspended particles, comprising hydrophilic solid particles having a cationic hydrophilic group on the surface in an amount of from 0.01 to 0.6% by weight .
【0005】[0005]
【発明の実施の形態】本発明において、熱溶融性の非水
溶性固体粒子(以下、単に基材ともいう)の表面に結合
している界面活性剤は、親水基と疎水基を有する界面活
性剤である。このような界面活性剤には、陰イオン性親
水基を有する陰イオン界面活性剤、陽イオン性親水基を
有する陽イオン界面活性剤、非イオン性親水基を有する
非イオン界面活性剤、及び陰イオン性親水基と陽イオン
性親水基を有する両性界面活性剤が包含される。また、
これらの界面活性剤に含まれる親水基としては、陰イオ
ン性親水基として、カルボキシル基、スルホン酸基、キ
サントゲン酸基、リン酸基、硫酸基等が例示され、陽イ
オン性親水基として、置換又は未置換の4級アンモニウ
ム基等が例示され、非イオン性親水基として、ポリオキ
シエチレン基やアルコール性水酸基が例示される。一
方、前記界面活性剤が有する疎水基としては多素数5以
上の炭化水素基やハロゲン化炭化水素基が挙げられ、こ
れらの疎水基には脂肪族基、環状脂肪族基及び芳香族基
が包含される。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a surfactant bonded to the surface of heat-meltable, water-insoluble solid particles (hereinafter, also simply referred to as a substrate) has a surfactant having a hydrophilic group and a hydrophobic group. Agent. Such surfactants include anionic surfactants having anionic hydrophilic groups, cationic surfactants having a cationic hydrophilic group, nonionic surfactants having a nonionic hydrophilic group, and anionic surfactants having a nonionic hydrophilic group. Amphoteric surfactants having an ionic hydrophilic group and a cationic hydrophilic group are included. Also,
Examples of the hydrophilic group contained in these surfactants include, as the anionic hydrophilic group, a carboxyl group, a sulfonic acid group, a xanthogenic acid group, a phosphoric acid group, a sulfate group, and the like. Or, an unsubstituted quaternary ammonium group or the like is exemplified, and as the nonionic hydrophilic group, a polyoxyethylene group or an alcoholic hydroxyl group is exemplified. On the other hand, examples of the hydrophobic group possessed by the surfactant include a hydrocarbon group having 5 or more prime numbers and a halogenated hydrocarbon group, and these hydrophobic groups include an aliphatic group, a cycloaliphatic group, and an aromatic group. Is done.
【0006】本発明の親水性固体粒子の表面に結合して
いる界面活性剤を具体的に例示すると以下の通りであ
る。 陰イオン界面活性剤:高級脂肪酸アルカリ塩、アルキル
硫酸エステルアルカリ塩、オレフィン硫酸エステルアル
カリ塩、アルキルベンゼンスルホン酸アルカリ塩、アル
キルナフタリンスルホン酸アルカリ塩、ジアルキルスル
ホコハク酸アルカリ塩、アルキルキサントゲン酸アルカ
リ塩、その他。 陽イオン界面活性剤:トリメチルアミノエチルアルキル
アミドハロゲニド、アルキルピリジニウム硫酸塩、アル
キルトリメチルアンモニウムハロゲニド、その他。 非イオン界面活性剤: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脂肪酸エステル、ポリオキシ
エチレンアルキルフェノールエーテル、ソルビタン脂肪
酸エステル、ポリオキシエチレンソルビタン脂肪酸エス
テル、しょ糖脂肪酸エステル、アルキルグルコシド、そ
の他。 両性界面活性剤:アルキルベタイン、アルキルジエチレ
ントリアミノ酢酸、その他。Specific examples of the surfactant bound to the surface of the hydrophilic solid particles of the present invention are as follows. Anionic surfactants: alkali salts of higher fatty acids, alkali salts of alkyl sulfates, alkali salts of olefin sulfates, alkali salts of alkyl benzene sulfonic acids, alkali salts of alkyl naphthalene sulfonic acids, alkali salts of dialkyl sulfosuccinic acids, alkali salts of alkyl xanthogenic acids, and others. Cationic surfactants: trimethylaminoethylalkylamide halides, alkylpyridinium sulfates, alkyltrimethylammonium halides, and others. Nonionic surfactants: polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkyl phenol ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, alkyl glucoside, and others. Amphoteric surfactants: alkyl betaines, alkyl diethylene triamino acetic acids, and others.
【0007】本発明で使用する基材は常温固体の非水溶
性物質であり、その融点は30℃以上、好ましくは50
℃以上である。融点の上限は制限されないが、通常は2
00℃以下、好ましくは150℃以下であり、製造面か
らは融点50〜90℃の基材が好ましい。また、基材は
単一品でも混合品であっても良いし、合成物でも天然物
であっても良い。本発明において基材となる物質を例示
すると、炭化水素、高級アルコール、高級脂肪酸、高級
エステル、高級酸アミド、オレフィン重合体等の合成
物;木ロウやキャンデリラワックス等の植物系ワック
ス、蜜ロウや鯨ロウ等の動物系ワックス、パラフィンワ
ックスやセレシン等の鉱物系ワックス、脱水ラノリンや
硬化ヒマシ油等の動植物系油脂及びその誘導体等の天然
物;等が挙げられる。The base material used in the present invention is a water-insoluble substance which is a solid at room temperature and has a melting point of 30 ° C. or more, preferably 50 ° C.
° C or higher. The upper limit of the melting point is not limited, but is usually 2
The temperature is not higher than 00 ° C, preferably not higher than 150 ° C, and a substrate having a melting point of 50 to 90 ° C is preferable from the viewpoint of production. Further, the base material may be a single product or a mixed product, or may be a synthetic product or a natural product. Examples of the substance serving as a base material in the present invention include synthetic compounds such as hydrocarbons, higher alcohols, higher fatty acids, higher esters, higher acid amides, and olefin polymers; vegetable waxes such as wood wax and candelilla wax; And animal waxes such as paraffin wax and ceresin; animal and plant fats such as dehydrated lanolin and hydrogenated castor oil; and natural products such as derivatives thereof.
【0008】本発明の親水性固体粒子は、基材粒子の表
面に界面活性剤の親水基を有する粒子である。該粒子中
の界面活性剤量は基材重量の0.01〜0.6%、好ま
しくは0.03〜0.15%の界面活性剤を含む粒子で
ある。また、粒径は1μm〜1mm、好ましくは10μ
m〜0.1mmである。本発明の親水性固体粒子は、表
面に親水基があるから水を加えると容易に水中油滴型エ
マルジョンとなり、クリーム状及び乳液状の医薬や化粧
品、食品を製造する際の油状基剤として有用である。ま
た、表面の親水基に特殊機能を持たせることによって機
能材とすることができる。例えば、親水基に電荷を持た
せたり、化学吸着能を持たせると下記のように懸濁粒子
の凝集剤とすることができる。表面に陰イオン性親水基
を有する親水性固体粒子を懸濁液に加えると、正帯電性
懸濁粒子は陰イオン性親水基との間の静電気力によって
凝集する。従って、表面に陰イオン性親水基を有する本
発明の親水性固体粒子は、正帯電性懸濁粒子の凝集剤と
することができる。The hydrophilic solid particles of the present invention are particles having a hydrophilic group of a surfactant on the surface of base particles. The amount of the surfactant in the particles is 0.01 to 0.6%, preferably 0.03 to 0.15% of the weight of the base material. The particle size is 1 μm to 1 mm, preferably 10 μm.
m to 0.1 mm. Since the hydrophilic solid particles of the present invention have hydrophilic groups on the surface, they easily become oil-in-water emulsions when water is added, and are useful as oil bases for producing creamy and emulsion liquid medicines, cosmetics, and foods. It is. Further, a functional material can be obtained by giving a special function to the hydrophilic group on the surface. For example, if a hydrophilic group is given a charge or has a chemisorption ability, it can be used as a flocculant for suspended particles as described below. When hydrophilic solid particles having an anionic hydrophilic group on the surface are added to the suspension, the positively charged suspended particles aggregate due to electrostatic force between the particles and the anionic hydrophilic group. Therefore, the hydrophilic solid particles of the present invention having an anionic hydrophilic group on the surface can be used as an aggregating agent for positively charged suspended particles.
【0009】表面に陽イオン性親水基を有する親水性固
体粒子を懸濁液に加えると、負帯電性懸濁粒子は陽イオ
ン性親水基との間の静電気力によって凝集する。従っ
て、表面に陽イオン性親水基を有する本発明の親水性固
体粒子は、負帯電性懸濁粒子の凝集剤とすることができ
る。表面にキサントゲン酸基を有する親水性固体粒子を
懸濁液に加えると、銅、亜鉛、鉛等の非鉄金属やその硫
化物の表面にキサントゲン酸基が化学吸着するから、前
記金属やその硫化物よりなる懸濁粒子の凝集剤とするこ
とができる。表面にカルボキシル基を有する親水性固体
粒子を懸濁液に加えると、金属鉄や酸化鉄の表面にカル
ボキシル基が化学吸着するから、金属鉄や酸化鉄よりな
る懸濁粒子が凝集する。従って、表面にカルボキシル基
を有する本発明の親水性固体粒子は、金属鉄や酸化鉄よ
りなる懸濁粒子の凝集剤とすることができる。When hydrophilic solid particles having a cationic hydrophilic group on the surface are added to a suspension, the negatively charged suspended particles are aggregated by electrostatic force between the suspension and the cationic hydrophilic group. Therefore, the hydrophilic solid particles of the present invention having a cationic hydrophilic group on the surface can be used as an aggregating agent for negatively charged suspended particles. When hydrophilic solid particles having a xanthate group on the surface are added to a suspension, the xanthate group is chemically adsorbed on the surface of a non-ferrous metal such as copper, zinc and lead or a sulfide thereof. And a flocculant for suspended particles. When hydrophilic solid particles having a carboxyl group on the surface are added to the suspension, the carboxyl groups are chemically adsorbed on the surface of the metallic iron or iron oxide, so that the suspended particles of metallic iron or iron oxide aggregate. Therefore, the hydrophilic solid particles of the present invention having a carboxyl group on the surface can be used as a flocculant for suspended particles composed of metallic iron or iron oxide.
【0010】前記のように、本発明の親水性固体粒子は
懸濁粒子の凝集剤として使うことができる。この凝集剤
は、粒子状のために固液分離が容易な上に、水不溶なの
で懸濁粒子を凝集後の廃水中に溶存することもないか
ら、該凝集剤は廃水中に混入して廃水処理困難や環境汚
染等の問題を起こすことがない。また、この凝集剤で凝
集させた凝集体を凝集剤の融点以上に加熱すると凝集剤
を分離回収できる。本発明の親水性固体粒子は、前記の
ように、水中に容易に乳化分散することから、クリーム
状及び乳液状の医薬や化粧品、食品を製造する際の油状
基剤として有用である。ここで使用する界面活性剤とし
ては、皮膚刺激性の少ない安全性の高い非イオン界面活
性剤が好ましい。As mentioned above, the hydrophilic solid particles of the present invention can be used as a flocculant for suspended particles. Since this flocculant is in particulate form, solid-liquid separation is easy, and since it is insoluble in water, the suspended particles do not dissolve in the wastewater after flocculation. It does not cause problems such as processing difficulties and environmental pollution. Further, when the aggregate aggregated with the flocculant is heated to a temperature higher than the melting point of the flocculant, the flocculant can be separated and recovered. Since the hydrophilic solid particles of the present invention are easily emulsified and dispersed in water as described above, they are useful as an oily base for producing creamy or milky medicines, cosmetics, and foods. As the surfactant used here, a nonionic surfactant with low skin irritation and high safety is preferable.
【0011】本発明の親水性固体粒子は、非水溶性物質
の溶融液を界面活性剤の存在下に水中で粒子化して水中
油滴型エマルジョンを形成する工程と、該エマルジョン
を冷却して該非水溶性物質の溶融液粒子を固体粒子化す
る工程と、該固体粒子を水中から分離する工程を順次行
うことで製造することができる(I法)。また、界面活
性剤が溶解している非水溶性物質の溶融液を水中で液滴
化して水中油滴型エマルジョンを形成する工程と、該エ
マルジョンを冷却して該非水溶性物質の溶融液粒子を固
体粒子化する工程と、該固体粒子を水中から分離する工
程を順次行うことで製造することができる(II法)。I
法で本発明の親水性固体粒子を製造する場合、水使用量
は非水溶性物質(基材)使用量の5〜100重量倍、好
ましくは10〜20重量倍とするのが望ましく、界面活
性剤使用量は基材使用量の0.1〜5重量%、好ましく
は0.5〜2重量%とするのが望ましい。また、エマル
ジョン形成温度は基材融点より5〜30℃、好ましくは
10〜15℃高温とするのが望ましく、エマルジョン冷
却温度は基材融点より10〜50℃、好ましくは25〜
40℃低温とするのが望ましい。The hydrophilic solid particles of the present invention are obtained by granulating a melt of a water-insoluble substance in water in the presence of a surfactant to form an oil-in-water emulsion, and cooling the emulsion to form the oil-in-water emulsion. It can be produced by sequentially performing a step of solidifying melt particles of a water-soluble substance into solid particles and a step of separating the solid particles from water (Method I). Further, a step of forming a droplet of the melt of the water-insoluble substance in which the surfactant is dissolved in water to form an oil-in-water emulsion, and cooling the emulsion to form particles of the melt of the water-insoluble substance. It can be produced by sequentially performing a step of forming solid particles and a step of separating the solid particles from water (Method II). I
When the hydrophilic solid particles of the present invention are produced by the method, the amount of water used is 5 to 100 times by weight, preferably 10 to 20 times by weight of the amount of water-insoluble substance (substrate) used. The use amount of the agent is desirably 0.1 to 5% by weight, preferably 0.5 to 2% by weight of the base material use amount. Further, the emulsion formation temperature is preferably 5 to 30 ° C., preferably 10 to 15 ° C. higher than the melting point of the substrate, and the emulsion cooling temperature is 10 to 50 ° C., preferably 25 to 50 ° C. above the melting point of the substrate.
It is desirable to keep the temperature at 40 ° C. low.
【0012】II法で本発明の親水性固体粒子を製造する
場合、水使用量は基材使用量の5〜100重量倍、好ま
しくは10〜20重量倍とするのが望ましく、界面活性
剤使用量は基材使用量の0.1〜2重量%、好ましくは
0.5〜1重量%とするのが望ましい。また、エマルジ
ョン形成温度は基材融点より5〜30℃、好ましくは1
0〜15℃高温とするのが望ましく、エマルジョン冷却
温度は基材融点より10〜50℃、好ましくは25〜4
0℃低温とするのが望ましい。上記I法及びII法で本発
明の親水性固体粒子を製造する場合、エマルジョンは撹
拌や超音波処理等の常法によって形成させることができ
る。また、生成した固体粒子は濾過や遠心分離等の常法
によって母液から分離することができる。親水性固体粒
子の粒径は、撹拌速度等のエマルジョン形成条件や基材
と界面活性剤との混合比等で調整することができる。When the hydrophilic solid particles of the present invention are produced by the method II, the amount of water used is preferably 5 to 100 times by weight, preferably 10 to 20 times by weight the amount of the substrate, The amount is desirably 0.1 to 2% by weight, preferably 0.5 to 1% by weight of the amount of the base material used. The emulsion formation temperature is 5 to 30 ° C., preferably 1 to 30 ° C. from the melting point of the substrate.
The temperature is preferably 0 to 15 ° C. higher, and the emulsion cooling temperature is 10 to 50 ° C., preferably 25 to 4 ° C. above the melting point of the base material.
It is desirable to keep the temperature at 0 ° C. When the hydrophilic solid particles of the present invention are produced by the methods I and II, the emulsion can be formed by a conventional method such as stirring or ultrasonic treatment. Further, the generated solid particles can be separated from the mother liquor by a conventional method such as filtration or centrifugation. The particle size of the hydrophilic solid particles can be adjusted by the emulsion forming conditions such as the stirring speed, the mixing ratio between the base material and the surfactant, and the like.
【0013】[0013]
【実施例】次に本発明を実施例及び比較例によって更に
具体的に説明するが、本発明はこの実施例によって限定
されるものではない。Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
【0014】実施例1 融点60〜62℃のパラフィン20gに200mlの精
製水を加え、これを湯浴で70℃に加熱してパラフィン
を液状にした。この液に0.1gのアミルキサントゲン
酸カリウムを加えてから、70℃に保持した該混合物を
ホモジナイザーで1分間撹拌して水中油滴型エマルジョ
ンを形成させ、このエマルジョンを室温まで冷却後に固
形物と母液を濾別した。この固形物は平均粒径約10μ
mの粒子状物で、乾燥した固形物1g中にアミルキサン
トゲン酸カリウムが0.0008g含まれていた。平均
粒径7μmの方鉛鉱粒子と平均粒径8μmの石英粒子を
固体成分とし、水を液体成分とする固体濃度0.1重量
%の懸濁液を500ml調製した。懸濁液中の石英粒子
と方鉛鉱粒子の混合比は、重量比で1:1である。この
懸濁液に前記の粒子状固形物1gを加え、10分間ゆる
やかに撹拌してから凝集物と母液を傾斜法で分離した。
分離した凝集物中の方鉛鉱粒子と石英粒子の重量比は
0.92:0.08であり、方鉛鉱粒子が選択的に凝集
された。Example 1 200 ml of purified water was added to 20 g of paraffin having a melting point of 60 to 62 ° C., and this was heated to 70 ° C. in a water bath to make the paraffin liquid. After 0.1 g of potassium amyl xanthogenate was added to this liquid, the mixture kept at 70 ° C. was stirred with a homogenizer for 1 minute to form an oil-in-water emulsion. The mother liquor was filtered off. This solid has an average particle size of about 10μ.
m of particulate matter, and 0.0008 g of potassium amyl xanthate was contained in 1 g of the dried solid. 500 ml of a suspension having a solid concentration of 0.1% by weight containing a galena particle having an average particle diameter of 7 μm and quartz particles having an average particle diameter of 8 μm as solid components and water as a liquid component was prepared. The mixing ratio of the quartz particles and the galena particles in the suspension is 1: 1 by weight. To the suspension was added 1 g of the above-mentioned particulate solid, and the mixture was gently stirred for 10 minutes, and then the aggregate and the mother liquor were separated by a gradient method.
The weight ratio of the galena particles to the quartz particles in the separated aggregate was 0.92: 0.08, and the galena particles were selectively aggregated.
【0015】実施例2 融点60〜62℃のパラフィン20gに200mlの精
製水を加え、これを湯浴で70℃に加熱してパラフィン
を液状にした。この液に0.1gのドデシルアンモニウ
ム塩酸塩を加えてから、該混合物をホモジナイザーで1
分間撹拌して水中油滴型エマルジョンを形成させ、この
エマルジョンを室温まで冷却後に固形物と母液を濾別し
た。この固形物は平均粒径約7μmの粒子状物で、乾燥
した固形物1g中にドデシルアンモニウム塩酸塩が0.
001g含まれていた。濃度300ppmの石英懸濁液
を500ml調製した。この懸濁液に前記の粒子状固形
物0.1gを加え、10分間ゆるやかに撹拌してから1
0分静置したところ、石英粒子が凝集し、懸濁液の上澄
液の濁度は5となった。なお、石英粒子が凝集する前の
懸濁液の濁度は78であった。Example 2 200 ml of purified water was added to 20 g of paraffin having a melting point of 60 to 62 ° C., and this was heated to 70 ° C. in a water bath to make the paraffin liquid. To this solution was added 0.1 g of dodecyl ammonium hydrochloride, and the mixture was homogenized with a homogenizer.
The mixture was stirred for 1 minute to form an oil-in-water emulsion, and after the emulsion was cooled to room temperature, the solid and the mother liquor were separated by filtration. This solid was a particulate matter having an average particle size of about 7 μm, and contained 0.1 g of dodecyl ammonium hydrochloride in 1 g of the dried solid.
001 g. 500 ml of a 300 ppm quartz suspension was prepared. 0.1 g of the above-mentioned particulate solid is added to this suspension, and gently stirred for 10 minutes.
After standing for 0 minutes, the quartz particles aggregated and the turbidity of the supernatant of the suspension became 5. The turbidity of the suspension before the aggregation of the quartz particles was 78.
【0016】比較例1 実施例2で使用したものと同様な石英懸濁液500ml
を調製し、濁度78の該懸濁液を10分間ゆるやかに撹
拌してから10分静置したが石英粒子は凝集せず、その
ために静置後の懸濁液上層部の濁度は静置前とほぼ同じ
78であった。Comparative Example 1 500 ml of the same quartz suspension as used in Example 2
The suspension having a turbidity of 78 was gently stirred for 10 minutes, and allowed to stand for 10 minutes. However, the quartz particles did not aggregate. It was 78, almost the same as before.
【0017】実施例3 融点60〜62℃のパラフィン10gに200mlの精
製水を加え、これを湯浴で70℃に加熱してパラフィン
を液状にした。この液に0.1gのポリオキシエチレン
ソルビタンラウレートを加えてから、該混合物をホモジ
ナイザーで1分間撹拌して水中油滴型エマルジョンを形
成させ、このエマルジョンを室温まで冷却後に固形物と
母液を濾別した。この固形物は平均粒径約10μmの粒
子状物で、乾燥した固形物1g中にポリオキシエチレン
ソルビタンラウレートが0.0015g含まれていた。
また、この固形物10gに200mlの精製水を加えて
撹拌すると容易に水中油滴型エマルジョンが形成され
た。Example 3 200 ml of purified water was added to 10 g of paraffin having a melting point of 60 to 62 ° C., and this was heated to 70 ° C. in a water bath to make the paraffin liquid. After 0.1 g of polyoxyethylene sorbitan laurate was added to this solution, the mixture was stirred with a homogenizer for 1 minute to form an oil-in-water emulsion. After cooling the emulsion to room temperature, the solid and mother liquor were filtered. Different. This solid was a particulate matter having an average particle diameter of about 10 μm, and 1 g of the dried solid contained 0.0015 g of polyoxyethylene sorbitan laurate.
When 200 ml of purified water was added to 10 g of the solid and stirred, an oil-in-water emulsion was easily formed.
【0018】実施例4 融点60〜62℃のパラフィン20gに200mlの精
製水を加え、これを湯浴で70℃に加熱してパラフィン
を液状にした。この液に0.1gのラウリルジエチレン
トリアミノ酢酸を加えてから、該混合物をホモジナイザ
ーで1分間撹拌して水中油滴型エマルジョンを形成さ
せ、このエマルジョンを室温まで冷却後に固形物と母液
を濾別した。この固形物は平均粒径約10μmの粒子状
物で、乾燥した固形物1g中にラウリルジエチレントリ
アミノ酢酸が0.001g含まれていた。また、この固
形物20gに200mlの精製水を加えて撹拌すると容
易に水中油滴型エマルジョンが形成された。Example 4 200 ml of purified water was added to 20 g of paraffin having a melting point of 60 to 62 ° C., and this was heated to 70 ° C. in a water bath to make the paraffin liquid. After 0.1 g of lauryl diethylene triaminoacetic acid was added to this solution, the mixture was stirred with a homogenizer for 1 minute to form an oil-in-water emulsion, and after cooling the emulsion to room temperature, a solid substance and a mother liquor were separated by filtration. . This solid was a particulate matter having an average particle size of about 10 μm, and 1 g of the dried solid contained 0.001 g of lauryldiethylenetriaminoacetic acid. When 200 ml of purified water was added to 20 g of the solid and stirred, an oil-in-water emulsion was easily formed.
【0019】実施例5 融点60〜62℃のパラフィン5gとステアリルアルコ
ール5gの混合物にステアリル硫酸エステルナトリウム
塩を0.12g加え、これを湯浴で70℃に加熱して均
一液とした。この液に、70℃に加熱して精製水250
mlを加えてホモジナイザーで1分間撹拌して水中油滴
型エマルジョンを形成させ、このエマルジョンを室温ま
で冷却後に固形物と母液を濾別した。この固形物は平均
粒径約10μmの粒子状物で、乾燥した固形物1g中に
ステアリル硫酸エステルナトリウム塩が0.003g含
まれていた。また、この固形物10gに200mlの精
製水を加えて撹拌すると容易に水中油滴型エマルジョン
が形成された。Example 5 0.12 g of sodium stearyl sulfate was added to a mixture of 5 g of paraffin having a melting point of 60 to 62 ° C. and 5 g of stearyl alcohol, and the mixture was heated to 70 ° C. in a water bath to obtain a uniform liquid. This solution was heated to 70 ° C. and purified water 250
Then, the mixture was stirred with a homogenizer for 1 minute to form an oil-in-water emulsion. After cooling the emulsion to room temperature, a solid substance and a mother liquor were separated by filtration. This solid was a particulate matter having an average particle size of about 10 μm, and 0.003 g of sodium stearyl sulfate was contained in 1 g of the dried solid. When 200 ml of purified water was added to 10 g of the solid and stirred, an oil-in-water emulsion was easily formed.
【0020】[0020]
【発明の効果】本発明の親水性固体粒子を懸濁粒子の凝
集剤にすると、従来の凝集剤使用時と異なって、凝集分
離後の廃液中に凝集剤が残存せず、そのため廃液中に凝
集剤が溶存することで起こる廃液処理困難や環境汚染等
の問題が起こらない。本発明の親水性固体粒子を医薬や
化粧品用の油状基剤として使用すると、該固体粒子に精
製水を加えるだけで容易にクリーム状又は乳液状の製品
を製造することができる。According to the present invention, when the hydrophilic solid particles of the present invention are used as a flocculant for suspended particles, unlike the conventional flocculant, the flocculant does not remain in the waste liquid after the flocculation and separation, and therefore, the waste liquid Problems such as difficulties in waste liquid treatment and environmental pollution caused by dissolution of the coagulant do not occur. When the hydrophilic solid particles of the present invention are used as an oil base for medicines or cosmetics, a creamy or milky product can be easily produced simply by adding purified water to the solid particles.
フロントページの続き (72)発明者 荒井 怜 茨城県つくば市小野川16番3 工業技術 院資源環境技術総合研究所内 (72)発明者 坂本 宏 茨城県つくば市小野川16番3 工業技術 院資源環境技術総合研究所内Continued on the front page (72) Inventor Rei Arai 16-3 Onogawa Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Hiroshi Sakamoto 16-3 Onogawa Tsukuba, Ibaraki Pref. In the laboratory
Claims (5)
び疎水基を有する界面活性剤とから成り、該界面活性剤
が該疎水基を介して該固体粒子と結合しており、かつ該
界面活性剤の結合量は前記非水溶性固体粒子の0.01
〜0.6重量%であることを特徴とする表面に親水基を
有する親水性固体粒子。1. A consists of a surfactant having a hot-melt water-insoluble solid particles and the hydrophilic and hydrophobic groups are bound with the solid particles said surfactant through said hydrophobic water group, and The
The amount of the surfactant bound is 0.01% of the water-insoluble solid particles.
A hydrophilic solid particle having a hydrophilic group on the surface, characterized in that the content of the hydrophilic solid particle is 0.6 to 0.6% by weight
在下に水中で粒子化して水中油滴型エマルジョンを形成
する工程と、該エマルジョンを冷却して該非水溶性物質
の溶融液粒子を固体粒子化する工程と、該固体粒子を水
中から分離する工程から成ることを特徴とする請求項1
に記載した親水基を有する親水性固体粒子の製造方法。2. A step of granulating a melt of a water-insoluble substance in water in the presence of a surfactant to form an oil-in-water emulsion, and cooling the emulsion to form particles of the melt of the water-insoluble substance. 2. The step of converting the solid particles into solid particles, and the step of separating the solid particles from water.
3. The method for producing hydrophilic solid particles having a hydrophilic group described in 1. above.
の溶融液を水中で液滴化して水中油滴型エマルジョンを
形成する工程と、該エマルジョンを冷却して該非水溶性
物質の溶融液粒子を固体粒子化する工程と、該固体粒子
を水中から分離する工程からなることを特徴とする請求
項1に記載した親水基を有する親水性固体粒子の製造方
法。3. A step of forming a droplet of a water-insoluble substance in which a surfactant is dissolved in water to form an oil-in-water emulsion, and cooling the emulsion to melt the water-insoluble substance. 2. The method for producing hydrophilic solid particles having a hydrophilic group according to claim 1, comprising a step of converting the liquid particles into solid particles and a step of separating the solid particles from water.
性親水基及び疎水基を有する陰イオン界面活性剤とから
なり、該界面活性剤が該疎水基を介して該固体粒子と結
合しており、かつ該界面活性剤の結合量は前記非水溶性
固体粒子の0.01〜0.6重量%である表面に陰イオ
ン性親水基を有する親水性固体粒子からなることを特徴
とする懸濁粒子の凝集剤。4. A method comprising: heat-fusible, water-insoluble solid particles; and an anionic surfactant having an anionic hydrophilic group and a hydrophobic group, wherein the surfactant binds to the solid particles via the hydrophobic group. And the amount of the surfactant bound is the water-insoluble
An aggregating agent for suspended particles, comprising hydrophilic solid particles having an anionic hydrophilic group on the surface which accounts for 0.01 to 0.6% by weight of the solid particles.
性親水基及び疎水基を有する陽イオン界面活性剤とから
なり、該界面活性剤が該疎水基を介して該固体粒子と結
合しており、かつ該界面活性剤の結合量は前記非水溶性
固体粒子の0.01〜0.6重量%である表面に陽イオ
ン性親水基を有する親水性固体粒子からなることを特徴
とする懸濁粒子の凝集剤。5. A method comprising: heat-fusible, water-insoluble solid particles; and a cationic surfactant having a cationic hydrophilic group and a hydrophobic group, wherein the surfactant is bonded to the solid particles via the hydrophobic group. And the amount of the surfactant bound is the water-insoluble
A flocculant for suspended particles, comprising hydrophilic solid particles having a cationic hydrophilic group on the surface, which is 0.01 to 0.6% by weight of the solid particles.
Priority Applications (1)
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JP08008978A JP3125023B2 (en) | 1996-01-23 | 1996-01-23 | Hydrophilic solid particles having a hydrophilic group on the surface, method for producing the same, and flocculant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP08008978A JP3125023B2 (en) | 1996-01-23 | 1996-01-23 | Hydrophilic solid particles having a hydrophilic group on the surface, method for producing the same, and flocculant |
Publications (2)
Publication Number | Publication Date |
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JPH09192408A JPH09192408A (en) | 1997-07-29 |
JP3125023B2 true JP3125023B2 (en) | 2001-01-15 |
Family
ID=11707790
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