JP2738640B2 - Oil absorbing material - Google Patents
Oil absorbing materialInfo
- Publication number
- JP2738640B2 JP2738640B2 JP5246491A JP24649193A JP2738640B2 JP 2738640 B2 JP2738640 B2 JP 2738640B2 JP 5246491 A JP5246491 A JP 5246491A JP 24649193 A JP24649193 A JP 24649193A JP 2738640 B2 JP2738640 B2 JP 2738640B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- parts
- absorbing
- monomer
- meth
- 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
- Treatment Of Liquids With Adsorbents In General (AREA)
- Removal Of Floating Material (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は吸油材に関する。さらに
詳しくは、油水混合系からでも広範な種類の油に対して
多量の油を吸収して膨潤し、しかも吸収した油の保油性
能に優れ、且つ吸油速度を著しく向上した貯蔵や取扱い
が容易な吸油材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil absorbing material. More specifically, a large amount of oil can be absorbed and swelled for a wide range of oils even from an oil-water mixed system, and the absorbed oil has excellent oil retention performance and has a significantly improved oil absorption rate, and is easy to store and handle. Oil absorbing material.
【０００２】[0002]
【従来の技術】近年、海上への流出油や廃水中の油分の
回収が環境保全上大きな問題となっている。また、家庭
や工場で廃棄される小規模の廃油や工場における機械油
などの漏油の簡便な処理方法が強く望まれている。2. Description of the Related Art In recent years, recovery of oil spilled into the sea and oil in wastewater has become a major problem in environmental conservation. Further, there is a strong demand for a simple treatment method for small-scale waste oil discarded in homes and factories and for leakage of machine oil and the like in factories.
【０００３】これらの流出油や廃水中の油分の回収ある
いは廃油や漏油の処理の有力な手段の一つとして、吸油
材で油を吸着したのち焼却その他の後処理を行なう手法
が従来より用いられている。このような吸油材として、
例えばポリプロピレン繊維、ポリスチレン繊維、ポリエ
チレン繊維などの疎水性繊維やその不織布からなる合成
繊維系吸油材が使用されていた。しかし、従来の合成繊
維系吸油材は、吸油作用が毛細管現象で吸油材中に存在
する空隙に油を吸着保持することによるため、吸油後の
保油性能に劣っており、低粘性油に対しては実質的に保
油能がなく、また粘性油に対してもわずかな外圧により
容易に吸収していた油を再放出するため液ダレを生じ易
く、後処理がきわめて煩雑になる欠点を有していた。ま
た、油水混合系の油分や水面に浮上している薄膜状油の
回収に適用した場合、水分を多量に吸収するため油の回
収率が悪く、しかも吸油材が水中に沈むため回収が困難
であったり、回収後の燃焼に不都合が生じる問題点があ
った。[0003] As one of the effective means of collecting oil in spilled oil or wastewater or treating waste oil or oil leakage, a method of adsorbing oil with an oil absorbing material and then performing post-treatment such as incineration has conventionally been used. Have been. As such an oil absorbing material,
For example, synthetic fiber-based oil-absorbing materials composed of hydrophobic fibers such as polypropylene fibers, polystyrene fibers, and polyethylene fibers and nonwoven fabrics thereof have been used. However, conventional synthetic fiber-based oil-absorbing materials are inferior in oil-retaining performance after oil absorption because the oil-absorbing action is due to the absorption and retention of oil in the voids existing in the oil-absorbing material by capillary action. Has the disadvantage that it has virtually no oil-retaining ability and easily re-releases the oil that was easily absorbed by viscous oil even with a slight external pressure, causing liquid dripping and making post-treatment extremely complicated. Was. In addition, when applied to the recovery of oil components in oil-water mixed systems and thin film oil floating on the water surface, the oil recovery rate is poor due to the absorption of a large amount of water, and the recovery is difficult because the oil absorbing material sinks in the water. And there is a problem that inconvenience occurs in combustion after recovery.
【０００４】これらの問題点を解決する手段として、本
発明者らは特定の架橋重合体の粒状物を疎水性多孔質布
からなる袋中に充填してなる吸油材（特開平４−１５２
８６）を報告している。この吸油材は、吸油作用が疎水
性構造からなる架橋重合体の分子内部に油を吸収して膨
潤することによるため、油水混合系の油分や水面に浮上
している薄膜状油に対しても油のみを選択的に吸収し、
しかも一旦吸収した油に対する保油能に優れるなどの利
点を有している。しかし、この吸油材は、合成繊維系吸
油材と比較して油の吸収に要する時間がきわめて長いと
いう欠点を有しており、特に高粘性油の吸油速度が小さ
いという問題点があった。As a means for solving these problems, the present inventors have proposed an oil-absorbing material (Japanese Patent Application Laid-Open No. 4-152) in which a particulate material of a specific crosslinked polymer is filled in a bag made of a hydrophobic porous cloth.
86). This oil-absorbing material absorbs oil inside the molecule of the crosslinked polymer having a hydrophobic structure and swells, so it can absorb oils in oil-water mixed systems and thin film oils floating on the water surface. Selectively absorbs only oil,
In addition, it has advantages such as excellent oil retaining ability for oil once absorbed. However, this oil-absorbing material has a disadvantage that the time required for oil absorption is extremely long as compared with a synthetic fiber-based oil-absorbing material, and in particular, has a problem that the oil absorbing speed of high-viscosity oil is low.
【０００５】そこで高粘性油に対する吸油速度を向上さ
せるため、これらの吸油材に用いられる架橋重合体を微
粒状に加工し吸油材の表面積を増大させる工夫がなされ
ている。しかし、架橋重合体の微粒化に伴い粒子同士の
凝集が起こり易くなるため、実際には期待される十分な
吸油速度が得られなかった。また、低粘性油に対する吸
収に際しては、油の接触面付近の架橋重合体のみが短時
間で油を吸収して膨潤するために、粒子間への油の通液
が阻害されるというゲルブロック現象によって、実質上
吸油速度が低下する現象さえ生じることがあった。従っ
て、これらの吸油材は、油の流出事故時などの油を短時
間に吸収処理することが要求される分野には適応が困難
である欠点を有していた。[0005] In order to improve the oil absorption rate for highly viscous oils, a method has been devised in which the crosslinked polymer used in these oil absorbents is processed into fine particles to increase the surface area of the oil absorbent. However, agglomeration of the particles is likely to occur as the crosslinked polymer becomes finer, and thus, a sufficient expected oil absorption rate cannot be obtained in practice. In addition, when absorbing low-viscosity oil, only the crosslinked polymer near the oil contact surface absorbs the oil in a short time and swells, so that the gel block phenomenon that the passage of the oil between the particles is hindered. As a result, a phenomenon in which the oil absorption speed substantially decreases may occur. Therefore, these oil-absorbing materials have a drawback that they are difficult to adapt to a field where it is required to absorb oil in a short time, such as in an oil spill accident.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、従来の吸油
材が有する前記問題点を解決するものである。すなわ
ち、本発明の目的は、広範な種類の油に対して、また油
水混合系からでも多量の油を吸収して膨潤し、しかも吸
収した油の保油性能に優れ、且つ吸油速度を著しく向上
した貯蔵や取扱いが容易な吸油材を提供することにあ
る。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional oil absorbing material. In other words, an object of the present invention is to absorb a large amount of oil from a wide variety of oils and even from an oil-water mixed system and to swell, and to further improve the oil retaining performance of the absorbed oil and significantly improve the oil absorption rate. Another object of the present invention is to provide an oil absorbing material which is easy to store and handle.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、特定の吸
油性架橋重合体と特定の疎水性無機化合物とを混合複合
化した吸油剤組成物を容器中に充填することによって前
記目的が達成されることを見いだし、本発明を完成する
に至った。Means for Solving the Problems The present inventors have achieved the above object by filling an oil absorbing composition obtained by mixing and compounding a specific oil absorbing cross-linked polymer and a specific hydrophobic inorganic compound into a container. It has been found that this has been achieved, and the present invention has been completed.
【０００８】すなわち本発明は、溶解度パラメーター
（ＳＰ値）が９以下の単量体を主成分としてなる分子中
に１個の重合性不飽和基を有する単量体（Ａ）９６〜９
９．９９９重量％および分子中に少なくとも２個の重合
性不飽和基を有する架橋性単量体（Ｂ）０．００１〜４
重量％（ただし単量体（Ａ）および（Ｂ）の合計は１０
０重量％である）からなる単量体成分を重合して得られ
る吸油性架橋重合体（Ｉ）３０〜９９．５重量部および
メタノール値（平均粒径が０．０１〜３００μｍの範囲
の粉体がメタノール水溶液に湿潤し始めるときの水溶液
中のメタノール容積％）が２５％以上の疎水性無機化合
物（ＩＩ）０．５〜７０重量部からなる吸油剤組成物
（ＩＩＩ）を油透過性材料からなる容器中に充填してな
る吸油材に関するものである。That is, the present invention relates to a monomer (A) having one polymerizable unsaturated group in a molecule containing a monomer having a solubility parameter (SP value) of 9 or less as a main component.
9.999% by weight and a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule, 0.001 to 4
% By weight (the sum of the monomers (A) and (B) is 10
0 to 99.5 parts by weight of an oil-absorbent crosslinked polymer (I) obtained by polymerizing a monomer component consisting of 0% by weight) and a methanol value ( average particle size of 0.01 to 300 µm ).
Oil permeates oil-absorbing composition (III) consisting of 0.5 to 70 parts by weight of hydrophobic inorganic compound (II) having a volume of 25% or more of a hydrophobic inorganic compound (II) when the powder starts to wet in aqueous methanol solution). The present invention relates to an oil absorbing material filled in a container made of a conductive material.
【０００９】[0009]
【作用】溶解度パラメーター（ＳＰ値）は、化合物の極
性を表す尺度として一般的に用いられており、本発明で
はＳｍａｌｌの計算式にＨｏｙの凝集エネルギー定数を
代入して導いた値を適用するものとし、単位（ｃａｌ／
ｃｍ3）1/2で表せる。The solubility parameter (SP value) is generally used as a measure of the polarity of a compound. In the present invention, a value derived by substituting the aggregation energy constant of Hoy into the calculation formula of Small is applied. And the unit (cal /
cm 3 ) 1/2 .
【００１０】本発明で用いられる単量体（Ａ）の主成分
を構成する単量体は、溶解度パラメーター（ＳＰ値）が
９以下で分子中に１個の重合性不飽和基を有する単量体
であり、溶解度パラメーター（ＳＰ値）が９を越える単
量体を単量体（Ａ）の主成分に用いると、吸油性能の不
十分な架橋重合体しか得られないため好ましくない。The monomer constituting the main component of the monomer (A) used in the present invention is a monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule. When a monomer having a solubility parameter (SP value) of more than 9 is used as the main component of the monomer (A), only a crosslinked polymer having insufficient oil absorption performance is obtained, which is not preferable.
【００１１】溶解度パラメーター（ＳＰ値）が９以下で
分子中に１個の重合性不飽和基を有する単量体として
は、例えば、メチル（メタ）アクリレート、エチル（メ
タ）アクリレート、プロピル（メタ）アクリレート、ブ
チル（メタ）アクリレート、iso-ブチル（メタ）アクリ
レート、t-ブチル（メタ）アクリレート、２−エチルヘ
キシル（メタ）アクリレート、n-オクチル（メタ）アク
リレート、ドデシル（メタ）アクリレート、ステアリル
（メタ）アクリレート、フェニル（メタ）アクリレー
ト、オクチルフェニル（メタ）アクリレート、ノニルフ
ェニル（メタ）アクリレート、ジノニルフェニル（メ
タ）アクリレート、シクロヘキシル（メタ）アクリレー
ト、メンチル（メタ）アクリレート、イソボルニル（メ
タ）アクリレート、ジブチルマレエート、ジドデシルマ
レエート、ドデシルクロトネート、ジドデシルイタコネ
ートなどの不飽和カルボン酸エステル；（ジ）ブチル
（メタ）アクリルアミド、（ジ）ドデシル（メタ）アク
リルアミド、（ジ）ステアリル（メタ）アクリルアミ
ド、（ジ）ブチルフェニル（メタ）アクリルアミド、
（ジ）オクチルフェニル（メタ）アクリルアミドなどの
炭化水素基を有する（メタ）アクリルアミド；１−ヘキ
セン、１−オクテン、イソオクテン、１−ノネン、１−
デセン、１−ドデセンなどのα−オレフィン；ビニルシ
クロヘキサンなどの脂環式ビニル化合物；ドデシルアリ
ルエーテルなどの炭化水素基を有するアリルエーテル；
カプロン酸ビニル、ラウリン酸ビニル、パルミチン酸ビ
ニル、ステアリン酸ビニルなどの炭化水素基を有するビ
ニルエステル；ブチルビニルエーテル、ドデシルビニル
エーテルなどの炭化水素基を有するビニルエーテル；ス
チレン、t-ブチルスチレン、オクチルスチレンなどの芳
香族ビニル化合物などをあげることができ、これらの単
量体を１種または２種以上用いることができる。これら
の中でも、より優れた吸油性能および保油性能を与える
単量体として、少なくとも１個の炭素数３〜３０の脂肪
族炭化水素基を有し、かつアルキル（メタ）アクリレー
ト、アルキルアリール（メタ）アクリレート、アルキル
（メタ）アクリルアミド、アルキルアリール（メタ）ア
クリルアミド、脂肪酸ビニルエステル、アルキルスチレ
ンおよびα−オレフィンからなる群より選ばれる少なく
とも１種の不飽和化合物（ａ）を主成分としてなる単量
体（Ａ）が特に好ましい。Examples of the monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in a molecule include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) Acrylate, phenyl (meth) acrylate, octylphenyl (meth) acrylate, nonylphenyl (meth) acrylate, dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, dibutyl Unsaturated carboxylic acid esters such as maleate, didodecyl maleate, dodecyl rotonate, didodecyl itaconate; (di) butyl (meth) acrylamide, (di) dodecyl (meth) acrylamide, (di) stearyl (meth) acrylamide, (Di) butylphenyl (meth) acrylamide,
(Di) acrylamide having a hydrocarbon group such as (di) octylphenyl (meth) acrylamide; 1-hexene, 1-octene, isooctene, 1-nonene, 1-
Α-olefins such as decene and 1-dodecene; alicyclic vinyl compounds such as vinylcyclohexane; allyl ethers having a hydrocarbon group such as dodecyl allyl ether;
Vinyl esters having a hydrocarbon group such as vinyl caproate, vinyl laurate, vinyl palmitate and vinyl stearate; vinyl ethers having a hydrocarbon group such as butyl vinyl ether and dodecyl vinyl ether; styrene, t-butyl styrene, octyl styrene and the like Examples thereof include aromatic vinyl compounds, and one or more of these monomers can be used. Among these, as a monomer that provides better oil absorption performance and oil retention performance, it has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, and has an alkyl (meth) acrylate and an alkylaryl (meth). A) a monomer having as a main component at least one unsaturated compound (a) selected from the group consisting of acrylates, alkyl (meth) acrylamides, alkylaryl (meth) acrylamides, fatty acid vinyl esters, alkylstyrenes and α-olefins (A) is particularly preferred.
【００１２】このような溶解度パラメーター（ＳＰ値）
が９以下の単量体の単量体（Ａ）中における使用量は、
単量体（Ａ）の全体量に対して５０重量％以上、より好
ましくは７０重量％以上となる割合である。溶解度パラ
メーター（ＳＰ値）が９以下の単量体の単量体（Ａ）中
の使用量が５０重量％未満では、吸油性能や保油性能に
劣った架橋重合体しか得られない。Such a solubility parameter (SP value)
Is 9 or less in the monomer (A),
The proportion is at least 50% by weight, more preferably at least 70% by weight, based on the total amount of the monomer (A). When the amount of the monomer having a solubility parameter (SP value) of 9 or less in the monomer (A) is less than 50% by weight, only a crosslinked polymer having poor oil absorption performance and oil retention performance can be obtained.
【００１３】したがって、本発明では、単量体（Ａ）中
に溶解度パラメーター（ＳＰ値）が９以下の単量体が５
０重量％以上含有される必要があるが、単量体（Ａ）中
に５０重量％未満の割合で溶解度パラメーター（ＳＰ
値）が９を越える分子中に１個の重合性不飽和基を有す
る単量体が含有されてもよい。このような単量体として
は、例えば（メタ）アクリル酸、アクリロニトリル、無
水マレイン酸、フマル酸、ヒドロキシエチル（メタ）ア
クリレート、ポリエチレングリコール（メタ）アクリレ
ート、メトキシポリエチレングリコール（メタ）アクリ
レートなどをあげることができる。Therefore, in the present invention, the monomer (A) having a solubility parameter (SP value) of 9 or less in 5
However, the solubility parameter (SP) in the monomer (A) should be less than 50% by weight.
(Value) of more than 9 may contain a monomer having one polymerizable unsaturated group. Examples of such a monomer include (meth) acrylic acid, acrylonitrile, maleic anhydride, fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. Can be.
【００１４】本発明で用いられる架橋性単量体（Ｂ）の
例としては、エチレングリコールジ（メタ）アクリレー
ト、ジエチレングリコールジ（メタ）アクリレート、ポ
リエチレングリコールジ（メタ）アクリレート、ポリエ
チレングリコール−ポリプロピレングリコールジ（メ
タ）アクリレート、プロピレングリコールジ（メタ）ア
クリレート、ポリプロピレングリコールジ（メタ）アク
リレート、１，３−ブチレングリコールジ（メタ）アク
リレート、ネオペンチルグリコールジ（メタ）アクリレ
ート、１，６−ヘキサンジオールジ（メタ）アクリレー
ト、Ｎ，Ｎ´−メチレンビスアクリルアミド、Ｎ，Ｎ´
−プロピレンビスアクリルアミド、グリセリントリ（メ
タ）アクリレート、トリメチロールプロパントリ（メ
タ）アクリレート、テトラメチロールメタンテトラ（メ
タ）アクリレート、多価アルコール（例えばグリセリ
ン、トリメチロールプロパンあるいはテトラメチロール
メタン）のアルキレンオキシド付加物と（メタ）アクリ
ル酸とのエステル化によって得られる多官能（メタ）ア
クリレートやジビニルベンゼンなどをあげることがで
き、これらの架橋性単量体を１種または２種以上用いる
ことができる。Examples of the crosslinkable monomer (B) used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polyethylene glycol-polypropylene glycol diacrylate. (Meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( Meth) acrylate, N, N'-methylenebisacrylamide, N, N '
-Alkylene oxide adducts of propylene bisacrylamide, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polyhydric alcohols (for example, glycerin, trimethylolpropane or tetramethylolmethane) And polyfunctional (meth) acrylates and divinylbenzenes obtained by esterification with methacrylic acid. One or more of these crosslinkable monomers can be used.
【００１５】吸油性架橋重合体（Ｉ）を製造する際に用
いられる単量体成分中の単量体（Ａ）および架橋性単量
体（Ｂ）の比率は、単量体（Ａ）および架橋性単量体
（Ｂ）の合計に対して、単量体（Ａ）が９６〜９９．９
９９重量％の範囲、架橋性単量体（Ｂ）が０．００１〜
４重量％の範囲である。The ratio of the monomer (A) and the crosslinkable monomer (B) in the monomer components used for producing the oil-absorbent crosslinked polymer (I) is as follows. The monomer (A) is 96 to 99.9 based on the total amount of the crosslinkable monomer (B).
In a range of 99% by weight, the crosslinkable monomer (B) is 0.001 to
It is in the range of 4% by weight.
【００１６】単量体（Ａ）が９６重量％未満であったり
架橋性単量体（Ｂ）が４重量％を越えると、得られる架
橋重合体の架橋密度が高くなりすぎて多量の油を吸収で
きなくなるため好ましくない。また、単量体（Ａ）が９
９．９９９重量％を越えたり架橋性単量体（Ｂ）が０．
００１重量％未満では、得られる架橋重合体の油に対す
る可溶性が増大して、吸油後に架橋重合体が流動化し吸
油材としての性能が得られないため好ましくない。If the amount of the monomer (A) is less than 96% by weight or the amount of the crosslinkable monomer (B) exceeds 4% by weight, the cross-linking density of the obtained cross-linked polymer becomes too high and a large amount of oil It is not preferable because it cannot be absorbed. Further, when the monomer (A) is 9
Exceeds 9.999% by weight or the amount of the crosslinkable monomer (B) is 0.1%.
If the amount is less than 001% by weight, the solubility of the obtained cross-linked polymer in oil increases, and the cross-linked polymer becomes fluid after oil absorption, so that the performance as an oil-absorbing material cannot be obtained.
【００１７】本発明における吸油性架橋重合体（Ｉ）
は、例えば前記単量体成分を水性媒体中にポリビニルア
ルコール、ヒドロキシエチルセルロース、ゼラチンなど
の保護コロイド剤やアルキルスルホン酸ナトリウム、ア
ルキルベンゼンスルホン酸ナトリウム、ポリオキシエチ
レンアルキルエーテル、脂肪酸石鹸などの界面活性剤の
存在下に分散させ油溶性ラジカル重合開始剤により懸濁
重合することにより製造できる。また必要により単量体
成分を水不溶性の有機溶剤に溶解させてから懸濁重合す
ることもできる。油溶性ラジカル重合開始剤としては、
例えばベンゾイルパーオキシド、ラウロイルパーオキシ
ド、クメンハイドロパーオキシドなどの有機過酸化物；
２，２´−アゾビスイソブチロニトリル、２，２´−ア
ゾビスジメチルバレロニトリルなどのアゾ化合物などを
挙げることができ、一般に単量体成分に対して０．１〜
５重量％の範囲で用いることができる。重合温度は、単
量体成分の種類や重合開始剤の種類により０〜１５０℃
の範囲で適宜選択することができる。The oil-absorbing crosslinked polymer (I) in the present invention
For example, in the aqueous medium polyvinyl alcohol, hydroxyethyl cellulose, a protective colloid agent such as gelatin and sodium alkyl sulfonate, sodium alkyl benzene sulfonate, polyoxyethylene alkyl ether, a surfactant such as fatty acid soap, for example, It can be produced by dispersing in the presence and subjecting to suspension polymerization with an oil-soluble radical polymerization initiator. If necessary, the suspension polymerization may be carried out after dissolving the monomer component in a water-insoluble organic solvent. As the oil-soluble radical polymerization initiator,
Organic peroxides such as, for example, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide;
Azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobisdimethylvaleronitrile can be exemplified.
It can be used in the range of 5% by weight. The polymerization temperature is 0 to 150 ° C. depending on the type of the monomer component and the type of the polymerization initiator.
Can be appropriately selected within the range.
【００１８】また、本発明において吸油性架橋重合体
（Ｉ）を製造する方法として、塊状重合で吸油性架橋重
合体（Ｉ）を重合した後、粉砕などの操作を加えて粒度
調整を行なう方法をあげることができる。塊状重合は例
えば、単量体成分を上記重合開始剤の存在下、型に流し
込み、５０〜１５０℃の条件下に重合を行なえばよい。In the present invention, as a method for producing the oil-absorbing crosslinked polymer (I), the oil-absorbing crosslinked polymer (I) is polymerized by bulk polymerization, and then the particle size is adjusted by adding operations such as pulverization. Can be given. In the bulk polymerization, for example, the monomer component may be poured into a mold in the presence of the above-mentioned polymerization initiator, and the polymerization may be performed at 50 to 150 ° C.
【００１９】本発明において吸油性架橋重合体（Ｉ）
は、懸濁重合時にホモミキサーなどによるプレ懸濁工程
の導入や重合時の攪拌動力を調節することにより、平均
粒径０．５〜５００μｍの範囲の粒状物とすることが好
ましい。架橋重合体（Ｉ）の粒状物の平均粒径が０．５
μｍ未満では、粒状物同士の凝集に基づくママコ現象の
ために表面積が低下し、吸油速度の向上した吸油剤を得
ることが困難となる。また、吸油性架橋重合体（Ｉ）の
粒状物の平均粒径が５００μｍを越えると、架橋重合体
の表面積の低下に伴って吸油速度も低下するため好まし
くない。In the present invention, the oil-absorbing crosslinked polymer (I)
The suspension is preferably formed into a granular material having an average particle size in the range of 0.5 to 500 μm by introducing a pre-suspension step using a homomixer or the like during suspension polymerization or adjusting the stirring power during polymerization. The average particle size of the granular material of the crosslinked polymer (I) is 0.5
If it is less than μm, the surface area decreases due to the Mamako phenomenon based on the aggregation of the granular materials, and it becomes difficult to obtain an oil absorbing agent with an improved oil absorption rate. On the other hand, if the average particle size of the oil-absorbent crosslinked polymer (I) exceeds 500 μm, the oil absorption rate decreases with a decrease in the surface area of the crosslinked polymer, which is not preferable.
【００２０】メタノール値（以下Ｍ値ということがあ
る）は、疎水性無機化合物の疎水化度を表わす尺度とし
て一般的に用いられており、メタノール水溶液に疎水性
無機化合物が湿潤しはじめる時のメタノールの容積％で
表わされる。本発明においては、所定濃度に調製された
メタノール水溶液中に疎水性無機化合物の粉体を入れ、
手振りにより２度振とうした後の該粉体の湿潤の有無に
より測定した値を採用するものとする。たとえば、Ｍ値
３０％の疎水性無機化合物（ＩＩ）とは、メタノールの
容積％が３０％以上のメタノール水溶液に湿潤し且つメ
タノールの容積％が３０％未満のメタノール水溶液に湿
潤しない疎水性無機化合物である。The methanol value (hereinafter sometimes referred to as M value) is generally used as a measure of the degree of hydrophobicity of a hydrophobic inorganic compound .
It is expressed as a percentage by volume of methanol when the inorganic compound starts to wet. In the present invention, a powder of a hydrophobic inorganic compound is placed in a methanol aqueous solution prepared at a predetermined concentration,
The value measured by the presence or absence of wetness of the powder after shaking twice by hand is adopted. For example, a hydrophobic inorganic compound (II) having an M value of 30% refers to a hydrophobic inorganic compound which is wetted by a methanol aqueous solution having a volume percentage of methanol of 30% or more and not wetted by a methanol aqueous solution having a methanol volume percentage of less than 30% . It is.
【００２１】本発明における疎水性無機化合物（II）
は、メタノール値が２５％以上の疎水化度を有するもの
であれば特に制限はなく、例えば酸化亜鉛、アルミナ
（酸化アルミニウム）、ケイ酸アルミニウム、シリカ
（酸化ケイ素）、酸化カルシウム、炭酸カルシウム、酸
化チタン、チタン酸バリウム、酸化鉄、硫酸バリウム、
炭酸バリウム、酸化バリウム、二酸化マンガン、炭酸マ
ンガン、炭酸マグネシウム、酸化マグネシウムなどの疎
水化変性物をあげることができ、これらの１種または２
種以上用いることができる。これらの疎水性無機化合物
の中でも種々の粒径の粉体として入手が容易な疎水性シ
リカや疎水性アルミナが好ましい。The hydrophobic inorganic compound (II) in the present invention
Is not particularly limited as long as the methanol value has a hydrophobicity of 25% or more. For example, zinc oxide, alumina (aluminum oxide), aluminum silicate, silica (silicon oxide), calcium oxide, calcium carbonate, oxide Titanium, barium titanate, iron oxide, barium sulfate,
Hydrophobized modified products such as barium carbonate, barium oxide, manganese dioxide, manganese carbonate, magnesium carbonate, magnesium oxide, etc., and one or two of these can be mentioned.
More than one species can be used. Among these hydrophobic inorganic compounds, hydrophobic silica and hydrophobic alumina, which are easily available as powders of various particle sizes, are preferred.
【００２２】また、前記無機化合物を疎水化変性し疎水
性無機化合物（II）を得る方法としては特に制限はな
く、例えば無機化合物の粉体の表面を化学的あるいは物
理的に不活性化すればよく、例えばアルキルアルコキシ
シラン、アルキルハロゲン化シランなどのシランカップ
リング剤を用いる方法、ジメチルシロキサンなどのポリ
シロキサンを用いる方法、合成ワックスや天然ワックス
を用いる方法、カルシウムなどにより金属表面処理する
方法などをあげることができる。The method for obtaining a hydrophobic inorganic compound (II) by hydrophobizing the inorganic compound to obtain a hydrophobic inorganic compound (II) is not particularly limited. For example, if the surface of the inorganic compound powder is chemically or physically inactivated. For example, a method using a silane coupling agent such as an alkylalkoxysilane or an alkyl halide silane, a method using a polysiloxane such as dimethylsiloxane, a method using a synthetic wax or a natural wax, and a method of treating a metal surface with calcium or the like can be used. I can give it.
【００２３】本発明で用いられる疎水性無機化合物（I
I）は、平均粒径が０．０１〜３００μｍの範囲の粉体
であることが好ましい。この平均粒径が０．０１μｍ未
満では、粉体同士の凝集が起こり、吸油速度を低下させ
るため好ましくない。また、この平均粒径が３００μｍ
を越えると、吸油性架橋重合体（Ｉ）との相乗効果が発
現され難く、吸油速度を向上させることができないため
好ましくない。The hydrophobic inorganic compound (I) used in the present invention
I) is preferably a powder having an average particle size in the range of 0.01 to 300 μm. If the average particle size is less than 0.01 μm, the powders are aggregated with each other and the oil absorption rate is reduced, which is not preferable. The average particle size is 300 μm
If it exceeds, the synergistic effect with the oil-absorbing crosslinked polymer (I) is hardly exhibited, and the oil-absorbing speed cannot be improved, which is not preferable.
【００２４】吸油性架橋重合体（Ｉ）および疎水性無機
化合物（II）を含有してなる吸油剤組成物（III）は、
これらの成分を混合して粒状物等に成形すればよい。粒
状物を製造するには、これらの成分を混合して造粒させ
ればよく、その製造方法には特に制限はない。混合方法
には湿式混合や乾式混合のいずれも採用することができ
る。湿式混合は、例えば吸油性架橋重合体（Ｉ）および
疎水性無機化合物（ＩＩ）を必要に応じて界面活性剤の
存在下に水性媒体中に混合分散した後、濾別乾燥する方
法等により行なうことができる。乾式混合は、例えばコ
ロイドミルやニーダーやミキサーにて吸油性架橋重合体
（Ｉ）と疎水性無機化合物（ＩＩ）を混合することによ
り行なうことができる。特に、湿式混合は、前記懸濁重
合で得られた吸油性架橋重合体（Ｉ）の水分散体をその
まま疎水性無機化合物（II）と混合できるため好まし
い。また、塊状重合で得られた架橋重合体（Ｉ）と疎水
性無機化合物（III）とを粉砕操作などで粒度調整を行
いながら混合する方法も採用することができる。The oil absorbing composition (III) comprising the oil absorbing cross-linked polymer (I) and the hydrophobic inorganic compound (II) comprises:
What is necessary is just to mix these components and shape | mold into a granular material. In order to produce granules, these components may be mixed and granulated, and the production method is not particularly limited. Either wet mixing or dry mixing can be adopted as the mixing method. The wet mixing is carried out, for example, by mixing and dispersing the oil-absorbing crosslinked polymer (I) and the hydrophobic inorganic compound (II) in an aqueous medium in the presence of a surfactant, if necessary, followed by filtration and drying. be able to. Dry mixing can be performed, for example, by mixing the oil-absorbent crosslinked polymer (I) and the hydrophobic inorganic compound (II) in a colloid mill, kneader or mixer. In particular, wet mixing is preferred because the aqueous dispersion of the oil-absorbent crosslinked polymer (I) obtained by the suspension polymerization can be directly mixed with the hydrophobic inorganic compound (II). Further, a method of mixing the crosslinked polymer (I) obtained by the bulk polymerization with the hydrophobic inorganic compound (III) while adjusting the particle size by a pulverizing operation or the like can also be adopted.
【００２５】なかでも、本発明においては、吸油性架橋
重合体（Ｉ）の粒状物と疎水性無機化合物（II）の粉体
とを水性媒体中に混合分散した後、両者を凝集造粒させ
てから造粒物を水性媒体から分離して得られる粒状物が
特に好ましい。また、この粒状物の平均粒径としては、
０．１〜５ｍｍの範囲が好ましい。In particular, in the present invention, after the particulate matter of the oil-absorbent crosslinked polymer (I) and the powder of the hydrophobic inorganic compound (II) are mixed and dispersed in an aqueous medium, the two are aggregated and granulated. Granules obtained by separating the granules from the aqueous medium afterwards are particularly preferred. Also, as an average particle size of the granular material,
A range of 0.1 to 5 mm is preferred.
【００２６】このようにして製造される吸油剤組成物
（III）中の吸油性架橋重合体（Ｉ）および疎水性無機
化合物（II）の配合割合は、吸油性架橋重合体（Ｉ）が
３０〜９９．５重量部および疎水性無機化合物（II）が
０．５〜７０重量部となる割合である。疎水性無機化合
物（II）の量が０．５重量部未満では、吸油性架橋重合
体（Ｉ）の粒子同士が凝集し、吸油剤の吸油速度が低下
するため好ましくない。また、疎水性無機化合物（II）
を７０重量部を越えて多量に使用すると、吸油材の吸油
量や保油性能が低下するため好ましくない。The mixing ratio of the oil-absorbent crosslinked polymer (I) and the hydrophobic inorganic compound (II) in the oil-absorbent composition (III) thus produced is such that the oil-absorbent crosslinked polymer (I) is 30%. -99.5 parts by weight and the proportion of the hydrophobic inorganic compound (II) is 0.5-70 parts by weight. If the amount of the hydrophobic inorganic compound (II) is less than 0.5 part by weight, the particles of the oil-absorbing crosslinked polymer (I) aggregate, and the oil-absorbing rate of the oil-absorbing agent decreases, which is not preferable. Also, a hydrophobic inorganic compound (II)
It is not preferable to use a large amount of over 70 parts by weight because the oil absorption of the oil absorbing material and the oil retaining performance are reduced.
【００２７】また吸油剤組成物（III）中には、吸油性
能を損なわない範囲の量で吸油性架橋重合体（Ｉ）と疎
水性無機化合物（II）以外の成分を含有してもよい。The oil absorbing composition (III) may contain components other than the oil absorbing cross-linked polymer (I) and the hydrophobic inorganic compound (II) in an amount that does not impair the oil absorbing performance.
【００２８】吸油剤組成物（III）中に含有できるその
他の成分として、例えば、シリカ、アルミナ、炭酸カル
シウムなどのメタノール値が２５％未満の親水性無機化
合物、金属石鹸などの有機酸金属塩類、ポリスチレンや
ポリエチレンや酢酸ビニルなどの樹脂類、ワックスなど
の有機化合物類、綿やパルプなどの繊維類などをあげる
ことができ、これらの１種または２種以上を用いること
ができる。Other components that can be contained in the oil-absorbing composition (III) include, for example, hydrophilic inorganic compounds having a methanol value of less than 25%, such as silica, alumina and calcium carbonate; organic acid metal salts such as metal soaps; Examples thereof include resins such as polystyrene, polyethylene, and vinyl acetate; organic compounds such as wax; and fibers such as cotton and pulp. One or more of these can be used.
【００２９】本発明に用いられる油透過性の材料の表面
状態は特に制限されるものでないが、その中でも多孔質
材料が好ましい。多孔質材料としては、それ自体が水に
溶解したり膨潤したりせず、しかも該材料からなる容器
の内部に充填する前記吸油剤組成物（III）を外部に漏
洩せず且つ油を容易に通過させるように吸油剤組成物
（III）の大きさより小さな孔径の孔を多数有するもの
であればよい。このような多孔質材料として例えば合成
繊維やパルプなどの天然繊維からなる布や紙、ステンレ
スメッシュなどの網などを用いることができる。中で
も、特に優れた吸油性能を有する吸油材を提供するもの
として、それ自体が疎水性を有し好ましくは油を吸着す
る高い親油性を有するポリプロピレンやポリエチレン等
のポリオレフィン、ポリエステル、ナイロンあるいはポ
リウレタンからなる群より選ばれる少なくとも１種の合
成樹脂製の不織布または織布であることが好ましい。ま
た、この多孔質材料からなる容器の形状としては特に制
限はなく、例えば布や紙製の袋状物、網製の篭状物など
を挙げることができる。The surface condition of the oil-permeable material used in the present invention is not particularly limited, but among them, a porous material is preferable. The porous material itself does not dissolve or swell in water, does not leak the oil absorbing agent composition (III) filled in a container made of the material to the outside, and easily removes oil. Any material may be used as long as it has a large number of pores having a diameter smaller than the size of the oil-absorbing agent composition (III) so that it can pass through. As such a porous material, for example, cloth or paper made of natural fibers such as synthetic fibers and pulp, and a mesh such as a stainless mesh can be used. Among them, to provide an oil-absorbing material having particularly excellent oil-absorbing performance, it is made of a polyolefin such as polypropylene or polyethylene, which itself has hydrophobicity and preferably has a high lipophilicity to adsorb oil, polyester, nylon or polyurethane. It is preferably at least one kind of synthetic resin non-woven fabric or woven fabric selected from the group. The shape of the container made of the porous material is not particularly limited, and examples thereof include a cloth or paper bag, a net basket, and the like.
【００３０】本発明の吸油材は、吸油性架橋重合体
（Ｉ）と疎水性無機化合物（II）からなる吸油剤組成物
（III）を油透過性材料からなる容器中に充填すること
によって得られる。充填方法は特に制限はなく、例えば
湿式混合後乾燥を施した粒状物や乾式混合によって得ら
れた粒状物を通常用いられる粉体充填装置などにより容
器中に充填する方法を挙げることができる。また、湿式
混合により得られた粒状物（III）の水分散体を容器中
に充填し、その後余剰の水を容器から排出させて乾燥す
る方法を採用することもできる。The oil absorbing material of the present invention is obtained by filling an oil absorbing composition (III) comprising an oil absorbing cross-linked polymer (I) and a hydrophobic inorganic compound (II) into a container made of an oil-permeable material. Can be The method of filling is not particularly limited, and examples thereof include a method in which granules obtained by wet mixing and then dried or granules obtained by dry mixing are filled in a container by a commonly used powder filling device or the like. Alternatively, a method in which an aqueous dispersion of the particulate matter (III) obtained by wet mixing is filled in a container, and then excess water is discharged from the container and dried.
【００３１】また、本発明の吸油材は、円筒状、直方体
状、球状、ソーセージ状など用途にあわせてあらゆる形
態に成形して用いることができる。Further, the oil-absorbing material of the present invention can be formed into any form such as a cylinder, a rectangular parallelepiped, a sphere, a sausage and the like according to the intended use.
【００３２】さらに、本発明の吸油材は、前記吸油剤組
成物（III）に併せて、例えば、もみがら、ワラ、パル
プ、綿、多孔質石灰、多孔質シリカ、多孔質パーライ
ト、ポリプロピレン繊維、発泡ポリウレタンフォームな
どの従来公知の吸油材を容器内に充填して用いたもので
もよい。Further, the oil-absorbing material of the present invention may be used in combination with the oil-absorbing agent composition (III), for example, husk, straw, pulp, cotton, porous lime, porous silica, porous pearlite, polypropylene fiber, A conventionally known oil absorbing material such as a foamed polyurethane foam may be used by filling it in a container.
【００３３】[0033]
【実施例】次に、本発明について実施例をあげて詳細に
説明するが、本発明はこれだけに限定されるものではな
い。なお、例中特にことわりのない限り、部は重量部を
表わすものとする。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts are by weight.
【００３４】[0034]
【実施例１】温度計、攪拌機、ガス導入管および還流冷
却器を備えた５００ｍｌフラスコに、ポリオキシエチレ
ンアルキルエーテル（株式会社日本触媒製、商品名：ソ
フタノール１５０、以下の実施例においてもこの商品を
使用した）３部を水３００部に溶解して仕込み、攪拌下
フラスコ内を窒素置換し、窒素気流下に４０℃に加熱し
た。その後、単量体（Ａ）としてイソブチルメタクリレ
ート（ＳＰ値：７．５）５９．７６２部およびステアリ
ルアクリレート（ＳＰ値：７．９）３９．８４２部、架
橋性単量体（Ｂ）として１，６−ヘキサンジオールジア
クリレート０．３９６部および重合開始剤としてベンゾ
イルパーオキシド０．５部からなる溶液をフラスコ内に
一度に加え、７５０ｒｐｍの条件下で激しく攪拌した。Example 1 In a 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser, polyoxyethylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., trade name: Softanol 150; 3 parts were dissolved in 300 parts of water and charged, and the flask was purged with nitrogen under stirring and heated to 40 ° C. under a nitrogen stream. Thereafter, 59.762 parts of isobutyl methacrylate (SP value: 7.5) and 39.842 parts of stearyl acrylate (SP value: 7.9) as the monomer (A), and 1 as the crosslinkable monomer (B) A solution consisting of 0.396 parts of 6-hexanediol diacrylate and 0.5 parts of benzoyl peroxide as a polymerization initiator was added all at once to the flask, followed by vigorous stirring at 750 rpm.
【００３５】ついで、フラスコ内の温度を８０℃に昇温
し、同温度で２時間維持して重合反応を行い、その後さ
らにフラスコ内を９０℃に昇温し、２時間維持して重合
を完了させることにより、平均粒径３０μｍの吸油性架
橋重合体（１）を含む水分散体（樹脂純分２５重量％）
を得た。Then, the temperature in the flask was raised to 80 ° C., and the polymerization reaction was carried out at the same temperature for 2 hours. Thereafter, the temperature in the flask was further raised to 90 ° C., and maintained for 2 hours to complete the polymerization. By doing so, an aqueous dispersion containing the oil-absorbent crosslinked polymer (1) having an average particle size of 30 μm (resin pure content: 25% by weight)
I got
【００３６】また、前記ポリオキシエチレンアルキルエ
ーテル１．５部を水１５０部に溶解した水溶液中に疎水
性シリカ（日本シリカ製、ニップシールＳＳ−７０、Ｍ
値：６５）の微粉体（平均粒径：４μｍ）５部を加え、
３００ｒｐｍの条件下で攪拌し疎水性シリカの水分散体
を得た。ついで、先の重合で得られた吸油性架橋重合体
（１）を含む水分散体８０部を徐々に加え１０分間攪拌
を続け、吸油性架橋重合体（１）と疎水性シリカとから
なる凝集物を得た。この凝集物をろ別し８０℃で乾燥後
に解砕することにより、吸油性架橋重合体（１）２０部
および疎水性シリカ５部からなる平均粒径２ｍｍの大き
さに造粒された粒状物を得た。In an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water, hydrophobic silica (Nip Seal SS-70, M
5 parts of fine powder (value: 65) (average particle size: 4 μm)
The mixture was stirred under the condition of 300 rpm to obtain an aqueous dispersion of hydrophobic silica. Next, 80 parts of an aqueous dispersion containing the oil-absorbent crosslinked polymer (1) obtained in the previous polymerization is gradually added, and stirring is continued for 10 minutes to form an aggregation comprising the oil-absorbent crosslinked polymer (1) and hydrophobic silica. I got something. This aggregate is filtered, dried at 80 ° C., and then crushed to obtain a granulated product having an average particle size of 2 mm, comprising 20 parts of the oil-absorbent crosslinked polymer (1) and 5 parts of hydrophobic silica. I got
【００３７】得られた粒状物１０ｇを１０cm×７．５cm
のポリプロピレン不織布（目付け５０ｇ／ｍ2 、孔径約
９０μｍ）製の袋に充填した後、充填口を熱融着して閉
じることにより本発明の吸油材（１）を得た。10 g of the obtained granular material is 10 cm × 7.5 cm.
Was filled in a bag made of polypropylene nonwoven fabric (having a basis weight of 50 g / m 2 and a hole diameter of about 90 μm), and then the filling port was heat-sealed and closed to obtain an oil-absorbing material (1) of the present invention.
【００３８】[0038]
【実施例２】実施例１において単量体（Ａ）としてヘキ
サデシルメタクリレート（ＳＰ値：７．８）４９．９３
０部およびＮ−オクチルメタクリルアミド（ＳＰ値：
８．６）４９．９３０部、架橋性単量体（Ｂ）としてジ
ビニルベンゼンＯ．１４０部を代わりに用い、また回転
数を３００ｒｐｍに変更した以外は実施例１と同様の方
法により、平均粒径１００μｍの吸油性架橋重合体
（２）を含む水分散体（樹脂純分２５重量％）を得た。Example 2 In Example 1, the monomer (A) was hexadecyl methacrylate (SP value: 7.8) 49.93.
0 parts and N-octyl methacrylamide (SP value:
8.6) 49.930 parts, divinylbenzene O.I. An aqueous dispersion containing an oil-absorbent crosslinked polymer (2) having an average particle size of 100 μm (resin pure content of 25 wt.) Was prepared in the same manner as in Example 1 except that 140 parts were used instead and the rotation speed was changed to 300 rpm. %).
【００３９】また、前記ポリオキシエチレンアルキルエ
ーテル１．５部を水１５０部に溶解した水溶液中に実施
例１で用いたのと同じ疎水性シリカの微粉体５部を加
え、３００ｒｐｍの条件下で攪拌し疎水性シリカの水分
散体を得た。ついで、吸油性架橋重合体（２）を含む水
分散体１８０部を徐々に加え１０分間攪拌を続け、吸油
性架橋重合体（２）と疎水性シリカとからなる凝集物を
得た。この凝集物をろ別し８０℃で乾燥後に解砕するこ
とにより、吸油性架橋重合体（２）４５部および疎水性
シリカ５部からなる平均粒径３ｍｍの大きさに造粒され
た粒状物を得た。この粒状物１０ｇを用い、実施例１と
同様の方法により吸油材（２）を得た。5 parts of the same hydrophobic silica fine powder as used in Example 1 was added to an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water. After stirring, an aqueous dispersion of hydrophobic silica was obtained. Next, 180 parts of an aqueous dispersion containing the oil-absorbing crosslinked polymer (2) was gradually added, and stirring was continued for 10 minutes to obtain an aggregate comprising the oil-absorbing crosslinked polymer (2) and hydrophobic silica. This aggregate is filtered, dried at 80 ° C., and then crushed to obtain a granular material having an average particle diameter of 3 mm, comprising 45 parts of the oil-absorbent crosslinked polymer (2) and 5 parts of hydrophobic silica. I got Using 10 g of this granular material, an oil absorbing material (2) was obtained in the same manner as in Example 1.
【００４０】[0040]
【実施例３】前記ポリオキシエチレンアルキルエーテル
３部を水３００部に溶解した水溶液中に単量体（Ａ）と
してドデシルアクリレート（ＳＰ値：７．９）５７．７
７２部およびＮ，Ｎ−ジオクチルアクリルアミド（ＳＰ
値：８．２）３８．５１５部、架橋性単量体（Ｂ）とし
てポリプロピレングリコールジメタクリレート（分子量
４０００）３．７１３部および重合開始剤として２，２
´−アゾビスイソブチロニトリルＯ．５部からなる溶液
を加え、ホモミキサーにて１００００回転で１０分間混
合し単量体の水分散液を得た。Example 3 Dodecyl acrylate (SP value: 7.9) 57.7 as a monomer (A) in an aqueous solution obtained by dissolving 3 parts of the above polyoxyethylene alkyl ether in 300 parts of water.
72 parts and N, N-dioctylacrylamide (SP
Value: 8.2) 38.515 parts, 3.713 parts of polypropylene glycol dimethacrylate (molecular weight 4000) as a crosslinkable monomer (B) and 2,2 as a polymerization initiator.
'-Azobisisobutyronitrile O.I. A solution consisting of 5 parts was added and mixed with a homomixer at 10,000 rpm for 10 minutes to obtain an aqueous dispersion of a monomer.
【００４１】ついで、温度計、攪拌機、ガス導入管およ
び還流冷却器を備えた５００ｍｌのフラスコに上記単量
体の水分散液を仕込み、４００ｒｐｍの条件下で激しく
攪拌しながらフラスコ内を窒素置換した。引き続き窒素
気流下にフラスコ内の温度を７０℃に昇温し、同温度で
２時間維持して重合反応を行い、その後さらに９０℃に
昇温して重合を完了させ、平均粒径５μｍの吸油性架橋
重合体（３）を含む水分散体（樹脂純分２５重量％）を
得た。Next, an aqueous dispersion of the above monomer was charged into a 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser, and the inside of the flask was purged with nitrogen while being vigorously stirred at 400 rpm. . Subsequently, the temperature in the flask was raised to 70 ° C. under a nitrogen stream, and the polymerization reaction was carried out at the same temperature for 2 hours. Thereafter, the temperature was further raised to 90 ° C. to complete the polymerization. An aqueous dispersion containing the water-soluble crosslinked polymer (3) (resin pure content: 25% by weight) was obtained.
【００４２】また、前記ポリオキシエチレンアルキルエ
ーテル１．５部を水１５０部に溶解した水溶液中に実施
例１で用いたのと同じ疎水性シリカ５部を加え、３００
ｒｐｍの条件下で攪拌し疎水性シリカの水分散体を得
た。ついで、吸油性架橋重合体（３）を含む水分散体３
０部を徐々に加え１０分間攪拌を続け、吸油性架橋重合
体（３）と疎水性シリカとからなる凝集物を得た。さら
に、この凝集物をろ別し８０℃で乾燥後に解砕すること
により、吸油性架橋重合体（３）７．５部および疎水性
シリカ５部からなる平均粒径０．２ｍｍの大きさに造粒
された粒状物を得た。Also, 5 parts of the same hydrophobic silica as used in Example 1 was added to an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water,
The mixture was stirred under the condition of rpm to obtain an aqueous dispersion of hydrophobic silica. Next, an aqueous dispersion 3 containing the oil-absorbing crosslinked polymer (3)
0 parts were gradually added and stirring was continued for 10 minutes to obtain an aggregate comprising the oil-absorbent crosslinked polymer (3) and hydrophobic silica. Further, this aggregate was filtered off, dried at 80 ° C., and then crushed to obtain an oil-absorbent crosslinked polymer (3) of 7.5 parts and hydrophobic silica of 5 parts with an average particle diameter of 0.2 mm. Granulated granules were obtained.
【００４３】この粒状物１０ｇを用い、実施例１と同様
の方法により吸油材（３）を得た。An oil absorbing material (3) was obtained in the same manner as in Example 1 using 10 g of the granular material.
【００４４】[0044]
【実施例４】実施例１において単量体（Ａ）としてドデ
シルアクリレート（ＳＰ値：７．９）９９．８２３部、
架橋性単量体（Ｂ）としてエチレングリコールジアクリ
レートＯ．１７７部を代わりに用いた以外は実施例１と
同様の方法により、平均粒径３０μｍの吸油性架橋重合
体（４）を含む水分散体（樹脂純分２５重量％）を得
た。Example 4 In Example 1, 99.823 parts of dodecyl acrylate (SP value: 7.9) as monomer (A),
As the crosslinkable monomer (B), ethylene glycol diacrylate O.I. A water dispersion containing an oil-absorbent crosslinked polymer (4) having an average particle size of 30 μm (resin pure content: 25% by weight) was obtained in the same manner as in Example 1 except that 177 parts was used instead.
【００４５】また、前記ポリオキシエチレンアルキルエ
ーテル１．５部を水１５０部に溶解した水溶液中に実施
例１で用いたのと同じ疎水性シリカ５部を加え、３００
ｒｐｍの条件下で攪拌し疎水性シリカの水分散体を得
た。ついで、吸油性架橋重合体（４）を含む水分散体８
０部を徐々に加え１０分間攪拌を続け、吸油性架橋重合
体（４）と疎水性シリカとからなる凝集物を得た。さら
に、この凝集物をろ別し８０℃で乾燥後に解砕すること
により、吸油性架橋重合体（４）２０部および疎水性シ
リカ５部からなる平均粒径２ｍｍの大きさに造粒された
粒状物を得た。To an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water, 5 parts of the same hydrophobic silica used in Example 1 was added.
The mixture was stirred under the condition of rpm to obtain an aqueous dispersion of hydrophobic silica. Then, an aqueous dispersion 8 containing the oil-absorbing crosslinked polymer (4)
0 parts were gradually added and stirring was continued for 10 minutes to obtain an aggregate composed of the oil-absorbent crosslinked polymer (4) and hydrophobic silica. Further, this aggregate was filtered off, dried at 80 ° C., and then crushed to obtain a granule having an average particle diameter of 2 mm composed of 20 parts of the oil-absorbent crosslinked polymer (4) and 5 parts of hydrophobic silica. Granules were obtained.
【００４６】この粒状物１０ｇを用い、実施例１と同様
の方法により吸油材（４）を得た。An oil absorbing material (4) was obtained in the same manner as in Example 1 using 10 g of the granular material.
【００４７】[0047]
【実施例５】実施例１において単量体（Ａ）としてｔ−
ブチルスチレン（ＳＰ値：７．９）５４．８８１部およ
び１−デセン（ＳＰ値：７．０）４４．９０３部、架橋
性単量体（Ｂ）としてジビニルベンゼンＯ．２１６部を
代わりに用いた以外は実施例１と同様の方法により、吸
油性架橋重合体（５）を含む水分散体（樹脂純分２５重
量％）を得た。ついで、この水分散体から樹脂分をろ別
乾燥したのちコロイドミルで粉砕することにより、平均
粒径５μｍの吸油性架橋重合体（５）の粒状物を得た。Example 5 In Example 1, the monomer (A) was replaced with t-
54.881 parts of butylstyrene (SP value: 7.9) and 44.903 parts of 1-decene (SP value: 7.0), and divinylbenzene O.P. A water dispersion containing the oil-absorbing crosslinked polymer (5) (resin pure content: 25% by weight) was obtained in the same manner as in Example 1 except that 216 parts were used instead. Next, the resin component was separated from the aqueous dispersion by filtration, dried, and then pulverized with a colloid mill to obtain a particulate oil-absorbent crosslinked polymer (5) having an average particle size of 5 μm.
【００４８】さらに、この吸油性架橋重合体（５）の粒
状物（平均粒径５μｍ）１５部および疎水性シリカ（日
本シリカ製、ニップシールＳＳ−７５、Ｍ値：３０）の
微粉体（平均粒径：４μｍ）５部をコロイドミルを用い
て混合することにより平均粒径１ｍｍの大きさに造粒さ
れた粒状物を得た。Further, 15 parts of a granular material (average particle size: 5 μm) of the oil-absorbing crosslinked polymer (5) and a fine powder (average particle size) of hydrophobic silica (Nipsil SS-75, manufactured by Nippon Silica, M value: 30) By mixing 5 parts with a colloid mill using a colloid mill, a granular material having an average particle size of 1 mm was obtained.
【００４９】この粒状物１０ｇを用い、実施例１と同様
の方法により吸油材（５）を得た。Using 10 g of the granular material, an oil absorbing material (5) was obtained in the same manner as in Example 1.
【００５０】[0050]
【実施例６】実施例１において単量体（Ａ）としてノニ
ルフェニルアクリレート（ＳＰ値：８．３）７４．７９
３部およびヒドロキシエチルアクリレート（ＳＰ値：１
０．３）２４．９３１部を代わりに用い、架橋性単量体
（Ｂ）としての１，６−ヘキサンジオールジアクリレー
トの量を０．２７６部に変更した以外は実施例１と同様
の方法により、平均粒径３０μｍの吸油性架橋重合体
（６）を含む水分散体（樹脂純分２５重量％）を得た。Example 6 In Example 1, nonylphenyl acrylate (SP value: 8.3) was used as the monomer (A) 74.79.
3 parts and hydroxyethyl acrylate (SP value: 1
0.3) A method similar to that of Example 1 except that 24.931 parts were used instead, and the amount of 1,6-hexanediol diacrylate as the crosslinkable monomer (B) was changed to 0.276 parts. As a result, an aqueous dispersion containing the oil-absorbent crosslinked polymer (6) having an average particle size of 30 μm (resin pure content: 25% by weight) was obtained.
【００５１】また、前記ポリオキシエチレンアルキルエ
ーテル１．５部を水１５０部に溶解した水溶液中に疎水
性アルミナ（日本アエロジル製、ＲＦＹ−Ｃ、Ｍ値：５
０）の微粉体（平均粒径：３μｍ）５部を加え、３００
ｒｐｍの条件下で攪拌し疎水性アルミナの水分散体を得
た。ついで、吸油性架橋重合体（６）を含む水分散体６
０部を徐々に加え１０分間攪拌を続け、吸油性架橋重合
体（６）と疎水性アルミナとからなる凝集物を得た。さ
らに、この凝集物をろ別し８０℃で乾燥後解砕すること
により、吸油性架橋重合体（６）１５部と疎水性アルミ
ナ５部とからなる凝集した粒状物を含む水分散体２１
６．５部を得た。In an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water, hydrophobic alumina (manufactured by Nippon Aerosil, RFY-C, M value: 5)
5) (5 parts) of fine powder (average particle size: 3 μm)
The mixture was stirred under the condition of rpm to obtain an aqueous dispersion of hydrophobic alumina. Next, an aqueous dispersion 6 containing the oil-absorbing crosslinked polymer (6)
0 parts were gradually added and stirring was continued for 10 minutes to obtain an aggregate composed of the oil-absorbing crosslinked polymer (6) and hydrophobic alumina. Further, this aggregate was filtered off, dried at 80 ° C., and then crushed to obtain an aqueous dispersion 21 containing aggregated particulates comprising 15 parts of the oil-absorbent crosslinked polymer (6) and 5 parts of hydrophobic alumina.
6.5 parts were obtained.
【００５２】得られた水分散体１０８．２５ｇ（粒状物
として１０ｇ）を１０cm×７．５cmのポリエステル不織
布（目付け５０ｇ／ｍ2 、孔径約１００μｍ）製の袋に
充填して水分を濾過したのち、充填口を熱融着して閉
じ、次いでローラーにて余剰な水を絞り出し６０℃で乾
燥させることにより、本発明の吸油材（６）を得た。The obtained aqueous dispersion (108.25 g, 10 g as a granular material) was filled in a bag of 10 cm × 7.5 cm polyester nonwoven fabric (basis weight: 50 g / m 2 , pore size: about 100 μm), and the water was filtered. Then, the filling port was heat-sealed and closed, and then excess water was squeezed out with a roller and dried at 60 ° C. to obtain an oil-absorbing material (6) of the present invention.
【００５３】[0053]
【実施例７】実施例１において単量体（Ａ）としてラウ
リン酸ビニル（ＳＰ値：７．９）９９．８１１部、架橋
性単量体（Ｂ）としてトリメチロールプロパントリアク
リレート０．１８７部を代わりに用いた以外は実施例１
と同様の方法により、平均粒径３０μｍの吸油性架橋重
合体（７）を含む水分散体（樹脂純分２５重量％）を得
た。Example 7 In Example 1, 99.811 parts of vinyl laurate (SP value: 7.9) was used as the monomer (A), and 0.187 parts of trimethylolpropane triacrylate was used as the crosslinkable monomer (B). Example 1 except that was used instead
In the same manner as in the above, an aqueous dispersion (pure resin content: 25% by weight) containing the oil-absorbent crosslinked polymer (7) having an average particle size of 30 μm was obtained.
【００５４】また、前記ポリオキシエチレンアルキルエ
ーテル１．５部を水１５０部に溶解した水溶液中に実施
例１で用いたのと同じ疎水性シリカの微粉体１部および
ステアリン酸アルミニウムの微粉体（平均粒径：５μ
ｍ）４部を加え、３００ｒｐｍの条件下で攪拌し疎水性
シリカとステアリン酸アルミニウムの水分散体を得た。
ついで、吸油性架橋重合体（７）を含む水分散体６０部
を徐々に加え１０分間攪拌を続け、吸油性架橋重合体
（７）と疎水性シリカおよびステアリン酸アルミニウム
とからなる凝集物を得た。さらに、この凝集物をろ別し
８０℃で乾燥後解砕することにより吸油性架橋重合体
（７）１５部、疎水性シリカ１部およびステアリン酸ア
ルミニウム４部からなる平均粒径２ｍｍの大きさに造粒
された粒状物を得た。Further, 1 part of the same fine powder of hydrophobic silica as used in Example 1 and the fine powder of aluminum stearate (1 part) in an aqueous solution obtained by dissolving 1.5 parts of the polyoxyethylene alkyl ether in 150 parts of water. Average particle size: 5μ
m) 4 parts were added, and the mixture was stirred under the condition of 300 rpm to obtain an aqueous dispersion of hydrophobic silica and aluminum stearate.
Next, 60 parts of an aqueous dispersion containing the oil-absorbing crosslinked polymer (7) is gradually added, and stirring is continued for 10 minutes to obtain an aggregate composed of the oil-absorbing crosslinked polymer (7), hydrophobic silica, and aluminum stearate. Was. Further, this aggregate is filtered, dried at 80 ° C., and then crushed to obtain an oil-absorbing crosslinked polymer (7) of 15 parts, hydrophobic silica of 1 part, and aluminum stearate of 4 parts with an average particle size of 2 mm. A granulated product was obtained.
【００５５】得られた粒状物１０ｇを１０cm×７．５cm
のナイロン織布（目付け５０ｇ／ｍ2 、孔径約９０μ
ｍ）製の袋に充填した後、充填口を接着剤で閉じること
により本発明の吸油材（７）を得た。[0055] 10 g of the obtained granules are sized 10 cm x 7.5 cm.
Nylon woven fabric (basis weight 50g / m 2 , pore size about 90μ)
m), and the filling port was closed with an adhesive to obtain the oil absorbing material (7) of the present invention.
【００５６】[0056]
【実施例８】前記ポリオキシエチレンアルキルエーテル
１．５部を水１５０部に溶解した水溶液中に実施例１で
用いた疎水性シリカの微粉体２部及びステアリン酸アル
ミニウムの微粉体（平均粒径：５μｍ）３部を加え、３
００ｒｐｍの条件下で攪拌し疎水性シリカとステアリン
酸アルミニウムの水分散体を得た。次いで、吸油性架橋
重合体（４）を含む水分散体６０部を徐々に加え１０分
間攪拌を続け、吸油性架橋重合体（４）と疎水性シリカ
及びステアリン酸アルミニウムからなる凝集物を得た。
さらに、この凝集物をろ別し８０℃で乾燥後解砕するこ
とにより吸油性架橋重合体（４）１５部、疎水性シリカ
２部およびステアリン酸アルミニウム３部からなる平均
粒径２ｍｍの大きさに造粒された粒状物を得た。Example 8 In an aqueous solution in which 1.5 parts of the above polyoxyethylene alkyl ether was dissolved in 150 parts of water, 2 parts of the fine powder of hydrophobic silica used in Example 1 and the fine powder of aluminum stearate (average particle diameter) : 5 μm) 3 parts were added, and
The mixture was stirred under the condition of 00 rpm to obtain an aqueous dispersion of hydrophobic silica and aluminum stearate. Next, 60 parts of an aqueous dispersion containing the oil-absorbing crosslinked polymer (4) was gradually added, and stirring was continued for 10 minutes to obtain an aggregate composed of the oil-absorbing crosslinked polymer (4), hydrophobic silica, and aluminum stearate. .
Further, this aggregate is separated by filtration, dried at 80 ° C. and then crushed to obtain an oil-absorbent crosslinked polymer (4) of 15 parts, hydrophobic silica of 2 parts, and aluminum stearate of 3 parts with an average particle diameter of 2 mm. A granulated product was obtained.
【００５７】この粒状物１０ｇを用い、実施例１と同様
の方法により吸油材（８）を得た。An oil absorbing material (8) was obtained in the same manner as in Example 1 using 10 g of the granular material.
【００５８】[0058]
【比較例１】実施例４においてドデシルアクリレートの
量を９４．６３７部に、エチレングリコールジアクリレ
ートの量を５．３６３部にそれぞれ変更した以外は実施
例４と同様の方法により、平均粒径３０μｍの比較重合
体（１）を含む水分散体を得た。この水分散体と実施例
１で用いたのと同じ疎水性シリカを用いて、実施例４と
同様の方法で比較重合体（１）２０部および疎水性シリ
カ５部からなる平均粒径２ｍｍの大きさに造粒された粒
状物を得た。Comparative Example 1 An average particle diameter of 30 μm was obtained in the same manner as in Example 4 except that the amount of dodecyl acrylate was changed to 94.637 parts and the amount of ethylene glycol diacrylate was changed to 5.363 parts. A water dispersion containing the comparative polymer (1) was obtained. Using this water dispersion and the same hydrophobic silica as used in Example 1, the same method as in Example 4 was used to prepare a comparative polymer (1) having 20 parts and hydrophobic silica having an average particle diameter of 2 mm. A granular material granulated to a size was obtained.
【００５９】この粒状物１０ｇを用い、実施例１と同様
の方法により比較吸油材（１）を得た。A comparative oil-absorbing material (1) was obtained in the same manner as in Example 1 using 10 g of the granular material.
【００６０】[0060]
【比較例２】実施例４においてドデシルアクリレート９
９．８２３部からなる単量体（Ａ）の代わりにドデシル
アクリレート３９．８５４部およびメタクリル酸（ＳＰ
値：１０．１）５９．７８０部を用い、エチレングリコ
ールジアクリレートの量を０．３６６部に変更した以外
は実施例４と同様の方法により、平均粒径３０μｍの比
較重合体（２）を含む水分散体を得た。この水分散体と
実施例１で用いたのと同じ疎水性シリカを用いて、実施
例４と同様の方法で比較重合体（２）２０部および疎水
性シリカ５部からなる平均粒径２ｍｍの大きさに造粒さ
れた粒状物を得た。Comparative Example 2 In Example 4, dodecyl acrylate 9
Instead of the monomer (A) consisting of 9.823 parts, 39.854 parts of dodecyl acrylate and methacrylic acid (SP
Value: 10.1) A comparative polymer (2) having an average particle size of 30 μm was prepared in the same manner as in Example 4 except that 59.780 parts was used and the amount of ethylene glycol diacrylate was changed to 0.366 parts. The resulting aqueous dispersion was obtained. Using this aqueous dispersion and the same hydrophobic silica as used in Example 1, the same method as in Example 4 was used to prepare a comparative polymer (2) having 20 parts and hydrophobic silica having an average particle diameter of 2 mm. A granular material granulated to a size was obtained.
【００６１】この粒状物１０ｇを用い、実施例１と同様
の方法により比較吸油材（２）を得た。A comparative oil absorbing material (2) was obtained in the same manner as in Example 1 using 10 g of the granular material.
【００６２】[0062]
【比較例３】実施例４において架橋性単量体（Ｂ）を用
いなかった以外は実施例４と同様の方法により、平均粒
径３０μｍの比較重合体（３）を含む水分散体を得た。
この水分散体と実施例１で用いたのと同じ疎水性シリカ
を用いて、実施例４と同様の方法で比較重合体（３）２
０部および疎水性シリカ５部からなる平均粒径４ｍｍの
大きさに造粒された粘着性のある粒状物を得た。Comparative Example 3 An aqueous dispersion containing a comparative polymer (3) having an average particle size of 30 μm was obtained in the same manner as in Example 4 except that the crosslinkable monomer (B) was not used. Was.
Using this aqueous dispersion and the same hydrophobic silica used in Example 1, the comparative polymer (3) 2 was produced in the same manner as in Example 4.
A sticky granular material having an average particle size of 4 mm, which was composed of 0 parts and 5 parts of hydrophobic silica, was obtained.
【００６３】この粒状物１０ｇを用い、実施例１と同様
の方法により比較吸油材（３）を得た。A comparative oil absorbing material (3) was obtained in the same manner as in Example 1 using 10 g of the granular material.
【００６４】[0064]
【比較例４】前記ポリオキシエチレンアルキルエーテル
１．５部を水１５０部に溶解した水溶液中に実施例１で
用いたのと同じ疎水性シリカの微粉体１部を加え、３０
０ｒｐｍの条件下で攪拌し疎水性シリカの水分散体を得
た。ついで、実施例４の重合で得られた吸油性架橋重合
体（４）を含む水分散体８００部を徐々に加え１０分間
攪拌を続け、吸油性架橋重合体（４）と疎水性シリカと
からなる凝集物を得た。Comparative Example 4 1 part of the same hydrophobic silica fine powder as used in Example 1 was added to an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water.
The mixture was stirred under the condition of 0 rpm to obtain an aqueous dispersion of hydrophobic silica. Then, 800 parts of an aqueous dispersion containing the oil-absorbing crosslinked polymer (4) obtained by the polymerization in Example 4 was gradually added, and stirring was continued for 10 minutes to prepare the oil-absorbing crosslinked polymer (4) and the hydrophobic silica. Aggregates were obtained.
【００６５】さらに、この凝集物をろ別し８０℃で乾燥
後に解砕することにより、吸油性架橋重合体（４）２０
０部および疎水性シリカ１部からなる平均粒径８ｍｍの
大きさに造粒された粘着性のある粒状物を得た。Further, this aggregate was filtered off, dried at 80 ° C. and then crushed to obtain an oil-absorbent crosslinked polymer (4) 20
A sticky granular material having an average particle diameter of 8 mm, which was composed of 0 parts and 1 part of hydrophobic silica, was obtained.
【００６６】この粒状物１０ｇを用い、実施例１と同様
の方法により比較吸油材（４）を得た。Using 10 g of the granular material, a comparative oil-absorbing material (4) was obtained in the same manner as in Example 1.
【００６７】[0067]
【比較例５】前記ポリオキシエチレンアルキルエーテル
１．５部を水１５０部に溶解した水溶液中に実施例１で
用いたのと同じ疎水性シリカの微粉体５部を加え、３０
０ｒｐｍの条件下で攪拌し疎水性シリカの水分散体を得
た。ついで、実施例４で得られた吸油性架橋重合体
（４）を含む水分散体８部を徐々に加え１０分間攪拌を
続け、吸油性架橋重合体（４）と疎水性シリカとからな
る凝集物を得た。さらに、この凝集物をろ別し８０℃で
乾燥後解砕することにより、吸油性架橋重合体（４）２
部と疎水性シリカ５部からなる平均粒径０．５ｍｍの大
きさに造粒された粒状物を得た。Comparative Example 5 To an aqueous solution obtained by dissolving 1.5 parts of the above polyoxyethylene alkyl ether in 150 parts of water, 5 parts of the same fine powder of hydrophobic silica as used in Example 1 was added.
The mixture was stirred under the condition of 0 rpm to obtain an aqueous dispersion of hydrophobic silica. Then, 8 parts of the aqueous dispersion containing the oil-absorbent crosslinked polymer (4) obtained in Example 4 was gradually added, and stirring was continued for 10 minutes to form an aggregation comprising the oil-absorbent crosslinked polymer (4) and hydrophobic silica. I got something. Further, this aggregate is filtered off, dried at 80 ° C. and then crushed to obtain an oil-absorbent crosslinked polymer (4) 2.
And 5 parts of hydrophobic silica, to obtain a granulated product having an average particle diameter of 0.5 mm.
【００６８】この粒状物１０ｇを用い、実施例１と同様
の方法により比較吸油材（５）を得た。A comparative oil absorbing material (5) was obtained in the same manner as in Example 1 using 10 g of the granular material.
【００６９】[0069]
【比較例６】実施例４において疎水性シリカ（日本シリ
カ製、ニップシールＳＳ−７０、Ｍ値：６５）の代わり
にシリカ（日本シリカ製、ニップシールＳＳ−７３、Ｍ
値：１５）の微粉末（平均粒径：３μｍ）を同量用いた
以外は実施例４と同様の方法により吸油性架橋重合体
（４）２０部とシリカ５部からなる平均粒径４ｍｍの大
きさに造粒された粒状物を得た。得られた粒状物は吸油
性架橋重合体（４）とシリカの単独凝集体を多く含む不
均一な凝集体であった。COMPARATIVE EXAMPLE 6 Instead of hydrophobic silica (Nihon Silica, Nip Seal SS-70, M value: 65) in Example 4, silica (Nihon Silica, Nip Seal SS-73, M value: 65) was used.
Value: 15) except that the same amount of the fine powder (average particle size: 3 μm) was used in the same manner as in Example 4 to obtain an oil-absorbent crosslinked polymer (4) having 20 parts and an average particle size of 4 mm. A granular material granulated to a size was obtained. The obtained granules were heterogeneous aggregates containing a large amount of single aggregates of the oil-absorbent crosslinked polymer (4) and silica.
【００７０】この粒状物１０ｇを用い、実施例１と同様
の方法により比較吸油材（５）を得た。Using 10 g of the granular material, a comparative oil-absorbing material (5) was obtained in the same manner as in Example 1.
【００７１】[0071]
【実施例９】実施例１〜８で得られた吸油材（１）〜
（８）、比較例１〜６で得られた比較吸油材（１）〜
（６）および市販のポリプロピレン不織布１０ｇ（１０
cm×２５cm、目付け４００ｇ／ｍ2，嵩密度０．１ｇ／c
m3）を実施例１で用いたポリプロピレン不織布に充填し
たもののそれぞれを２０℃の条件下に灯油中に１分間浸
漬した後引き上げ、２００メッシュの金網上に１分間放
置して油切りした。その後秤量により吸油材に吸収され
た吸油量を測定した。次いで吸油後の吸油材を２００メ
ッシュの金網上に置き、上部に２０ｇ／cm2の荷重を１
分間かけ、流出した油量を測定し、次式に従い荷重後の
保油率を計算した。Example 9 The oil absorbing material (1) obtained in Examples 1 to 8
(8) Comparative oil-absorbing materials (1) obtained in Comparative Examples 1 to 6
(6) and 10 g (10
cm × 25cm, basis weight 400g / m 2 , bulk density 0.1g / c
Each of m 3 ) filled in the polypropylene nonwoven fabric used in Example 1 was immersed in kerosene at 20 ° C. for 1 minute, pulled up, left on a 200-mesh wire mesh for 1 minute, and drained. Thereafter, the amount of oil absorbed by the oil absorbing material was measured by weighing. Next, the oil-absorbing material after oil absorption was placed on a 200-mesh wire mesh, and a load of 20 g / cm 2 was applied to the upper part by 1 g.
Over a period of minutes, the amount of oil that flowed out was measured, and the oil retention after loading was calculated according to the following equation.
【００７２】保油率（％）＝｛（吸油量−流出油量）／
吸油量｝×１００ それらの評価結果を表１に示す。Oil retention (%) = ｛(oil absorption−oil spillage) /
Oil absorption amount x 100 The evaluation results are shown in Table 1.
【００７３】[0073]
【表１】 [Table 1]
【００７４】[0074]
【発明の効果】本発明の吸油材は、特定の吸油性架橋重
合体と疎水性無機化合物とからなる粒状物を多孔質材料
からなる容器中に充填してなり、それらの複合効果によ
り、油水混合系からも油のみを選択的に吸収でき一旦吸
収した油の保油性能に優れる。さらに本発明の吸油材中
の粒状物は、高粘性の油に対する濡れ性が改善されてお
り、また低粘性の油の吸油に際して油の接触面付近での
吸油膨潤による吸油剤内部への油の通液阻害（ゲルブロ
ックの生成）が有効に防止されているため、広範な種類
の油に対して吸油速度のきわめて速いものとなる。ま
た、本発明の吸油材は取扱い性に問題があった粉体を容
器に収納した状態で吸油能を発揮するため、使用時の取
扱いがきわめて容易であり、しかもコンパクトに貯蔵で
きる利点を有している。The oil-absorbing material of the present invention is obtained by filling a granular material composed of a specific oil-absorbing crosslinked polymer and a hydrophobic inorganic compound into a container made of a porous material, and by using a composite effect of these, oil-water Only the oil can be selectively absorbed from the mixed system, and the oil once absorbed is excellent in oil retention performance. Further, the particulate matter in the oil-absorbing material of the present invention has improved wettability to high-viscosity oil, and also absorbs oil into the oil-absorbing agent due to oil absorption swelling near the oil contact surface when absorbing low-viscosity oil. Since the passage inhibition (formation of a gel block) is effectively prevented, the oil absorption rate is extremely high for a wide variety of oils. Further, the oil-absorbing material of the present invention exhibits an oil-absorbing ability in a state in which powder having a problem in handling properties is stored in a container, so that it has an advantage that handling at the time of use is extremely easy and that it can be stored compactly. ing.
【００７５】したがって、本発明の吸油剤は、海上流出
油回収、浮上油回収、廃水中の油分回収、エマルション
ブレーカー、廃油処理剤、食用廃油処理剤、機械油廃油
処理剤、家庭用または工業用ふきとり剤、化学ぞうき
ん、漏油センサー、オイルシール剤、各種保油剤などの
非常に広範な用途に適応できるほか、各種芳香剤、殺虫
剤、集魚剤などの徐放性基材としても使用することがで
きる。Accordingly, the oil absorbing agent of the present invention can be used for recovery of spilled oil at sea, recovery of floating oil, recovery of oil in wastewater, emulsion breakers, waste oil treatment agents, edible waste oil treatment agents, machine oil waste oil treatment agents, household or industrial use. It can be used in a wide range of applications such as wipes, chemical wipes, oil leak sensors, oil sealants, various oil retention agents, and can be used as a sustained-release base material for various fragrances, insecticides, fish collectors, etc. Can be.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 23/00 Ｃ０８Ｌ 23/00 25/16 25/16 31/02 31/02 // Ｃ０８Ｌ 33/04 33/04 33/26 33/26 (72)発明者 田村 俊雄 神奈川県川崎市川崎区千鳥町14−１ 株 式会社日本触媒 川崎研究所内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 23/00 C08L 23/00 25/16 25/16 31/02 31/02 // C08L 33/04 33/04 33/26 33/26 (72) Inventor Toshio Tamura 14-1 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Co., Ltd.
Claims (3)
単量体を主成分としてなる分子中に１個の重合性不飽和
基を有する単量体（Ａ）９６〜９９．９９９重量％およ
び分子中に少なくとも２個の重合性不飽和基を有する架
橋性単量体（Ｂ）０．００１〜４重量％（ただし単量体
（Ａ）および（Ｂ）の合計は１００重量％である）から
なる単量体成分を重合して得られる吸油性架橋重合体
（Ｉ）３０〜９９．５重量部およびメタノール値（平均
粒径が０．０１〜３００μｍの範囲の粉体がメタノール
水溶液に湿潤し始めるときの水溶液中のメタノール容積
％）が２５％以上の疎水性無機化合物（ＩＩ）０．５〜
７０重量部からなる吸油剤組成物（ＩＩＩ）を油透過性
材料からなる容器中に充填してなる吸油材。(1) 96 to 99.999% by weight of a monomer (A) having one polymerizable unsaturated group in a molecule mainly composed of a monomer having a solubility parameter (SP value) of 9 or less; 0.001 to 4% by weight of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule (however, the total of the monomers (A) and (B) is 100% by weight) obtained by polymerizing a monomer component consisting of oil-absorbing cross-linked polymer (I) 30 to 99.5 parts by weight of methanol (mean
When the powder having a particle size in the range of 0.01 to 300 μm starts to be wetted by the aqueous methanol solution, the volume of the hydrophobic inorganic compound (II) is from 25% to 25%.
An oil-absorbing material obtained by filling 70 parts by weight of an oil-absorbing composition (III) into a container made of an oil-permeable material.
数３〜３０の脂肪族炭化水素基を有し且つアルキル（メ
タ）アクリレート、アルキルアリール（メタ）アクリレ
ート、アルキル（メタ）アクリルアミド、アルキルアリ
ール（メタ）アクリルアミド、脂肪酸ビニルエステル、
アルキルスチレンおよびα−オレフィンからなる群より
選ばれる少なくとも１種の不飽和化合物（ａ）を主成分
としてなるものである請求項１記載の吸油材。2. The monomer (A) has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, and is an alkyl (meth) acrylate, an alkylaryl (meth) acrylate, or an alkyl (meth) acrylamide. , Alkylaryl (meth) acrylamide, fatty acid vinyl ester,
The oil-absorbing material according to claim 1, wherein the oil-absorbing material mainly comprises at least one unsaturated compound (a) selected from the group consisting of alkylstyrene and α-olefin.
合体（Ｉ）の粒状物と疎水性無機化合物（II）の粉体と
を水性媒体中に混合分散した後に両者を凝集造粒するこ
とによって得られる粒状物である請求項１記載の吸油
材。3. The oil absorbing agent composition (III) is obtained by mixing and dispersing a particulate substance of the oil absorbing cross-linked polymer (I) and a powder of the hydrophobic inorganic compound (II) in an aqueous medium, and then coagulating the two. The oil-absorbing material according to claim 1, which is a granular material obtained by granulating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5246491A JP2738640B2 (en) | 1993-10-01 | 1993-10-01 | Oil absorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5246491A JP2738640B2 (en) | 1993-10-01 | 1993-10-01 | Oil absorbing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07102248A JPH07102248A (en) | 1995-04-18 |
| JP2738640B2 true JP2738640B2 (en) | 1998-04-08 |
Family
ID=17149195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5246491A Expired - Lifetime JP2738640B2 (en) | 1993-10-01 | 1993-10-01 | Oil absorbing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2738640B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990026192A (en) * | 1997-09-23 | 1999-04-15 | 구광시 | Oil absorbent |
| KR19990026191A (en) * | 1997-09-23 | 1999-04-15 | 구광시 | Oil absorbent |
| KR20020075351A (en) * | 2002-09-05 | 2002-10-04 | 차연선 | moisture filter |
| KR100692212B1 (en) * | 2005-07-06 | 2007-03-14 | 주식회사 태성환경연구소 | Adsorbent agent for removal of volatile organic compounds in air or oily material in water contaning effetive amount of organic-inorganic hybrid mesoporous silica gel |
| CN101220528B (en) * | 2007-09-26 | 2010-10-06 | 天津工业大学 | Production method for oil suction fibre |
| KR101121263B1 (en) | 2007-12-17 | 2012-03-22 | 에누오케 가부시키가이샤 | Rubber composition and use thereof |
| KR101156303B1 (en) * | 2008-03-31 | 2012-06-13 | 에누오케 가부시키가이샤 | Rubber composition and use thereof |
| CA2767437C (en) * | 2009-07-08 | 2015-05-12 | Kabushiki Kaisha Toshiba | Oil adsorbent and method of manufacturing oil adsorbent |
| CN101845756B (en) * | 2010-05-07 | 2011-08-31 | 天津工业大学 | Manufacturing method of sandwich type compound oil absorption material |
| CN109679279B (en) * | 2018-12-18 | 2021-08-31 | 陕西科技大学 | Preparation method of silanized carbon fiber/nano manganese dioxide reinforced resin matrix composite material |
| CN110560006A (en) * | 2019-08-23 | 2019-12-13 | 华南理工大学 | Squid bone adsorbent for oil-water separation and preparation method thereof |
-
1993
- 1993-10-01 JP JP5246491A patent/JP2738640B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07102248A (en) | 1995-04-18 |
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