JPH06192432A - Production of granular water-soluble high-molecular compound - Google Patents
Production of granular water-soluble high-molecular compoundInfo
- Publication number
- JPH06192432A JPH06192432A JP3059767A JP5976791A JPH06192432A JP H06192432 A JPH06192432 A JP H06192432A JP 3059767 A JP3059767 A JP 3059767A JP 5976791 A JP5976791 A JP 5976791A JP H06192432 A JPH06192432 A JP H06192432A
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble polymer
- silica
- polymer compound
- granular water
- 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.)
- Granted
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、廃水処理、下水処理等
水処理に有用な粒状水溶性高分子化合物の製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a granular water-soluble polymer compound useful for water treatment such as wastewater treatment and sewage treatment.
【０００２】[0002]
【従来の技術】水溶性高分子化合物を取扱う場合、吸湿
による固結によって投入等の工程のトラブル、あるいは
微粉の飛散によって作業環境を悪化させる欠点を有す
る。水溶性高分子化合物の吸湿による固結の防止には、
特公昭５９−４５００３公報に見られる如く、重合体分
子内にある塩型カルボキシル基が酸型であった場合に示
す重合体の解離恒数よりも大きい解離恒数を有する酸で
処理したり、特公昭５８−５１９６６公報、特公昭６１
−４８５４６公報に記載される如く、水溶性高分子重合
体粉末に硫酸水素アルカリ金属塩及び塩基性無機塩、さ
らに必要に応じて、硫酸マグネシウム含水塩及び／また
は吸湿剤を配合して、易分散性とともに固結対策にも効
果を発揮することが知られる。2. Description of the Related Art When handling a water-soluble polymer compound, there is a drawback that the work environment is deteriorated due to troubles in the process such as charging due to solidification due to moisture absorption or scattering of fine powder. To prevent solidification due to moisture absorption of water-soluble polymer compounds,
As disclosed in JP-B-59-45003, treatment with an acid having a dissociation constant larger than the dissociation constant of the polymer shown when the salt-type carboxyl group in the polymer molecule is acid-type, Japanese Patent Publication 58-51966, Japanese Patent Publication 61
As described in JP-A-48546, a water-soluble polymer powder is mixed with an alkali metal hydrogensulfate and a basic inorganic salt, and if necessary, a magnesium sulfate hydrate and / or a hygroscopic agent to facilitate dispersion. It is known that it exerts an effect as a measure against caking together with the sex.
【０００３】微粉の飛散による防塵対策としては、特開
昭５７−８５８４４公報では、水溶性粒状ポリマーに、
ポリエチレングリコールまたはポリプロピレングリコー
ルの１〜５０重量％水溶液を前記ポリマーに対し、１〜
２０重量％添加することが開示され、特公昭６１−２１
４９２公報では、水溶性高分子化合物粉末、水溶性無機
化合物粉末及び沸点１５０℃以上の常温液状有機化合物
を配合し、防塵処理による自由流動性の低下を防止する
事と、溶解時の水分散性を良好とした技術が知見として
得られている。以上の従来の技術では、水溶性高分子化
合物に対する添加剤の添加率が高く、有効分が極めて低
くなったり、処理するための工程の新設を要するなどの
問題点を有する。As measures against dust due to scattering of fine powder, Japanese Patent Application Laid-Open No. 57-85844 discloses that a water-soluble granular polymer is used.
A 1 to 50% by weight aqueous solution of polyethylene glycol or polypropylene glycol is added to the polymer in an amount of 1 to
It is disclosed that 20% by weight is added.
In 492 publication, a water-soluble polymer compound powder, a water-soluble inorganic compound powder, and a room-temperature liquid organic compound having a boiling point of 150 ° C. or more are blended to prevent reduction of free-flowing property due to dustproof treatment, and water dispersibility during dissolution. Has been obtained as knowledge. The above-mentioned conventional techniques have problems that the addition rate of the additive to the water-soluble polymer compound is high, the effective content is extremely low, and a new process for treatment is required.
【０００４】水溶性高分子化合物にシリカを応用した技
術としては、特開昭５８−１３４１０６公報で成形され
た含水ケーキの表面を無水ケイ酸を主成分とする高分散
性軽質シリカ粉末で被覆した後乾燥することにより、乾
燥工程での相互接着の防止を行なうことが開示されてい
る。また、特開昭６３−２６０９２８公報では、粉末状
の水溶性高分子化合物に対して、疎水性シリカを添加混
合することにより、易分散性水溶性ポリマーの製造を行
ない、いわゆる「まま粉」対策を行なっている。As a technique of applying silica to a water-soluble polymer compound, the surface of a water-containing cake formed in JP-A-58-134106 is coated with a highly dispersible light silica powder containing silicic acid as a main component. It is disclosed that post-drying prevents mutual adhesion in the drying step. Further, in Japanese Patent Laid-Open No. 63-260928, a readily dispersible water-soluble polymer is produced by adding hydrophobic silica to a powdery water-soluble polymer compound, which is a so-called “as-is” measure. Are doing.
【０００５】[0005]
【発明が解決しようとする課題】水溶性高分子化合物
は、その性質上湿度の高い環境下では速やかに吸湿し、
粒子同志が相互粘着を起こし、流動性を失い、さらには
ケーキングを生ずることとなり供給作業の際には、供給
装置のホッパーあるいはフィーダーを閉塞したり、溶解
時には「まま粉」を生じたりする現象が見られる。ま
た、水溶性高分子化合物は製造時乾燥後粉砕し、篩別工
程を通しているがそれでも供給作業時には、微粉の飛散
による作業環境悪化を生ずる。The water-soluble polymer compound absorbs moisture quickly in an environment with high humidity due to its nature,
Particles stick to each other, lose fluidity, and cause caking, which may cause the hopper or feeder of the feeder to be clogged during the feeding operation, or "the powder remains" during the melting. Can be seen. Further, the water-soluble polymer compound is pulverized after being dried at the time of manufacturing, and is passed through a sieving process, but even during the supplying operation, the working environment is deteriorated due to scattering of fine powder.
【０００６】本発明者は、粒状水溶性高分子化合物の吸
湿、防塵を更に自然流動性をも保持することを課題とし
検討を行なった。これらの問題を解決すれば工程の自動
化、省力化、究極的には無人化が可能となり、その上、
防塵できれば通常行なわれている微粉の篩別工程を省略
出来、このため製品の収率は向上し、収益にも寄与す
る。The present inventor has conducted studies with the objective of maintaining moisture absorption and dust protection of the granular water-soluble polymer compound and also maintaining natural fluidity. If these problems are solved, it will be possible to automate the process, save labor, and ultimately unmanned.
If dust can be prevented, the usual fine powder sieving process can be omitted, which improves the product yield and contributes to profits.
【０００７】[0007]
【課題を解決するための手段】本発明は、含有水分３〜
１５％、粒径２．０ｍｍ以下の粒状水溶性高分子化合物
に一次粒子の平均径５〜５０μｍで親水性のシリカ０．
１〜０．５重量％を均一に混合し被覆することを特徴と
する粒状水溶性高分子化合物の製造方法にある。SUMMARY OF THE INVENTION The present invention has a water content of 3 to 3.
15%, granular water-soluble polymer compound having a particle diameter of 2.0 mm or less, hydrophilic silica with an average primary particle diameter of 5 to 50 μm.
A method for producing a granular water-soluble polymer compound is characterized by uniformly mixing and coating 1 to 0.5% by weight.
【０００８】本発明で対象とする水溶性高分子化合物と
しては次のものが挙げられる。 （１）（メタ）アクリルアミド （２）（メタ）アクリル酸 （３）２−アクリルアミド−２−メチルプロパンスルホ
ン酸 （４）（メタ）アクリル酸ジメチルアミノエチルの３級
塩、４級塩The water-soluble polymer compounds targeted by the present invention include the following. (1) (meth) acrylamide (2) (meth) acrylic acid (3) 2-acrylamido-2-methylpropanesulfonic acid (4) tertiary salt of dimethylaminoethyl (meth) acrylate, quaternary salt
【０００９】[0009]
【化１】 [Chemical 1]
【化２】 [Chemical 2]
【００１０】（５）（メタ）アクリルアミドプロピルト
リメチルの３級塩、４級塩(5) Tertiary salt of (meth) acrylamidopropyltrimethyl, quaternary salt
【化３】 （ここでＲ3 、Ｒ4 はＨまたはＣＨ3 ，ＸはＣｌ、Ｂ
ｒ，1/2 ＳＯ4 を表す。）から選ばれる単独重合体又は
共重合体であり、通常微粉状又は微粒子状をなしてお
り、一般にその粒径は、２０ｍｍ以下である。[Chemical 3] (Here, R 3 and R 4 are H or CH 3 , X is Cl, B
represents r, 1/2 SO 4 . 1) is a homopolymer or a copolymer, which is usually in the form of fine powder or fine particles, and generally has a particle size of 20 mm or less.
【００１１】粒状の水溶性高分子化合物を工業的に製造
する場合、（１）乾燥直後に粉砕し梱包する方法と、
（２）乾燥後、一時貯蔵した後、粉砕し梱包する方法が
ある。乾燥は、通常５０〜１２０℃の温度範囲で行なわ
れるが、乾燥直後は粒子表面の水分は極めて低く、中心
部は高く粒子内で水分の分布を生じている。水分の分布
は高分子化合物を構成するモノマーの種類組成により異
なるが、放置すれば水分は粒子内で均一となり、表面に
水分が含まれる様になると考えられる。When industrially producing a granular water-soluble polymer compound, (1) a method of crushing and packing immediately after drying,
(2) After drying, there is a method of temporarily storing, then crushing and packing. Drying is usually performed in a temperature range of 50 to 120 ° C., but immediately after the drying, the water content on the surface of the particles is extremely low, the central portion is high, and the water distribution is generated within the particles. The distribution of water varies depending on the type and composition of the monomers constituting the polymer compound, but it is considered that if left to stand, the water becomes uniform in the particles and the surface contains water.
【００１２】本発明は、粉状を含めた粒状の水溶性高分
子化合物にシリカを均一に混合し、高分子粒子を被覆す
る。使用するシリカとしては親水性シリカを用いる。シ
リカには表面のシラノール基を有機珪素ハロゲン化物等
によって疎水性にした製品もあるが、水溶性高分子化合
物は親水性であるため親水性シリカとの相互作用は強い
と考えられる。In the present invention, silica is uniformly mixed with a granular water-soluble polymer compound including powder to coat polymer particles. Hydrophilic silica is used as silica. Some silicas have a silanol group on the surface thereof made hydrophobic by an organic silicon halide or the like, but since the water-soluble polymer compound is hydrophilic, it is considered that the interaction with the hydrophilic silica is strong.
【００１３】疎水性シリカと粒子状水溶性高分子化合物
を混合し、表面を均一に被覆するには、親水性シリカよ
り強い混合を要し固結、防塵の効果を発現させるために
は添加量を多く要する。しかも疎水性シリカの欠点は、
高分子化合物を水に溶解するため投入した際、粒子が疎
水性のため浮遊しやすく、撹拌してもフロック状態とな
り、親水性シリカの場合より可成の長時間を要するので
親水性シリカより高価な疎水性シリカの使用は好ましく
ない。In order to mix the hydrophobic silica and the particulate water-soluble polymer compound and uniformly coat the surface, stronger mixing than that of the hydrophilic silica is required, and the addition amount is required in order to exert the effect of consolidation and dust prevention. Takes a lot. Moreover, the disadvantage of hydrophobic silica is
It is more expensive than hydrophilic silica because when it is added to dissolve a high molecular compound in water, the particles tend to float because of its hydrophobicity, and it becomes a floc state even if it is stirred, and it takes a longer period of time than hydrophilic silica. The use of transparent hydrophobic silica is not preferred.
【００１４】使用する親水性シリカの一次粒子の平均粒
径は５〜５０ｎｍの範囲のものである。シリカは二次粒
子となっているが水溶性高分子と混合するときシェアー
により、より小さな二次粒子となる。このとき新たなシ
リカ表面のシラノール基の水素原子が水溶性高分子と結
合または粘着により水溶性高分子粒子を被覆する。シリ
カの粒径が大きくなると水溶性高分子を被覆するシリカ
の量を多く要し、又、付着、粘着状態を保持できなくな
る。The average particle size of the primary particles of the hydrophilic silica used is in the range of 5 to 50 nm. Silica is a secondary particle, but when mixed with a water-soluble polymer, it becomes a smaller secondary particle due to shear. At this time, a new hydrogen atom of the silanol group on the surface of silica covers the water-soluble polymer particles by binding or adhering with the water-soluble polymer. If the particle size of silica is large, a large amount of silica is required to coat the water-soluble polymer, and it becomes impossible to maintain the state of adhesion and adhesion.
【００１５】親水性シリカを添加混合する時期はシリカ
表面のＳｉ・ＯＨが水溶性高分子化合物の粒子表面の水
分と相互作用をし、付着させる必要があるのでシリカの
混合により、微粉の飛散防止効果を発現させるためには
乾燥直後より、１０分以上好ましくは３０分以上放置し
た後混合する。又この方が混合に要する動力は小さくな
る。At the time of adding and mixing the hydrophilic silica, Si.OH on the surface of the silica interacts with the water on the surface of the particles of the water-soluble polymer compound, and it is necessary to attach them. Therefore, by mixing the silica, the fine powder is prevented from scattering. In order to bring out the effect, the mixture is left for 10 minutes or more, preferably 30 minutes or more immediately after drying and then mixed. Also, this requires less power for mixing.
【００１６】処理時の水溶性高分子化合物の含有水分
は、高いほど親水性シリカ添加の効果が明確となるが、
３％以下は熱負荷が大きく５％程度以上が好ましい。
又、高分子化合物の種類に依存する所は大きいが、略々
１５％以下、通常取り扱われる製品で１０％程度以下が
好ましい。従って、乾燥直後に粉砕する方法では粉砕後
に、乾燥後一時貯蔵後粉砕する方法の場合には粉砕時、
あるいは粉砕後に混合することが効果的である。The higher the water content of the water-soluble polymer compound during treatment, the more clearly the effect of adding hydrophilic silica becomes,
If it is 3% or less, the heat load is large, and it is preferably about 5% or more.
Although it depends largely on the kind of the polymer compound, it is preferably about 15% or less, and about 10% or less for the products usually handled. Therefore, in the method of crushing immediately after drying, after crushing, in the case of the method of crushing after temporary storage after drying, during crushing,
Alternatively, mixing after crushing is effective.
【００１７】シリカの添加量は粒子状水溶性高分子化合
物の平均粒子径を１．０ｍｍとし、シリカを１０ｎｍと
すると、重量で約０．０２％の添加で単粒子で被覆する
ことになるが、シリカはフロック状で特に強いシェアー
を掛けていないため、必要添加量は微分の飛散防止の為
には０．０５％以上好ましくは０．１％以上が必要であ
り、吸湿しても固結防止あるいは自然流動性保持の為に
は０．２％以上、好ましくは０．５％以上を要する。し
かし、約５％以上の添加では効果の向上が現われず、更
に多くすればシリカ単独で混存することになり好ましく
ない。本発明の実施に好適に用いることのできる親水性
シリカとしては、日本アエロジル株式会社製のアエロジ
ル、シオノギ製薬株式会社製のカープレックス＃８０，
＃６７，ＸＲ等である。If the average particle diameter of the particulate water-soluble polymer compound is 1.0 mm and the silica is 10 nm, about 0.02% by weight of silica will be added to cover the particles with single particles. Since silica is a floc and does not have a particularly strong shear, the necessary addition amount is required to be 0.05% or more, preferably 0.1% or more for preventing differential scattering, and even if moisture is absorbed, the solidification occurs. 0.2% or more, preferably 0.5% or more is required to prevent or maintain natural fluidity. However, addition of about 5% or more does not improve the effect, and if the amount is further increased, silica alone is present as a mixture, which is not preferable. Hydrophilic silica that can be preferably used in the practice of the present invention includes Aerosil manufactured by Nippon Aerosil Co., Ltd., Carplex # 80 manufactured by Shionogi Pharmaceutical Co., Ltd.,
# 67, XR, etc.
【００１８】粒状の水溶性高分子化合物は、親水性シリ
カで被覆する前に、液状の消泡剤で処理しておくと本発
明の効果を一層高めることができる。消泡剤を添加被覆
しておくと、親水性シリカとの漏れがよくなり、粒状水
溶性高分子化合物の使用時、煙状となって飛散する微粒
子が発生するのを防止し、作業性、作業環境の改善を果
すことができる。If the granular water-soluble polymer compound is treated with a liquid defoaming agent before being coated with hydrophilic silica, the effect of the present invention can be further enhanced. When an antifoaming agent is added and coated, leakage with hydrophilic silica is improved, and when using a granular water-soluble polymer compound, it is possible to prevent generation of fine particles that become smoke-like and scatter, and workability, The working environment can be improved.
【００１９】使用できる消泡剤としてはポリエーテル
型、エマルション型、鉱油配合型の何れでもよく、これ
らは例えばダイヤフロック株式会社製ＡＦ１０３、旭電
化工業株式会社製アデカノールＬＧ６７８、アデカネー
トＢ５５６の商品名で市販されている。As the defoaming agent which can be used, any of a polyether type, an emulsion type and a mineral oil blending type may be used, and these are, for example, AF103 manufactured by Diafloc Co., Ltd., Adekanol LG678 manufactured by Asahi Denka Kogyo Co., Ltd., and Adecanate B556. It is commercially available.
【００２０】本発明は、粒状の水溶性高分子化合物を親
水性シリカで被覆処理する前に、水溶性高分子化合物に
界面活性剤を添加被覆することを包含する。界面活性剤
の付着量は純分で０．０１〜１．０重量％になるようそ
の水溶液を水溶性高分子化合物製造時に添加する。The present invention includes adding a surfactant to the water-soluble polymer compound before coating the granular water-soluble polymer compound with the hydrophilic silica. The aqueous solution of the surfactant is added at the time of producing the water-soluble polymer compound so that the amount of the attached surfactant is 0.01 to 1.0% by weight in pure content.
【００２１】使用する界面活性剤は、カルボン酸塩、ス
ルホン酸塩、硫酸エステル塩の陰イオン系、脂肪族の４
級アンモニウム塩の陽イオン系、エーテル型、エーテル
エステル型、エステル型の非イオン系の界面活性剤であ
る。これらは何れも水溶液の形で用いる。界面活性剤を
水溶性高分子を製造する工程で添加しておくと、高含水
分で水溶性高分子化合物を粗砕する工程で高分子化合物
同志の付着を防止すると共に、親水性シリカと水溶性高
分子の濡れを良くし、均一混合を助長する。界面活性剤
は消泡剤と同時に用いてもよい。The surfactants used are carboxylate, sulfonate, sulfate ester salt anionic, and aliphatic 4
It is a cationic, ether-type, ether-ester, or ester-type nonionic surfactant of a primary ammonium salt. All of these are used in the form of an aqueous solution. If a surfactant is added in the step of producing a water-soluble polymer, the adhesion of polymer compounds will be prevented and the hydrophilic silica and water Improves the wetting of the polymer and promotes uniform mixing. The surfactant may be used together with the defoaming agent.
【００２２】[0022]
【実施例】次に、実施例で本発明を説明する。なお、実
施例中「部」とあるのは重量部を意味する。 〔実施例１〕容器に７９％のジメチルアミノエチルアク
リレートのメチルクロライド４級塩水溶液８９０部、５
０％アクリルアミド水溶液１５５部、純水２５５部を採
取した。光重合開始剤としてベンゾインエチルエーテル
を３０ｐｐｍ、エチレンジアミン４酢酸２ナトリウム塩
を５０ｐｐｍ、花王（株）製サニーゾールＢ−５０を純
分で１０００ｐｐｍ、ダイヤフロック（株）製消泡剤Ａ
Ｆ−１０３を５００ｐｐｍ（いずれも単量体溶液に対
し）を添加した。２０℃に保持し撹拌しながら１０Ｎ硫
酸を加え、ｐＨを４．５±０．１に調整し、次いで窒素
置換を２０分間行なった。EXAMPLES Next, the present invention will be explained with reference to examples. In addition, "part" in an Example means a weight part. [Example 1] 890 parts of an aqueous solution of 79% dimethylaminoethyl acrylate quaternary salt in a container, 5
155 parts of 0% acrylamide aqueous solution and 255 parts of pure water were collected. As a photopolymerization initiator, 30 ppm of benzoin ethyl ether, 50 ppm of ethylenediamine tetraacetic acid disodium salt, 1000 ppm of Saniosol B-50 manufactured by Kao Co., Ltd. in pure content, Defoamer A manufactured by Diafloc Co., Ltd.
F-103 was added at 500 ppm (both to the monomer solution). The pH was adjusted to 4.5 ± 0.1 by adding 10N sulfuric acid while maintaining the temperature at 20 ° C. with stirring, and then performing nitrogen replacement for 20 minutes.
【００２３】次にステンレス板に深さが２０ｍｍとなる
ような堰を作り、底面が約２３ｃｍ×２ｃｍの容器と
し、側面、底面をポリエチレンテフタレートフィルム
（厚さ１２μ）で覆い、上記の溶液を注ぎその上をポリ
エチレンテレフタレートフィルム（厚さ１２μ）にポリ
塩化ビニルデンを塗布（厚さ４μ）したフィルムで覆っ
た。下方より２０℃の水を霧状として吹き付け、上方よ
り三菱電機（株）製蛍光ケミカルランプを用い、２Ｗ／
ｍ2 の照射強度で、溶液表面温度が４℃上昇するまで照
射しその後０．５Ｗ／ｍ2 の照射強度で５０分、その後
６０Ｗ／ｍ2 で１０分間紫外線を照射した。重合体を容
器より取り出し、鋏で約３ｍｍ×５ｍｍ×４０ｍｍの棒
状に切断し、６０℃で１２時間乾燥し、ウィレー型粉砕
機で粉砕しサンプルとした。２００ｍｌのポリエチレン
製広口ビンに表１記載の所定量のシリカ（日本アエロジ
ル（株）製アエロジル３００）を採取し、所定量の上記
ポリマーを採取し、蓋をし、手で激しく２分間振盪した
後アルミ皿上に５．０ｇを採取し均一に広げ室内に放置
し水分、サンプルの性状を観察した。その結果を表１に
示した。水分は吸収するが固結は完全に防止されている
ことが確認された。また、シリカ無添加と１％添加の物
につき安息角を測定したところ無添加で４１．０度が３
６．０度となり、自然流動性は向上することが確認され
た。Next, a weir having a depth of 20 mm was formed on the stainless steel plate to make a container having a bottom of about 23 cm × 2 cm, the side and bottom were covered with a polyethylene terephthalate film (thickness 12 μ), and the above solution was added. After pouring, the film was covered with a film of polyvinyl terephthalate film (thickness 12 μm) coated with polyvinylidene chloride (thickness 4 μm). Spray water of 20 ° C as a mist from below and use a fluorescent chemical lamp from Mitsubishi Electric Corp. from above to 2W /
In the irradiation intensity of m 2, followed by irradiation to the surface of the solution temperature rises 4 ° C. 50 minutes at an irradiation intensity of 0.5 W / m 2, and then irradiated for 10 minutes ultraviolet rays 60 W / m 2. The polymer was taken out of the container, cut into a rod shape having a size of about 3 mm × 5 mm × 40 mm with scissors, dried at 60 ° C. for 12 hours, and pulverized with a Willey pulverizer to obtain a sample. A predetermined amount of silica (Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.) shown in Table 1 was collected in a 200 ml polyethylene wide-mouthed bottle, and a predetermined amount of the above polymer was collected, covered with a cap, and vigorously shaken by hand for 2 minutes. 5.0 g was sampled on an aluminum dish, spread uniformly, and allowed to stand in a room to observe water and sample properties. The results are shown in Table 1. It was confirmed that water was absorbed but caking was completely prevented. In addition, the angle of repose was measured for the product with no added silica and the product with 1% added.
It was 6.0 degrees, and it was confirmed that the natural fluidity was improved.
【００２４】[0024]
【表１】 [Table 1]
【００２５】〔実施例２〕８０％のジメチルアミノエチ
ルメタアクリレートのメチルクロライド４級塩水溶液１
３００部を採取した。光重合開始剤としてベンゾインエ
チルエーテルを１００ｐｐｍ、エチレンジアミン４酢酸
２ナトリウム塩を５０ｐｐｍを単量体溶液に添加した。
３０℃に保持し撹拌しながら１０Ｎ硫酸を加え、ｐＨを
５．０±０．５に調整し、次いで窒素置換を３０分間行
なった。冷却水を３０℃とする以外は実施例１と同様に
して重合し、容器より取り出し室温まで冷却した後、粗
砕し８０℃で８時間乾燥し、ウィレー型粉砕機で粉砕し
サンプルとした。２００ｍｌのポリエチレン製広口ビン
に所定量のシリカを実施例１と同様に採取し、所定量の
上記ポリマーを採取し蓋をし、手で激しく２分間振盪し
た直後に蓋をとり微粉の飛散状況を観察した。その結果
を表２に示した。比較のためシリカ無添加と、１％添加
したサンプルの粒度分布を測定した。その結果を表３に
示した。超微粉のシリカを１％添加したにもかかわらず
１００メッシュ通過分は、むしろ減少し、粒径の大なる
方は激しい振盪中に粉砕されているものと判断でき、防
塵効果は絶大なものである。[Example 2] 80% dimethylaminoethyl methacrylate methyl chloride quaternary salt aqueous solution 1
300 parts were collected. As a photopolymerization initiator, 100 ppm of benzoin ethyl ether and 50 ppm of ethylenediaminetetraacetic acid disodium salt were added to the monomer solution.
The pH was adjusted to 5.0 ± 0.5 by adding 10N sulfuric acid while maintaining the temperature at 30 ° C. with stirring, and then nitrogen substitution was performed for 30 minutes. Polymerization was carried out in the same manner as in Example 1 except that the cooling water was changed to 30 ° C., taken out of the container, cooled to room temperature, roughly crushed, dried at 80 ° C. for 8 hours, and crushed by a Wiley crusher to obtain a sample. A predetermined amount of silica was sampled in a 200 ml polyethylene wide-mouthed bottle in the same manner as in Example 1, a predetermined amount of the above polymer was sampled, the lid was covered, and immediately after shaking vigorously for 2 minutes by hand, the lid was removed and the fine powder was scattered. I observed. The results are shown in Table 2. For comparison, the particle size distributions of the sample without silica addition and the sample with 1% addition were measured. The results are shown in Table 3. Even though 1% of ultrafine silica was added, the amount passing through 100 mesh was rather reduced, and the one with a larger particle size can be judged to have been crushed during vigorous shaking, and the dustproof effect is great. is there.
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【表３】 [Table 3]
【００２８】〔実施例３〕粒状水溶性高分子であるダイ
ヤフロック（株）製凝集剤、ＫＰ−５００，ＫＰ−１２
０１Ｂ，ＫＰ−１２０７Ｂ，ＮＰ−８００，ＡＰ−７４
１を入手、ウィレー型粉砕機で２回粉砕し微分の発生す
るサンプルを作り、実施例１で用いたと同じ親水性シリ
カ０．５重量％添加したものと無添加のものとの微粉の
飛散状況を判定した結果を表４に示した。ＫＰ５００に
ついては親水性シリカを１％添加しても全く飛散は見ら
れなかった。Example 3 Flocculant KP-500, KP-12 manufactured by Diafloc Co., Ltd., which is a granular water-soluble polymer.
01B, KP-1207B, NP-800, AP-74
1 was obtained, and the sample was pulverized twice with a Willey-type pulverizer to produce a sample in which differentiation occurs, and the same fine powder as in Example 1 with 0.5% by weight of hydrophilic silica added and without addition of fine powder Table 4 shows the result of the judgment. Regarding KP500, no scattering was observed even when 1% of hydrophilic silica was added.
【００２９】 表 ４ 水溶性高分子化合物 シリカ無添加 ０．５％シリカ添加 銘 柄 ＫＰ−５００ 可成の飛散が見られる 極々僅かに飛散が見られる ＫＰ−１２０１Ｂ 僅かに飛散する 全く飛散しない ＫＰ−１２０７Ｂ 少し飛散する 同 上 ＮＰ−８００ 同 上 同 上 ＡＰ−７４１ 同 上 同 上Table 4 Water-soluble polymer compound No silica added 0.5% silica added Brand KP-500 A slight amount of scattering is observed KP-1201B A slight amount of scattering is observed KP-120B A slight amount of scattering KP- 1207B Slightly scattered Same as above NP-800 Same as above Same as above AP-741 Same as above Same as above
【００３０】〔実施例４〕実施例２で得た重合体に、固
形分に対し純分が０．５％重量となるように ダイヤフロック（株）製消泡剤ＡＦ−１０３ 花王（株）製カチオン界面活性剤サニゾールＢ−５０ を表面に塗布した後、実施例２と同様にサンプルを作成
した。夫々のサンプルに日本アエロジル（株）製アエロ
ジル３００を０．２％を混合し、微粉の飛散状況を観察
した結果を表５に示す。[Example 4] The polymer obtained in Example 2 was mixed so that the pure content was 0.5% by weight based on the solid content. Defoamer AF-103 manufactured by Diafloc Co., Ltd. Kao Corporation. A cationic surfactant Sanizole B-50 was applied to the surface, and then a sample was prepared in the same manner as in Example 2. Table 5 shows the results obtained by mixing 0.2% of Aerosil 300 manufactured by Nippon Aerosil Co., Ltd. into each sample and observing the dispersion state of fine powder.
【００３１】 表 ５ サンプル 微粉飛散状況 無添加 極僅か粉立ちする程度 ＡＦ−１０３ 全く粉立ちしない サニゾールＢ−５０ 同 上Table 5 Samples Fine powder scattering status Additive-less powdery degree AF-103 No powdery Sanizole B-50 Same as above
【００３２】[0032]
【発明の効果】本発明は、粒状水溶性高分子化合物の製
造時、保管時、使用時に於ける作業環境の改善、製造工
程の安定化、省力化に寄与すると共に、粒状水溶性高分
子化合物の収率向上をもたらす。即ち微粒子を篩別する
ことなく親水性シリカで粒子表面を被覆するので微粒子
の飛散がなく、又、篩別工程を省略できそのため製品の
収率が向上する。収率の上昇は高分子化合物の種類、組
成によって異なるが約０．３％から１０％程度期待でき
る。親水性シリカで被覆された粒状水溶性高分子化合物
は、粒子相互の付着を生せず、安息角、流動性が向上す
る。このため保管、移送中流動性を保ち溶解時に「まま
粉」を生ずることもなく、作業性がよく、又、微粉の発
生が少ないので作業環境を良好に保つ等優れた効果を奏
しその価値は大である。INDUSTRIAL APPLICABILITY The present invention contributes to improvement of the working environment during production, storage and use of a granular water-soluble polymer compound, stabilization of the production process, and labor saving. Yield improvement. That is, since the surface of the particles is coated with the hydrophilic silica without sieving the particles, the particles are not scattered, and the sieving step can be omitted, so that the product yield is improved. The increase in yield depends on the type and composition of the polymer compound, but can be expected to be about 0.3% to 10%. The granular water-soluble polymer compound coated with hydrophilic silica does not cause mutual adhesion of particles, and improves repose angle and fluidity. For this reason, it retains fluidity during storage and transfer, does not generate "as-is powder" during dissolution, has good workability, and produces little fine powder, so it has excellent effects such as maintaining a good working environment and its value. Is large.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年５月１０日[Submission date] May 10, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】[0007]
【課題を解決するための手段】本発明は、含有水分３〜
１５％、粒径２．０ｍｍ以下の粒状水溶性高分子化合物
に一次粒子の平均径５〜５０ｎｍで親水性のシリカ０．
１〜５．０重量％を均一に混合し被覆することを特徴と
する粒状水溶性高分子化合物の製造方法にある。SUMMARY OF THE INVENTION The present invention has a water content of 3 to 3.
15%, granular water-soluble polymer compound having a particle size of 2.0 mm or less, hydrophilic silica with an average primary particle size of 5 to 50 nm .
A method for producing a granular water-soluble polymer compound is characterized in that 1 to 5.0 % by weight is uniformly mixed and coated.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】（５）（メタ）アクリルアミドプロピルト
リメチルの３級塩、４級塩(5) Tertiary salt of (meth) acrylamidopropyltrimethyl, quaternary salt
【化３】（ここでＲ３、Ｒ４はＨまたはＣＨ３、ＸはＣ
ｌ，Ｂｒ，１／２ＳＯ４を表す。）から選ばれる単独重
合体又は共重合体であり、通常微粉状又は微粒子状をな
しており、一般にその粒径は、２ｍｍ以下である。Embedded image (wherein R 3 and R 4 are H or CH 3 , and X is C
1, Br, and 1 / 2SO 4 . 1) is a homopolymer or a copolymer, which is usually in the form of fine powder or fine particles, and generally has a particle size of 2 mm or less.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１８】粒状の水溶性高分子化合物は、親水性シリ
カで被覆する前に、液状の消泡剤で処理しておくと本発
明の効果を一層高めることができる。消泡剤を添加被覆
しておくと、親水性シリカとの濡れがよくなり、粒状水
溶性高分子化合物の使用時、煙状となって飛散する微粒
子が発生するのを防止し、作業性、作業環境の改善を果
すことができる。If the granular water-soluble polymer compound is treated with a liquid defoaming agent before being coated with hydrophilic silica, the effect of the present invention can be further enhanced. When an antifoaming agent is added and coated, the wettability with hydrophilic silica is improved, and when using a granular water-soluble polymer compound, it is possible to prevent generation of fine particles that become smoke-like and scatter, and workability, The working environment can be improved.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２８[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２８】〔実施例３〕粒状水溶性高分子であるダイ
ヤフロック（株）製凝集剤、ＫＰ−５００，ＫＰ−１２
０１Ｂ，ＫＰ−１２０７Ｂ，ＮＰ−８００，ＡＰ−７４
１を入手、ウィレ−型粉砕機で２回粉砕し微分の発生す
るサンプルを作り、実施例１で用いたと同じ親水性シリ
カ０．５重量％添加したものと無添加のものとの微粉の
飛散状況を判定した結果を表４に示した。ＫＰ５００に
ついては親水性シリカを１％添加すれば全く飛散は見ら
れなくなった。Example 3 Flocculant KP-500, KP-12 manufactured by Diafloc Co., Ltd., which is a granular water-soluble polymer.
01B, KP-1207B, NP-800, AP-74
1 was obtained, and the sample was crushed twice with a Wille-type crusher to produce a sample in which a differential was generated, and the same fine powder as that used in Example 1 with 0.5% by weight of hydrophilic silica added and no added powder scattering The results of judging the situation are shown in Table 4. Completely scattered be added hydrophilic Silica 1% for KP500 was Kuna' such observed.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】化３[Name of item to be corrected]
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【化３】 [Chemical 3]
【手続補正書】[Procedure amendment]
【提出日】平成６年３月８日[Submission date] March 8, 1994
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】（５）（メタ）アクリルアミドプロピルト
リメチルの３級塩、４級塩(5) Tertiary salt of (meth) acrylamidopropyltrimethyl, quaternary salt
【化３】 [Chemical 3]
Claims (3)
下の粒状水溶性高分子化合物に一次粒子の平均径５〜５
０ｎｍで親水性のシリカ０．１〜５．０重量％を均一に
混合し被覆することを特徴とする粒状水溶性高分子化合
物の製造方法。1. A granular water-soluble polymer compound having a water content of 3 to 15% and a particle diameter of 2.0 mm or less, and an average diameter of primary particles of 5 to 5
A process for producing a granular water-soluble polymer compound, characterized in that 0.1 to 5.0% by weight of hydrophilic silica at 0 nm is uniformly mixed and coated.
１〜１．０重量％の液体の消泡剤で被覆した後、親水性
のシリカを混合し被覆することを特徴とする請求項１の
粒状水溶性高分子化合物の製造方法。2. The surface of the granular water-soluble polymer compound is 0.0
2. The method for producing a granular water-soluble polymer compound according to claim 1, which comprises coating with 1 to 1.0% by weight of a liquid antifoaming agent and then mixing and coating hydrophilic silica.
性剤の純成分が０．０１〜１．０重量％となるように界
面活性剤の水溶液で被覆した後、親水性のシリカを混合
し被覆することを特徴とする請求項１の粒状水溶性高分
子化合物の製造方法。3. The surface of the granular water-soluble polymer compound is coated with an aqueous solution of a surfactant so that the pure component of the surfactant is 0.01 to 1.0% by weight, and then hydrophilic silica is mixed. The method for producing the granular water-soluble polymer compound according to claim 1, wherein the method is a coating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03059767A JP3113687B2 (en) | 1991-03-01 | 1991-03-01 | Method for producing granular water-soluble polymer compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03059767A JP3113687B2 (en) | 1991-03-01 | 1991-03-01 | Method for producing granular water-soluble polymer compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06192432A true JPH06192432A (en) | 1994-07-12 |
| JP3113687B2 JP3113687B2 (en) | 2000-12-04 |
Family
ID=13122766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03059767A Expired - Lifetime JP3113687B2 (en) | 1991-03-01 | 1991-03-01 | Method for producing granular water-soluble polymer compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3113687B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004535167A (en) * | 2001-04-02 | 2004-11-25 | ジェネンコー・インターナショナル・インク | Granules with reduced potential for dust generation |
| JP2006111711A (en) * | 2004-10-14 | 2006-04-27 | Japan Exlan Co Ltd | Flyable fine particle |
| JP2019522062A (en) * | 2016-04-14 | 2019-08-08 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Coated polymer particles comprising a water swellable polymer core and a sol-gel coating |
-
1991
- 1991-03-01 JP JP03059767A patent/JP3113687B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004535167A (en) * | 2001-04-02 | 2004-11-25 | ジェネンコー・インターナショナル・インク | Granules with reduced potential for dust generation |
| JP2006111711A (en) * | 2004-10-14 | 2006-04-27 | Japan Exlan Co Ltd | Flyable fine particle |
| JP4752235B2 (en) * | 2004-10-14 | 2011-08-17 | 日本エクスラン工業株式会社 | Flying fine particles |
| JP2019522062A (en) * | 2016-04-14 | 2019-08-08 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Coated polymer particles comprising a water swellable polymer core and a sol-gel coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3113687B2 (en) | 2000-12-04 |
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