JPH05222107A - Production of water-absorbing fine polymer particle - Google Patents
Production of water-absorbing fine polymer particleInfo
- Publication number
- JPH05222107A JPH05222107A JP2535692A JP2535692A JPH05222107A JP H05222107 A JPH05222107 A JP H05222107A JP 2535692 A JP2535692 A JP 2535692A JP 2535692 A JP2535692 A JP 2535692A JP H05222107 A JPH05222107 A JP H05222107A
- Authority
- JP
- Japan
- Prior art keywords
- water
- particle size
- polymer
- monomer
- polymerization
- 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
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は吸水性ポリマーの製造法
に関し、更に詳細には制汗剤素材等として好適な吸水能
と粒径を有する吸水性ポリマー微粒子を、工業的に容易
かつ安価に製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a water-absorbent polymer, and more specifically, to easily and inexpensively industrially produce water-absorbent polymer fine particles having a water-absorbing ability and a particle size suitable as an antiperspirant material. It relates to a method of manufacturing.
【０００２】[0002]
【従来の技術】近年吸水性ポリマーは生理用品、おむつ
等の衛生剤や農業分野での保水剤、土壌改良剤、更には
人工スキー場の人工雪、洗顔料のスクラブ剤等、広範な
分野で利用されてきている。またこれらの用途の他に化
粧品分野、特に汗を吸収する制汗剤として利用しようと
する例も欧州特許第１１６２号、特開昭５０−１２６８
２０号、同５０−７７５４８号、同６０−８１１２０
号、特開平３−１０９３１６号等に開示されている。こ
の場合、人体に使用するため、安全性は言うまでもな
く、使用時の感触、特に吸汗時の感触、さっぱり感の持
続性等が重要視される。2. Description of the Related Art In recent years, water-absorbent polymers have been used in a wide range of fields such as sanitary products, sanitary agents for diapers, water retention agents in the agricultural field, soil conditioners, artificial snow on artificial ski slopes, and scrub agents for facial cleansers. It has been used. In addition to these applications, there is also an example in which it is used in the field of cosmetics, in particular, as an antiperspirant that absorbs sweat, European Patent No. 1162 and JP-A No. 50-1268.
No. 20, No. 50-77548, No. 60-81120
And Japanese Patent Application Laid-Open No. 3-109316. In this case, since it is used for the human body, not only the safety but also the feeling during use, especially the feeling during sweating, the persistence of a refreshing feeling, etc. are emphasized.
【０００３】この種の用途に使用される吸水性ポリマー
としてはアクリル酸塩重合体の架橋物、アクリルアミド
−アクリル酸塩共重合体の架橋物、ビニルアルコール−
アクリル酸塩共重合体の架橋物、アクリル酸塩−メタク
リル酸塩共重合体の架橋物、澱粉−アクリル酸塩グラフ
ト共重合体の架橋物、澱粉−アクリロニトリルグラフト
共重合体の加水分解物の架橋物、カルボキシメチルセル
ロース架橋物等が知られているが、アクリル酸塩重合体
の架橋物が安価で容易に高吸水能を有することから、最
も好ましい吸水性ポリマーであるとされている。The water-absorbing polymer used for this type of application includes a cross-linked product of an acrylate polymer, a cross-linked product of an acrylamide-acrylate copolymer, a vinyl alcohol-
Acrylate copolymer cross-linked product, acrylate-methacrylate copolymer cross-linked product, starch-acrylic acid graft copolymer cross-linked product, starch-acrylonitrile graft copolymer hydrolyzed product cross-linked product And carboxymethyl cellulose cross-linked products are known, but they are considered to be the most preferable water-absorbing polymers because the cross-linked products of acrylate polymers are inexpensive and easily have high water absorption ability.
【０００４】従来、アクリル酸塩の重合方法としては、
重合熱の除去の容易さという利点から逆相乳化重合およ
び逆相懸濁重合が工業的に一般化している。これらの重
合法を用いてα，β−不飽和カルボン酸から粉末重合体
を得る方法は、例えば特公昭３４−１０６４４号、同５
３−４５３５７号、同５３−４６３８９号、同５４−３
０７１０号、特開昭５６−２６９０９号、特公昭６０−
２５０４５号、特開昭５７−１６７３０２号、同６１−
４３６０６号等に開示されている。Conventionally, as a method for polymerizing an acrylate,
Reverse phase emulsion polymerization and reverse phase suspension polymerization have been industrially generalized because of the advantage of easy removal of the heat of polymerization. A method for obtaining a powder polymer from an α, β-unsaturated carboxylic acid by using these polymerization methods is described in, for example, JP-B-34-10644 and JP-A-5-10644.
3-45357, 53-46389, 54-3
0710, JP-A-56-26909, JP-B-60-
25045, JP-A-57-167302, 61-
No. 43606 and the like.
【０００５】[0005]
【発明が解決しようとする課題】しかし、これら従来の
重合法では、重合反応槽の温度制御が困難であり、反応
の暴走、凝集物の生成等が起こり、粒径が小さく、凝集
物のないまたは少ない吸水性ポリマー微粒子を得ること
は困難であった。従って、本発明の目的は制汗剤素材等
のような化粧品材料として利用できる、好適な吸水能と
小さな粒径を有する吸水性ポリマー微粒子を工業的に容
易に製造する方法を提供することにある。However, in these conventional polymerization methods, it is difficult to control the temperature of the polymerization reaction tank, reaction runaway, agglomerate formation, etc. occur, and the particle size is small and there is no agglomerate. Alternatively, it has been difficult to obtain few water-absorbent polymer fine particles. Therefore, an object of the present invention is to provide a method for industrially easily producing water-absorbing polymer fine particles having a suitable water-absorbing capacity and a small particle size, which can be used as a cosmetic material such as an antiperspirant material. ..
【０００６】[0006]
【課題を解決するための手段】そこで本発明者等は、こ
のような観点から逆相懸濁重合法および逆相乳化重合法
の条件を種々検討した結果、分散安定化剤として特定の
ＨＬＢを有する化合物を用い、重合前にモノマーを油中
水型微小分散滴を形成しておき、これを滴下しつつ重合
させることにより、重合反応を徐々に進行させることが
でき、凝集が抑制されるため優れた性能を有する吸水性
ポリマー微粒子が得られることを見出し、本発明を完成
した。Therefore, as a result of various studies on the conditions of the reverse phase suspension polymerization method and the reverse phase emulsion polymerization method from the above viewpoints, the present inventors have found that a specific HLB is used as a dispersion stabilizer. By using the compound having a monomer to form water-in-oil type micro-dispersed droplets before polymerization, and polymerizing while dropping the droplets, the polymerization reaction can be gradually progressed and aggregation is suppressed. The inventors have found that water-absorbent polymer fine particles having excellent performance can be obtained, and completed the present invention.
【０００７】すなわち、本発明は、α，β−不飽和カル
ボン酸モノマーまたは／およびその塩を油中水型の逆相
懸濁重合させる吸水性ポリマーの製造法において、分散
安定化剤としてＨＬＢが３〜９のショ糖脂肪酸エステ
ル、ソルビタンエステルおよびこれらのポリオキシアル
キレン付加物から選ばれる１種または２種以上を用い、
重合前に予めモノマーの油中水型の微小分散滴を形成せ
しめ、その微小分散滴を昇温した有機溶媒中に滴下して
重合させることを特徴とする吸水性ポリマー微粒子の製
造法を提供するものである。That is, according to the present invention, HLB is used as a dispersion stabilizer in a method for producing a water-absorbing polymer in which an α, β-unsaturated carboxylic acid monomer or / and a salt thereof is subjected to water-in-oil type reverse phase suspension polymerization. 3 to 9 sucrose fatty acid ester, sorbitan ester and one or more selected from polyoxyalkylene adducts thereof,
Provided is a method for producing water-absorbing polymer fine particles, characterized in that water-in-oil type fine dispersion droplets of a monomer are formed in advance before polymerization, and the fine dispersion droplets are dropped into an organic solvent to be polymerized for polymerization. It is a thing.
【０００８】本発明に用いられるα，β−不飽和カルボ
ン酸モノマーとしては、アクリル酸、メタクリル酸、イ
タコン酸、クロトン酸、マレイン酸、フマール酸等を挙
げることができる。これらの中で最も好適なものはアク
リル酸である。その塩としては、ナトリウム塩、カリウ
ム塩等のアルカリ金属塩を挙げることができるが、ナト
リウム塩が最も安価であり好ましい。これらのα，β−
不飽和カルボン酸モノマー塩のうち、アクリル酸ナトリ
ウムはポリアクリル酸ナトリウムが化粧品原料基準合格
品であり、安全性の点から特に好ましい。Examples of the α, β-unsaturated carboxylic acid monomer used in the present invention include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid. The most preferred of these is acrylic acid. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, but sodium salt is the most inexpensive and preferred. These α, β-
Among the unsaturated carboxylic acid monomer salts, sodium acrylate is a sodium polyacrylate that passes the cosmetic material standard, and is particularly preferable from the viewpoint of safety.
【０００９】本発明においては、通常α，β−不飽和カ
ルボン酸をアルカリで中和して重合に供するが、その中
和度は５０〜９５％、特に６５〜７５％が好ましい。低
すぎるとポリマーの酸性度が増し、高すぎるとモノマー
水溶液の濃度を高くすることが困難となり好ましくな
い。In the present invention, the .alpha.,. Beta.-unsaturated carboxylic acid is usually neutralized with an alkali for polymerization, and the degree of neutralization is preferably 50 to 95%, particularly preferably 65 to 75%. If it is too low, the acidity of the polymer increases, and if it is too high, it is difficult to increase the concentration of the aqueous monomer solution, which is not preferable.
【００１０】モノマー濃度は４０重量％以上が好まし
く、それ未満では経済的でなく、またジエポキシ化合物
のような水と反応して失活する架橋剤を用いる場合は、
効率的な架橋が進行しない問題が発生する。The monomer concentration is preferably 40% by weight or more, and if it is less than 40% by weight, it is not economical, and in the case of using a crosslinking agent such as a diepoxy compound which is deactivated by reacting with water,
There is a problem that efficient crosslinking does not proceed.
【００１１】本発明においては、架橋剤は必らずしも必
要ではないが、架橋剤の存在下に重合を行うこともでき
る。吸水性ポリマーは、一般に架橋度を高めれば吸水量
が低下するが、ある程度架橋させることにより必要以上
に膨潤し、皮膚上での感触、特に異物感が生じることを
防止することができる。In the present invention, the crosslinking agent is not always necessary, but the polymerization can be carried out in the presence of the crosslinking agent. Generally, the water absorption amount of a water-absorbent polymer decreases as the degree of cross-linking is increased. However, it is possible to prevent the water-absorbent polymer from swelling more than necessary by being cross-linked to some extent and causing a feeling on the skin, particularly a feeling of foreign matter.
【００１２】本発明に用いられる架橋剤としては、α，
β−不飽和カルボン酸モノマーまたは／およびその塩か
ら得られる重合体を架橋させ得るものであれば如何なる
ものであってもよく、重合性架橋剤として例えば、メチ
レンビスアクリルアミド、メチレンビスメタクリルアミ
ド等のビスアミド類や、エチレングリコールジアクリレ
ート、エチレングリコールジメタクリレート、プロピレ
ングリコールジアクリレート、プロピレングリコールジ
メタクリレート、ポリオキシエチレングリコールジアク
リレート、グリセリントリアクリレート等のポリオール
類のジまたはトリ（メタ）アクリレートが挙げられ；
α，β−不飽和カルボン酸モノマーおよびその塩または
その重合体中に存在するカルボキシル基との反応性を利
用した架橋剤として、例えば（ポリ）エチレングリコー
ルジグリシジルエーテル、（ポリ）プロピレングリコー
ルジグリシジルエーテル、（ポリ）グリセロールジグリ
シジルエーテル、（ポリ）グリセロールトリグリシジル
エーテル、（ポリ）グリセロールテトラグリシジルエー
テル、ソルビトールジグリシジルエーテル、ソルビトー
ルトリグリシジルエーテル、ソルビトールテトラグリシ
ジルエーテル、ペンタエリスリトールジグリシジルエー
テル、ペンタエリスリトールトリグリシジルエーテル、
ペンタエリスリトールテトラグリシジルエーテル等のポ
リグリシジル化合物類や、エピクロルヒドリン、エピブ
ロムヒドリン、α−メチルエピクロルヒドリン等のハロ
エポキシ化合物類や、２，４−トリレンジイソシアネー
ト、ヘキサメチレンンジイソシアネート等のイソシアネ
ート化合物類が挙げられる。この中でメチレンビスアク
リルアミド、エチレングリコールジグリシジルエーテル
が最も好ましい。The cross-linking agent used in the present invention includes α,
Any polymer may be used as long as it can crosslink the polymer obtained from the β-unsaturated carboxylic acid monomer or / and its salt, and examples of the polymerizable crosslinking agent include methylenebisacrylamide and methylenebismethacrylamide. Bisamides and di- or tri (meth) acrylates of polyols such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, polyoxyethylene glycol diacrylate, and glycerin triacrylate;
Examples of the cross-linking agent utilizing the reactivity with the carboxyl group present in the α, β-unsaturated carboxylic acid monomer and its salt or its polymer include, for example, (poly) ethylene glycol diglycidyl ether and (poly) propylene glycol diglycidyl. Ether, (poly) glycerol diglycidyl ether, (poly) glycerol triglycidyl ether, (poly) glycerol tetraglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tri Glycidyl ether,
Examples include polyglycidyl compounds such as pentaerythritol tetraglycidyl ether, haloepoxy compounds such as epichlorohydrin, epibromhydrin, α-methylepichlorohydrin, and isocyanate compounds such as 2,4-tolylene diisocyanate and hexamethylene diisocyanate. Be done. Of these, methylenebisacrylamide and ethylene glycol diglycidyl ether are most preferable.
【００１３】架橋剤は一般にモノマーに対し、０．００
１〜１０重量％、特に０．０１〜６重量％の割合で使用
されるのが好ましい。０．００１重量％より少ないと得
られる吸水性ポリマーが必要以上に膨潤し感触低下をも
たらし、１０重量％を超えると吸水能力が著しく低下
し、べたつきを感じることとなり好ましくない。The cross-linking agent is generally 0.00
It is preferably used in a proportion of 1 to 10% by weight, in particular 0.01 to 6% by weight. If it is less than 0.001% by weight, the resulting water-absorbing polymer swells more than necessary and the feel is deteriorated, and if it exceeds 10% by weight, the water-absorbing ability is remarkably lowered and stickiness is felt, which is not preferable.
【００１４】重合開始剤としては、通常の水溶性ラジカ
ル重合開始剤を用いることができる。水溶性アゾ系開始
剤では、２，２’−アゾビス（２−アミジノプロパン）
ハイドロクロライド、２，２’−アゾビス〔２−メチル
−Ｎ−（２−ヒドロキシエチル）−プロピオンアミ
ド〕、２，２’−アゾビス｛２−〔１−（２−ヒドロキ
シエチル）−２−イミダゾリン−２−イル〕プロパン｝
ジハイドライド等を例示することができ、水溶性過酸化
物では、過硫酸カリウム、過硫酸アンモニウム、過酸化
水素等を例示することができ、これらと例えば亜硫酸塩
の如き還元性物質、またはアミン等と組み合わせてレド
ックス開始剤としてもよい。As the polymerization initiator, a usual water-soluble radical polymerization initiator can be used. Water-soluble azo initiators include 2,2'-azobis (2-amidinopropane)
Hydrochloride, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazoline- 2-yl] propane}
Examples thereof include dihydride, and examples of the water-soluble peroxide include potassium persulfate, ammonium persulfate, hydrogen peroxide, etc., and a reducing substance such as sulfite, or an amine and the like. The redox initiator may be used in combination.
【００１５】重合開始剤の使用量はモノマーに対して、
０．０１〜１重量％が好ましく、少なすぎるとスムーズ
な重合が開始されにくく、１重量％を超えるとモノマー
分散滴の有機溶媒への滴下以前に重合が開始される危険
性が高くなり好ましくない。The amount of the polymerization initiator used is based on the monomer.
0.01 to 1% by weight is preferable, and if it is too small, smooth polymerization is difficult to start, and if it exceeds 1% by weight, there is a high risk of polymerization being started before dropping the monomer dispersion droplets into the organic solvent, which is not preferable. ..
【００１６】本発明において有機溶媒は、モノマーを油
中水型の微小分散滴とする場合の油相成分として、また
この分散滴を滴下する反応槽の溶媒としても使用され
る。かかる有機溶媒としては石油系炭化水素が好まし
く、例えばノルマルヘキサン、ノルマルヘプタン、リグ
ロイン等の脂肪族炭化水素、シクロヘキサン、メチルシ
クロヘキサン等の脂環族炭化水素、ベンゼン、トルエ
ン、キシレン等の芳香族炭化水素が使用し得るが、乾燥
吸水性ポリマー微粒子の融着を引き起こす恐れのある芳
香族炭化水素より、ノルマルヘキサン、シクロヘキサン
等の脂肪族或は脂環族炭化水素がより好ましい。有機溶
媒の使用量はモノマー水溶液の量に対して広い範囲に渡
って可変であるが、経済的な面から一般に有機溶媒は少
ない方が有利である。しかし、少なすぎると発熱の除去
が困難になり、また反応槽には反応液を撹拌可能な程度
に仕込んでおくことも必要である。従って、通常モノマ
ー水溶液と有機溶媒の容量比は１：１〜１：６の間が適
当である。In the present invention, the organic solvent is used as an oil phase component when the monomer is made into water-in-oil type finely dispersed droplets, and also as a solvent in a reaction vessel for dropping the dispersed droplets. As the organic solvent, petroleum hydrocarbons are preferable, for example, normal hexane, normal heptane, aliphatic hydrocarbons such as ligroin, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, benzene, toluene, aromatic hydrocarbons such as xylene. However, aliphatic or alicyclic hydrocarbons such as normal hexane and cyclohexane are more preferable than aromatic hydrocarbons that may cause fusion of dry water-absorbing polymer particles. The amount of the organic solvent used can be varied over a wide range with respect to the amount of the aqueous monomer solution, but it is generally advantageous from the economical viewpoint that the amount of the organic solvent is small. However, if the amount is too small, it becomes difficult to remove the heat generation, and it is also necessary to prepare the reaction solution in a reaction tank so that the reaction solution can be stirred. Therefore, it is usually appropriate that the volume ratio of the aqueous monomer solution to the organic solvent be 1: 1 to 1: 6.
【００１７】本発明において分散安定化剤は、α，β−
不飽和カルボン酸モノマーまたは／およびその塩の水溶
液を油相（有機溶媒）中に分散安定化させるために使用
されるものであり、油溶性界面活性剤であるＨＬＢ３〜
９のショ糖脂肪酸エステル、ソルビタンエステルおよび
これらのポリオキシアルキレン付加物から選ばれる１種
または２種以上が使用される。ショ糖脂肪酸エステルと
しては、脂肪酸がステアリン酸、パルミチン酸、ラウリ
ン酸、オレイン酸等の飽和または不飽和の脂肪酸から成
るショ糖エステルが好ましい。そのエステル個数はショ
糖１単位当り１〜６個であり得る。具体的なショ糖脂肪
酸エステルとしては、ショ糖モノステアレート、ショ糖
ジステアレート、ショ糖トリステアレート、ショ糖モノ
パルミテート、ショ糖ジパルミテート、ショ糖トリパル
ミテート、ショ糖モノラウレート、ショ糖ジラウレー
ト、ショ糖トリラウレート、ショ糖モノオレート、ショ
糖ジオレート、ショ糖トリオレート、ショ糖ポリステア
レート、ショ糖ポリパルミテート、ショ糖ポリラウレー
ト、ショ糖ポリオレート等が挙げられる。ソルビタンエ
ステルとしては、脂肪酸がステアリン酸、パルミチン
酸、ラウリン酸、オレイン酸等の飽和または不飽和の脂
肪酸から成るソルビタンエステルが好ましく、そのエス
テル個数はソルビタン１単位当り１〜４個であり得る。
具体的にはソルビタンモノステアレート、ソルビタンジ
ステアレート、ソルビタントリステアレート、ソルビタ
ンモノパルミテート、ソルビタンジパルミテート、ソル
ビタントリパルミテート、ソルビタンモノラウレート、
ソルビタンジラウレート、ソルビタントリラウレート、
ソルビタンモノオレート、ソルビタンジオレート、ソル
ビタントリオレート等が挙げられる。また、これらのポ
リオキシアルキレン付加物としては、ポリオキシエチレ
ン付加物、ポリオキシプロピレン付加物が挙げられ、例
えばポリオキシエチレンソルビタンモノステアレート、
ポリオキシエチレンソルビタンモノパルミテート、ポリ
オキシエチレンソルビタンモノラウレート、ポリオキシ
エチレンソルビタンモノオレート、ポリオキシエチレン
ソルビタントリステアレート等が挙げられる。また、こ
れらの分散安定化剤は１種または２種以上を混合して用
いることができる。ＨＬＢは３〜９が適当範囲であり、
低すぎると微粒子以外にゲル化物を生じてしまい、高す
ぎると石油系炭化水素溶媒への溶解性が低下し、分散能
が落ち不経済である。In the present invention, the dispersion stabilizer is α, β-
It is used to stabilize an aqueous solution of an unsaturated carboxylic acid monomer or / and a salt thereof in an oil phase (organic solvent), and is an oil-soluble surfactant of HLB3 to
One or more selected from sucrose fatty acid ester, sorbitan ester and polyoxyalkylene adduct thereof of 9 are used. The sucrose fatty acid ester is preferably a sucrose ester in which the fatty acid is a saturated or unsaturated fatty acid such as stearic acid, palmitic acid, lauric acid and oleic acid. The number of esters can be 1 to 6 per unit of sucrose. Specific sucrose fatty acid esters include sucrose monostearate, sucrose distearate, sucrose tristearate, sucrose monopalmitate, sucrose dipalmitate, sucrose tripalmitate, sucrose monolaurate, sucrose. Examples thereof include dilaurate, sucrose trilaurate, sucrose monooleate, sucrose dioleate, sucrose trioleate, sucrose polystearate, sucrose polypalmitate, sucrose polylaurate and sucrose polyoleate. The sorbitan ester is preferably a sorbitan ester in which the fatty acid is a saturated or unsaturated fatty acid such as stearic acid, palmitic acid, lauric acid and oleic acid, and the number of the ester can be 1 to 4 per 1 unit of sorbitan.
Specifically, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monolaurate,
Sorbitan dilaurate, sorbitan trilaurate,
Examples thereof include sorbitan monooleate, sorbitan diolate and sorbitan trioleate. Examples of these polyoxyalkylene adducts include polyoxyethylene adducts and polyoxypropylene adducts, such as polyoxyethylene sorbitan monostearate,
Examples thereof include polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan tristearate. These dispersion stabilizers can be used alone or in combination of two or more. HLB is a suitable range of 3-9,
If it is too low, a gelled substance other than the fine particles will be produced, and if it is too high, the solubility in petroleum hydrocarbon solvents will be reduced, and the dispersibility will be reduced, which is uneconomical.
【００１８】分散安定化剤の適当な添加量はモノマーに
対して、通常０．１〜１５重量％であり、好ましくは１
〜５重量％である。少なすぎると安定な油中分散滴を形
成せず、多すぎると不経済であり、かつ生成したポリマ
ー中に多量の分散安定化剤が混入するため、吸水能が低
下する。A suitable amount of the dispersion stabilizer added is usually 0.1 to 15% by weight, preferably 1
~ 5% by weight. When the amount is too small, stable dispersed droplets in oil are not formed, and when the amount is too large, it is uneconomical, and a large amount of the dispersion stabilizer is mixed in the produced polymer, so that the water absorption ability is lowered.
【００１９】本発明における重合反応は、重合反応前に
予めモノマー水溶液の微小分散滴を調製し、これを反応
槽の有機溶媒中に滴下して重合させることにより行われ
る。微小分散滴の調製法は、ポリマー微粒子として所望
の平均粒径が得られるような分散方法であれば特に限定
されないが、例えばモノマー水溶液と有機溶媒、重合開
始剤、分散安定化剤、および必要であれば架橋剤とを混
合し、強力な水流を利用したホモジナイザー、回転羽根
と機壁あるいは回転羽根同士のギャップにかかる高シェ
アーを利用した連続乳化分散機、超音波分散機等を用い
て分散したり、特開平２−９５４３３号に開示されてい
るようなセラミックミクロ多孔膜にモノマー水溶液を加
圧して通し分散媒に圧入する方法等を用いて分散する方
法等が好ましい。The polymerization reaction in the present invention is carried out by preparing finely dispersed droplets of an aqueous monomer solution in advance before the polymerization reaction and dropping them into an organic solvent in a reaction vessel to carry out polymerization. The method for preparing the fine dispersion droplets is not particularly limited as long as it is a dispersion method that can obtain a desired average particle size as polymer fine particles, and for example, an aqueous monomer solution and an organic solvent, a polymerization initiator, a dispersion stabilizer, and if necessary. If necessary, mix with a cross-linking agent and disperse using a homogenizer using a strong water flow, a continuous emulsification disperser using a high shear applied to the rotating blade and the machine wall or the gap between the rotating blades, an ultrasonic disperser, etc. Alternatively, a method of dispersing by using a method of pressurizing an aqueous monomer solution through a ceramic microporous membrane as disclosed in JP-A No. 2-95433 and pressurizing it into a dispersion medium is preferable.
【００２０】得られた分散滴は、有機溶媒と必要により
分散安定化剤を仕込み、撹拌下で窒素置換し昇温した反
応槽へ滴下する。この時の分散安定化剤量は滴下する分
散滴の分散安定化剤濃度に合わせた濃度が好ましく、少
なすぎると反応槽に滴下したモノマーの分散滴が重合前
に崩れゲル化したり、反応槽内壁への付着、平均粒径の
増大をもたらす恐れがあり、多すぎると不経済となる。
反応温度は５０〜８５℃が好ましい。この場合滴下と同
時に重合が起こることが好ましい。必要以上に温度を上
げることは、不経済であり、滴下途中でのモノマー分散
滴の安定滴下が難しくなる。途中発熱の状態によって適
宜冷却もしくは加熱を行うこともできる。The obtained dispersion droplets are added to an organic solvent and, if necessary, a dispersion stabilizer, and are dropped into a reaction tank whose temperature is raised by nitrogen substitution with stirring. The amount of the dispersion stabilizer at this time is preferably a concentration according to the concentration of the dispersion stabilizer of the added dispersion drops, and if it is too small, the dispersion drops of the monomer dropped in the reaction tank collapse and gel before polymerization, or the inner wall of the reaction tank. If it is too much, it becomes uneconomical.
The reaction temperature is preferably 50 to 85 ° C. In this case, it is preferable that the polymerization occurs at the same time as the dropping. It is uneconomical to raise the temperature more than necessary, and it becomes difficult to stably drop the monomer-dispersed drops during the dropping. It is also possible to appropriately perform cooling or heating depending on the state of heat generation during the process.
【００２１】モノマー分散滴を全量滴下した後、重合反
応と架橋反応を完結させるために、還流温度で熟成を行
うこともできる。反応終了後、冷却し、目的ポリマー微
粒子をそのまま抜き出して、乾燥してもよいし、冷却の
前に共沸により適当量の脱水を行い、その後冷却して乾
燥してもよいし、脱水と溶媒の濃縮を行った後に冷却し
て乾燥してもよい。また適度に脱水した後に、更に熟成
を行い残存している架橋剤による架橋反応を更に進める
方法をとることもできる。製造の簡便さから考えれば、
脱水をせずに、そのまま乾燥することが有利ではある
が、水によって膨潤したポリマー微粒子をそのまま乾燥
すると微粒子同士の融着が起こり易い。従って反応終了
後、適当な脱水を行って乾燥することが好ましい。After the entire amount of the monomer dispersed droplets has been dropped, aging may be carried out at the reflux temperature in order to complete the polymerization reaction and the crosslinking reaction. After completion of the reaction, the reaction mixture may be cooled and the target polymer fine particles may be directly extracted and dried, or an appropriate amount of dehydration may be performed by azeotropy before cooling, and then cooling and drying may be performed. May be cooled and dried after concentration. It is also possible to adopt a method in which after adequate dehydration, further aging is carried out to further promote the crosslinking reaction with the remaining crosslinking agent. Considering the ease of manufacturing,
It is advantageous to dry the particles as they are without dehydration, but if the polymer particles swollen with water are dried as they are, fusion of the particles is likely to occur. Therefore, it is preferable to perform appropriate dehydration and dry after the completion of the reaction.
【００２２】このようにして得られるポリマー微粒子は
安全性が著しく重要視される用途のためには、水と親水
性溶媒の混合液で洗浄を行うのが好ましい。その方法
は、例えば特公昭４３−１０９６号、特開平１−２９２
００３号等に開示されている。The polymer fine particles thus obtained are preferably washed with a mixed solution of water and a hydrophilic solvent for applications where safety is extremely important. The method is described, for example, in Japanese Examined Patent Publication No. 43-1096 and Japanese Patent Laid-Open No. 1-292.
No. 003 and the like.
【００２３】かくして得られる吸水性ポリマー微粒子
は、通常１〜５０μｍの平均粒径を有し、粒度分布が狭
く、均質な１次粒子、あるいは物理的に弱く凝集した２
次粒子として得られる。従って、そのままでも吸汗剤素
材として供することができるが、必要に応じて簡単な解
砕、分級を行って極僅かな不純物を除去後、吸汗剤素材
として供するのが好ましい。The water-absorbent polymer fine particles thus obtained usually have an average particle size of 1 to 50 μm, have a narrow particle size distribution, are homogeneous primary particles, or are physically weakly aggregated.
Obtained as secondary particles. Therefore, it can be used as it is as a sweat absorbent material, but it is preferable to use it as a sweat absorbent material after performing simple crushing and classification to remove a very small amount of impurities as necessary.
【００２４】[0024]
【発明の効果】本発明の方法によって得られるポリマー
は微粒子で、粒度分布の狭い均質な粒子であり、自重の
５倍以上の吸水性能を有し、化粧品分野、特に汗を吸収
する制汗剤素材として極めて有効なポリマーであるばか
りか、通常、吸水性ポリマーが大量に用いられている生
理用品、紙おむつ等の衛生剤、保水剤、土壌改良剤等の
農業分野等にも広く利用され得る。EFFECT OF THE INVENTION The polymer obtained by the method of the present invention is a fine particle, is a homogeneous particle having a narrow particle size distribution, has a water absorption capacity of 5 times or more of its own weight, and is an antiperspirant which absorbs sweat in the field of cosmetics. Not only is it a polymer that is extremely effective as a raw material, but it can also be widely used in the fields of agriculture, such as sanitary products in which large amounts of water-absorbing polymers are usually used, sanitizers such as paper diapers, water retention agents, soil conditioners, and the like.
【００２５】[0025]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明するが、本発明はこれら実施例に限定されるもので
はない。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
【００２６】実施例１ ８０重量％の工業用アクリル酸２５５ｇを２ｌのビーカ
ーに取り、冷却しつつ撹拌下、３０重量％の苛性ソーダ
水溶液２８０ｇを滴下して７４％の中和を行った後、過
硫酸カリウム０．８ｇを２０mlの水に溶解した溶液と架
橋剤であるエチレングリコールジグリシジルエーテル
（商品名、デナコールＥＸ８１０、長瀬化成（株）製）
１０．２ｇを加え、均一に溶解した。得られた溶液を２
ｌのビーカー中、シクロヘキサン１kgに分散安定化剤で
あるショ糖ステアリン酸エステル（商品名、リョートー
シュガーエステルＳ−５７０とＳ−７７０の等重量混合
物、三菱食品化学（株）製）５ｇを加熱溶解して得られ
た溶液に添加し、ホモミキサーを用い、回転数１０００
０rpm で５分間強撹拌を行い微細な油中水型分散滴を作
った。次に還流冷却器を付した、５ｌのステンレス製反
応釜に上記分散安定化剤と同種の分散安定化剤５ｇとシ
クロヘキサン１kgを入れ４００rpm で撹拌し、予め系内
を８０℃に加熱し、窒素置換した溶液の中に、前述のア
クリル酸部分中和油中水型分散滴を滴下し、同時に重合
を開始させた。全量を１時間で滴下した後、還流温度
（７２℃）で更に４時間熟成を行った。その後脱水管を
取り付け、昇温し２７０mlの脱水を行い、更に１５００
mlのシクロヘキサンを蒸発留去後、放冷し反応を完結し
た。減圧下で蒸発乾固を行うことによって２５０ｇの微
粉末状の白色乾燥ポリマーを得た。更にこのポリマーを
１２５０ｇの７０重量％エタノールと９５重量％エタノ
ールによって洗浄した後、再び減圧下で蒸発乾固を行っ
た。コーヒーミルにより解砕を行い、２００ｇの微粉末
状の白色乾燥ポリマーを得た。得られた乾燥ポリマー微
粒子の平均粒径は２．０μｍであり、最大粒子の粒径が
１０μｍという粒度分布の狭い均質な微粒子であること
がわかった。また、大過剰の生理食塩水で膨潤した粒子
は平均粒径が７．４μｍで最大粒子の粒径も３０μｍ以
下であり、制汗剤素材として使用された場合、発汗時に
も異物感を感じることのない大きさであり、好適な素材
であることが判明した。Example 1 255 g of 80% by weight industrial acrylic acid was placed in a 2 l beaker, and 280 g of a 30% by weight caustic soda aqueous solution was added dropwise under cooling with stirring to neutralize 74%. Solution of 0.8 g of potassium sulfate dissolved in 20 ml of water and ethylene glycol diglycidyl ether as a cross-linking agent (trade name, Denacol EX810, manufactured by Nagase Kasei Co., Ltd.)
10.2 g was added and uniformly dissolved. The resulting solution is 2
In a 1-liter beaker, 1 g of cyclohexane is heated with 5 g of sucrose stearate (trade name, equal weight mixture of Ryoto sugar ester S-570 and S-770, manufactured by Mitsubishi Food Chemical Co., Ltd.) which is a dispersion stabilizer. Add to the solution obtained by dissolving and use a homomixer to rotate at 1000 rpm.
The mixture was vigorously stirred at 0 rpm for 5 minutes to form fine water-in-oil type dispersed droplets. Next, in a 5 liter stainless steel reaction kettle equipped with a reflux condenser, 5 g of the dispersion stabilizer of the same kind as the above dispersion stabilizer and 1 kg of cyclohexane were put and stirred at 400 rpm, and the system was preheated to 80 ° C. and nitrogen was added. Into the replaced solution, the above-mentioned water-in-oil type partially dispersed oil neutralized with acrylic acid was added dropwise to initiate polymerization at the same time. After the entire amount was added dropwise over 1 hour, the mixture was aged at reflux temperature (72 ° C.) for 4 hours. After that, attach a dehydration tube, raise the temperature to dehydrate 270 ml, and further 1500
After evaporating and distilling off ml of cyclohexane, the mixture was allowed to cool to complete the reaction. By evaporating to dryness under reduced pressure, 250 g of fine powdery white dry polymer was obtained. Further, this polymer was washed with 1250 g of 70% by weight ethanol and 95% by weight ethanol, and then evaporated to dryness under reduced pressure again. Crushing was performed with a coffee mill to obtain 200 g of a fine powdery white dry polymer. It was found that the average particle diameter of the obtained dry polymer fine particles was 2.0 μm, and the maximum particle diameter was 10 μm, which were homogeneous fine particles having a narrow particle size distribution. Further, the particles swollen with a large excess of saline have an average particle size of 7.4 μm and a maximum particle size of 30 μm or less, and when used as a material for an antiperspirant, feel a foreign body sensation during sweating. It was proved to be a suitable material because of its size.
【００２７】実施例２ 分散安定化剤をリョートーシュガーエステルＳ−９７０
（三菱食品化学（株）製）に変えた以外は、実施例１と
同条件で製造を行い、２１０ｇの微粉末状の白色乾燥ポ
リマーを得た。この乾燥ポリマーの平均粒径は２．１μ
ｍであり、最大粒子の粒径は、１２μｍという粒度分布
であった。また大過剰の生理食塩水で膨潤した粒子は、
平均粒径が７．８μｍであり、最大粒子の粒径が２８μ
ｍであった。Example 2 Ryoto-Sugar Ester S-970 was used as the dispersion stabilizer.
Production was carried out under the same conditions as in Example 1 except that the product was manufactured by Mitsubishi Food Chemical Co., Inc., and 210 g of fine powdery white dry polymer was obtained. The average particle size of this dry polymer is 2.1μ
m, and the particle size of the largest particles was 12 μm. Particles swollen with a large excess of saline solution
The average particle size is 7.8 μm, and the maximum particle size is 28 μm.
It was m.
【００２８】実施例３ 分散安定化剤をリョートーシュガーエステルＳ−５７０
（三菱食品化学（株）製）に変えた以外は、実施例１と
同条件で製造を行い、２０５ｇの微粉末状の白色乾燥ポ
リマーを得た。この乾燥ポリマーの平均粒径は１．９μ
ｍであり、最大粒子の粒径は、１０μｍという粒度分布
であった。また大過剰の生理食塩水で膨潤した粒子は、
平均粒径が７．３μｍであり、最大粒子の粒径が２５μ
ｍであった。Example 3 Ryoto Sugar Ester S-570 was used as a dispersion stabilizer.
Production was carried out under the same conditions as in Example 1 except that the product was manufactured by Mitsubishi Food Chemical Co., Inc., and 205 g of fine powdery white dry polymer was obtained. The average particle size of this dry polymer is 1.9μ.
m, and the maximum particle size was 10 μm. Particles swollen with a large excess of saline solution
The average particle size is 7.3 μm, and the maximum particle size is 25 μm.
It was m.
【００２９】実施例４ 分散安定化剤をソルビタンモノステアレートに変え、有
機溶媒をノルマルヘキサンに変え、重合開始時の昇温温
度を６８℃にした以外は、実施例１と同条件で製造を行
い、２００ｇの微粉末状の白色乾燥ポリマーを得た。こ
の乾燥ポリマーの平均粒径は２．３μｍであり、最大粒
子の粒径は、１８μｍという粒度分布であった。また大
過剰の生理食塩水で膨潤した粒子は、平均粒径が１２．
５μｍであり、最大粒子の粒径が５０μｍであった。Example 4 Production was carried out under the same conditions as in Example 1 except that the dispersion stabilizer was changed to sorbitan monostearate, the organic solvent was changed to normal hexane, and the temperature elevation temperature at the start of polymerization was 68 ° C. Then, 200 g of fine powdery white dry polymer was obtained. The average particle size of this dry polymer was 2.3 μm, and the maximum particle size was 18 μm. The particles swollen with a large excess of physiological saline have an average particle size of 12.
It was 5 μm, and the maximum particle size was 50 μm.
【００３０】実施例５ 分散安定化剤をソルビタンモノステアレート、ソルビタ
ンジステアレート、ソルビタントリステアレートおよび
ポリオキシエチレンソルビタンモノステアレートの配合
比が１０：４：３：３重量比で混合したものを用いた以
外は、実施例４と同条件で製造を行い、１９５ｇの微粉
末状の白色乾燥ポリマーを得た。この乾燥ポリマーの平
均粒径は２．０μｍであり、最大粒子の粒径は、２０μ
ｍという粒度分布であった。また大過剰の生理食塩水で
膨潤した粒子は、平均粒径が１０．３μｍであり、最大
粒子の粒径が４２μｍであった。Example 5 A dispersion stabilizer mixed with sorbitan monostearate, sorbitan distearate, sorbitan tristearate and polyoxyethylene sorbitan monostearate in a mixing ratio of 10: 4: 3: 3 by weight. Was used under the same conditions as in Example 4 except that was used to obtain 195 g of a fine powdery white dry polymer. The average particle size of this dry polymer is 2.0 μm, and the maximum particle size is 20 μm.
The particle size distribution was m. The particles swollen with a large excess of physiological saline had an average particle size of 10.3 μm and a maximum particle size of 42 μm.
【００３１】実施例６ 分散安定化剤をソルビタンモノパルミテートに変えた以
外は、実施例４と同条件で製造を行い、２１５ｇの微粉
末状の白色乾燥ポリマーを得た。この乾燥ポリマーの平
均粒径は２．１μｍであり、最大粒子の粒径は、１５μ
ｍという粒度分布であった。また大過剰の生理食塩水で
膨潤した粒子は、平均粒径が７．８μｍであり、最大粒
子の粒径が２８μｍであった。Example 6 Production was carried out under the same conditions as in Example 4 except that sorbitan monopalmitate was used as the dispersion stabilizer, and 215 g of fine powdery white dry polymer was obtained. The average particle size of this dry polymer is 2.1 μm and the maximum particle size is 15 μm.
The particle size distribution was m. The particles swollen with a large excess of physiological saline had an average particle size of 7.8 μm and a maximum particle size of 28 μm.
【００３２】実施例７ 架橋剤をメチレンビスアクリルアミドに変えた以外は、
実施例１と同条件で製造を行い、２００ｇの微粉末状の
白色乾燥ポリマーを得た。この乾燥ポリマーの平均粒径
は２．３μｍであり、最大粒子の粒径は、１８μｍとい
う粒度分布であった。また大過剰の生理食塩水で膨潤し
た粒子は、平均粒径が１４．８μｍであり、最大粒子の
粒径が７２μｍであった。Example 7 Except that the cross-linking agent was changed to methylenebisacrylamide.
The production was performed under the same conditions as in Example 1 to obtain 200 g of a fine powdery white dry polymer. The average particle size of this dry polymer was 2.3 μm, and the maximum particle size was 18 μm. The particles swollen with a large excess of physiological saline had an average particle size of 14.8 μm and a maximum particle size of 72 μm.
【００３３】実施例８ 予備分散する分散機をホモミキサーから連続乳化分散機
に変え、回転数１５０００rpm で分散しながら滴下し、
脱水量を２２０mlに変えた以外は、実施例１と同条件で
製造を行い、２１０ｇの微粉末状の白色乾燥ポリマーを
得た。この乾燥ポリマーの平均粒径は１．５μｍであ
り、最大粒子の粒径は、８μｍという粒度分布であっ
た。また大過剰の生理食塩水で膨潤した粒子は、平均粒
径が６．９μｍであり、最大粒子の粒径が２２μｍであ
った。Example 8 The disperser for predispersion was changed from a homomixer to a continuous emulsification disperser, which was added dropwise while dispersing at a rotation speed of 15000 rpm.
Production was carried out under the same conditions as in Example 1 except that the dehydration amount was changed to 220 ml, and 210 g of fine powdery white dry polymer was obtained. The average particle size of this dried polymer was 1.5 μm, and the maximum particle size was 8 μm. The particles swollen with a large excess of physiological saline had an average particle size of 6.9 μm and a maximum particle size of 22 μm.
【００３４】実施例９ 連続乳化分散機の回転数を１００００rpm に変えた以外
は、実施例８と同条件で製造を行い、２３０ｇの微粉末
状の白色乾燥ポリマーを得た。この乾燥ポリマーの平均
粒径は５．０μｍであり、最大粒子の粒径は、２０μｍ
という粒度分布であった。また大過剰の生理食塩水で膨
潤した粒子は、平均粒径が２４．０μｍであり、最大粒
子の粒径が６１μｍであった。Example 9 Production was carried out under the same conditions as in Example 8 except that the rotation speed of the continuous emulsification disperser was changed to 10000 rpm, and 230 g of fine powdery white dry polymer was obtained. The average particle size of this dry polymer is 5.0 μm, and the maximum particle size is 20 μm.
It was the particle size distribution. The particles swollen with a large excess of physiological saline had an average particle size of 24.0 μm and a maximum particle size of 61 μm.
【００３５】実施例１０ 架橋剤量を０．２６ｇに変えた以外は、実施例３と同条
件で製造を行い、２２０ｇの微粉末状の白色乾燥ポリマ
ーを得た。この乾燥ポリマーの平均粒径は２．０μｍで
あり、最大粒子の粒径は、１２μｍという粒度分布であ
った。また大過剰の生理食塩水で膨潤した粒子は、平均
粒径が３１．９μｍであり、最大粒子の粒径が１２５μ
ｍであった。また、この乾燥ポリマー１ｇに対して４０
０ｇのイオン交換水を加えて膨潤させたところ、２５０
ｇの水を吸収した。従って、得られたポリマーは自重の
２００倍以上の水を吸収するため、衛生剤及び農業用の
保水剤等にも有用である。Example 10 Production was carried out under the same conditions as in Example 3 except that the amount of the crosslinking agent was changed to 0.26 g, and 220 g of fine powdery white dry polymer was obtained. The average particle size of this dry polymer was 2.0 μm, and the maximum particle size was 12 μm. The particles swollen with a large excess of physiological saline had an average particle size of 31.9 μm and a maximum particle size of 125 μm.
It was m. Also, 40 g per 1 g of this dry polymer
When 0 g of ion-exchanged water was added to swell, 250
g of water was absorbed. Therefore, since the obtained polymer absorbs 200 times or more of its own weight of water, it is useful as a sanitary agent and a water retention agent for agriculture.
【００３６】実施例１１ モノマーのアクリル酸をメタクリル酸に変えて、８０重
量％のメタクリル酸３０５ｇを用いた以外は実施例１と
同条件で製造を行い、２３０ｇの微粉末状の白色乾燥ポ
リマーを得た。この乾燥ポリマーの平均粒径は２．３μ
ｍであり、最大粒子の粒径は、１４μｍという粒度分布
であった。また大過剰の生理食塩水で膨潤した粒子は、
平均粒径が６．５μｍであり、最大粒子の粒径が２８μ
ｍであった。Example 11 The same procedure as in Example 1 was repeated except that 305 g of 80% by weight methacrylic acid was used instead of methacrylic acid as the monomer acrylic acid, and 230 g of fine powdery white dry polymer was obtained. Obtained. The average particle size of this dry polymer is 2.3μ.
The particle size of the largest particles was 14 μm. Particles swollen with a large excess of saline solution
The average particle size is 6.5 μm, and the maximum particle size is 28 μm.
It was m.
【００３７】実施例１２ 連続乳化分散機の回転数を５０００rpm に変えた以外
は、実施例８と同条件で製造を行い、２２５ｇの微粉末
状の白色乾燥ポリマーを得た。この乾燥ポリマーの平均
粒径は１４．４μｍであり、最大粒子の粒径は、７１．
８μｍという粒度分布であった。また大過剰の生理食塩
水で膨潤した粒子は、平均粒径が３２．３μｍであり、
最大粒子の粒径が１５８．６μｍであった。Example 12 Production was carried out under the same conditions as in Example 8 except that the rotation speed of the continuous emulsification disperser was changed to 5000 rpm, to obtain 225 g of a fine powdery white dry polymer. The average particle size of this dry polymer was 14.4 μm, and the maximum particle size was 71.
The particle size distribution was 8 μm. The particles swollen with a large excess of saline have an average particle size of 32.3 μm,
The maximum particle size was 158.6 μm.
【００３８】比較例１ 予備分散を行わず、モノマー水溶液を滴下する以外は、
全仕込量も実施例１と同等とし、製造条件も同等として
洗浄工程以前に２５０ｇの白色ポリマーを得た。しか
し、生成物には微粒子以外に相当量のゲル化物が混入し
ていた。乾燥ポリマーの平均粒径は１２０μｍであり、
１mm以上の凝集物も混在していた。Comparative Example 1 Except that an aqueous monomer solution was added dropwise without performing preliminary dispersion.
The total amount charged was the same as in Example 1 and the manufacturing conditions were the same, and 250 g of a white polymer was obtained before the washing step. However, the product contained a considerable amount of gelled substance in addition to the fine particles. The average particle size of the dried polymer is 120 μm,
Aggregates of 1 mm or more were also mixed.
【００３９】比較例２ 重合のために昇温する以前にモノマー分散滴を全て反応
槽に添加し、その後昇温し重合を開始させた以外は実施
例１と同等の製造条件で製造した。途中、急激な重合熱
の発生により突沸を生じた。急冷し反応を続け、反応終
了後得られたポリマーは白色の粉末状ポリマー１６０ｇ
であった。この乾燥ポリマーの平均粒径は６．８μｍで
あり、最大粒子の粒径は、５８μｍという粒度分布であ
った。また大過剰の生理食塩水で膨潤した粒子は、平均
粒径が１８．２μｍであり、最大粒子の粒径が１mmに近
い大粒子であった。Comparative Example 2 The same production conditions as in Example 1 were used except that all the monomer dispersed droplets were added to the reaction tank before the temperature was raised for the polymerization and then the temperature was raised to start the polymerization. On the way, bumping occurred due to the rapid generation of polymerization heat. The polymer obtained after the reaction was quenched was 160 g of a white powdery polymer.
Met. The average particle size of this dry polymer was 6.8 μm, and the maximum particle size was 58 μm. The particles swollen with a large excess of physiological saline had an average particle size of 18.2 μm, and the maximum particle size was a large particle close to 1 mm.
【００４０】比較例３ 分散安定化剤をソルビタントリステアレート（ＨＬＢ
２．１）に変えた以外は、実施例４と同条件で製造を行
い、２３０ｇの微粉末状の白色乾燥ポリマーを得た。こ
の乾燥ポリマーの平均粒径は１４．５μｍであり、最大
粒子の粒径は、１０５μｍという粒度分布であった。ま
た大過剰の生理食塩水で膨潤した粒子は、平均粒径が４
３．５μｍであり、最大粒子の粒径が９８０μｍであ
り、ゲル化物も含まれていた。Comparative Example 3 The dispersion stabilizer was sorbitan tristearate (HLB).
Except having changed to 2.1), it manufactured on the same conditions as Example 4, and obtained 230g of fine powdery white dry polymer. The average particle size of this dry polymer was 14.5 μm, and the maximum particle size was 105 μm. Particles swollen with a large excess of saline have an average particle size of 4
The particle size was 3.5 μm, the maximum particle size was 980 μm, and a gelled product was also included.
【００４１】試験例 本発明で得られた吸水性ポリマーの物理的評価として乾
燥ポリマー粒子の平均粒径と粒度分布（Ｃｕ値）を測定
し、その結果を表１に示した。Ｃｕ値が小さい程粒度分
布が狭いことを表している。なおＣｕ値とは、平均値
（平均粒径）に対する相対的なちらばりの大きさを表す
値であり、下記の一般式で求めることができる。Test Example As a physical evaluation of the water-absorbent polymer obtained in the present invention, the average particle size and particle size distribution (Cu value) of dry polymer particles were measured, and the results are shown in Table 1. The smaller the Cu value, the narrower the particle size distribution. The Cu value is a value representing the size of the relative scattering with respect to the average value (average particle diameter), and can be calculated by the following general formula.
【００４２】[0042]
【数１】 [Equation 1]
【００４３】[0043]
【表１】 [Table 1]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年３月１６日[Submission date] March 16, 1992
【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】００４１[Correction target item name] 0041
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４１】試験例 本発明で得られた吸水性ポリマーの物理的評価として乾
燥ポリマー粒子の平均粒径と粒度分布（Ｃｖ値）を測定
し、その結果を表１に示した。Ｃｖ値が小さい程粒度分
布が狭いことを表している。なおＣｖ値とは、平均値
（平均粒径）に対する相対的なちらばりの大きさを表す
値であり、下記の一般式で求めることができる。Test Example As a physical evaluation of the water-absorbent polymer obtained in the present invention, the average particle size and particle size distribution ( Cv value) of dry polymer particles were measured, and the results are shown in Table 1. The smaller the Cv value, the narrower the particle size distribution. The Cv value is a value representing the size of the relative scattering with respect to the average value (average particle diameter), and can be calculated by the following general formula.
【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】００４２[Correction target item name] 0042
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４２】[0042]
【数１】 [Equation 1]
【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】００４３[Correction target item name] 0043
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４３】[0043]
【表１】 [Table 1]
Claims (2)
は／およびその塩を油中水型の逆相懸濁重合させる吸水
性ポリマーの製造法において、分散安定化剤としてＨＬ
Ｂが３〜９のショ糖脂肪酸エステル、ソルビタンエステ
ルおよびこれらのポリオキシアルキレン付加物から選ば
れる１種または２種以上を用い、重合前に予めモノマー
の油中水型の微小分散滴を形成せしめ、その微小分散滴
を昇温した有機溶媒中に滴下して重合させることを特徴
とする吸水性ポリマー微粒子の製造法。1. A method for producing a water-absorbing polymer in which an α, β-unsaturated carboxylic acid monomer or / and a salt thereof is subjected to water-in-oil type reverse phase suspension polymerization, and HL is used as a dispersion stabilizer.
By using one or more selected from sucrose fatty acid ester having B of 3 to 9, sorbitan ester and polyoxyalkylene adducts thereof, the water-in-oil type micro-dispersed droplets of the monomer are formed in advance before the polymerization. A method for producing fine particles of a water-absorbing polymer, characterized in that the finely dispersed droplets are dropped into an organic solvent having a raised temperature and polymerized.
径が１〜５０μｍである請求項１記載の製造法。2. The production method according to claim 1, wherein the average particle diameter of the water-absorbent polymer fine particles after drying is 1 to 50 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04025356A JP3120887B2 (en) | 1992-02-12 | 1992-02-12 | Method for producing water-absorbing polymer fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04025356A JP3120887B2 (en) | 1992-02-12 | 1992-02-12 | Method for producing water-absorbing polymer fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05222107A true JPH05222107A (en) | 1993-08-31 |
| JP3120887B2 JP3120887B2 (en) | 2000-12-25 |
Family
ID=12163571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04025356A Expired - Fee Related JP3120887B2 (en) | 1992-02-12 | 1992-02-12 | Method for producing water-absorbing polymer fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3120887B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006001976A (en) * | 2004-06-15 | 2006-01-05 | Sumitomo Seika Chem Co Ltd | Method for producing water-absorbing resin |
| JP2007146078A (en) * | 2005-11-30 | 2007-06-14 | Dainippon Ink & Chem Inc | Process for production of liquid absorptive resin |
| WO2009096300A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| WO2009096268A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| WO2009096301A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| WO2009096266A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd | Process for the production of polymer microparticles |
| JP2013521363A (en) * | 2010-03-02 | 2013-06-10 | ビーエイエスエフ・ソシエタス・エウロパエア | Block copolymer and use thereof |
| JP2014012793A (en) * | 2012-07-05 | 2014-01-23 | Kao Corp | Water-insoluble polymer builder |
-
1992
- 1992-02-12 JP JP04025356A patent/JP3120887B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006001976A (en) * | 2004-06-15 | 2006-01-05 | Sumitomo Seika Chem Co Ltd | Method for producing water-absorbing resin |
| JP2007146078A (en) * | 2005-11-30 | 2007-06-14 | Dainippon Ink & Chem Inc | Process for production of liquid absorptive resin |
| WO2009096300A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| WO2009096268A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| WO2009096301A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| WO2009096266A1 (en) | 2008-02-01 | 2009-08-06 | Toagosei Co., Ltd | Process for the production of polymer microparticles |
| US8058370B2 (en) | 2008-02-01 | 2011-11-15 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| US8288491B2 (en) | 2008-02-01 | 2012-10-16 | Toagosei Co. Ltd. | Process for the production of polymer microparticles |
| US8362166B2 (en) | 2008-02-01 | 2013-01-29 | Taogosei Co., Ltd. | Process for the production of polymer microparticles |
| US8362165B2 (en) | 2008-02-01 | 2013-01-29 | Toagosei Co., Ltd. | Process for the production of polymer microparticles |
| JP2013521363A (en) * | 2010-03-02 | 2013-06-10 | ビーエイエスエフ・ソシエタス・エウロパエア | Block copolymer and use thereof |
| JP2014012793A (en) * | 2012-07-05 | 2014-01-23 | Kao Corp | Water-insoluble polymer builder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3120887B2 (en) | 2000-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102105733B1 (en) | Absorbent and manufacturing method therefor | |
| US4833222A (en) | Crosslinker stabilizer for preparing absorbent polymers | |
| EP0497623B1 (en) | Method for production of particulate hydrated gel polymer and absorbent resin | |
| EP2411422B2 (en) | Method for producing surface post-cross-linked, water absorbing polymer particles | |
| JP4150252B2 (en) | Method for producing water absorbent resin | |
| EP3124502B1 (en) | Method for producing water-absorbent resin particle | |
| JPS648006B2 (en) | ||
| JPH07242709A (en) | Preparation of water-absorbent resin | |
| JPH05508674A (en) | Method for manufacturing water-swellable products using ultrafine water-swellable polymer powder | |
| JPH0615574B2 (en) | Method for producing water absorbent resin | |
| JPH04501877A (en) | Manufacturing method of super absorbent resin | |
| EP2821419A1 (en) | Method for producing water absorbent resin particles | |
| JP3175790B2 (en) | Method for producing particulate hydrogel polymer and water absorbent resin | |
| JP3120887B2 (en) | Method for producing water-absorbing polymer fine particles | |
| JPH02153903A (en) | Production of highly hygroscopic resin | |
| JPH01292004A (en) | Production of highly water-absorbable resin | |
| CN110713566B (en) | Fine powder reconstituted pellet and method for producing super absorbent resin | |
| JP6890190B2 (en) | Water-absorbent resin powder for heating element composition, and heating element composition | |
| JP2001040014A (en) | Production of highly water-absorbable resin | |
| JPH08157606A (en) | Production of highly water-absorbing resin | |
| JPS61157513A (en) | Production of polymer having high water absorption property | |
| JP7270828B2 (en) | Water absorbent resin and method for producing the same | |
| JP2023514628A (en) | SUPER ABSORBENT RESIN AND METHOD FOR MANUFACTURING SAME | |
| WO2021049451A1 (en) | Method for producing water-absorbable resin particles | |
| JP7100742B1 (en) | Poly (meth) acrylic acid (salt) -based water-absorbent resin and absorber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071020 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20081020 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 9 Free format text: PAYMENT UNTIL: 20091020 |
|
| LAPS | Cancellation because of no payment of annual fees |