JP2001040014A - Production of highly water-absorbable resin - Google Patents
Production of highly water-absorbable resinInfo
- Publication number
- JP2001040014A JP2001040014A JP11220987A JP22098799A JP2001040014A JP 2001040014 A JP2001040014 A JP 2001040014A JP 11220987 A JP11220987 A JP 11220987A JP 22098799 A JP22098799 A JP 22098799A JP 2001040014 A JP2001040014 A JP 2001040014A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- water
- producing
- group
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は紙おむつ等に用いる
のに好適な高吸水性樹脂の製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a superabsorbent resin suitable for use in disposable diapers and the like.
【０００２】[0002]
【従来の技術】最近、高吸水性樹脂に対する需要が急増
している。その主たる用途は紙おむつや生理用品等の衛
生材料である。高吸水性樹脂としては種々のものが提案
されているが、現在のところ主流をなしているのは水溶
性モノマーを重合して得られるものである。重合方法と
しては、水溶性モノマー水溶液をそのままバルク重合さ
せてゲル状の重合体とし、次いでこれを粉砕したのち脱
水・乾燥する方法と、水溶性モノマー水溶液を疎水性有
機溶媒中で懸濁重合させる方法とが主に用いられてい
る。このうち前者のバルク重合法は、重合後の粉砕及び
脱水・乾燥が困難なので、粉砕工程を必要とせず、かつ
脱水・乾燥の容易な後者の懸濁重合法が好ましいと考え
られている。この方法では、疎水性有機溶媒として水と
共沸混合物を形成するものを用いることにより、生成し
た重合体粒子に含まれている水を、疎水性有機溶媒との
共沸蒸留により容易に除去することができる。2. Description of the Related Art Recently, the demand for superabsorbent resins has been rapidly increasing. Its main use is in sanitary materials such as disposable diapers and sanitary products. Various types of superabsorbent resins have been proposed, but currently the mainstream is obtained by polymerizing a water-soluble monomer. As a polymerization method, a water-soluble monomer aqueous solution is bulk polymerized as it is to form a gel polymer, which is then pulverized, then dehydrated and dried, and a suspension polymerization of the water-soluble monomer aqueous solution in a hydrophobic organic solvent is performed. The method is mainly used. Among them, the former bulk polymerization method is considered to be preferable because the pulverization, dehydration and drying after the polymerization are difficult, and thus the latter suspension polymerization method which does not require a pulverization step and is easily dehydrated and dried. In this method, the water contained in the produced polymer particles is easily removed by azeotropic distillation with a hydrophobic organic solvent by using a hydrophobic organic solvent that forms an azeotrope with water. be able to.
【０００３】[0003]
【発明が解決しようとする課題】高吸水性樹脂に要求さ
れる基本的物性は、当然のことながら吸水能すなわち樹
脂単位重量当りの吸水能力が大きいことであるが、市場
では吸水能と並んで吸水速度が大きいこと及び吸水した
樹脂粒子が膨潤・軟化して樹脂粒子層を水が浸透・拡散
するのを阻害しないことも要求されている。吸水能を大
きくするには、吸水に際し樹脂粒子が大きく膨潤し得る
ように、樹脂粒子の架橋密度が小さいことが望ましいと
考えられる。しかしこのような樹脂粒子は、一般には吸
水に際して膨潤・軟化が著しく、市場の要求を満足しな
い。従って高吸水性樹脂の製造に際してどのような架橋
を行わせるかは、得られる高吸水性樹脂の諸物性に大き
く影響する。The basic physical properties required for a super water-absorbent resin are, of course, a high water absorption capacity, that is, a high water absorption capacity per unit weight of the resin. It is also required that the water absorption rate be high and that the water-absorbed resin particles not swell and soften to prevent water from penetrating and diffusing through the resin particle layer. In order to increase the water absorption capacity, it is considered desirable that the crosslink density of the resin particles is small so that the resin particles can swell greatly upon water absorption. However, such resin particles generally remarkably swell and soften upon absorption of water, and do not satisfy market requirements. Therefore, what kind of crosslinking is performed in the production of the superabsorbent resin greatly affects various physical properties of the obtained superabsorbent resin.
【０００４】架橋の好ましい態様の一つは、生成する樹
脂の主体をなすモノビニルモノマーに対して小割合の架
橋剤を含有するモノマー水溶液を重合させて架橋密度の
小さい樹脂を生成させ、次いで得られた樹脂粒子に更に
架橋剤を反応させて表面近傍の架橋密度を向上させる方
法であると考えられている。この方法によれば諸物性の
バランスの比較的良い高吸水性樹脂が得られるとされて
いるが、表面近傍にのみ架橋剤を反応させるには、架橋
剤が内部にまで浸透しないように、樹脂粒子の含水率を
低下させておくことが必要である。特公昭６３−４８４
３号公報には、架橋剤を含有しないモノマー水溶液を重
合させて樹脂粒子を製造し、これに架橋剤を含浸させて
架橋構造を形成することが記載されているが、樹脂粒子
は含水率１０〜４０％に脱水しておくことが必要とされ
ている。そして含水率の大きい樹脂粒子に架橋剤を含浸
させて架橋構造を形成させたのでは、高吸水性樹脂とし
て好ましい物性のものが得られないことが示されてい
る。しかしながら、モノマー水溶液を重合させて得られ
る樹脂の含水率は通常は４０％以上なので、この方法で
は架橋反応の前に樹脂を所望の含水率にまで脱水しなけ
ればならない。本発明は高含水率の樹脂粒子に架橋剤を
反応させて、諸物性に優れた高吸水性樹脂を製造する方
法を提供しようとするものである。One of the preferred embodiments of crosslinking is to polymerize an aqueous monomer solution containing a small proportion of a crosslinking agent with respect to the monovinyl monomer, which is the main component of the resin to be formed, to produce a resin having a low crosslinking density, and then obtain the resin. It is considered to be a method of further increasing a crosslinking density near the surface by further reacting a crosslinking agent with the resin particles. According to this method, a highly water-absorbent resin having a relatively good balance of various physical properties can be obtained.However, in order to cause the cross-linking agent to react only near the surface, the resin must be prevented from penetrating inside. It is necessary to keep the water content of the particles low. JP-B-63-484
No. 3 describes that resin particles are produced by polymerizing an aqueous monomer solution containing no cross-linking agent, and the resin particles are impregnated with the cross-linking agent to form a cross-linked structure. There is a need to dehydrate to ~ 40%. It has been shown that when a crosslinking agent is formed by impregnating a resin particle having a high water content with a crosslinking agent, a resin having preferable physical properties as a superabsorbent resin cannot be obtained. However, since the water content of the resin obtained by polymerizing the aqueous monomer solution is usually 40% or more, in this method, the resin must be dehydrated to a desired water content before the crosslinking reaction. An object of the present invention is to provide a method for producing a highly water-absorbent resin having excellent physical properties by reacting a crosslinking agent with resin particles having a high water content.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、少なく
とも部分的に中和された不飽和カルボン酸を主体とする
モノビニルモノマー、重合開始剤および次亜リン酸化合
物を含有するモノマー水溶液を重合させ、生成した樹脂
に、含水率が少なくとも４０％の状態で、カルボキシル
基と反応し得る官能基を複数個有する架橋剤を含浸させ
て架橋反応させることにより、諸物性に優れた高吸水性
樹脂を製造することができる。According to the present invention, an aqueous monomer solution containing at least partially neutralized monovinyl monomer mainly composed of unsaturated carboxylic acid, a polymerization initiator and a hypophosphorous acid compound is polymerized. The resulting resin is impregnated with a cross-linking agent having a plurality of functional groups capable of reacting with a carboxyl group in a state where the water content is at least 40% to cause a cross-linking reaction. Can be manufactured.
【０００６】[0006]
【発明の実施の形態】本発明で高吸水性樹脂の製造に用
いるモノマーは不飽和カルボン酸、特にアクリル酸又は
メタクリル酸である。不飽和カルボン酸は、少なくとも
部分的にアルカリ金属塩又はアンモニウム塩に中和され
た形で重合に供する。通常は少なくとも２０％以上、好
ましくは３０％以上がナトリウム塩又はカリウム塩に中
和された形で重合に供する。なお、本発明では、これら
の不飽和カルボン酸以外に、所望ならば他の水溶性モノ
ビニルモノマーも少量共重合させることができる。この
ような共重合成分としては、２−アクリルアミド−２−
メチルスルホン酸のようなイオン性モノマー、（メタ）
アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、２
−ヒドロキシエチル（メタ）アクリレート、Ｎ−メチロ
ール（メタ）アクリルアミド等の非イオン性モノマー、
ジエチルアミノエチル（メタ）アクリレート、ジメチル
アミノプロピル（メタ）アクリレート等のアミノ基を有
するモノマーやその４級化物などが挙げられる。これら
は上述の不飽和カルボン酸に対して２０モル％以下の量
で用いるのが好ましい。重合反応に供するモノマー水溶
液中のモノマー濃度は、通常は２０重量％以上であり、
好ましくは２５重量％ないし飽和濃度である。BEST MODE FOR CARRYING OUT THE INVENTION The monomer used in the production of a superabsorbent resin in the present invention is an unsaturated carboxylic acid, especially acrylic acid or methacrylic acid. The unsaturated carboxylic acid is subjected to the polymerization in a form at least partially neutralized by an alkali metal salt or an ammonium salt. Usually, at least 20% or more, preferably 30% or more, is subjected to polymerization in a form neutralized with a sodium salt or a potassium salt. In the present invention, in addition to these unsaturated carboxylic acids, if desired, other water-soluble monovinyl monomers can be copolymerized in a small amount. As such a copolymer component, 2-acrylamide-2-
Ionic monomers such as methyl sulfonic acid, (meth)
Acrylamide, N, N-dimethylacrylamide, 2
Non-ionic monomers such as -hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide,
Examples thereof include monomers having an amino group such as diethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate, and quaternized products thereof. These are preferably used in an amount of 20 mol% or less based on the above-mentioned unsaturated carboxylic acid. The monomer concentration in the monomer aqueous solution used for the polymerization reaction is usually 20% by weight or more,
Preferably, the concentration is from 25% by weight to a saturation concentration.
【０００７】重合反応に供するモノマー水溶液中には、
重合開始剤及び連鎖移動剤としての次亜リン酸化合物を
含有させる。重合開始剤としては常用の水溶性ラジカル
重合開始剤を用いればよく、例えば過酸化水素；過硫酸
カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の
過硫酸塩；２，２′−アゾビス−（２−アミジノプロパ
ン）・２塩酸塩、２，２′−アゾビス−（Ｎ，Ｎ′−ジ
メチレンイソブチルアミジン）・２塩酸塩、２，２′−
アゾビス−｛２−メチル−Ｎ−（１，１−ビス（ヒドロ
キシメチル）−２−ヒドロキシエチル）プロピオンアミ
ド｝等のアゾ系化合物などが用いられる。重合開始剤は
所望ならばいくつか併用することもできる。また、過酸
化水素や過硫酸塩は亜硫酸塩やＬ−アスコルビン酸等の
還元性物質やアミン塩等と組み合せて、レドックス系の
開始剤として用いることもできる。重合開始剤は共存す
るモノマーに対し０．００１〜５重量％、好ましくは
０．０１〜１重量％となるように用いればよい。[0007] In the aqueous monomer solution to be subjected to the polymerization reaction,
A hypophosphorous compound as a polymerization initiator and a chain transfer agent is contained. As the polymerization initiator, a conventional water-soluble radical polymerization initiator may be used, for example, hydrogen peroxide; persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; 2,2'-azobis- (2-amidino Propane) dihydrochloride, 2,2'-azobis- (N, N'-dimethyleneisobutylamidine) dihydrochloride, 2,2'-
An azo compound such as azobis- {2-methyl-N- (1,1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide} or the like is used. Some polymerization initiators can be used in combination if desired. In addition, hydrogen peroxide or persulfate can be used as a redox initiator in combination with a reducing substance such as sulfite or L-ascorbic acid, or an amine salt. The polymerization initiator may be used in an amount of 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on the coexisting monomer.
【０００８】次亜リン酸化合物としては、次亜リン酸又
はその塩、例えば次亜リン酸のナトリウム塩、カリウム
塩、アンモニウム塩、カルシウム塩、バリウム塩などを
用いればよいが、所望ならば他の塩を用いることもでき
る。また、これらを併用することもできる。次亜リン酸
化合物は共存するモノマーに対して通常１０〜５０００
ｐｐｍ、好ましくは１０〜１０００ｐｐｍとなるように
用いる。本発明における次亜リン酸化合物の作用は不詳
であるが、重合過程で起る自己架橋を抑制するのではな
いかと考えられる。すなわち重合時の自己架橋という制
御し難い現象が、次亜リン酸化合物により抑制されるの
で、生成する樹脂の構造が均一になるものと考えられ
る。As the hypophosphorous acid compound, hypophosphorous acid or a salt thereof, for example, sodium, potassium, ammonium, calcium, barium salts of hypophosphorous acid may be used. Can also be used. These can be used in combination. The hypophosphorous acid compound is usually 10 to 5000 relative to the coexisting monomer.
ppm, preferably 10 to 1000 ppm. Although the action of the hypophosphorous acid compound in the present invention is unclear, it is thought that it may suppress self-crosslinking occurring in the polymerization process. That is, it is considered that the uncontrollable phenomenon of self-crosslinking during polymerization is suppressed by the hypophosphorous acid compound, so that the structure of the generated resin becomes uniform.
【０００９】本発明における不飽和脂肪酸を主体とする
モノビニルモノマー、重合開始剤及び次亜リン酸化合物
を含有するモノマー水溶液の重合は、常用の任意の方法
で行うことができるが、架橋反応に供する含水樹脂粒子
が直接得られるので疎水性有機溶媒を媒体とする懸濁重
合が好ましい。疎水性有機溶媒としては、基本的には水
に溶け難く、重合に不活性なものであれば任意のものを
用いることができる。そのいくつかを例示すると、ｎ−
ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン
等の脂肪族炭化水素類；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類；ベンゼン、トルエン、
キシレン等の芳香族炭化水素類などが挙げられる。これ
らのなかでもｎ−ヘキサン、ｎ−ヘプタン又はシクロヘ
キサンを用いるのが好ましい。疎水性有機溶媒は、モノ
マー水溶液に対し０．５〜１０重量倍、好ましくは０．
８〜３重量倍となるように用いる。モノマー水溶液に対
する疎水性有機溶媒の比率が過少であると、重合途中で
樹脂粒子が凝集し易い。逆にこの比率が過大であると生
産性が低下する。In the present invention, the polymerization of the monomer aqueous solution containing a monovinyl monomer containing an unsaturated fatty acid as a main component, a polymerization initiator and a hypophosphorous acid compound can be carried out by any conventional method. Suspension polymerization using a hydrophobic organic solvent as a medium is preferred because water-containing resin particles can be directly obtained. As the hydrophobic organic solvent, any one can be used as long as it is basically insoluble in water and inert to polymerization. Some examples are n-
Aliphatic hydrocarbons such as pentane, n-hexane, n-heptane and n-octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, toluene,
And aromatic hydrocarbons such as xylene. Among them, n-hexane, n-heptane or cyclohexane is preferably used. The amount of the hydrophobic organic solvent is 0.5 to 10 times by weight, preferably 0.1 to 10 times the weight of the aqueous monomer solution.
It is used so as to be 8 to 3 times by weight. If the ratio of the hydrophobic organic solvent to the aqueous monomer solution is too small, the resin particles tend to aggregate during the polymerization. Conversely, if this ratio is excessive, the productivity will decrease.
【００１０】疎水性有機溶媒には、モノマー水溶液を液
滴として分散させるため、常法により分散剤を含有させ
るのが好ましい。分散剤としては式（１）で示されるリ
ン酸エステル系のものを用いるのが好ましい。このもの
は毒性及び刺激性が少なく、安全性の高い分散剤であ
る。[0010] In order to disperse the aqueous monomer solution as droplets in the hydrophobic organic solvent, it is preferable to add a dispersant by a conventional method. It is preferable to use a phosphate ester-based dispersant represented by the formula (1). This is a highly safe dispersant with low toxicity and irritation.
【化２】 （式中、Ｒ1 は炭素数８ないし３０のフェニル基で置換
されていてもよいアルキル基又はアルキル基で置換され
ていてもよいアリール基を表わし、Ｒ2 は水酸基又はＲ
1 Ｏ−（ＣＨ2 ＣＨ2 Ｏ）n −基を表わし、ｎは１ない
し３０の整数を表わす）Embedded image (In the formula, R 1 represents an alkyl group which may be substituted with a phenyl group having 8 to 30 carbon atoms or an aryl group which may be substituted with an alkyl group, and R 2 represents a hydroxyl group or R 2
Represents a 1 O- (CH 2 CH 2 O) n -group, wherein n represents an integer of 1 to 30)
【００１１】式（１）において、Ｒ1 は好ましくは炭素
数８ないし２３のアルキル基又はモノアルキルフェニル
基である。ｎは１ないし２０であるのが好ましい。Ｒ2
がＲ 1 Ｏ−（ＣＨ2 ＣＨ2 Ｏ）n −基である場合には、
２つのＲ1 Ｏ−（ＣＨ2 ＣＨ 2 Ｏ）n −基は同一である
のが好ましい。代表的かつ好ましいＲ1 の例としては、
ノニルフェニル基、オクチルフェニル基、トリデシル
基、ラウリル基、２−エチルヘキシル基、オクタデシル
基及びドデシルフェニル基等が挙げられる。市場で入手
し得るこのリン酸エステル系分散剤は、通常はリン酸モ
ノエステルとリン酸ジエステルとの混合物である。In the equation (1), R1Is preferably carbon
An alkyl group of the formulas 8 to 23 or monoalkylphenyl
Group. n is preferably 1 to 20. RTwo
Is R 1O- (CHTwoCHTwoO)n-If it is a group,
Two R1O- (CHTwoCH TwoO)n-Groups are identical
Is preferred. Representative and preferred R1An example of
Nonylphenyl group, octylphenyl group, tridecyl
Group, lauryl group, 2-ethylhexyl group, octadecyl
And a dodecylphenyl group. Available in the market
This phosphate ester-based dispersant which can be
It is a mixture of a monoester and a phosphoric acid diester.
【００１２】分散剤の使用量は、重合反応に供するモノ
マーの種類や重合操作条件により異なるが、通常は疎水
性有機溶媒に対して０．０１ないし５重量％である。
０．０５ないし２重量％、特に０．１０ないし１．０重
量％が好ましい。分散剤の使用量が過少であると、モノ
マー水溶液の分散がうまく行かない。逆に使用量が過大
であると、得られた樹脂粒子を乾燥する際に樹脂粒子が
凝集を起す傾向がある。The amount of the dispersant used varies depending on the type of the monomer to be subjected to the polymerization reaction and the polymerization operation conditions, but is usually 0.01 to 5% by weight based on the hydrophobic organic solvent.
0.05 to 2% by weight, especially 0.10 to 1.0% by weight, is preferred. If the amount of the dispersant is too small, the aqueous monomer solution cannot be dispersed well. Conversely, if the amount used is excessive, the resin particles tend to aggregate when the obtained resin particles are dried.
【００１３】懸濁重合は、分散剤を含有する疎水性有機
溶媒を重合条件下に保ち、これにモノマー水溶液を逐次
供給しつつ重合させる方法によるのが好ましい。重合は
重合開始剤にもよるが、通常４０ないし１５０℃で行
う。温度が高過ぎると、次亜リン酸化合物が存在してい
ても自己架橋が盛んになるためか、得られる高吸水性樹
脂の吸水能が低下する。逆に低温に過ぎると重合に長時
間を要するばかりでなく、突発的な重合を引き起こして
塊状物を生成する恐れがある。好適な重合温度は６０な
いし９０℃であり、特に疎水性有機溶媒の還流条件下で
重合を行うのが好ましい。The suspension polymerization is preferably carried out by a method in which a hydrophobic organic solvent containing a dispersant is kept under polymerization conditions, and a monomer aqueous solution is successively supplied thereto to carry out polymerization. The polymerization is usually carried out at 40 to 150 ° C., although it depends on the polymerization initiator. If the temperature is too high, the water-absorbing ability of the resulting highly water-absorbent resin is reduced, probably because self-crosslinking becomes active even when a hypophosphorous acid compound is present. Conversely, if the temperature is too low, not only long time is required for the polymerization, but also there is a possibility that a sudden polymerization may be caused to form a lump. The preferred polymerization temperature is 60 to 90 ° C., and it is particularly preferable to carry out the polymerization under the reflux condition of a hydrophobic organic solvent.
【００１４】本発明ではモノマー水溶液を重合して得た
樹脂に架橋剤を含浸させて反応させ、架橋構造を有する
高吸水性樹脂とする。重合を上述の懸濁重合により行っ
た場合には、生成する樹脂粒子は大部分が高吸水性樹脂
として用いるのに好適な３００ないし１０００μｍの粒
径を有しているので、そのまま後続する架橋反応に供す
るが、モノマー水溶液をそのまま重合させてゲル状樹脂
を生成させた場合には、高吸水性樹脂として用いるのに
好適な大きさに細断してから架橋反応に供する。In the present invention, a resin obtained by polymerizing an aqueous monomer solution is impregnated with a crosslinking agent and reacted to obtain a superabsorbent resin having a crosslinked structure. When the polymerization is carried out by the above-described suspension polymerization, most of the resulting resin particles have a particle size of 300 to 1000 μm, which is suitable for use as a superabsorbent resin. When the monomer aqueous solution is polymerized as it is to form a gel-like resin, the gel-like resin is shredded to a size suitable for use as a superabsorbent resin, and then subjected to a crosslinking reaction.
【００１５】架橋剤としては、カルボキシル基と反応す
る官能基を複数個有する化合物を用いる。通常はポリグ
リシジルエーテル化合物、ハロエポキシ化合物、イソシ
アネート化合物などを用いる。なかでもジグリシジルエ
ーテル化合物、例えばエチレングリコールジグリシジル
エーテル、プロピレングリコールジグリシジルエーテ
ル、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、グリセ
リンジグリシジルエーテル、ポリグリセリンジグリシジ
ルエーテル等を用いるのが好ましい。特に好ましいのは
エチレングリコールジグリシジルエーテルである。ハロ
エポキシ化合物としてはエピクロロヒドリン、β−メチ
ルエピクロロヒドリン等が、イソシアネート化合物とし
ては、２，４−トリレンジイソシアネート、ヘキサメチ
レンジイソシアネート等がそれぞれ用いられる。架橋剤
は樹脂粒子に対して乾量基準で０．０１ないし５重量％
となるように用いる。０．０５ないし２重量％、特に
０．０５ないし１重量％となるように用いるのが好まし
い。架橋剤の比率が大き過ぎると、吸水能が低下し、逆
に比率が低く過ぎると加圧下での吸水速度が低下する。As the crosslinking agent, a compound having a plurality of functional groups which react with a carboxyl group is used. Usually, a polyglycidyl ether compound, a haloepoxy compound, an isocyanate compound or the like is used. Among them, it is preferable to use diglycidyl ether compounds such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, and polyglycerin diglycidyl ether. Particularly preferred is ethylene glycol diglycidyl ether. As the haloepoxy compound, epichlorohydrin, β-methylepichlorohydrin and the like are used, and as the isocyanate compound, 2,4-tolylene diisocyanate, hexamethylene diisocyanate and the like are used. The crosslinking agent is 0.01 to 5% by weight based on the dry weight of the resin particles.
It is used so that It is preferably used in an amount of 0.05 to 2% by weight, particularly 0.05 to 1% by weight. If the ratio of the cross-linking agent is too large, the water absorption capacity decreases, and if the ratio is too low, the water absorption rate under pressure decreases.
【００１６】架橋剤は樹脂中に均一に浸透するように、
水性溶液として樹脂粒子に含浸させる。また、樹脂粒子
の含水率は４０％以上、好ましくは５０％以上として、
架橋剤が内部に均一に浸透し易いようにする。樹脂粒子
の含水率が低すぎると、所望の物性の高吸水性樹脂を得
るのが困難となるが、これは架橋剤が内部にまで均一に
浸透しないので、架橋が不均一になるためと思われる。
樹脂粒子の含水率が多少低い場合には、架橋剤を希薄な
水性溶液として用い、架橋剤を含浸した状態で、換言す
れば生成する架橋樹脂の含水率が、所望の値となるよう
にしてもよい。[0016] The cross-linking agent is so penetrated uniformly into the resin that
The resin particles are impregnated as an aqueous solution. Further, the water content of the resin particles is 40% or more, preferably 50% or more,
The cross-linking agent is easily and uniformly penetrated into the inside. If the water content of the resin particles is too low, it is difficult to obtain a highly water-absorbent resin having desired physical properties, but this is because the cross-linking agent does not uniformly penetrate to the inside, so that the cross-linking becomes uneven. It is.
When the water content of the resin particles is somewhat low, the cross-linking agent is used as a dilute aqueous solution, and in a state in which the cross-linking agent is impregnated, in other words, the water content of the formed cross-linked resin is set to a desired value. Is also good.
【００１７】なお、架橋剤を含浸した状態での樹脂粒子
の含水率の上限は８０％以下、特に６０％以下であるの
が好ましい。含水率をこれ以上高くしても、得られる高
吸水性樹脂の物性は向上しない。また生成した架橋樹脂
の脱水には相当のエネルギーを要するので、必要以上に
樹脂粒子の含水率を高くすることは不利である。従って
樹脂粒子の含水率と架橋剤溶液の濃度は、上記した架橋
剤の均一な含浸を可能とし、かつ生成する架橋樹脂の含
水率が過大とならないように選択すべきである。架橋反
応は、通常は架橋剤を十分に含浸させたのち加熱するこ
とにより行うが、架橋反応条件下に含浸させることもで
きる。架橋反応終了後は、常法により脱水・乾燥して高
吸水性樹脂を取得する。The upper limit of the water content of the resin particles impregnated with the crosslinking agent is preferably 80% or less, particularly preferably 60% or less. Even if the water content is further increased, the physical properties of the resulting superabsorbent resin are not improved. Also, since considerable energy is required for dehydrating the formed crosslinked resin, it is disadvantageous to increase the water content of the resin particles more than necessary. Therefore, the water content of the resin particles and the concentration of the cross-linking agent solution should be selected so that the above-mentioned cross-linking agent can be uniformly impregnated and the water content of the formed cross-linked resin does not become excessive. The cross-linking reaction is usually carried out by sufficiently impregnating the cross-linking agent and then heating, but the impregnation may be carried out under cross-linking reaction conditions. After completion of the cross-linking reaction, dehydration and drying are performed by a conventional method to obtain a superabsorbent resin.
【００１８】[0018]
【実施例】以下に実施例により本発明をさらに具体的に
説明する。なお、以下の実施例において吸水能、吸水速
度、平均粒子径及びゲル強度は下記により測定した。 吸水能；２５０メッシュのナイロン袋（２０ｃｍ×１０
ｃｍの大きさ）を５００ｃｃの脱イオン水に３０分間浸
漬する。ナイロン袋を引き上げ、空中に懸垂して１５分
間水切りしたのち、その重量（Ｗ1 （ｇ））を測定す
る。樹脂粒子約１．０ｇを採取し、その重量（Ｗ
2 （ｇ））を精秤してナイロン袋に入れる。これを５０
０ｃｃの脱イオン水に３０分間浸漬したのちナイロン袋
を引き上げ、空中に懸垂して１５分間水切りしたのち、
その重量（Ｗ3 （ｇ））を測定する。 吸水能＝（Ｗ3 −Ｗ1 ）／Ｗ2 （ｇ／ｇ）The present invention will be described more specifically with reference to the following examples. In the following examples, the water absorption capacity, water absorption rate, average particle size, and gel strength were measured as described below. Water absorption capacity: 250 mesh nylon bag (20 cm × 10
cm size) in 500 cc of deionized water for 30 minutes. The nylon bag is pulled up, suspended in the air and drained for 15 minutes, and its weight (W 1 (g)) is measured. About 1.0 g of resin particles were collected and their weight (W
2 (g)) is precisely weighed and placed in a nylon bag. This is 50
After soaking in 0 cc of deionized water for 30 minutes, pull up the nylon bag, hang it in the air and drain it for 15 minutes,
The weight (W 3 (g)) is measured. Absorption capacity = (W 3 -W 1) / W 2 (g / g)
【００１９】吸水速度；ＪＩＳ Ｋ−７２２４に準じ、
図１に示す装置を用いて測定した。樹脂粒子１．０ｇを
小孔のあいた支持板に敷いた不織布上に均一な厚さとな
るようにのせた。樹脂粒子層の下面を下記組成の人工尿
と接触させて、樹脂粒子が人工尿を吸収する量を測定し
た。開始後１０分間に吸収した人工尿の量をもって吸水
速度とした。 人工尿の組成（重量％） 尿素 １．９４ 塩化ナトリウム ０．８０ 塩化カルシウム ０．０６ 硫酸マグネシウム ０．１１ 純水 ９７．０９Water absorption rate: According to JIS K-7224
It measured using the apparatus shown in FIG. 1.0 g of resin particles were placed on a nonwoven fabric spread on a support plate having small holes so as to have a uniform thickness. The lower surface of the resin particle layer was brought into contact with artificial urine having the following composition, and the amount of the resin particles absorbing artificial urine was measured. The amount of artificial urine absorbed 10 minutes after the start was defined as the water absorption rate. Composition of artificial urine (% by weight) Urea 1.94 Sodium chloride 0.80 Calcium chloride 0.06 Magnesium sulfate 0.11 Pure water 97.09
【００２０】平均粒子径；ＡＳＴＭ式標準篩を上から８
メッシュ、１２メッシュ、２０メッシュ、３２メッシ
ュ、４０メッシュ、６０メッシュ、８０メッシュ、１０
０メッシュ、１２０メッシュ、１５０メッシュ及び受け
皿の順に組み合わせ、最上段の篩に樹脂粒子を約５０ｇ
入れ、ロータップ式自動震盪器で１分間震盪させた。各
篩に残った樹脂粒子の重量を秤量し、全体重を１００％
として、重量分率により粒径分布を求め、重量基準の５
０％粒子径を平均粒子径とした。Average particle size: 8 from the top using an ASTM standard sieve
Mesh, 12 mesh, 20 mesh, 32 mesh, 40 mesh, 60 mesh, 80 mesh, 10 mesh
Combine in order of 0 mesh, 120 mesh, 150 mesh and a saucer, and put about 50 g of resin particles on the top sieve.
And shaken for 1 minute with a low tap automatic shaker. The weight of the resin particles remaining on each sieve is weighed, and the total weight is 100%.
The particle size distribution is determined by weight fraction, and the weight-based
The 0% particle size was defined as the average particle size.
【００２１】ゲル強度；内径４５ｍｍの容器に室温の脱
イオン水１００ｍｌと、長さ２５ｍｍの磁気回転子を入
れた。回転子を６００ｒｐｍで回転させながら、下記式
により算出された量の樹脂粒子をゆっくりと投入し、３
０分間吸水させた。 樹脂粒子投入量＝１００／樹脂粒子の吸水能 レオメーター（不動工業社製品、ＮＭＲ−２００２Ｊ、
直径２０ｍｍの圧縮弾性用アダプター装着、移動速度５
０ｍｍ／分）を用いて、上記で吸水させた樹脂粒子につ
き、セルが樹脂粒子に入り込む時点での圧力を測定し、
その値をゲル強度とした。Gel strength: A container having an inner diameter of 45 mm was charged with 100 ml of room temperature deionized water and a magnetic rotor having a length of 25 mm. While rotating the rotor at 600 rpm, the amount of resin particles calculated by
Water was absorbed for 0 minutes. Resin particle input amount = 100 / water absorption capacity of resin particles Rheometer (Fudo Industry Co., Ltd., NMR-2002J,
Attach a compression elastic adapter with a diameter of 20 mm, moving speed 5
0 mm / min), the pressure at the time when the cell enters the resin particles was measured for the resin particles absorbed above,
The value was defined as gel strength.
【００２２】実施例１ アクリル酸１４５．４ｇに水９．４ｇを加え、これに２
５重量％水酸化ナトリウム水溶液２４２．３ｇを冷却し
つつ加えて中和したのち、過硫酸カリウム０．０８７３
ｇ及び次亜リン酸ナトリウム・１水和物０．０１４６ｇ
（アクリル酸に対して１００ｐｐｍ）を添加してモノマ
ー水溶液を調製した。攪拌機、還流冷却器、温度計及び
窒素ガス導入管を付設した容量３リットルの四つ口丸底
フラスコにシクロヘキサン６２４ｇを入れ、これに分散
剤としてポリオキシエチレンオクチルフェニルエーテル
リン酸エステル（第一工業製薬社製品、プライサーフ
Ａ２１０Ｇ、オキシエチレン基の平均重合度 約７）
１．５６ｇを加え、５１０ｒｐｍで攪拌した。フラスコ
を窒素ガスで置換したのち７５℃に昇温してシクロヘキ
サンを還流させた。これに上記で調製したモノマー水溶
液を１３．２ｇ／ｇの滴下速度で３０分間にわたって供
給した。滴下終了後、７５℃でさらに３０分間保持し
た。Example 1 9.4 g of water was added to 145.4 g of acrylic acid, and 2
After neutralizing by adding 242.3 g of a 5% by weight aqueous solution of sodium hydroxide while cooling, 0.0873 of potassium persulfate was added.
g and sodium hypophosphite monohydrate 0.0146 g
(100 ppm based on acrylic acid) was added to prepare an aqueous monomer solution. 624 g of cyclohexane was placed in a three-liter four-necked round-bottom flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet tube, and polyoxyethylene octyl phenyl ether phosphate (Daiichi Kogyo Co., Ltd.) was added thereto as a dispersant. Pharmaceutical products, Price Surf
A210G, average degree of polymerization of oxyethylene group about 7)
1.56 g was added, and the mixture was stirred at 510 rpm. After replacing the flask with nitrogen gas, the temperature was raised to 75 ° C. to reflux cyclohexane. To this, the monomer aqueous solution prepared above was supplied at a dropping rate of 13.2 g / g for 30 minutes. After completion of the dropwise addition, the temperature was maintained at 75 ° C. for another 30 minutes.
【００２３】生成した樹脂の含水率は５５％であった。
この生成した樹脂を含む７５℃のスラリーに、架橋剤の
エチレングリコールジグリシジルエーテル（ナガセ化成
社製品、デナコール ＥＸ８１０）０．１４５４ｇ（ア
クリル酸に対して１０００ｐｐｍ）を水１０ｇに溶解し
た溶液を加え、７５℃で３０分間保持した。次いでシク
ロヘキサンとの共沸によって樹脂の含水率が７％になる
まで脱水した。攪拌を停止すると樹脂が沈降したのでデ
カンテーションにより樹脂を回収し、９０℃で乾燥して
顆粒状の高吸水性樹脂とした。このものの物性を表−１
に示す。The water content of the produced resin was 55%.
A solution prepared by dissolving 0.1454 g (1000 ppm based on acrylic acid) of ethylene glycol diglycidyl ether (a product of Nagase Kasei Co., Denacol EX810) as a cross-linking agent in 10 g of water was added to the slurry at 75 ° C. containing the generated resin. Hold at 75 ° C. for 30 minutes. Subsequently, the resin was dehydrated by azeotropic distillation with cyclohexane until the water content of the resin became 7%. When the stirring was stopped, the resin settled, and the resin was recovered by decantation and dried at 90 ° C. to obtain a granular superabsorbent resin. Table 1 shows the physical properties of this product.
Shown in
【００２４】実施例２ 実施例１において、エチレングリコールジグリシジルエ
ーテル０．０７２７ｇ（アクリル酸に対して５００ｐｐ
ｍ）を水１０ｇに溶解した溶液を用いた以外は、実施例
１と全く同様にして高吸水性樹脂を製造した。このもの
の物性を表−１に示す。Example 2 In Example 1, 0.0727 g of ethylene glycol diglycidyl ether (500 pp based on acrylic acid)
A superabsorbent resin was produced in exactly the same manner as in Example 1 except that a solution of m) dissolved in 10 g of water was used. Table 1 shows the physical properties of this product.
【００２５】実施例３ 実施例１において、エチレングリコールジグリシジルエ
ーテル０．７２７ｇ（アクリル酸に対して５０００ｐｐ
ｍ）を水１０ｇに溶解した溶液を用いた以外は、実施例
１と全く同様にして高吸水性樹脂を製造した。このもの
の物性を表−１に示す。Example 3 In Example 1, 0.727 g of ethylene glycol diglycidyl ether (5000 pp based on acrylic acid)
A superabsorbent resin was produced in exactly the same manner as in Example 1 except that a solution of m) dissolved in 10 g of water was used. Table 1 shows the physical properties of this product.
【００２６】実施例４ 実施例１において、エチレングリコールジグリシジルエ
ーテルを溶解する水量を５０ｇに変更した以外は、実施
例１と全く同様にして高吸水性樹脂を製造した。このも
のの物性を表−１に示す。なお、この実施例において、
エチレングリコールジグリシジルエーテルを溶解した水
を樹脂に吸収させた時点での樹脂の含水率は６０％であ
る。Example 4 A superabsorbent resin was produced in the same manner as in Example 1 except that the amount of water in which ethylene glycol diglycidyl ether was dissolved was changed to 50 g. Table 1 shows the physical properties of this product. In this example,
The water content of the resin at the time when the water in which ethylene glycol diglycidyl ether is dissolved is absorbed by the resin is 60%.
【００２７】実施例５ 実施例１において、エチレングリコールジグリシジルエ
ーテルを溶解する水量を１００ｇに変更した以外は、実
施例１と全く同様にして高吸水性樹脂を製造した。この
ものの物性を表−１に示す。なお、この実施例におい
て、エチレングリコールジグリシジルエーテルを溶解し
た水を樹脂に吸収させた時点での樹脂の含水率は６４％
である。Example 5 A superabsorbent resin was produced in the same manner as in Example 1 except that the amount of water in which ethylene glycol diglycidyl ether was dissolved was changed to 100 g. Table 1 shows the physical properties of this product. In this example, the water content of the resin at the time when the water in which ethylene glycol diglycidyl ether was dissolved was absorbed by the resin was 64%.
It is.
【００２８】実施例６ 実施例１において、モノマー水溶液の滴下終了後、７５
℃で３０分間保持して樹脂を生成させたのち、シクロヘ
キサンとの共沸によって樹脂の含水率が４２％となるま
で脱水した。次いでこれに実施例１と同じくエチレング
リコールジグリシジルエーテル０．１４５４ｇを水１０
ｇに溶解した溶液を加え、７５℃で３０分間保持した。
以後は実施例１と同様に処理して高吸水性樹脂を得た。
このものの物性を表−１に示す。なお、この実施例にお
いて、エチレングリコールジグリシジルエーテルを溶解
した水を樹脂に吸収させた時点での樹脂の含水率は４４
％である。Example 6 In Example 1, after the dropping of the aqueous monomer solution was completed, 75
After holding at 30 ° C. for 30 minutes to form a resin, the resin was dehydrated by azeotropic distillation with cyclohexane until the water content of the resin became 42%. Then, similarly to Example 1, 0.1454 g of ethylene glycol diglycidyl ether was added to water 10
g, and kept at 75 ° C. for 30 minutes.
Thereafter, the same treatment as in Example 1 was carried out to obtain a superabsorbent resin.
Table 1 shows the physical properties of this product. In this example, the water content of the resin at the time when the water in which ethylene glycol diglycidyl ether was dissolved was absorbed by the resin was 44.
%.
【００２９】実施例７ 実施例１において、次亜リン酸ナトリウム・１水和物の
量をアクリル酸に対して２００ｐｐｍとしたモノマー水
溶液を用いた以外は、実施例１と全く同様にして高吸水
性樹脂を製造した。このものの物性を表−１に示す。Example 7 The procedure of Example 1 was repeated, except that an aqueous monomer solution was used in which the amount of sodium hypophosphite monohydrate was 200 ppm with respect to acrylic acid. A reactive resin was manufactured. Table 1 shows the physical properties of this product.
【００３０】実施例８ 実施例１において、シクロヘキサンに添加する分散剤と
してポリオキシエチレントリデシルエーテルリン酸エス
テル（第一工業製薬社製品、プライサーフ Ａ２１２
Ｃ）１．５６ｇを用いた以外は、実施例１と全く同様に
して高吸水性樹脂を製造した。このものの物性を表−１
に示す。Example 8 In Example 1, polyoxyethylene tridecyl ether phosphate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Plysurf A212) was used as a dispersant to be added to cyclohexane.
C) A super water-absorbent resin was produced in exactly the same manner as in Example 1 except that 1.56 g was used. Table 1 shows the physical properties of this product.
Shown in
【００３１】比較例１ 実施例１において、重合により生成した樹脂に架橋剤を
含浸させる代りに、架橋剤を含むモノマー水溶液を用い
て高吸水性樹脂を製造した。すなわち、実施例１におい
て、モノマー水溶液にエチレングリコールジグリシジル
エーテル０．１４５４ｇを加え、このモノマー水溶液を
１３．２ｇ／分の供給速度で３０分間供給し、引続いて
７５℃で３０分間保持したのち、シクロヘキサンとの共
沸により樹脂の含水率が７％になるまで脱水した。得ら
れた高吸水性樹脂の物性を表−１に示す。Comparative Example 1 Instead of impregnating the resin produced by polymerization with the crosslinking agent in Example 1, a superabsorbent resin was produced using an aqueous monomer solution containing the crosslinking agent. That is, in Example 1, 0.1454 g of ethylene glycol diglycidyl ether was added to the aqueous monomer solution, and the aqueous monomer solution was supplied at a supply speed of 13.2 g / min for 30 minutes, and subsequently maintained at 75 ° C. for 30 minutes. The resin was dehydrated by azeotropy with cyclohexane until the water content of the resin became 7%. Table 1 shows the physical properties of the obtained superabsorbent resin.
【００３２】比較例２ 比較例１において、モノマー水溶液に加えるエチレング
リコールジグリシジルエーテルを０．３６８３ｇに増加
させた以外は、比較例１と全く同様にして高吸水性樹脂
を製造した。このものの物性を表−１に示す。Comparative Example 2 A super water-absorbent resin was produced in exactly the same manner as in Comparative Example 1, except that the amount of ethylene glycol diglycidyl ether added to the aqueous monomer solution was increased to 0.3683 g. Table 1 shows the physical properties of this product.
【００３３】比較例３ 実施例１において、モノマー水溶液の調製に際し次亜リ
ン酸ナトリウムを用いなかった以外は、実施例１と全く
同様にして高吸水性樹脂を製造した。このものの物性を
表−１に示す。Comparative Example 3 A super water-absorbent resin was produced in the same manner as in Example 1 except that sodium hypophosphite was not used in preparing the aqueous monomer solution. Table 1 shows the physical properties of this product.
【００３４】比較例４ 比較例３において、モノマー水溶液にエチレングリコー
ルジグリシジルエーテル０．１５４５ｇを添加した以外
は、比較例３と全く同様にして高吸水性樹脂を製造し
た。このものの物性を表−１に示す。Comparative Example 4 A superabsorbent resin was produced in the same manner as in Comparative Example 3, except that 0.1545 g of ethylene glycol diglycidyl ether was added to the aqueous monomer solution. Table 1 shows the physical properties of this product.
【００３５】[0035]
【表１】 [Table 1]
【図１】吸水速度測定装置の概略図であるFIG. 1 is a schematic diagram of a water absorption rate measuring device.
１：ビュレット ２：ゴム栓 ３：小孔のあいた支持板 ４：不織布 ５：樹脂粒子 1: Bullet 2: Rubber stopper 3: Support plate with small holes 4: Non-woven fabric 5: Resin particles
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J011 BB01 BB09 JA04 JA06 JB09 JB26 JB27 NB06 PA10 PB40 PC02 PC07 4J100 AJ02P AK03Q AK07Q CA04 CA05 CA31 DA37 FA03 FA21 HA53 HC39 HC40 HC51 JA19 JA60 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 BB01 BB09 JA04 JA06 JB09 JB26 JB27 NB06 PA10 PB40 PC02 PC07 4J100 AJ02P AK03Q AK07Q CA04 CA05 CA31 DA37 FA03 FA21 HA53 HC39 HC40 HC51 JA19 JA60
Claims (9)
ルボン酸を主体とするモノビニルモノマー、重合開始剤
及び次亜リン酸化合物を含有するモノマー水溶液を重合
させ、生成した樹脂に、含水率が少なくとも４０％の状
態で、カルボキシル基と反応し得る官能基を複数個有す
る架橋剤を含浸させて架橋反応させることを特徴とする
高吸水性樹脂の製造方法。1. An aqueous monomer solution containing a monovinyl monomer mainly composed of an unsaturated carboxylic acid which is at least partially neutralized, a polymerization initiator and a hypophosphorous acid compound is polymerized. A method for producing a super water-absorbent resin, wherein a crosslinking reaction is performed by impregnating a crosslinking agent having a plurality of functional groups capable of reacting with a carboxyl group in a state of at least 40%.
０％の状態で、カルボキシル基と反応し得る官能基を複
数個有する架橋剤を含浸させて架橋反応させることを特
徴とする請求項１記載の高吸水性樹脂の製造方法。2. The resin produced has a water content of at least 5
The method for producing a superabsorbent resin according to claim 1, wherein a crosslinking reaction is performed by impregnating a crosslinking agent having a plurality of functional groups capable of reacting with a carboxyl group in a 0% state.
ルボン酸を主体とするモノビニルモノマー、重合開始剤
及び次亜リン酸化合物を含有するモノマー水溶液を重合
させ、生成した樹脂にカルボキシル基を反応し得る官能
基を複数個有する架橋剤の水性溶液を含浸させて架橋反
応させ、含水率が少なくとも４０％の含水した架橋樹脂
を生成させることを特徴とする高吸水性樹脂の製造方
法。3. A method of polymerizing a monomer aqueous solution containing at least partially neutralized monovinyl monomer mainly composed of unsaturated carboxylic acid, a polymerization initiator and a hypophosphorous acid compound, and reacting a carboxyl group with the produced resin. A method for producing a highly water-absorbent resin, comprising: impregnating an aqueous solution of a crosslinking agent having a plurality of functional groups capable of undergoing crosslinking reaction to form a water-containing crosslinked resin having a water content of at least 40%.
橋樹脂を生成させることを特徴とする請求項３記載の高
吸水性樹脂の製造方法。4. The method according to claim 3, wherein a crosslinked resin having a water content of at least 50% is formed.
であることを特徴とする請求項１ないし４のいずれかに
記載の高吸水性樹脂の製造方法。5. The method for producing a superabsorbent resin according to claim 1, wherein the crosslinking agent is a polyglycidyl ether compound.
疎水性有機溶媒を重合条件下に維持し、これにモノマー
水溶液を逐次供給して、疎水性有機溶媒中にモノマー水
溶液が液滴として懸濁している状態で行うことを特徴と
する請求項１ないし５のいずれかに記載の高吸水性樹脂
の製造方法。6. The polymerization of an aqueous monomer solution is performed by maintaining a hydrophobic organic solvent containing a dispersant under polymerization conditions, and sequentially supplying the aqueous monomer solution to the aqueous monomer solution, and suspending the aqueous monomer solution as droplets in the hydrophobic organic solvent. The method according to any one of claims 1 to 5, wherein the method is performed in a cloudy state.
テル系分散剤であることを特徴とする請求項６記載の高
吸水性樹脂の製造方法 【化１】 （式中、Ｒ1 は炭素数８〜３０のフェニル基で置換され
ていてもよいアルキル基又はアルキル基で置換されてい
てもよいアリール基を表わし、Ｒ2 は水酸基又はＲ1 Ｏ
−（ＣＨ2 ＣＨ2 Ｏ）n −基を表わし、ｎは１〜３０の
整数を表わす。）7. The method for producing a superabsorbent resin according to claim 6, wherein the dispersant is a phosphate dispersant represented by the formula (1). (Wherein, R 1 represents an alkyl group which may be substituted with a phenyl group having 8 to 30 carbon atoms or an aryl group which may be substituted with an alkyl group, and R 2 represents a hydroxyl group or R 1 O
- (CH 2 CH 2 O) n - represents a radical, n represents an integer of 1 to 30. )
あることを特徴とする請求項７記載の高吸水性樹脂の製
造方法。8. The method according to claim 7, wherein R 1 in the formula (1) is an octylphenyl group.
とを特徴とする請求項７又は８記載の高吸水性樹脂の製
造方法。9. The method according to claim 7, wherein n in the formula (1) is an integer of 2 to 15.
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|---|---|---|---|
| JP11220987A JP2001040014A (en) | 1999-08-04 | 1999-08-04 | Production of highly water-absorbable resin |
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|---|---|---|---|
| JP11220987A JP2001040014A (en) | 1999-08-04 | 1999-08-04 | Production of highly water-absorbable resin |
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ID=16759704
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| Country | Link |
|---|---|
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