JPH05140236A - Fine porous water-absorbent resin particle as additive - Google Patents
Fine porous water-absorbent resin particle as additiveInfo
- Publication number
- JPH05140236A JPH05140236A JP17770791A JP17770791A JPH05140236A JP H05140236 A JPH05140236 A JP H05140236A JP 17770791 A JP17770791 A JP 17770791A JP 17770791 A JP17770791 A JP 17770791A JP H05140236 A JPH05140236 A JP H05140236A
- Authority
- JP
- Japan
- Prior art keywords
- water
- structural formula
- chemical structural
- present
- vinyl ester
- 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
- C08F8/12—Hydrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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、吸水性樹脂添加剤に関
するものであり、更に詳しく述べると、塗料や壁材に添
加して、乾燥後の塗膜や壁材に吸水性を付与出来る多孔
性の添加剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-absorbent resin additive. More specifically, it is a porous material which can be added to paints and wall materials to impart water absorbency to coating films and wall materials after drying. It relates to a sex additive.
【０００２】[0002]
【従来の技術】例えば、屋内と屋外を仕切る壁やドア−
は、その両面で、屋内と屋外の温度差をもつ。この温度
差が大きい時、温かく湿度の高い屋内に面した壁やドア
−の表面には、常に露滴が付着しジメジメしたり、カビ
が繁殖するだけでなく壁材や屋内に置かれた種々の物品
を汚す原因となる。こう言った困った問題は、大勢の人
が経験しているが、決定的な解決法は見出されていな
い。しかし最近になって、吸水性樹脂の発達に伴って、
これを用いた成形物を露滴が付着する壁やドア−の近辺
に置くことにより、ある程度は解決が図られているが、
根本的な解決には、到底なり得ないのが実状である。
又、これら吸水性樹脂を壁材や塗料に混合して問題解決
を図ろうとの試みもなされようとしているが、元来、こ
れら吸水性樹脂は吸水にともなって、その体積が大幅に
増加するものであるので、塗料や、壁材を基本的に破壊
してしまい意味をなさないのが現状である。更に、これ
ら吸水性樹脂はその原料の吸水に寄与する部分は、−Ｓ
Ｏ3Ｘや−ＣＯＯＸ（ここで、ＸはＨ，Ｎａ，ＮＨ4等）
の基に限られている。これらの基は、酸性基であり水に
対する親和性が強く多量の水を吸水する能力を有する
が、水の拘束力が極めて強く、容易に水を手放そうとは
しない。このため、かえって、壁やドア−などをジメジ
メした状態に何時も置くことになり逆効果にもなる。2. Description of the Related Art For example, a wall or a door that separates an indoor from an outdoor
Has a temperature difference between indoor and outdoor on both sides. When this temperature difference is large, dewdrops are constantly adhering to the surface of walls and doors facing indoors, which are warm and humid, and not only do mold grow, but also various wall materials and indoors are placed. Will cause the items to become dirty. Many people have experienced these troublesome problems, but no definitive solution has been found. However, recently, with the development of water-absorbent resin,
By placing the molded product using this near the wall or door where dew drops adhere, some solution has been achieved,
The reality is that a fundamental solution cannot be achieved.
Attempts have also been made to mix these water-absorbent resins with wall materials and paints to solve the problem, but originally, these water-absorbent resins increase their volume significantly with water absorption. Therefore, the current situation is that it basically destroys paints and wall materials and does not make sense. Further, these water-absorbent resins have a -S
O 3 X or -COOX (wherein, X is H, Na, NH 4 and the like)
It is limited to the base of. These groups are acidic groups and have a strong affinity for water and have the ability to absorb a large amount of water, but they have a very strong binding force for water and do not easily release water. For this reason, rather, the wall or door is always left in a jumbled state, which has the opposite effect.
【０００３】[0003]
【発明が解決しようとする課題】解決しようとする問題
点は、吸水し易く、吸水しても体積変化が小さく、周り
の湿度が低くなった場合には、容易に吸水した水を手放
すことが出来る吸水性樹脂であって、壁材や塗料に、容
易に混合できる樹脂を得ることである。The problem to be solved is that water is easily absorbed, the volume change is small even if water is absorbed, and when the surrounding humidity becomes low, the absorbed water can be easily released. A water-absorbing resin that can be easily mixed with wall materials and paints.
【０００４】[0004]
【課題を解決するための手段】本発明は、このような吸
水性樹脂添加剤を得べく検討を重ねた結果得られたもの
である。即ち、吸水性樹脂の原料の吸水に寄与する部分
に、吸水、離水の容易な非イオン性の親水基の代表と言
える水酸基を用いる。これを樹脂中多量に持つ材料とし
て、ポリビニルアルコ−ルを主原料とする。次に、水に
溶解することを防止する為吸水時の体積変化を少なくす
る為、多量の水を吸水出来る様に、更に壁材や塗料に、
容易に混合できる為に、このポリビニルアルコ−ルを強
固に架橋すると共に、多孔性の球状粒子とすることによ
り、目的に合致した吸水性樹脂添加剤を得ることを可能
にした。The present invention was obtained as a result of repeated studies to obtain such a water absorbent resin additive. That is, a hydroxyl group, which can be said to be a representative of nonionic hydrophilic groups that easily absorb and separate water, is used in the portion of the raw material of the water-absorbent resin that contributes to water absorption. Polyvinyl alcohol is used as a main raw material as a material having a large amount of this in the resin. Next, in order to prevent the volume from changing when absorbing water to prevent it from dissolving in water, it is possible to absorb a large amount of water, and further to wall materials and paints.
Since it can be easily mixed, it is possible to obtain a water-absorbent resin additive suitable for the purpose by strongly crosslinking this polyvinyl alcohol and forming it into porous spherical particles.
【０００５】以下、本発明を詳述する。本発明で用いら
れる吸水性樹脂の主原料は、前述の如くポリビニルアル
コ−ルである。本発明では、ポリビニルアルコ−ルに架
橋を行なって、吸水性樹脂を得るのではなく、下記化学
構造式（１）で示される特定のビニルエステルとこれと
共重合可能な下記化学構造式（２）で示される特定のラ
ジカル重合性の官能基を２個有する単量体とを共重合さ
せ、この共重合体を加水分解させることにより、高度に
架橋されたポリビニルアルコ−ルを主原料とする吸水性
樹脂を得るものである。The present invention will be described in detail below. The main raw material of the water absorbent resin used in the present invention is polyvinyl alcohol as described above. In the present invention, the polyvinyl alcohol is not crosslinked to obtain a water absorbent resin, but a specific vinyl ester represented by the following chemical structural formula (1) and the following chemical structural formula (2) copolymerizable therewith ) Is copolymerized with a monomer having two specific radically polymerizable functional groups, and the copolymer is hydrolyzed to obtain a highly crosslinked polyvinyl alcohol as a main raw material. A water absorbent resin is obtained.
【０００６】[0006]
【化１】[Chemical 1]
【０００７】[0007]
【化２】[Chemical 2]
【０００８】本発明で用いられる化学構造式（１）で示
される特定のビニルエステルは、ラジカル重合性に富
み、又、これら重合体は、アルカリ水溶液中で容易に加
水分解され、ポリビニルアルコ−ルに変化する。該ビニ
ルエステル中のアルキル基Ｒ1の大きさは、本発明で
は、Ｃ1〜Ｃ6の範囲が好ましく用いられる。Ｃ6以下の
アルキル基が本発明で使われる理由は、Ｃ6を超える大
きいアルキル基では、ラジカル重合性が顕著に低下する
と共に、水に対する親和性がなく、アルカリ水溶液中で
の加水分解が、起こり難くなるためである。The specific vinyl ester represented by the chemical structural formula (1) used in the present invention is highly radically polymerizable, and these polymers are easily hydrolyzed in an aqueous alkaline solution to give polyvinyl alcohol. Changes to. In the present invention, the size of the alkyl group R 1 in the vinyl ester is preferably C 1 to C 6 . The reason why an alkyl group having C 6 or less is used in the present invention is that a large alkyl group having more than C 6 has a marked decrease in radical polymerizability and has no affinity for water, resulting in hydrolysis in an alkaline aqueous solution. This is because it will not happen easily.
【０００９】本発明の主原料となる化学構造式（１）で
示される特定のビニルエステルの具体例を示すと、次の
ようなものである。酢酸ビニル（Ｒ1：−ＣＨ3），エチ
ルビニルエステル（Ｒ1：−Ｃ2Ｈ5），ｎ−プロピルビ
ニルエステル（Ｒ1：−Ｃ3Ｈ7），ｎ−ブチルビニルエ
ステル（Ｒ1：−Ｃ4Ｈ9），ｎ−ヘキシルビニルエステ
ル（Ｒ1：−Ｃ6Ｈ13）等を挙げることが出来る。これら
は、一例であり、本発明はこれらのみに限定されない。Specific examples of the specific vinyl ester represented by the chemical structural formula (1), which is the main raw material of the present invention, are as follows. Vinyl acetate (R 1: -CH 3), ethyl vinyl esters (R 1: -C 2 H 5 ), n- propyl vinyl ester (R 1: -C 3 H 7 ), n- butyl vinyl ester (R 1: -C 4 H 9), n- hexyl vinyl ester (R 1: -C 6 H 13 ) or the like can be mentioned. These are examples, and the present invention is not limited to these.
【００１０】次に、化学構造式（１）で示される該ビニ
ルエステルと共重合させる特定のラジカル重合性の官能
基を２個有する単量体は、次のような、特性を具備しな
くてはならない。即ち、化学構造式（１）で示される該
ビニルエステルとある程度の共重合性を有すること。化
学構造式（１）で示される該ビニルエステルと同じ条件
では、化学構造式（１）で示される該ビニルエステルよ
り耐加水分解性が劣ること。且つ、目的が吸水性樹脂で
あるので、ある程度の親水性を有していること等の性質
を持つものでなくてはならない。この様な特性をある程
度満足するものとして、本発明では、化学構造式（１）
で示される該ビニルエステルと共重合させる特定のラジ
カル重合性の官能基を２個有する単量体として化学構造
式（２）で示されるジアクリルエステル又は、ジメタク
リルエステルが用いられる。Next, the monomer having two specific radically polymerizable functional groups to be copolymerized with the vinyl ester represented by the chemical structural formula (1) does not have the following characteristics. Don't That is, it should have some degree of copolymerizability with the vinyl ester represented by the chemical structural formula (1). Under the same conditions as the vinyl ester represented by the chemical structural formula (1), hydrolysis resistance is inferior to that of the vinyl ester represented by the chemical structural formula (1). In addition, since the purpose is a water-absorbent resin, it must have properties such as having a certain degree of hydrophilicity. In the present invention, the chemical structural formula (1)
The diacrylic ester or dimethacrylic ester represented by the chemical structural formula (2) is used as a monomer having two specific radically polymerizable functional groups to be copolymerized with the vinyl ester represented by
【００１１】化学構造式（２）で示されるモノマ−は、
二官能性であるので樹脂に架橋を行なうことが出来る。
一般にアクリルエステル又は、メタクリルエステルは、
アルカリにより加水分解を受けるが、その程度は、化学
構造式（１）で示される該ビニルエステルより弱いの
で、該ビニルエステルの加水分解時にも条件を適当に選
ぶことにより加水分解を防ぐことが出来る。The monomer represented by the chemical structural formula (2) is
The bifunctionality allows the resin to be crosslinked.
Generally, acrylic ester or methacrylic ester is
Although it is hydrolyzed by alkali, its degree is weaker than that of the vinyl ester represented by the chemical structural formula (1). Therefore, the hydrolysis can be prevented by appropriately selecting the conditions during the hydrolysis of the vinyl ester. ..
【００１２】又、ここでＲ2がＣ2〜Ｃ6のアルキル基で
あることは、Ｒ2がＣ6より大きいと架橋効果が乏しくな
る他、親水性が欠如し吸水性樹脂として好ましくない。
又、Ｒ2の下記化学構造式（３）でｎが１〜３の整数で
ある理由は、３を越すと架橋効果が乏しくなるためであ
る。この様な、化学構造式（２）で示されるモノマ−の
具体例を示すと、エチレングリコ−ルジアクリレ−ト
（ジメタクリレ−ト）、プロピレングリコ−ルジアクリ
レ−ト（ジメタクリレ−ト）、ブチレングリコ−ルジア
クリレ−ト（ジメタクリレ−ト）、ジエチレングリコ−
ルジアクリレ−ト（ジメタクリレ−ト）、トリエチレン
グリコ−ルジアクリレ−ト（ジメタクリレ−ト）等を挙
げることが出来るが、本発明では、これらのみに限定さ
れない。When R 2 is a C 2 -C 6 alkyl group, a crosslinking effect is poor when R 2 is larger than C 6 and the hydrophilicity is lacking, which is not preferable as a water-absorbent resin.
The reason that n is an integer of 1 to 3 in the following chemical structural formula (3) of R 2 is that when it exceeds 3, the crosslinking effect becomes poor. Specific examples of the monomer represented by the chemical structural formula (2) are ethylene glycol diacrylate (dimethacrylate), propylene glycol diacrylate (dimethacrylate), butylene glycol diacrylate. -Dimethacrylate, diethyleneglycol-
Ludia acrylate (dimethacrylate), triethylene glycol diacrylate (dimethacrylate) and the like can be mentioned, but the present invention is not limited thereto.
【００１３】次に、本発明で用いられる化学構造式
（１）で示される該ビニルエステルと化学構造式（２）
で示される該ジアクリルエステル又はジメタクリルエス
テルは、ビニルエステル６０〜９９重量部及び該ジアク
リルエステル又は、ジメタクリルエステル１〜４０重量
部が用いられる。化学構造式（２）のモノマ−は、二官
能性であるので、４０重量部を越して用いられると、架
橋が進み過ぎ、加水分解後の該吸水性樹脂は吸水能力に
劣ることになり易い。又、１重量部より少ないと、架橋
効果に乏しく、吸水時に体積変化が大きくなる為であ
る。次に本発明では、化学構造式（１）で示される該ビ
ニルエステルと化学構造式（２）で示される該ジアクリ
ルエステル又はジメタクリルエステルは、本発明の範囲
内で混合され、ラジカル重合されて架橋重合体となる。Next, the vinyl ester represented by the chemical structural formula (1) used in the present invention and the chemical structural formula (2)
As for the diacrylic ester or dimethacrylic ester represented by, 60 to 99 parts by weight of vinyl ester and 1 to 40 parts by weight of diacrylic ester or dimethacrylic ester are used. Since the monomer of the chemical structural formula (2) is bifunctional, if it is used in an amount of more than 40 parts by weight, crosslinking will proceed too much, and the water absorbent resin after hydrolysis will be inferior in water absorbing ability. .. On the other hand, if the amount is less than 1 part by weight, the crosslinking effect will be poor and the volume change will be large when absorbing water. Next, in the present invention, the vinyl ester represented by the chemical structural formula (1) and the diacrylic ester or dimethacrylic ester represented by the chemical structural formula (2) are mixed within the scope of the present invention and radical-polymerized. And becomes a crosslinked polymer.
【００１４】本発明で特に重要なのは、この架橋重合体
を作る際に、用いられる重合方法である。即ち、本発明
の該吸水性樹脂が、多量の水を吸水出来る様に、更に、
壁材や塗料に容易に混合できる為に、このポリビニルア
ルコ−ルを強固に架橋すると共に、多孔性の球状粒子と
することにある。この為、化学構造式（１）で示される
該ビニルエステルと化学構造式（２）で示される該ジア
クリルエステル又は、ジメタクリルエステルのラジカル
重合時に多孔性とするために、重合にあずからない有機
溶剤を添加することが本発明では行なわれる。又、壁材
や塗料に容易に混合できる球状粒子とする為に、懸濁重
合法が採用される。本発明で用いられる重合にあずから
ない有機溶剤は、特に限定はしない。しかしながら、添
加することにより、重合を阻害するものであってはなら
ないことは言うまでもないことである。一般に該有機溶
剤は、本発明で用いられる化学構造式（１）で示される
該ビニルエステルと化学構造式（２）で示される該ジア
クリルエステル又は、ジメタクリルエステル共重合体と
非常に良好な相溶性を有している場合には、添加量にも
依るが、比較的均一な小さな細孔が共重合体に形成され
る。一方、該有機溶剤が該共重合体と非相溶の場合に
は、一般に、比較的大きい細孔が形成される。本発明で
は目的に応じて種々の有機溶剤を選択することが出来
る。本発明では、室温で液体の高級アルコ−ル、各種ケ
トン、種々のエステル等が多用される。これら有機溶剤
の使用量は、本発明では、化学構造式（１）で示される
該ビニルエステルと化学構造式（２）で示される該ジア
クリルエステル又は、ジメタクリルエステル共重合体混
合モノマ−１００重量部当り１０〜５００重量部が用い
られる。１０重量部以下であると吸水可能な充分な細孔
ができない。又、５００重量部を超えると、充分強度の
ある共重合体となり得ない。Of particular importance to the present invention is the polymerization method used in making this crosslinked polymer. That is, the water-absorbent resin of the present invention can absorb a large amount of water,
Since it can be easily mixed with wall materials and paints, it is intended to strongly crosslink this polyvinyl alcohol and to form porous spherical particles. Therefore, since the vinyl ester represented by the chemical structural formula (1) and the diacrylic ester or dimethacrylic ester represented by the chemical structural formula (2) are made to be porous at the time of radical polymerization, they are not required for polymerization. Addition of an organic solvent is performed in the present invention. In addition, a suspension polymerization method is adopted to obtain spherical particles that can be easily mixed with a wall material or a paint. There is no particular limitation on the organic solvent used in the present invention and which is not involved in the polymerization. However, it goes without saying that the addition should not hinder the polymerization. Generally, the organic solvent is very good with the vinyl ester represented by the chemical structural formula (1) and the diacrylic ester or dimethacrylic ester copolymer represented by the chemical structural formula (2) used in the present invention. When they are compatible, relatively uniform small pores are formed in the copolymer, depending on the amount added. On the other hand, when the organic solvent is incompatible with the copolymer, generally large pores are formed. In the present invention, various organic solvents can be selected according to the purpose. In the present invention, higher alcohols which are liquid at room temperature, various ketones, various esters and the like are frequently used. In the present invention, the amount of these organic solvents used is such that the vinyl ester represented by the chemical structural formula (1) and the diacrylic ester or dimethacrylic ester copolymer mixed monomer-100 represented by the chemical structural formula (2). 10 to 500 parts by weight are used per part by weight. If it is 10 parts by weight or less, sufficient pores capable of absorbing water cannot be formed. If it exceeds 500 parts by weight, a sufficiently strong copolymer cannot be obtained.
【００１５】次に、本発明では、化学構造式（１）で示
される該ビニルエステルと化学構造式（２）で示される
該ジアクリルエステル又はジメタクリルエステル共重合
体混合モノマ−及び、該有機溶剤が混合され、懸濁重合
される。懸濁重合方法は、通常用いられる方法と何等変
わりはない。ポリビニルアルコ−ル、メチルセルロ−
ス、ポリエチレンオキサイド、プロピレンオキサイド、
ポリビニルピロリドンなどの水溶性高分子懸濁剤を適量
水に溶解させ、この中に、該有機溶剤と適量のラジカル
重合開始剤を含む該モノマ−混合物を入れ、系内を窒素
置換後、攪拌しながら、加温下に重合を進めれば良い。
加温は、通常４０℃〜８０℃程度行なわれる。本発明で
出来る懸濁共重合粒子の適当な大きさは、１０ミクロン
〜１ｍｍ程度が用いられるので、懸濁剤の種類と量、モ
ノマ−と水の割合、攪拌速度、重合速度等を適当に選ぶ
ことにより容易に達成される。Next, in the present invention, the vinyl ester represented by the chemical structural formula (1) and the diacrylic ester or dimethacrylic ester copolymer mixed monomer represented by the chemical structural formula (2) and the organic compound are mixed. Solvents are mixed and suspension polymerized. The suspension polymerization method is no different from the method usually used. Polyvinyl alcohol, methyl cellulose
, Polyethylene oxide, propylene oxide,
A water-soluble polymer suspending agent such as polyvinylpyrrolidone is dissolved in an appropriate amount of water, and the monomer mixture containing the organic solvent and an appropriate amount of a radical polymerization initiator is added thereto, and the system is replaced with nitrogen, followed by stirring. However, it suffices to proceed with the polymerization while heating.
The heating is usually performed at about 40 ° C to 80 ° C. Since the suitable size of the suspension copolymerized particles in the present invention is about 10 microns to 1 mm, the kind and amount of the suspending agent, the ratio of the monomer and water, the stirring speed, the polymerization speed, etc. are appropriately selected. Easily achieved by choosing.
【００１６】次に、この様にして出来た本発明になる有
機溶剤を含んだ懸濁粒子は、瀘過後よく水で洗浄され
る。この後、メタノ−ルやアセトン等の低沸点の手短な
溶媒で洗浄し、懸濁粒子に含まれている有機溶剤を予め
除去しておいても良い。又、場合に依っては、次の懸濁
粒子の加水分解の時に、該有機溶剤を除去することも可
能である。次に、分離洗浄された懸濁粒子は、アルカリ
溶液に入れられ加水分解される。本発明では、アルカリ
として、一般にＮａＯＨ０．５〜３０％程度の濃度の水
溶液が室温〜８０℃で用いられる。この際、加水分解を
容易にさせるためＮａＯＨ水溶液に、メタノ−ルやエタ
ノ−ルなどの種々のアルコ−ルを加えることも有用な方
法である。一般に、数分〜５時間程度で、加水分解は終
了し、該ビニルエステルは、かくして、非イオン性の水
酸基を多量有するポリビニルアルコ−ルになるが、加水
分解は、必ずしも１００％行なう必要はなく、目的に応
じた吸水量を得るために、加水分解量を調節できるのも
本発明の特徴である。Next, the thus-prepared suspended particles containing the organic solvent according to the present invention are thoroughly washed with water after filtration. After that, the organic solvent contained in the suspended particles may be removed in advance by washing with a short solvent having a low boiling point such as methanol or acetone. In some cases, it is possible to remove the organic solvent during the subsequent hydrolysis of the suspended particles. Then, the separated and washed suspended particles are put into an alkaline solution and hydrolyzed. In the present invention, an aqueous solution having a concentration of about 0.5 to 30% NaOH is generally used as the alkali at room temperature to 80 ° C. At this time, it is also a useful method to add various alcohols such as methanol and ethanol to the aqueous NaOH solution in order to facilitate hydrolysis. Generally, the hydrolysis is completed in about several minutes to 5 hours, and the vinyl ester thus becomes a polyvinyl alcohol having a large amount of nonionic hydroxyl groups, but the hydrolysis does not necessarily have to be 100%. It is also a feature of the present invention that the amount of hydrolysis can be adjusted to obtain the amount of water absorption according to the purpose.
【００１７】以上の方法で、本発明の吸水性樹脂微粒子
は得られるが、この樹脂粒子は吸水に寄与する部分が、
非イオン性の水酸基を有するポリビニルアルコ−ルであ
り、これは、周りの湿度に応じて、水の吸水、離水が容
易である。又、本発明の製造方法により多くの細孔を有
する微粒子であるので、吸水量も豊富で、塗料や壁材等
に簡単に混合でき、極めて有用な吸水性添加剤である。
以下、本発明を実施例で説明する。By the above method, the water-absorbent resin fine particles of the present invention can be obtained. However, in the resin particles, the portion contributing to water absorption is
It is a polyvinyl alcohol having a nonionic hydroxyl group, and it is easy to absorb and release water depending on the ambient humidity. Further, since it is fine particles having many pores according to the production method of the present invention, it is a very useful water-absorbing additive that has a large water absorption amount and can be easily mixed with paints and wall materials.
Hereinafter, the present invention will be described with reference to examples.
【００１８】[0018]
実施例（１） 酢酸ビニル８２重量部、エチレングリコ−ルジメタクリ
レ−ト１８重量部を良く混合し、これに重合開始剤とし
て、アゾビスイソブチロニトリル１．２重量部及び有機
溶剤として、酢酸エチル１００重量部を添加し、モノマ
−溶液とした。このモノマ−溶液を均一に混合された懸
濁剤としての０．１２％のポリビニルアルコ−ル水溶液
４２０重量部中に入れ、系内を窒素置換した後、強く攪
拌しながら温度を５０℃とし、２６時間重合させた。瀘
過、水で洗浄後の共重合体は無色透明な平均粒子径、約
２０ミクロンの球状を呈していた。次に、この共重合体
を多量のメタノ−ル中に入れ重合体中の酢酸エチルを抽
出した。次に、水３００重量部、メタノ−ル７００重量
部、ＮａＯＨ４５重量部の混合溶液中にこの共重合体微
粒子を入れ、攪拌しながら４０℃に昇温し、６０分間加
水分解を行なった。瀘過、洗浄を行なって、本発明の多
孔性吸水性樹脂微粒子を得た。次に、この樹脂を６０℃
で真空下に一昼夜乾燥した。一定量のこの乾燥された樹
脂を、２０℃の水中に１０分間入れた後、瀘過した。含
水した共重合体微粒子瀘過物を瀘紙で拭った後、重量を
測定し、吸水量を求めたところ、乾燥樹脂１グラム当り
２０グラムの水を含んでいることが分かった。又、吸水
前後の微粒子を顕微鏡を用いてその外径を測定し、体積
変化率を求めたところ、平均約４％しか増加していなか
った。次に、この乾燥された樹脂を粉砕し、赤外スペク
トルを測定したところビニルエステルは、９２％が加水
分解されており、一方メタクリルエステルは、殆ど分解
されていないことが分かった。Example (1) 82 parts by weight of vinyl acetate and 18 parts by weight of ethylene glycol dimethacrylate were mixed well, and 1.2 parts by weight of azobisisobutyronitrile as a polymerization initiator and ethyl acetate as an organic solvent were mixed therein. 100 parts by weight was added to obtain a monomer solution. This monomer solution was put into 420 parts by weight of a 0.12% polyvinyl alcohol aqueous solution as a suspending agent that had been uniformly mixed, the system was replaced with nitrogen, and the temperature was raised to 50 ° C. while stirring vigorously. It was polymerized for 26 hours. The copolymer after filtration and washing with water had a colorless and transparent average particle size, and had a spherical shape of about 20 microns. Next, this copolymer was put in a large amount of methanol to extract ethyl acetate in the polymer. Next, the fine particles of the copolymer were put into a mixed solution of 300 parts by weight of water, 700 parts by weight of methanol and 45 parts by weight of NaOH, heated to 40 ° C. with stirring, and hydrolyzed for 60 minutes. After filtration and washing, the porous water-absorbent resin fine particles of the present invention were obtained. Next, this resin is treated at 60 ° C.
It was dried under vacuum overnight. An aliquot of this dried resin was placed in 20 ° C. water for 10 minutes and then filtered. After the water-containing copolymer fine particle filter was wiped with a filter paper, the weight was measured and the amount of water absorption was determined. As a result, it was found that 20 g of water was contained per 1 g of the dry resin. The outer diameter of the fine particles before and after water absorption was measured using a microscope, and the volume change rate was determined. As a result, the average increase was only about 4%. Next, the dried resin was pulverized and the infrared spectrum was measured. As a result, it was found that 92% of the vinyl ester was hydrolyzed, while the methacrylic ester was hardly decomposed.
【００１９】実施例（２） 実施例（１）で作製した吸水性多孔性微粒子１０重量部
を市販のアクリル系塗料１５０重量部（固形分４０％）
に添加し良く攪拌した。これをガラス板に塗布し８０℃
で乾燥固化させた後、相対湿度８０％に調節された雰囲
気に１時間放置した。重量を測定することにより、塗膜
は約１６％重量が増加していることが認められた。又、
塗膜にはクラック等は生じていなかった。次に、吸水し
たこのガラスに塗布された塗料を相対湿度１５％に調節
された雰囲気に１時間放置したところ、吸水した水の実
に約８７％が離水していることが認められた。Example (2) 10 parts by weight of the water-absorbing porous fine particles prepared in Example (1) was used in an amount of 150 parts by weight of a commercially available acrylic paint (solid content 40%).
And stirred well. Apply this to a glass plate and apply at 80 ℃
After being dried and solidified with, the mixture was left for 1 hour in an atmosphere adjusted to a relative humidity of 80%. By measuring the weight, the coating was found to have gained about 16% weight. or,
The coating film was free from cracks and the like. Next, when the coating material applied to this absorbed water was left for 1 hour in an atmosphere adjusted to a relative humidity of 15%, it was confirmed that about 87% of the absorbed water had separated.
【００２０】[0020]
【発明の効果】以上説明したように、本発明の多孔性吸
水性樹脂微粒子添加剤に依れば、特に吸水し易く、吸水
しても体積変化が小さく、周りの湿度が低くなった場合
には、容易に吸水した水を手放すことが出来る吸水性樹
脂であって、壁材や塗料に、容易に混合できる樹脂を得
ることが可能である。As described above, according to the porous water-absorbent resin fine particle additive of the present invention, it is particularly easy to absorb water, the volume change is small even if water is absorbed, and the surrounding humidity becomes low. Is a water-absorbent resin that can easily release water that has absorbed water, and it is possible to obtain a resin that can be easily mixed with wall materials and paints.
【化３】 [Chemical 3]
【手続補正書】[Procedure amendment]
【提出日】平成４年９月２日[Submission date] September 2, 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】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【化１】[Chemical 1]
【化２】[Chemical 2]
【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】０００５[Correction target item name] 0005
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００５】以下、本発明を詳述する。本発明で用いら
れる吸水性樹脂の主原料は、前述のごとくポリビニルア
ルコ−ルである。本発明では、ポリビニルアルコ−ルに
架橋を行なって、吸水性樹脂を得るのではなく、下記化
学構造式化３で示される特定のビニルエステルとこれと
共重合可能な下記化学構造式化２で示される特定のラジ
カル重合性の官能基を２個有する単量体とを共重合さ
せ、この共重合体を加水分解させることにより、高度に
架橋されたポリビニルアルコ−ルを主原料とする吸水性
樹脂を得るものである。The present invention will be described in detail below. The main raw material of the water absorbent resin used in the present invention is polyvinyl alcohol as described above. In the present invention, polyvinyl alcohol - by performing crosslinking in Le, rather than obtaining a water-absorbent resin, in particular vinyl esters and copolymerizable therewith following chemical structural formula of 2 represented by the following chemical structural formula of 3 A water-absorbing agent containing a highly cross-linked polyvinyl alcohol as a main raw material by copolymerizing with a monomer having two specific radical-polymerizable functional groups shown below and hydrolyzing the copolymer. The resin is obtained.
【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】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】[0006]
【化３】 [Chemical 3]
【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】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】[0007]
【化４】 [Chemical 4]
【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】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】本発明で用いられる化学構造式化３で示さ
れる特定のビニルエステルは、ラジカル重合性に富み、
又、これら重合体は、アルカリ水溶液中で容易に加水分
解され、ポリビニルアルコ−ルに変化する。該ビニルエ
ステル中のアルキル基Ｒ1の大きさは、本発明では、Ｃ1
〜Ｃ6の範囲が好ましく用いられる。Ｃ6以下のアルキル
基が本発明で使われる理由は、Ｃ6を超える大きいアル
キル基では、ラジカル重合性が顕著に低下すると共に、
水に対する親和性がなく、アルカリ水溶液中での加水分
解が、起こり難くなるためである。[0008] Certain vinyl ester represented by the chemical structural formula of 3 used in the present invention are rich in radical-polymerizable,
Further, these polymers are easily hydrolyzed in an alkaline aqueous solution and converted into polyvinyl alcohol. In the present invention, the size of the alkyl group R 1 in the vinyl ester is C 1
The range of to C 6 is preferably used. The reason why an alkyl group having C 6 or less is used in the present invention is that a large alkyl group having more than C 6 causes a marked decrease in radical polymerizability and
This is because it has no affinity for water and hydrolysis in an alkaline aqueous solution is less likely to occur.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】本発明の主原料となる化学構造式化３で示
される特定のビニルエステルの具体例を示すと、次の様
なものである。酢酸ビニル（Ｒ1：−ＣＨ3）、エチルビ
ニルエステル（Ｒ1：−Ｃ2Ｈ5）、ｎープロピルビニル
エステル（Ｒ1：−Ｃ3Ｈ7）、ｎーブチルビニルエステ
ル（Ｒ1：−Ｃ4Ｈ9）、ｎーヘキシルビニルエステル
（Ｒ1：−Ｃ6Ｈ13）等を挙げることが出来る。これら
は、一例であり、本発明は、これらのみに限定されな
い。[0009] Specific examples of the specific vinyl ester represented by the chemical structural formula of 3 as a main raw material of the present invention is such follows. Vinyl acetate (R 1: -CH 3), ethyl vinyl esters (R 1: -C 2 H 5 ), n chromatography propyl vinyl ester (R 1: -C 3 H 7 ), n chromatography butyl vinyl ester (R 1: -C 4 H 9), n over hexyl vinyl ester (R 1: -C 6 H 13 ) or the like can be mentioned. These are examples, and the present invention is not limited to these.
【手続補正７】[Procedure Amendment 7]
【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】次に、化学構造式化３で示される該ビニル
エステルと共重合させる特定のラジカル重合性の官能基
を２個有する単量体は、次のような、特性を具備しなく
てはならない。即ち、化学構造式化３で示される該ビニ
ルエステルとある程度の共重合性を有すること。化学構
造式化３で示される該ビニルエステルと同じ条件では、
化学構造式化３で示される該ビニルエステルより耐加水
分解性が劣ること。且つ、目的が吸水性樹脂であるの
で、ある程度の親水性を有していること等の性質を持つ
ものでなくてはならない。この様な特性をある程度満足
するものとして、本発明では、化学構造式化３で示され
る該ビニルエステルと共重合させる特定のラジカル重合
性の官能基を２個有する単量体として化学構造式化４で
示されるジアクリルエステル又は、ジメタクリルエステ
ルが用いられる。[0010] Next, the monomer having two specific radically polymerizable functional groups to be copolymerized with the vinyl esters represented by the chemical structural formula of 3, as follows, is not provided with the characteristics I won't. That is, to have some copolymerizable with the vinyl esters represented by the chemical structural formula of 3. In the same conditions as the vinyl esters represented by the chemical structural formula of 3,
Poor that hydrolysis resistance than the vinyl esters represented by the chemical structural formula of 3. In addition, since the purpose is a water-absorbent resin, it must have properties such as having a certain degree of hydrophilicity. As satisfying such a characteristic to some extent, in the present invention, the chemical structural formula of the specific radical-polymerizable functional group to be copolymerized with the vinyl esters represented by the chemical structural formula of 3 as a monomer having two diacrylic esters or represented by 4, dimethacrylate ester.
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】化学構造式化４で示されるモノマ−は、二
官能性であるので樹脂に架橋を行うことが出来る。一般
にアクリルエステル又は、メタクリルエステルは、アル
カリにより加水分解を受けるが、その程度は、化学構造
式化３で示される該ビニルエステルより弱いので、該ビ
ニルエステルの加水分解時にも条件を適当に選ぶことに
より加水分解を防ぐことが出来る。[0011] monomer represented by the chemical structural formula of 4 - can be carried out crosslinking resin because it is bifunctional. Generally the acrylic ester or methacrylic ester, an alkali by undergo hydrolysis, but the extent, because weaker than the vinyl esters represented by the chemical structural formula of 3, appropriately chooses that the conditions in the hydrolysis of the vinyl ester Can prevent hydrolysis.
【手続補正９】[Procedure Amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】又、ここでＲ2がＣ2〜Ｃ6のアルキル基で
あることは、Ｒ2がＣ6より大きいと架橋効果が乏しくな
る他、親水性が欠如し吸水性樹脂として好ましくない。
又、下記化学構造式化５でｎが１〜３の整数である理由
は、３を越すと、架橋効果が乏しくなるためである。こ
の様な、化学構造式化４で示されるモノマ−の具体例を
示すと、エチレングリコールジアクリレート（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（ジ
メタクリレート）、ブチレングリコールジアクリレート
（ジメタクリレート）、ジエチレングリコールジアクリ
レート（ジメタクリレート）、トリエチレングリコール
ジアクリレート（ジメタクリレート）、等を挙げること
が出来るが、本発明では、これらのみに限定されない。When R 2 is a C 2 -C 6 alkyl group, a crosslinking effect is poor when R 2 is larger than C 6 and the hydrophilicity is lacking, which is not preferable as a water-absorbent resin.
The reason is n by the following chemical structural formula of 5 an integer of 1 to 3 is, it exceeds 3, because the crosslinking effect becomes poor. Such a monomer represented by the chemical structural formula of 4 - When a specific example of ethylene glycol diacrylate (dimethacrylate), propylene glycol diacrylate (dimethacrylate), butylene glycol diacrylate (dimethacrylate), diethylene glycol di Examples thereof include acrylate (dimethacrylate) and triethylene glycol diacrylate (dimethacrylate), but the present invention is not limited thereto.
【化５】 [Chemical 5]
【手続補正１０】[Procedure Amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１３】次に、本発明で用いられる化学構造式化３
で示される該ビニルエステルと化学構造式化４で示され
る該ジアクリルエステル又はジメタクリルエステルは、
ビニルエステル６０〜９９重量部及び該ジアクリルエス
テル又は、ジメタクリルエステル１〜４０重量部が用い
られる。化学構造式化４のモノマ−は、二官能性である
ので、４０重量部を越して用いられると、架橋が進み過
ぎ、加水分解後の該吸水性樹脂は吸水能力に劣ることに
なり易い。又、１重量部より少ないと、架橋効果に乏し
く、吸水時に体積変化が大きくなる為である。次に本発
明では、化学構造式化３で示される該ビニルエステルと
化学構造式化４で示される該ジアクリルエステル又はジ
メタクリルエステルは、本発明の範囲内で混合され、ラ
ジカル重合されて架橋重合体となる。[0013] Then, the chemical structural formula of 3 used in the present invention
The diacrylic esters or dimethacrylic esters represented in at the vinyl ester and the chemical structural formula of 4 shown is,
60 to 99 parts by weight of vinyl ester and 1 to 40 parts by weight of the diacrylic ester or dimethacrylic ester are used. Monomer of formula of 4 - is a two because it is functional, when used past the 40 parts by weight, crosslinking proceeds too far, the water absorbent resin after the hydrolysis tends to be inferior in water absorption capacity. On the other hand, if the amount is less than 1 part by weight, the crosslinking effect will be poor and the volume change will be large when absorbing water. In the present invention then, the diacrylic ester or di-methacrylic esters represented by the vinyl ester and the chemical structural formula of 4 represented by the chemical structural formula of 3 are mixed within the scope of the present invention, is a radical polymerization crosslinking It becomes a polymer.
【手続補正１１】[Procedure Amendment 11]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】本発明で特に重要なのは、この架橋重合体
を作る際に、用いられる重合方法である。即ち、本発明
の該吸水性樹脂が、多量の水を吸水出来る様に、更に、
壁材や塗料に容易に混合できる為に、このポリビニルア
ルコ−ルを強固に架橋すると共に、多孔性の球状粒子と
することにある。この為、化学構造式化３で示される該
ビニルエステルと化学構造式化４で示される該ジアクリ
ルエステル又は、ジメタクリルエステルのラジカル重合
時に多孔性とするために、重合にあずからない有機溶剤
を添加することが本発明では行われる。又、壁材や塗料
に容易に混合できる球状粒子とする為に、懸濁重合法が
採用される。本発明で用いられる重合にあずからない有
機溶剤は、特に限定はない。しかしながら、添加するこ
とにより、重合を阻害するものであってはならないこと
は言うまでもないことである。一般に該有機溶剤は、本
発明で用いられる化学構造式化３で示される該ビニルエ
ステルと化学構造式化４で示される該ジアクリルエステ
ル又は、ジメタクリルエステル共重合体と非常に良好な
相溶性を有している場合には、添加量にも依るが、比較
的均一な小さな細孔が共重合体に形成される。一方、該
有機溶剤が該共重合体と非相溶の場合には、一般に、比
較的大きい細孔が形成される。本発明では目的に応じて
種々の有機溶剤を選択することが出来る。本発明では、
室温で液体の高級アルコ−ル、各種ケトン、種々のエス
テル等が多用される。これら有機溶剤の使用量は、本発
明では、化学構造式化３で示される該ビニルエステルと
化学構造式化４で示される該ジアクリルエステル又は、
ジメタクリルエステル共重合体混合モノマ−１００重量
部当り１０〜５００重量部が用いられる。１０重量部以
下であると吸水可能な充分な細孔ができない。又、５０
０重量部を超えると、充分強度のある共重合体となり得
ない。Of particular importance to the present invention is the polymerization method used in making this crosslinked polymer. That is, the water-absorbent resin of the present invention can absorb a large amount of water,
Since it can be easily mixed with wall materials and paints, it is intended to strongly crosslink this polyvinyl alcohol and to form porous spherical particles. Therefore, the diacrylic esters or represented by the vinyl ester and the chemical structural formula of 4 represented by the chemical structural formula of 3, to a porous during radical polymerization of di-methacrylic esters, organic solvent which does not Azukara the polymerization Is added in the present invention. In addition, a suspension polymerization method is adopted to obtain spherical particles that can be easily mixed with a wall material or a paint. There is no particular limitation on the organic solvent used in the present invention that is not involved in the polymerization. However, it goes without saying that the addition should not hinder the polymerization. In general the organic solvent, the diacrylic esters or represented by the vinyl ester and the chemical structural formula of 4 represented by the chemical structural formula of 3 used in the present invention, a very good compatibility with dimethacrylic ester copolymer In the case of having, the relatively uniform small pores are formed in the copolymer depending on the addition amount. On the other hand, when the organic solvent is incompatible with the copolymer, generally large pores are formed. In the present invention, various organic solvents can be selected according to the purpose. In the present invention,
Higher alcohols, various ketones, various esters, etc. that are liquid at room temperature are often used. The amount of the organic solvent, present in the invention, the diacrylic esters or represented by the vinyl ester and the chemical structural formula of 4 represented by the chemical structural formula of 3,
10 to 500 parts by weight are used per 100 parts by weight of the dimethacrylic ester copolymer mixed monomer. If it is 10 parts by weight or less, sufficient pores capable of absorbing water cannot be formed. Also, 50
If it exceeds 0 parts by weight, a sufficiently strong copolymer cannot be obtained.
【手続補正１２】[Procedure Amendment 12]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】次に、本発明では、化学構造式化３で示さ
れる該ビニルエステルと化学構造式化４で示される該ジ
アクリルエステル又はジメタクリルエステル共重合体混
合モノマ−及び、該有機溶剤が混合され、懸濁重合され
る。懸濁重合方法は、通常用いられる方法と何等変わり
はない。ポリビニルアルコ−ル、メチルセルロ−ス、ポ
リエチレンオキサイド、プロピレンオキサイド、ポリビ
ニルピロリドンなどの水溶性高分子懸濁剤を適量水に溶
解させ、この中に、該有機溶剤と適量のラジカル重合開
始剤を含む該モノマ−混合物を入れ、系内を窒素置換
後、撹拌しながら、加温下に重合を進めれば良い。加温
は、通常４０℃〜８０℃程度で行われる。本発明で出来
る懸濁共重合粒子の適当な大きさは、１０ミクロン〜１
ｍｍ程度が用いられるので、懸濁剤の種類と量、モノマ
−と水の割合、撹拌速度、重合速度等を適当に選ぶこと
により容易に達成される。 ─────────────────────────────────────────────────────
[0015] Next, in the present invention, the di-acrylate ester or di-methacrylic ester copolymer mixed monomer represented by the vinyl ester and the chemical structural formula of 4 represented by the chemical structural formula of 3 - and, the organic solvent Mix and suspension polymerize. The suspension polymerization method is no different from the method usually used. A water-soluble polymer suspending agent such as polyvinyl alcohol, methylcellulose, polyethylene oxide, propylene oxide, or polyvinylpyrrolidone is dissolved in an appropriate amount of water, in which the organic solvent and an appropriate amount of a radical polymerization initiator are added. The monomer mixture may be added, the system may be purged with nitrogen, and the polymerization may be carried out while heating while stirring. The heating is usually performed at about 40 ° C to 80 ° C. A suitable size of the suspension copolymer particles prepared in the present invention is 10 microns to 1
Since a thickness of about mm is used, it can be easily achieved by appropriately selecting the type and amount of the suspending agent, the ratio of the monomer and water, the stirring rate, the polymerization rate and the like. ─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年１１月２７日[Submission date] November 27, 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】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【化１】 [Chemical 1]
【化２】 [Chemical 2]
Claims (1)
ルエステル６０〜９９重量部及び化学構造式（２）で示
されるラジカル重合性の官能基を２個有する単量体１〜
４０重量部をラジカル重合させる際に、重合を阻害しな
い有機溶剤を１０〜５００重量部を添加し、懸濁重合さ
せることにより得られる架橋重合体懸濁粒子を加水分解
することによって得られる水酸基を吸水基とすることを
特徴とする架橋された多孔性吸水性樹脂微粒子添加剤 【化１】 【化２】 1. A monomer having 1 to 60 parts by weight of a specific vinyl ester represented by the chemical structural formula (1) and two radically polymerizable functional groups represented by the chemical structural formula (2).
When radically polymerizing 40 parts by weight, 10 to 500 parts by weight of an organic solvent which does not inhibit polymerization is added, and a hydroxyl group obtained by hydrolyzing the crosslinked polymer suspension particles obtained by suspension polymerization is added. Crosslinked porous water-absorbent resin fine particle additive characterized by having a water-absorbing group [Chemical 2]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17770791A JPH05140236A (en) | 1991-06-24 | 1991-06-24 | Fine porous water-absorbent resin particle as additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17770791A JPH05140236A (en) | 1991-06-24 | 1991-06-24 | Fine porous water-absorbent resin particle as additive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05140236A true JPH05140236A (en) | 1993-06-08 |
Family
ID=16035702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17770791A Pending JPH05140236A (en) | 1991-06-24 | 1991-06-24 | Fine porous water-absorbent resin particle as additive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05140236A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5677407A (en) * | 1995-06-07 | 1997-10-14 | Amcol International Corporation | Process for producing an oil sorbent polymer and the product thereof |
| US5712358A (en) * | 1995-06-07 | 1998-01-27 | Amcol International Corporation | Process for producing an oil sorbent copolymer and the product thereof |
| US5830967A (en) * | 1994-10-24 | 1998-11-03 | Amcol International Corporation | Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US5830960A (en) * | 1994-10-24 | 1998-11-03 | Amcol International Corporation | Precipitation Polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US6107429A (en) * | 1994-10-24 | 2000-08-22 | Amcol International Corporation | Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| JP2006522047A (en) * | 2003-04-03 | 2006-09-28 | ビーエーエスエフ アクチェンゲゼルシャフト | Mixtures of compounds with at least two double bonds and uses thereof |
-
1991
- 1991-06-24 JP JP17770791A patent/JPH05140236A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5830967A (en) * | 1994-10-24 | 1998-11-03 | Amcol International Corporation | Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US5830960A (en) * | 1994-10-24 | 1998-11-03 | Amcol International Corporation | Precipitation Polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US5837790A (en) * | 1994-10-24 | 1998-11-17 | Amcol International Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US5955552A (en) * | 1994-10-24 | 1999-09-21 | Amcol International Corporation | Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US6107429A (en) * | 1994-10-24 | 2000-08-22 | Amcol International Corporation | Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US6248849B1 (en) | 1994-10-24 | 2001-06-19 | Amcol Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US6387995B1 (en) | 1994-10-24 | 2002-05-14 | Amcol International Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US5677407A (en) * | 1995-06-07 | 1997-10-14 | Amcol International Corporation | Process for producing an oil sorbent polymer and the product thereof |
| US5712358A (en) * | 1995-06-07 | 1998-01-27 | Amcol International Corporation | Process for producing an oil sorbent copolymer and the product thereof |
| US5834577A (en) * | 1995-06-07 | 1998-11-10 | Amcol International Corporation | Process for producing an oil sorbent copolymer and the product thereof |
| JP2006522047A (en) * | 2003-04-03 | 2006-09-28 | ビーエーエスエフ アクチェンゲゼルシャフト | Mixtures of compounds with at least two double bonds and uses thereof |
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