JPS61243805A - Production of highly water-absorptive resin composite - Google Patents
Production of highly water-absorptive resin compositeInfo
- Publication number
- JPS61243805A JPS61243805A JP8669485A JP8669485A JPS61243805A JP S61243805 A JPS61243805 A JP S61243805A JP 8669485 A JP8669485 A JP 8669485A JP 8669485 A JP8669485 A JP 8669485A JP S61243805 A JPS61243805 A JP S61243805A
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- Prior art keywords
- water
- pulp
- polymerization
- acrylic acid
- polymer
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Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は高吸水性樹脂複合体の製造方法に関する。高吸
水性樹脂は、パルプ綿などの従来使用されてきた吸水材
料に比べて著しく大きな吸水能を有し、紙おむつ、生理
用ナプキンなどの吸収材料とし℃使用され、その他保水
材料とじ℃種々の用途を有する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a superabsorbent resin composite. Super absorbent resins have significantly greater water absorption capacity than conventionally used water absorbing materials such as pulp cotton, and are used as absorbent materials such as disposable diapers and sanitary napkins, as well as in various other water-retaining materials. has.
従来の技術
アクリル酸を主成分とする高吸水性樹脂は公知であり、
その製造方法に関して多数の出願特許が公開されている
。Conventional technology Super absorbent resins whose main component is acrylic acid are well known.
A large number of patent applications have been published regarding the manufacturing method.
ポリアクリルば系高吸水性樹脂の基本構造は、中性域に
あるポリアクリル酸部分アルカリ金属塩を架橋し、水に
不溶化してなる高分子電解質である。The basic structure of a polyacrylic resin with high water absorption properties is a polymer electrolyte made by crosslinking partial alkali metal salts of polyacrylic acid in the neutral range to make them insoluble in water.
アクリル一部分アルカリ金属塩水溶液のラジカル重合に
おいて、濃度が４０％以上の場合、自己架橋が生じて架
橋重合体が生成する。重合反応は烈しく生じ、重合の進
行に伴ない水溶液の粘度が上昇し、架橋によってゲル化
する。重合反応は反忠熱による温度の上昇で促進される
一方、発生した水蒸気は粘度増大とゲル形成によって系
外に放散が妨げられ、反も熱の除去が困難となシ、その
結果、反応が港発的に暴走する。In radical polymerization of an acrylic partially alkali metal salt aqueous solution, if the concentration is 40% or more, self-crosslinking occurs and a crosslinked polymer is produced. The polymerization reaction occurs vigorously, and as the polymerization progresses, the viscosity of the aqueous solution increases and gelation occurs due to crosslinking. While the polymerization reaction is accelerated by the rise in temperature caused by the heat of the reaction, the generated water vapor is prevented from dissipating out of the system due to increased viscosity and gel formation, making it difficult to remove the heat and, as a result, the reaction slows down. It goes out of control starting from the port.
こうした困難を避ける手段として次のよ５な重合方法が
提案されている。（１） 水性原液を微細な水滴とし
て油相に分散させる逆相懸濁重合法忙よる。（２）
水性原液濃度を３０％以下に低下させ自己架橋の形成を
抑制し、工業プロセスとして制御可能な条件下で重合し
、生成物の乾燥時に架橋剤によ〕架橋を導入する、（３
） 水性原液を反応熱の除去が可能な薄層状態で重合
する。As a means to avoid these difficulties, the following five polymerization methods have been proposed. (1) It is based on a reverse-phase suspension polymerization method in which an aqueous stock solution is dispersed in an oil phase as fine water droplets. (2)
reducing the concentration of the aqueous stock solution to below 30% to suppress the formation of self-crosslinks, polymerizing under conditions that can be controlled as an industrial process, and introducing crosslinks with a crosslinking agent during drying of the product (3)
) Polymerize an aqueous stock solution in a thin layer that allows the heat of reaction to be removed.
架橋密度の調節は、自己架橋、架橋性単量体の共重合に
よる架橋の導入あるいはポリマーの架橋剤による架橋に
よって行なわれる。また、アクリル酸以外に少量成分と
して、アクリルアミド、メタクリル酸、マレイン酸等の
水溶性単量体を共重合成分として添加する方法、あるい
はポリビニルアルコール、デンプンおよびセルロース誘
導体等の水溶比ポリマーの存在で重合する方法も仰られ
ている。The crosslinking density is controlled by self-crosslinking, introduction of crosslinking by copolymerization of a crosslinkable monomer, or crosslinking using a polymer crosslinking agent. Additionally, in addition to acrylic acid, small amounts of water-soluble monomers such as acrylamide, methacrylic acid, and maleic acid can be added as copolymerization components, or polymerization can be carried out in the presence of water-soluble polymers such as polyvinyl alcohol, starch, and cellulose derivatives. There are also instructions on how to do it.
発明が解決しようとする問題点
前記のポリアクリル酸系高吸水性樹脂の製造法における
問題点は、急速な重合反応を制御するための反応熱の除
去にある。逆相懸濁重合法、低濃度水浴液重合と後架橋
法および薄Ｕ重合法などの従来方法はいずれも複雑な装
置と工程を必要とし、製造コストが著しく上昇すること
が避けられない。Problems to be Solved by the Invention The problem in the method for producing the polyacrylic acid superabsorbent resin described above lies in the removal of reaction heat to control the rapid polymerization reaction. Conventional methods such as reverse-phase suspension polymerization, low-concentration water bath polymerization and post-crosslinking, and thin U polymerization all require complicated equipment and processes, which inevitably leads to a significant increase in production costs.
アクリル酸部分アルカリ金属塩を主成分とする水性原液
を重合して高吸水性樹脂を製造するに際して、水性原液
をバルク状態で重合し、急速な重合によシ生成する反応
熱を水の蒸発熱として円滑に除去することができれば、
高吸水性４Ｍ脂の製造コストを大幅に低下させることが
可能になる。When producing a super absorbent resin by polymerizing an aqueous stock solution mainly composed of a partial alkali metal salt of acrylic acid, the aqueous stock solution is polymerized in bulk, and the heat of reaction generated by rapid polymerization is converted into the heat of evaporation of water. If it can be removed smoothly as
It becomes possible to significantly reduce the manufacturing cost of highly absorbent 4M fat.
問題点を解決するための手段
本発明者は先に新規な高吸水性粉粒体を発明した（特願
昭６Ｏ−６６９１）。本発明は該先行発明の改良法に関
するものである。Means for Solving the Problems The present inventor previously invented a new highly water-absorbent powder (Japanese Patent Application No. 60-6691). The present invention relates to an improvement on the prior invention.
アクリル酸を主成分とし、ラジカル重合反応によって高
吸水性重合体を生成する水性原液をパルプに含浸させ、
該含浸物を加熱すると急速な重合が生ずる。その際に、
反応熱は水蒸気の円滑な放散によって有効に除去され、
重合系の温度は自動的に一定に調節される結果、重合反
応は暴走することなく円滑に進行する。反応は約１００
℃の温度で数分以内に終了し、パルプ繊維に高吸水性樹
脂の水利ゲルが被覆した形態の反応物が得られる。The pulp is impregnated with an aqueous stock solution containing acrylic acid as the main component and producing a super absorbent polymer through a radical polymerization reaction.
Heating the impregnation results in rapid polymerization. At that time,
The reaction heat is effectively removed by the smooth dissipation of water vapor,
As the temperature of the polymerization system is automatically adjusted to a constant value, the polymerization reaction proceeds smoothly without runaway. The reaction is about 100
The process is completed within a few minutes at a temperature of 10°C, and a reaction product in the form of pulp fibers coated with a water-use gel made of a super-absorbent resin is obtained.
水性原液はアクリル酸部分アルカリ金属塩な主成分とし
、水溶性共重合単量体、架橋性単量体および水溶性ポリ
マーの少量成分が選択的に添加され、あるいは添加され
ないで調製される。重合開始剤としては過硫酸塩等の水
溶性ラジカル開始剤が選ばれる。高吸水性樹脂を生成す
る水性原液は、従来の技術の項目で説明した如く、概し
て公知であシ、これら公知の組成が本発明の水性原液に
含まれる。水性原液の濃度は通常４０〜５０％の範囲に
ある。また、アクリル酸をはじめとする単量体に含まれ
るカルボキシル基は６０〜８５チがアルカリ金属塩とし
て存在し、実質質に中性な水溶液である。The aqueous stock solution is prepared with the main component being a partial alkali metal salt of acrylic acid, with or without selective addition of minor components of a water-soluble copolymerizable monomer, a crosslinkable monomer, and a water-soluble polymer. As the polymerization initiator, a water-soluble radical initiator such as persulfate is selected. Aqueous stock solutions for producing superabsorbent resins are generally known, as explained in the section of the prior art, and these known compositions are included in the aqueous stock solutions of the present invention. The concentration of the aqueous stock solution is usually in the range of 40-50%. Further, 60 to 85 carboxyl groups contained in monomers such as acrylic acid exist as alkali metal salts, and the aqueous solution is substantially neutral.
パルプはセルロース系繊維小片の集合体を意味し、自重
の１０倍程度の水性原液を吸収する能力を有し、該含浸
物は嵩高で、重合反応において、反応熱によりて発生し
た水蒸気は円滑に系外に放散される。その結果、重合系
の温度は約１００℃の一定に保時され、烈しい反応にお
いても、反応は有効に制御される。Pulp is an aggregate of small pieces of cellulose fibers, and has the ability to absorb about 10 times its own weight of an aqueous solution. Dissipated outside the system. As a result, the temperature of the polymerization system is kept constant at about 100° C., and the reaction can be effectively controlled even in intense reactions.
上記に示される重合反応の自動的制御が該先行発明の大
きな特徴であるが、それ以外の特徴も次に示される。（
１） 水性原液に含まれる水分のかなシの部分は重合
熱によって除去され、反応物は生乾きの状態にあるばか
りでなく、パルプ繊維に支持された水和ゲルは多孔性で
広い表面積を有し、乾燥が容易である。（２） 乾燥
生成物は次に粉砕されて粉粒体になるが、粉砕が容易で
あるばかりでなく、該粉粒体は極めて大きな表面積を有
するので、吸水速度が他の方法で得られる粉粒体に比べ
て大である。Although the automatic control of the polymerization reaction shown above is a major feature of the prior invention, other features are also shown below. (
1) The water content in the aqueous stock solution is removed by the heat of polymerization, and the reactant is not only half-dried, but the hydrated gel supported by pulp fibers is porous and has a large surface area. , easy to dry. (2) The dried product is then ground into powder, which is not only easy to grind, but also has a very large surface area, so that the water absorption rate is higher than that of powder obtained by other methods. It is large compared to granules.
以上が水性原液をパルプに含浸して重合する先行発明の
あらましである。The above is an overview of the prior invention in which pulp is impregnated with an aqueous stock solution and polymerized.
本発明の方法は、アクリル酸を主成分とし、ラジカル重
合反応によって高吸水性重合体を生成する水性原液をパ
ルプに含浸してなる混合物を、パルプ繊維が重合体と緊
密に分散するようにせん断応力下に混合しながら加熱重
合し、反応によシ発生する水蒸気を系外に円滑に放散さ
せることを特徴とする高吸水性樹脂複合体の製造方法で
ある。In the method of the present invention, a mixture obtained by impregnating pulp with an aqueous stock solution containing acrylic acid as a main component and producing a superabsorbent polymer through a radical polymerization reaction is sheared so that the pulp fibers are tightly dispersed with the polymer. This is a method for producing a super-absorbent resin composite, which is characterized by carrying out heating polymerization while mixing under stress, and smoothly dissipating the water vapor generated by the reaction out of the system.
水性原液をパルプに含浸してなる混合物を加熱して重合
反応が開始されると、水性原液の粘度が増大し、反応の
進行に伴なってゲルが形成される。When a polymerization reaction is initiated by heating a mixture obtained by impregnating pulp with an aqueous stock solution, the viscosity of the aqueous stock solution increases and a gel is formed as the reaction progresses.
重合反応は混合物を静置した状態で行なうこともできる
が、せん断応力下に混合して行なうことによシ、パルプ
繊維が一段と緊密均一に高吸水性重合体に分散した生成
物が得られる。重合反応の進行によって、水性原液は粘
度が先ず増大し、さらに水和ゲル状の生成物に転化する
。その際パルプ繊維は微細状で均一に水和グルに混合分
散する。The polymerization reaction can be carried out while the mixture is standing still, but by carrying out the mixing under shear stress, a product in which the pulp fibers are more closely and uniformly dispersed in the superabsorbent polymer can be obtained. As the polymerization reaction progresses, the aqueous stock solution first increases in viscosity and is further converted into a hydrated gel-like product. At this time, the pulp fibers are finely and uniformly mixed and dispersed in the hydration glue.
作用
重合反応生成物は乾燥後に粉砕され、粉粒体の状態で高
吸水性材料に供される。本発明の方法によシ製造された
高吸水性樹脂複合体を乾燥粉砕し℃得られる粉粒体は、
従来公知の方法ばかシでな（、静置重合したものに比べ
ても、吸水性能、特に吸水速度が著しく改善されること
が判明した。After drying, the polymerization reaction product is pulverized and used as a superabsorbent material in the form of powder or granules. The powder obtained by drying and pulverizing the super absorbent resin composite produced by the method of the present invention is as follows:
It has been found that the water absorption performance, especially the water absorption rate, is significantly improved compared to the conventionally known method, which is performed by static polymerization.
吸収速度は紙おむつあるいは生理用ナプキンの吸収材と
して重視される性能である。Absorption speed is an important performance for absorbent materials in disposable diapers or sanitary napkins.
本発明の方法によシ製造された高吸水性樹脂複合体の粉
粒体を水で膨潤し、これを顕微鏡下に観察すると、パル
プ繊維が粒子全体にわたって微細状に均一に分散してい
る。When the powder of the superabsorbent resin composite produced by the method of the present invention is swollen with water and observed under a microscope, pulp fibers are finely and uniformly dispersed throughout the particles.
水性原液とパルプの比率および重合時における反応混合
物の混合榮件を変化して、粒子中におけるパルプ繊維の
分散状態と吸水性能の関係を調べた。混合条件としては
、パルプに水性原液を均一に含浸させた混合物および該
混合物るさらにミキサー中で粉砕混合した後に静置重合
して得られた生成物、および混合物なせん断応力下に混
合しながら重合した生成物について比較し、次の顕著な
る事実が見出された。重合反応なせん断応力下に混合し
て行なうことにより、（１） パルプの１０倍程度に
達する大量の水性原液を含浸させても、均一な生成物が
得られる。（２） パルプ繊維が重合体と微細緊密に
分散することによシ、吸水能および吸水速度が大幅に改
善される。The relationship between the dispersion state of pulp fibers in particles and water absorption performance was investigated by changing the ratio of the aqueous stock solution to the pulp and the mixing conditions of the reaction mixture during polymerization. The mixing conditions include a mixture in which pulp is uniformly impregnated with an aqueous stock solution, a product obtained by pulverizing and mixing the pulp in a mixer and then standing polymerization, and a product obtained by polymerizing while mixing under shear stress. The following remarkable facts were discovered by comparing the products obtained. By carrying out the polymerization reaction by mixing under shear stress, (1) a uniform product can be obtained even if a large amount of aqueous stock solution, about 10 times the amount of pulp, is impregnated. (2) The fine and intimate dispersion of pulp fibers and polymers greatly improves water absorption capacity and water absorption rate.
重合反応は一般にニーダ−塁混合機中で行なわれる。混
合物の粘度は重合反応の進行とともに増大し、架橋の形
成により水利ゲルに転化する段階に達すると混合に大き
な応力を要する。パルプ繊維の分散は系の粘度が適度に
上昇し、せん断応力が作用する段階で有効に生ずる。従
って重合反応を連続的に行なう場合、ゲル生成の初期の
段階で有効な混合が行なわれ、ゲルが形成して系の粘度
が著しく増大した段階では過重な応力が加わらないよう
な反応機の設計が好ましい。The polymerization reaction is generally carried out in a kneader mixer. The viscosity of the mixture increases as the polymerization reaction progresses, and when it reaches the stage where it is converted into an aqueous gel due to the formation of crosslinks, a large stress is required for mixing. Dispersion of pulp fibers occurs effectively when the viscosity of the system increases to an appropriate degree and shear stress is applied. Therefore, when conducting a polymerization reaction continuously, the reactor should be designed so that effective mixing occurs in the early stages of gel formation and that excessive stress is not applied at the stage when gel is formed and the viscosity of the system increases significantly. is preferred.
実施列１゜
苛性ソーダ（Ｍ１度９３チ）３２部を水７３部に溶解し
た水ｌ１ｌｌ液にアクリル酸７２部を加える。この水溶
液はアクリル酸のカルボキシル基の７５チがナトリウム
塩で、濃度は５０％に相当する。この水溶液に過硫酸力
！ｊＯ，３部を添加して水性原液を調製した。Example 1: 72 parts of acrylic acid is added to 111 parts of water prepared by dissolving 32 parts of caustic soda (M1 degree 93 degrees) in 73 parts of water. In this aqueous solution, 75 of the carboxyl groups of acrylic acid are sodium salts, and the concentration corresponds to 50%. Persulfuric acid power in this aqueous solution! An aqueous stock solution was prepared by adding 3 parts of jO.
ニーダ−に加え、容器を窒素ガスで置換してから混合し
ながら加熱する。約８０℃の温度で重合が開始され、重
合熱によって温度は約１００’Ｃに上昇し、水蒸気が烈
しく発生する。重合反応は５分以内に終了し、その間反
応系の温度は一定であ、った。反応物はパルプ繊維が均
一に分散された水利ゲル体である。Add to the kneader, replace the container with nitrogen gas, and heat while mixing. Polymerization is initiated at a temperature of about 80°C, and the heat of polymerization raises the temperature to about 100°C, with intense evolution of water vapor. The polymerization reaction was completed within 5 minutes, during which time the temperature of the reaction system remained constant. The reactant is an aqueous gel in which pulp fibers are uniformly dispersed.
該反応物を細断して乾燥した後、粉砕して４Ｂメツシー
以下の高吸水性樹脂複合体の粉粒体を得た。The reaction product was shredded, dried, and then pulverized to obtain a granular material of a super absorbent resin composite having a size of 4B or less.
吸水性の測定は次のようにして行なった。粉粒体Ｏ，Ｓ
ｔを７ ｃｌＩＸ ７ ｃｍの不織布製のティーバッ
グに入れ、ティーバッグを０．９％食塩水（生理食塩水
）中に投入し、時間毎の重量を測定して、樹脂１を換算
の吸収した水溶液の重量を求めた。その結果、生理食塩
水の吸収量は５分以内に飽和に達し、１を当りの吸収量
は５４９であった。Water absorption was measured as follows. Powder O, S
t was placed in a 7 cm non-woven tea bag, the tea bag was placed in 0.9% saline (physiological saline), the weight was measured every hour, and the resin 1 was absorbed in terms of equivalent amount. The weight of the aqueous solution was determined. As a result, the absorption amount of physiological saline reached saturation within 5 minutes, and the absorption amount per unit was 549.
比較のため、反応混合物と静置下に重合して得られた生
成物から同様の粉粒体を調製し、生理食塩水の吸収量を
測定した。吸収は飽和に達するまで約１０分間を要し、
樹脂１ｆ換算の吸収量は５１ｔであった。For comparison, similar powders were prepared from the reaction mixture and a product obtained by polymerization under standing conditions, and the amount of physiological saline absorbed was measured. Absorption takes approximately 10 minutes to reach saturation.
The absorbed amount in terms of 1f of resin was 51t.
実施例２゜
苛性ソーダ（純度９３％’＞ ３４．５部を水１０７部
に溶解した水浴液にアクリル酸７２部および架橋性単量
体としてＮ、Ｎ’−メチレンビスアクリルアミド０．０
７部を加え、さらに過硫酸アンモ７０．３部を添加して
水性原液を調製した。この水性原液はアクリル酸のカル
ボキシル基の８０％がナトリ施例１と同様にして重合し
、パルプ繊維の均一に分散された水和ゲル状の生成物を
得た。Example 2 72 parts of acrylic acid and 0.0 N,N'-methylenebisacrylamide as a crosslinking monomer were added to a water bath solution in which 34.5 parts of caustic soda (purity 93%'>) was dissolved in 107 parts of water.
7 parts and further added 70.3 parts of ammonium persulfate to prepare an aqueous stock solution. In this aqueous stock solution, 80% of the carboxyl groups of acrylic acid were polymerized in the same manner as in Natori Example 1 to obtain a hydrated gel-like product in which pulp fibers were uniformly dispersed.
実施例１と同様に乾燥した高吸水性樹脂複合体粉粒体を
つ（す、吸水性を測定した。In the same manner as in Example 1, the dried super absorbent resin composite powder was used to measure water absorption.
生理食塩水の吸収量は５分以内に飽和に達し、樹脂１を
当シ換算の吸収量は５０ｔと求められた。The absorbed amount of physiological saline reached saturation within 5 minutes, and the absorbed amount of resin 1 was determined to be 50 tons.
比較のため、上記含浸物を静置して重合したが、含浸物
から水性原液の一部がはみ出し、また含浸物の上部と下
部の間でパルプと水性原液の組成に差が生じ、均一な生
成物は得られなかった。反応物と乾燥粉砕して同様な粉
粒体とし、吸収性を測定した。生理食塩水の吸収量は飽
和に達するのに約１０分間を要し、樹脂１ｆ換算の吸収
量は４７ｔであった。For comparison, the above-mentioned impregnated material was polymerized by standing still, but some of the aqueous stock solution protruded from the impregnated material, and there was also a difference in the composition of the pulp and aqueous stock solution between the upper and lower parts of the impregnated material, resulting in a uniform polymerization. No product was obtained. The reactant was dried and crushed to obtain a similar granular material, and the absorbency was measured. It took about 10 minutes for the absorbed amount of physiological saline to reach saturation, and the absorbed amount in terms of 1f of resin was 47 tons.
発明の効果
上記実施例に示される如く、アクリル酸を主成分とし、
高吸水性樹脂を生成する水性原液をパルプに含浸してな
る混合物なせん断応力下に混合しながら重合反応を行な
うことによシ、大量の水性原液をパルプに含浸させた場
合にも、パルプ繊維が微細緊密に分散した高吸水性樹脂
複合体が得られる。さらに、該複合体粉粒体は吸水速度
および吸水能が著しく改善される。Effects of the invention As shown in the above examples, the main component is acrylic acid,
A mixture obtained by impregnating pulp with an aqueous stock solution that produces a superabsorbent resin.By carrying out a polymerization reaction while mixing under shear stress, even when pulp is impregnated with a large amount of aqueous stock solution, the pulp fiber A superabsorbent resin composite in which particles are finely and tightly dispersed is obtained. Furthermore, the composite powder has significantly improved water absorption rate and water absorption capacity.
Claims (1)
性重合体を生成する水性原液をパルプに含浸してなる混
合物を、せん断応力下に混合しながら加熱重合して、パ
ルプ繊維を微細緊密に重合体に分散させ、発生する水蒸
気を反応系外に円滑に放散させることを特徴とする高吸
水性樹脂複合体の製造方法。A mixture made by impregnating pulp with an aqueous stock solution containing acrylic acid as the main component and producing a superabsorbent polymer through radical polymerization is heat-polymerized while being mixed under shear stress, and the pulp fibers are finely and tightly polymerized. A method for producing a super-absorbent resin composite, characterized by dispersing the water vapor into the water vapor and smoothly dissipating the generated water vapor out of the reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8669485A JPS61243805A (en) | 1985-04-22 | 1985-04-22 | Production of highly water-absorptive resin composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8669485A JPS61243805A (en) | 1985-04-22 | 1985-04-22 | Production of highly water-absorptive resin composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61243805A true JPS61243805A (en) | 1986-10-30 |
Family
ID=13894065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8669485A Pending JPS61243805A (en) | 1985-04-22 | 1985-04-22 | Production of highly water-absorptive resin composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61243805A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63260906A (en) * | 1987-04-17 | 1988-10-27 | Mitsubishi Petrochem Co Ltd | Manufacture of water-absorptive composite material |
| US4833222A (en) * | 1987-10-22 | 1989-05-23 | The Dow Chemical Company | Crosslinker stabilizer for preparing absorbent polymers |
| US5241011A (en) * | 1990-02-19 | 1993-08-31 | Alfons Landscheidt | Process for the production of polyacrylic acids |
| JP2009242466A (en) * | 2008-03-28 | 2009-10-22 | San-Dia Polymer Ltd | Method for producing absorptive resin particle |
| US10059035B2 (en) | 2005-03-24 | 2018-08-28 | Xyleco, Inc. | Fibrous materials and composites |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167307A (en) * | 1981-04-09 | 1982-10-15 | Sumitomo Chem Co Ltd | Production of highly water-absorbing polymeric material having improved water absorption rate |
-
1985
- 1985-04-22 JP JP8669485A patent/JPS61243805A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167307A (en) * | 1981-04-09 | 1982-10-15 | Sumitomo Chem Co Ltd | Production of highly water-absorbing polymeric material having improved water absorption rate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63260906A (en) * | 1987-04-17 | 1988-10-27 | Mitsubishi Petrochem Co Ltd | Manufacture of water-absorptive composite material |
| US4833222A (en) * | 1987-10-22 | 1989-05-23 | The Dow Chemical Company | Crosslinker stabilizer for preparing absorbent polymers |
| US5241011A (en) * | 1990-02-19 | 1993-08-31 | Alfons Landscheidt | Process for the production of polyacrylic acids |
| US5297740A (en) * | 1990-02-19 | 1994-03-29 | Alfons Landscheidt | Process for the production of polyacrylic acids |
| US10059035B2 (en) | 2005-03-24 | 2018-08-28 | Xyleco, Inc. | Fibrous materials and composites |
| JP2009242466A (en) * | 2008-03-28 | 2009-10-22 | San-Dia Polymer Ltd | Method for producing absorptive resin particle |
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