JP2559447B2 - Water-absorbent resin composition with excellent stability - Google Patents
Water-absorbent resin composition with excellent stabilityInfo
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- JP2559447B2 JP2559447B2 JP63036048A JP3604888A JP2559447B2 JP 2559447 B2 JP2559447 B2 JP 2559447B2 JP 63036048 A JP63036048 A JP 63036048A JP 3604888 A JP3604888 A JP 3604888A JP 2559447 B2 JP2559447 B2 JP 2559447B2
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- water
- absorbent resin
- acid
- resin composition
- excellent stability
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は多量の水性液体を素早く吸収し、かつ膨潤状
態で優れた安定性を有する吸水性樹脂組成物に関するも
のである。TECHNICAL FIELD The present invention relates to a water absorbent resin composition which rapidly absorbs a large amount of aqueous liquid and has excellent stability in a swollen state.
更に詳しくは、通常の使用条件下で、水性液体を吸収
した膨潤ゲル状態を長時間保つことができる安定性の優
れた吸水性樹脂組成物に関するものである。More specifically, it relates to a water-absorbent resin composition having excellent stability capable of maintaining a swollen gel state absorbing an aqueous liquid for a long time under normal use conditions.
近年、多量の水を吸収し、これを保持するという、吸
水性や保水性に優れた吸水性樹脂が開発され、衛生用品
分野では生理用ナプキンや使い捨ておむつ、農園芸分野
では保水剤等、土木建築分野では汚泥の凝固剤、結露防
止剤、止水剤などとして広く利用されている。In recent years, a water-absorbent resin that absorbs and retains a large amount of water and has excellent water-absorbing and water-retaining properties has been developed. Sanitary napkins and disposable diapers in the hygiene field, water-retaining agents, etc. In the construction field, it is widely used as a coagulant for sludge, an anti-condensation agent, and a water blocking agent.
このような吸水性樹脂としては、例えば、デンプン−
アクリロニトリルグラフト重合体の加水分解物、デンプ
ン−アクリル酸グラフト重合体、酢酸ビニル−アクリル
酸エステル共重合体の加水分解物、ポリアクリル酸塩架
橋体、カルボキシメチル加セルロースなどが提案されて
いる。Examples of such a water absorbent resin include starch-
A hydrolyzate of an acrylonitrile graft polymer, a starch-acrylic acid graft polymer, a hydrolyzate of a vinyl acetate-acrylic acid ester copolymer, a polyacrylate crosslinked product, carboxymethyl cellulose, and the like have been proposed.
一般に、吸水性樹脂の性能は、給水量、吸水速度、膨
潤時のゲル強度などで評価される。このうち吸水量や吸
水速度といった吸水性能の向上については数多くの提案
がなされてきた（例えば特開昭57−158210号公報、特開
昭59−62665号公報、特開昭61−97301号公報等）。In general, the performance of a water-absorbent resin is evaluated by the amount of water supplied, the rate of water absorption, the gel strength during swelling, and the like. Of these, many proposals have been made to improve water absorption performance such as water absorption amount and speed (for example, JP-A-57-158210, JP-A-59-62665, JP-A-61-97301, etc.). ).
一方、膨潤時のゲル強度は、吸水量とは負の相関にあ
り、ゲル強度を上げると吸水量が低下する傾向がある。
上記のような吸水性能と膨潤時のゲル強度の両者を満足
するものが理想的な吸水性樹脂と言えるが、このような
ものは未だ得られていないのが現状である。On the other hand, the gel strength during swelling has a negative correlation with the water absorption amount, and increasing the gel strength tends to decrease the water absorption amount.
It is possible to say that an ideal water-absorbent resin is one that satisfies both the water-absorbing performance and the gel strength at the time of swelling as described above, but such a resin has not yet been obtained.
上記のような吸水性樹脂が吸水し、膨潤したゲルの状
態においては、膨潤圧などの力学的な力を受ける他に、
高温あるいは日光に曝露される等の環境要因、更には空
気中の酸素の影響などの要因により該ゲル状樹脂が劣化
するという問題がある。極端な場合、数時間のうちに膨
潤ゲルの形態を保持できなくなり、吸水性・保水性の機
能が失われてしまう。また、尿を吸収し膨潤した吸水性
樹脂でも同様な劣化が起こり、膨潤ゲルの形態を保持で
きなくなる場合もある。The water-absorbent resin as described above absorbs water, and in a swollen gel state, in addition to receiving a mechanical force such as swelling pressure,
There is a problem that the gel-like resin deteriorates due to environmental factors such as exposure to high temperature or sunlight, and factors such as the influence of oxygen in the air. In an extreme case, the swelling gel form cannot be maintained within a few hours, and the functions of water absorption and water retention are lost. In addition, the water-absorbent resin swollen by absorbing urine also undergoes the same deterioration, and the morphology of the swollen gel may not be retained.
このような現象は、吸水性樹脂を種々の用途に使用す
る際に大きな障害となり、膨潤ゲルの経時安定性の優れ
た吸水性樹脂の開発が望まれている。Such a phenomenon becomes a great obstacle when the water-absorbent resin is used for various purposes, and development of a water-absorbent resin having excellent swelling gel stability over time has been desired.
本発明者らは、上記のような課題を解決し、良好な吸
水性能を維持し、かつ、膨潤時のゲル強度及び膨潤ゲル
の経時安定性に優れた吸水性樹脂を得るべく鋭意検討を
重ねた結果、本発明に至った。The present inventors have solved the problems as described above, maintain good water absorption performance, and have earnestly studied to obtain a water absorbent resin having excellent gel strength during swelling and stability of the swollen gel over time. As a result, the present invention has been achieved.
即ち、本発明は、吸水性樹脂、ラジカル連鎖禁止剤及
び金属キレート剤を必須成分として含有し、ラジカル連
鎖禁止剤の含有量が乾燥した吸水性樹脂に対して0.01〜
10重量％、金属キレート剤の含有量が乾燥した吸水性樹
脂に対して0.01〜10重量％であることを特徴とする安定
性の優れた吸水性樹脂組成物を提供するものである。That is, the present invention contains a water absorbent resin, a radical chain inhibitor and a metal chelating agent as essential components, and the content of the radical chain inhibitor is 0.01 to 0.01 with respect to the dried water absorbent resin.
The present invention provides a water-absorbent resin composition having excellent stability, wherein the content of the metal chelating agent is from 10 to 10% by weight based on the dry water-absorbent resin.
以下、本発明を詳しく説明する。 Hereinafter, the present invention will be described in detail.
本発明において使用することのできる吸水性樹脂とし
ては、例えばデンプン−アクリロニトリルグラフト重合
体の加水分解物、デンプン−アクリル酸グラフト重合
体、酢酸ビニル−アクリル酸エステル共重合体の加水分
解物、ポリアクリル酸塩架橋体、イソブチレン−無水マ
レイン酸共重合体架橋体、カルボキシメチル化セルロー
スなどを例示する事が出来、これらは本発明に好ましく
使用し得る。特に好ましいものは、吸水性能の観点より
ポリアクリル酸塩架橋体であり、重合方法や共重合成分
に関して、特に限定するものではない。Examples of the water absorbent resin that can be used in the present invention include starch-acrylonitrile graft polymer hydrolysates, starch-acrylic acid graft polymers, vinyl acetate-acrylic acid ester copolymer hydrolysates, and polyacrylics. Examples include acid salt cross-linked products, isobutylene-maleic anhydride copolymer cross-linked products, carboxymethylated cellulose, and the like, which can be preferably used in the present invention. From the viewpoint of water absorption performance, a polyacrylate crosslinked product is particularly preferable, and the polymerization method and the copolymerization component are not particularly limited.
次に本発明に使用されるラジカル連鎖禁止剤としては
ラジカル連鎖禁止能を有する化合物であれば良く、従来
公知の酸化防止剤、重合禁止剤、ラジカル捕捉剤等が挙
げられる。これらラジカル連鎖禁止剤の中でも特に25℃
で水100gに対し、0.1g以上溶解するものが望ましい。The radical chain inhibitor used in the present invention may be any compound having a radical chain inhibiting ability, and examples thereof include conventionally known antioxidants, polymerization inhibitors and radical scavengers. Among these radical chain inhibitors, especially 25 ℃
It is desirable that 0.1 g or more be dissolved in 100 g of water.
このようなラジカル連鎖禁止剤としては、ハイドロキ
ノン、ｐ−メトキシフェノール、ベンゾキノン、メチル
ハイドロキノン、ｔ−ブチルハイドロキノン、ヒロガロ
ール、没食子酸、没食子酸メチル、没食子酸エチル、没
食子酸プロピル、五倍子または没食子等から得られる加
水分解型タンニンやガンビア等から得られる縮合型タン
ニン等のタンニン酸及びその塩、リグニンスルホン酸
塩、クェルセチンやエラグ酸等のフラボノイド類及びそ
の塩、カテコール、レゾルシン等のフェノール系化合物
及びその誘導体類、Ｎ−ニトロソフェニルヒドロキシア
ミンアンモニウム塩、チオ尿素等のアミン系化合物が好
ましいものとして例示できるが、これらに限定するもの
ではない。Such radical chain inhibitors include hydroquinone, p-methoxyphenol, benzoquinone, methylhydroquinone, t-butylhydroquinone, hirogallol, gallic acid, methyl gallate, ethyl gallate, propyl gallate, quintuple or gallic etc. Condensed tannins obtained from hydrolyzed tannins and Gambia and their salts, lignin sulfonates, flavonoids and salts thereof such as quercetin and ellagic acid, and phenolic compounds such as catechol and resorcin and their derivatives Amine compounds such as N-nitrosophenylhydroxyamine ammonium salt and thiourea can be exemplified as preferable ones, but not limited thereto.
これらの中でも特に好ましいものとして、ピロガロー
ル、没食子酸、没食子塩エステル、タンニン酸、フラボ
ノイド類、チオ尿素等が挙げられる。Among these, pyrogallol, gallic acid, gallic salt esters, tannic acid, flavonoids, thiourea and the like are particularly preferable.
これらは各々単独で使用しても、あるいは２種類以上
を併用してもよい。These may be used alone or in combination of two or more.
次に本発明に使用される金属キレート剤としては、金
属イオンと結合してキレート化合物を形成する二座以上
の配粒子を持つ、金属キレート能を有する化合物が挙げ
られる。これらの中でも、特に25℃で水100gに対し、0.
1g以上の溶解性を有するものが望ましい。このような金
属キレート剤としては、例えば、りん酸等の無機酸類；
酒石酸、グルコン酸、クエン酸、サリチル酸等のオキシ
カルボン酸類；グリコール、グリセリン等のジオキシ
類；エチレンジアミン、1,10−フェナントロリン、2,
2′−ビピリジン、ターピリジン等のアミン系化合物；
トリポリリン酸塩等の縮合リン酸塩類；エチレンジアミ
ン４酢酸、ジエチレントリアミン５酢酸、トリエチレン
テトラミン６酢酸、エチレンジアミンビス０−ヒドロキ
シフェニル酢酸等のポリアミノカルボン酸類及びそれら
の塩；ニトリロトリス（メチレンホスホン酸）、エチレ
ンジアミン−N,N′−ジ（メチレンホスホン酸）、エチ
レンジアミンテトラ（メチレンホスホン酸）、ジエチレ
ントリアミンペンタ（メチレンホスホン酸）等のポリア
ミノホスホン酸類及びそれらの塩；シュウ酸等のジカル
ボン酸類等が例示できるが、これらに限定するものでは
ない。これらは各々単独で使用しても、あるいは２種類
以上を併用してもよい。Next, examples of the metal chelating agent used in the present invention include compounds having a metal chelating ability, which have a bidentate or more bipartite particles that form a chelate compound by binding with a metal ion. Among these, especially at 25 ℃ to 100 g of water, 0.
A substance having a solubility of 1 g or more is desirable. Examples of such metal chelating agents include inorganic acids such as phosphoric acid;
Oxycarboxylic acids such as tartaric acid, gluconic acid, citric acid, salicylic acid; dioxys such as glycol and glycerin; ethylenediamine, 1,10-phenanthroline, 2,
Amine compounds such as 2'-bipyridine and terpyridine;
Condensed phosphates such as tripolyphosphate; ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine 6 acid, ethylenediamine bis 0 - poly-amino acids and their salts such as hydroxyphenyl acetic acid; nitrilotris (methylenephosphonic acid), ethylenediamine -N, N'-di (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), polyethylenephosphonic acids such as diethylenetriaminepenta (methylenephosphonic acid) and salts thereof; dicarboxylic acids such as oxalic acid can be exemplified. It is not limited to these. These may be used alone or in combination of two or more.
本発明は、特定量の上記ラジカル連鎖禁止剤及び金属
キレート剤を吸水性樹脂に含有せしめることにより、吸
水性能及び膨潤時のゲル強度を低下させることなく、膨
潤ゲルの経時安定性を著しく向上させるものである。The present invention, by containing a specific amount of the radical chain inhibitor and the metal chelating agent in the water-absorbent resin, the water-absorbing performance and the gel strength at the time of swelling are not lowered, and the temporal stability of the swollen gel is significantly improved. It is a thing.
本発明の組成物中のラジカル連鎖禁止剤（ａ）及び金
属キレート剤（ｂ）の含有量は、乾燥した吸水性樹脂に
対してそれぞれ0.01〜10重量％の範囲である。（ａ）成
分及び（ｂ）成分の含有量が0.01重量％未満の場合は、
前述の光、熱、酸素酸化等に対する安定性向上の効果が
乏しく、また、10重量％を越えると、吸水性樹脂組成物
の吸水性能が低下し、本発明の意図するところではな
い。The contents of the radical chain inhibitor (a) and the metal chelating agent (b) in the composition of the present invention are each in the range of 0.01 to 10% by weight based on the dried water absorbent resin. When the content of the components (a) and (b) is less than 0.01% by weight,
The effect of improving the stability against light, heat, oxygen oxidation and the like described above is poor, and when it exceeds 10% by weight, the water absorbing performance of the water absorbent resin composition is deteriorated, which is not intended by the present invention.
また、ラジカル連鎖禁止剤（ａ）と金属キレート剤
（ｂ）との比率は、上記範囲において任意に選ぶことが
できるが、（ａ）成分及び（ｂ）成分の合計量は乾燥し
た吸水性樹脂に対し15重量％以下が好ましく、より好ま
しくは10重量％以下である。Further, the ratio of the radical chain inhibitor (a) to the metal chelating agent (b) can be arbitrarily selected within the above range, but the total amount of the components (a) and (b) is a dry water-absorbent resin. However, it is preferably 15% by weight or less, more preferably 10% by weight or less.
本発明において、ラジカル連鎖禁止剤及び金属キレー
ト剤の添加方法は樹脂の製造に支障をきたさない限り特
に制限されるものではなく、吸水性樹脂の製造工程中ま
たは製造後に、それらの添加剤を直接、あるいはそれら
を溶解しうる溶媒、好ましくは水、エタノール等にて溶
液としたものを加え、混合後、乾燥させることにより達
成される。In the present invention, the method of adding the radical chain inhibitor and the metal chelating agent is not particularly limited as long as it does not hinder the production of the resin, and those additives are directly added during or after the production process of the water absorbent resin. Alternatively, a solvent capable of dissolving them, preferably a solution in water, ethanol or the like, is added, mixed, and dried.
このようにして、特定量のラジカル連鎖禁止剤及び金
属キレート剤を含有させた本発明の吸水性樹脂組成物
は、吸水後の膨潤ゲルの状態での安定性が著しく向上し
ており、長期にわたってその形態を維持することができ
る。Thus, the water-absorbent resin composition of the present invention containing a specific amount of the radical chain inhibitor and the metal chelating agent, the stability in the state of swollen gel after water absorption is significantly improved, over a long period of time. The form can be maintained.
これら異なる２種類の成分の作用は、それぞれ次のよ
うに考えることができる。The actions of these two different types of components can be considered as follows.
即ち、例えば光、熱、酸素等の作用によりラジカル種
が発生しても、ラジカル連鎖禁止剤がこれを効果的に捕
捉すること、また、樹脂あるいは尿等に由来する微量の
遷移金属を金属キレート剤が有効に捕捉するため、これ
ら金属が介在してラジカル種が発生するのが抑制される
ことにより、これらラジカル種に起因する樹脂の分解、
切断等好ましくない反応が防止されるものと思われる。That is, for example, even if a radical species is generated by the action of light, heat, oxygen, etc., the radical chain inhibitor effectively captures this, and a trace amount of transition metal derived from resin, urine, etc. is chelated with a metal chelate. Since the agent effectively captures, by suppressing the generation of radical species through these metals, the decomposition of the resin due to these radical species,
It is thought that undesirable reactions such as cleavage are prevented.
以下、合成例、実施例、及び比較例によって本発明を
具体的に説明するが、本発明はこれらの実施例に限定さ
れるものではない。Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples.
尚、以下の実施例及び比較例における吸水量とは、次
の操作によって求められる値である。The water absorption amount in the following examples and comparative examples is a value obtained by the following operation.
即ち、樹脂約1gを大過剰の生理食塩水に分散し、十分
膨潤させ、次いで80メッシュの金網で濾過し、得られた
膨潤樹脂重量（Ｗ）を測定し、この値を未膨潤の、即ち
初めの樹脂重量（W0）で割って得られる値である。That is, about 1 g of resin was dispersed in a large excess of physiological saline, sufficiently swelled, and then filtered through a wire mesh of 80 mesh, and the obtained swollen resin weight (W) was measured. It is a value obtained by dividing by the initial resin weight (W 0 ).
つまり、吸水量（g/g）＝W/W0である。That is, the water absorption amount (g / g) = W / W 0 .
また、吸水速度は樹脂1gが20分間に吸収した生理食塩
水の量でもって表わした。The water absorption rate was expressed by the amount of physiological saline absorbed by 1 g of resin in 20 minutes.
一方、膨潤ゲルの安定性は次のように光及び熱で評価
した。On the other hand, the stability of the swollen gel was evaluated by light and heat as follows.
＜耐光性評価＞ イオン交換水で平衡飽和膨潤させた樹脂をガラス瓶に
入れ、微量の鉄イオンを加える促進試験を行った。即
ち、上記樹脂に硫酸第一鉄FeSO4・7H2O（乾燥樹脂に対
し1000ppmの量）を微量のイオン交換水に溶かした水溶
液を加えて混合し、ウェザーメーター（WEL−SUN−DC−
Ｂ型，スガ試験機（株）製）にて照射試験を行ない（内
温60℃）、ゲルの様子を経時的に観察した。<Evaluation of light resistance> A resin subjected to equilibrium saturated swelling with ion-exchanged water was put in a glass bottle, and an acceleration test was conducted to add a trace amount of iron ion. That is, an aqueous solution prepared by dissolving ferrous sulfate FeSO 4 .7H 2 O (amount of 1000 ppm with respect to dry resin) in a small amount of ion-exchanged water was added to the above resin and mixed, and a weather meter (WEL-SUN-DC-
An irradiation test was carried out (type B, manufactured by Suga Test Instruments Co., Ltd.) (internal temperature: 60 ° C.), and the state of the gel was observed with time.
＜耐熱性評価＞ イオン交換水で平衡飽和膨潤させた樹脂をガラス瓶に
入れ、80℃恒温槽中にてゲルの様子を経日的に観察し
た。<Heat resistance evaluation> The resin equilibrium saturated and swollen with ion-exchanged water was put in a glass bottle, and the gel state was observed daily in an 80 ° C constant temperature bath.
上記耐光性、耐熱性の評価の尺度は次の３段階とし
た。The evaluation scale of the light resistance and the heat resistance was the following three levels.
○…膨潤粒子はそのままの形状を示す。◯: The swollen particles have the same shape.
△…溶解までには至らないが膨潤粒子の形状が不明瞭化
する。Δ: The shape of the swollen particles is obscured, although the dissolution is not reached.
×…溶解が一部生じ、液状のものが見られる。×: Partial dissolution occurred, and liquid was observed.
合成例１｛吸水性樹脂（Ｉ），（II）の合成｝ 撹拌装置、還流冷却器、滴下漏斗、窒素ガス導入管を
付した２−４つの口丸底フラスコにシクロヘキサン1,
150ml、エチルセルロールＮ−200（ハーキュレス社製）
9.0gを仕込み、窒素ガスを吹き込んで溶存酸素を追い出
し、75℃まで昇温した。Synthesis Example 1 {Synthesis of water-absorbent resins (I) and (II)} Cyclohexane 1, in a 2-4 necked round bottom flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube.
150 ml, ethyl cellulose N-200 (manufactured by Hercules)
9.0 g was charged, nitrogen gas was blown in to expel dissolved oxygen, and the temperature was raised to 75 ° C.
別にフラスコ中でアクリル酸150gを外部より冷却しつ
つ、イオン交換水200gに溶解した65.8gの98％苛性ソー
ダで中和した。次いで過硫酸カリウム0.33gとN,N′−メ
チレンビスアクリルアミド0.015gを添加溶解した後、上
記滴下漏斗に移した。これを上記４つ口フラスコに１時
間かけて滴下した。滴下終了後も75℃に保持して１時間
反応を続けた。この溶媒中に分散している含水吸水性樹
脂を吸水性樹脂（Ｉ）とする。Separately, 150 g of acrylic acid was cooled from the outside in a flask and neutralized with 65.8 g of 98% caustic soda dissolved in 200 g of ion-exchanged water. Then, 0.33 g of potassium persulfate and 0.015 g of N, N'-methylenebisacrylamide were added and dissolved, and then transferred to the dropping funnel. This was added dropwise to the above four-necked flask over 1 hour. After the dropping was completed, the temperature was kept at 75 ° C. and the reaction was continued for 1 hour. The water-containing water-absorbent resin dispersed in this solvent is referred to as water-absorbent resin (I).
その後シクロヘキサンを減圧下に留去し、残った含水
した吸水性樹脂を減圧下に乾燥し、粉末状の吸水性樹脂
（II）を得た。Then, cyclohexane was distilled off under reduced pressure, and the remaining water-containing water-absorbent resin was dried under reduced pressure to obtain powdery water-absorbent resin (II).
実施例１ 吸水性樹脂（II）100gを双腕型ニーダーに入れ、撹拌
しながらクエン酸1g及び没食子酸プロピル0.1gを100gの
水に溶解した水溶液をスプレー噴霧した。その後、これ
らの樹脂を減圧下にて乾燥させた。Example 1 100 g of the water absorbent resin (II) was placed in a double-arm kneader, and an aqueous solution prepared by dissolving 1 g of citric acid and 0.1 g of propyl gallate in 100 g of water was spray-sprayed with stirring. Then, these resins were dried under reduced pressure.
実施例２ 吸水性樹脂（Ｉ）100g（但し、乾燥品に換算した量）
を双腕型ニーダーに入れ、1,10−フェナントロリン0.1g
及びチオ尿素5gを100gのエタノールに溶解した溶液を加
え、撹拌混合した。その後、これらの樹脂を減圧下にて
乾燥させた。Example 2 100 g of the water absorbent resin (I) (however, the amount converted to a dry product)
In a double-arm kneader, 0.10 g of 1,10-phenanthroline
And a solution of 5 g of thiourea dissolved in 100 g of ethanol were added and mixed with stirring. Then, these resins were dried under reduced pressure.
比較例１ ラジカル連鎖禁止剤及び金属キレート剤のいずれも添
加しない吸水性樹脂（II）を比較例１とした。Comparative Example 1 A water absorbent resin (II) containing neither a radical chain inhibitor nor a metal chelating agent was used as Comparative Example 1.
比較例２ 吸水性樹脂（II）100gを双腕型ニーダーに入れ、撹拌
しながらクエン酸1gを水100gに溶解した水溶液をスプレ
ー噴霧した。その後、これらの樹脂を減圧下にて乾燥さ
せた。Comparative Example 2 100 g of the water absorbent resin (II) was placed in a double-armed kneader, and an aqueous solution prepared by dissolving 1 g of citric acid in 100 g of water was sprayed while stirring. Then, these resins were dried under reduced pressure.
比較例３ 吸水性樹脂（II）100gを双腕型ニーダーに入れ、没食
子酸プロピル0.1gを水100gに溶解した水溶液を、撹拌下
スプレー噴霧した。その後、これらの樹脂を減圧下にて
乾燥させた。Comparative Example 3 100 g of the water absorbent resin (II) was placed in a double-arm kneader, and an aqueous solution prepared by dissolving 0.1 g of propyl gallate in 100 g of water was sprayed with stirring. Then, these resins were dried under reduced pressure.
比較例４ 吸水性樹脂（Ｉ）100g（但し、乾燥品に換算した量）
を双腕型ニーダーに入れ、1,10−フェナントロリン0.1g
を100gのエタノールに溶解した溶液を加え、撹拌した。
その後、これらの樹脂を減圧下にて乾燥させた。Comparative Example 4 100 g of water-absorbent resin (I) (however, converted to dry product)
In a double-arm kneader, 0.10 g of 1,10-phenanthroline
Was dissolved in 100 g of ethanol, and the mixture was stirred.
Then, these resins were dried under reduced pressure.
比較例５ 吸水性樹脂（Ｉ）100g（但し、乾燥品に換算した量）
を双腕型ニーダーに入れ、チオ尿素5gを100gのエタノー
ルに溶解した溶液を加え、撹拌混合した。その後、これ
らの樹脂を減圧下にて乾燥させた。Comparative Example 5 100 g of water absorbent resin (I) (however, the amount converted to a dry product)
Was put in a double-armed kneader, and a solution of 5 g of thiourea dissolved in 100 g of ethanol was added and mixed with stirring. Then, these resins were dried under reduced pressure.
実施例３ 吸水性樹脂（Ｉ）100g（但し、乾燥品に換算した量）
を双腕型ニーダーに入れ、ジエチレントリアミン５酢酸
・Na塩40％水溶液0.25g及び没食子酸プロピル0.1gを100
gの水に溶解した水溶液を加え、撹拌した。その後、こ
れらの樹脂を減圧下にて乾燥させた。Example 3 100 g of the water absorbent resin (I) (however, the amount converted to a dry product)
In a double-arm kneader, and add 0.25 g of 40% aqueous solution of diethylenetriamine pentaacetic acid / Na salt and 0.1 g of propyl gallate to 100 g.
An aqueous solution dissolved in g of water was added and stirred. Then, these resins were dried under reduced pressure.
実施例４ 吸水性樹脂（Ｉ）100g（但し、乾燥品に換算した量）
を双腕型ニーダーに入れ、トリエチレンテトラミン６酢
酸0.1g及び没食子酸プロピル0.1gを100gの水に溶解した
水溶液を加え、撹拌した。その後、これらの樹脂を減圧
下にて乾燥させた。Example 4 100 g of the water absorbent resin (I) (however, the amount converted to a dry product)
Was placed in a double-arm kneader, and an aqueous solution prepared by dissolving 0.1 g of triethylenetetramine hexaacetic acid and 0.1 g of propyl gallate in 100 g of water was added and stirred. Then, these resins were dried under reduced pressure.
比較例６〜７ 吸水性樹脂（Ｉ）100g（但し、乾燥品に換算した量）
を双腕型ニーダーに入れ、ジエチレントリアミン５酢酸
・Na塩40％水溶液0.25g（比較例６）又はトリエチレン
テトラミン６酢酸0.1g（比較例７）を100gの水に溶解し
た水溶液を加え、撹拌した。その後、これらの樹脂を減
圧下にて乾燥させた。Comparative Examples 6 to 7 100 g of the water absorbent resin (I) (however, the amount converted to a dry product)
Was placed in a double-arm kneader, and an aqueous solution prepared by dissolving 0.25 g of a 40% aqueous solution of diethylenetriamine pentaacetic acid / Na salt (Comparative Example 6) or 0.1 g of triethylenetetramine hexaacetic acid (Comparative Example 7) in 100 g of water was added and stirred. . Then, these resins were dried under reduced pressure.
実施例１〜４及び比較例１〜７で得られた吸水性樹脂
組成物について吸水量、吸水速度、並びに耐光性、耐熱
性の評価を行った。その結果を表−１に示した。The water-absorbent resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 7 were evaluated for water absorption, water absorption rate, light resistance, and heat resistance. The results are shown in Table-1.
表−１に示す結果より、本発明の吸水性樹脂組成物は
吸収物性に優れ、かつ耐久性に優れていることが明らか
である。 From the results shown in Table-1, it is apparent that the water absorbent resin composition of the present invention has excellent absorbent properties and durability.
実施例においても具体的に示したように、本発明の吸
水性樹脂組成物は吸水性能に優れ、しかも膨潤時のゲル
形状の安定性が光、熱等の作用下においても良好であ
る。As shown concretely in Examples, the water-absorbent resin composition of the present invention has excellent water-absorbing performance, and the stability of the gel shape upon swelling is good even under the action of light, heat and the like.
従って、本発明の吸水性樹脂組成物は例えば農園芸用
保水剤、土木建築用止水材、脱水剤、生理用ナプキンや
使い捨ておむつ等の衛生用品の吸収材等の用途に好適に
用いることができる。Therefore, the water-absorbent resin composition of the present invention can be suitably used, for example, as a water retention agent for agricultural and horticultural use, a waterproofing material for civil engineering and construction, a dehydrating agent, an absorbent material for sanitary articles such as sanitary napkins and disposable diapers. it can.
Claims (2)
キレート剤を必須として含有し、ラジカル連鎖禁止剤の
含有量が乾燥した吸水性樹脂に対して0.01〜10重量％、
金属キレート剤の含有量が乾燥した吸水性樹脂に対して
0.01〜10重量％であることを特徴とする安定性の優れた
吸水性樹脂組成物。1. A water-absorbent resin, a radical chain inhibitor and a metal chelating agent as essential components, and the content of the radical chain inhibitor is 0.01 to 10% by weight based on the dried water-absorbent resin,
For dry water-absorbent resin with metal chelating agent content
A water-absorbent resin composition having excellent stability, which is 0.01 to 10% by weight.
る請求光１記載の安定性の優れた吸水性樹脂組成物。2. The water-absorbent resin composition having excellent stability according to claim 1, wherein the water-absorbent resin is a crosslinked polyacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63036048A JP2559447B2 (en) | 1988-02-18 | 1988-02-18 | Water-absorbent resin composition with excellent stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63036048A JP2559447B2 (en) | 1988-02-18 | 1988-02-18 | Water-absorbent resin composition with excellent stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01210463A JPH01210463A (en) | 1989-08-24 |
| JP2559447B2 true JP2559447B2 (en) | 1996-12-04 |
Family
ID=12458826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63036048A Expired - Fee Related JP2559447B2 (en) | 1988-02-18 | 1988-02-18 | Water-absorbent resin composition with excellent stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2559447B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6599989B2 (en) | 1998-03-03 | 2003-07-29 | Nippon Skokubai Co., Ltd. | Water-absorbent agents containing polycarboxylic amine chelating agents |
| JP2009154155A (en) * | 1998-03-03 | 2009-07-16 | Nippon Shokubai Co Ltd | Method for manufacturing water absorbent |
| CN101143229A (en) * | 1998-03-03 | 2008-03-19 | 株式会社日本触媒 | Water-absorbing agent and body liquid absorbing production |
| JP4942235B2 (en) * | 1998-04-15 | 2012-05-30 | 株式会社日本触媒 | Water-absorbing agent, absorber, absorbent article, and method for measuring absorption characteristics |
| US6346600B1 (en) | 1999-04-22 | 2002-02-12 | Nippon Shokubai Co., Ltd. | Vinylpyrrolidone polymer and its stabilization and preservation processes |
| JP2003206381A (en) * | 2002-01-15 | 2003-07-22 | Sumitomo Seika Chem Co Ltd | Discoloration prevention method for water-absorbent resin |
| JP3940103B2 (en) * | 2003-07-11 | 2007-07-04 | 住友精化株式会社 | Water absorbent resin composition |
| JP2005225921A (en) * | 2004-02-10 | 2005-08-25 | Asahi Kasei Chemicals Corp | Water-absorbing resin and water-absorbing resin composition and water absorbent |
| US20220176347A1 (en) * | 2019-03-29 | 2022-06-09 | Sumitomo Seika Chemicals Co., Ltd. | Water-absorbing resin and water-blocking material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5689838A (en) * | 1979-12-25 | 1981-07-21 | Shinko Kagaku Kogyo Kk | Water absorbing material |
| US4863989A (en) * | 1986-06-04 | 1989-09-05 | Seitetsu Kagaku Co., Ltd. | Water-absorbent resin composition |
| JPH0724769B2 (en) * | 1986-11-17 | 1995-03-22 | 株式会社日本触媒 | Body fluid absorbent article |
-
1988
- 1988-02-18 JP JP63036048A patent/JP2559447B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01210463A (en) | 1989-08-24 |
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