JPH0586251A - Highly water-absorbable polymer composition - Google Patents
Highly water-absorbable polymer compositionInfo
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- JPH0586251A JPH0586251A JP27667891A JP27667891A JPH0586251A JP H0586251 A JPH0586251 A JP H0586251A JP 27667891 A JP27667891 A JP 27667891A JP 27667891 A JP27667891 A JP 27667891A JP H0586251 A JPH0586251 A JP H0586251A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高吸水性ポリマー組成
物に関する。更に詳しくは、高温多湿下に長期保存して
も経時着色し難い高吸水性ポリマー組成物に関する。This invention relates to superabsorbent polymer compositions. More specifically, it relates to a highly water-absorbent polymer composition which is less likely to be colored over time even when stored under high temperature and high humidity for a long time.
【０００２】[0002]
【従来の技術】自重の数十倍から数百倍の水を吸収する
高吸水性ポリマーは紙オムツ、生理用ナプキンを始めと
して、その他多くの分野の製品に幅広く利用されてい
る。2. Description of the Related Art Superabsorbent polymers which absorb several tens to several hundreds of times their own weight of water are widely used in paper diapers, sanitary napkins and many other fields.
【０００３】このような高吸水性ポリマーとしては、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、カルボキシメチル化セルロース等
が周知である。Examples of such superabsorbent polymers include starch-acrylonitrile graft polymer hydrolysates, starch-acrylic acid graft polymers, vinyl acetate-acrylic acid ester copolymer hydrolysates, and polyacrylic acid. Cross-linked salts, carboxymethylated cellulose and the like are well known.
【０００４】[0004]
【発明が解決しようとする課題】ところで、これらの高
吸水性ポリマーは高温多湿下に長期保存すると褐色ない
し黄色に着色するから、これらポリマーを利用した製品
は保存の間にその商品価値が著しく低下するという問題
があった。By the way, since these superabsorbent polymers are colored brown or yellow when stored for a long time under high temperature and high humidity, the products using these polymers have remarkably reduced commercial value during storage. There was a problem to do.
【０００５】そこで、本発明は、高吸水性ポリマーに有
機リン酸化合物またはその塩を添加することによって前
記問題を解決することを課題にしている。Therefore, the object of the present invention is to solve the above problems by adding an organic phosphoric acid compound or a salt thereof to a superabsorbent polymer.
【０００６】尚、ここで言う着色にはポリマーが変色す
る意味も含まれる。The coloring referred to herein includes the meaning that the polymer is discolored.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、高温多湿
下に長期保存しても経時着色し難い高吸水性ポリマーを
得るべく鋭意検討を重ねた結果、本発明を完成するに至
った。Means for Solving the Problems The present inventors have conducted intensive studies to obtain a superabsorbent polymer which is difficult to be colored over time even if it is stored under high temperature and high humidity for a long time, and as a result, the present invention has been completed. ..
【０００８】かかる本発明は高吸水性ポリマーに対して
有機リン酸化合物またはその塩が０．０１〜１０重量％
添加されていることを特徴とする。In the present invention, the organic phosphoric acid compound or its salt is 0.01 to 10% by weight based on the superabsorbent polymer.
It is characterized by being added.
【０００９】ここで、本発明において使用することので
きる高吸水性ポリマーとしては、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、カルボキシメチル化セルロース等を挙げることがで
きる。特に好ましいものは吸収性能の点でポリアクリル
塩架橋体である。高吸水性ポリマーの重合方法や共重合
成分は、特に限定しない。また、高吸水性ポリマーの使
用形態に関しては、粉体、繊維質基体との複合体等があ
るが、それについても特に限定はしない。Here, examples of the super absorbent polymer which can be used in the present invention include starch-acrylonitrile graft polymer hydrolyzate and starch-
Examples thereof include an acrylic acid graft polymer, a hydrolyzate of a vinyl acetate-acrylic acid ester copolymer, a polyacrylate crosslinked product, and carboxymethyl cellulose. Particularly preferred is a crosslinked polyacrylic salt in terms of absorption performance. The polymerization method and the copolymerization component of the super absorbent polymer are not particularly limited. Further, regarding the usage form of the superabsorbent polymer, there are powder, a composite with a fibrous substrate, and the like, but there is no particular limitation.
【００１０】本発明においては、上記高吸水性ポリマー
に対して有機リン酸化合物またはその塩を添加して高吸
水性ポリマー組成物としてある。有機リン酸化合物とし
てはエチリデンホスホン酸；１−ヒドロキシエチリデン
−１、１−ジホスホン酸；アミノトリメチレンホスホン
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
を挙げることができるが、特に好ましいものは１−ヒド
ロキシエチリデン−１、１−ジホスホン酸；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）である。塩として
好ましいものは、Ｎａ塩、Ｋ塩等のアルカリ金属塩、ア
ンモニウム塩、アミン塩を挙げることができる。これら
の化合物は、金属封鎖剤の一種として知られているもの
である。In the present invention, an organic phosphoric acid compound or a salt thereof is added to the above superabsorbent polymer to give a superabsorbent polymer composition. Organic phosphoric acid compounds include ethylidenephosphonic acid; 1-hydroxyethylidene-1,1-diphosphonic acid; aminotrimethylenephosphonic acid; ethylenediaminetetra (methylenephosphonic acid);
Diethylenetriaminepenta (methylenephosphonic acid) and the like can be mentioned, but particularly preferred are 1-hydroxyethylidene-1,1-diphosphonic acid; ethylenediaminetetra (methylenephosphonic acid); diethylenetriaminepenta (methylenephosphonic acid). Preferable salts include alkali metal salts such as Na salt and K salt, ammonium salts, and amine salts. These compounds are known as a type of sequestering agent.
【００１１】金属封鎖剤を含有する高吸水性ポリマー
は、特開昭５６ー８９８３８号、特開昭５９ー２３００
４６号、特開平１ー２７５６６１号等の公報に記載され
ており、例えばエチレンジアミン４酢酸（ＥＤＴＡ）、
トリポリリン酸ソーダ等を用いることにより、塩やイオ
ン類を含む水の場合でも吸水性能が低下しないことが明
らかにされている。しかしながら、本発明者らの検討に
よれば、ＥＤＴＡやトリポリリン酸ソーダは本発明の目
的である高温多湿下に長期保存する高吸水性ポリマーの
経時着色の防止に大きな効果がなく、本発明に係る上記
特定の化合物を用いることにより初めてその目的が達成
された。Superabsorbent polymers containing a sequestering agent are disclosed in JP-A-56-89838 and JP-A-59-2300.
No. 46, JP-A No. 1-275661, etc., for example, ethylenediaminetetraacetic acid (EDTA),
It has been clarified that the use of sodium tripolyphosphate or the like does not reduce the water absorption performance even in the case of water containing salts and ions. However, according to the studies by the present inventors, EDTA and sodium tripolyphosphate have no significant effect on the prevention of coloration over time of the superabsorbent polymer which is the object of the present invention for long-term storage under high temperature and high humidity. The purpose was achieved only by using the above specific compound.
【００１２】本発明において有機リン酸化合物またはそ
の塩は、各々単独で使用してもよいし、これらを併用し
てもよく、それらの添加量は高吸水性ポリマーに対して
０．０１〜１０重量％であり、より好ましくは０．０５
〜５重量％である。０．０１重量％未満では経時着色の
防止効果が乏しく、１０重量％を越えると吸水性能が低
下するから、これらの範囲は本発明の意図するところで
はない。有機リン酸化合物またはその塩の添加方法は特
に限定されず、それらの溶液を高吸水性ポリマーの製造
工程で加えたり、重合後のポリマーに噴霧、含浸させた
りする方法で添加することができる。In the present invention, the organic phosphoric acid compound or its salt may be used alone or in combination, and the addition amount thereof is 0.01 to 10 relative to the superabsorbent polymer. % By weight, more preferably 0.05
~ 5% by weight. If it is less than 0.01% by weight, the effect of preventing coloration over time is poor, and if it exceeds 10% by weight, the water absorption performance deteriorates, so these ranges are not intended by the present invention. The method for adding the organic phosphoric acid compound or the salt thereof is not particularly limited, and the solution can be added by a method of adding the solution in the step of producing the superabsorbent polymer, or a method of spraying and impregnating the polymer after polymerization.
【００１３】本発明に係る高吸水性ポリマー組成物に
は、必要に応じて他の添加剤を添加してもよい。中でも
他の金属封鎖剤を併用すると、本発明の目的とする高吸
水性ポリマーの経時着色の防止効果が一層向上する場合
がある。If desired, other additives may be added to the superabsorbent polymer composition of the present invention. In particular, when other metal sequestering agents are used in combination, the effect of preventing coloration with time of the superabsorbent polymer, which is the object of the present invention, may be further improved.
【００１４】[0014]
【作用】０．０１〜１０重量％の有機リン酸化合物また
はその塩を添加した本発明に係る高吸水性ポリマー組成
物は、高温多湿下に保存しても経時着色が無添加のもの
に比べて著しく少ない。The superabsorbent polymer composition of the present invention containing 0.01 to 10% by weight of an organic phosphoric acid compound or a salt thereof has a coloring property over time which is higher than that of the composition without addition of color even when stored under high temperature and high humidity. Are extremely few.
【００１５】この効果の得られる理由は明らかではない
が、高吸水性ポリマー組成物中の微量の遷移金属を有機
リン酸化合物またはその塩が捕捉することによって、遷
移金属が介在してラジカル種が発生し高吸水性ポリマー
の分解・ポリマー鎖の切断等の好ましくない反応が引き
起こされるのを防止するからであろうと考えられる。Although the reason why this effect is obtained is not clear, by capturing a trace amount of the transition metal in the superabsorbent polymer composition by the organic phosphoric acid compound or its salt, the radical species is mediated by the transition metal. It is considered that this is because it is possible to prevent undesired reactions such as decomposition of the superabsorbent polymer and breakage of the polymer chain from occurring.
【００１６】[0016]
【実施例】次に、実施例及び比較例によって本発明を更
に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。EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００１７】尚、実施例及び比較例における吸水量と経
時着色の程度とは、次の手順によって求める。 （吸水量の求め方）１０ｃｍ×２０ｃｍのナイロンメッ
シュ製ティーバッグに高吸水性ポリマー組成物約１ｇを
入れ、これを１リットルのビーカーに入れた濃度０．９
重量％の生理食塩水中に１時間浸漬し、１５分間水切り
をした後、次式によってポリマーの自重に対する吸水量
を求める。The water absorption and the degree of coloration over time in the examples and comparative examples are determined by the following procedure. (How to obtain water absorption amount) About 1 g of a super absorbent polymer composition was placed in a 10 cm × 20 cm nylon mesh tea bag, which was placed in a 1 liter beaker to obtain a concentration of 0.9.
After immersing in a physiological saline solution of weight% for 1 hour and draining for 15 minutes, the water absorption amount with respect to the own weight of the polymer is determined by the following formula.
【００１８】吸水量（ｇ／ｇ）＝（浸漬後の全体重量
（ｇ）−浸漬後のティーバッグ重量（ｇ））／（浸漬前
の高吸水性ポリマー組成物の重量（ｇ）） （経時着色の評価方法）高吸水性ポリマー組成物を厚さ
６０μｍのポリエチレンの袋に入れて密封し、７０℃、
６５％ＲＨの雰囲気に１週間及び２週間保存し、その後
に着色度（ＹＩ値）を測定する。着色度の測定には、ス
ガ試験機（株）製「ＳＭカラーコンピューター」（型式
ＳＭ−５−１Ｓ−２Ｂ）を用いる。Water absorption (g / g) = (total weight after immersion (g) -tea bag weight after immersion (g)) / (weight of super absorbent polymer composition before immersion (g)) Coloring evaluation method) The superabsorbent polymer composition was placed in a polyethylene bag having a thickness of 60 μm and hermetically sealed at 70 ° C.
It is stored in an atmosphere of 65% RH for 1 week and 2 weeks, and then the degree of coloring (YI value) is measured. A "SM color computer" (model SM-5-1S-2B) manufactured by Suga Test Instruments Co., Ltd. is used for the measurement of the coloring degree.
【００１９】実施例１ ６０ｍｏｌ％がカリウム塩となったアクリル酸部分中和
物水溶液３００ｇ（モノマー濃度３０重量％）を撹拌
棒、窒素吹き込み管、温度計を備え付けた反応容器に採
取し、更にＮ，Ｎ’−メチレンビスアクリルアミド０．
１５ｇを加え完全に溶解せしめた。窒素雰囲気下にて１
０重量％の２，２’−アゾビス（Ｎ，Ｎ’−ジメチレン
イソブチラミジン）塩酸塩水溶液３ｇを加え、液温を６
０℃にして、重合をおだやかに進行させた。重合開始か
ら３時間後に反応容器を開き生成したゲル状含水重合体
を取り出し粉砕し高吸水性ポリマーを得た。Example 1 300 g of a partially neutralized acrylic acid aqueous solution (monomer concentration: 30% by weight) in which 60 mol% was a potassium salt was sampled in a reaction vessel equipped with a stirring rod, a nitrogen blowing tube, and a thermometer. , N'-methylenebisacrylamide 0.
15 g was added and completely dissolved. 1 under nitrogen atmosphere
3 g of 0% by weight 2,2′-azobis (N, N′-dimethyleneisobutyramidine) hydrochloride aqueous solution was added, and the liquid temperature was adjusted to 6
The temperature was brought to 0 ° C. and the polymerization was allowed to proceed gently. After 3 hours from the initiation of polymerization, the reaction vessel was opened and the gel-like hydropolymer formed was taken out and pulverized to obtain a superabsorbent polymer.
【００２０】次に０．１重量％の１−ヒドロキシエチリ
デン−１、１−ジホスホン酸水溶液をこの高吸水性ポリ
マーに均一に噴霧、含浸させた後、乾燥して高吸水性ポ
リマーに１−ヒドロキシエチリデン−１、１−ジホスホ
ン酸が添加された高吸水性ポリマー組成物を得た。高吸
水性ポリマーに対する１−ヒドロキシエリデン−１、１
−ジホスホン酸の添加量は、０．３重量％（ポリマー１
ｇあたり１．５×１０-5ｍｏｌ添加）であった。Next, 0.1% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution was uniformly sprayed and impregnated on the superabsorbent polymer, and then dried to give 1-hydroxy on the superabsorbent polymer. A super absorbent polymer composition containing ethylidene-1,1-diphosphonic acid was obtained. 1-Hydroxyelidene-1, 1 for superabsorbent polymer
-The addition amount of diphosphonic acid is 0.3% by weight (polymer 1
It was 1.5 × 10 −5 mol per g).
【００２１】この高吸水性ポリマー組成物について吸水
量および経時着色を評価し、結果を表１に示した。With respect to this highly water-absorbent polymer composition, the water absorption amount and coloration with time were evaluated, and the results are shown in Table 1.
【００２２】実施例２ 実施例１と同様にして高吸水性ポリマーを製造した後
に、１−ヒドロキシエチリデン−１、１−ジホスホン酸
水溶液に代えてエチレンジアミンテトラ（メチレンホス
ホン酸）水溶液を噴霧、含浸させ、乾燥して高吸水性ポ
リマーを得た。高吸水性ポリマーに対するエチレンジア
ミンテトラ（メチレンホスホン酸）の添加量は０．６３
重量％（ポリマー１ｇあたり１．５×１０-5ｍｏｌ添
加）であった。その評価結果を表１に示した。Example 2 A superabsorbent polymer was prepared in the same manner as in Example 1, and then an ethylenediaminetetra (methylenephosphonic acid) aqueous solution was sprayed and impregnated in place of the 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution. Then, it was dried to obtain a super absorbent polymer. The amount of ethylenediaminetetra (methylenephosphonic acid) added to the superabsorbent polymer is 0.63.
It was a weight% (1.5 × 10 −5 mol was added per 1 g of the polymer). The evaluation results are shown in Table 1.
【００２３】実施例３ ６０ｍｏｌ％がカリウム塩となったアクリル酸部分中和
物水溶液３００ｇ（モノマー濃度３０重量％）を撹拌
棒、窒素吹き込み管、温度計を備え付けた反応容器に採
取し、更にＮ，Ｎ’−メチレンビスアクリルアミド０．
１５ｇ、５重量％の１−ヒドロキシエチリデン−１、１
−ジホスホン酸水溶液１．８ｇを加え完全に溶解せしめ
た。窒素雰囲気下にて１０重量％の２，２’−アゾビス
（Ｎ，Ｎ’−ジメチレンイソブチラミジン）塩酸塩水溶
液３ｇを加え、液温を６０℃にして、重合をおだやかに
進行させた。Example 3 300 g of a partially neutralized acrylic acid aqueous solution (monomer concentration 30% by weight) in which 60 mol% was a potassium salt was sampled in a reaction vessel equipped with a stir bar, a nitrogen blowing tube, and a thermometer, and further N , N'-methylenebisacrylamide 0.
15 g, 5% by weight of 1-hydroxyethylidene-1, 1,
-1.8 g of an aqueous solution of diphosphonic acid was added and completely dissolved. Under a nitrogen atmosphere, 3 g of a 10% by weight 2,2′-azobis (N, N′-dimethyleneisobutyramidine) hydrochloride aqueous solution was added, and the liquid temperature was set to 60 ° C. to allow the polymerization to proceed gently. ..
【００２４】重合開始から３時間後に反応容器を開き、
生成したゲル状含水重合体を取り出し、乾燥、粉砕し高
吸水性ポリマー組成物を得た。高吸水性ポリマーに対す
る１−ヒドロキシエチリデン−１、１−ジホスホン酸の
添加量は０．１重量％（ポリマー１ｇあたり４．９×１
０-6ｍｏｌ添加）であった。その評価を表１に示した。3 hours after the initiation of polymerization, the reaction vessel was opened,
The resulting gel-like hydropolymer was taken out, dried and pulverized to obtain a super absorbent polymer composition. The amount of 1-hydroxyethylidene-1,1-diphosphonic acid added to the superabsorbent polymer was 0.1% by weight (4.9 × 1 per 1 g of the polymer).
Was 0 -6 mol added). The evaluation is shown in Table 1.
【００２５】実施例４ ６０ｍｏｌ％がカリウム塩となったアクリル酸部分中和
物水溶液１００ｇ（モノマー濃度６７％）に、Ｎ，Ｎ’
ーメチレンビスアクリルアミド０．１ｇ、３０重量％の
過酸化水素０．６ｇを加え完全に溶解せしめた。これを
別に用意した３ｇのポリエステル不織布の全面に含浸さ
せ恒温反応槽内にて４０℃に保った。含浸させたモノマ
ー量は、不織布に対して５重量倍であった。Example 4 N, N 'was added to 100 g of an aqueous solution of partially neutralized acrylic acid in which 60 mol% was a potassium salt (monomer concentration 67%).
-Methylenebisacrylamide (0.1 g) and 30% by weight of hydrogen peroxide (0.6 g) were added and completely dissolved. This was impregnated onto the entire surface of a separately prepared 3 g of polyester nonwoven fabric and kept at 40 ° C. in a constant temperature reaction tank. The amount of the impregnated monomer was 5 times the weight of the nonwoven fabric.
【００２６】次に還元剤として０．５重量％のＬ−アス
コルビン酸水溶液をスプレーノズルにより上記不織布全
面に噴霧した。アクリル酸部分中和水溶液に対するＬ−
アスコルビン酸の添加量は０．０４３重量％であった。
重合が直ちに起こり、高吸水性ポリマーがポリエステル
不織布に強く固着した高吸水性ポリマー複合体を得た。Next, a 0.5 wt% L-ascorbic acid aqueous solution as a reducing agent was sprayed onto the entire surface of the non-woven fabric using a spray nozzle. L- for partially neutralized acrylic acid aqueous solution
The amount of ascorbic acid added was 0.043% by weight.
Polymerization immediately occurred, and a superabsorbent polymer composite in which the superabsorbent polymer was strongly adhered to the polyester nonwoven fabric was obtained.
【００２７】更に、１重量％の１−ヒドロキシエチリデ
ン−１、１−ジホスホン酸水溶液をこの高吸水性ポリマ
ー複合体全面に噴霧し、乾燥して高吸水性ポリマーに１
−ヒドロキシエチリデン−１、１−ジホスホン酸が添加
された高吸水性ポリマー組成物を得た。高吸水性ポリマ
ーに対する１−ヒドロキシエチリデン−１、１−ジホス
ホン酸の添加量は、０．５重量％（ポリマー１ｇあたり
２．４×１０-5ｍｏｌ添加）であった。Further, 1% by weight of an aqueous solution of 1-hydroxyethylidene-1,1-diphosphonic acid was sprayed on the entire surface of the superabsorbent polymer composite and dried to form a superabsorbent polymer.
A highly water-absorbent polymer composition to which -hydroxyethylidene-1,1-diphosphonic acid was added was obtained. The amount of 1-hydroxyethylidene-1,1-diphosphonic acid added to the superabsorbent polymer was 0.5% by weight (2.4 × 10 −5 mol added per 1 g of polymer).
【００２８】この高吸水性ポリマー組成物について吸水
量および経時着色を評価し、結果を表１に示した。The water absorption amount and coloration over time of this highly water-absorbent polymer composition were evaluated, and the results are shown in Table 1.
【００２９】実施例５ 実施例４と同様にして高吸水性ポリマー複合体を製造し
た後、１−ヒドロキシエチリデン−１、１−ジホスホン
酸水溶液に代えてジエチレントリアミンペンタ（メチレ
ンホスホン酸）７Ｎａ塩水溶液を噴霧、含浸させ、乾燥
して高吸水性ポリマー組成物を得た。高吸水性ポリマー
に対するジエチレントリアミンペンタ（メチレンホスホ
ン酸）７Ｎａ塩の添加量は１．８重量％（ポリマー１ｇ
あたり２．４×１０-5ｍｏｌ）であった。その評価結果
を表１に示した。Example 5 After producing a superabsorbent polymer composite in the same manner as in Example 4, an aqueous solution of diethylenetriaminepenta (methylenephosphonic acid) 7Na salt was used instead of the aqueous solution of 1-hydroxyethylidene-1,1-diphosphonic acid. It was sprayed, impregnated and dried to obtain a super absorbent polymer composition. The amount of diethylenetriaminepenta (methylenephosphonic acid) 7Na salt added to the superabsorbent polymer was 1.8% by weight (1 g of the polymer).
Per 2.4 × 10 −5 mol). The evaluation results are shown in Table 1.
【００３０】比較例１ 実施例１と同様にして高吸水性ポリマーを製造したが、
１−ヒドロキシエチリデン−１、１−ジホスホン酸水溶
液を加えなかった。その評価結果を表１に示した。Comparative Example 1 A superabsorbent polymer was produced in the same manner as in Example 1, except that
No 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution was added. The evaluation results are shown in Table 1.
【００３１】比較例２ 実施例１と同様にして高吸水性ポリマーを製造した後、
１−ヒドロキシエチリデン−１、１−ジホスホン酸水溶
液に代えてエチレンジアミン４酢酸−４Ｎａ塩水溶液を
噴霧、含浸させ、乾燥して高吸水性ポリマー組成物を得
た。高吸水性ポリマーに対するエチレンジアミン４酢酸
−４Ｎａ塩の添加量は０．５５重量％（ポリマー１ｇあ
たり１．５×１０-5ｍｏｌ添加）であった。その評価を
表１に示した。Comparative Example 2 After producing a superabsorbent polymer in the same manner as in Example 1,
Instead of the 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution, an ethylenediaminetetraacetic acid-4Na salt aqueous solution was sprayed, impregnated and dried to obtain a superabsorbent polymer composition. The amount of ethylenediaminetetraacetic acid-4Na salt added to the superabsorbent polymer was 0.55% by weight (1.5 × 10 −5 mol added per 1 g of the polymer). The evaluation is shown in Table 1.
【００３２】比較例３ 実施例３において５重量％の１−ヒドロキシエチリデン
−１、１−ジホスホン酸水溶液１．８ｇを加える代わり
に５重量％のエチレンジアミン４酢酸−４Ｎａ水溶液１
０．０ｇを加えた。それ以外は実施例３と同様にして高
吸水性ポリマー組成物を製造し、評価した。高吸水性ポ
リマーに対するエチレンジアミン４酢酸−４Ｎａの添加
量は０．５５重量％（ポリマー１ｇあたり１．５×１０
-5ｍｏｌ添加）であった。その結果を表１に示した。Comparative Example 3 Instead of adding 1.8 g of a 5 wt% 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution in Example 3, 5 wt% of an ethylenediaminetetraacetic acid-4Na aqueous solution 1 was added.
0.0 g was added. Otherwise in the same manner as in Example 3, a superabsorbent polymer composition was produced and evaluated. The amount of ethylenediaminetetraacetic acid-4Na added to the superabsorbent polymer was 0.55% by weight (1.5 × 10 5 per 1 g of the polymer).
-5 mol). The results are shown in Table 1.
【００３３】比較例４ 実施例４と同様にして高吸水性ポリマーを製造したが、
１−ヒドロキシエチリデン−１、１−ジホスホン酸水溶
液を加えなかった。その評価結果を表１に示した。Comparative Example 4 A superabsorbent polymer was prepared in the same manner as in Example 4, except that
No 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution was added. The evaluation results are shown in Table 1.
【００３４】比較例５ 実施例４と同様にして高吸水性ポリマー複合体を製造し
た後、１−ヒドロキシエチリデン−１、１−ジホスホン
酸水溶液に代えてエチレンジアミン４酢酸−４Ｎａ塩水
溶液を噴霧、含浸させ、乾燥して高吸水性ポリマー組成
物を得た。高吸水性ポリマーに対するエチレンジアミン
４酢酸−４Ｎａ塩の添加量は０．９２重量％（ポリマー
１ｇあたり２．４×１０-5ｍｏｌ添加）であった。その
評価結果を表１に示した。Comparative Example 5 A superabsorbent polymer composite was prepared in the same manner as in Example 4, and then an ethylenediaminetetraacetic acid-4Na salt aqueous solution was sprayed and impregnated in place of the 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution. And dried to obtain a super absorbent polymer composition. The amount of ethylenediaminetetraacetic acid-4Na salt added to the superabsorbent polymer was 0.92% by weight (2.4 × 10 −5 mol added per 1 g of the polymer). The evaluation results are shown in Table 1.
【００３５】[0035]
【表１】 表１において明らかなように、実施例により得られた高
吸水性ポリマー組成物は着色度（ＹＩ値）の変化が比較
例よりもはるかに小さく、高温多湿下に保存しても経時
着色が起こりにくい。[Table 1] As is clear from Table 1, in the superabsorbent polymer compositions obtained in Examples, the change in coloring degree (YI value) is much smaller than that in Comparative Examples, and coloring over time occurs even when stored under high temperature and high humidity. Hateful.
【００３６】[0036]
【発明の効果】高吸水性ポリマーに有機リン酸化合物ま
たはその塩を添加した高吸水性ポリマー組成物は高温多
湿下でも経時着色が起こりにくいから、この組成物であ
れば外観を重視する商品に使用しても保存期間中にその
商品価値を損なうことがない。EFFECTS OF THE INVENTION A superabsorbent polymer composition obtained by adding an organic phosphoric acid compound or a salt thereof to a superabsorbent polymer is less likely to be colored over time even under high temperature and high humidity. Even if it is used, its commercial value will not be lost during the storage period.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 隆司 東京都江戸川区北葛西１丁目16番13号 第 一製薬株式会社東京研究開発センター内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Yamamoto 1-16-13 Kitakasai, Edogawa-ku, Tokyo Daiichi Pharmaceutical Co., Ltd. Tokyo Research and Development Center
Claims (2)
合物またはその塩が０．０１〜１０重量％添加されてい
ることを特徴とする高吸水性ポリマー組成物。1. A superabsorbent polymer composition comprising an organic phosphoric acid compound or a salt thereof in an amount of 0.01 to 10% by weight based on the superabsorbent polymer.
エチリデン−１、１−ジホスホン酸；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）および／またはそれらの
塩である請求項１記載の高吸水性ポリマー組成物。2. The organic phosphoric acid compound is 1-hydroxyethylidene-1,1-diphosphonic acid; ethylenediaminetetra (methylenephosphonic acid); diethylenetriaminepenta (methylenephosphonic acid) and / or salts thereof. The superabsorbent polymer composition described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03276678A JP3107873B2 (en) | 1991-09-26 | 1991-09-26 | Method for preventing temporal coloring of superabsorbent polymer and agent for preventing temporal coloring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03276678A JP3107873B2 (en) | 1991-09-26 | 1991-09-26 | Method for preventing temporal coloring of superabsorbent polymer and agent for preventing temporal coloring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0586251A true JPH0586251A (en) | 1993-04-06 |
| JP3107873B2 JP3107873B2 (en) | 2000-11-13 |
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ID=17572796
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03276678A Expired - Lifetime JP3107873B2 (en) | 1991-09-26 | 1991-09-26 | Method for preventing temporal coloring of superabsorbent polymer and agent for preventing temporal coloring |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3107873B2 (en) |
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