JPS62158701A - Production of water-absorptive polymeric material - Google Patents
Production of water-absorptive polymeric materialInfo
- Publication number
- JPS62158701A JPS62158701A JP60297367A JP29736785A JPS62158701A JP S62158701 A JPS62158701 A JP S62158701A JP 60297367 A JP60297367 A JP 60297367A JP 29736785 A JP29736785 A JP 29736785A JP S62158701 A JPS62158701 A JP S62158701A
- Authority
- JP
- Japan
- Prior art keywords
- water
- acid
- polymeric compound
- absorbing
- side chain
- 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
Landscapes
- Absorbent Articles And Supports Therefor (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、紙おむつや生理用品等の吸水機能を必要とす
るところに使用される吸水性高分子材料の製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a water-absorbing polymeric material used in disposable diapers, sanitary products, and other places that require a water-absorbing function.
（従来技術とその問題点）
従来から使用されているポリアクリル酸系架橋化物の吸
水性高分子は、吸水能力が弱く、又、吸水時のゲル強度
が弱いために、吸水材料としての利用価値が低いもので
ある。(Prior art and its problems) Water-absorbing polymers made from cross-linked polyacrylic acid that have been used in the past have low water-absorbing ability and weak gel strength when absorbing water, so their utility as water-absorbing materials is limited. is low.
これに対して、例えば、特公昭５３−４６１９９号公報
に記載されているように、デンプンなどのモノマーであ
るアクリル酸、アクリロニトリルなどをグラフト重合さ
せて合成された、デンプン−アクリル酸系、又はデンプ
ン−アクリロニトリル系のグラフト重合体加水分解物が
、高吸水性という点において優れている。On the other hand, for example, as described in Japanese Patent Publication No. 53-46199, starch-acrylic acid type or starch synthesized by graft polymerization of monomers such as starch such as acrylic acid, acrylonitrile, etc. - Acrylonitrile-based graft polymer hydrolyzate is excellent in terms of high water absorption.
しかしながら、これらも、吸水速度という点においては
未だ十分満足できる吸水材料とは言い難いのが現状であ
る。However, it is currently difficult to say that these materials are water-absorbing materials that are fully satisfactory in terms of water-absorbing speed.
又、これらグラフト重合体加水分解物の場合、製造過程
において、生成物中のアクリルモノマー残存による毒性
という点に問題がある。Furthermore, in the case of these graft polymer hydrolysates, there is a problem in that they are toxic due to residual acrylic monomer in the product during the manufacturing process.
本発明はこのような問題点を解消した吸水性高分子材料
の製造方法の提供を目的とするものである。The object of the present invention is to provide a method for producing a water-absorbing polymer material that solves these problems.
（問題点を解決するための手段）
上記目的を達成するために、本発明による吸水性高分子
材料の製造方法は、ポリアクリル酸、アルギン酸及び／
又はそれ等の塩類等の水溶性で側鎖にカルボキシル基を
持つ高分子化合物と、グリセリン又はペンタエリスリト
ール等の多価アルコールとを水溶液中において酸触媒と
減圧下で５０〜ｌＯＯ℃の加熱によりエステル化させる
ことによって、架橋化、水不溶化したことを特徴とする
ものであり、毒性のない水溶性で側鎖にカルボキシ基を
持つ高分子化合物と多価アルコールを材料とし、従来の
吸水性高分子材料に比べて吸水能、吸水速度、ゲル強度
及び安全性という点においてほぼ満足できる吸水性高分
子材料を得ることができるものである。(Means for Solving the Problems) In order to achieve the above object, the method for producing a water-absorbing polymer material according to the present invention includes polyacrylic acid, alginic acid and/or
Or a water-soluble polymeric compound having a carboxyl group in the side chain, such as a salt thereof, and a polyhydric alcohol such as glycerin or pentaerythritol are mixed into an ester with an acid catalyst in an aqueous solution by heating at 50 to 100°C under reduced pressure. It is characterized by being cross-linked and made water-insoluble by oxidation, and is made from a non-toxic, water-soluble polymer compound with carboxyl groups in the side chain and a polyhydric alcohol, and is different from conventional water-absorbing polymers. It is possible to obtain a water-absorbing polymer material that is almost satisfactory in terms of water-absorbing ability, water-absorbing rate, gel strength, and safety compared to other materials.
本発明に用いられる水溶性ポリカルボン酸、例えば、ポ
リアクリル酸、アルギン酸及び／又はそれらの塩類は、
平均重合度が約１ 、０００〜１００．０００のもの、
好ましくは、２０，０００〜７０．０００のものであれ
ば特に限定されない。The water-soluble polycarboxylic acids used in the present invention, such as polyacrylic acid, alginic acid and/or salts thereof, are
Those with an average degree of polymerization of about 1,000 to 100,000,
Preferably, it is not particularly limited as long as it is 20,000 to 70,000.
又、多価アルコールの使用量は、一種又は二種以上の混
合物を使用する場合でも、水溶性ポリカルボン酸、例え
ば、ポリアクリル酸、アルギン酸及び／又はそれらの塩
類の重量の約０．０１倍〜３０倍、特に、約０．１〜１
０倍が好適である。In addition, the amount of polyhydric alcohol to be used is approximately 0.01 times the weight of the water-soluble polycarboxylic acid, such as polyacrylic acid, alginic acid, and/or their salts, even when one type or a mixture of two or more types is used. ~30 times, especially about 0.1-1
0 times is preferable.
本発明に係る吸水性高分子材料を製造するには、水溶性
ポリカルボン酸、例えば、ポリアクリル酸、アルギン酸
及び／又はそれらの塩類と、多価アルコール、例えば、
グリセリン又はペンタエリスリトールとを水溶液中に均
一に溶解させ、この水溶液に酸触媒、例えば、塩酸又は
ｐ−ｔ−ルエンスルホン酸を加え、気密容器中にて減圧
状態で水浴中、約６０℃〜１００℃に加熱して反応させ
ればよい。To produce the water-absorbing polymer material according to the present invention, a water-soluble polycarboxylic acid, such as polyacrylic acid, alginic acid, and/or their salts, and a polyhydric alcohol, such as
Glycerin or pentaerythritol is uniformly dissolved in an aqueous solution, an acid catalyst such as hydrochloric acid or pt-luenesulfonic acid is added to the aqueous solution, and the mixture is heated in an airtight container under reduced pressure in a water bath at about 60°C to 100°C. The reaction may be caused by heating to ℃.
ここで用いられる触媒は、無機酸又は有機酸を用いるこ
とができる。The catalyst used here can be an inorganic acid or an organic acid.
次に、本発明の実施例を示すが、本発明はこの実施例に
制限されるべきものではない。Next, examples of the present invention will be shown, but the present invention should not be limited to these examples.
（実施例の説明）
実施例 １
水溶性ポリアクリル酸ナトリウム１重量部（以下、単に
部とする゛）を脱イオン水（以下、単に水と称する）５
０部中に溶解させ、この溶液中にグリセリン３部を加え
、充分均一に溶解させる。(Description of Examples) Example 1 1 part by weight of water-soluble sodium polyacrylate (hereinafter simply referred to as part) was mixed with deionized water (hereinafter simply referred to as water) 5
Add 3 parts of glycerin to this solution and dissolve it uniformly.
完全に溶解させた後、塩酸０．５部を加え、気密容器に
入れて水浴中、６０〜１００℃に加熱し、約２０璽■Ｈ
ｇの減圧下で脱水留去を最大限に行うか或いは常圧状態
で完全に水を除去するために、ポリエチレングリコール
＃３００〜４００を１５０℃に加熱し、その溶液中に生
成物を投入して脱水留去を最大限に行ってもよい。After completely dissolving, add 0.5 part of hydrochloric acid, place in an airtight container, heat to 60-100℃ in a water bath, and boil for about 20 hours.
In order to maximize dehydration and distillation under reduced pressure of 1.5 g or to completely remove water under normal pressure, polyethylene glycol #300-400 is heated to 150°C and the product is poured into the solution. Dehydration and distillation may be carried out to the maximum extent.
減圧状態で脱水留去を最大限に行った後、常圧に戻して
生成物にベンゼン２０部を加え、気密容器中、約８０〜
１００℃で共沸状態とし、さらに生成物中の水分を除去
させる。完全にベンゼンが蒸発した後に、生成物を容器
より取り出し、アセトンを約５０部、中に投入する。こ
のアセトン溶液を濾過することにより、生成物中に残存
するグリセリン及び塩酸を抽出し、除去する。After maximum dehydration and distillation under reduced pressure, the pressure was returned to normal, 20 parts of benzene was added to the product, and the mixture was heated in an airtight container to about 80 to 80 parts.
The mixture is brought to an azeotropic state at 100° C., and water in the product is further removed. After the benzene has completely evaporated, the product is taken out of the container and about 50 parts of acetone are poured into it. By filtering this acetone solution, glycerin and hydrochloric acid remaining in the product are extracted and removed.
ポリエチレングリコールを用いる場合でも同様に行う。The same procedure is applied when polyethylene glycol is used.
次に、生成物に水５０部を加え、まだ多少生成物中に残
留していると思われる塩酸を水酸化ナトリウム溶液で中
和する。中和が完全に終了した後、生成物を濾過する。Next, 50 parts of water are added to the product, and any hydrochloric acid that may still remain in the product is neutralized with sodium hydroxide solution. After complete neutralization, the product is filtered.
再度、１００〜２００部の水を生成物に加え、充分に攪
拌し、濾過する。Again, 100-200 parts of water are added to the product, stirred thoroughly and filtered.
この操作を、２〜４回繰り返し、生成物中の塩を除去す
る。この際、生成物は吸水のため堆積が増大してくる。This operation is repeated 2 to 4 times to remove salts in the product. At this time, the product accumulates more and more due to water absorption.
充分に洗滌した後に、この吸水した状態の生成物を約９
０〜９９％のエタノール又はアセトン中に投入し、生成
物中の水分を取り除く。こうして充分に水分を除去した
生成物を、エタノール又はアセトン中より取り出し、デ
シケータ中、減圧下で充分乾燥させることにより吸水性
高分子材料を得た。After thorough washing, this water-absorbed product is
Pour into 0-99% ethanol or acetone to remove water in the product. The product from which water had been sufficiently removed in this way was taken out from ethanol or acetone and sufficiently dried under reduced pressure in a desiccator to obtain a water-absorbing polymer material.
実施例 ２
水溶性ポリアクリル酸１部を水５０部中に溶解させ、こ
の水溶液中に、ペンタエリスリトール０．１部を加え、
充分均一に溶解させる。完全に溶解させた後、前記実施
例１と同様の方法により吸水性高分子材料を得た。Example 2 1 part of water-soluble polyacrylic acid was dissolved in 50 parts of water, 0.1 part of pentaerythritol was added to this aqueous solution,
Dissolve thoroughly and uniformly. After complete dissolution, a water-absorbing polymer material was obtained in the same manner as in Example 1 above.
次に、上記の実施例１及び実施例２により得られた吸水
性高分子材料と、比較例として市販されているポリアク
リル酸系吸水性高分子材料（日本触媒部、商品名アクア
リックＣＡ−Ｋ）とを用いて、吸水能、吸水速度、ゲル
強度を調べた。その結果を次に表示する。Next, the water-absorbing polymer materials obtained in Example 1 and Example 2 above and the polyacrylic acid-based water-absorbing polymer material commercially available as a comparative example (Nippon Shokubai Department, trade name Aqualic CA- K) was used to examine water absorption capacity, water absorption rate, and gel strength. The results are shown below.
なお、吸水能測定は、濾過法によりメツシュ８０号を用
い、自重の何倍の吸水Ｍｋ （ｇ ：脱イオン水／ｇ：
本品）であるかを示す。The water absorption capacity was measured using a mesh No. 80 using a filtration method, and the water absorption Mk (g: deionized water/g:
This product).
これらの結果より、本発明に係る吸水性高分子材料は、
優れた吸水能、吸水速度及びゲル強度を有し、かつ安全
性の高い吸水性高分子材料であることが明らかである。From these results, the water-absorbing polymer material according to the present invention is
It is clear that this water-absorbing polymer material has excellent water-absorbing ability, water-absorbing rate, and gel strength, and is highly safe.
（発明の効果）
以上のように、本発明による吸水性高分子材料の製造方
法によれば、ポリアクリル酸、アルギン酸及び／又はそ
れ等の塩類等の水溶性で側鎖にカルボキシル基を持つ高
分子化合物と、多価アルコールとを水溶液中において酸
触媒と減圧下で５０〜１００℃の加熱により反応させる
ことを特徴とするものであるから、従来の吸水性高分子
材料に比べて、吸水能、吸水速度、ゲル強度及び安全性
に優れた吸水性高分子材料を得ることができるものであ
る。(Effects of the Invention) As described above, according to the method for producing a water-absorbing polymer material according to the present invention, water-soluble polymers such as polyacrylic acid, alginic acid, and/or salts thereof, having a carboxyl group in the side chain Because it is characterized by reacting a molecular compound and a polyhydric alcohol with an acid catalyst in an aqueous solution by heating at 50 to 100°C under reduced pressure, it has a higher water absorption capacity than conventional water-absorbing polymer materials. , it is possible to obtain a water-absorbing polymer material with excellent water absorption rate, gel strength, and safety.
喝−１１，ＣＩKake-11, CI
Claims (1)
の水溶性で側鎖にカルボキシル基を持つ高分子化合物と
、多価アルコールとを水溶液中において酸触媒と減圧下
で５０〜１００℃の加熱により反応させることを特徴と
する吸水性高分子材料の製造方法。A water-soluble polymeric compound having a carboxyl group in a side chain such as polyacrylic acid, alginic acid and/or salts thereof, and a polyhydric alcohol are mixed in an aqueous solution with an acid catalyst and heated at 50 to 100°C under reduced pressure. A method for producing a water-absorbing polymer material, which comprises causing a reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60297367A JPS62158701A (en) | 1985-12-30 | 1985-12-30 | Production of water-absorptive polymeric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60297367A JPS62158701A (en) | 1985-12-30 | 1985-12-30 | Production of water-absorptive polymeric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62158701A true JPS62158701A (en) | 1987-07-14 |
Family
ID=17845572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60297367A Pending JPS62158701A (en) | 1985-12-30 | 1985-12-30 | Production of water-absorptive polymeric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62158701A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998044950A1 (en) * | 1997-04-04 | 1998-10-15 | Kuraray Co., Ltd. | Therapeutic material for periodontosis |
| KR100349495B1 (en) * | 2000-06-12 | 2002-08-21 | 한웅코텍 주식회사 | Elastic aqueous gel sheet(EA gel sheet) |
| JPWO2004081055A1 (en) * | 2003-02-21 | 2006-06-08 | テルモ株式会社 | Crosslinkable polysaccharide derivative, method for producing the same, crosslinkable polysaccharide composition, and medical treatment material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116903A (en) * | 1984-07-02 | 1986-01-24 | Nippon Shokubai Kagaku Kogyo Co Ltd | Water-absorbent |
-
1985
- 1985-12-30 JP JP60297367A patent/JPS62158701A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116903A (en) * | 1984-07-02 | 1986-01-24 | Nippon Shokubai Kagaku Kogyo Co Ltd | Water-absorbent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998044950A1 (en) * | 1997-04-04 | 1998-10-15 | Kuraray Co., Ltd. | Therapeutic material for periodontosis |
| KR100349495B1 (en) * | 2000-06-12 | 2002-08-21 | 한웅코텍 주식회사 | Elastic aqueous gel sheet(EA gel sheet) |
| JPWO2004081055A1 (en) * | 2003-02-21 | 2006-06-08 | テルモ株式会社 | Crosslinkable polysaccharide derivative, method for producing the same, crosslinkable polysaccharide composition, and medical treatment material |
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