JP2005305236A - Water absorbing material, manufacturing method therefor, and water absorbent article - Google Patents
Water absorbing material, manufacturing method therefor, and water absorbent article Download PDFInfo
- Publication number
- JP2005305236A JP2005305236A JP2004122939A JP2004122939A JP2005305236A JP 2005305236 A JP2005305236 A JP 2005305236A JP 2004122939 A JP2004122939 A JP 2004122939A JP 2004122939 A JP2004122939 A JP 2004122939A JP 2005305236 A JP2005305236 A JP 2005305236A
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- JP
- Japan
- Prior art keywords
- water
- acid
- absorbing material
- galactomannan
- carboxyalkylated
- 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.)
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- 239000011358 absorbing material Substances 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002250 absorbent Substances 0.000 title claims abstract description 9
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- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical class O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims abstract description 40
- 238000010521 absorption reaction Methods 0.000 claims abstract description 40
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Landscapes
- Absorbent Articles And Supports Therefor (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
本発明は、優れた生分解性、吸水性、保水性を有する吸水材及びその製造方法並びにそれを含む吸水性物品に関する。 The present invention relates to a water-absorbing material having excellent biodegradability, water absorption, and water retention, a method for producing the same, and a water-absorbing article including the same.
［吸水材の技術的背景］
吸水材は、自重の数十倍から数千倍の水を吸水できる樹脂であり、例えばアクリル系吸水材などが知られている。これらの吸水材は、その高い吸水性から広く使い捨て衛生用品に使用されている。しかし、これまでの吸水材は生分解性がなく、それを含む衛生用品の処理方法に問題があった。
[Technical background of water-absorbing materials]
The water-absorbing material is a resin that can absorb water several tens to several thousand times its own weight. For example, an acrylic water-absorbing material is known. These water-absorbing materials are widely used for disposable sanitary products because of their high water absorption. However, conventional water-absorbing materials are not biodegradable, and there has been a problem in the method for treating sanitary products containing them.
［生分解性吸水材の技術的背景］
生分解性を有する吸水材としては、例えばポリエチレンオキシド架橋体（例えば、特許文献１参照）、ポリビニルアルコール架橋体、カルボキシメチルセルロース架橋体（例えば、特許文献２参照）、アルギン酸架橋体、澱粉架橋体（例えば、特許文献３参照）、ポリアミノ酸架橋体（例えば、特許文献４〜８参照）、ガラクトマンナン−金属イオン架橋体（例えば、特許文献９〜１１参照）、キサンタンガム架橋体（例えば、特許文献１２）などが知られている。
[Technical background of biodegradable water-absorbing material]
Examples of the water-absorbing material having biodegradability include, for example, a polyethylene oxide crosslinked body (for example, see Patent Document 1), a polyvinyl alcohol crosslinked body, a carboxymethylcellulose crosslinked body (for example, see Patent Document 2), an alginate crosslinked body, and a starch crosslinked body ( For example, patent document 3 reference), polyamino acid crosslinked body (for example, refer patent documents 4-8), galactomannan-metal ion crosslinked body (for example, refer patent documents 9-11), xanthan gum crosslinked body (for example, patent document 12). ) Etc. are known.
これらの生分解性を有する吸水材を非生分解性の合成高分子系吸水材と比較した場合、生分解性を有する吸水材の方が製造コストが高い、吸水性能が低い、吸水後のゲル強度が弱いなどの問題があり実用化には至っていない。そこで、本発明者らはガラクトマンナンとホウ酸イオン及び／又はホウ酸以外の三価以上の多価金属イオンからなる、生分解性を有し吸水性能が優れている吸水材を提案した（例えば、特許文献１３〜１５）。 When these water-degradable water-absorbing materials are compared with non-biodegradable synthetic polymer water-absorbing materials, bio-degradable water-absorbing materials have higher manufacturing costs, lower water-absorbing performance, and gel after water absorption. There are problems such as weak strength, and it has not been put to practical use. Accordingly, the present inventors have proposed a water-absorbing material that is composed of galactomannan and borate ions and / or trivalent or higher polyvalent metal ions other than boric acid and has biodegradability and excellent water-absorbing performance (for example, And Patent Documents 13 to 15).
多糖類をポリカルボン酸で架橋してなる吸水材としてはヒアルロン酸のポリカルボン酸架橋物（特許文献１６）、カルボキシアルキルセルロースやカルボキシアルキルデンプンのアミノ酸類架橋物（特許文献１７）やカルボキシアルキルセルロースのポリカルボン酸架橋物（特許文献１８）、酸性多糖類の生分解性架橋剤による架橋物（特許文献１９）が知られている。 Examples of water-absorbing materials obtained by cross-linking polysaccharides with polycarboxylic acid include polycarboxylic acid cross-linked products of hyaluronic acid (Patent Document 16), cross-linked products of amino acids of carboxyalkyl cellulose and carboxyalkyl starch (Patent Document 17), and carboxyalkyl cellulose. A crosslinked product of a polycarboxylic acid (Patent Document 18) and a crosslinked product of an acidic polysaccharide biodegradable crosslinking agent (Patent Document 19) are known.
多糖類の水酸基とポリカルボン酸のカルボキシル基は加熱することでエステル交換反応が生じ、結果として多糖類ポリマーが架橋される。このような架橋物を乾燥したものには吸水性能を有するものが多く、前述のように特許文献１６〜１９のような架橋物が既に報告されている。 The hydroxyl group of the polysaccharide and the carboxyl group of the polycarboxylic acid are heated to cause a transesterification reaction. As a result, the polysaccharide polymer is crosslinked. Many dried products of such a crosslinked product have water absorption performance, and as described above, crosslinked products as described in Patent Documents 16 to 19 have already been reported.
しかしながら、特許文献１６記載の架橋物は創傷被覆材用途であるため非常に高価なヒアルロン酸をベースポリマーとして用いており衛生材用途には不適当であり、また架橋物の吸水性能についての言及はない。
特許文献１７、１８については、得られている吸水材の性能があまり高いものとはいえず実用化できるものではなかった。さらに特許文献１７においては水存在下での加熱処理により多糖類とポリカルボン酸類との架橋反応を行っており、特許文献１８においてはアルコールなどの親水性揮発性有機溶媒存在下で加熱による架橋反応を行っている。このように加熱において液体溶媒を用いる場合、多量の熱量が必要とされる。また使用したアルコール等の溶媒の回収にも熱量が必要なため不経済である。
特許文献１９記載の架橋物は、二硫化炭素やジオキサン、ジオキシエタンなどの環境や人体に影響を与える溶媒を多量に用いるため実用化するには問題が多く、得られた吸水材の安全性にも疑問が残る。
Regarding patent documents 17 and 18, the performance of the obtained water-absorbing material cannot be said to be so high that it cannot be put into practical use. Further, in Patent Document 17, a crosslinking reaction between a polysaccharide and a polycarboxylic acid is carried out by heat treatment in the presence of water. In Patent Document 18, a crosslinking reaction by heating in the presence of a hydrophilic volatile organic solvent such as alcohol. It is carried out. Thus, when a liquid solvent is used in heating, a large amount of heat is required. In addition, it is uneconomical because the amount of heat is also required to recover the solvent such as alcohol used.
The cross-linked product described in Patent Document 19 has many problems for practical use because it uses a large amount of solvents that affect the environment and the human body, such as carbon disulfide, dioxane, and dioxyethane, and also the safety of the resulting water-absorbing material The question remains.
本発明の目的は、生分解性を有し、安全性が高く、優れた吸水性能を有し、且つ揮発性親水性溶媒を必要としない製造方法により、容易に製造することが可能な吸水材、該吸水材を製造する方法、およびそれを含む物品を提供することにある。 An object of the present invention is to provide a water-absorbing material that is biodegradable, highly safe, has excellent water-absorbing performance, and can be easily manufactured by a manufacturing method that does not require a volatile hydrophilic solvent. Another object of the present invention is to provide a method for producing the water-absorbing material, and an article including the method.
本発明者らは、上記課題を解決するため鋭意検討した結果、ポリカルボン酸又はその塩で架橋されたカルボキシアルキル化ガラクトマンナンを主成分として含む吸水材が優れた吸水性能と安全性、生分解性を有することを見出し本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have obtained excellent water absorption performance, safety, and biodegradation of a water absorbing material containing as a main component a carboxyalkylated galactomannan crosslinked with a polycarboxylic acid or a salt thereof. As a result, the present invention has been completed.
すなわち、本発明は第一に、ポリカルボン酸又はその塩で架橋されたカルボキシアルキル化ガラクトマンナンを主成分として含み、０．９質量％塩化ナトリウム水溶液に対する吸水量が自重の２０倍以上であり、該水溶液に対する保水量が自重の１５倍以上であることを特徴とする吸水材を提供する。
ここで「主成分」とは、全固形分質量に対する、ポリカルボン酸又はその塩で架橋されたカルボキシアルキル化ガラクトマンナンの固形分質量が５０％以上であることをいう。
That is, the present invention firstly includes a carboxyalkylated galactomannan crosslinked with a polycarboxylic acid or a salt thereof as a main component, and has a water absorption of 20 times or more of its own weight with respect to a 0.9 mass% sodium chloride aqueous solution. Provided is a water-absorbing material characterized in that the amount of water retained in the aqueous solution is 15 times or more of its own weight.
Here, the “main component” means that the solid content mass of the carboxyalkylated galactomannan crosslinked with a polycarboxylic acid or a salt thereof is 50% or more with respect to the total solid content mass.
好ましくは、カルボキシアルキル化ガラクトマンナンは、カルボキシメチルヒドロキシプロピル化グアガムである。 Preferably, the carboxyalkylated galactomannan is carboxymethylhydroxypropylated guar gum.
また好ましくは、ポリカルボン酸は、酒石酸、クエン酸、α−ケトグルタル酸、リンゴ酸、フマル酸、コハク酸、マレイン酸、イタコン酸、セバシン酸、１，２，３，４−ブタンテトラカルボン酸、アスパラギン酸、グルタミン酸又はこれらのポリマー、キサンタンガム、カラヤガム、アルギン酸又はこれらの部分分解物から選ばれる１種以上である。 Also preferably, the polycarboxylic acid is tartaric acid, citric acid, α-ketoglutaric acid, malic acid, fumaric acid, succinic acid, maleic acid, itaconic acid, sebacic acid, 1,2,3,4-butanetetracarboxylic acid, It is at least one selected from aspartic acid, glutamic acid or a polymer thereof, xanthan gum, karaya gum, alginic acid or a partial decomposition product thereof.
また本発明は第二に、
ａ）ポリカルボン酸又はその塩、および、固形分濃度が水とカルボキシアルキル化ガラクトマンナンの合計質量に対して１質量％以上１５質量％以下であるカルボキシアルキル化ガラクトマンナンを、水に混合して溶解及び水和させる工程、
ｂ）工程ａ）で得られた水和物を乾燥する工程、および、
ｃ）工程ｂ）で得られた乾燥物を１２０℃以上１８０℃以下で加熱処理する工程、
を含む吸水材の製造方法を提供する。
The present invention secondly,
a) Mixing a polycarboxylic acid or a salt thereof and a carboxyalkylated galactomannan having a solid concentration of 1% by mass or more and 15% by mass or less with respect to the total mass of water and the carboxyalkylated galactomannan in water. Dissolving and hydrating,
b) drying the hydrate obtained in step a), and
c) a step of heat-treating the dried product obtained in step b) at 120 ° C. or higher and 180 ° C. or lower;
The manufacturing method of the water absorbing material containing is provided.
さらに本発明は第三に、本発明の吸水材を含んでなることを特徴とする吸水性物品を提供する。 Thirdly, the present invention provides a water-absorbing article comprising the water-absorbing material of the present invention.
［用語の定義］
（吸水量）
本発明における吸水量とは、以下のティーバッグ法にて０．９質量％塩化ナトリウム水溶液を用いて行うものである。すなわち、２５５メッシュのナイロン製ティーバッグに、粒径が２００〜１０００μｍの吸水材１ｇを入れ、１Ｌの０．９質量％塩化ナトリウム水溶液に吸水材を含むティーバッグを６０分間浸して引き上げ、１０分間吊るして自重による水切りを行った後、ティーバッグと吸水材の質量合計を測定する。また空のティーバッグを同様に６０分間生理食塩水に浸漬後水切りし、その重量をブランクとする。吸水後のティーバッグと吸水材の質量合計から膨潤前の吸水材の重量１ｇとブランクの重量を減じ、その値を膨潤前の吸水材の重量１ｇで除した値を吸水量（ｇ／ｇ樹脂）とする。
[Definition of terms]
(Water absorption)
The water absorption amount in the present invention is carried out using a 0.9% by mass sodium chloride aqueous solution by the following tea bag method. That is, 1 g of a water-absorbing material having a particle diameter of 200 to 1000 μm is put in a 255 mesh nylon tea bag, and the tea bag containing the water-absorbing material is immersed in 1 L of 0.9 mass% sodium chloride aqueous solution for 60 minutes and pulled up for 10 minutes. After hanging and draining by its own weight, the total mass of the tea bag and the water absorbing material is measured. Similarly, the empty tea bag is dipped in physiological saline for 60 minutes and then drained, and the weight is used as a blank. The amount of water absorption (g / g resin) is obtained by subtracting 1 g of the weight of the water absorbent material before swelling and the weight of the blank from the total mass of the tea bag and the water absorbent material after water absorption and dividing the value by 1 g of the weight of the water absorbent material before swelling. ).
（保水量）
本発明における保水量とは、以下の方法で測定するものである。すなわち、上記吸水量の測定において６０分間吸水後に１０分間自重で水切りして秤量したティーバッグ（膨潤した吸水材を含む）をさらに１５０×ｇにて９０秒間遠心分離し、余分な水分を完全に除去した後、その重量を測定する。空のティーバッグを同様に６０分間浸漬後、１０分間自重水切り、遠心分離したティーバッグの重量をブランクとする。遠心分離した吸水材とティーバッグの質量合計から膨潤前の吸水材の重量１ｇとブランクの重量を減じた値を、膨潤前の吸水材の重量１ｇで除した値を保水量（ｇ／ｇ樹脂）とする。
(Water retention amount)
The water retention amount in the present invention is measured by the following method. That is, in the measurement of the amount of water absorption, the tea bag (including the swollen water absorption material) weighed by weighing for 10 minutes after water absorption for 60 minutes was further centrifuged at 150 × g for 90 seconds to completely remove excess water. After removal, the weight is measured. An empty tea bag is dipped in the same manner for 60 minutes, drained by its own weight for 10 minutes, and the weight of the centrifuged tea bag is defined as a blank. The value obtained by subtracting 1 g of the weight of the water-absorbing material before swelling and the weight of the blank from the total mass of the centrifuged water-absorbing material and tea bag and dividing the value by 1 g of the weight of the water-absorbing material before swelling is the water retention amount (g / g resin ).
（吸水速度）
本発明における吸水速度とは、以下の方法で測定するものである。すなわち、１００ｍｌのビーカーに０．９質量％塩化ナトリム水溶液５０ｇと撹拌子とを入れ、マグネチックスターラーにて６００ｒｐｍの速度で撹拌しながら、この中に粒径が２００μｍ〜１０００μｍの吸水材２ｇを投入する。吸水膨潤作用により内容物の流動性が急速に低下し、含水ゲル状となり、撹拌中心の水流渦が消えるという現象が観測される。吸水材の投入時から水流渦が消えるまでの所要時間（秒）を吸水速度とする。
(Water absorption speed)
The water absorption rate in the present invention is measured by the following method. That is, 50 g of 0.9 mass% sodium chloride aqueous solution and a stirrer are placed in a 100 ml beaker, and 2 g of a water absorbing material having a particle diameter of 200 μm to 1000 μm is added to this while stirring at a speed of 600 rpm with a magnetic stirrer. To do. A phenomenon is observed in which the fluidity of the contents rapidly decreases due to the water-absorbing swelling action, becomes a hydrous gel, and the water vortex at the center of stirring disappears. The required time (seconds) from when the water-absorbing material is introduced until the water vortex disappears is taken as the water absorption speed.
本発明によれば、単純で容易な製造方法により、吸水性能に優れ、実用的なゲル強度を有し、且つ安全性の高い吸水材が製造できる。かかる吸水材は、生理用品や紙おむつ等の衛生材料分野をはじめとして、動物用屎尿処理材、飼料添加剤、農園芸用分野、鮮度保持等の食品分野、結露防止や保冷材等の産業分野等、吸水や保水を必要とする種々の用途に好適に利用できる。 According to the present invention, a simple and easy production method can produce a water-absorbing material having excellent water absorption performance, practical gel strength, and high safety. Such water absorbent materials include sanitary materials such as sanitary products and disposable diapers, animal sewage treatment materials, feed additives, agricultural and horticultural fields, food fields such as freshness preservation, industrial fields such as anti-condensation and cold insulation materials, etc. It can be suitably used for various applications that require water absorption or water retention.
以下に本発明を詳細に説明する。
工程ａ）は、ポリカルボン酸又はその塩およびカルボキシアルキル化ガラクトマンナンを、水に混合して溶解及び水和させる工程である。カルボキシルアルキル化ガラクトマンナンとポリカルボン酸又はその塩は、同時に水に添加混合しても良いし、片方を先に水に添加して均一な溶液又は水和物を得た後で他方を加えて混合してもよい。また、ポリカルボン酸又はその塩およびカルボキシアルキル化ガラクトマンナンに水を添加してもよく、
かかる混合物を作成する順序は特に限定しない。
The present invention is described in detail below.
Step a) is a step in which polycarboxylic acid or a salt thereof and carboxyalkylated galactomannan are mixed in water and dissolved and hydrated. Carboxyl alkylated galactomannan and polycarboxylic acid or salt thereof may be added to water and mixed at the same time, or one of them may be added to water first to obtain a uniform solution or hydrate and then the other. You may mix. Further, water may be added to the polycarboxylic acid or a salt thereof and the carboxyalkylated galactomannan,
The order of preparing such a mixture is not particularly limited.
本発明において用いられるカルボキシアルキル化ガラクトマンナンはガラクトマンナンを化学的に修飾した多糖類である。ガラクトマンナンは、Ｄ−マンノース主鎖にＤ−ガラクトース側鎖を持つ多糖類の総称で、グアガム、ローカストビーンガム、タラガム、アカシアガム等が知られている。例えば、グアガムの製造方法としては、グア豆の種子から胚乳部分（スプリット）を取り出した後に、湿潤状態で加熱し、ガラクトマンナンをα化（糊化）させ、スプリットをすり潰し、熱風乾燥したあと、破砕する方法などが知られている。このようにして得たガラクトマンナンを化学的にカルボキシアルキル化することにより本発明に用いるカルボキシアルキル化ガラクトマンナンを得ることができる。 The carboxyalkylated galactomannan used in the present invention is a polysaccharide obtained by chemically modifying galactomannan. Galactomannan is a general term for polysaccharides having a D-galactose side chain in the D-mannose main chain, and guar gum, locust bean gum, tara gum, acacia gum and the like are known. For example, as a method for producing guar gum, after removing the endosperm part (split) from the seed of guar bean, heating it in a wet state, alphalyzing (gelatinizing) galactomannan, grinding the split, and drying with hot air, A method of crushing is known. A carboxyalkylated galactomannan used in the present invention can be obtained by chemically carboxyalkylating the galactomannan thus obtained.
ここで、カルボキシアルキル化は、例えばカルボキシメチル化の場合、メタノール中にモノクロル酢酸を加え、さらに水酸化ナトリウムを徐々に加えて強アルカリ性とする。これに修飾したい多糖類粉末を分散させ、３０〜５０℃で２０〜６０時間反応させる。次いで、氷酢酸にてｐＨ６．５に中和し、アルコールによる沈殿・洗浄などを経て精製すればよい。
「カルボキシアルキルメチルヒドロキシプロピル化」された多糖類とは、カルボキシメチル基とヒドロキシプロピル基が多糖類分子中の別々の水酸基に対して修飾されたもののことをいう。
また、構成単位分子であるガラクトースまたはマンノースには修飾可能な水酸基がそれぞれ３箇所あり、これら全てが修飾された場合が置換度３．０である。本発明のカルボキシアルキル化ガラクトマンナンにおける置換度は０．０３〜１．５が好ましく、０．０５〜１．０がさらに好ましい。置換度が０．０３以下では吸水速度が不充分であり、置換度が１．５以上であれば製造コストが高い上、多糖類が疎水性を帯びるため吸水性能が低下する。
Here, carboxyalkylation, for example, in the case of carboxymethylation, monochloroacetic acid is added to methanol and sodium hydroxide is gradually added to make it strongly alkaline. The polysaccharide powder to be modified is dispersed in this and reacted at 30-50 ° C. for 20-60 hours. Next, it may be neutralized with glacial acetic acid to pH 6.5 and purified through precipitation and washing with alcohol.
A “carboxyalkylmethylhydroxypropylated” polysaccharide refers to one in which the carboxymethyl and hydroxypropyl groups are modified to separate hydroxyl groups in the polysaccharide molecule.
In addition, the structural unit molecule galactose or mannose has three modifiable hydroxyl groups, and the degree of substitution is 3.0 when all of these are modified. The degree of substitution in the carboxyalkylated galactomannan of the present invention is preferably 0.03 to 1.5, more preferably 0.05 to 1.0. If the degree of substitution is 0.03 or less, the water absorption rate is insufficient. If the degree of substitution is 1.5 or more, the production cost is high, and the polysaccharide is hydrophobic, so that the water absorption performance is lowered.
本発明に用いることが可能なカルボキシアルキル化ガラクトマンナンとしては、例えば、カルボキシメチル化グアガム、カルボキシメチルヒドロキシプロピル化グアガム、カルボキシメチル化ローカストビーンガム、カルボキシエチルグアガム、カルボキシエチルヒドロキシプロピルグアガムなどが挙げられるが、好ましくは吸水能の観点からカルボキシメチルヒドロキシプロピル化グアガムである。カルボキシメチルヒドロキシプロピル化グアガムは市販のものでもよく、例えばローディア社のジャガー８６００を使用すればよい。 Examples of carboxyalkylated galactomannans that can be used in the present invention include carboxymethylated guar gum, carboxymethylhydroxypropylated guar gum, carboxymethylated locust bean gum, carboxyethyl guar gum, carboxyethylhydroxypropyl guar gum, and the like. However, carboxymethylhydroxypropylated guar gum is preferable from the viewpoint of water absorption ability. Carboxymethylhydroxypropylated guar gum may be commercially available, for example, Rhodia Jaguar 8600 may be used.
カルボキシアルキル化ガラクトマンナンの固形分濃度（カルボキシアルキル化ガラクトマンナンの質量を水とカルボキシアルキル化ガラクトマンナンの質量合計で除し百分率にしたもの）は１〜１５質量％が好ましく、さらに好ましくは２〜１０質量％である。１質量％未満では製造効率が低いし、１５質量％を超えると均一な水和物を作成するのが困難である。 The solid content concentration of carboxyalkylated galactomannan (percentage obtained by dividing the mass of carboxyalkylated galactomannan by the total mass of water and carboxyalkylated galactomannan) is preferably 1 to 15% by mass, more preferably 2 to 2% by mass. 10% by mass. If it is less than 1% by mass, the production efficiency is low, and if it exceeds 15% by mass, it is difficult to produce a uniform hydrate.
本発明で用いられるカルボキシアルキル化ガラクトマンナンの分子量は、１万以上が好ましく、より好ましくは５万以上である。分子量が１万未満の場合は架橋しても水に溶解してしまい吸水材にならないので不適当である。 The molecular weight of the carboxyalkylated galactomannan used in the present invention is preferably 10,000 or more, more preferably 50,000 or more. If the molecular weight is less than 10,000, it is not suitable because even if it is crosslinked, it dissolves in water and does not become a water-absorbing material.
本発明においては、必要に応じて、グアガム、ローカストビーンガム、タラガム、カシアガム、カラギーナン、キサンタンガム、寒天、ペクチン、タラガントガム、プルラン、ジェランガム、タマリンドシードガム、カードラン、アラビアガム、グルコマンナン、デンプン、セルロース、キチン、キトサン、ヒアルロン酸又はこれらの誘導体などのカルボキシアルキル化ガラクトマンナン以外の天然多糖類を混合してもよい。誘導体としてはカルボキシル基、ヒドロキシアルキル基、硫酸基、リン酸基などを導入したものが挙げられる。これらを混合する割合としては、多糖類の組み合わせ等にもよるが、カルボキシアルキル化ガラクトマンナン１００質量部に対し１〜４０質量部の範囲内、より好ましくは５〜２０質量部の範囲内とすればよい。 In the present invention, as needed, guar gum, locust bean gum, tara gum, cassia gum, carrageenan, xanthan gum, agar, pectin, tarragant gum, pullulan, gellan gum, tamarind seed gum, curdlan, gum arabic, glucomannan, starch, cellulose , Natural polysaccharides other than carboxyalkylated galactomannans such as chitin, chitosan, hyaluronic acid or derivatives thereof may be mixed. Derivatives include those introduced with a carboxyl group, a hydroxyalkyl group, a sulfate group, a phosphate group, and the like. The ratio of mixing them depends on the combination of the polysaccharides, but is within the range of 1 to 40 parts by mass, more preferably within the range of 5 to 20 parts by mass with respect to 100 parts by mass of the carboxyalkylated galactomannan. That's fine.
本発明において用いるポリカルボン酸又はその塩は、分子内に２つ以上のカルボキシル基を有し、且つ生分解性を有し、加熱処理によりカルボキシアルキル化ガラクトマンナンを架橋できるものであれば特に限定するものではない。すなわち本発明においてポリカルボン酸又はその塩は、架橋剤として作用する。 The polycarboxylic acid or salt thereof used in the present invention is particularly limited as long as it has two or more carboxyl groups in the molecule, is biodegradable, and can crosslink the carboxyalkylated galactomannan by heat treatment. Not what you want. That is, in this invention, polycarboxylic acid or its salt acts as a crosslinking agent.
ポリカルボン酸としては、例えば酒石酸、クエン酸、α−ケトグルタル酸、リンゴ酸、フマル酸、コハク酸、マレイン酸、イタコン酸、セバシン酸、１，２，３，４−ブタンテトラカルボン酸（BTC）などの低分子ポリカルボン酸類、アスパラギン酸、グルタミン酸などのアミノ酸類、又はこれらのポリマー、キサンタンガム、カラヤガム、アルギン酸などの多糖類、又はこれらの部分分解物などを挙げることができるが、好ましくは安価で安全性の高いリンゴ酸、クエン酸、コハク酸、BTC、カラヤガム又はその部分分解物である。 Examples of the polycarboxylic acid include tartaric acid, citric acid, α-ketoglutaric acid, malic acid, fumaric acid, succinic acid, maleic acid, itaconic acid, sebacic acid, 1,2,3,4-butanetetracarboxylic acid (BTC). Low molecular polycarboxylic acids such as amino acids such as aspartic acid and glutamic acid, or polymers thereof, polysaccharides such as xanthan gum, karaya gum, and alginic acid, or partial decomposition products thereof. It is highly safe malic acid, citric acid, succinic acid, BTC, karaya gum or a partially decomposed product thereof.
ポリカルボン酸又はその塩の添加量としては、これらが低分子化合物の場合、カルボキシアルキル化ガラクトマンナン質量１ｋｇ当たり概ね０．５〜１００ミルモルが好ましく、さらに好ましくは５〜５０ミリモルである。
ポリカルボン酸又はその塩が多糖類やポリアミノ酸のような高分子化合物の場合、分子中にいくつのカルボキシル基が存在するが、その高分子とカルボキシアルキル化ガラクトマンナンとの立体化学的な反応性によって得られる吸水材の性能が大きく異なるため一概に添加量を限定できないが、カルボキシアルキル化ガラクトマンナン質量１ｋｇ当たり１〜５０質量％が好ましく、さらに好ましくは５〜３０質量％である。
ここで分子量が１万以上のものを高分子、１万未満のものを低分子という。
When these are low molecular weight compounds, the addition amount of the polycarboxylic acid or a salt thereof is preferably about 0.5 to 100 millimoles, more preferably 5 to 50 millimoles, per 1 kg of the carboxyalkylated galactomannan mass.
When the polycarboxylic acid or its salt is a polymer compound such as a polysaccharide or polyamino acid, there are several carboxyl groups in the molecule, but the stereochemical reactivity between the polymer and the carboxyalkylated galactomannan. However, the amount of the water-absorbing material obtained varies depending on the weight of the carboxyalkylated galactomannan, preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
Here, those having a molecular weight of 10,000 or more are referred to as polymers, and those having a molecular weight of less than 10,000 are referred to as low molecules.
また、カルボキシアルキル化ガラクトマンナンの水酸基とポリカルボン酸又はその塩のカルボキシル基とのエステル交換反応を促進するため、リン酸イオンや水酸化ナトリウムなどの触媒をこれらの混合水和物に加えても良い。触媒の添加量はカルボキシアルキル化ガラクトマンナン質量１ｋｇ当たり０．０５〜２ミリモルが好ましく、０．２〜１ミリモルがさらに好ましい。 Further, in order to promote the transesterification reaction between the hydroxyl group of carboxyalkylated galactomannan and the carboxyl group of polycarboxylic acid or a salt thereof, a catalyst such as phosphate ion or sodium hydroxide may be added to these mixed hydrates. good. The addition amount of the catalyst is preferably 0.05 to 2 mmol, more preferably 0.2 to 1 mmol, per 1 kg of the carboxyalkylated galactomannan.
工程ａ）における攪拌混合装置としてはカルボキシアルキル化ガラクトマンナン粉末をママコなく水に水和させることが可能な攪拌能力を有する装置であれば特に限定されるものではなく、下羽根式ミキサー、上羽根式ミキサー、二軸ニーダーなど一般的な攪拌装置が使用可能である。 The stirring / mixing device in step a) is not particularly limited as long as it is a device having a stirring ability capable of hydrating carboxyalkylated galactomannan powder in water without mamako. Lower blade mixer, upper blade A general stirring apparatus such as a mixer or a twin-screw kneader can be used.
カルボキシアルキル化ガラクトマンナンを水に水和させるときの水温は特に限定されるのものではなく、５〜８０℃が好ましいが、より好ましくは水和が早い１０〜６０℃である。 The water temperature when the carboxyalkylated galactomannan is hydrated with water is not particularly limited, and is preferably 5 to 80 ° C., more preferably 10 to 60 ° C., which allows quick hydration.
水和させる時間は水和温度にもよるが概ね３０分〜５時間であり、好ましくは１時間〜３時間である。水和時間が短いと分子鎖が充分に水中で拡散しないため、吸水性能が低下する。 Although depending on the hydration temperature, the hydration time is generally 30 minutes to 5 hours, preferably 1 hour to 3 hours. When the hydration time is short, the molecular chain does not diffuse sufficiently in water, and the water absorption performance is reduced.
また水和物のｐＨはｐＨ４．０〜９．０が好ましく、ｐＨ５．０〜８．０がより好ましい。ｐＨ４．０未満又はｐＨ９．０を超える場合では、吸水材として吸水性物品に適用して使用した場合、装着者の皮膚に対する悪影響が懸念され、かぶれや紅斑の原因となるため好ましくない。このためｐＨがこの範囲外にある場合は、適宜水酸化ナトリウムや塩酸などを添加してｐＨを調整すればよい。なおｐＨ調整は本水和物の状態で行っても良いが、後に表面架橋処理を行う場合は表面架橋処理時でもよい。 The pH of the hydrate is preferably from 4.0 to 9.0, more preferably from 5.0 to 8.0. When the pH is less than 4.0 or exceeds pH 9.0, when it is used as a water-absorbing material applied to a water-absorbent article, there is a concern about adverse effects on the wearer's skin, which may cause rash and erythema. Therefore, when the pH is outside this range, sodium hydroxide or hydrochloric acid may be added as appropriate to adjust the pH. In addition, although pH adjustment may be performed in the state of this hydrate, when performing surface crosslinking treatment later, it may be at the time of surface crosslinking treatment.
本発明の方法における工程ｂ）は、工程ａ）で得られた水和物を乾燥する工程である。乾燥は、水分含量が約５質量％以下となるまで行なう。乾燥する方法としては、吸水性能（吸水量、保水量、吸水速度など）を低下させるような方法でなければいかなる乾燥方法でも限定されず、例えば常温乾燥、加熱乾燥、凍結乾燥、減圧乾燥、真空乾燥が挙げられるが、好ましくは加熱乾燥である。加熱乾燥では装置内を風が循環しないものでもよいが、速やかな乾燥を行うためには発生させた熱風が装置内を循環する熱風循環式乾燥機を用いるのが好ましい。また技術的に可能な場合にはスプレードライなどの方法でも乾燥してもよい。 Step b) in the method of the present invention is a step of drying the hydrate obtained in step a). Drying is performed until the water content is about 5% by mass or less. The drying method is not limited to any drying method as long as the water absorption performance (water absorption amount, water retention amount, water absorption speed, etc.) is not reduced. For example, room temperature drying, heat drying, freeze drying, vacuum drying, vacuum Although drying is mentioned, Heat drying is preferable. In heat drying, the air may not be circulated in the apparatus, but in order to perform quick drying, it is preferable to use a hot air circulation dryer in which the generated hot air circulates in the apparatus. Further, if technically possible, it may be dried by a method such as spray drying.
該混合水和物の乾燥温度は１１０℃以下が好ましい。１１０℃より高温で乾燥するとポリカルボン酸内のカルボキシル基がカルボキシアルキル化ガラクトマンナン分子内の水酸基とエステル交換（架橋）反応せずに、先に水分子と反応してしまい、工程ｃ）における加熱処理を行っても架橋が不能又は不充分となり満足な吸水材を得ることができない。
乾燥時間は乾燥機の温度、仕様、風量などによって異なるが乾燥物の水分含量が５質量％以下になるように適宜選択すればよい。
The drying temperature of the mixed hydrate is preferably 110 ° C. or lower. When drying at a temperature higher than 110 ° C., the carboxyl group in the polycarboxylic acid does not undergo transesterification (crosslinking) reaction with the hydroxyl group in the carboxyalkylated galactomannan molecule, but reacts with the water molecule first, and heating in step c) Even if the treatment is performed, crosslinking is impossible or insufficient, and a satisfactory water-absorbing material cannot be obtained.
The drying time varies depending on the temperature, specifications, air volume, etc. of the dryer, but may be appropriately selected so that the moisture content of the dried product is 5% by mass or less.
本発明における工程ｃ）は、工程ｂ）で得られた乾燥物を１２０℃以上１８０℃以下で加熱処理する工程である。かかる加熱処理により、カルボキシアルキル化ガラクトマンナン分子内の水酸基とポリカルボン酸内のカルボキシル基がエステル交換反応を行い、エステル結合が生じ、これが架橋点となり水に不溶な吸水材が得られる。 Step c) in the present invention is a step in which the dried product obtained in step b) is subjected to a heat treatment at 120 ° C. or higher and 180 ° C. or lower. By such heat treatment, the hydroxyl group in the carboxyalkylated galactomannan molecule and the carboxyl group in the polycarboxylic acid undergo an ester exchange reaction to form an ester bond, which becomes a crosslinking point, and a water-insoluble material that is insoluble in water is obtained.
この時の加熱処理温度は加熱処理時間にもよるが、１２０℃以上１８０℃以下が好ましく、さらに好ましくは１３０℃以上１６０℃以下である。１２０℃未満では充分にエステル交換反応させるためには長時間を要するし、１８０℃を超えるとカルボキシアルキル化ガラクトマンナンそのものが熱により分解され低分子化されやすいため、吸水能の低下を招くだけでなく、黄色〜褐色の着色が生じ外見が悪くなり好ましくない。 The heat treatment temperature at this time is preferably from 120 ° C. to 180 ° C., more preferably from 130 ° C. to 160 ° C., although it depends on the heat treatment time. If it is less than 120 ° C, it takes a long time to sufficiently transesterify, and if it exceeds 180 ° C, the carboxyalkylated galactomannan itself is easily decomposed by heat and reduced in molecular weight. And yellow-brown coloration occurs, and the appearance is unfavorable.
加熱処理時間は加熱処理温度にもよるが、概ね１０秒〜１２０分である。加熱温度が低い場合は反応完了までに長時間を要するし、加熱温度が高い場合には短くしないと熱分解が進行してしまうので好ましくない。なお、反応条件は予め加熱処理温度と処理時間について吸水量と吸水後ゲル状態を指標にした予備検討を行い、必要最小限の条件を見出しておく必要がある。例えば１５０℃で加熱処理を行う場合、加熱時間は２０分でよいが、１２０℃で行う場合は６０分以上が好ましい。 Although the heat treatment time depends on the heat treatment temperature, it is generally from 10 seconds to 120 minutes. When the heating temperature is low, it takes a long time to complete the reaction, and when the heating temperature is high, thermal decomposition proceeds unless it is shortened. As for the reaction conditions, it is necessary to carry out preliminary studies on the heat treatment temperature and treatment time in advance using the water absorption amount and the gel state after water absorption as indices, and find the minimum necessary conditions. For example, when heat treatment is performed at 150 ° C., the heating time may be 20 minutes, but when performed at 120 ° C., 60 minutes or more is preferable.
加熱装置は乾燥物が均一に加熱されるような装置であれば特に限定せず、一定温度で一定処理時間加熱できるものであれば良い。例えば熱風循環式乾燥機、加圧加熱プレス機などが挙げられる。 The heating device is not particularly limited as long as the dried product is uniformly heated, and any device capable of heating at a constant temperature for a certain treatment time may be used. For example, a hot air circulation type dryer, a pressure heating press machine, etc. are mentioned.
このようにして得られた加熱処理物を必要に応じて種々の形態に加工して使用することが可能である。例えば工程ａ）で得られる混合水和物を薄く広げて乾燥・加熱処理した場合にはフィルム状やシート状の吸水材が得られるのでこれをそのまま用いても良いし、さらに繊維状にカットして繊維状吸水材として使用しても良い。また従来品のようにこれを裁断機や破砕機により粒径制御しながら破砕し、粉末状或いは鱗片状の吸水材として使用することも可能である。該混合水和物を厚い状態で乾燥・加熱処理した場合は、乾燥物を既存の破砕機を用いて破砕すれば粉末状の吸水材を得ることができる。 The heat-treated product thus obtained can be used after being processed into various forms as required. For example, when the mixed hydrate obtained in step a) is thinly spread and dried and heat-treated, a film-like or sheet-like water-absorbing material can be obtained, so that it can be used as it is, or further cut into fibers. It may be used as a fibrous water absorbing material. Further, as in the conventional product, it can be crushed while controlling the particle size with a cutter or a crusher, and used as a powdery or scaly water-absorbing material. When the mixed hydrate is dried and heat-treated in a thick state, a powdery water-absorbing material can be obtained by crushing the dried product using an existing crusher.
またさらに必要に応じて工程ｃ）により得られる加熱処理物を表面架橋剤により処理することも可能である。
ここで用いられる表面架橋剤としては、前述のａ）工程で記載したポリカルボン酸又はその塩の他に、カルボキシアルキル化ガラクトマンナンの有する官能基と反応しうる官能基を２個以上有する化合物であり、親水性、より好ましくは水溶性の化合物が挙げられる。このようなものの具体例としては、グルタルアルデヒド、グリオキサール等の如き多価アルデヒド類；エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等の如き多価グリシジル化合物類；二塩化エタン、テトラメチレンクロロブロマイド、ジブロモプロパン、ジブロモブタン等の如き多価ハロゲン化物類、エピクロルヒドリン、α−メチルクロルヒドリン等の如きハロエポキシ化合物類、チタンイオン、ジルコニウムイオン、アルミニウムイオン、イットリウムイン、セリウムイオン、カルシウムイオン、バリウムイオン、ホウ酸イオンなどの多価金属イオン類を例示することができる。
Furthermore, if necessary, the heat-treated product obtained in step c) can be treated with a surface crosslinking agent.
The surface cross-linking agent used here is a compound having two or more functional groups capable of reacting with the functional group possessed by the carboxyalkylated galactomannan in addition to the polycarboxylic acid or salt thereof described in step a) above. And hydrophilic, more preferably water-soluble compounds. Specific examples of such are polyvalent aldehydes such as glutaraldehyde, glyoxal, etc .; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, Polyvalent glycidyl compounds such as sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Haloepoxy compounds such as halides, epichlorohydrin, α-methylchlorohydrin, etc. Titanium ions, zirconium ions, aluminum ions, yttrium-in, cerium ions, calcium ions, barium ions, can be exemplified polyvalent metal ions such as borate ions.
固形物に対する表面架橋剤の使用量は、固形物および表面架橋剤の組み合わせ等にもよるが、多価アルデヒドやハロエポキシ化合物、ポリカルボン酸又はその塩類などの有機化合物系架橋剤の場合は乾燥状態の吸水材１００質量％に対して０．０１〜１０質量％の範囲内、より好ましくは０．０５〜５質量％の範囲内とすればよい。上記の範囲内で表面架橋剤を用いることにより、尿や汗、経血等の体液に対する吸水特性をさらに一層向上させることができる。 The amount of surface cross-linking agent used for solids depends on the combination of solids and surface cross-linking agents, but in the case of organic compound cross-linking agents such as polyhydric aldehydes, haloepoxy compounds, polycarboxylic acids or their salts, etc. What is necessary is just to set it in the range of 0.01-10 mass% with respect to 100 mass% of water absorbing material of this, More preferably, it may exist in the range of 0.05-5 mass%. By using the surface cross-linking agent within the above range, the water absorption property for body fluids such as urine, sweat and menstrual blood can be further improved.
有機化合物系表面架橋剤の使用量が０．０１質量％未満では、吸水材としての表面近傍の架橋密度をほとんど高めることができない。また、有機化合物系表面架橋剤の使用量が１０質量％より多い場合は、該表面架橋剤が過剰となり、不経済である。 If the usage-amount of an organic compound type surface crosslinking agent is less than 0.01 mass%, the crosslinking density of the surface vicinity as a water absorbing material can hardly be raised. Moreover, when there are more usage-amounts of an organic compound type surface crosslinking agent than 10 mass%, this surface crosslinking agent will become excess and it is uneconomical.
固形物を表面架橋剤により処理する際の処理方法は、特に限定されない。例えば、工程ｃ）において加熱処理物を回収後に加工した粉末状、鱗片状又は繊維状の場合、回収物と表面架橋剤とを無溶媒で混合する方法、シクロヘキサンやペンタン等の疎水性揮発性溶媒に回収物を分散させた後、表面架橋剤を混合する方法、親水性揮発性溶媒又はその含水液に表面架橋剤を溶解又は分散させた後、該溶液もしくは分散液を回収物に噴霧あるいは滴下して混合する方法等が挙げられる。また加熱処理物がフィルム状又はシート状の場合、該溶液又は分散液をこれらに噴霧、塗布或いはこれらを該溶液又は分散液中を浴する方法などが挙げられる。 The processing method at the time of processing a solid substance with a surface crosslinking agent is not specifically limited. For example, in the case of powder, scale or fiber processed after recovering the heat-treated product in step c), a method of mixing the recovered product and the surface cross-linking agent without solvent, a hydrophobic volatile solvent such as cyclohexane or pentane After the recovered material is dispersed in the surface, a method of mixing the surface cross-linking agent, after dissolving or dispersing the surface cross-linking agent in the hydrophilic volatile solvent or water-containing liquid thereof, the solution or dispersion is sprayed or dropped onto the recovered material. And a method of mixing them. In addition, when the heat-treated product is in the form of a film or a sheet, a method of spraying, applying, or bathing the solution or dispersion in the solution or dispersion may be used.
ここで使用する親水性揮発性有機溶媒は特に制限されないが、例えばメチルアルコール、エチルアルコール、ｎ−プロピルアルコール、ｉｓｏ−プロピルアルコール、ｎ−ブチルアルコール、ｉｓｏ−ブチルアルコール、ｔ−ブチルアルコール等の低級アルコール類、アセトン、メチルエチルケトン等のケトン類、ジオキサン、テトラヒドロフラン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等のアミド類、ジメチルスルホキシド等のスルホキシド類等を挙げることができるが、コストや安全性の面からメタノール、エタノール、ｉｓｏ−プロピルアルコールなどの低級アルコール類が好ましい。 The hydrophilic volatile organic solvent used here is not particularly limited, but may be a lower level such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, t-butyl alcohol and the like. Examples include alcohols, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, amides such as N, N-dimethylformamide, and sulfoxides such as dimethyl sulfoxide. To lower alcohols such as methanol, ethanol and iso-propyl alcohol.
本発明の吸水材には、上記の製造方法により得られる吸水材に必要に応じて、界面活性剤、消臭剤、香料、各種の無機粉末、顔料、染料、抗菌剤、発泡剤、親水性短繊維、可塑剤、粘着剤、肥料、酸化剤、還元剤、水、塩類等を添加してもよい。これにより、種々の機能が付与された吸水性物品が得られる。 In the water-absorbing material of the present invention, a surfactant, a deodorant, a fragrance, various inorganic powders, a pigment, a dye, an antibacterial agent, a foaming agent, a hydrophilic property, if necessary, in the water-absorbing material obtained by the above production method Short fibers, plasticizers, adhesives, fertilizers, oxidizing agents, reducing agents, water, salts and the like may be added. Thereby, the water absorptive article provided with various functions is obtained.
ここで用いられる無機粉末としては、水性液体等に対して不活性な物質、例えば、各種の無機化合物の微粒子、粘土鉱物の微粒子等が挙げられる。該無機粉体は、水に対して適度な親和性を有し、かつ、水に不溶もしくは難溶であるものが好ましい。具体的には、例えば、二酸化珪素や酸化チタン等の金属酸化物、天然ゼオライトや合製ゼオライト等の珪酸（塩）、カオリン、タルク、クレー、ベントナイト等が挙げられる。このうち、二酸化珪素および珪酸（塩）がより好ましく、コールターカウンター法により測定された平均粒子径が２００μｍ以下の二酸化珪素および珪酸（塩）がさらに好ましい。 Examples of the inorganic powder used herein include substances that are inert to aqueous liquids, such as fine particles of various inorganic compounds, fine particles of clay minerals, and the like. The inorganic powder preferably has an appropriate affinity for water and is insoluble or hardly soluble in water. Specific examples include metal oxides such as silicon dioxide and titanium oxide, silicic acid (salts) such as natural zeolite and synthetic zeolite, kaolin, talc, clay, bentonite and the like. Among these, silicon dioxide and silicic acid (salt) are more preferable, and silicon dioxide and silicic acid (salt) having an average particle diameter measured by a Coulter counter method of 200 μm or less are more preferable.
ここでの無機粉末の使用量は、吸水材および無機粉体の組み合わせ等にもよるが、吸水材１００質量％に対し０．００１〜１０質量％の範囲内、より好ましくは０．０１〜５質量％の範囲内とすればよい。吸水材と無機粉体との混合方法は、特に限定されるものではなく、例えば湿式混合法等を採用できる。 The amount of the inorganic powder used here depends on the combination of the water-absorbing material and the inorganic powder, but is within the range of 0.001 to 10% by mass, more preferably 0.01 to 5% with respect to 100% by mass of the water-absorbing material. What is necessary is just to be in the range of the mass%. The mixing method of the water absorbing material and the inorganic powder is not particularly limited, and for example, a wet mixing method or the like can be adopted.
本発明による吸水材は、上記のような製造方法により得られるものであって、ポリカルボン酸又はその塩で架橋されたカルボキシアルキル化ガラクトマンナンを主成分として含み、０．９質量％塩化ナトリウム水溶液に対する吸水量が自重の２０倍以上であり、該水溶液に対する保水量が自重の１５倍以上であることを特徴とする吸水材である。ここでの吸水量及び保水量は、上述した方法により測定された値をいう。 The water-absorbing material according to the present invention is obtained by the production method as described above, and contains a carboxyalkylated galactomannan crosslinked with a polycarboxylic acid or a salt thereof as a main component, and a 0.9% by mass sodium chloride aqueous solution. The water-absorbing material is characterized in that the amount of water absorbed in water is 20 times or more of its own weight, and the amount of water retained in the aqueous solution is 15 times or more of its own weight. Here, the water absorption amount and the water retention amount are values measured by the method described above.
また、本発明による吸水性物品は、本発明の吸水材を含んでなることを特徴とするものであり、具体例としては、血液や尿、汗、膿、胃液、唾液、鼻分泌粘液などの体液を吸収することを目的とした吸水物品、例えば、子供用紙オムツ、大人用紙オムツ、生理用ナプキン、タンポン、パンティーライナー、生理用シーツ、失禁用パッド、携帯用トイレ、携帯用汚物処理袋、動物用屎尿処理剤、医療用手当材、創傷被覆材、肉や魚などの鮮度保持材、さらには家畜の飼料添加物等が挙げられる。また体液だけでなく、泥水や海水、河川水などを吸水することを目的とした建材や土壌保水材、汚泥固化剤、止水材、パッキング材、ゲル水嚢等の土木建築用資材、保冷材等の食品用物品、油水分離材、結露防止材などの各種産業用物品、植物や土壌等の保水材、種子被覆材等の農園芸用物品なども挙げることができる。 Further, the water-absorbent article according to the present invention is characterized by comprising the water-absorbing material of the present invention, and specific examples thereof include blood, urine, sweat, pus, gastric juice, saliva, nasal secretion mucus and the like. Water-absorbing articles intended to absorb body fluids, such as children's paper diapers, adult paper diapers, sanitary napkins, tampons, panty liners, sanitary sheets, incontinence pads, portable toilets, portable waste disposal bags, animals Examples include urine treatment agents, medical care materials, wound dressings, freshness-maintaining materials such as meat and fish, and livestock feed additives. In addition to body fluids, building materials and soil water retention materials, sludge solidifying agents, water-stopping materials, packing materials, gel water sacs, and other civil engineering and building materials intended to absorb mud, seawater, river water, and cold insulation materials Examples include food articles such as food, various industrial articles such as oil-water separators and anti-condensation materials, water retention materials such as plants and soil, and agricultural and horticultural articles such as seed coating materials.
以下、実施例にて本発明を具体的に説明するが、本発明は本実施例に限定されるものではない。
実施例中での吸水量、保水量および吸水速度は上述のようにして測定した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a present Example.
The water absorption, water retention and water absorption rate in the examples were measured as described above.
（実施例１）
予め２質量％のリン酸２水素ナトリウム水溶液と２質量％の1,2,3,4-ブタンテトラカルボン酸（ナカライテスク社：BTC）水溶液を調製し、リン酸２水素ナトリウム水溶液０．１３４ｍｌ（カルボキシメチル化グアガム質量１ｋｇに対して０．５５ミリモルに相当）と、ＢＴＣ水溶液０．６６ｍｌ（カルボキシメチル化グアガム質量１ｋｇに対して１４．１ミリモルに相当）を水１９５．２０６ｍｌに加えて混合し、この水溶液にカルボキシメチル化グアガム粉末（メイホールケミカル社メイプロイド８７０）４ｇを攪拌しながら添加し、室温にて２時間水和させて均一な混合水和物を得た。得られた混合水和物をステンレストレイに広げ、５０℃にて熱風乾燥機中で一夜乾燥させ、フィルム状乾燥物を得た。このフィルム状乾燥物をさらに同じ乾燥機にて１５０℃で２０分間加熱処理し、得られた加熱処理物をブレンダーにより破砕し粉末状吸水材を得た。
得られた吸水材について分級し、２００〜１０００μｍの範囲の粒子を得、これを用いて０．９質量％塩化ナトリウム水溶液に対する吸水量、保水量測定及び吸水速度試験を行った。結果を表１に示す。
(Example 1)
A 2% by weight aqueous sodium dihydrogen phosphate solution and a 2% by weight 1,2,3,4-butanetetracarboxylic acid (Nacalai Tesque: BTC) aqueous solution were prepared in advance, and 0.134 ml of a sodium dihydrogen phosphate aqueous solution ( Add 0.56 mmol of carboxymethylated guar gum to 1 kg) and 0.66 ml of BTC aqueous solution (14.1 mmol to 1 kg of carboxymethylated guar gum) in 195.206 ml of water and mix. To this aqueous solution, 4 g of carboxymethylated guar gum powder (Mayprod 870, Mayhole Chemical Co., Ltd.) was added with stirring, and hydrated at room temperature for 2 hours to obtain a uniform mixed hydrate. The obtained mixed hydrate was spread on a stainless steel tray and dried overnight in a hot air dryer at 50 ° C. to obtain a dried film. This film-like dried product was further heat-treated at 150 ° C. for 20 minutes in the same dryer, and the obtained heat-treated product was crushed with a blender to obtain a powdery water-absorbing material.
The obtained water-absorbing material was classified to obtain particles in the range of 200 to 1000 μm, and the water absorption amount, water retention amount measurement, and water absorption rate test for a 0.9 mass% sodium chloride aqueous solution were performed using this. The results are shown in Table 1.
（実施例２）
実施例１で用いたカルボキシメチル化グアガムの代わりにカルボキシメチルヒドロキシプロピル化グアガム（ローディア社ジャガー８６００）を用いた以外は実施例１と同様に操作し、吸水材を得た。これらについての測定結果を表１に示す。
(Example 2)
A water-absorbing material was obtained in the same manner as in Example 1 except that carboxymethylhydroxypropylated guar gum (Rhodia Jaguar 8600) was used instead of the carboxymethylated guar gum used in Example 1. The measurement results for these are shown in Table 1.
（実施例３）
実施例２で用いた１４．１ミリモル相当の1,2,3,4-ブタンテトラカルボン酸の代わりに４９．３ミリモル相当のリンゴ酸を用いた以外は実施例２と同様に操作し、吸水材を得た。これらについての測定結果を表１に示す。
(Example 3)
In the same manner as in Example 2 except that malic acid equivalent to 49.3 mmol was used instead of 14.1, mmol equivalent to 1,2,3,4-butanetetracarboxylic acid used in Example 2, water absorption I got the material. The measurement results for these are shown in Table 1.
（実施例４）
実施例２で用いた１４．１ミリモル相当の1,2,3,4-ブタンテトラカルボン酸の代わりに４９．３ミリモル相当のアスパラギン酸を用いた以外は実施例２と同様に操作し、吸水材を得た。これらについての測定結果を表１に示す。
Example 4
The water absorption was carried out in the same manner as in Example 2 except that 49.3 mmol of aspartic acid was used in place of the 14.1, mmol of 1,2,3,4-butanetetracarboxylic acid used in Example 2. The material was obtained. The measurement results for these are shown in Table 1.
（実施例５）
加熱処理温度を１２０℃、加熱処理時間を７０分に変更した以外は実施例３と同様に操作し、吸水材を得た。これらについての測定結果を表１に示す。
(Example 5)
A water absorbing material was obtained in the same manner as in Example 3 except that the heat treatment temperature was changed to 120 ° C. and the heat treatment time was changed to 70 minutes. The measurement results for these are shown in Table 1.
（実施例６）
水の量を１８８ｍｌ、カルボキシメチルヒドロキシプロピル化ガラクトマンナンの添加量を１２ｇに変更した以外は実施例３と同様に操作し、吸水材を得た。これらについての測定結果を表１に示す。
(Example 6)
A water-absorbing material was obtained in the same manner as in Example 3 except that the amount of water was changed to 188 ml and the addition amount of carboxymethylhydroxypropylated galactomannan was changed to 12 g. The measurement results for these are shown in Table 1.
（実施例７）
カラヤガム（三栄薬品貿易カラヤコール）０．５ｇとカルボキシメチルヒドロキシプロピル化グアガム３．５ｇを水１９６ｍｌに溶解・水和し、カルボキシメチルヒドロキシプロピル化グアガム質量１ｋｇに対して０．５５ミリモルのリン酸をさらに加えて攪拌し、室温にて２時間水和させて均一な混合水和物を得た。これらについて実施例１と同様に操作して吸水材を得た。各測定結果を表１に示す。
(Example 7)
Dissolve and hydrate 0.5 g of Karaya gum (Sanei Pharmaceutical Trading Karayacol) and 3.5 g of carboxymethylhydroxypropylated guar gum in 196 ml of water, and add 0.55 mmol of phosphoric acid to 1 kg of carboxymethylhydroxypropylated guar gum. In addition, the mixture was stirred and hydrated at room temperature for 2 hours to obtain a uniform mixed hydrate. These were operated in the same manner as in Example 1 to obtain water-absorbing materials. Table 1 shows the measurement results.
（比較例１）
加熱処理温度を１００℃、加熱処理時間を１２０分に変更した以外は実施例３と同様に操作し、吸水材を得た。これらについて測定を試みたところ、吸水後のゲルはドロドロの液状となり測定不能となった。
(Comparative Example 1)
A water absorbing material was obtained in the same manner as in Example 3 except that the heat treatment temperature was changed to 100 ° C. and the heat treatment time was changed to 120 minutes. Attempts were made to measure these, and the gel after water absorption became muddy and became unmeasurable.
（比較例２）
加熱処理温度を１９０℃、加熱処理時間を２０分に変更した以外は実施例３と同様に操作し、吸水材を得た。これらについての測定結果を表１に示す。なお吸水材は褐色に着色していた。
(Comparative Example 2)
A water absorbing material was obtained in the same manner as in Example 3 except that the heat treatment temperature was changed to 190 ° C. and the heat treatment time was changed to 20 minutes. The measurement results for these are shown in Table 1. The water absorbing material was colored brown.
Claims (5)
ｂ）工程ａ）で得られた水和物を乾燥する工程、および、
ｃ）工程ｂ）で得られた乾燥物を１２０℃以上１８０℃以下で加熱処理する工程、
を含む請求項１〜３のいずれかに記載の吸水材の製造方法。 a) Mixing a polycarboxylic acid or a salt thereof and a carboxyalkylated galactomannan having a solid concentration of 1% by mass or more and 15% by mass or less with respect to the total mass of water and the carboxyalkylated galactomannan in water. Dissolving and hydrating,
b) drying the hydrate obtained in step a), and
c) a step of heat-treating the dried product obtained in step b) at 120 ° C. or higher and 180 ° C. or lower;
The manufacturing method of the water absorbing material in any one of Claims 1-3 containing.
A water-absorbent article comprising the water-absorbing material according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2004122939A JP2005305236A (en) | 2004-04-19 | 2004-04-19 | Water absorbing material, manufacturing method therefor, and water absorbent article |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004122939A JP2005305236A (en) | 2004-04-19 | 2004-04-19 | Water absorbing material, manufacturing method therefor, and water absorbent article |
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| JP2005305236A true JP2005305236A (en) | 2005-11-04 |
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| JP2004122939A Pending JP2005305236A (en) | 2004-04-19 | 2004-04-19 | Water absorbing material, manufacturing method therefor, and water absorbent article |
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| Country | Link |
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| JP (1) | JP2005305236A (en) |
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2004
- 2004-04-19 JP JP2004122939A patent/JP2005305236A/en active Pending
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