JP2909692B2 - Water absorbing agent - Google Patents
Water absorbing agentInfo
- Publication number
- JP2909692B2 JP2909692B2 JP5061143A JP6114393A JP2909692B2 JP 2909692 B2 JP2909692 B2 JP 2909692B2 JP 5061143 A JP5061143 A JP 5061143A JP 6114393 A JP6114393 A JP 6114393A JP 2909692 B2 JP2909692 B2 JP 2909692B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- absorbing agent
- absorption
- fiber
- absorbing
- 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.)
- Expired - Fee Related
Links
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は吸収特性および繊維に対
する固着性に優れた吸水剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-absorbing agent which is excellent in absorption characteristics and adhesion to fibers.
【０００２】[0002]
【従来の技術】従来、水性液体に対して吸収能を有する
粉粒状吸水剤としては、吸水性樹脂と呼ばれる親水性架
橋ポリマーが知られている。この吸水性樹脂の例として
は、デンプン−アクリル酸塩共重合体、架橋アクリル酸
塩、アクリル酸およびその塩とその他の単量体との共重
合体架橋物、イソブチレン−無水マレイン酸共重合体架
橋物、ポリビニルアルコール−（メタ）アクリル酸共重
合体、変性セルロース誘導体、変性ポリエチレンオキシ
ド、変性ポリビニルアルコール等各種の樹脂が知られて
おり、主として紙おむつ、生理用品などの衛生材料に使
用されてきた。2. Description of the Related Art Heretofore, a hydrophilic cross-linked polymer called a water-absorbing resin has been known as a powdery / granular water-absorbing agent having an absorbing ability for an aqueous liquid. Examples of the water-absorbent resin include starch-acrylate copolymers, cross-linked acrylates, cross-linked copolymers of acrylic acid and its salts with other monomers, isobutylene-maleic anhydride copolymers Various resins such as a crosslinked product, a polyvinyl alcohol- (meth) acrylic acid copolymer, a modified cellulose derivative, a modified polyethylene oxide, and a modified polyvinyl alcohol are known, and have been mainly used for sanitary materials such as disposable diapers and sanitary articles. .
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
粉粒状吸水性樹脂は優れた吸収特性を有するものの、パ
ルプ等の天然繊維やポリエチレン繊維、ポリプロピレン
繊維、ポリエステル繊維およびこれらが複合化された繊
維などの合成繊維に対する固着性という点では不十分で
あった。特に、繊維に対する吸水性樹脂の比率が大きく
なるほど（例えば、吸水性樹脂／繊維の比率が重量比で
３０／７０を越える場合）、吸水性樹脂と繊維との固着
性が低下し、衛生材料等に使用した場合該吸水性樹脂の
移動、遍在、繊維からの脱落等の問題をを生じ易い。ま
た、水徐溶性および／または加水分解性の熱可塑性樹脂
で吸水性樹脂の表面全体を被覆した吸水剤が繊維などへ
の固着性を有するとの提案（特開平２−２４２８５８号
公報）があるが、この場合繊維への固着性は向上するも
のの、吸水性樹脂本来のもつ吸収特性、特に吸収速度や
初期吸収率が極端に悪化するという欠点があり、排泄さ
れた尿や経血を瞬時に吸収・保持する性能が要求される
紙おむつ、生理用品などの衛生材料には上記の吸水剤の
適用は難しい。However, although conventional powdery water-absorbent resins have excellent absorption properties, natural fibers such as pulp, polyethylene fibers, polypropylene fibers, polyester fibers, and fibers obtained by compounding these fibers, etc. Was inadequate in terms of adhesion to synthetic fibers. In particular, as the ratio of the water-absorbent resin to the fiber increases (for example, when the weight ratio of the water-absorbent resin / fiber exceeds 30/70), the adhesiveness between the water-absorbent resin and the fiber decreases, and the sanitary material, etc. When used in water, the water-absorbent resin tends to cause problems such as migration, ubiquity, and falling off from the fiber. There is also a proposal that a water-absorbing agent in which the entire surface of a water-absorbent resin is coated with a water-soluble and / or hydrolysable thermoplastic resin has an adhesive property to fibers or the like (Japanese Patent Application Laid-Open No. 242858/1990). However, in this case, although the adhesiveness to the fiber is improved, there is a drawback that the absorption characteristics inherent to the water-absorbent resin, particularly the absorption rate and the initial absorption rate, are extremely deteriorated, and the excreted urine and menstrual blood are instantly removed. It is difficult to apply the above water-absorbing agent to sanitary materials such as disposable diapers and sanitary products that require absorption and retention performance.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記問題
点に鑑み、吸収特性（特に初期吸収率）および繊維への
固着性に優れた吸水剤について鋭意検討した結果、本発
明に到達した。Means for Solving the Problems In view of the above problems, the present inventors have made intensive studies on a water-absorbing agent having excellent absorption characteristics (particularly, initial absorption rate) and adhesion to fibers, and as a result, have reached the present invention. did.
【０００５】即ち本発明は、下記吸水性樹脂粒子（Ａ）
と下記熱融着性樹脂粉末（Ｂ）からなり、（Ａ）１００
重量部に対する（Ｂ）の量が１〜２０重量部である吸水
剤である。 吸水性樹脂粒子（Ａ）：生理食塩水に対する吸収能が自
重の３５〜１００倍であり、９０重量％以上が、０．１
〜０．９ｍｍの粒度分布を有する吸水性樹脂粒子。 熱融着性樹脂粉末（Ｂ）：カルボン酸変性ポリオレフィ
ン樹脂、オレフィン−アクリル酸共重合体およびオレフ
ィン−無水マレイン酸共重合体からなる群から選ばれ、
融点が５０〜１８０℃であり、通常の水に２４時間接触
させても溶解も加水分解もしない少なくとも１種の熱融
着性樹脂の粒子径３００ミクロン以下の粉末。吸収能は
吸収量で表し、吸収量は下記の方法にて測定する。 吸収量の測定法： ２５０メッシュのナイロンネット製
ティーバッグに吸水剤１ｇを入れ、これを大過剰の０．
９％食塩水中に１時間浸して吸収させた後、引き上げて
１５分間水切りを行って増加重量を測定する。この値を
吸収量（Ｓ）とする。 That is, the present invention relates to the following water-absorbent resin particles (A)
And the following heat-fusible resin powder (B), and (A) 100
A water-absorbing agent in which the amount of (B) is 1 to 20 parts by weight with respect to parts by weight. Water-absorbent resin particles (A): The absorbent capacity for physiological saline is 35 to 100 times its own weight, and 90% by weight or more is 0.1%.
Water-absorbing resin particles having a particle size distribution of ０．９0.9 mm. Heat-fusible resin powder (B): selected from the group consisting of carboxylic acid-modified polyolefin resin, olefin-acrylic acid copolymer and olefin-maleic anhydride copolymer,
A powder having a melting point of 50 to 180 ° C. and a particle diameter of at least one kind of heat-fusible resin, which does not dissolve or hydrolyze even when contacted with ordinary water for 24 hours, having a particle diameter of 300 μm or less. Absorption capacity
It is represented by the amount of absorption, and the amount of absorption is measured by the following method. Measuring method of absorption: Made of 250 mesh nylon net
1 g of a water-absorbing agent is put in a tea bag, and a large excess of 0.1 g of a water-absorbing agent is added.
Soak in 9% saline for 1 hour to absorb, then pull up
Drain for 15 minutes and measure weight gain. This value
The amount of absorption (S).
【０００６】本発明において、吸水性樹脂粒子（Ａ）と
しては、通常自重の３０倍以上から１０００倍程度の水
を吸収する能力のある親水性架橋高分子であり、その構
成単位にカルボン酸（塩）基［カルボン酸および／また
はカルボン酸塩基を言う。以下同様の記載を用い
る。］、スルホン酸（塩）基、リン酸（塩）基、第三級
アミノ基、第四級アンモニウム塩基、水酸基、ポリエチ
レンオキシド基などの親水性基を有する吸水性樹脂であ
れば樹脂の種類および製造方法は特に限定しない。本発
明に好適に使用しうる吸水性樹脂の例としては、特公昭
５３−４６１９９号、特公昭５３−４６２００号各公報
などに記載のデンプン−アクリル酸（塩）共重合体、特
公昭５４−３０７１０号、特開昭５６−２６９０９号各
公報などに記載の逆相懸濁重合法による架橋あるいは自
己架橋されたポリアクリル酸塩、特開昭５５−１３３４
１３号公報などに記載の水溶液重合（断熱重合、薄膜重
合、噴霧重合など）により得られる架橋ポリアクリル酸
（塩）、特開昭５２−１４６８９号、特開昭５２−２７
４５５号各公報などに記載のビニルエステルと不飽和カ
ルボン酸またはその誘導体との共重合体ケン化物、特開
昭５８−２３１２号、特開昭６１−３６３０９号各公報
などに記載のスルホン酸（塩）基含有吸水性樹脂、イソ
ブチレン−無水マレイン酸共重合体架橋物、デンプン−
アクリロニトリル共重合体の加水分解物、架橋カルボキ
シメチル誘導体、架橋ポリエチレンオキシド誘導体、架
橋ポリビニルアルコール誘導体、ポリアクリルアミドの
部分加水分解物などが挙げられる。また、上記吸水性樹
脂を更に表面架橋せしめた吸水性樹脂も使用できる。上
記吸水性樹脂は２種以上併用してもよい。In the present invention, the water-absorbent resin particles (A) are usually hydrophilic cross-linked polymers capable of absorbing water of 30 times or more to about 1000 times their own weight, and a carboxylic acid ( Salt) group [refers to carboxylic acid and / or carboxylic acid base. Hereinafter, the same description is used. ], A water-absorbing resin having a hydrophilic group such as a sulfonic acid (salt) group, a phosphoric acid (salt) group, a tertiary amino group, a quaternary ammonium base, a hydroxyl group, and a polyethylene oxide group. The manufacturing method is not particularly limited. Examples of the water-absorbing resin which can be preferably used in the present invention include starch-acrylic acid (salt) copolymers described in JP-B-53-46199 and JP-B-53-46200, and JP-B-54-46200. No. 30710, JP-A-56-26909, crosslinked or self-crosslinked polyacrylates by the reversed-phase suspension polymerization method, and JP-A-55-1334.
No. 13, JP-A-52-14689, JP-A-52-27, crosslinked polyacrylic acid (salt) obtained by aqueous solution polymerization (adiabatic polymerization, thin-film polymerization, spray polymerization, etc.)
No. 455, and the like. Saponified copolymers of vinyl esters and unsaturated carboxylic acids or derivatives thereof described in JP-A Nos. 455-455 and sulfonic acids described in JP-A Nos. 58-2312 and 61-36309. Salt) group-containing water-absorbing resin, cross-linked isobutylene-maleic anhydride copolymer, starch
Examples include a hydrolyzate of an acrylonitrile copolymer, a crosslinked carboxymethyl derivative, a crosslinked polyethylene oxide derivative, a crosslinked polyvinyl alcohol derivative, and a partial hydrolyzate of polyacrylamide. Further, a water-absorbing resin obtained by further surface-cross-linking the above-mentioned water-absorbing resin can also be used. Two or more of the above water-absorbing resins may be used in combination.
【０００７】上記吸水性樹脂の生理食塩水（０．９％の
塩化ナトリウム水溶液）に対する吸収能は通常自重の３
５〜１００倍、好ましくは４０〜８０倍である。吸収能
は吸収量で表し、後述する測定法で測定する。 The absorption capacity of the water-absorbent resin for physiological saline (0.9% aqueous sodium chloride solution) is usually 3% of its own weight.
It is 5 to 100 times, preferably 40 to 80 times. Absorption capacity
Is represented by an absorption amount and is measured by a measurement method described later.
【０００８】該吸水性樹脂粒子（Ａ）の形状について
は、粉粒状であれば特に限定はなく、粒状、顆粒状、造
粒状、リン片状、塊状、パール状、微粉末状などいずれ
の形状であってもよいが、好ましくは粒状、顆粒状、造
粒状、リン片状あるいは塊状の粒子である。又、（Ａ）
は、通常９０重量％以上が０．１〜０．９ｍｍの粒度分
布を有する。The shape of the water-absorbent resin particles (A) is not particularly limited as long as it is in the form of powder, and may be any of granular, granular, granulated, scaly, massive, pearl, fine powder and the like. It may be in the form of a particle, but is preferably a granular, granular, granulated, scaly or massive particle. Also, (A)
Usually has a particle size distribution of 0.1 to 0.9 mm at 90% by weight or more.
【０００９】本発明における熱融着性樹脂粉末（Ｂ）に
おける該熱融着性樹脂のうち、カルボン酸変性ポリオレ
フィン樹脂としては、マレイン酸変性ポリエチレン、マ
レイン酸変性ポリプロピレンなどが挙げられ、マレイン
酸含量が１〜３０重量％のものが好ましい。オレフィン
−アクリル酸共重合体としては、エチレン−アクリル酸
共重合体、プロピレン−アクリル酸共重合体などが挙げ
られ、アクリル酸含量が１〜３０重量％のものが好まし
い。オレフィン−無水マレイン酸共重合体としては、エ
チレン−無水マレイン酸共重合体、プロピレン−無水マ
レイン酸共重合体、イソブチレン−無水マレイン酸共重
合体などが挙げられ、無水マレイン酸含量が１〜３０重
量％のものが好ましい。Among the heat-fusible resins in the heat-fusible resin powder (B) of the present invention, examples of the carboxylic acid-modified polyolefin resin include maleic acid-modified polyethylene and maleic acid-modified polypropylene. Is preferably 1 to 30% by weight. Examples of the olefin-acrylic acid copolymer include an ethylene-acrylic acid copolymer and a propylene-acrylic acid copolymer, and those having an acrylic acid content of 1 to 30% by weight are preferred. Examples of the olefin-maleic anhydride copolymer include an ethylene-maleic anhydride copolymer, a propylene-maleic anhydride copolymer, an isobutylene-maleic anhydride copolymer, and a maleic anhydride content of 1 to 30. % By weight is preferred.
【００１０】該（Ｂ）の融点は５０〜１８０℃であり、
好ましくは６０〜１６０℃である。融点が５０℃未満の
場合、吸水剤の保存中あるいは使用中にブロッキングを
起こしたり、吸水剤どうしが融着するという問題を生じ
易い。一方融点が１８０℃を越えると、繊維へ固着させ
る際に高い温度が必要であり多大の熱エネルギーを必要
として経済的でないばかりか、高い温度での処理により
吸収性能の低下や着色現象を生じる場合があり好ましく
ない。The melting point of (B) is 50 to 180 ° C.,
Preferably it is 60-160 degreeC. When the melting point is less than 50 ° C., problems tend to occur such as blocking during storage or use of the water absorbing agent, and fusion of the water absorbing agents. On the other hand, when the melting point exceeds 180 ° C., a high temperature is required for fixing to the fiber, and a large amount of heat energy is required, which is not economical, and a treatment at a high temperature causes a decrease in absorption performance or a coloring phenomenon. Is not preferred.
【００１１】（Ｂ）の粒径は、通常３００ミクロン以
下、好ましくは１〜２５０ミクロン、さらに好ましくは
１０〜２００ミクロンである。粒径が３００ミクロンを
越えると、吸水性樹脂（Ａ）との混合状態が不均一とな
り繊維への固着性が低下するとともに、吸水剤の初期吸
収率の低下をまねく。さらに、混合状態が不均一によ
り、吸水剤の保存、輸送あるいは使用過程で（Ａ）と
（Ｂ）との相分離を生じるという問題がある。The particle size of (B) is usually not more than 300 microns, preferably 1 to 250 microns, more preferably 10 to 200 microns. When the particle size exceeds 300 microns, the mixed state with the water-absorbent resin (A) becomes uneven, and the fixation to the fiber is reduced, and the initial absorption of the water-absorbing agent is reduced. Further, there is a problem that due to the uneven mixing state, phase separation between (A) and (B) occurs during storage, transportation or use of the water absorbing agent.
【００１２】該（Ｂ）は、通常の水に少なくとも２４時
間程度接触させても溶解あるいは加水分解しない樹脂の
粒子である。この理由は、本発明の吸水剤を紙おむつや
生理用品のような衛生材料に適用した場合、尿あるいは
経血を吸収した後においても着用期間中はある程度の固
着性を維持できるからである。逆に短時間で水に溶解し
たり加水分解により水溶性となる樹脂の場合、ドライな
状態での繊維への固着には問題はなくても、尿あるいは
経血を吸収した後に樹脂が溶解してヌルミ感を生じた
り、吸水後のゲルの移動や脱落の問題を生じる。The resin (B) is a resin particle which does not dissolve or hydrolyze even when it is brought into contact with ordinary water for at least about 24 hours. The reason for this is that when the water absorbing agent of the present invention is applied to sanitary materials such as disposable diapers and sanitary articles, it is possible to maintain a certain degree of adhesiveness during the wearing period even after absorbing urine or menstrual blood. Conversely, in the case of a resin that dissolves in water in a short time or becomes water-soluble by hydrolysis, even if there is no problem in fixing to the fiber in a dry state, the resin dissolves after absorbing urine or menstrual blood. This may cause a slimy feeling, and may cause problems such as gel migration or falling off after water absorption.
【００１３】本発明において、（Ａ）１００重量部に対
する（Ｂ）の量は、通常１〜２０重量部、好ましくは３
〜１５重量部である。（Ｂ）の量が２０重量部を越える
と、繊維への固着性は向上するものの、（Ｂ）が（Ａ）
の表面の大部分（例えば８０％以上）を覆ってしまうた
め、吸水剤の吸収性能、吸収速度および初期吸収率が低
下する。一方１重量部未満では繊維への固着性が不十分
となる。In the present invention, the amount of (B) is usually 1 to 20 parts by weight, preferably 3 to 100 parts by weight of (A).
１５15 parts by weight. When the amount of (B) exceeds 20 parts by weight, the fixing property to the fiber is improved, but (B) is changed to (A).
Because most of the surface (for example, 80% or more) is covered, the absorption performance, absorption rate, and initial absorption rate of the water absorbing agent are reduced. On the other hand, if it is less than 1 part by weight, the adhesion to the fiber becomes insufficient.
【００１４】本発明の吸水剤の製造法としては、（Ａ）
と（Ｂ）とを粉体混合する方法が最も簡便であり経済的
である。さらに、（Ａ）と（Ｂ）の混合時あるいは混合
後、（Ｂ）の融点以上の温度で処理して、（Ｂ）を
（Ａ）の表面に部分的に固着させることにより、（Ａ）
と（Ｂ）との均一混合性と繊維への固着性を向上させる
ことができる。また、ハイブリダイゼーション法、コー
トマイザー法などの機械的操作により、（Ｂ）を（Ａ）
の表面に部分的に固着させることも可能である。尚、こ
こでいう部分的とは、（Ｂ）で（Ａ）の表面が覆いつく
されていないという意味であり、例えば（Ａ）の表面の
約８０％以下の面積、好ましくは６０〜１０％の面積が
（Ｂ）で固着されていることを意味している。（Ｂ）で
（Ａ）の表面を覆いつくすと、吸水剤の吸収速度、初期
吸収率が極端に低下する。The method for producing the water-absorbing agent of the present invention includes (A)
And (B) are the simplest and most economical method. Further, at the time of or after mixing (A) and (B), the mixture is treated at a temperature equal to or higher than the melting point of (B) to partially fix (B) to the surface of (A).
And (B) can be improved in uniform mixing properties and adhesion to fibers. Further, (B) was converted to (A) by a mechanical operation such as a hybridization method and a coatmizer method.
It is also possible to partially adhere to the surface of. The term “partial” as used herein means that the surface of (A) is not covered with (B), and for example, an area of about 80% or less of the surface of (A), preferably 60 to 10% Means that the area is fixed at (B). When the surface of (A) is covered with (B), the absorption rate and the initial absorption of the water absorbing agent are extremely reduced.
【００１５】（Ａ）と（Ｂ）とを混合する装置としては
通常の粉体混合装置でよく、例えばコニカルブレンダ
ー、ナウターミキサー、Ｖ型混合機、流動層式混合機、
タービュライザー、スクリュー式のラインブレンド装
置、ハニカム方式のスタティックミキサーなどが挙げら
れる。また、（Ａ）と（Ｂ）とを混合後に加熱処理する
装置としては、例えば熱風加熱機、ナウター式加熱機、
パドルドライヤー、流動層式加熱機、赤外線加熱機、高
周波加熱機などが挙げられる。（Ａ）と（Ｂ）とを混合
と同時に加熱処理する装置としては、例えばナウター式
加熱機、パドルドライヤー、流動層式加熱機などが挙げ
られる。As a device for mixing (A) and (B), a conventional powder mixing device may be used, such as a conical blender, a Nauter mixer, a V-type mixer, a fluidized-bed mixer,
Examples include a turbulizer, a screw type line blending device, and a honeycomb type static mixer. Examples of an apparatus for performing heat treatment after mixing (A) and (B) include, for example, a hot air heater, a Nauter type heater,
Paddle dryers, fluidized bed heaters, infrared heaters, high-frequency heaters and the like can be mentioned. Examples of an apparatus that heat-treats (A) and (B) simultaneously with mixing include a Nauter-type heater, a paddle dryer, and a fluidized-bed heater.
【００１６】本発明の方法により得られる吸水剤の初期
吸収率は通常４０％以上である。好ましい条件の選択に
より５０％以上となる。初期吸収率が４０％未満の場
合、排泄された尿や経血を瞬時に吸収・保持する性能が
要求される紙おむつ、生理用品などの衛生材料への適用
には不適当となり、本発明の目的するところではない。
なお、初期吸収率は後述する方法で測定される値であ
る。The initial absorption of the water-absorbing agent obtained by the method of the present invention is usually 40% or more. It becomes 50% or more by selection of preferable conditions. If the initial absorption rate is less than 40%, it is unsuitable for application to sanitary materials such as disposable diapers and sanitary products which require the ability to instantly absorb and retain excreted urine and menstrual blood. It is not where to do.
Note that the initial absorption rate is a value measured by a method described later.
【００１７】本発明の方法により得られる吸水剤の繊維
への固着率は、通常４０％以上であり、好ましい条件の
選択により６０％以上となる。ここで固着率とは、後記
のように、繊維層に吸水剤を散粒し、（Ｂ）の融点以上
の温度で加熱処理した時の繊維への固着率である。繊維
への固着率が４０％未満では、紙おむつ、生理用品など
の衛生材料へ適用した場合、これら商品の保存、輸送な
どの過程で吸水剤の移動・遍在を生じることがある。The fixing rate of the water-absorbing agent obtained by the method of the present invention to the fiber is usually 40% or more, and can be 60% or more by selecting preferable conditions. Here, the sticking rate is a sticking rate to fibers when a water absorbing agent is dispersed in the fiber layer and heat-treated at a temperature equal to or higher than the melting point of (B), as described later. If the rate of fixation to fibers is less than 40%, when applied to sanitary materials such as disposable diapers and sanitary goods, the water absorbing agent may move or be ubiquitous in the process of storing and transporting these products.
【００１８】本発明の吸水剤には、必要により増量剤、
添加剤として有機質粉体（例えばパルプ粉末、セルロー
ス誘導体、天然多糖類など）、無機質粉末（例えばゼオ
ライト、シリカ、アルミナ、ベントナイト、活性炭な
ど）、酸化防止剤、防腐剤、殺菌剤、界面活性剤、着色
剤、香料などを配合することができる。これらの量は吸
水剤の重量に対して通常１０重量％以下である。The water-absorbing agent of the present invention may optionally include a bulking agent,
As additives, organic powders (eg, pulp powder, cellulose derivatives, natural polysaccharides, etc.), inorganic powders (eg, zeolite, silica, alumina, bentonite, activated carbon, etc.), antioxidants, preservatives, bactericides, surfactants, Coloring agents, fragrances and the like can be blended. These amounts are usually 10% by weight or less based on the weight of the water absorbing agent.
【００１９】[0019]
【実施例】以下実施例および比較例により本発明をさら
に説明するが、本発明はこれらに限定されるものではな
い。吸収量、初期吸収率、繊維（パルプまたは合成繊
維）への固着率は下記の方法により測定した。以下特に
定めない限り、％は重量％を示す。The present invention will be further described with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The absorption amount, initial absorption rate, and sticking rate to fiber (pulp or synthetic fiber) were measured by the following methods. Hereinafter, unless otherwise specified,% indicates% by weight.
【００２０】吸収量： ２５０メッシュのナイロンネッ
ト製ティーバッグに吸水剤１ｇを入れ、これを大過剰の
０．９％食塩水中に１時間浸して吸収させた後、引き上
げて１５分間水切りを行って増加重量を測定する。この
値を吸収量（Ｓ）とした。 初期吸収率： ２５０メッシュのナイロンネット製ティ
ーバッグに吸水剤１ｇを入れ、これを大過剰の０．９％
食塩水中に１０分間浸して吸収させた後、引き上げて１
５分間水切りを行って増加重量を測定する。この値を１
０分後の吸収量（Ｓ１０）とする。 初期吸収率＝（Ｓ１０／Ｓ）×１００ 繊維への固着率： ２００ｇ／ｍ２のフラッフパルプあ
るいは合成繊維（ＥＳ繊維ＥＡ；チッソ（株）製）の層
を直径１５ｃｍの円形に裁断し、繊維層の下面から吸引
しながら、この上に２ｇの吸水剤を均一に散粒する。次
いで（Ｂ）の融点より約１０℃高い温度で２分間加熱処
理した後、室温にまで冷却し、固着されていない吸水剤
を振るい落として重量（Ｗ）を測定する。 繊維への固着率＝［（２−Ｗ）／２］×１００Absorption: 1 g of a water-absorbing agent was placed in a 250-mesh nylon net tea bag, immersed in a large excess of 0.9% saline for 1 hour, absorbed, and drained for 15 minutes. Measure the weight gain. This value was taken as the absorption amount (S). Initial absorption: 1 g of a water-absorbing agent was placed in a 250 mesh nylon net tea bag, and the excess was 0.9%.
Soak in saline for 10 minutes to absorb, then pull up to 1
Drain for 5 minutes and measure weight gain. Set this value to 1
The absorption amount after 0 minutes (S10). Initial absorption rate = (S10 / S) × 100 Fixing rate to fiber: A layer of fluff pulp or synthetic fiber (ES fiber EA; manufactured by Chisso Corporation) of 200 g / m 2 was cut into a circular shape having a diameter of 15 cm. While sucking from the lower surface of the layer, 2 g of the water-absorbing agent is evenly dispersed on this. Next, after a heat treatment at a temperature about 10 ° C. higher than the melting point of (B) for 2 minutes, the mixture is cooled to room temperature, and the water-absorbing agent that is not fixed is shaken off, and the weight (W) is measured. Adhesion rate to fiber = [(2-W) / 2] × 100
【００２１】実施例１ 架橋アクリル酸ナトリウム系吸水性樹脂（三洋化成工業
（株）製「サンウェットＩＭ−５０００Ｄ」；粒状）９
３部と、粒径が５０〜１００ミクロンのマレイン酸変性
ポリエチレン（三洋化成工業（株）製「ユーメックス２
０００Ｐ」；融点１０８℃）７部とをＶ型混合機に入
れ、２０分間混合して本発明の吸水剤（ａ）を得た。こ
の吸水剤（ａ）の吸収量、初期吸収率、繊維への固着率
を測定した結果を表１に示す。Example 1 Crosslinked sodium acrylate-based water-absorbent resin ("Sunwet IM-5000D" manufactured by Sanyo Chemical Industries, Ltd .; granular) 9
3 parts and maleic acid-modified polyethylene having a particle size of 50 to 100 microns ("UMEX 2" manufactured by Sanyo Chemical Industries, Ltd.)
000P "; melting point 108 ° C) in a V-type mixer and mixed for 20 minutes to obtain a water-absorbing agent (a) of the present invention. Table 1 shows the measurement results of the absorption amount, initial absorption rate, and fixing rate of the water absorbing agent (a) to the fiber.
【００２２】実施例２および３ 「サンウエットＩＭ−５０００Ｄ」と「ユーメックス２
０００Ｐ」の混合比を以下のように代える以外は実施例
１と同様にして、吸水剤（ｂ）および（ｃ）を得た。こ
れらの吸水剤の性能測定結果を表１に示す。 吸水剤（ｂ）： 「サンウエットＩＭ−５０００Ｄ」／「ユーメックス２
０００Ｐ」＝９８／２吸水剤（ｃ）： 「サンウエットＩＭ−５０００Ｄ」／「ユーメックス２
０００Ｐ」＝８０／２０Examples 2 and 3 "Sunwet IM-5000D" and "UMEX 2"
Water absorbing agents (b) and (c) were obtained in the same manner as in Example 1 except that the mixing ratio of “000P” was changed as follows. Table 1 shows the performance measurement results of these water absorbing agents. Water absorbing agent (b): "Sun wet IM-5000D" / "UMEX 2
000P "= 98/2 water-absorbing agent (c):" Sunwet IM-5000D "/" UMEX 2
000P "= 80/20
【００２３】実施例４および５ マレイン酸変性ポリエチレンの粒径を以下のように代え
る以外は実施例１と同様にして、吸水剤（ｄ）および
（ｅ）を得た。これらの吸水剤の性能測定結果を表１に
示す。 吸水剤（ｄ）：粒径１０〜５０ミクロン 吸水剤（ｅ）：粒径１５０〜２００ミクロンExamples 4 and 5 Water absorbing agents (d) and (e) were obtained in the same manner as in Example 1 except that the particle size of the maleic acid-modified polyethylene was changed as follows. Table 1 shows the performance measurement results of these water absorbing agents. Water-absorbing agent (d): particle size of 10 to 50 microns Water-absorbing agent (e): particle size of 150 to 200 microns
【００２４】実施例６ 実施例１で得られた吸水剤（ａ）を、さらに１３０℃で
３０秒間熱風処理して、吸水性樹脂粒子の表面にマレイ
ン酸変性ポリエチレン粉末が部分的に固着した吸水剤
（ｆ）を得た。この吸水剤（ｆ）の性能測定結果を表１
に示す。Example 6 The water-absorbing agent (a) obtained in Example 1 was further treated with hot air at 130 ° C. for 30 seconds, so that the maleic acid-modified polyethylene powder partially adhered to the surface of the water-absorbing resin particles. Agent (f) was obtained. Table 1 shows the performance measurement results of the water absorbing agent (f).
Shown in
【００２５】実施例７および８ 「サンウエットＩＭ−５０００Ｄ」に代え、以下の吸水
性樹脂を使用する以外は実施例６と同様にして吸水剤
（ｇ）および（ｈ）を得た。これらの吸水剤の性能測定
結果を表１に示す。 吸水剤（ｇ）：酢酸ビニル−メチルアクリレート共重合
体ケン化物（住友化学工業（株）製「スミカゲルＳ−５
０」；パール状） 吸水剤（ｈ）：デンプン−アクリル酸塩グラフト重合体
（三洋化成工業（株）製「サンウェットＩＭ−１００
０」；リン片状）Examples 7 and 8 Water-absorbing agents (g) and (h) were obtained in the same manner as in Example 6 except that the following water-absorbing resin was used instead of "Sunwet IM-5000D". Table 1 shows the performance measurement results of these water absorbing agents. Water-absorbing agent (g): Saponified vinyl acetate-methyl acrylate copolymer (“Sumikagel S-5” manufactured by Sumitomo Chemical Co., Ltd.)
0; pearl) Water-absorbing agent (h): Starch-acrylate graft polymer (“Sanwet IM-100” manufactured by Sanyo Chemical Industries, Ltd.)
0 "; scaly)
【００２６】比較例１〜３ 市販の吸水性樹脂である架橋アクリル酸ナトリウム系吸
水性樹脂、酢酸ビニル−メチルアクリレート共重合体ケ
ン化物およびデンプン−アクリル酸塩グラフト重合体を
各々比較吸水剤（イ）〜（ハ）とし、これらの吸収量、
初期吸収率、繊維への固着率を測定した結果を表１に示
す。Comparative Examples 1-3 Commercially available water-absorbing resins, a crosslinked sodium acrylate-based water-absorbing resin, a saponified vinyl acetate-methyl acrylate copolymer and a starch-acrylate graft polymer were each used as a comparative water-absorbing agent (a). ) To (c), and these absorption amounts,
Table 1 shows the results of measurement of the initial absorption rate and the fixation rate to the fiber.
【００２７】比較例４ 実施例１において、「サンウエットＩＭ−５０００Ｄ」
と「ユーメックス２０００Ｐ」の混合比を６０／４０に
代える以外は実施例１と同様にして、比較吸水剤（ニ）
を得た。この比較吸水剤の性能測定結果を表１に示す。Comparative Example 4 In Example 1, "Sunwet IM-5000D"
Comparative water-absorbing agent (d) in the same manner as in Example 1 except that the mixing ratio between “Umex 2000P” and “UMEX 2000P” was changed to 60/40.
I got Table 1 shows the performance measurement results of this comparative water absorbing agent.
【００２８】比較例５ 特開平２−２４２８５８号公報明細書に記載の実施例１
と同様にして、吸水性樹脂の表面が熱可塑性樹脂で覆わ
れた比較吸水剤（ホ）を得た。この比較吸水剤（ホ）の
性能測定結果を表１に示す。Comparative Example 5 Example 1 described in JP-A-2-242858
In the same manner as in the above, a comparative water-absorbing agent (e) in which the surface of the water-absorbing resin was covered with the thermoplastic resin was obtained. Table 1 shows the performance measurement results of the comparative water absorbing agent (e).
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【発明の効果】本発明の吸水剤は次のような特長および
効果を有する。優れた吸収性能、吸収速度および初期
吸収率を有する。繊維基材（例えば、フラッフパル
プ、合成繊維ウェブ、合成繊維フィラメント、不織布、
布、織物、紙など）への固着性に優れる。高湿度雰囲
気下に放置しても、従来の吸水性樹脂のようにブロッキ
ングすることがない。（Ａ）と（Ｂ）とを混合すると
いう簡単な操作で製造することができる。本発明の吸
水剤を熱融着性繊維を含有した繊維基材に適用すること
により、吸収後の形状保持性に優れた吸収体が得られ
る。The water absorbing agent of the present invention has the following features and effects. Has excellent absorption performance, absorption rate and initial absorption rate. Fiber substrates (eg, fluff pulp, synthetic fiber webs, synthetic fiber filaments, nonwoven fabrics,
Excellent adhesion to fabrics, fabrics, paper, etc.) Even when left in a high-humidity atmosphere, there is no blocking unlike a conventional water-absorbent resin. It can be manufactured by a simple operation of mixing (A) and (B). By applying the water-absorbing agent of the present invention to a fiber base material containing heat-fusible fibers, an absorber having excellent shape retention after absorption can be obtained.
【００３１】上記効果を奏することから、本発明の吸水
剤は、紙おむつ、生理用品、産褥マット、医療用アンダ
ーパッドなどの各種衛生材料用途に有用である。特に、
吸水性樹脂／繊維（パルプおよび／または熱有着性繊
維）の比率が大きい薄型紙おむつや薄型生理用品に有用
である。更に、青果物の鮮度保持材、ドリップ吸収材、
水分あるいは湿度調節シート、結露防止材、水稲用の育
苗シート、コンクリート養生シート、通信ケーブルおよ
び光ファイバーケーブルの止水材などのシート状あるい
はテープ状吸水材を製造する際にも有用である。Because of the above effects, the water-absorbing agent of the present invention is useful for various sanitary materials such as disposable diapers, sanitary products, puerperal mats, and medical underpads. Especially,
It is useful for thin paper diapers and thin sanitary articles having a high ratio of water-absorbent resin / fiber (pulp and / or heat-adherable fiber). In addition, freshness preserving material for fruits and vegetables, drip absorbing material,
It is also useful when producing sheet or tape-shaped water-absorbing materials such as moisture or humidity control sheets, dew condensation preventing materials, seedling raising sheets for rice, concrete curing sheets, and waterproof materials for communication cables and optical fiber cables.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−95211（ＪＰ，Ａ) 特開 平１−252669（ＪＰ，Ａ) 特開 平４−119154（ＪＰ，Ａ) 特表 平３−501494（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 1/00 - 101/14 B01J 20/26 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-95211 (JP, A) JP-A-1-252669 (JP, A) JP-A-4-119154 (JP, A) 501494 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) C08L 1/00-101/14 B01J 20/26
Claims (4)
性樹脂粉末（Ｂ）からなり、（Ａ）１００重量部に対す
る（Ｂ）の量が１〜２０重量部である吸水剤。 吸水性樹脂粒子（Ａ）：生理食塩水に対する吸収能が自
重の３５〜１００倍であり、９０重量％以上が、０．１
〜０．９ｍｍの粒度分布を有する吸水性樹脂粒子。 熱融着性樹脂粉末（Ｂ）：カルボン酸変性ポリオレフィ
ン樹脂、オレフィン−アクリル酸共重合体およびオレフ
ィン−無水マレイン酸共重合体からなる群から選ばれ、
融点が５０〜１８０℃であり、通常の水に２４時間接触
させても溶解も加水分解もしない少なくとも１種の熱融
着性樹脂の粒子径３００ミクロン以下の粉末。吸収能は
吸収量で表し、吸収量は下記の方法にて測定する。 吸収量の測定法： ２５０メッシュのナイロンネット製
ティーバッグに吸水剤１ｇを入れ、これを大過剰の０．
９％食塩水中に１時間浸して吸収させた後、引き上げて
１５分間水切りを行って増加重量を測定する。この値を
吸収量（Ｓ）とする。 1. A water-absorbing agent comprising the following water-absorbing resin particles (A) and the following heat-fusible resin powder (B), wherein the amount of (B) is 1 to 20 parts by weight based on 100 parts by weight of (A). Water-absorbent resin particles (A): The absorbent capacity for physiological saline is 35 to 100 times its own weight, and 90% by weight or more is 0.1%.
Water-absorbing resin particles having a particle size distribution of ０．９0.9 mm. Heat-fusible resin powder (B): selected from the group consisting of carboxylic acid-modified polyolefin resin, olefin-acrylic acid copolymer and olefin-maleic anhydride copolymer,
A powder having a melting point of 50 to 180 ° C. and a particle diameter of at least one kind of heat-fusible resin, which does not dissolve or hydrolyze even when contacted with ordinary water for 24 hours, having a particle diameter of 300 μm or less. Absorption capacity
It is represented by the amount of absorption, and the amount of absorption is measured by the following method. Measuring method of absorption: Made of 250 mesh nylon net
1 g of a water-absorbing agent is put in a tea bag, and a large excess of 0.1 g of a water-absorbing agent is added.
Soak in 9% saline for 1 hour to absorb, then pull up
Drain for 15 minutes and measure weight gain. This value
The amount of absorption (S).
以上である請求項１記載の吸水材。初期吸収率の測定法： ２５０メッシュのナイロンネッ
ト製ティーバッグに吸水剤１ｇを入れ、これを大過剰の
０．９％食塩水中に１０分間浸して吸収させた後、引き
上げて１５分間水切りを行って増加重量を測定する。こ
の値を１０分後の吸収量（Ｓ１０）とする。 初期吸収率＝（Ｓ１０／Ｓ）×１００ 2. The initial absorption rate in physiological saline is 40%.
The water-absorbing material according to claim 1, which is as described above. Initial absorption rate measurement method: 250 mesh nylon net
1 g of a water-absorbing agent in a tea bag made of
Soak in 0.9% saline for 10 minutes to absorb, then pull
Raise and drain for 15 minutes and measure weight gain. This
Is the absorption amount after 10 minutes (S10). Initial absorption rate = (S10 / S) × 100
り、（Ａ）と（Ｂ）との混合時または混合後、（Ｂ）の
融点以上の温度で加熱処理され、（Ｂ）が（Ａ）の表面
に部分的に固着されてなる請求項１または２記載の吸水
剤。3. A mixture of (A) and (B).
The heat treatment is performed at a temperature equal to or higher than the melting point of (B) during or after mixing (A) and (B), and (B) is partially fixed to the surface of (A). Or the water-absorbing agent according to 2.
以上の温度で加熱処理した時の繊維への固着率が４０％
以上である請求項１〜３のいずれか記載の吸水剤。繊維への固着率の測定法： ２００ｇ／ｍ 2 のフラッフ
パルプあるいは合成繊維（ＥＳ繊維ＥＡ；チッソ(株)
製）の層を直径１５ｃｍの円形に裁断し、繊維層の下面
から吸引しながら、この上に２ｇの吸水剤を均一に散粒
する。次いで（Ｂ）の融点より約１０℃高い温度で２分
間加熱処理した後、室温にまで冷却し、固着されていな
い吸水剤を振るい落として重量（Ｗ）を測定する。 繊維への固着率＝［（２−Ｗ）／２］×１００ 4. When the water-absorbing agent is sprinkled on the fiber layer and heat-treated at a temperature not lower than the melting point of (B), the fixation rate to the fiber is 40%.
The water absorbing agent according to any one of claims 1 to 3, which is the above. Method for measuring sticking rate to fiber: 200 g / m 2 fluff
Pulp or synthetic fiber (ES fiber EA; Chisso Corporation)
Made into a circle with a diameter of 15 cm, and the lower surface of the fiber layer
2g of water-absorbing agent is uniformly dispersed on this
I do. Then at a temperature about 10 ° C. higher than the melting point of (B) for 2 minutes
After heat treatment for a while, cool to room temperature and remove
The water absorbing agent is shaken off and the weight (W) is measured. Adhesion rate to fiber = [(2-W) / 2] × 100
Priority Applications (16)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5061143A JP2909692B2 (en) | 1993-02-24 | 1993-02-24 | Water absorbing agent |
| TW82111042A TW320647B (en) | 1993-02-24 | 1993-12-27 | |
| EP19940101065 EP0612533B1 (en) | 1993-02-24 | 1994-01-25 | Water absorbent composition and material |
| DE1994621634 DE69421634T2 (en) | 1993-02-24 | 1994-01-25 | Water absorbing composition and material |
| AT94101065T ATE186649T1 (en) | 1993-02-24 | 1994-01-25 | WATER ABSORBENT COMPOSITION AND MATERIAL |
| ES94101065T ES2138003T3 (en) | 1993-02-24 | 1994-01-25 | WATER ABSORBENT MATERIAL COMPOUND. |
| AU54849/94A AU663240B2 (en) | 1993-02-24 | 1994-02-02 | Water absorbent composition and material |
| CA 2116160 CA2116160C (en) | 1993-02-24 | 1994-02-22 | Water absorbent composition and water absorbing material |
| MXPA94001372A MXPA94001372A (en) | 1993-02-24 | 1994-02-23 | Water absorbent composition and material. |
| NO940618A NO940618L (en) | 1993-02-24 | 1994-02-23 | Water-absorbent and water-absorbing material |
| KR1019940003178A KR0138239B1 (en) | 1993-02-24 | 1994-02-23 | Water absorbing material |
| FI940845A FI940845A (en) | 1993-02-24 | 1994-02-23 | Water absorbent composition and material |
| CN94102107A CN1105578C (en) | 1993-02-24 | 1994-02-24 | Water absorbent and water absorging material |
| TR13894A TR28964A (en) | 1993-02-24 | 1994-02-24 | Water-absorbing composition and material. |
| US08/526,194 US5672419A (en) | 1993-02-24 | 1995-09-11 | Water absorbent composition and material |
| US08/782,031 US5716707A (en) | 1993-02-24 | 1997-01-15 | Water absorbent compositon and material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5061143A JP2909692B2 (en) | 1993-02-24 | 1993-02-24 | Water absorbing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06248187A JPH06248187A (en) | 1994-09-06 |
| JP2909692B2 true JP2909692B2 (en) | 1999-06-23 |
Family
ID=13162587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5061143A Expired - Fee Related JP2909692B2 (en) | 1993-02-24 | 1993-02-24 | Water absorbing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2909692B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003082250A (en) * | 2001-06-27 | 2003-03-19 | San-Dia Polymer Ltd | Water-absorbing resin composition and method for producing the same |
| EP1594557B1 (en) | 2003-02-10 | 2019-05-01 | Nippon Shokubai Co., Ltd. | Water-absorbent resin composition and its production process |
| US7173086B2 (en) * | 2003-10-31 | 2007-02-06 | Stockhausen, Inc. | Superabsorbent polymer with high permeability |
| WO2005107940A1 (en) * | 2004-05-12 | 2005-11-17 | Nippon Shokubai Co., Ltd. | Waste solution solidifying agent, process for preparing the same and use of the same |
| US7812082B2 (en) * | 2005-12-12 | 2010-10-12 | Evonik Stockhausen, Llc | Thermoplastic coated superabsorbent polymer compositions |
| JP2009280667A (en) * | 2008-05-21 | 2009-12-03 | San-Dia Polymer Ltd | Absorbent resin particle |
| KR101792968B1 (en) | 2014-05-23 | 2017-11-02 | 에스디피 글로벌 가부시키가이샤 | Water-absorbing resin particles, absorber comprising same, and absorbent article |
| JP6749116B2 (en) * | 2016-03-24 | 2020-09-02 | 花王株式会社 | Composite water-absorbing polymer and sanitary article containing the same |
| JP2017221275A (en) * | 2016-06-13 | 2017-12-21 | 花王株式会社 | Absorbent body |
| JP2018094246A (en) * | 2016-12-15 | 2018-06-21 | 花王株式会社 | Absorber |
| JP2019041859A (en) * | 2017-08-30 | 2019-03-22 | 花王株式会社 | Absorber |
| JP6975109B2 (en) * | 2018-08-31 | 2021-12-01 | 株式会社イノアックコーポレーション | Polyurethane foam and its molded product and method for manufacturing a molded product of polyurethane foam |
| JP7275017B2 (en) * | 2019-12-13 | 2023-05-17 | 株式会社リブドゥコーポレーション | ABSORBENT SHEET MANUFACTURING APPARATUS AND ABSORBENT SHEET MANUFACTURING METHOD |
| CN111068629A (en) * | 2019-12-25 | 2020-04-28 | 太仓运通新材料科技有限公司 | Water absorbent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2222780C3 (en) * | 1972-05-10 | 1975-05-07 | Vereinigte Papierwerke Schickedanz & Co, 8500 Nuernberg | Process for determining finely divided hydrocolloid swelling substances to be used in hygiene articles on documents |
| DE3741157A1 (en) * | 1987-12-04 | 1989-06-15 | Stockhausen Chem Fab Gmbh | METHOD FOR THE AGGLOMERATION OF WATER-SOILABLE POLYMER BY MELTING (SINTER) GRANULATION WITH POWDER-SUBSTANCES AND USE OF THE GRANULES |
| JP2831648B2 (en) * | 1988-03-31 | 1998-12-02 | 住友精化株式会社 | Water-absorbing water retention material |
| JPH0395211A (en) * | 1989-09-07 | 1991-04-19 | Sanyo Chem Ind Ltd | Moldable water-absorbing resin composition |
| JPH0819609B2 (en) * | 1990-08-30 | 1996-02-28 | 株式会社日本触媒 | Absorbent manufacturing method |
-
1993
- 1993-02-24 JP JP5061143A patent/JP2909692B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06248187A (en) | 1994-09-06 |
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