JP2613934B2 - Method for producing water-absorbing composite - Google Patents
Method for producing water-absorbing compositeInfo
- Publication number
- JP2613934B2 JP2613934B2 JP63308929A JP30892988A JP2613934B2 JP 2613934 B2 JP2613934 B2 JP 2613934B2 JP 63308929 A JP63308929 A JP 63308929A JP 30892988 A JP30892988 A JP 30892988A JP 2613934 B2 JP2613934 B2 JP 2613934B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- absorbing
- absorbing polymer
- weight
- monomer
- 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Polymerisation Methods In General (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paper (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、吸水性複合体の製造方法に関するものであ
る。更に詳しくは、吸水性ポリマーが繊維質基材に強固
に固定化されると共に吸水性能および柔軟性に優れ、し
かも残存モノマーが格段に少ない吸水性複合体を製造す
る方法に関するものであり、この吸水性複合体は紙オム
ツや生理用ナプキン等の各種吸水性物品に有利に使用す
ることができる。The present invention relates to a method for producing a water-absorbing composite. More specifically, the present invention relates to a method for producing a water-absorbing composite in which a water-absorbing polymer is firmly immobilized on a fibrous base material, has excellent water-absorbing performance and flexibility, and has significantly less residual monomer. The water-soluble composite can be advantageously used for various water-absorbing articles such as disposable diapers and sanitary napkins.
（従来の技術） 近年、自重の数十倍から数百倍の水を吸収する吸水性
ポリマーが開発され、紙オムツ、生理用ナプキン等の衛
生分野をはじめとして農林業分野、園芸分野、土木業分
野等に幅広く利用されている。(Prior art) In recent years, a water-absorbing polymer has been developed that absorbs water tens to hundreds of times its own weight. Widely used in various fields.
これらの吸水性ポリマーは一般に粉末状のものであ
り、生理用ナプキンや紙オムツ等の衛材用に使用する場
合には、吸水性ポリマーを不織布・紙・綿等の基材とサ
ンドイッチしたりパルプ等と混合するなどして吸水体を
構成し、柔軟性・通液性・通気性・吸水速度等を付与し
ている。These water-absorbing polymers are generally in the form of powder, and when used for sanitary materials such as sanitary napkins and disposable diapers, the water-absorbing polymer can be sandwiched with a base material such as nonwoven fabric, paper, cotton, or pulp. And the like to form a water-absorbing body, which imparts flexibility, liquid permeability, air permeability, water absorption speed, and the like.
しかしながら、これらの方法では、吸水体中に吸水性
ポリマーを安定に固定することは困難であり、吸水性ポ
リマーの吸水体中での移動や吸水体からの脱落を防止す
ることはできなかった。However, with these methods, it is difficult to stably fix the water-absorbing polymer in the water-absorbing body, and it has not been possible to prevent the water-absorbing polymer from moving in the water-absorbing body or falling off from the water-absorbing body.
粉末状の吸水性ポリマーを用いた事に基づくこれらの
欠点を改良すべく、シート状あるいはフィルム状や繊維
状の吸水性ポリマーが提案されている。しかしながら、
シート状あるいはフィルム状の吸水性ポリマーは、通気
性や柔軟性に欠け、又表面積が小さいために吸水速度が
小さいものであった。また、繊維状の吸水性ポリマー
は、吸水時のゲル強度が弱く、実際の使用に耐えず、し
かも複雑な製造工程を経るためにコスト的にも不利であ
った。In order to improve these drawbacks based on the use of a powdery water-absorbing polymer, a sheet-like, film-like or fibrous water-absorbing polymer has been proposed. However,
The sheet-like or film-like water-absorbing polymer lacks air permeability and flexibility, and has a low water absorption rate due to its small surface area. Further, the fibrous water-absorbing polymer has a low gel strength at the time of water absorption, cannot withstand actual use, and is disadvantageous in cost due to a complicated manufacturing process.
一方、粉末状の吸水性ポリマーを基材と組み合わせて
シート状あるいはフィルム状に成形するに際して接着剤
等により吸水性ポリマーを基材と一体化する方法も提案
されている。しかしながら、この方法では、接着力が不
十分で吸水性ポリマーの基材からの脱落が起こり易く、
また接着剤によって吸水性ポリマー表面が覆われるた
め、吸水性ポリマーの吸水速度や吸水倍率が低下すると
いう問題があった。On the other hand, a method has also been proposed in which, when a powdery water-absorbing polymer is combined with a substrate to form a sheet or film, the water-absorbing polymer is integrated with the substrate using an adhesive or the like. However, in this method, the adhesive force is insufficient and the water-absorbing polymer is likely to fall off from the substrate,
In addition, since the surface of the water-absorbing polymer is covered with the adhesive, there is a problem that the water-absorbing speed and the water-absorbing capacity of the water-absorbing polymer are reduced.
さらに、最近では繊維質基材にモノマーを噴霧や塗布
などの方法によって施した後、重合させることによって
吸水性ポリマーを固定化し吸水性複合体を製造する方法
が提案されている（特公表昭57−500546、特開昭61−27
5355、特開昭62−22811）。しかし、これらの方法によ
って得られる吸水性複合体は、吸水性ポリマーの脱落を
防止できるものの、残存モノマーは多く且つその吸水特
性も満足できるものではなかった。Further, recently, a method of producing a water-absorbing composite by immobilizing a water-absorbing polymer by applying a monomer to a fibrous base material by a method such as spraying or coating and then polymerizing the same has been proposed (Japanese Patent Publication No. -500546, JP-A-61-27
5355, JP-A-62-22811). However, although the water-absorbing composite obtained by these methods can prevent the water-absorbing polymer from falling off, it has a large amount of residual monomers and its water-absorbing properties are not satisfactory.
（発明が解決しようとする課題） 本発明は上記現状に鑑みなされたものである。従っ
て、本発明の目的は、吸水性ポリマーが繊維質基材に強
固に固定化されると共に吸水性能や柔軟性に優れ、しか
も残存モノマーが格段に低減された吸水性複合体を製造
するための方法を提供することにある。(Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned current situation. Accordingly, an object of the present invention is to produce a water-absorbing composite in which a water-absorbing polymer is firmly fixed to a fibrous base material, has excellent water-absorbing performance and flexibility, and has a significantly reduced residual monomer. It is to provide a method.
（課題を解決するための手段および作用） 本発明は、重合により吸水性ポリマーとなる親水性ア
クリル系モノマーを繊維質基材に付着させ、酸化性ラジ
カル重合開始剤および架橋剤の存在下に該モノマーを架
橋重合して繊維質基材に一体化した状態で吸水性ポリマ
ーを生成させた後、生成した吸水性ポリマーに対してポ
リマー100重量部あたり0.1〜20重量部の還元剤を接触吸
収させて乾燥することを特徴とする吸水性ポリマーと繊
維質基材とからなる吸水性複合体の製造方法に関するも
のである。(Means and Action for Solving the Problems) The present invention provides a method in which a hydrophilic acrylic monomer which becomes a water-absorbing polymer by polymerization is attached to a fibrous base material, and the hydrophilic acrylic monomer is added in the presence of an oxidizing radical polymerization initiator and a crosslinking agent. After producing a water-absorbing polymer in a state where the monomer is cross-linked and integrated into the fibrous base material, 0.1 to 20 parts by weight of a reducing agent per 100 parts by weight of the polymer is contact-absorbed with respect to the generated water-absorbing polymer. The present invention relates to a method for producing a water-absorbing composite comprising a water-absorbing polymer and a fibrous base material, wherein the composite is dried by drying.
本発明を更に詳しく説明する。 The present invention will be described in more detail.
本発明に用いられる重合により吸水性ポリマーとなる
親水性アクリル系モノマーとしては、従来より吸水性ポ
リマーの原料モノマーとしてよく知られているものが使
用でき、例えばアクリル酸、メタクリル酸、２−（メ
タ）アクリルアミド−２−メチルプロパンスルホン酸、
２−（メタ）アクリロイルエタンスルホン酸、２−（メ
タ）アクリロイルプロパンスルホン酸等の不飽和酸及び
これらの不飽和酸のアルカリ金属塩およびアンモニウム
塩；アクリルアミド、メタクリルアミド等の不飽和酸ア
ミド;2−ヒドロキシエチル（メタ）アクリレート、ポリ
エチレングリコールモノ（メタ）アクリレート等の水酸
基含有（メタ）アクリレート；ジメチルアミノエチル
（メタ）アクリレート等のカチオン性（メタ）アクリレ
ート及びその４級塩等を挙げることができ、これらの群
から選ばれる１種又は２種以上を主成分として使用する
ことができる。特に、アクリル酸およびアクリル酸アル
カリ金属塩が好適に使用され、その際アクリル酸とアク
リル酸アルカリ金属塩との使用比率は吸水能の点からモ
ル比で０〜70/100〜30とするのが好ましい。また、本発
明における親水性アクリル系モノマーは、前記した親水
性モノマーを主成分とするものであるが、得られる吸水
性複合体の吸水能を阻害しない範囲で（メタ）アクリル
酸メチル等の疎水性アクリル系モノマーやマレイン酸、
ビニルスルホン酸等の他の親水性モノマーを含んでいて
もよい。As the hydrophilic acrylic monomer that becomes a water-absorbing polymer by polymerization used in the present invention, those well-known as raw material monomers for a water-absorbing polymer can be used. For example, acrylic acid, methacrylic acid, 2- (meth) ) Acrylamide-2-methylpropanesulfonic acid,
Unsaturated acids such as 2- (meth) acryloylethanesulfonic acid and 2- (meth) acryloylpropanesulfonic acid and alkali metal salts and ammonium salts of these unsaturated acids; unsaturated acid amides such as acrylamide and methacrylamide; Hydroxy-containing (meth) acrylates such as hydroxyethyl (meth) acrylate and polyethylene glycol mono (meth) acrylate; cationic (meth) acrylates such as dimethylaminoethyl (meth) acrylate and quaternary salts thereof. One or more selected from these groups can be used as the main component. In particular, acrylic acid and alkali metal acrylate are preferably used, in which case the use ratio of acrylic acid and alkali metal acrylate should be 0 to 70/100 to 30 in terms of molar ratio from the viewpoint of water absorption capacity. preferable. The hydrophilic acrylic monomer in the present invention contains the above-mentioned hydrophilic monomer as a main component. However, the hydrophilic acrylic monomer such as methyl (meth) acrylate may be used as long as the water-absorbing ability of the resulting water-absorbing composite is not impaired. Acrylic monomers, maleic acid,
Other hydrophilic monomers such as vinyl sulfonic acid may be included.
前記モノマーを重合反応させる際には、後述の酸化性
ラジカル重合開始剤ともに、架橋剤を使用する。この架
橋剤は、重合で得られるポリマーの水溶性を制御して吸
水性ポリマーとして水膨潤性を付与するために慣用のも
のであり、例えばメチレンビスアクリルアミド、エチレ
ングイコールジ（メタ）アクリレート、ポリエチレング
リコールジ（メタ）アクリレート、トリメチロールプロ
パントリ（メタ）アクリレート、トリアリルシアヌレー
ト、トリアリルイソシアヌレート等の重合性不飽和基を
２個以上有する架橋性単量体や分子内に前記親水性アク
リル系モノマー中の官能基と反応しうる官能基を２個以
上有する化合物を挙げることができる。また、親水性ア
クリル系モノマーにアクリル酸及び／又はメタクリル酸
を用いる場合には、例えばエチレ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、脂肪族多価アルコールのジ又はポリグリシジルエ
ーテル、グリセリン、ペンタエリスリトール等のポリオ
ールおよびエチレンジアミン等のポリアミンなどのカル
ボキシ基に対し反応性の基を分子内に２個以上有する化
合物を架橋剤として使用できる。このような架橋剤はそ
れ自身単独で或いは２種以上の混合物としても使用でき
る。When the monomers are polymerized, a crosslinking agent is used together with an oxidative radical polymerization initiator described below. The crosslinking agent is commonly used to control the water solubility of the polymer obtained by polymerization and to impart water swelling properties as a water-absorbing polymer. For example, methylene bisacrylamide, ethylene glycol di (meth) acrylate, polyethylene A crosslinkable monomer having two or more polymerizable unsaturated groups such as glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, or the above-mentioned hydrophilic acrylic in the molecule. A compound having two or more functional groups capable of reacting with a functional group in the system monomer can be exemplified. When acrylic acid and / or methacrylic acid is used as the hydrophilic acrylic monomer, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, di- or polyglycidyl ether of aliphatic polyhydric alcohol, glycerin, pentaerythritol A compound having two or more groups reactive with a carboxy group in a molecule, such as a polyol such as a polyol and a polyamine such as ethylenediamine, can be used as a crosslinking agent. Such a crosslinking agent can be used alone or as a mixture of two or more kinds.
親水性アクリル系モノマーを重合させる際に用いられ
る酸化性ラジカル重合開始剤としては、水溶性のもので
あれば特に制限されず、例えば過硫酸カリウム、過硫酸
アンモニウム、過硫酸ナトリウム等の過硫酸塩；過酸化
水素、ｔ−ブチルハイドロパーオキサイド、クメンハイ
ドロパーオキサイド等のハイドロパーオキサイド；その
他、亜塩素酸塩、次亜塩素酸塩、第二セリウム塩、過マ
ンガン酸塩等が挙げられる。また上記酸化性ラジカル重
合開始剤と還元剤を併用してレドックス系開始剤として
用いてもよい。用いられる還元剤としては、例えば亜硫
酸ナトリウム、亜硫酸水素ナトリウム等の亜硫酸（水
素）塩；チオ硫酸ナトリウム等のチオ硫酸塩；亜二チオ
ン酸塩；亜リン酸水素ナトリウム、次亜リン酸水素ナト
リウム等の亜リン酸塩又は次亜リン酸塩；酢酸コバル
ト、硫酸第一銅、硫酸第一鉄等の金属塩;L−アスコルビ
ン酸等の有機還元剤；アニリン、モノエタノールアミ
ン、ヘキサメチレンジアミン等の第１級アミン；ジエタ
ノールアミン等の第２級アミン；ジメチルアニリン、ト
リエタノールアミン、テトラメチルエチレンジアミン等
の第３級アミン等が挙げられる。The oxidizing radical polymerization initiator used when polymerizing the hydrophilic acrylic monomer is not particularly limited as long as it is water-soluble, and examples thereof include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; Hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide and cumene hydroperoxide; and others, chlorite, hypochlorite, ceric salt, permanganate and the like. Further, the oxidizing radical polymerization initiator and the reducing agent may be used in combination as a redox initiator. Examples of the reducing agent to be used include sulfurous acid (hydrogen) salts such as sodium sulfite and sodium hydrogen sulfite; thiosulfate salts such as sodium thiosulfate; dithionites; sodium hydrogen phosphite, sodium hydrogen hypophosphite and the like Phosphites or hypophosphites; metal salts such as cobalt acetate, cuprous sulfate and ferrous sulfate; organic reducing agents such as L-ascorbic acid; aniline, monoethanolamine, hexamethylenediamine and the like Primary amines; secondary amines such as diethanolamine; tertiary amines such as dimethylaniline, triethanolamine, and tetramethylethylenediamine.
これらの前記した酸化性ラジカル重合開始剤の使用量
は、広い範囲とすることができるが、通常親水性アクリ
ル系モノマーに対して0.0002〜５重量％であり、好まし
くは0.01〜１重量％である。The amount of the oxidizing radical polymerization initiator described above can be in a wide range, but is usually 0.0002 to 5% by weight, and preferably 0.01 to 1% by weight, based on the hydrophilic acrylic monomer. .
本発明に用いられる繊維質基材としては、例えば紙、
不織布及び織布等のシート状物やスポンジなどの多孔性
シート状物であって、その素材は特に制限されることな
く、例えばセルロース等の天然繊維、ポリオレフィンや
ポリエステル等の合成繊維及び無機繊維等とすることが
できる。Examples of the fibrous base material used in the present invention include paper,
It is a sheet material such as a nonwoven fabric or a woven fabric or a porous sheet material such as a sponge, and the material is not particularly limited. For example, natural fibers such as cellulose, synthetic fibers such as polyolefin and polyester, and inorganic fibers. It can be.
本発明においては、先ず繊維質基材に親水性アクリル
系モノマーを付着させ、酸化性ラジカル重合開始剤およ
び架橋剤の存在下に該モノマーを架橋重合して繊維質基
材に一体化した状態で吸水性ポリマーを生成させる。In the present invention, first, a hydrophilic acrylic monomer is attached to a fibrous base material, and the monomer is cross-linked and polymerized in the presence of an oxidizing radical polymerization initiator and a cross-linking agent to be integrated with the fibrous base material. Produce a water-absorbing polymer.
繊維質基材に親水性アクリル系モノマーを付着させる
には、従来から公知の方法によることができ、通常該モ
ノマーの付着操作や後の重合反応の制御を容易とするた
めに該モノマーの水溶液が用いられる。付着させる方法
として、具体的には例えば、そのモノマー水溶液に基材
を浸漬・含浸する方法、スプレーを用いて基材に対して
モノマー水溶液の噴霧や吹き付けを行なう方法、ローラ
ーやスクリーン等の公知の印刷あるいは印捺方法によっ
てモノマー水溶液を縞状・点状・水玉模様等に塗布する
方法等が挙げられる。また、モノマー水溶液の付着の効
率を高めるために、増粘剤などの添加も可能である。The hydrophilic acrylic monomer can be attached to the fibrous base material by a conventionally known method. Usually, an aqueous solution of the monomer is used to facilitate the operation of attaching the monomer and controlling the polymerization reaction afterwards. Used. As a method of attaching, specifically, for example, a method of immersing and impregnating the substrate in the aqueous monomer solution, a method of spraying or spraying the aqueous monomer solution on the substrate using a spray, a known method such as a roller or a screen Examples include a method of applying an aqueous monomer solution in a striped, dot-like, polka-dot pattern, or the like by printing or printing. In order to increase the efficiency of the adhesion of the monomer aqueous solution, a thickener or the like can be added.
繊維質基材に対する親水性アクリル系モノマーの付着
量は特に制限はないが、一般的には繊維質基材１重量部
に対して該モノマー0.1〜100重量部の範囲である。好ま
しくは0.5〜25重量部である。The amount of the hydrophilic acrylic monomer attached to the fibrous base material is not particularly limited, but is generally in the range of 0.1 to 100 parts by weight of the monomer per 1 part by weight of the fibrous base material. Preferably it is 0.5 to 25 parts by weight.
架橋重合方法としては、例えばあらかじめ酸化性ラジ
カル重合開始剤および架橋剤を前記を親水性アクリル系
モノマーまたはそのモノマー水溶液中に溶かして繊維質
基材に付着させたのち熱重合する方法、モノマー（水溶
液）を繊維質基材に付着させたのち酸化性ラジカル重合
開始剤および架橋剤を散布等で基材に付着させて熱重合
する方法、あらかじめ酸化性ラジカル重合開始剤および
架橋剤をモノマー（水溶液）中に溶かして繊維質基材に
付着させたのち還元剤をさらに基材に付着せてレドック
ス重合する方法、あるいは還元剤を調整されたモノマー
水溶液中に溶かして繊維質基材に付着させたのち酸化性
ラジカル重合開始剤および架橋剤をさらに基材に付着さ
せレドックス重合する方法等が採用できる。いずれの重
合方法においても酸化性ラジカル重合開始剤の存在下で
行われるものであり、その際アゾ系の重合開始剤を併用
してもよい。このように重合反応は、熱重合、レドック
ス重合など公知のいずれの方法も取り得ることができる
が、残存モノマーが特に低減された吸水性複合体を得る
ために、重合反応は重合不活性な雰囲気下、例えば窒素
雰囲気下で行なわれるのが好ましい。また、酸化性ラジ
カル重合開始剤の存在下であれば放射線重合の方法も取
り得る。Examples of the cross-linking polymerization method include a method in which the oxidizing radical polymerization initiator and the cross-linking agent are dissolved in a hydrophilic acrylic monomer or an aqueous solution of the monomer in advance and attached to the fibrous base material, and then thermally polymerized. ) Is attached to the fibrous base material, and then an oxidizing radical polymerization initiator and a cross-linking agent are applied to the base material by spraying or the like to carry out thermal polymerization. A method in which redox polymerization is performed by dissolving the reducing agent into the fibrous substrate and then adhering the reducing agent to the substrate, or dissolving the reducing agent in the adjusted aqueous monomer solution and adhering to the fibrous substrate. A method in which an oxidizing radical polymerization initiator and a cross-linking agent are further adhered to a base material to carry out redox polymerization can be employed. In any of the polymerization methods, the polymerization is carried out in the presence of an oxidizing radical polymerization initiator, and in that case, an azo-based polymerization initiator may be used in combination. As described above, the polymerization reaction can be performed by any known method such as thermal polymerization and redox polymerization.However, in order to obtain a water-absorbing complex in which residual monomers are particularly reduced, the polymerization reaction is performed in an atmosphere in a polymerization inert atmosphere. It is preferably carried out under a nitrogen atmosphere, for example. In addition, a radiation polymerization method may be employed as long as the initiator is in the presence of an oxidizing radical polymerization initiator.
次に繊維質基材に一体化して生成した吸水性ポリマー
に還元剤を接触吸収させて乾燥することによって、目的
とする吸水性複合体が得られる。Next, the desired water-absorbing composite is obtained by contact-absorbing the reducing agent with the water-absorbing polymer formed integrally with the fibrous base material and drying.
なお、生成した吸水性ポリマーにそのまま還元剤を接
触吸収させる方法や、吸水性ポリマーが含水ゲル状物の
場合それを一度乾燥した後に還元剤を接触吸収させる方
法とが考えられるが、どちらの方法を用いても良い。In addition, a method in which the reducing agent is contact-absorbed with the produced water-absorbing polymer as it is, or a method in which the reducing agent is contact-absorbed after once drying the water-absorbing polymer in the case of a hydrogel, are considered. May be used.
本発明において、吸水性ポリマーに接触吸収させて用
いられる還元剤としては、前記したレドックス重合法に
用いられるのと同様のものが挙げられる。中でも、吸水
性ポリマーに対する接触吸収操作が容易で乾燥後の吸水
性複合体中の残存モノマー低減効果が大きいことから、
亜硫酸塩または亜硫酸水素塩が好ましく、それらを水溶
液の形態で用いるのが好ましい。In the present invention, examples of the reducing agent that is used by being contact-absorbed with the water-absorbing polymer include those similar to those used in the above-described redox polymerization method. Among them, the contact absorption operation for the water-absorbing polymer is easy, and the residual monomer reduction effect in the water-absorbing composite after drying is large,
Sulfites or bisulfites are preferred, and they are preferably used in the form of an aqueous solution.
本発明において吸水性ポリマーに還元剤を接触吸収さ
せる方法は、例えば還元剤あるいはその水溶液や水と親
水性有機溶媒の混合液に溶かした溶液に繊維質基材に一
体化して生成した吸水性ポリマーを浸漬する方法、還元
剤あるいはその溶液を噴霧する方法等がある。また、溶
液を用いる場合その還元剤濃度は0.01〜50重量％が好ま
しい。この溶液濃度があまり濃すぎると還元剤が吸収性
ポリマー中に吸収されにくく、逆に薄ければ吸水性ポリ
マー中に吸収された水分の乾燥に長時間を要し経済的に
好ましくない。In the present invention, the method of contacting and absorbing the reducing agent to the water-absorbing polymer is, for example, a water-absorbing polymer produced by integrating the reducing agent or an aqueous solution thereof or a mixed solution of water and a hydrophilic organic solvent with the fibrous base material. And a method of spraying a reducing agent or a solution thereof. When a solution is used, the concentration of the reducing agent is preferably 0.01 to 50% by weight. If the solution concentration is too high, the reducing agent is less likely to be absorbed in the absorbent polymer, while if it is too thin, it takes a long time to dry the water absorbed in the water-absorbent polymer, which is economically undesirable.
吸水性ポリマーに吸収させるための還元剤の使用量は
吸水性ポリマー100重量部に対して0.1〜20重量部である
が、好ましくは0.5〜10重量部である。添加量が、0.1重
量部未満であると残存モノマーの低減が不十分であり、
また10重量部を越える多量でも使用量にみあった残存モ
ノマーの低減効果が見られず不経済である。The amount of the reducing agent to be absorbed by the water-absorbing polymer is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the water-absorbing polymer. If the addition amount is less than 0.1 part by weight, the reduction of the residual monomer is insufficient,
In addition, even if the amount exceeds 10 parts by weight, the effect of reducing the residual monomer in view of the amount used is not seen, and it is uneconomical.
吸水性ポリマーに還元剤を接触吸収させる際、先に示
した還元剤の群の中から、一種又は二種以上の組合せを
用いてもよい。When the reducing agent is contact-absorbed to the water-absorbing polymer, one or a combination of two or more of the above-described reducing agents may be used.
本発明において、吸水性ポリマーに対する還元剤処理
は重要な要件であり、架橋重合前のモノマーに対して還
元剤を添加しても、得られる吸水性複合体の残存モノマ
ー量は低減しない。また、繊維質基材に一体化した状態
の吸水性ポリマーに対して還元剤を接触吸収させる処理
方法も重要な要件であり、粉末状の吸水性ポリマーに対
して還元剤を接触吸収させたのでは、操作中に吸水性ポ
リマーの飛散等が起こって取扱いが困難となるだけでな
く、比較的多量の還元剤を使用して残存モノマー低減効
果を高めようとしても、吸水性ポリマーが団粒化してし
まいこれを乾燥しても充分な残存モノマー低減が達成で
きない。In the present invention, the treatment of the water-absorbing polymer with a reducing agent is an important requirement, and even if a reducing agent is added to the monomer before cross-linking polymerization, the amount of the residual monomer in the obtained water-absorbing composite does not decrease. Another important requirement is a treatment method in which the reducing agent is contact-absorbed to the water-absorbing polymer integrated with the fibrous base material, and the reducing agent is contact-absorbed to the powdery water-absorbing polymer. In addition, not only does the water-absorbing polymer scatter during operation, making handling difficult.In addition, the water-absorbing polymer becomes agglomerated even if a relatively large amount of reducing agent is used to increase the residual monomer reduction effect. Even if this is dried, a sufficient reduction of the residual monomer cannot be achieved.
本発明において吸水性ポリマーに還元剤を接触吸収さ
せたのちの乾燥方法としては、熱風、赤外線、マイクロ
波等による方法が挙げられるが、特に限定されるもので
はない。乾燥時の温度は、乾燥効果および残存モノマー
低減効果の点から100〜200℃の範囲が好ましい。In the present invention, examples of a drying method after contacting and absorbing the reducing agent to the water-absorbing polymer include methods using hot air, infrared rays, microwaves, and the like, but are not particularly limited. The temperature at the time of drying is preferably in the range of 100 to 200 ° C from the viewpoint of the drying effect and the residual monomer reduction effect.
（発明の効果） 本発明の方法に従えば、繊維質基材に吸水性ポリマー
が強固に固定化され繊維質基材からの吸水性ポリマーの
脱落が防止できると共に吸水性能や柔軟性に優れ、しか
も残存モノマーが格段に少ない吸水性複合体が得られ
る。(Effects of the Invention) According to the method of the present invention, the water-absorbing polymer is firmly fixed to the fibrous base material, so that the water-absorbing polymer can be prevented from falling off from the fibrous base material, and has excellent water-absorbing performance and flexibility. In addition, a water-absorbing composite having much less residual monomer can be obtained.
従って、本発明の方法で製造される吸水性複合体は、
人体や環境への悪影響がなく、衛材用、食品用、土木、
農林等の分野に幅広く使用でき、しかも従来品にない優
れた吸水特性を有するものである。Therefore, the water-absorbing composite produced by the method of the present invention is
It has no adverse effect on human body and environment, and is used for protection materials, food, civil engineering,
It can be widely used in fields such as agriculture and forestry, and has excellent water absorption properties not found in conventional products.
（実施例） 以下、実施例および比較例をあげて本発明をさらに詳
述するが、本発明の範囲がこれらの実施例により限定さ
れるものではない。なお、実施例に記載の吸水性能、残
存モノマー量は下記試験方法によって測定した。(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples. In addition, the water absorption performance and residual monomer amount described in the examples were measured by the following test methods.
吸水倍率 細かく裁断した吸水性複合体約0.5g（Wp）を不織布製
のティーバック式袋（40mm×150mm）に入れ、0.9重量％
塩化ナトリウム水溶液中に30分間浸漬した。ティーバッ
ク式袋を引きあげ、５分間水切りを行った後、ティーバ
ック式袋の重量（Ｗ）を測定し、以下の式で吸水倍率を
算出した。Water absorption capacity About 0.5 g (Wp) of the water-absorbing complex cut into fine pieces is placed in a non-woven tea bag bag (40 mm x 150 mm), and 0.9% by weight.
It was immersed in an aqueous solution of sodium chloride for 30 minutes. After the tea bag bag was pulled out and drained for 5 minutes, the weight (W) of the tea bag bag was measured, and the water absorption capacity was calculated by the following formula.
Ｗ＝吸水性複合体入りティーバック式袋の吸水後の重量
（ｇ） Wo＝ブランクのティーバック式袋の吸水後の重量（ｇ） Wp＝吸水性複合体の重量（ｇ） 残存モノマー量 吸水性複合体に含まれている吸水性ポリマー量が0.5g
になるように吸水性複合体をはかりとり、細かく裁断後
１リットルの純水中に攪拌しながら分散した。２時間後
に分散液をワットマン紙で過し、液中の残存モノ
マー量を高速液体クロマトグラフィーを用いて測定し
た。その測定値より吸水性ポリマー中の残存モノマー量
を求めた。 W = Weight (g) of water-absorbent composite-containing bag after absorption Wo = Weight of blank tea-bag-type bag after absorption (g) Wp = Weight of water-absorbent composite (g) Residual monomer amount Water absorption 0.5 g of water-absorbing polymer contained in the water-soluble composite
The water-absorbing composite was weighed so as to obtain a finely cut piece, and after fine cutting, dispersed in 1 liter of pure water with stirring. Two hours later, the dispersion was passed through Whatman paper, and the amount of the residual monomer in the liquid was measured using high performance liquid chromatography. The amount of residual monomer in the water-absorbing polymer was determined from the measured value.
実施例 １ 75モル％が水酸化ナトリウムにより中和された部分中
和アクリル酸水溶液（モノマー濃度:37重量％）にN,N−
メチレンビスアクリルアミド0.06モル％（対部分中和ア
クリル酸）および過硫酸アンモニウム1.0重量％（対部
分中和アクリル酸）を溶解し、次に窒素ガスを吹き込ん
で溶存酸素を除去した。こうして得られたモノマー水溶
液を目付100g/m2のポリエステル不織布の上にモノマー
純分の付着量が150g/m2となるようにスプレーで均一に
噴霧した。Example 1 N, N- was added to an aqueous solution of partially neutralized acrylic acid (monomer concentration: 37% by weight) in which 75 mol% was neutralized with sodium hydroxide.
0.06 mol% of methylenebisacrylamide (partially neutralized acrylic acid) and 1.0% by weight of ammonium persulfate (partially neutralized acrylic acid) were dissolved, and then nitrogen gas was blown to remove dissolved oxygen. The aqueous monomer solution thus obtained was sprayed evenly on a polyester nonwoven fabric having a basis weight of 100 g / m 2 so that the amount of pure monomer attached was 150 g / m 2 .
これを反応器の中に入れ75℃で15分間保持して、不織
布に付着しているモノマーを重合させたのち乾燥して、
該不織布に吸水性ポリマー含水ゲルに付着した複合物
（１）を得た。こうして得られた複合物（１）中の吸水
性ポリマー含水ゲルの固形分は、87重量％であり、吸水
性ポリマー中の残存モノマー量は18000ppmであった。This is put in a reactor and kept at 75 ° C. for 15 minutes to polymerize the monomers adhering to the nonwoven fabric, and then dried,
The composite (1) attached to the water-absorbing polymer hydrogel on the nonwoven fabric was obtained. The solid content of the water-absorbing polymer hydrogel in the composite (1) thus obtained was 87% by weight, and the amount of residual monomers in the water-absorbing polymer was 18000 ppm.
次いで、この複合物（１）を濃度1.0重量％の亜硫酸
水素ナトリウム水溶液に浸漬し複合物（１）の還元剤水
溶液吸収量が750g/m2になるように調整したのち、150℃
で20分間乾燥した。Next, the composite (1) is immersed in a 1.0% by weight aqueous solution of sodium hydrogen sulfite to adjust the composite (1) to have an absorption amount of a reducing agent aqueous solution of 750 g / m 2, and then to 150 ° C.
For 20 minutes.
こうして得られた吸水性ポリマーと繊維質基材とから
なる吸水性複合体（１）の吸水倍率は40.1g/g、残存モ
ノマー量は50ppmであった。The water-absorbing composite (1) composed of the water-absorbing polymer thus obtained and the fibrous base material had a water absorption capacity of 40.1 g / g and a residual monomer content of 50 ppm.
実施例 ２ 75モル％が水酸化ナトリウムにより中和された部分中
和アクリル酸水溶液（モノマー濃度:50重量％）にN,N−
メチレンビスアクリルアミド0.006モル％（対部分中和
アクリル酸）および過硫酸アンモニウム1.0重量％（対
部分中和アクリル酸）を溶解し、次に窒素ガスを吹き込
んで溶存酸素を除去した。こうして得られたモノマー水
溶液を目付100g/m2のポリエステル不織布の上にモノマ
ー純分の付着量が150g/m2となるようにスプレーで均一
に噴霧した。Example 2 N, N- was added to a partially neutralized acrylic acid aqueous solution (monomer concentration: 50% by weight) in which 75 mol% was neutralized with sodium hydroxide.
0.006 mol% of methylenebisacrylamide (based on partially neutralized acrylic acid) and 1.0% by weight of ammonium persulfate (based on partially neutralized acrylic acid) were dissolved, and then nitrogen gas was blown to remove dissolved oxygen. The aqueous monomer solution thus obtained was sprayed evenly on a polyester nonwoven fabric having a basis weight of 100 g / m 2 so that the amount of pure monomer attached was 150 g / m 2 .
これを反応器の中に入れ85℃で20分間保持して、不織
布に付着しているモノマーを重合させて、該不織布に吸
水性ポリマー含水ゲルに付着した複合物（２）を得た。
こうして得られた複合物（２）中の吸水性ポリマー含水
ゲルの固形分は、85重量％であり、吸水性ポリマー中の
残存モノマー量は12000ppmであった。This was placed in a reactor and kept at 85 ° C. for 20 minutes to polymerize the monomer adhering to the nonwoven fabric, thereby obtaining a composite (2) attached to the water-absorbing polymer hydrogel on the nonwoven fabric.
The solid content of the water-absorbing polymer hydrogel in the composite (2) thus obtained was 85% by weight, and the amount of residual monomers in the water-absorbing polymer was 12000 ppm.
次いで、この複合物（２）を濃度1.0重量％の亜硫酸
水素ナトリウム水溶液に浸漬し複合物（２）の還元剤水
溶液吸収量が750g/m2になるように調整したのち、150℃
で20分間乾燥した。Next, the composite (2) is immersed in a 1.0% by weight aqueous solution of sodium bisulfite to adjust the composite (2) to have an absorption amount of a reducing agent aqueous solution of 750 g / m 2, and then to 150 ° C.
For 20 minutes.
こうして得られた吸水性ポリマーと繊維質基材とから
なる吸水性複合体（２）の吸水倍率は40.5g/g、残存モ
ノマー量は40ppmであった。The water-absorbing composite (2) comprising the water-absorbing polymer thus obtained and the fibrous base material had a water absorption capacity of 40.5 g / g and a residual monomer content of 40 ppm.
実施例 ３ 実施例１において用いた還元剤の亜硫酸水素ナトリウ
ム水溶液を1.0重量％モノエタノールアミン水溶液に代
えた他は実施例１と同様にして吸水性複合体（３）を得
た。Example 3 A water-absorbing complex (3) was obtained in the same manner as in Example 1, except that the aqueous sodium hydrogen sulfite solution as the reducing agent used in Example 1 was replaced with a 1.0% by weight aqueous solution of monoethanolamine.
この吸水性複合体（３）の吸水倍率は40.2g/g、残存
モノマー量は110ppmであった。This water-absorbing composite (3) had a water absorption capacity of 40.2 g / g and a residual monomer amount of 110 ppm.
実施例 ４ 実施例１において用いた還元剤の亜硫酸水素ナトリウ
ム水溶液を1.0重量％Ｌ−アルコルビン酸水溶液に代え
た他は実施例１と同様にして吸水性複合体（４）を得
た。Example 4 A water-absorbing complex (4) was obtained in the same manner as in Example 1, except that the aqueous solution of sodium hydrogen sulfite as the reducing agent used in Example 1 was replaced with an aqueous solution of 1.0% by weight of L-alcorbic acid.
この吸水性複合体（４）の吸水倍率は42.5g/g、残存
モノマー量は90ppmであった。This water-absorbing composite (4) had a water absorption capacity of 42.5 g / g and a residual monomer content of 90 ppm.
実施例 ５ 実施例１において用いた還元剤の亜硫酸水素ナトリウ
ムの水溶液濃度を0.2重量％代えた他は実施例１と同様
にして吸水性複合体（５）を得た。Example 5 A water-absorbing composite (5) was obtained in the same manner as in Example 1, except that the concentration of the aqueous solution of sodium hydrogen sulfite as the reducing agent used in Example 1 was changed to 0.2% by weight.
この吸水性複合体（５）の吸水倍率は41.2g/g、残存
モノマー量は220ppmであった。The water absorbing composite (5) had a water absorption capacity of 41.2 g / g and a residual monomer content of 220 ppm.
実施例 ６ 実施例１において用いた還元剤の亜硫酸水素ナトリウ
ムの水溶液濃度を0.05重量％代えた他は実施例１と同様
にして吸水性複合体（６）を得た。Example 6 A water-absorbing composite (6) was obtained in the same manner as in Example 1, except that the concentration of the aqueous solution of sodium hydrogen sulfite as the reducing agent used in Example 1 was changed to 0.05% by weight.
この吸水性複合体（６）の吸水倍率は41.5g/g、残存
モノマー量は490ppmであった。This water-absorbing composite (6) had a water absorption capacity of 41.5 g / g and a residual monomer content of 490 ppm.
実施例 ７ 75モル％が水酸化ナトリウムにより中和された部分中
和アクリル酸水溶液（モノマー濃度:37重量％）にN,N−
メチレンビスアクリルアミド0.06モル％（対部分中和ア
クリル酸）および過硫酸アンモニウム1.0重量％（対部
分中和アクリル酸）を溶解し、次に窒素ガスを吹き込ん
で溶存酸素を除去した。こうして得られたモノマー水溶
液を目付90g/m2のポリエステル不織布の上に、モノマー
純分の付着量が120g/m2となるようにスプレーで均一に
噴霧した。Example 7 N, N- was added to an aqueous solution of partially neutralized acrylic acid (monomer concentration: 37% by weight) in which 75 mol% was neutralized with sodium hydroxide.
0.06 mol% of methylenebisacrylamide (partially neutralized acrylic acid) and 1.0% by weight of ammonium persulfate (partially neutralized acrylic acid) were dissolved, and then nitrogen gas was blown to remove dissolved oxygen. The aqueous monomer solution thus obtained was uniformly sprayed on a polyester nonwoven fabric having a basis weight of 90 g / m 2 so that the amount of pure monomer attached was 120 g / m 2 .
これを反応器の中に入れ75℃で15分間保持して、不織
布に付着しているモノマーを重合させて、該不織布に吸
水性ポリマー含水ゲルの付着した複合物（７）を得た。
こうして得られた複合物（７）中の吸水性ポリマー含水
ゲルの固形分は、55重量％であり、吸水性ポリマー中の
残存モノマー量は19000ppmであった。This was placed in a reactor and kept at 75 ° C. for 15 minutes to polymerize the monomer adhering to the nonwoven fabric, thereby obtaining a composite (7) having the water-absorbing polymer hydrogel adhered to the nonwoven fabric.
The solid content of the hydrogel of the water-absorbing polymer in the composite (7) thus obtained was 55% by weight, and the amount of the residual monomer in the water-absorbing polymer was 19,000 ppm.
次いで、この複合物（７）に濃度1.0重量％の亜硫酸
水素ナトリウム水溶液を、複合物（７）の還元剤水溶液
吸収量が600g/m2になるように噴霧したのち、150℃で20
分間乾燥した。Next, an aqueous solution of sodium bisulfite having a concentration of 1.0% by weight was sprayed on the composite (7) so that the absorption amount of the aqueous solution of the reducing agent of the composite (7) was 600 g / m 2, and then the mixture was heated at 150 ° C. for 20 minutes.
Dried for minutes.
こうして得られた吸水性ポリマーと繊維質基材とから
なる吸水性複合体（７）の吸水倍率は41.3g/g、残存モ
ノマー量は60ppmであった。The water-absorbing composite (7) comprising the water-absorbing polymer thus obtained and the fibrous base material had a water absorption capacity of 41.3 g / g and a residual monomer content of 60 ppm.
実施例 ８ 75モル％が水酸化カリウムにより中和された部分中和
アクリル酸水溶液（モノマー濃度:60重量％）にポリエ
チレングリコールジアクリレート（新中村化学株式会社
製Ａ−600）0.006モル％（対部分中和アクリル酸）およ
び過硫酸アンモニウム0.5重量％（対部分中和アクリル
酸）を溶解し、次に窒素ガスを吹き込んで溶存酸素を除
去した。こうして得られたモノマー水溶液に目付75g/m2
のレーヨン不織布を、モノマー純分の付着量が113g/m2
となるように浸漬した。Example 8 0.006 mol% of polyethylene glycol diacrylate (A-600 manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to a partially neutralized acrylic acid aqueous solution (monomer concentration: 60% by weight) in which 75 mol% was neutralized with potassium hydroxide. Partially neutralized acrylic acid) and 0.5% by weight of ammonium persulfate (relative to partially neutralized acrylic acid) were dissolved, and then nitrogen gas was blown to remove dissolved oxygen. The aqueous monomer solution thus obtained has a basis weight of 75 g / m 2.
Of rayon non-woven fabric with a monomer content of 113 g / m 2
It was immersed so that it became.
続いて、この不織布に濃度0.5重量％の亜硫酸水素ナ
トリウム水溶液を付着量が20g/m2となるように噴霧して
付着せしめ、直ちに反応器の中に入れ60℃で20分間保持
して、不織布に付着しているモノマーを重合させて、該
不織布に吸水性ポリマー含水ゲルの付着した複合物
（８）を得た。こうして得られた複合物（８）中の吸水
性ポリマー含水ゲルの固形分は70重量％であり、吸水性
ポリマー中の残存モノマー量は9000ppmであった。Subsequently, an aqueous solution of sodium bisulfite having a concentration of 0.5% by weight was sprayed onto the non-woven fabric so that the applied amount became 20 g / m 2, and the non-woven fabric was immediately placed in a reactor and maintained at 60 ° C. for 20 minutes. The monomer adhering to the polymer was polymerized to obtain a composite (8) in which the water-absorbing polymer hydrogel was adhered to the nonwoven fabric. The solid content of the water-absorbing polymer hydrogel in the composite (8) thus obtained was 70% by weight, and the amount of residual monomers in the water-absorbing polymer was 9000 ppm.
次いで、この複合物（８）を濃度1.0重量％の亜硫酸
水素ナトリウム水溶液に浸漬し複合物（８）の還元剤水
溶液吸収量が580g/m2になるように調整したのち、150℃
で20分間乾燥した。Next, the composite (8) is immersed in an aqueous solution of sodium bisulfite having a concentration of 1.0% by weight to adjust the absorption of the reducing agent aqueous solution of the composite (8) to 580 g / m 2, and then to 150 ° C.
For 20 minutes.
こうして得られた吸水性ポリマーと繊維質基材とから
なる吸水性複合体（８）の吸水倍率は35.3g/g、残存モ
ノマー量は40ppmであった。The water-absorbing composite (8) comprising the water-absorbing polymer and the fibrous base material thus obtained had a water absorption capacity of 35.3 g / g and a residual monomer content of 40 ppm.
比較例 １ 実施例１において用いた還元剤の亜硫酸水素ナトリウ
ム水溶液を蒸留水に代えた他は実施例１と同様にして比
較吸水性複合体（１）を得た。Comparative Example 1 A comparative water-absorbing complex (1) was obtained in the same manner as in Example 1, except that the aqueous solution of sodium hydrogen sulfite as the reducing agent used in Example 1 was replaced with distilled water.
この比較吸水性複合体（１）の吸水倍率は41.2g/g、
残存モノマー量は15000ppmであった。The water absorption capacity of this comparative water-absorbing composite (1) was 41.2 g / g,
The residual monomer amount was 15000 ppm.
比較例 ２ 実施例１において用いた還元剤の亜硫酸水素ナトリウ
ムの水溶液濃度を0.005重量％に代えた他は実施例１と
同様にして比較吸水性複合体（２）を得た。Comparative Example 2 A comparative water-absorbing complex (2) was obtained in the same manner as in Example 1 except that the concentration of the aqueous solution of sodium hydrogen sulfite as the reducing agent used in Example 1 was changed to 0.005% by weight.
この比較吸水性複合体（２）の吸水倍率は41.5g/g、
残存モノマー量は11000ppmであった。This comparative water-absorbing composite (2) has a water absorption capacity of 41.5 g / g,
The residual monomer amount was 11000 ppm.
比較例 ３ 実施例１において用いた還元剤の亜硫酸水素ナトリウ
ムの水溶液濃度を0.01重量％に代えた他は実施例１と同
様にして比較吸水性複合体（３）を得た。Comparative Example 3 A comparative water-absorbent composite (3) was obtained in the same manner as in Example 1 except that the concentration of the aqueous solution of sodium hydrogen sulfite as the reducing agent used in Example 1 was changed to 0.01% by weight.
この比較吸水性複合体（３）の吸水倍率は41.3g/g、
残存モノマー量は4300ppmであった。The comparative water-absorbing composite (3) had a water absorption capacity of 41.3 g / g,
The residual monomer amount was 4,300 ppm.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ２１Ｈ 21/22 Ｄ２１Ｈ 5/22 Ｃ (56)参考文献 特開 平２−68365（ＪＰ，Ａ) 特開 昭62−142561（ＪＰ，Ａ) 特開 昭63−291908（ＪＰ，Ａ) 特公 昭48−17636（ＪＰ，Ｂ１)──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location D21H 21/22 D21H 5/22 C (56) References JP-A-2-68365 (JP, A) JP-A-62-142561 (JP, A) JP-A-63-291908 (JP, A) JP-B-48-17636 (JP, B1)
Claims (4)
クリル系モノマーを繊維質基材に付着させ、酸化性ラジ
カル重合開始剤および架橋剤の存在下に該モノマーを架
橋重合して繊維質基材に一体化した状態で吸水性ポリマ
ーを生成させた後、生成した吸水性ポリマーに対してポ
リマー100重量部あたり0.1〜20重量部の還元剤を接触吸
収させて乾燥することを特徴とする吸水性ポリマーと繊
維質基材とからなる吸水性複合体の製造方法。1. A fibrous base material obtained by attaching a hydrophilic acrylic monomer which becomes a water-absorbing polymer by polymerization to a fibrous base material, and cross-linking and polymerizing the monomer in the presence of an oxidizing radical polymerization initiator and a cross-linking agent. After producing a water-absorbing polymer in an integrated state, the water-absorbing polymer is characterized by being contact-absorbed with 0.1 to 20 parts by weight of a reducing agent per 100 parts by weight of the produced water-absorbing polymer and dried. A method for producing a water-absorbing composite comprising a polymer and a fibrous base material.
り、それらを水溶液の形態で吸水性ポリマーに接触吸収
させる請求項１記載の吸水性複合体の製造方法。2. The method for producing a water-absorbing composite according to claim 1, wherein the reducing agent is a sulfite or a hydrogen sulfite, and the water-absorbing polymer is brought into contact with the reducing agent in the form of an aqueous solution.
項１記載の吸水性複合体の製造方法。3. The method for producing a water-absorbent composite according to claim 1, wherein the fibrous base material is paper, nonwoven fabric, or woven fabric.
量が吸水性ポリマー100重量部に対して0.5〜10重量部の
範囲である請求項１記載の吸水性複合体の製造方法。4. The method for producing a water-absorbing composite according to claim 1, wherein the amount of the reducing agent to be contact-absorbed with the water-absorbing polymer is in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the water-absorbing polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63308929A JP2613934B2 (en) | 1988-12-08 | 1988-12-08 | Method for producing water-absorbing composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63308929A JP2613934B2 (en) | 1988-12-08 | 1988-12-08 | Method for producing water-absorbing composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02160975A JPH02160975A (en) | 1990-06-20 |
| JP2613934B2 true JP2613934B2 (en) | 1997-05-28 |
Family
ID=17986978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63308929A Expired - Lifetime JP2613934B2 (en) | 1988-12-08 | 1988-12-08 | Method for producing water-absorbing composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2613934B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10052611B2 (en) | 2014-12-10 | 2018-08-21 | Lg Chem, Ltd. | Method of preparing superabsorbent polymer |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2680670B1 (en) * | 1991-09-02 | 1995-07-13 | Elysees Balzac Financiere | DRYING COMBINATION. |
| KR20010053079A (en) * | 1998-06-29 | 2001-06-25 | 데이비드 엠 모이어 | Absorbent article including a reducing agent for feces |
| US6562743B1 (en) * | 1998-12-24 | 2003-05-13 | Bki Holding Corporation | Absorbent structures of chemically treated cellulose fibers |
| US20010044614A1 (en) * | 1999-12-23 | 2001-11-22 | Damay Emmanuelle Cecile | Reducing agents for feminine care products |
| US7018497B2 (en) * | 2001-12-14 | 2006-03-28 | Kimberly-Clark Worldwide, Inc. | Method of making an absorbent structure having high integrity |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069604B2 (en) * | 1985-12-18 | 1994-02-09 | 東レ株式会社 | Deodorant material |
| JPH07121976B2 (en) * | 1987-05-26 | 1995-12-25 | ユニ・チャーム株式会社 | Method for producing water-absorbent composite |
| JPH0268365A (en) * | 1988-09-01 | 1990-03-07 | Norin Suisansyo Sanshi Shikenjiyou | Graft polymerization processing for silk |
-
1988
- 1988-12-08 JP JP63308929A patent/JP2613934B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10052611B2 (en) | 2014-12-10 | 2018-08-21 | Lg Chem, Ltd. | Method of preparing superabsorbent polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02160975A (en) | 1990-06-20 |
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