【発明の詳細な説明】［産業上の利用分野］本発明は、吸水速度、ゲル強度などの性質が改良された
吸水剤及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a water absorbing agent with improved properties such as water absorption rate and gel strength, and a method for producing the same.
ポリアクリル酸塩等からなる吸水剤は自重の数百倍の水
を吸収し、尿や血液に対しても高度の吸収能を有するの
で、生理用ナプキン、紙オムツ等に用いられる。Water-absorbing agents made of polyacrylates and the like absorb several hundred times their own weight in water and have a high ability to absorb urine and blood, so they are used in sanitary napkins, disposable diapers, and the like.
［従来の技術］吸水剤として種々のタイプのものが知られているが、ポ
リアクリル酸塩系樹脂が主流を占めている。[Prior Art] Various types of water absorbing agents are known, but polyacrylate resins are the most popular.
吸水剤は、通常、粉末状、繊維状あるいは被膜状の形態
で実用に供される。吸水剤の性能は吸水速度、吸水倍率
、ゲル強度などの性質によって評価されるが、吸水倍率
の高い軟質ゲルは吸水速度、ゲル強度が劣り、一方、吸
水速度、ゲル強度の優れた硬質ゲルは吸水倍率が低い傾
向が見られる。Water-absorbing agents are usually put into practical use in the form of powder, fibers, or film. The performance of water absorbing agents is evaluated by properties such as water absorption rate, water absorption capacity, and gel strength. Soft gels with high water absorption capacity have poor water absorption rate and gel strength, while hard gels with excellent water absorption rate and gel strength have poor water absorption rate and gel strength. There is a tendency for the water absorption capacity to be low.
カルボキシル基を有する吸水性樹脂の粉末を吸水剤とし
て用いた場合の実用上の問題として、“ままこ“の生成
があげられる。“ままこ”が生成すると、樹脂粉末の水
に接した部分が吸水膨潤して塊状のゲルとなり、水の内
部への浸透を妨げてしまう。また、粉末粒子−個のみを
みても、表面部のゲルが内部への水の浸透を妨げ、吸水
速度が低下するという傾向が見られる。こうした現象は
吸水倍率の高い軟質ゲルで著しい。A practical problem when using a water-absorbing resin powder having a carboxyl group as a water-absorbing agent is the formation of "mamako". When "mamako" is formed, the part of the resin powder that comes into contact with water absorbs water and swells, forming a lumpy gel, which prevents water from penetrating into the interior. Furthermore, even when looking only at the powder particles, there is a tendency that the gel on the surface prevents water from penetrating into the interior, resulting in a decrease in the water absorption rate. This phenomenon is remarkable in soft gels with high water absorption capacity.
“ままこ”現象を防止するために樹脂の表面を処理する
方法が知られている。第一の方法として、樹脂粒子の表
面部を浸透性の架橋により硬質ゲルにする方法（特公昭
５９−６６９６号公報、特公昭６０１８６９０号公報、
特公昭６１−４８５２１号公報）があり、架橋剤として
、多価エポキシ化合物が多く用いられる。また、第二の
方法として、無機物添加により吸水速度を改良する方法
（特開昭６１−５８６５７号公報）、あるいは、吸水性
樹脂及び無機質粉末の撹拌下、架橋剤および水を噴霧添
加し、ついで加熱して架橋反応させ、そののち水を留去
して吸水性樹脂をうる方法（特公昭６３−４３４１０号
公報）がある。A method of treating the surface of a resin in order to prevent the "sticky" phenomenon is known. The first method is to make the surface of resin particles into a hard gel by permeable crosslinking (Japanese Patent Publication No. 59-6696, Japanese Patent Publication No. 6018690,
(Japanese Patent Publication No. 61-48521), and polyvalent epoxy compounds are often used as crosslinking agents. A second method is to improve the water absorption rate by adding an inorganic substance (Japanese Unexamined Patent Publication No. 61-58657), or by spraying and adding a crosslinking agent and water to a water-absorbing resin and an inorganic powder while stirring, and then There is a method (Japanese Patent Publication No. 63-43410) in which a crosslinking reaction is caused by heating, and then water is distilled off to obtain a water-absorbing resin.
［発明が解決しようとする課題］カルボキシル基を有する吸水性樹脂の粉末は、吸水時に
“ままこ”ができやすく、また、吸水倍率、吸水速度、
ゲル強度などの性質が必ずしも両立せず、そのため、前
述のような二次架橋（樹脂の表面部の架橋剤による処理
）又は無機物による処理を必須とする。[Problems to be solved by the invention] Powder of water-absorbing resin having a carboxyl group tends to form "sticks" when absorbing water, and also has poor water absorption capacity, water absorption rate,
Properties such as gel strength are not necessarily compatible, and therefore, secondary crosslinking (treatment of the surface portion of the resin with a crosslinking agent) or treatment with an inorganic substance as described above is essential.
上記第一の二次架橋の方法は、“ままこ”防止及び吸水
速度の改善には効果を示すが、架橋のバラツキが大きく
、ゲル強度が弱く、ゲル強度を強くすると、吸水倍率の
かなりの低下を伴うという欠点があった。The first method of secondary crosslinking described above is effective in preventing "stickiness" and improving the water absorption rate, but the variation in crosslinking is large and the gel strength is weak. The disadvantage was that it was accompanied by a decline.
一方、上記第二の方法は、吸水倍率、ゲル強度の向上に
は有効であるが、吸水速度が充分でなく、架橋時のバラ
ツキが大きく、無機質粉末も大量に必要とするという欠
点があった。On the other hand, the second method described above is effective in improving water absorption capacity and gel strength, but has the drawbacks of insufficient water absorption rate, large variations in crosslinking, and a large amount of inorganic powder required. .
［課題を解決するための手段］上記問題点を解決するために種々の処理剤、処理方法に
ついて検討したところ、水不溶性の無機質と特定の架橋
剤の相乗効果により、実用的性質のバランスした、改良
された吸水剤が得られること、及び、これを工業的に安
価に製造する方法を見出し、本発明を完成した。[Means for Solving the Problems] In order to solve the above problems, we investigated various processing agents and processing methods, and found that due to the synergistic effect of a water-insoluble inorganic substance and a specific crosslinking agent, we found a product with balanced practical properties. The present invention was completed by discovering that an improved water absorbing agent can be obtained and a method for manufacturing it industrially at low cost.
即ち本発明は、（１）カルボキシル基を有する吸水性樹脂を、水酸基を
有するモノエポキシ化合物を用いて架橋処理してなり、
水不溶性の無機物を含有する吸水剤、（２）カルボキシ
ル基を有する吸水性樹脂に、水不溶性の無機物及び水酸
基を有するモノエポキシ化合物を添加し、次いで架橋処
理することを特徴とする吸水剤の製造方法、（３）水酸基を有するモノエポキシ化合物の添加が、吸
水性樹脂の表面部に、水酸基を有するモノエポキシ化合
物を含浸させるものである上記（２）に記載の吸水剤の
製造方法、（４）水酸基を有するモノエポキシ化合物の添加を、有
機溶媒と水不溶性の無機物の存在下に行なう、上記 （
２）又は（３）に記載の吸水剤の製造方法、（５）カル
ボキシル基を有する吸水性樹脂に、水不溶性の無機物と
水酸基を有するモノエポキシ化合物とを同時に添加する
上記 （２）又は（３）に記載の吸水剤の製造方法、（６）カルボキシル基を有する吸水性樹脂に、水酸基を
有するモノエポキシ化合物を添加し、次いで、水不溶性
の無機物を添加する上記 （２）又は（３）に記載の吸
水剤の製造方法、（７）カルボキシル基を有する吸水性樹脂が有機溶媒に
分散されている上記 （５）又は（６）に記載の吸水剤
の製造方法、（８）水酸基を有するモノエポキシ化合物をその水性溶
液の形で添加する上記 （２）〜（７）のいずれかに記
載の吸水剤の製造方法、（９）架橋処理が、１００〜２５０℃の温度で加熱処理
するものである上記 （２）〜（８）のいずれかに記載
の吸水剤の製造方法、に関する。That is, the present invention provides: (1) a water-absorbing resin having a carboxyl group is crosslinked using a monoepoxy compound having a hydroxyl group;
A water absorbing agent containing a water-insoluble inorganic substance; (2) Production of a water-absorbing agent characterized by adding a water-insoluble inorganic substance and a monoepoxy compound having a hydroxyl group to a water-absorbing resin having a carboxyl group, and then subjecting it to crosslinking treatment. (3) The method for producing a water-absorbing agent according to (2) above, wherein the addition of the monoepoxy compound having a hydroxyl group impregnates the surface portion of the water-absorbing resin with the monoepoxy compound having a hydroxyl group; ) The above-mentioned (
2) or (3), the method for producing a water-absorbing agent according to (5) above (2) or (3), in which a water-insoluble inorganic substance and a monoepoxy compound having a hydroxyl group are simultaneously added to a water-absorbing resin having a carboxyl group. ), (6) Adding a monoepoxy compound having a hydroxyl group to a water absorbing resin having a carboxyl group, and then adding a water-insoluble inorganic substance to the above (2) or (3). (7) The method for producing a water-absorbing agent as described in (5) or (6) above, in which a water-absorbing resin having a carboxyl group is dispersed in an organic solvent; (8) A monomer having a hydroxyl group. The method for producing a water absorbing agent according to any one of (2) to (7) above, in which the epoxy compound is added in the form of an aqueous solution; (9) the crosslinking treatment is a heat treatment at a temperature of 100 to 250°C; The present invention relates to a method for producing a water absorbing agent according to any one of (2) to (8) above.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
カルボキシル基を有する吸水性樹脂（以下、「吸水性樹
脂」という）としては、種々のものが使用でき、特に限
定されず、カルボキシル基を有し、実質的に水に不溶で
あるが水を吸収して膨潤する能力を有する樹脂であれば
いずれも使用できる。好ましいものとしては、ＯＯＨで示される構造単位を有する重合体が挙げられ、例・え
ば、アクリル酸−アクリル酸塩系架橋共重合体、デンプ
ン−アクリル酸グラフト架橋重合体、デンプン−アクリ
ロニトリルグラフト重合体加水分解物の架橋物、酢酸ビ
ニル−アクリル酸エステル共重合体ケン化物の架橋物等
が挙げられる。Various types of water-absorbing resins having carboxyl groups (hereinafter referred to as "water-absorbing resins") can be used, and are not particularly limited. Any resin that has the ability to swell and swell can be used. Preferred examples include polymers having a structural unit represented by OOH, such as acrylic acid-acrylate crosslinked copolymers, starch-acrylic acid graft crosslinked polymers, and starch-acrylonitrile graft polymers. Examples include crosslinked products of hydrolysates, and crosslinked products of saponified vinyl acetate-acrylic acid ester copolymers.
通常は、これらの重合体に含まれるカルボキシル基の５
０〜９５％がアルカリ金属塩として中和された状態にあ
る。Usually, 5 of the carboxyl groups contained in these polymers are
0 to 95% is in a neutralized state as an alkali metal salt.
特に好ましい吸水性樹脂としては、アクリル酸５〜５０
モル％、アクリル酸アルカリ金属塩４５〜９４モル％、
架橋剤０．０１〜５モル％、その他のエチレン性不飽和
単量体０〜１０モル％の重合体が挙げられる。Particularly preferable water-absorbing resins include acrylic acid 5 to 50%
mol%, acrylic acid alkali metal salt 45-94 mol%,
Examples include polymers containing 0.01 to 5 mol% of a crosslinking agent and 0 to 10 mol% of other ethylenically unsaturated monomers.
アクリル酸アルカリ金属塩としては、ナトリウム塩、カ
リウム塩等が挙げられる。Examples of the alkali metal salts of acrylic acid include sodium salts, potassium salts, and the like.
架橋剤としては公知の種々のものが使用でき、例えば、
ジビニルベンゼン、メチレンビス（メタ）アクリルアミ
ド、エチレングリコールジ（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、グリセリ
ンジ（メタ）アクリレート、ジペンタエリスリトールト
リ （メタ）アクリレート、ペンタエリスリトールテト
ラ（メタ）アクリレート、ペンタエリスリトールエチレ
ンオキサイド変性テトラ（メタ）アクリレート等が挙げ
られる。Various known crosslinking agents can be used, for example,
Divinylbenzene, methylene bis(meth)acrylamide, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, dipentaerythritol tri(meth)acrylate, Examples include pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, and the like.
又、任意成分であるその他のエチレン性不飽和単量体と
しては例えば、メタクリル酸又はその塩、（メタ）アク
リルアミド、（メタ）アクリ口ニトリル、（メタ）アク
リル酸アルキルエステル等が挙げられる。Other optional ethylenically unsaturated monomers include, for example, methacrylic acid or a salt thereof, (meth)acrylamide, (meth)acrylic nitrile, (meth)acrylic acid alkyl ester, and the like.
なお、本発明で原料として用いる吸水性樹脂の形態は特
に限定されないが、粉末状が好ましく、通常ｌＧ〜６０
０メツシュの粒径の微粒子を用いるのが好ましい。Note that the form of the water-absorbing resin used as a raw material in the present invention is not particularly limited, but powder form is preferable, and usually 1G to 60
It is preferable to use fine particles having a particle size of 0 mesh.
水不溶性の無機物（以下、「無機物」という）としては
、例えば、カオリン、タルク、珪藻土、ベントナイト、
シリカ、アルミナ、アルミノシリケート、ゼオライト、
珪酸カルシウム、珪酸マグネシウム、リン酸カルシウム
、酸化チタン、酸化亜鉛、ジルコニア等が挙げられ、好
ましいものとしては、コロイド状シリカ、アエロジル粉
末、コロイド状アルミナ、微粉末アルミナ、微粉末酸化
チタン、微粉末カオリン等が挙げられる。Examples of water-insoluble inorganic substances (hereinafter referred to as "inorganic substances") include kaolin, talc, diatomaceous earth, bentonite,
Silica, alumina, aluminosilicate, zeolite,
Examples include calcium silicate, magnesium silicate, calcium phosphate, titanium oxide, zinc oxide, zirconia, etc., and preferred examples include colloidal silica, Aerosil powder, colloidal alumina, fine powder alumina, fine powder titanium oxide, fine powder kaolin, etc. Can be mentioned.
無機物の粒径は小さい程よく、例えば、平均粒径が１０
０μ以下のものが好ましく、特に１μ以下のものが好ま
しい。The smaller the particle size of the inorganic material, the better; for example, the average particle size is 10
It is preferably 0μ or less, particularly preferably 1μ or less.
無機物は、吸水性樹脂１００重量部に対して、好ましく
は０．０１〜ｌＯ重量部、特に好ましくは０．１〜１重
量部用いられる。The inorganic substance is preferably used in an amount of 0.01 to 10 parts by weight, particularly preferably 0.1 to 1 part by weight, per 100 parts by weight of the water absorbent resin.
水酸基を有するモノエポキシ化合物（以下、「モノエポ
キシ化合物」という）としては、例えば、グリシドール
、エチレングリコールモノグリシジルエーテル、プロピ
レングリコールモノグリシジルエーテル、グリセリンモ
ノグリシジルエーテル、トリメチロールプロパンモノグ
リシジルエーテル、ジエチレングリコールモノグリシジ
ルエーテル、ポリエチレングリコールモノグリシジルエ
ーテル、ポリプロピレングリコールモノグリシジルエー
テル、ｐ−キシリレングリコールモノグリシジルエーテ
ル等が挙げられるが、これらに限定されるものではない
。Examples of monoepoxy compounds having a hydroxyl group (hereinafter referred to as "monoepoxy compounds") include glycidol, ethylene glycol monoglycidyl ether, propylene glycol monoglycidyl ether, glycerin monoglycidyl ether, trimethylolpropane monoglycidyl ether, and diethylene glycol monoglycidyl ether. Examples include, but are not limited to, ether, polyethylene glycol monoglycidyl ether, polypropylene glycol monoglycidyl ether, p-xylylene glycol monoglycidyl ether, and the like.
モノエポキシ化合物の使用量は、吸水性樹脂に対して、
好ましくは０．０１〜１０重量％、特に好ましくは０．
１〜５重量％である。The amount of monoepoxy compound used is based on the water absorbent resin.
Preferably 0.01 to 10% by weight, particularly preferably 0.01 to 10% by weight.
It is 1 to 5% by weight.
吸水性樹脂に無機物及びモノエポキシ化合物を添加する
方法としては、種々の方法が採用でき、特に限定されな
い。Various methods can be used to add the inorganic substance and monoepoxy compound to the water-absorbing resin, and there are no particular limitations.
例えば、吸水性樹脂を有機溶媒に分散させ又は分散させ
ないで、これに無機物又はそれが水及び／又は有機溶媒
中に分散したものと、モノエポキシ化合物又はその水及
び／又は有機溶媒溶液を加える。無機物とモノエポキシ
化合物の添加順序は特に限定されず、いずれを先に加え
てもよく、又、両者を同時に添加してもよい。特に好ま
しい方法としては、吸水性樹脂に有機溶媒と無機物を添
加し、有機溶媒中に吸水性樹脂が分散した状態となし、
これにモノエポキシ化合物を添加する方法、又は、吸水
性樹脂に（好ましくは、吸水性樹脂を有機溶媒に分散さ
せたものに）、無機物とモノエポキシ化合物を同時に添
加する方法である。モノエポキシ化合物は、水性溶液の
形で添加するのが好ましい。ここで、水性溶液とは、水
溶液あるいは水に対して好ましくは１０重量％以下の有
機溶媒を含む溶液であり、無機物を含んでいてもよい。For example, an inorganic substance or its dispersion in water and/or an organic solvent, and a monoepoxy compound or its solution in water and/or an organic solvent are added to the water-absorbing resin, with or without dispersing it in an organic solvent. The order of addition of the inorganic substance and the monoepoxy compound is not particularly limited, and either may be added first, or both may be added at the same time. A particularly preferable method is to add an organic solvent and an inorganic substance to a water-absorbing resin to form a state in which the water-absorbing resin is dispersed in the organic solvent;
A method of adding a monoepoxy compound to this, or a method of simultaneously adding an inorganic substance and a monoepoxy compound to a water-absorbing resin (preferably, a water-absorbing resin dispersed in an organic solvent). Preferably, the monoepoxy compound is added in the form of an aqueous solution. Here, the aqueous solution is an aqueous solution or a solution containing preferably 10% by weight or less of an organic solvent based on water, and may also contain an inorganic substance.
吸水性樹脂に無機物及びモノエポキシ化合物を添加する
際、吸水性樹脂を撹拌しながら添加を行なうのが好まし
く、又、噴霧等により添加を行なってもよい。When adding the inorganic substance and monoepoxy compound to the water-absorbing resin, it is preferable to add the water-absorbing resin while stirring the resin, and the addition may also be carried out by spraying or the like.
モノエポキシ化合物の添加は、吸水性樹脂の表面部に、
モノエポキシ化合物を含浸させるように行なうのが好ま
しい。The addition of the monoepoxy compound to the surface of the water-absorbing resin
It is preferable to impregnate it with a monoepoxy compound.
モノエポキシ化合物を添加する際の水の量又は有機溶媒
の量を適宜選択することにより、吸水性樹脂の主として
表面部に、モノエポキシ化合物を含浸させることができ
る。ここで表面部とは、樹脂の外側表面だけでなく表面
近傍部をも意味する。By appropriately selecting the amount of water or the amount of organic solvent when adding the monoepoxy compound, it is possible to impregnate mainly the surface portion of the water-absorbing resin with the monoepoxy compound. Here, the surface portion means not only the outer surface of the resin but also the portion near the surface.
有機溶媒としては、メタノール、エタノール、イソプロ
パツール、アセトン、メチルエチルケトン、テトラヒド
ロフラン、ジオキサン、イソプロピルエーテル、アセト
ニトリル等が用いられる。As the organic solvent, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, isopropyl ether, acetonitrile, etc. are used.
吸水性樹脂の表面部にモノエポキシ化合物を含浸させる
場合、分散媒及び溶媒等として用いる有機溶媒の総量は
、吸水性樹脂１００重量部に対して、好ましくは１〜５
０重量部、特に好ましくは３〜３０重量部であり、又、
使用する水の総量は、吸水性樹脂１００重量部に対し好
ましくは３〜５０重量部、特に好ましくは ５〜３０重
量部である。When impregnating the surface of the water absorbent resin with a monoepoxy compound, the total amount of organic solvent used as a dispersion medium, solvent, etc. is preferably 1 to 5 parts by weight per 100 parts by weight of the water absorbent resin.
0 parts by weight, particularly preferably 3 to 30 parts by weight, and
The total amount of water used is preferably 3 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, based on 100 parts by weight of the water absorbent resin.
このようにして得られた含浸樹脂を架橋処理することに
より、主として表面部が内部より架橋密度の高い吸水剤
かえられる。架橋処理は、通常、含浸樹脂を加熱処理す
ることにより行なわれる。By crosslinking the impregnated resin thus obtained, a water absorbing agent having a higher crosslinking density mainly in the surface area than in the interior can be obtained. The crosslinking treatment is usually performed by heating the impregnated resin.
本発明において、吸水性樹脂は、無機物によってコーテ
ィングされた状態にあり、又、有機溶媒を用いる場合は
それが該有機溶媒に分散された状態にあり、モノエポキ
シ化合物のエポキシ基は、加熱により、吸水性樹脂に含
まれるカルボキシル基と反応しエステル結合を形成する
。一方、残った水酸基は、さらに加熱することにより、
水がなくなって、吸水性樹脂が析出した状態において、
吸水性樹脂のカルボキシル基と反応して、架橋構造が生
成する。この際、エポキシ基とカルボキシル基の反応は
５０℃以上に加熱することにより起こり、又、水酸基と
カルボキシル基のエステル化反応は、１００℃以上に加
熱し水が蒸発した後に起こり、これにより架橋が生成す
る。従って、本発明において、架橋処理は、好ましくは
１００〜２５０℃、特に好ましくは１５０〜２００℃
で０１〜１０時間加熱処理することにより行なうことが
できる。In the present invention, the water-absorbing resin is coated with an inorganic substance, or when an organic solvent is used, it is dispersed in the organic solvent, and the epoxy group of the monoepoxy compound is heated to It reacts with the carboxyl group contained in the water-absorbing resin to form an ester bond. On the other hand, the remaining hydroxyl groups can be removed by further heating.
When the water is gone and the water-absorbing resin has precipitated,
A crosslinked structure is generated by reacting with the carboxyl group of the water absorbent resin. At this time, the reaction between epoxy groups and carboxyl groups occurs by heating to 50°C or higher, and the esterification reaction between hydroxyl groups and carboxyl groups occurs after water evaporates by heating to 100°C or higher, thereby causing crosslinking. generate. Therefore, in the present invention, the crosslinking treatment is preferably performed at a temperature of 100 to 250°C, particularly preferably 150 to 200°C.
This can be carried out by heat treatment for 01 to 10 hours.
本発明の方法によれば、無機物の使用量は従来の技術の
１７３〜１／ｌＯ以下に減らすことができ、しかも吸
水剤の性能においては何等劣る点はない。According to the method of the present invention, the amount of inorganic substances used can be reduced to less than 173 to 1/1O of the conventional technique, and there is no deterioration in the performance of the water absorbing agent.
又、本発明の方法において、吸水性樹脂を有機溶媒に分
散させた場合には、ブロッキングを起こすという心配も
全くなくなる。Furthermore, in the method of the present invention, when the water-absorbing resin is dispersed in an organic solvent, there is no fear that blocking will occur.
また、この際使用される有機溶媒の量も吸水性樹脂１０
０重量部に対し従来の技術が８０〜５００重量部である
のに対し、本発明ではその１／１０〜１／１００の１〜
５０重量部で十分であり、工業的にも非常に有利な方法
である。本発明の方法を用いることにより、吸水能が良
好で、吸水速度が速く、吸水時のゲルがべとつかず、し
かもゲル強度の大きい吸水剤を容易に作ることができる
。In addition, the amount of organic solvent used at this time is also 10% of the water absorbent resin.
While the conventional technology uses 80 to 500 parts by weight, the present invention uses 1 to 1/10 of 1/10 to 1/100 parts by weight.
50 parts by weight is sufficient, and this is a very industrially advantageous method. By using the method of the present invention, it is possible to easily produce a water-absorbing agent that has a good water-absorbing ability, a high water-absorbing rate, a non-sticky gel upon water absorption, and a high gel strength.
本発明による吸水剤は、紙オムツ、生理用ナプキン等の
衛生材料、土壌に対する保水剤、土木建築用の止水剤、
結露防止剤、パップ剤、シップ剤、乾燥剤、水分調整剤
等に広範に使用できる。The water absorbing agent according to the present invention can be used for sanitary materials such as disposable diapers and sanitary napkins, water retention agents for soil, water stop agents for civil engineering and construction,
It can be widely used in anti-condensation agents, poultices, sip agents, desiccants, moisture regulators, etc.
［実施例］以下、実施例、比較例及び応用例により、本発明を更に
具体的に説明する。なお、実施例及び比較例中の「部」
は「重量部」を示す。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Application Examples. In addition, "part" in Examples and Comparative Examples
indicates "parts by weight".
実施例１アクリル酸ナトリウム７５部、アクリル酸２４．７部及
びメチレンビスアクリルアミド０．１２部からなるアク
リル系単量体の４３％水溶液２３３部に、過硫酸アンモ
ニウム０．０３部及び亜硫酸水素ナトリウム００１部を
加え、窒素雰囲気中３０〜１００℃で５時間静置重合し
、ゲル状含水重合体を得た。このゲル状含水重合体を１
７０℃の熱風乾燥器で乾燥後、１８メツシユ金網で篩分
けし、１８メツシュ通過物（粉体Ａ）を得た。Example 1 To 233 parts of a 43% aqueous solution of acrylic monomers consisting of 75 parts of sodium acrylate, 24.7 parts of acrylic acid, and 0.12 parts of methylenebisacrylamide, 0.03 parts of ammonium persulfate and 001 parts of sodium bisulfite were added. was added and polymerized by standing at 30 to 100° C. for 5 hours in a nitrogen atmosphere to obtain a gel-like hydropolymer. This gel-like water-containing polymer is
After drying in a hot air dryer at 70° C., the mixture was sieved through an 18-mesh wire mesh to obtain a product that passed through the 18-mesh mesh (powder A).
この粉体Ａ４０部に対し、コロイダルシリカ（日産化学
製スノーテックス０；２０％水溶液）０８部及びメタノ
ール４部の混合物を加えて分散し、これに、グリシドー
ル０．２４部を水２．４部に溶かした溶液を加え撹拌し
た。得られた混合物を、１８０℃の熱風乾燥器で３０分
間加熱乾燥し吸水剤Ｊを得た。To 40 parts of this powder A, a mixture of 08 parts of colloidal silica (Nissan Chemical's Snowtex 0; 20% aqueous solution) and 4 parts of methanol was added and dispersed, and 0.24 parts of glycidol was added to 2.4 parts of water. A solution dissolved in was added and stirred. The resulting mixture was heated and dried in a hot air dryer at 180° C. for 30 minutes to obtain water absorbing agent J.
比較例１実施例１で得られた粉体Ａ４０部に、メタノール４部を
加えて分散し、これに、エチレングリコールジグリシジ
ルエーテル０．２４部及び水２．４部の混合液を撹拌し
ながら加え１８０℃で３０分間加熱乾燥して吸水剤Ｘを
得た。Comparative Example 1 To 40 parts of the powder A obtained in Example 1, 4 parts of methanol was added and dispersed, and to this was added a mixed solution of 0.24 parts of ethylene glycol diglycidyl ether and 2.4 parts of water with stirring. The mixture was added and dried by heating at 180° C. for 30 minutes to obtain water absorbing agent X.
比較例２実施例１で得られた粉体Ａ４０部にコロイド状シリカ（
日産化学製スノーテックスＯ；２０％水溶液）０．８部
を加えて分散し、これにエチレングリコールジグリシジ
ルエーテル０．１部を水４部に溶かした溶液を加え、得
られた混合物を １５０℃の熱風乾燥機で５０分間加熱
乾燥させ吸水剤Ｙを得た。Comparative Example 2 Colloidal silica (
0.8 part of Snowtex O manufactured by Nissan Chemical (20% aqueous solution) was added and dispersed, a solution of 0.1 part of ethylene glycol diglycidyl ether dissolved in 4 parts of water was added, and the resulting mixture was heated at 150°C. The water absorbing agent Y was obtained by heating and drying for 50 minutes in a hot air dryer.
実施例２実施例１で得られた粉体Ａ４０部に、メタノール４部を
加えて分散し、これに、エチレングリコールモノグリシ
ジルエーテル０．１部を水４部に溶かした溶液を加えて
混合した。Example 2 4 parts of methanol was added to 40 parts of the powder A obtained in Example 1 and dispersed, and a solution of 0.1 part of ethylene glycol monoglycidyl ether dissolved in 4 parts of water was added and mixed. .
これに、コロイダルアルミナ（日産化学製アルミナ１０
０ 、１０％水分散液）２．０部及びメタノール２部の
混合物を加えて、得られた混合物を１５０℃の熱風乾燥
機で５０分間加熱乾燥させ吸水剤Ｋを得た。To this, colloidal alumina (Nissan Chemical Alumina 10
A mixture of 2.0 parts (2.0 parts, 10% aqueous dispersion) and 2 parts of methanol was added, and the resulting mixture was heated and dried in a hot air dryer at 150° C. for 50 minutes to obtain water absorbing agent K.
実施例３反応器にｎ−へキサン３００部を取り、ソルビタンモノ
ステアレート ０．９部を溶解した。次いで、この中に
、アクリル酸３０部を水４０部に溶解した後１２．５部
のカセイソーダで中和し更に過硫酸カリ００６部を溶解
して得たモノマー水溶液を加えて分散させ、窒素気流下
６５℃に保って、５時間重合を行った。Example 3 300 parts of n-hexane was placed in a reactor, and 0.9 parts of sorbitan monostearate was dissolved therein. Next, an aqueous monomer solution obtained by dissolving 30 parts of acrylic acid in 40 parts of water, neutralizing it with 12.5 parts of caustic soda, and further dissolving 0.06 parts of potassium persulfate was added and dispersed, and the mixture was dispersed in a nitrogen stream. Polymerization was carried out for 5 hours while maintaining the temperature at 65°C.
重合終了後、ｎ−ヘキサンを濾別した後、減圧乾燥し粉
体Ｂを得た。粉体Ｂ２Ｏ部を微粒子状シリカ（日本アエ
ロジル製アエロジル２００） ０．３部を含むテトラ
ヒドロフラン１０部に分散させ、これにグリセリンモノ
グリシジルエーテル０３部を水４部に溶解して加え、
１８０℃で３０分間加熱乾燥して吸水剤りを得た。After the polymerization was completed, n-hexane was filtered off, and powder B was obtained by drying under reduced pressure. Part of the powder B2O was dispersed in 10 parts of tetrahydrofuran containing 0.3 parts of particulate silica (Aerosil 200 manufactured by Nippon Aerosil), and 0.3 parts of glycerin monoglycidyl ether dissolved in 4 parts of water was added thereto.
A water-absorbing agent was obtained by heating and drying at 180° C. for 30 minutes.
実施例４実施例３で得た粉体Ｂ２Ｏ部に対し、アルミナシリケー
ト微粉末（日本ジ−クライト製ジ−クライト）０．４部
及びエタノール１０部を加えて分散し、これに、ポリエ
チレングリコールモノグリシジルエーテル（分子量４５
０） ２部を水３部に溶解した溶液を加えて混合し、
１９０℃で１０分間加熱乾燥して吸水剤Ｍを得た。Example 4 To part of the powder B2O obtained in Example 3, 0.4 parts of fine alumina silicate powder (Zikryte manufactured by Nippon Zikryte) and 10 parts of ethanol were added and dispersed, and polyethylene glycol monomer was added to this and dispersed. Glycidyl ether (molecular weight 45
0) Add and mix a solution of 2 parts dissolved in 3 parts water,
Water absorbing agent M was obtained by heating and drying at 190° C. for 10 minutes.
実施例５実施例３で得た粉体Ｂ２Ｏ部に対しアルミナ微粉末（日
本アエロジル製アルミニウムオキサイド）０．４部及び
ジオキサ２１０部を加えて分散し、グリシドール０．４
部、水２部の混合溶液を加えて混合し、１５０℃で５０
分間加熱乾燥して吸水剤Ｎを得た。Example 5 0.4 parts of alumina fine powder (aluminum oxide manufactured by Nippon Aerosil) and 210 parts of dioxa were added and dispersed to 20 parts of the powder obtained in Example 3, and 0.4 parts of glycidol was added.
Add and mix a mixed solution of 1 part and 2 parts of water, and heat at 150°C for 50 minutes.
Water absorbing agent N was obtained by heating and drying for a minute.
実施例６実施例３に準じて重合を行った。但しソルビタンモノス
テアレートの代りにイソブチレン−無水マレイン酸共重
合体（粘度平均分子盟約１０．０ｎ）２．５部を用いた
。重合終了後、減圧乾燥して水２０重量％を含む粉体Ｃ
を得た。粉体Ｃ４０部にエチレングリコールモノグリシ
ジルエーテル０．２部とメタノール３部の混合溶液を加
えて良く混合し、更に、酸化チタン微粉末（日本アエロ
ジル製チタンオキサイド）０．３部及びメタノール３部
を加えて、１６０℃で４０分間加熱乾燥して吸水剤０を
得た。Example 6 Polymerization was carried out according to Example 3. However, 2.5 parts of isobutylene-maleic anhydride copolymer (viscosity average molecular weight approximately 10.0 n) was used instead of sorbitan monostearate. After completion of polymerization, dry under reduced pressure to obtain powder C containing 20% by weight of water.
I got it. Add a mixed solution of 0.2 parts of ethylene glycol monoglycidyl ether and 3 parts of methanol to 40 parts of powder C, mix well, and then add 0.3 parts of fine titanium oxide powder (titanium oxide manufactured by Nippon Aerosil) and 3 parts of methanol. In addition, water absorbent 0 was obtained by heating and drying at 160° C. for 40 minutes.
実施例７実施例６に準じて重合を行った。但し、重合終了前にグ
リシドール０．２０部を加えて減圧乾燥し、粉体りを得
た。粉体Ｄ４０部にシリカ微粉末（日本アエロジル製ア
エロジル １３０） ０．３部及びメタノール１０部
を加えて分散し、これにグリシドール０．２部と水２部
の混合溶液を加えて良く混合し、１６０℃で４０分間加
熱乾燥し吸水剤Ｐを得た。Example 7 Polymerization was carried out according to Example 6. However, before the polymerization was completed, 0.20 part of glycidol was added and dried under reduced pressure to obtain a powder. Add 0.3 parts of fine silica powder (Aerosil 130 manufactured by Nippon Aerosil) and 10 parts of methanol to 40 parts of Powder D and disperse, add a mixed solution of 0.2 parts of glycidol and 2 parts of water, and mix well. Water absorbing agent P was obtained by heating and drying at 160° C. for 40 minutes.
実施例８アクリル酸ナトリウム７５部、アクリル酸２４．８部及
びポリエチレングリコールジアクリレート（分子量３０
２） ［１，２０部からなるアクリル系単量体の４０％
水溶液２５０部に過硫酸アンモニウム０．０３部、３５
％過酸化水素０．５部及びＬ−アスコルビン酸０．０１
部を加え、窒素雰囲気中２０〜１００℃で５時間静置重
合し、ゲル状含水重合体を得た。このゲル状含水重合体
を１８０℃の熱風乾燥器で乾燥後、１８メツシユ金網で
篩分けし、１８メツシュ通過物（粉体Ｅ）を得た。Example 8 75 parts of sodium acrylate, 24.8 parts of acrylic acid and polyethylene glycol diacrylate (molecular weight 30
2) [40% of acrylic monomer consisting of 1.20 parts
0.03 part of ammonium persulfate in 250 parts of aqueous solution, 35
% hydrogen peroxide 0.5 part and L-ascorbic acid 0.01
20 to 100°C in a nitrogen atmosphere for 5 hours to obtain a gel-like hydropolymer. This gel-like water-containing polymer was dried in a hot air dryer at 180° C., and then sieved through an 18-mesh wire gauze to obtain a product passing through the 18-mesh mesh (powder E).
この粉体Ｆ４Ｏ部に対し、コロイド状シリカ（日照化学
製スノーテックスＯ；２０％分散液）１．５部及びメタ
ノール４部の混合物を加えて分散しこれに、グリシドー
ル０．１６部を水２．０部に溶かした溶液を加え撹拌し
た。得られた混合物を、１８０℃の熱風乾燥器で３０分
間加熱乾燥し吸水剤Ｑを得た。To 4 parts of this powder F4O, a mixture of 1.5 parts of colloidal silica (Snowtex O manufactured by Nissho Kagaku; 20% dispersion) and 4 parts of methanol was added and dispersed, and 0.16 parts of glycidol was added to 2 parts of water. 0 part of the solution was added and stirred. The resulting mixture was heated and dried in a hot air dryer at 180° C. for 30 minutes to obtain water absorbing agent Q.
実施例９アクリル酸ナトリウム７５凡、アクリル酸２４９部及び
、ジペンタエリスリトールトリアクリレート０．０５部
からなるアクリル酸塩系単量体の４３％水溶液２３３部
に過硫酸カリウム０．０３部、３５％過酸化水素０．１
部及びＬ−アスコルビン酸０．０１部を加え、窒素雰囲
気中２０〜１００℃で５時間静置重合し、ゲル状含水重
合体を得た。このゲル状含水重合体を１５０℃の熱風乾
燥器で乾燥後、１８メツシユ金網で篩分けし、１８メツ
シュ通過物（粉体Ｆ）を得た。Example 9 To 233 parts of a 43% aqueous solution of acrylate monomers consisting of 75 parts of sodium acrylate, 249 parts of acrylic acid, and 0.05 parts of dipentaerythritol triacrylate, 0.03 parts of potassium persulfate and 35% potassium persulfate were added. hydrogen peroxide 0.1
1 part and 0.01 part of L-ascorbic acid were added thereto, and polymerization was carried out at 20 to 100° C. for 5 hours in a nitrogen atmosphere to obtain a gel-like hydropolymer. This gel-like water-containing polymer was dried in a hot air dryer at 150° C., and then sieved through an 18-mesh wire gauze to obtain a material passing through the 18-mesh mesh (powder F).
この粉体Ｆ２Ｏ部に対し、アルミナ微粉末（日本アエロ
ジル製アルミニウムオキサイドＣ） ０．４部、メタ
ノール８部を加えて分散しこれに、グリシドール０．２
４部を水２．０部に溶かした溶液を加え撹拌した。To this powder F2O part, 0.4 parts of fine alumina powder (Aluminum Oxide C manufactured by Nippon Aerosil Co., Ltd.) and 8 parts of methanol were added and dispersed.
A solution of 4 parts dissolved in 2.0 parts of water was added and stirred.
得られた混合物を、１５０℃の熱風乾燥器で５０分間加
熱乾燥し吸水剤Ｒを得た。The resulting mixture was heated and dried in a hot air dryer at 150° C. for 50 minutes to obtain water absorbent R.
実施例１０実施例９で得られた吸水性樹脂粉体Ｆ２Ｏ部に対し、メ
タノール８部を加えて分散し、これにコロイド状シリカ
（日照化学製スノーテックスＯ；２０％分散液）１．０
部、グリシドール０．２部及び水１．２部の混合物を加
えて撹拌した。得られた混合物を、２００℃の熱風乾燥
器で１５分間加熱乾燥して、吸水剤Ｓを得た。Example 10 To 20 parts of the water-absorbing resin powder obtained in Example 9, 8 parts of methanol was added and dispersed, and 1.0 parts of colloidal silica (Snowtex O manufactured by Nichijo Kagaku; 20% dispersion) was added to this.
1 part, 0.2 parts of glycidol, and 1.2 parts of water were added and stirred. The resulting mixture was heated and dried in a hot air dryer at 200° C. for 15 minutes to obtain a water absorbing agent S.
なお、上記のいずれの実施例においても、モノエポキシ
化合物を添加したのち加熱乾燥する前の時点で得られる
ものは、モノエポキシ化合物が吸水性樹脂の表面部に含
浸されたものであった。In any of the above examples, the monoepoxy compound was impregnated onto the surface of the water-absorbing resin in the product obtained before heating and drying after adding the monoepoxy compound.
応用例実施例１〜１０で得られた吸水剤Ｊ−８．未処理の粉体
Ａ−Ｆ及び比較例１〜２で得られた吸水剤Ｘ−Ｙの吸水
倍率、吸水速度、ゲル強度及び“ままこ”の有無を表１
に示した。Application Example Water absorbing agent J-8 obtained in Examples 1 to 10. Table 1 shows the water absorption capacity, water absorption rate, gel strength, and presence or absence of "Mamako" of the untreated powder A-F and the water absorbing agents X-Y obtained in Comparative Examples 1 and 2.
It was shown to.
表なお、吸水倍率、吸水速度及びゲル強度は次のように測
定した。In addition, water absorption capacity, water absorption rate, and gel strength were measured as follows.
○吸水倍率吸水剤又は粉体０．５ｇに０．９％食塩水を２００ ｇ
加え、１時間後２００メツシユの金網で濾過し、吸水し
た樹脂の重量を量り、これを吸水させる前の重量で割っ
て吸水倍率を求める。○Water absorption capacity 0.5g of water absorbing agent or powder and 200g of 0.9% saline
In addition, after 1 hour, the resin was filtered through a 200-mesh wire mesh, the weight of the absorbed resin was measured, and the water absorption capacity was determined by dividing this by the weight before water absorption.
Ｏ吸水速度測定装置として径７ａｎの０１ガラスフイルターと径１
．４−の目盛つき試験管をＵ字に繋ぐ。吸水剤又は粉体
０．３ｇをガラスフィルター上に均一に広げ、等水位に
人工尿を加え、１分、５分、２０分後の吸収した量を水
位の下降を読取ることにより測る。人工尿は尿素１．９
４ ｇ 、食塩０．８０ｇ、硫酸マグネシウムＯ，１１
ｇ及び塩化カルシウム０．０６ｇを純水９７．０９ｇに
溶かして１００ ｇとする。01 glass filter with diameter 7an and diameter 1 as O water absorption rate measuring device
．． 4- Connect the scaled test tubes in a U shape. Spread 0.3 g of the water-absorbing agent or powder evenly on a glass filter, add artificial urine to the same water level, and measure the absorbed amount after 1 minute, 5 minutes, and 20 minutes by reading the drop in the water level. Artificial urine contains urea 1.9
4 g, salt 0.80 g, magnesium sulfate O,11
g and 0.06 g of calcium chloride are dissolved in 97.09 g of pure water to make 100 g.
○ゲル強度２００ ｍｌのビーカーに吸水剤又は粉体２ｇを量り取
り、２ｇのメタノールを加えて浸漬させた後、４０ｇの
純水を一気に加えかき混ぜて、吸水ゲルを形成させる。○ Gel strength Weigh out 2 g of water absorbing agent or powder into a 200 ml beaker, add 2 g of methanol and immerse it, then add 40 g of pure water at once and stir to form a water absorbing gel.
その後、ビーカー内の吸水ゲル上に径６０の円柱状のア
ダプターを乗せ、テンシロンで圧縮して、ゲルが流動し
始めるときの強度を測定する。ゲル強度は円柱の単位面
積当たりの応力で表す。Thereafter, a cylindrical adapter with a diameter of 60 mm is placed on the water-absorbing gel in the beaker, compressed with Tensilon, and the strength when the gel starts to flow is measured. Gel strength is expressed as stress per unit area of cylinder.
又、“ままこ”については、吸水剤粉末１部に水１００
部を加えて、“ままこ°の有無を観察した。In addition, for "Mamako", 1 part water-absorbing agent powder and 100 parts water
The presence or absence of mamako was observed.
［発明の効果］本発明の吸水剤は、吸水倍率、吸水速度及びゲル強度と
も良好な性能を示し、しがち、“ままこ”の発生がない
等、どの性質もバランスのとれた吸水剤である。[Effects of the Invention] The water absorbing agent of the present invention exhibits good performance in terms of water absorption capacity, water absorption rate, and gel strength, and is a water absorbing agent that is well-balanced in all properties, such as no tendency to cause "stickiness". be.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2240990AJP2862357B2 (en) | 1990-09-11 | 1990-09-11 | Water absorbing agent and method for producing the same |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2240990AJP2862357B2 (en) | 1990-09-11 | 1990-09-11 | Water absorbing agent and method for producing the same |
| Publication Number | Publication Date |
|---|---|
| JPH04120176Atrue JPH04120176A (en) | 1992-04-21 |
| JP2862357B2 JP2862357B2 (en) | 1999-03-03 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2240990AExpired - LifetimeJP2862357B2 (en) | 1990-09-11 | 1990-09-11 | Water absorbing agent and method for producing the same |
| Country | Link |
|---|---|
| JP (1) | JP2862357B2 (en) |
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