JP3582089B2 - Crosslinking agent, crosslinkable composition, and method for producing crosslinkable composition - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明は、水酸基を有する水溶性高分子の架橋剤、架橋方法および架橋性組成物に関する。 さらに詳しくは、ポリビニルアルコールのような水酸基を有する水溶性高分子を、バインダー、剛度付与剤、寸法安定化剤などととして用いる際に、その耐湿性や耐水性を高めたり、あるいは水不溶性化するのに好ましい架橋剤およびその適用に関するものである。
【０００２】
【従来の技術】
ポリビニルアルコール、変性ポリビニルアルコール、でんぷんまたはその誘導体など、水酸基を有する水溶性高分子は、各種接着剤や、繊維、紙および不織布の加工、保護コロイドの増粘剤、塗料など、多くの産業分野で用いられている。このような高分子は、水溶性であるがために、耐湿性および耐水性に劣り、それが利用分野によっては大きな障害となっている。
【０００３】
かかる水溶性高分子の耐湿性や耐水性を向上させるため、これまでにも多くの提案がなされている。例えば、Ｎ−メチロールメラミン樹脂のようなＮ−メチロール化合物は、水酸基を有する水溶性高分子を架橋し、かかる水溶性高分子に優れた耐水性を付与する。同様の目的で、グリオキザールやグルタルアルデヒドのようなジアルデヒド類、ジイソシアネート類、ブロック化ジイソシアネート類、銅、ホウ素、アルミニウム、チタン、亜鉛、スズ、クロムなどの化合物からなる錯化剤、二塩基性以上のカルボン酸などを用いる方法が提案されている。
【０００４】
【発明が解決しようとする課題】
ところが、Ｎ−メチロール化合物にはホルムアルデヒドを発生するという問題がある。また他の化合物を用いる方法も、適用後の水溶性高分子に着色や黄変を生じたり、水溶性高分子に適用する際に著しい増粘をきたしたり、水溶性高分子を不溶化させるために高温で長時間の熱処理を必要とするなどの問題があり、さらには得られる架橋効果が必ずしも十分でないといった問題もある。
【０００５】
かかる事情に鑑み、本発明者らは鋭意研究を行った結果、本発明に至った。したがって本発明の目的の一つは、従来品の問題点を解決した水酸基含有水溶性高分子の架橋剤を提供することにある。
【０００６】
本発明の別の目的は、ホルムアルデヒド起因成分を含有せず、したがってホルムアルデヒドを発生しない架橋剤を提供することにある。
【０００７】
本発明のさらなる目的は、架橋により着色や黄変を生じることのない架橋剤を提供することにある。
【０００８】
さらに本発明の別の目的は、水酸基を有する水溶性高分子を工業的に有用かつ簡便な方法で水不溶化させることができ、それにより、その水溶性高分子に対して耐湿性および耐水性を付与することができる架橋剤を提供することにある。
【０００９】
本発明のさらに別の目的は、かかる架橋剤を用いて水酸基含有水溶性高分子を架橋する方法を提供し、さらには、水酸基含有水溶性高分子の架橋性組成物を提供することにある。
【００１０】
【課題を解決するための手段】
本発明は、以上の課題を解決することを目的としてなされたものであり、その要旨とするところは、水酸基を有する水溶性高分子に、ポリカルボン酸と次亜リン酸の塩とからなる架橋剤を使用することを特徴とする水に不溶性化された架橋性組成物の製造方法である。また本発明は、水酸基を有する水溶性高分子、ポリカルボン酸および次亜リン酸の塩を含有し、ポリカルボン酸の含有量が該水溶性高分子に対し３〜２０重量％の割合であり、次亜リン酸の塩の含有量が該ポリカルボン酸に対し５〜１００重量％の割合であることを特徴とする水に不溶性化された架橋性組成物を提供するものである。本発明はさらに、ポリ（メタ）アクリル酸を２５重量％含有する水溶液の２５℃における粘度が２０ cps 以上であるポリ（メタ）アクリル酸と、次亜リン酸の塩とからなる架橋剤を提供する。以下、本発明を詳細に説明する。
【００１１】
本発明の架橋剤の適用対象となる水酸基を有する水溶性高分子とは、ポリビニルアルコールおよび各種変性ポリビニルアルコール、 でんぷんおよびその誘導体、さらにはカルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロースのようなセルロース誘導体など、その化学構造中に水酸基を有し、実質的に水溶性である高分子をいう。かかる水酸基を有する水溶性高分子に対して適用される本発明の架橋剤は、ポリカルボン酸とリンのオキソ酸の塩とからなるものである。
【００１２】
架橋剤の一方の成分であるポリカルボン酸とは、１分子中に２個以上のカルボキシル基を有する化合物をいい、クエン酸、マレイン酸、酒石酸、コハク酸、イタコン酸、１，２，３，４−ブタンテトラカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸、ポリアクリル酸、ポリメタクリル酸などが例示される。とりわけ、１，２，３，４−ブタンテトラカルボン酸およびポリ（メタ）アクリル酸が、好ましく用いられる。ポリ（メタ）アクリル酸の場合は、その２５重量％水溶液の２５℃における粘度が２０cps 以上のものが、良好な加工効果を与える点で好ましく、さらには作業性などの点から、かかる粘度が５０００cps 以下のものがより好ましい。
【００１３】
ここでいうポリ（メタ）アクリル酸は、アクリル酸またはメタクリル酸の単独重合体のほか、アクリル酸および／またはメタクリル酸に、クロトン酸、ビニル乳酸、マレイン酸、フマル酸、アコニット酸、イタコン酸、メサコン酸、シトラコン酸、メチレンマロン酸のような、（メタ）アクリル酸以外のエチレン性不飽和カルボン酸を共重合させたものであってもよい。さらには、他の共重合可能なエチレン性不飽和化合物を共重合させたものでもよく、例えばアクリルアミド、メタクリルアミド、アクリロニトリル、メチルアクリレート、エチルアクリレート、メチルメタクリレート、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレートのような、Ｃ3 〜Ｃ5 のエチレン性不飽和カルボン酸のアミド、ニトリルもしくはエステル類、または、酢酸ビニル、２−アクリルアミド−２−メチルプロパンスルホン酸、ビニルスルホン酸、エチレン、プロピレン、スチレン、α−メチルスチレン、核メチル置換スチレンなどを共重合させることもできる。
【００１４】
（メタ）アクリル酸以外の不飽和カルボン酸を共重合させる場合は、かかる不飽和カルボン酸を任意の割合で用いることができるが、カルボキシル基を有しないモノマーを共重合成分とする場合は、ポリ（メタ）アクリル酸の水溶性を阻害しない範囲で、好ましくは（メタ）アクリル酸を含むモノマーの全重量を基準として２０重量％以下で用いることができる。
【００１５】
ポリ（メタ）アクリル酸は、塊状重合、水溶液重合、有機溶媒中での重合、照射重合、ポリ（メタ）アクリル酸エステルのケン化などの方法で合成することができる。いずれの方法で合成されたものであっても本発明に適用できるが、本発明では通常水溶液として用いるため、水溶液重合が工業的に有利である。
【００１６】
本発明の架橋剤を構成するもう一方の成分は、リンのオキソ酸の塩である。ここでリンのオキソ酸とは、例えば、次亜リン酸などを包含する。これらリンのオキソ酸の水溶性塩、例えばアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、有機アミン塩などが、本発明において用いることができる。なかでも、ナトリウム塩が工業的には有利に用いられる。リンのオキソ酸が多塩基酸である場合、その正塩はもちろん、酸性塩も用いることができる。リンのオキソ酸の塩としては、特に次亜リン酸ソーダが好ましい。
【００１７】
本発明の架橋剤は、以上説明したようなポリカルボン酸および次亜リン酸の塩からなるものであるが、これらは予め混合しておいてもよく、また水酸基を有する水溶性高分子にそれぞれ別々に添加してもよい。ポリカルボン酸とリンのオキソ酸の塩との割合は特に制限されるものでないが、通常は、ポリカルボン酸に対し、リンのオキソ酸の塩を５〜１００重量％の割合で用いるのが好ましい。ポリカルボン酸がポリ（メタ）アクリル酸であるときは、そのポリ（メタ）アクリル酸に対し、リンのオキソ酸の塩を１０〜３０重量％の割合で使用するのがより好ましい。
【００１８】
水酸基を有する水溶性高分子に本発明の架橋剤を適用するにあたって、その方法に特別な制限はないが、一般的には、水溶性高分子の水溶液にポリカルボン酸およびリンのオキソ酸の塩を加えて溶解させるといった方法を採用することができる。ポリカルボン酸およびリンのオキソ酸の塩は、それぞれの水溶液または、両者を含有する混合水溶液の形で用いるのが好ましい。こうしてポリカルボン酸およびリンのオキソ酸の塩を配合された水溶性高分子は、従来と同様の方法でフィルム化したり、あるいは紙、繊維、不織布などに含浸またはコーティングし、必要に応じて乾燥したあと、１２０〜２００℃で１５秒〜５分間熱処理するといった方法により、最終製品とすることができる。
【００１９】
本発明の架橋剤を適用するにあたって、水酸基を有する水溶性高分子は、先に例示したものをそれぞれ単独で、または２種以上を混合して使用することができる。さらにはこうした水酸基を有する水溶性高分子以外に、水溶性または水分散性の高分子が含まれてもよく、また充填剤、防腐剤、着色剤、消泡剤、発泡剤、分散剤、乳化剤、流動性調整剤、可塑剤、ｐＨ調整剤、各種油剤などの各種添加剤が含まれていてもよい。
【００２０】
水酸基を有する水溶性高分子に対する架橋剤の使用割合も特に制限されるものでないが、一般には、その水溶性高分子に対して、ポリカルボン酸が３〜２０重量％となるように用いるのが好ましい。
【００２１】
【実施例】
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例によって限定されるものではない。なお例中、含有量を表す％および量比を表す割合または部は、特にことわらないかぎり、いずれも重量基準である。
【００２２】
実施例１
ケン化度９９モル％、平均重合度１７００のポリビニルアルコール（ＰＶＡ）を水に溶解し、１０％水溶液とした。別途、１，２，３，４−ブタンテトラカルボン酸（ＢＴＣＡ）と次亜リン酸ソーダ(NaH2PO2・H2O) を、それぞれ１０％水溶液とした。そしてこれらを表１に示す割合で配合し、混合した。この配合液を内径約５.5 cm のアルミニウムカップに１０ｇ採取し、５０〜６０℃にて一昼夜乾燥して、厚さ約０.3 mm 、直径約５.5 cm のフィルムを得た。
【００２３】
こうして得たポリビニルアルコールフィルムを、オーブンにて１５０℃で２０分間熱処理したあと、約１００倍量の水中に浸漬し、２時間煮沸処理した。そして、処理後のフィルムの形状、フィルムの膨潤率およびフィルムの残存率（不溶解率）を観察、測定し、表１の結果を得た。なお、膨潤率および残存率は、それぞれ次式により算出した。
【００２４】
実施例２〜５
実施例１で用いた１，２，３，４−ブタンテトラカルボン酸を表１に示す他のポリカルボン酸に置き換え、また次亜リン酸ソーダの量を一部変更した以外は、実施例１と同様のテストを行い、表１の結果を得た。表中のポリアクリル酸は、２５％水溶液の２５℃における粘度が６２cps であった。
【００２７】
比較例１
架橋剤を用いずに、ポリビニルアルコールのみで実施例１と同様に処理した。この場合、水中で２時間煮沸後にフィルムは完全に溶解していたため、フィルム膨潤率の測定はできなかった。
【００２８】
【表１】
実施例６
ケン化度８８モル％、平均重合度５００のポリビニルアルコール（ＰＶＡ）を水に溶解し、１０％水溶液とした。別途、１，２，３，４−ブタンテトラカルボン酸（ＢＴＣＡ）と次亜リン酸ソーダ(NaH2PO2・H2O) を、それぞれ１０％水溶液とした。そしてこれらを表２に示す割合で配合し、混合した。この配合液を実施例１と同様の方法で乾燥して、フィルムを得た。
【００３０】
こうして得たフィルムを、オーブンにて１３０℃で３０分間熱処理したあと、フィルムの着色状態を観察した。また、熱処理後のフィルムを約１００倍量の水中に２０℃で２４時間浸漬したあと、フィルムの膨潤率およびフィルムの残存率（不溶解率）を実施例１と同様の計算式で求めた。結果を表２に示す。
【００３１】
実験例７および８
実施例６で用いた次亜リン酸ソーダを表２に示す他のリンのオキソ酸の塩に変えた以外は、実施例６と同様にテストし、表２の結果を得た。
【００３２】
比較例２〜５
表２に示す配合液を用いた以外は実施例６と同様にテストし、表２の結果を得た。なお、ポリカルボン酸および触媒を用いなかった比較例５では、水中浸漬後のフィルムがほとんど原形をとどめない程度に溶解していたため、膨潤率の測定はできなかった。
【００３３】
【表２】
実施例９〜１２
実施例６で用いた１，２，３，４−ブタンテトラカルボン酸に代えて、２５％水溶液の２５℃における粘度が１０cps 、２１cps 、１００cps および１０００cps である４種類のポリアクリル酸のいずれかを用い、実施例６と同様の方法でフィルムを作成し、熱処理および水中浸漬に供した。そして水中浸漬後のフィルムの残存率（不溶解率）を実施例１と同様の計算式で求め、表３の結果を得た。
【００３５】
実施例１３および１４ならびに比較例６
表３に示す割合の配合液を用いた以外は、実施例９と同様にテストし、表３の結果を得た。
【００３６】
【表３】
【００３７】
実施例１５〜１７および比較例７〜９
水酸基を有する高分子として、日食 MS-3600（変性でんぷん、日本食品化工社品）を１０％濃度で糊化したもの、セロゲン PR-P （カルボキシメチルセルロース、第一工業製薬社品）を１０％の水溶液としたもの、およびスミカフレックス 400（ポリビニルアルコールを保護コロイドとして含有するエチレン−酢酸ビニルコポリマーエマルジョン、住友化学工業社品）を固形分１０％の水溶液としたもの、それぞれを用いた。一方、ポリカルボン酸として、２５％水溶液の２５℃における粘度が６２cps であるポリアクリル酸の１０％水溶液を、またリンのオキソ酸の塩として、次亜リン酸ソーダの１０％水溶液を用いた。これらから表４に示す配合液を調製した。ただし比較例７〜９では、水酸基を有する高分子の糊化液または水溶液のみを用いた。
【００３８】
これらの配合液それぞれにつき、実施例６と同様の方法で、フィルム化、得られたフィルムの熱処理、および熱処理後のフィルムの水中浸漬を行った。水中浸漬後のフィルムの残存率（不溶解率）を実施例１に示した計算式で求め、またフィルムを浸漬したあとの水の状態、および水中浸漬後のフィルムの状態を観察した。結果を表４に示す。
【００３９】
【表４】
【発明の効果】
本発明によれば、水酸基を有する水溶性高分子を有効に架橋し、耐水化することができる。[0001]
[Industrial applications]
The present invention relates to a crosslinking agent, a crosslinking method, and a crosslinking composition for a water-soluble polymer having a hydroxyl group. More specifically, when a water-soluble polymer having a hydroxyl group such as polyvinyl alcohol is used as a binder, a stiffness imparting agent, a dimensional stabilizer, or the like, the moisture resistance or the water resistance is increased or the water is insoluble. And the application thereof.
[0002]
[Prior art]
Water-soluble polymers having a hydroxyl group, such as polyvinyl alcohol, modified polyvinyl alcohol, starch or derivatives thereof, are used in many industrial fields, such as various adhesives, processing of fibers, paper and nonwoven fabrics, thickeners of protective colloids, and paints. Used. Such polymers are poor in moisture resistance and water resistance because of their water solubility, which is a major obstacle in some applications.
[0003]
Many proposals have been made to improve the moisture resistance and water resistance of such water-soluble polymers. For example, an N-methylol compound such as an N-methylol melamine resin crosslinks a water-soluble polymer having a hydroxyl group, and gives such a water-soluble polymer excellent water resistance. For the same purpose, dialdehydes such as glyoxal and glutaraldehyde, diisocyanates, blocked diisocyanates, complexing agents consisting of compounds such as copper, boron, aluminum, titanium, zinc, tin, chromium, dibasic or more A method using a carboxylic acid or the like has been proposed.
[0004]
[Problems to be solved by the invention]
However, the N-methylol compound has a problem that formaldehyde is generated. In addition, the method using other compounds also causes coloring or yellowing of the water-soluble polymer after application, causes a significant increase in viscosity when applied to the water-soluble polymer, or insolubilizes the water-soluble polymer. There is a problem that a long-time heat treatment is required at a high temperature, and also a problem that the obtained crosslinking effect is not always sufficient.
[0005]
In view of such circumstances, the present inventors have conducted intensive studies, and as a result, have reached the present invention. Therefore, one of the objects of the present invention is to provide a crosslinking agent for a hydroxyl group-containing water-soluble polymer which has solved the problems of the conventional products.
[0006]
Another object of the present invention is to provide a cross-linking agent which does not contain any formaldehyde-derived components and therefore does not generate formaldehyde.
[0007]
A further object of the present invention is to provide a crosslinking agent which does not cause coloring or yellowing due to crosslinking.
[0008]
Still another object of the present invention is to make a water-soluble polymer having a hydroxyl group water-insoluble by an industrially useful and simple method, thereby increasing the moisture resistance and water resistance to the water-soluble polymer. It is to provide a crosslinker that can be applied.
[0009]
Still another object of the present invention is to provide a method for crosslinking a hydroxyl group-containing water-soluble polymer using such a crosslinking agent, and further to provide a crosslinkable composition of a hydroxyl group-containing water-soluble polymer.
[0010]
[Means for Solving the Problems]
The present invention, above problems has been made for the purpose of solving the, and a place to its gist, the water-soluble polymer having a hydroxyl group, with a salt of a polycarboxylic acid and hypophosphorous acid crosslinking A method for producing a water-insoluble crosslinkable composition , characterized by using an agent . The present invention also includes a water-soluble polymer having a hydroxyl group, a polycarboxylic acid and a salt of hypophosphorous acid, wherein the content of the polycarboxylic acid is 3 to 20% by weight based on the water-soluble polymer. A water-insoluble crosslinkable composition, characterized in that the content of a salt of hypophosphorous acid is 5 to 100% by weight based on the polycarboxylic acid . The present invention further provides a crosslinking agent comprising a poly (meth) acrylic acid having a viscosity at 25 ° C. of 20 cps or more at 25 ° C. in an aqueous solution containing 25% by weight of poly (meth) acrylic acid, and a salt of hypophosphorous acid. I do. Hereinafter, the present invention will be described in detail.
[0011]
The water-soluble polymer having a hydroxyl group to which the crosslinking agent of the present invention is applied includes polyvinyl alcohol and various modified polyvinyl alcohols, starch and derivatives thereof, and further carboxymethylcellulose, methylcellulose, cellulose derivatives such as hydroxyethylcellulose, and the like. A polymer having a hydroxyl group in its chemical structure and being substantially water-soluble. The crosslinking agent of the present invention applied to such a water-soluble polymer having a hydroxyl group comprises a polycarboxylic acid and a salt of an oxo acid of phosphorus.
[0012]
The polycarboxylic acid as one component of the crosslinking agent refers to a compound having two or more carboxyl groups in one molecule, and includes citric acid, maleic acid, tartaric acid, succinic acid, itaconic acid, 1,2,3, Examples thereof include 4-butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polyacrylic acid, and polymethacrylic acid. In particular, 1,2,3,4-butanetetracarboxylic acid and poly (meth) acrylic acid are preferably used. In the case of poly (meth) acrylic acid, a 25% by weight aqueous solution having a viscosity at 25 ° C. of 20 cps or more is preferred in terms of giving a good processing effect. Further, from the viewpoint of workability and the like, the viscosity is 5000 cps. The following are more preferred.
[0013]
As used herein, poly (meth) acrylic acid is a homopolymer of acrylic acid or methacrylic acid, acrylic acid and / or methacrylic acid, crotonic acid, vinyl lactic acid, maleic acid, fumaric acid, aconitic acid, itaconic acid, Ethylene unsaturated carboxylic acids other than (meth) acrylic acid, such as mesaconic acid, citraconic acid and methylenemalonic acid, may be copolymerized. Furthermore, those obtained by copolymerizing other copolymerizable ethylenically unsaturated compounds may be used, such as acrylamide, methacrylamide, acrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate. , amides of ethylenically unsaturated carboxylic acids C 3 -C 5, nitriles or esters, or vinyl acetate, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, ethylene, propylene, styrene, alpha-methyl Styrene, nucleated methyl-substituted styrene and the like can also be copolymerized.
[0014]
When an unsaturated carboxylic acid other than (meth) acrylic acid is copolymerized, such an unsaturated carboxylic acid can be used in an arbitrary ratio. However, when a monomer having no carboxyl group is used as a copolymerization component, It can be used within a range that does not impair the water solubility of (meth) acrylic acid, and preferably 20% by weight or less based on the total weight of the monomer containing (meth) acrylic acid.
[0015]
Poly (meth) acrylic acid can be synthesized by a method such as bulk polymerization, aqueous solution polymerization, polymerization in an organic solvent, irradiation polymerization, or saponification of poly (meth) acrylate. Any of the methods synthesized by this method can be applied to the present invention. However, in the present invention, aqueous solution polymerization is industrially advantageous because it is usually used as an aqueous solution.
[0016]
The other component constituting the crosslinking agent of the present invention is a salt of phosphorus oxo acid. Here, the oxo acids of phosphorus, if example embodiment encompasses etc. hypophosphorous acid. Water-soluble salts of these phosphorus oxo acids, such as alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts, can be used in the present invention. Among them, sodium salts are advantageously used industrially. When the oxo acid of phosphorus is a polybasic acid, not only its normal salt but also its acidic salt can be used. As the oxo acid salt of phosphorus, sodium hypophosphite is particularly preferred.
[0017]
The cross-linking agent of the present invention comprises a salt of the polycarboxylic acid and the hypophosphorous acid as described above.These may be mixed in advance, and may be added to a water-soluble polymer having a hydroxyl group. They may be added separately. The ratio between the polycarboxylic acid and the phosphorus oxo acid salt is not particularly limited, but it is usually preferable to use the phosphorus oxo acid salt at a ratio of 5 to 100% by weight based on the polycarboxylic acid. . When the polycarboxylic acid is poly (meth) acrylic acid, it is more preferable to use a salt of oxoacid of phosphorus at a ratio of 10 to 30% by weight based on the poly (meth) acrylic acid.
[0018]
In applying the crosslinking agent of the present invention to a water-soluble polymer having a hydroxyl group, there is no particular limitation on the method, but in general, an aqueous solution of a water-soluble polymer is a salt of a polycarboxylic acid and an oxo acid salt of phosphorus. And dissolving it. The polycarboxylic acid and the oxo acid salt of phosphorus are preferably used in the form of respective aqueous solutions or a mixed aqueous solution containing both. The water-soluble polymer thus compounded with the salt of the polycarboxylic acid and the oxo acid of phosphorus is formed into a film by the same method as in the past, or is impregnated or coated on paper, fiber, nonwoven fabric, etc., and dried as necessary. After that, a final product can be obtained by a method of performing heat treatment at 120 to 200 ° C. for 15 seconds to 5 minutes.
[0019]
In applying the crosslinking agent of the present invention, as the water-soluble polymer having a hydroxyl group, those exemplified above can be used alone or in combination of two or more. Further, in addition to such a water-soluble polymer having a hydroxyl group, a water-soluble or water-dispersible polymer may be contained, and a filler, a preservative, a coloring agent, an antifoaming agent, a foaming agent, a dispersant, and an emulsifier And various additives such as a fluidity adjuster, a plasticizer, a pH adjuster, and various oils.
[0020]
The ratio of the crosslinking agent to the water-soluble polymer having a hydroxyl group is not particularly limited, but generally, the polycarboxylic acid is used in an amount of 3 to 20% by weight based on the water-soluble polymer. preferable.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, all the percentages and parts representing the contents and the ratios or parts representing the amount ratios are based on weight unless otherwise specified.
[0022]
Example 1
Polyvinyl alcohol (PVA) having a saponification degree of 99 mol% and an average polymerization degree of 1700 was dissolved in water to prepare a 10% aqueous solution. Separately, 1,2,3,4-butanetetracarboxylic acid (BTCA) and sodium hypophosphite (NaH 2 PO 2 .H 2 O) were each made into a 10% aqueous solution. These were blended at the ratio shown in Table 1 and mixed. 10 g of this compounded liquid was collected in an aluminum cup having an inner diameter of about 5.5 cm and dried at 50 to 60 ° C. for 24 hours to obtain a film having a thickness of about 0.3 mm and a diameter of about 5.5 cm.
[0023]
The thus obtained polyvinyl alcohol film was heat-treated in an oven at 150 ° C. for 20 minutes, immersed in about 100 times the amount of water, and boiled for 2 hours. Then, the shape of the processed film, the swelling ratio of the film, and the residual ratio (insoluble ratio) of the film were observed and measured, and the results shown in Table 1 were obtained. In addition, the swelling ratio and the residual ratio were calculated by the following equations, respectively.
[0024]
Examples 2 to 5
Example 1 Example 1, except that 1,2,3,4-butanetetracarboxylic acid used in Example 1 was replaced with another polycarboxylic acid shown in Table 1, and the amount of sodium hypophosphite was partially changed. A test similar to the above was performed, and the results shown in Table 1 were obtained. The polyacrylic acid in the table had a viscosity of 62 cps at 25 ° C. of a 25% aqueous solution.
[0027]
Comparative Example 1
The same treatment as in Example 1 was performed using only polyvinyl alcohol without using a crosslinking agent. In this case, since the film was completely dissolved after boiling in water for 2 hours, the film swelling ratio could not be measured.
[0028]
[Table 1]
Example 6
Polyvinyl alcohol (PVA) having a saponification degree of 88 mol% and an average polymerization degree of 500 was dissolved in water to prepare a 10% aqueous solution. Separately, 1,2,3,4-butanetetracarboxylic acid (BTCA) and sodium hypophosphite (NaH 2 PO 2 .H 2 O) were each made into a 10% aqueous solution. These were blended at the ratio shown in Table 2 and mixed. This mixed solution was dried in the same manner as in Example 1 to obtain a film.
[0030]
After the thus obtained film was heat-treated in an oven at 130 ° C. for 30 minutes, the coloring state of the film was observed. After the heat-treated film was immersed in about 100 times the volume of water at 20 ° C. for 24 hours, the swelling ratio of the film and the residual ratio (insoluble ratio) of the film were determined by the same formula as in Example 1. Table 2 shows the results.
[0031]
Experimental Examples 7 and 8
A test was conducted in the same manner as in Example 6, except that the sodium hypophosphite used in Example 6 was changed to another phosphorus oxoacid salt shown in Table 2, and the results in Table 2 were obtained.
[0032]
Comparative Examples 2 to 5
A test was conducted in the same manner as in Example 6 except that the liquid formulations shown in Table 2 were used, and the results in Table 2 were obtained. In Comparative Example 5 in which the polycarboxylic acid and the catalyst were not used, the swelling ratio could not be measured because the film after immersion in water was dissolved to such an extent that it hardly retained its original shape.
[0033]
[Table 2]
Examples 9 to 12
Instead of 1,2,3,4-butanetetracarboxylic acid used in Example 6, one of four kinds of polyacrylic acids having a viscosity of 10 cps, 21 cps, 100 cps and 1000 cps at 25 ° C. of a 25% aqueous solution was used. A film was prepared in the same manner as in Example 6, and subjected to heat treatment and immersion in water. Then, the residual ratio (insoluble ratio) of the film after immersion in water was determined by the same formula as in Example 1, and the results in Table 3 were obtained.
[0035]
Examples 13 and 14 and Comparative Example 6
A test was conducted in the same manner as in Example 9 except that the compounding liquids in the proportions shown in Table 3 were used, and the results in Table 3 were obtained.
[0036]
[Table 3]
[0037]
Examples 15 to 17 and Comparative Examples 7 to 9
As a polymer having a hydroxyl group, Eclipse MS-3600 (modified starch, manufactured by Nippon Shokuhin Kako Co., Ltd.) is gelatinized at a concentration of 10%, and cellogen PR-P (carboxymethylcellulose, manufactured by Daiichi Kogyo Seiyaku) is 10%. And an aqueous solution of Sumikaflex 400 (an ethylene-vinyl acetate copolymer emulsion containing polyvinyl alcohol as a protective colloid, manufactured by Sumitomo Chemical Co., Ltd.) having a solid content of 10% was used. On the other hand, a 10% aqueous solution of polyacrylic acid having a viscosity of 62 cps at 25 ° C. of a 25% aqueous solution was used as the polycarboxylic acid, and a 10% aqueous solution of sodium hypophosphite was used as the salt of the oxoacid of phosphorus. From these, the compounding solutions shown in Table 4 were prepared. However, in Comparative Examples 7 to 9, only a gelatinizing solution or aqueous solution of a polymer having a hydroxyl group was used.
[0038]
In the same manner as in Example 6, a film was formed, the resulting film was heat-treated, and the film after the heat treatment was immersed in water for each of these compounding solutions. The residual ratio (insoluble ratio) of the film after immersion in water was determined by the calculation formula shown in Example 1, and the state of water after immersion of the film and the state of the film after immersion in water were observed. Table 4 shows the results.
[0039]
[Table 4]
【The invention's effect】
According to the present invention, a water-soluble polymer having a hydroxyl group can be effectively crosslinked and made water-resistant.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25321493A JP3582089B2 (en) | 1993-10-08 | 1993-10-08 | Crosslinking agent, crosslinkable composition, and method for producing crosslinkable composition |
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| Application Number | Priority Date | Filing Date | Title |
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| JP25321493A JP3582089B2 (en) | 1993-10-08 | 1993-10-08 | Crosslinking agent, crosslinkable composition, and method for producing crosslinkable composition |
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| Publication Number | Publication Date |
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| JPH07102110A JPH07102110A (en) | 1995-04-18 |
| JP3582089B2 true JP3582089B2 (en) | 2004-10-27 |
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| TW513472B (en) * | 2000-07-12 | 2002-12-11 | Dainichiseika Color & Amp Chem | Aqueous compositions and process for the surface modification of articles by use of the aqueous compositions |
| AU782722B2 (en) | 2000-12-12 | 2005-08-25 | Unitika Ltd. | Gas-barrier resin composition, gas-barrier coating material, and gas-barrier molding |
| US6709735B2 (en) * | 2001-11-14 | 2004-03-23 | Mitsubishi Polyester Film, Llc | Oxygen barrier coating and coated film |
| BRPI0611449A2 (en) * | 2005-05-06 | 2010-09-08 | Dynea Oy | Formaldehyde-free curable aqueous composition based on polyvinyl alcohol |
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