JPH06136221A - Aqueous dispersion of polyvinyl alcoholic resin - Google Patents
Aqueous dispersion of polyvinyl alcoholic resinInfo
- Publication number
- JPH06136221A JPH06136221A JP4309212A JP30921292A JPH06136221A JP H06136221 A JPH06136221 A JP H06136221A JP 4309212 A JP4309212 A JP 4309212A JP 30921292 A JP30921292 A JP 30921292A JP H06136221 A JPH06136221 A JP H06136221A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- aqueous dispersion
- resin
- polymerization
- based resin
- 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.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、紙加工、接着剤、糊剤
等の多用途に利用可能なポリビニルアルコール系樹脂の
水性分散液に関し、更に詳しくは、高濃度においても良
好な流動性を有するポリビニルアルコール系樹脂の水性
分散液に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of a polyvinyl alcohol resin which can be used for various purposes such as paper processing, adhesives and sizing agents. More specifically, it has good fluidity even at high concentration. It relates to an aqueous dispersion of the polyvinyl alcohol resin.
【０００２】[0002]
【従来の技術】従来、ポリビニルアルコール系樹脂は、
その水溶性、接着性を利用して種々の分野、例えば接着
剤、フィルム、シートなどの成型物の他、分散剤、繊維
用糊剤等の用途の分野に広く用いられている。そして、
近年その接着強度、フィルム強度、紙加工時のバリヤー
性等の改良のため、比較的重合度の高いポリビニルアル
コール系樹脂が多用される傾向にある。2. Description of the Related Art Conventionally, polyvinyl alcohol resins are
Utilizing its water solubility and adhesiveness, it is widely used in various fields such as molded articles such as adhesives, films and sheets, as well as fields such as dispersants and sizing agents for fibers. And
In recent years, polyvinyl alcohol-based resins having a relatively high degree of polymerization have tended to be frequently used in order to improve their adhesive strength, film strength, barrier properties during paper processing and the like.
【０００３】[0003]
【発明が解決しようとする課題】かかる用途においてポ
リビニルアルコール系樹脂は、水溶液として用いられる
ことが多いが、重合度が高くなるにつれてポリビニルア
ルコール系樹脂の粘度は非常に高くなり、例えば、平均
重合度３０００、平均ケン化度９９モル％のポリビニル
アルコール系樹脂４重量％の水溶液の場合、粘度（Ｂ型
粘度計にて測定）は、約１００ｃｐｓ（２０℃）にも達
し、その取り扱いや塗工操作等に著しい障害が起こり易
い。又、上記のポリビニルアルコール系樹脂水溶液の場
合、水溶液自体を得ることが困難であるうえ、貯蔵安定
性や特に低温での流動安定性が不良である等の問題が生
じている。これらの問題を解決すべく、ポリビニルアル
コール系樹脂を変性したり、水溶液の濃度を下げたり、
あるいは、高温で貯蔵する等の工夫が試みられている
が、満足できる解決策がないのが現状である。In such applications, the polyvinyl alcohol-based resin is often used as an aqueous solution, but the viscosity of the polyvinyl alcohol-based resin becomes very high as the polymerization degree becomes high. In the case of an aqueous solution of 3000% and an average saponification degree of 99 mol% of a polyvinyl alcohol resin 4% by weight, the viscosity (measured by a B-type viscometer) reaches about 100 cps (20 ° C.), and its handling and coating operation are performed. It is easy to have a serious trouble in In addition, in the case of the above polyvinyl alcohol-based resin aqueous solution, it is difficult to obtain the aqueous solution itself, and there are problems such as poor storage stability and flow stability especially at low temperatures. In order to solve these problems, denature polyvinyl alcohol resin, reduce the concentration of the aqueous solution,
Alternatively, attempts have been made to store it at a high temperature, but the current situation is that there is no satisfactory solution.
【０００４】[0004]
【課題を解決するための手段】そこで、本発明者等は、
かかる問題を解決すべく鋭意研究を重ねた結果、結晶化
度３０％以上、平均重合度３０００以上、平均粒径５０
μ以下のポリビニルアルコール系樹脂微粒子を０．１重
量％以上の濃度で水に分散させた水性分散液は、ポリビ
ニルアルコール系樹脂が高重合度、高濃度であっても塗
工性良好な流動性を示し、保存安定性にも優れ、分散液
の調整も容易であり、しかもポリビニルアルコール系樹
脂水溶液を用いた場合と同様の物性が期待でき、接着剤
や紙加工用途等に好適である等の顕著な効果が得られる
ことを見出し、本発明を完成するに至った。Therefore, the present inventors have
As a result of intensive studies to solve such problems, the crystallinity is 30% or more, the average degree of polymerization is 3000 or more, and the average particle size is 50.
An aqueous dispersion prepared by dispersing polyvinyl alcohol-based resin fine particles of μ or less in water at a concentration of 0.1% by weight or more has a high degree of polymerization of the polyvinyl alcohol-based resin and a fluidity with good coatability even at a high concentration. It has excellent storage stability, is easy to adjust the dispersion, and can be expected to have the same physical properties as when an aqueous solution of polyvinyl alcohol resin is used, and is suitable for adhesives, paper processing applications, etc. They have found that a remarkable effect can be obtained, and have completed the present invention.
【０００５】以下、本発明について詳述する。本発明で
用いるポリビニルアルコール系樹脂とは、ポリ酢酸ビニ
ルをケン化して得られるもので、更には、酢酸ビニルを
主成分としてこれと重合可能な単量体の共重合体ケン化
物が挙げられる。該単量体としては、例えばアクリル
酸、メタクリル酸、クロトン酸、マレイン酸、無水マレ
イン酸、イタコン酸等の不飽和酸類あるいはその塩、モ
ノ又はジアルキルエステル等、アクリロニトリル等のニ
トリル類、アクリルアミド、メタアクリルアミド等のア
ミド類、エチレンスルホン酸、アリルスルホン酸、メタ
アリルスルホン酸等のオレフィンスルホン酸等のオレフ
ィンスルホン酸あるいはその塩、エチレン、プロピレ
ン、イソブチレン、α−オクテン、α−ドデセン、α−
オクタデセン等のオレフィン類、アルキルビニルエーテ
ル類、ビニルケトン、Ｎ−ビニルピロリドン、塩化ビニ
ル、塩化ビニリデン、オキシアルキレン類等の共重合体
ケン化物が挙げられ、また、かかる樹脂をグラフト変
性、又はブロック共重合した樹脂も含まれるが、これら
に限定されるものではない。The present invention will be described in detail below. The polyvinyl alcohol-based resin used in the present invention is obtained by saponifying polyvinyl acetate, and further, a saponified product of a copolymer of vinyl acetate as a main component and a polymerizable monomer can be used. Examples of the monomer include unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, and itaconic acid, or salts thereof, mono- or dialkyl esters, nitriles such as acrylonitrile, acrylamide, and meta. Amides such as acrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, olefin sulfonic acid such as methallyl sulfonic acid or salts thereof, ethylene, propylene, isobutylene, α-octene, α-dodecene, α-
Examples include olefins such as octadecene, alkyl vinyl ethers, vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, oxyalkylenes, and other saponified copolymers. Further, such resins are graft-modified or block-copolymerized. Resins are also included, but are not limited to these.
【０００６】本発明に用いるポリビニルアルコール系樹
脂は、上記のいずれであっても良いが、結晶化度３０％
以上、平均重合度３０００以上、平均粒子径５０μ以下
のものが用いられる。ポリビニルアルコール系樹脂の結
晶化度が３０％未満では、水分散性が著しく低下し、良
好な流動性が得られず不適当である。通常、工業的に製
造された平均重合度３０００を越えるポリビニルアルコ
ール系樹脂の結晶化度は０〜２５％程度であるので、本
発明では熱処理等の処理を施してかかる範囲内に結晶化
度を調整しなければならない。なお、本発明に言う結晶
化度とは、示差走査型熱量計による結晶融解熱測定値
（ｘ）を、式（ｘ／１．６４）×１００（％）に代入し
算出した値である。［１．６４；ポリビニルアルコール
系樹脂の融解潜熱（ｋｃａｌ／ｍｏｌ）Ｒ．Ｋ．Ｔｕｂ
ｂｓ，Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．，Ａ３，４１８（１９
６５）より］The polyvinyl alcohol resin used in the present invention may be any of those mentioned above, but the crystallinity is 30%.
As described above, those having an average degree of polymerization of 3000 or more and an average particle size of 50 μ or less are used. If the crystallinity of the polyvinyl alcohol-based resin is less than 30%, the dispersibility in water is remarkably reduced, and good fluidity cannot be obtained, which is unsuitable. Usually, the crystallinity of an industrially produced polyvinyl alcohol-based resin having an average polymerization degree of more than 3000 is about 0 to 25%. Therefore, in the present invention, the crystallinity is controlled within such a range by subjecting it to a treatment such as heat treatment. I have to adjust. The crystallinity referred to in the present invention is a value calculated by substituting the crystal fusion heat measurement value (x) by a differential scanning calorimeter into the formula (x / 1.64) × 100 (%). [1.64; latent heat of fusion of polyvinyl alcohol-based resin (kcal / mol) R.I. K. Tub
bs, J .; Polym. Sci. , A3, 418 (19
From 65)]
【０００７】また、平均重合度が３０００未満になる
と、水溶液でも使用可能であるので本発明の効果を期待
する意味がなく、ポリビニルアルコール系樹脂塗布成型
膜のバリヤー性や接着性等も低下し、要求されるポリビ
ニルアルコール系樹脂の特性が得られない。更に、ポリ
ビニルアルコール系樹脂の平均粒子径が５０μを越える
とポリビニルアルコール系樹脂水分散液の安定性が低下
し、ブロッキング、ゲル化等が起こり易くなるとともに
製膜時の均質性が劣り、薄くて均一な膜生成性が損なわ
れる恐れが生じてくる。上記の中でも、結晶化度３５％
以上、平均重合度３５００以上、平均粒子径３０μ以下
の時、本発明の効果が最大限に発揮される。本発明に用
いるポリビニルアルコール系樹脂は、上記条件を満足し
ていれば良く、平均ケン化度は特に限定されないが水分
散性を考慮すれば、９０モル％以上が好ましく、さらに
好ましくは９５モル以上のものが好適に用いられる。If the average degree of polymerization is less than 3,000, it is meaningless to expect the effect of the present invention because it can be used in an aqueous solution, and the barrier property and adhesiveness of the polyvinyl alcohol resin-coated molded film are deteriorated. The required characteristics of polyvinyl alcohol resin cannot be obtained. Further, when the average particle diameter of the polyvinyl alcohol resin exceeds 50 μ, the stability of the polyvinyl alcohol resin aqueous dispersion is lowered, blocking and gelation are likely to occur, and the homogeneity at the time of film formation is poor and thin. There is a risk that the uniform film forming property will be impaired. Among the above, crystallinity 35%
As described above, when the average degree of polymerization is 3500 or more and the average particle size is 30 μ or less, the effect of the present invention is maximized. The polyvinyl alcohol-based resin used in the present invention has only to satisfy the above conditions, and the average saponification degree is not particularly limited, but in view of water dispersibility, it is preferably 90 mol% or more, more preferably 95 mol or more. Those of are preferably used.
【０００８】本発明に用いるポリビニルアルコール系樹
脂微粒子は、通常の工業的製法で得られるポリビニルア
ルコール系樹脂を前記した様に特定の結晶化度に調整す
ることと、微粒子化することが必要となる。結晶化度の
調整と粒度調整とは同時に行っても、別々に行ってもよ
い。例えば、上記のポリビニルアルコール系樹脂の粗粒
を機械的粉砕法により微粒子化する方法やケン化触媒を
含むポリ酢酸ビニル系樹脂のアルコール溶液を噴霧・乾
燥処理するというケン化と微粒子化を同時に行う方法等
がある。前者の方法においては、常法に従ってポリ酢酸
ビニル樹脂あるいは前述の酢酸ビニルと共重合可能な単
量体との共重合体をケン化してポリビニルアルコール系
樹脂の微粒子を得るのである。The polyvinyl alcohol-based resin fine particles used in the present invention require the polyvinyl alcohol-based resin obtained by an ordinary industrial production method to be adjusted to a specific crystallinity as described above and to be finely divided. . The adjustment of crystallinity and the adjustment of particle size may be performed simultaneously or separately. For example, the saponification and the atomization are performed at the same time by a method of atomizing the coarse particles of the polyvinyl alcohol resin by a mechanical pulverization method or by spraying and drying an alcohol solution of a polyvinyl acetate resin containing a saponification catalyst. There are ways. In the former method, polyvinyl acetate resin or a copolymer of the above-mentioned vinyl acetate and a copolymerizable monomer is saponified according to a conventional method to obtain fine particles of polyvinyl alcohol resin.
【０００９】具体的には、以下の通りである。単量体と
酢酸ビニルとを共重合するに当たっては、特に制限はな
く公知の重合方法が任意に用いられるが普通メタノール
やエタノール等のアルコールを溶媒とする溶液重合が実
施される。かかる方法に於いて単量体の仕込み方法とし
ては、まず酢酸ビニルの全量と前記単量体の一部を仕込
み、重合を開始し、残りの単量体を重合期間中に連続的
に又は分割的に添加する方法、両者を一括仕込みする方
法等任意の手段を用いることができる。共重合反応は、
アゾビスブチロニトリル、過酸化アセチル、過酸化ベン
ゾイル、過酸化ラウロイルなどの公知のラジカル重合触
媒を用いて行われる。また、反応温度は５０℃〜沸点程
度の範囲から選択される。上記のごとく得られる酢酸ビ
ニル系共重合体あるいはポリ酢酸ビニルは、次にケン化
される。ケン化に当たっては、該共重合体あるいはポリ
酢酸ビニルをアルコールに溶解しアルカリ触媒の存在下
にケン化が行われる。アルコールとしては、メタノー
ル、エタノール、ブタノール等が挙げられる。アルコー
ル中の共重合体あるいはポリ酢酸ビニルの濃度は、通常
２０〜７０重量％の範囲から選ばれる。Specifically, it is as follows. In copolymerizing the monomer and vinyl acetate, there is no particular limitation and any known polymerization method can be optionally used. Usually, solution polymerization is carried out using an alcohol such as methanol or ethanol as a solvent. In such a method, as a method of charging a monomer, first, the entire amount of vinyl acetate and a part of the monomer are charged, polymerization is started, and the remaining monomer is continuously or divided during the polymerization period. It is possible to use any means such as a method of adding the same and a method of charging both at once. The copolymerization reaction is
It is carried out using a known radical polymerization catalyst such as azobisbutyronitrile, acetyl peroxide, benzoyl peroxide and lauroyl peroxide. The reaction temperature is selected from the range of 50 ° C to the boiling point. The vinyl acetate copolymer or polyvinyl acetate obtained as described above is then saponified. In the saponification, the copolymer or polyvinyl acetate is dissolved in alcohol and saponification is performed in the presence of an alkali catalyst. Examples of alcohols include methanol, ethanol, butanol and the like. The concentration of the copolymer or polyvinyl acetate in the alcohol is usually selected from the range of 20 to 70% by weight.
【００１０】ケン化触媒としては、水酸化ナトリウム、
水酸化カリウム、ナトリウムメチラート、ナトリウムエ
チラート、カリウムメチラート等のアルカリ金属の水酸
化物やアルコラートのごときアルカリ触媒を用いること
が通常であるが、硫酸等の酸触媒も使用可能である。か
かる触媒の使用量は、酢酸ビニルに対して５〜２００ミ
リモル当量にすることが必要である。また、ケン化温度
は、特に制限はないが、通常２０〜６０℃が好ましく、
さらに好ましく３０〜５０℃の範囲が適している。反応
は、通常数分〜２，３時間にわたって行われる。かくし
て得られたポリビニルアルコール系樹脂は、２００〜３
００μ程度の粗粒として得られるので、次に機械的な粉
砕によって微粒子化される。さらに必要に応じて熱処理
等を行うことも可能である。As the saponification catalyst, sodium hydroxide,
Alkaline catalysts such as alkali metal hydroxides and alcoholates such as potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate are usually used, but acid catalysts such as sulfuric acid can also be used. The amount of such a catalyst to be used needs to be 5 to 200 millimole equivalent to vinyl acetate. The saponification temperature is not particularly limited, but is usually preferably 20 to 60 ° C,
More preferably, the range of 30 to 50 ° C is suitable. The reaction is usually performed for a few minutes to a few hours. The polyvinyl alcohol resin thus obtained is 200 to 3
Since it is obtained as coarse particles of about 00 μ, it is then finely divided into particles by mechanical pulverization. Further, heat treatment or the like can be performed if necessary.
【００１１】粉砕方法に特に制限はなく任意の方法が採
用され、例えばロールミル、スタンプミル、エッジラン
ナー、切断・せん断ミル、ロッドミル、自生粉砕機、ロ
ーラミル、高速回転粉砕機（ハンマーミル、ゲージミ
ル、ピンミル、ディスインテグレーター、スクリーンミ
ル、ターボ型ミル、遠心分級ミル等）、ボールミル（転
動ミル、振動ボールミル、遊星ミル）、撹拌ミル（タワ
ーミル、撹拌槽型ミル、流通管型ミル、アニュラーミ
ル）、ジェットミル、せん断ミル、圧縮摩砕型粉砕機、
コロイドミル等が用いられる。後者の方法（噴霧・乾燥
処理）においては、ポリ酢酸ビニルと前記のアルコール
及びケン化触媒とのペースト物をディスクタイプあるい
はノズルタイプの噴霧装置より５０〜２００℃の空気中
にスプレー噴霧することによりポリビニルアルコール系
樹脂の微粒子を得ることができる。必要に応じて、再ケ
ン化を行いケン化度を調整することも可能である。かく
して本発明に用いるポリビニルアルコール系樹脂微粒子
が得られるのである。The crushing method is not particularly limited and any method can be adopted. For example, a roll mill, a stamp mill, an edge runner, a cutting / shearing mill, a rod mill, an autogenous crusher, a roller mill, a high speed rotary crusher (hammer mill, gauge mill, pin mill). , Disintegrators, screen mills, turbo type mills, centrifugal classification mills, etc.), ball mills (rolling mills, vibration ball mills, planetary mills), stirring mills (tower mills, stirring tank type mills, flow tube type mills, annular mills), jets Mill, shear mill, compression grinding type crusher,
A colloid mill or the like is used. In the latter method (spraying / drying treatment), a paste of polyvinyl acetate and the above-mentioned alcohol and saponification catalyst is sprayed in the air of 50 to 200 ° C. from a disk type or nozzle type spraying device. It is possible to obtain fine particles of polyvinyl alcohol resin. It is also possible to re-saponify and adjust the degree of saponification, if necessary. Thus, the polyvinyl alcohol-based resin fine particles used in the present invention can be obtained.
【００１２】ポリビニルアルコール系樹脂微粒子の製造
方法は、上記の方法に限定されるものではないが、本発
明においては、上記の噴霧・乾燥処理による方法（スプ
レードライ法）がケン化及び微粒子化が同時に行え、か
つ球状の均一な粒子が得られるのでより効果的である。
本発明のポリビニルアルコール系樹脂の水性分散液は、
上記の如くして得られたポリビニルアルコール系樹脂微
粒子を０．１重量％以上の濃度で水に分散させたもの
で、該微粒子濃度が０．１重量％未満では、接着剤、紙
加工、糊剤等の用途において目的とする物性が得難くな
る。該分散液の調整法としては、公知の方法が用いら
れ、通常は、５０℃以下の水に撹拌下で該微粒子を添加
する方法が採用される。また、上記の分散液には、必要
に応じて各種の保護コロイド類、界面活性剤、消泡剤、
防腐剤等適宜他の助剤を添加することもできる。The method for producing fine particles of polyvinyl alcohol resin is not limited to the above-mentioned method, but in the present invention, the method of spraying / drying (spray dry method) does not cause saponification and fine particles. This is more effective because it can be carried out simultaneously and spherical uniform particles can be obtained.
Aqueous dispersion of polyvinyl alcohol resin of the present invention,
The polyvinyl alcohol-based resin fine particles obtained as described above are dispersed in water at a concentration of 0.1% by weight or more. If the concentration of the fine particles is less than 0.1% by weight, an adhesive, paper processing, paste It becomes difficult to obtain the desired physical properties in applications such as agents. As a method for preparing the dispersion liquid, a known method is used, and usually, a method of adding the fine particles to water at 50 ° C. or lower with stirring is adopted. Further, in the above dispersion liquid, various protective colloids, surfactants, defoamers, and
Other auxiliaries such as antiseptics may be added as appropriate.
【００１３】かくして得られたポリビニルアルコール系
樹脂の水性分散液は、非常に有用なものであり、種々の
用途が考えられ、例えば、繊維，フイルム，シート，パ
イプ，チューブ等の成型物類、木材，紙，アルミ箔，プ
ラスチックス等の接着剤、粘着剤、再湿剤、保湿剤、ホ
ットメルト接着剤，感圧接着剤，不織布用バインダー，
セメント混和用等の接着剤類、紙，繊維製品へのコーテ
ィング剤、成型物の添加剤、インキ，塗料等の添加剤、
塩化ビニル，酢酸ビニル，アクリル酸エステル等の不飽
和単量体の懸濁重合並びに乳化重合用の分散安定剤等種
々の用途が挙げられ、更には、５０℃以下の状態で水性
分散液として使用されることが好ましいが、必ずしもこ
れらの用途や使用法に限定されるものではない。The aqueous dispersion of polyvinyl alcohol resin thus obtained is very useful and can be used for various purposes. For example, moldings such as fibers, films, sheets, pipes and tubes, and wood. , Adhesives for paper, aluminum foil, plastics, adhesives, remoisturizers, moisturizers, hot melt adhesives, pressure sensitive adhesives, non-woven fabric binders,
Adhesives such as cement admixtures, coating agents for paper and textile products, additives for moldings, additives for inks, paints, etc.
It has various uses such as dispersion stabilizer for suspension polymerization and emulsion polymerization of unsaturated monomers such as vinyl chloride, vinyl acetate, acrylic acid ester, etc. Furthermore, it is used as an aqueous dispersion at 50 ° C or lower. However, it is not necessarily limited to these uses and usages.
【００１４】[0014]
【作用】本発明のポリビニルアルコール系樹脂の水性分
散液は、該樹脂が高重合度、高濃度であっても低粘度
で、塗工性に優れ、紙加工、接着剤、糊剤等の用途に大
変有用である。The aqueous dispersion of the polyvinyl alcohol resin of the present invention has a high degree of polymerization, a low viscosity even at a high concentration, and an excellent coatability, and is used for paper processing, adhesives, sizing agents, etc. Very useful for
【００１５】[0015]
【実施例】以下、実施例を挙げて本発明を具体的に説明
する。尚、実施例中、「部」、「％」とあるのは、特に
ことわりのない限り重量基準を示す。 実施例１ 平均重合度３５００のポリ酢酸ビニル１００部、メタノ
ール溶液３００部及び水酸化ナトリウム１部を撹拌機付
の缶で混合撹拌し、ポリ酢酸ビニルのペーストを得た。
次に該ペーストを２０℃に保ち、ノズル（φ＝０．５ｍ
ｍ）より、噴霧圧１．０ｋｇ／ｃｍ2で１８０℃の窒素
ガス雰囲気中に噴霧し、同時に乾燥させた後、メタノー
ル中で再ケン化を行い乾燥させて、結晶化度３５％、平
均重合度３５００、ケン化度９７モル％、平均粒子径１
０μのポリビニルアルコール系樹脂微粒子を得た。上記
の如く、スプレードライ法で得られた該ポリビニルアル
コール系樹脂１００部を１９００部の水に撹拌下に充分
分散させ、安定なポリビニルアルコール系樹脂の水性分
散液を得た。該水性分散液の粘度は、１．６ｃｐｓ（２
０℃）であり、２０℃で１０日間放置後の粘度も、１．
６ｃｐｓ（２０℃）であり、外観は、均一分散状態を示
し良好であった。また、上質紙（坪量５０ｇ／ｍ2）に
ロールコーターで２０℃にて該水性分散液を塗工（ポリ
ビニルアルコール系樹脂着量０．５ｇ／ｍ2）し、乾燥
後該塗工紙に常法でインキを印刷してＪＩＳ Ｐ ８１
４２に準拠して７５度鏡面光沢度を測定した。EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "parts" and "%" are based on weight unless otherwise specified. Example 1 100 parts of polyvinyl acetate having an average degree of polymerization of 3500, 300 parts of a methanol solution and 1 part of sodium hydroxide were mixed and stirred in a can equipped with a stirrer to obtain a polyvinyl acetate paste.
Next, the paste was kept at 20 ° C., and the nozzle (φ = 0.5 m
m) was sprayed in a nitrogen gas atmosphere at 180 ° C. with a spraying pressure of 1.0 kg / cm 2 , dried at the same time, re-saponified in methanol and dried to obtain a crystallinity of 35% and an average polymerization. Degree 3500, saponification degree 97 mol%, average particle size 1
0 μm of polyvinyl alcohol resin fine particles were obtained. As described above, 100 parts of the polyvinyl alcohol resin obtained by the spray drying method was sufficiently dispersed in 1900 parts of water with stirring to obtain a stable aqueous dispersion of the polyvinyl alcohol resin. The viscosity of the aqueous dispersion is 1.6 cps (2
0 ° C.) and the viscosity after standing at 20 ° C. for 10 days is 1.
It was 6 cps (20 ° C.), and the appearance was good, showing a uniformly dispersed state. Further, a fine paper (basis weight: 50 g / m 2 ) is coated with the aqueous dispersion at 20 ° C. by a roll coater (polyvinyl alcohol-based resin coating amount: 0.5 g / m 2 ), and the coated paper is dried. Ink is printed by a conventional method to JIS P 81
According to No. 42, the 75 degree specular gloss was measured.
【００１６】実施例２ 常法によりアルカリケン化して平均重合度５０００、ケ
ン化度９９．８モル％、平均粒子径４３０μのポリビニ
ルアルコール系樹脂を得た。次に１８０℃で５分間熱処
理を行い、結晶化度を４０％として、該樹脂をジェット
ミル（日本ニューマチック工業社製、超音速ジェット粉
砕機 ＬＡＢＯ ＪＥＴ ＬＪ）で粉砕し、平均粒子径
２５μのポリビニルアルコール系樹脂を得た。該樹脂を
用いて実施例１と同様にポリビニルアルコール系樹脂の
水性分散液を調製し、同様に評価を行った。Example 2 Alkali saponification was carried out by a conventional method to obtain a polyvinyl alcohol resin having an average degree of polymerization of 5000, a degree of saponification of 99.8 mol% and an average particle size of 430 μ. Next, heat treatment was performed at 180 ° C. for 5 minutes to adjust the crystallinity to 40%, and the resin was crushed with a jet mill (manufactured by Nippon Pneumatic Mfg. Co., Ltd., LABO JET LJ, a supersonic jet crusher) to obtain an average particle size of 25 μm. A polyvinyl alcohol resin was obtained. Using the resin, an aqueous dispersion of polyvinyl alcohol resin was prepared in the same manner as in Example 1 and evaluated in the same manner.
【００１７】実施例３，４ 表１に示すポリビニルアルコール系樹脂を用い、実施例
１と同様にポリビニルアルコール系樹脂の水性分散液を
得て、同様に評価を行った。 比較例１〜３ 表１に示すポリビニルアルコール系樹脂を用いて実施例
１と同様にポリビニルアルコール系樹脂の水性分散液を
得て、同様に評価を行った。Examples 3 and 4 Using the polyvinyl alcohol resins shown in Table 1, aqueous polyvinyl alcohol resin dispersions were obtained in the same manner as in Example 1 and evaluated in the same manner. Comparative Examples 1 to 3 Using the polyvinyl alcohol-based resins shown in Table 1, aqueous dispersions of polyvinyl alcohol-based resins were obtained in the same manner as in Example 1 and evaluated in the same manner.
【００１８】比較例４ 常法によりアルカリケン化して得られた平均重合度３５
００、ケン化度９９．０モル％、平均粒子径４３０μの
ポリビニルアルコール系樹脂を９０℃にて加熱溶解させ
て５％のポリビニルアルコール系樹脂の水溶液を得て、
実施例１と同様に評価を行った。実施例及び比較例の評
価結果を表２に示す。Comparative Example 4 Average degree of polymerization of 35 obtained by alkali saponification by a conventional method
00, saponification degree 99.0 mol%, polyvinyl alcohol resin having an average particle diameter of 430 μm is heated and dissolved at 90 ° C. to obtain an aqueous solution of 5% polyvinyl alcohol resin,
The evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of Examples and Comparative Examples.
【００１９】[0019]
【表１】 ポリビニルアルコール系樹脂 微粒子化法 平均粒径 平均重合度 ケン化度 結晶化度 （μ） (モル％) （％） 実施例１ ３５００ ９７．０ ３５ 噴霧乾燥法 １０ 〃 ２ ５０００ ９９．８ ４０ 機械粉砕法 ２５ 〃 ３ ３０００ ９８．０ ３６ 噴霧乾燥法 ２０ 〃 ４ ４０００ ９９．０ ４５ 〃 １５ 比較例１ ３５００ ９７．０ ２０ 噴霧乾燥法 １０ 〃 ２ １７００ ９７．０ ３５ 〃 ２５ 〃 ３ ３５００ ９７．０ ３５ 〃 ８０ 〃 ４ ３５００ ９９．０ ３５ 加熱溶解法 −− [Table 1] Polyvinyl alcohol-based resin atomization method Average particle size Average degree of polymerization Saponification degree Crystallinity (μ) (mol%) (%) Example 1 3500 97.0 35 Spray drying method 10 〃 2 5000 99. 8 40 Mechanical pulverization method 25 〃 3 3000 98.0 36 Spray drying method 20 〃 4 4000 99.0 45 〃 15 Comparative example 1 3500 97.0 20 Spray drying method 10 〃 2 1700 97.0 35 〃 25 3 500 97.0 35 〃 80 〃 4 3500 99.0 35 Heat melting method ---
【００２０】[0020]
【表２】 ポリビニルアルコール系樹脂液 保存安定性* 塗工性** ＰＶＡ濃度 ＰＶＡ粒子 粘 度 外観 増粘度 （％） の分散状態 (cps/20℃) 実施例１ ５．０ 均一分散 １．６ ○ ○ ○ 〃 ２ ４．８ 〃 １．５ ○ ○ ○ 〃 ３ ７．０ 〃 １．６ ○ ○ ○ 〃 ４ １０．０ 〃 ３．９ ○ ○ ○ 比較例１ ５．０ 均一分散 ８．５ × △ × 〃 ２ ５．０ 〃 ２．７ × △ △ 〃 ３ ５．０ 不均一分散 １．９ × ○ × 〃 ４ ５．０ 溶解 ３００ ゲル化 塗工不可 [Table 2] Storage stability of polyvinyl alcohol resin solution * Coatability ** PVA concentration PVA particles Viscosity Appearance Viscosity (%) dispersion state (cps / 20 ° C) Example 1 5.0 Uniform dispersion 1.6 ○ ○ ○ 〃 2 4.8 〃 1.5 ○ ○ ○ 〃 3 7.0 〃 1.6 ○ ○ ○ 〃 4 10.0 〃 3.9 ○ ○ ○ Comparative example 1 5.0 Uniform dispersion 8.5 × △ × 〃 2 5.0 〃 2.7 × △ △ 〃 3 5.0 Heterogeneous dispersion 1.9 × ○ × × 〃 4 5.0 Melt 300 Gelled No coating
【００２１】＊保存安定性評価の方法及び基準 （外観）目視観察により、分散液の状態を調べた。 ○ −−− 層分離が認められず均一分散状態 × −−− 層分離が認められ不均一分散状態 （増粘度）初期の粘度と１０日放置後の粘度から、次式
より粘度変化率を算出し、以下の通り評価した。 粘度変化率＝放置後の粘度（ｃｐｓ）／初期の粘度（ｃ
ｐｓ） ○ −−− １．５未満 △ −−− １．５以上３．０未満 × −−− ３．０以上 ＊＊塗工性評価の方法及び基準 上記の方法で７５度鏡面光沢度を測定し、以下の通り評
価した。 ○ −−− 光沢度５５％以上 △ −−− 光沢度５５％未満５０％以上 × −−− 光沢度５０％未満* Storage stability evaluation method and standard (appearance) The state of the dispersion was examined by visual observation. ○ --- Homogeneous dispersion state with no layer separation observed x --- Homogeneous dispersion state with layer separation observed (Thickening) The viscosity change rate was calculated from the following formula from the initial viscosity and the viscosity after standing for 10 days. And evaluated as follows. Viscosity change rate = viscosity after standing (cps) / initial viscosity (c
ps) ○ --- Less than 1.5 △ --- 1.5 or more and less than 3.0 × --- 3.0 or more ** Method and standard of applicability evaluation 75 degree specular gloss is determined by the above method. It measured and evaluated as follows. ○ --- Gloss 55% or more △ --- Gloss less than 55% 50% or more X --- Gloss less than 50%
【００２２】[0022]
【発明の効果】本発明のポリビニルアルコール系樹脂の
水性分散液は、該樹脂が高重合度、高濃度であっても低
粘度で、塗工性に優れ、紙加工、接着剤、糊剤等の用途
に大変有用である。EFFECT OF THE INVENTION The aqueous dispersion of polyvinyl alcohol resin of the present invention has a high degree of polymerization, a low viscosity even at a high concentration, excellent coatability, paper processing, adhesives, sizing agents, etc. Very useful for applications.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 129/04 ＪＣＳ 6904−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C09J 129/04 JCS 6904-4J
Claims (2)
０以上、平均粒径５０μ以下のポリビニルアルコール系
樹脂微粒子を０．１重量％以上の濃度で水に分散させた
ことを特徴とするポリビニルアルコール系樹脂の水性分
散液。1. A crystallinity of 30% or more and an average degree of polymerization of 300.
An aqueous dispersion of a polyvinyl alcohol-based resin, characterized in that fine particles of polyvinyl alcohol-based resin having an average particle diameter of 0 or more and 50 μ or less are dispersed in water at a concentration of 0.1% by weight or more.
化触媒を添加した組成物をノズルより噴霧及び乾燥処理
することによって得られたポリビニルアルコール系樹脂
球形粉末をポリビニルアルコール系樹脂微粒子として用
いることを特徴とする請求項１記載のポリビニルアルコ
ール系樹脂の水性分散液。2. A polyvinyl alcohol-based resin spherical powder obtained by spraying and drying a composition obtained by adding a saponification catalyst to a methanol solution of polyvinyl acetate from a nozzle is used as polyvinyl alcohol-based resin fine particles. An aqueous dispersion of the polyvinyl alcohol resin according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30921292A JP3322918B2 (en) | 1992-10-22 | 1992-10-22 | Aqueous dispersion of polyvinyl alcohol resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30921292A JP3322918B2 (en) | 1992-10-22 | 1992-10-22 | Aqueous dispersion of polyvinyl alcohol resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06136221A true JPH06136221A (en) | 1994-05-17 |
| JP3322918B2 JP3322918B2 (en) | 2002-09-09 |
Family
ID=17990282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30921292A Expired - Fee Related JP3322918B2 (en) | 1992-10-22 | 1992-10-22 | Aqueous dispersion of polyvinyl alcohol resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3322918B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0782384A (en) * | 1993-09-20 | 1995-03-28 | Kuraray Co Ltd | Production of fine polyvinyl alcohol particle |
| JPH07109698A (en) * | 1993-08-20 | 1995-04-25 | Kuraray Co Ltd | Paper coating agent |
| JPH0827219A (en) * | 1994-07-19 | 1996-01-30 | Nippon Synthetic Chem Ind Co Ltd:The | Production of polyvinyl alcohol-based resin fine particle |
| WO1998050476A1 (en) * | 1997-05-08 | 1998-11-12 | Polyval Manufacturing Limited | Coating method polyvinyl alcohol |
| JP2005132994A (en) * | 2003-10-31 | 2005-05-26 | Toppan Printing Co Ltd | Gas barrier film laminate |
| JP2011515558A (en) * | 2008-03-27 | 2011-05-19 | ダウ グローバル テクノロジーズ エルエルシー | Water-based paint composition based on polyvinyl ester |
| JP2013127036A (en) * | 2011-12-19 | 2013-06-27 | Riso Kagaku Corp | Water-in-oil type emulsion adhesive |
| JP2019509380A (en) * | 2016-03-08 | 2019-04-04 | 株式会社クラレ | Granular polyvinyl alcohol, production method and use thereof |
| WO2019132030A1 (en) * | 2017-12-28 | 2019-07-04 | 株式会社クラレ | Water-absorbent resin and agricultural water-retaining material |
| WO2022244790A1 (en) * | 2021-05-18 | 2022-11-24 | 花王株式会社 | Method for improving dispersibility of crystalline resin having hydrophilic group into neutral water |
-
1992
- 1992-10-22 JP JP30921292A patent/JP3322918B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07109698A (en) * | 1993-08-20 | 1995-04-25 | Kuraray Co Ltd | Paper coating agent |
| JPH0782384A (en) * | 1993-09-20 | 1995-03-28 | Kuraray Co Ltd | Production of fine polyvinyl alcohol particle |
| JPH0827219A (en) * | 1994-07-19 | 1996-01-30 | Nippon Synthetic Chem Ind Co Ltd:The | Production of polyvinyl alcohol-based resin fine particle |
| WO1998050476A1 (en) * | 1997-05-08 | 1998-11-12 | Polyval Manufacturing Limited | Coating method polyvinyl alcohol |
| JP2005132994A (en) * | 2003-10-31 | 2005-05-26 | Toppan Printing Co Ltd | Gas barrier film laminate |
| JP2011515558A (en) * | 2008-03-27 | 2011-05-19 | ダウ グローバル テクノロジーズ エルエルシー | Water-based paint composition based on polyvinyl ester |
| US8647427B2 (en) | 2008-03-27 | 2014-02-11 | Styron Europe Gmbh | Polyvinyl ester-based latex coating compositions |
| JP2013127036A (en) * | 2011-12-19 | 2013-06-27 | Riso Kagaku Corp | Water-in-oil type emulsion adhesive |
| JP2019509380A (en) * | 2016-03-08 | 2019-04-04 | 株式会社クラレ | Granular polyvinyl alcohol, production method and use thereof |
| WO2019132030A1 (en) * | 2017-12-28 | 2019-07-04 | 株式会社クラレ | Water-absorbent resin and agricultural water-retaining material |
| US11787751B2 (en) | 2017-12-28 | 2023-10-17 | Kuraray Co., Ltd. | Water-absorbent resin and agricultural water-retaining material |
| WO2022244790A1 (en) * | 2021-05-18 | 2022-11-24 | 花王株式会社 | Method for improving dispersibility of crystalline resin having hydrophilic group into neutral water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3322918B2 (en) | 2002-09-09 |
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