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JPH1060015A - Dispersion stabilizer for emulsion polymerization - Google Patents

Dispersion stabilizer for emulsion polymerization

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Publication number
JPH1060015A
JPH1060015A JP21843596A JP21843596A JPH1060015A JP H1060015 A JPH1060015 A JP H1060015A JP 21843596 A JP21843596 A JP 21843596A JP 21843596 A JP21843596 A JP 21843596A JP H1060015 A JPH1060015 A JP H1060015A
Authority
JP
Japan
Prior art keywords
sulfonic acid
polyvinyl alcohol
emulsion
mol
polymerization
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.)
Pending
Application number
JP21843596A
Other languages
Japanese (ja)
Inventor
Masato Nakamae
昌人 仲前
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to JP21843596A priority Critical patent/JPH1060015A/en
Publication of JPH1060015A publication Critical patent/JPH1060015A/en
Pending legal-status Critical Current

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  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain the subject stabilizer stable during polymerization, having little time-dependent change in a viscosity and capable of obtaining an emulsion capable of imparting a coating having high water resistance by comprising a sulfonic acid-modified polyvinyl alcohol having a specific degree of saponification and a specific content of the sulfonic acid groups. SOLUTION: This dispersion stabilizer for emulsion polymerization consists of a modified polyvinyl alcohol having <=90 mole % average degree of saponification and 0.1-20 mole % sulfonic acid group. E.g. when the alcohol contains sulfonic acid groups or their alkali salts in a molecule, the alcohol can be obtained by copolymerizing a vinyl ester-based monomer typically expressed by vinyl acetate with an ethylene-based unsaturated monomer such as allyl sulfonic acid, etc., then saponifying the copolymer.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は乳化重合用分散安定
剤に関し、さらに詳しくは、耐水性に優れる水性エマル
ジョンが得られる乳化重合用分散安定剤に関する。
The present invention relates to a dispersion stabilizer for emulsion polymerization, and more particularly to a dispersion stabilizer for emulsion polymerization capable of obtaining an aqueous emulsion having excellent water resistance.

【0002】[0002]

【従来の技術】ポリビニルアルコールを保護コロイド
(分散安定剤)に用いて製造したエマルジョンは、古く
から塗料,接着剤,繊維加工剤,紙加工剤などの多くの
用途で賞用されている。しかし、ポリビニルアルコール
は、水溶性であるため、上記エマルジョンから水分を蒸
発させて得られる皮膜は水に膨潤しやすい上、その皮膜
を水に浸漬した場合には、ポリビニルアルコールが溶出
しやすく、耐水性が不充分である。さらに、この皮膜を
水に入れて煮沸すると、上述した膨潤,溶出が促進さ
れ、皮膜はその原形をとどめなくなる。
2. Description of the Related Art Emulsions produced using polyvinyl alcohol as a protective colloid (dispersion stabilizer) have long been used in paints, adhesives, fiber processing agents, paper processing agents, and many other applications. However, since polyvinyl alcohol is water-soluble, a film obtained by evaporating water from the above emulsion easily swells in water, and when the film is immersed in water, the polyvinyl alcohol is easily eluted and water resistant. Insufficient properties. Further, when this film is boiled in water, the above-mentioned swelling and elution are promoted, and the film does not remain its original shape.

【0003】このようなことから、今までに、ポリビニ
ルアルコール系重合体を分散安定剤とするエマルジョン
から得られる皮膜の耐水性を高めるために、種々の手段
が試みられてきた。その代表例としては、ポリビニルア
ルコールの耐水化剤(架橋剤)を配合する方法や、乳化
分散安定剤として使用するポリビニルアルコールにアセ
トアセチル基等の架橋性基を導入する方法がある。しか
しながら、いずれも耐水性を発現するために架橋(化
学)反応を伴うものであり、耐水性の向上の反面、ポッ
トライフの短縮、作業性の低下等の問題を抱えていた。
また、高ケン化度のポリビニルアルコールを用いても、
ある程度耐水性は高くなるものの、この場合、乳化重合
時の安定性低下や低温時の経時増粘の問題がある。
[0003] For these reasons, various means have been attempted so far to increase the water resistance of a film obtained from an emulsion using a polyvinyl alcohol-based polymer as a dispersion stabilizer. Typical examples thereof include a method of blending a water-resistant agent (crosslinking agent) of polyvinyl alcohol and a method of introducing a crosslinkable group such as an acetoacetyl group into polyvinyl alcohol used as an emulsion dispersion stabilizer. However, all of them involve a crosslinking (chemical) reaction in order to exhibit water resistance, and have problems such as shortening of pot life and deterioration of workability, while improving water resistance.
In addition, even if polyvinyl alcohol having a high degree of saponification is used,
Although the water resistance is increased to some extent, in this case, there are problems such as a decrease in stability during emulsion polymerization and an increase in viscosity over time at low temperatures.

【0004】さらに、特公昭51−5871号には特定
の条件で製造されたスルホン酸基変性ポリビニルアルコ
ールを乳化重合用分散安定剤に用いるエチレン性不飽和
単量体の乳化重合方法の開示がある。しかしながら、こ
こで開示されているスルホン酸基変性ポリビニルアルコ
ールを用いた乳化重合においては、必ずしも、高い耐水
性を有するエマルジョンが得られないのが現状であり、
さらなる耐水性の向上が強く要望されている。
Further, Japanese Patent Publication No. 51-5871 discloses a method for emulsion polymerization of an ethylenically unsaturated monomer using a sulfonic acid group-modified polyvinyl alcohol produced under specific conditions as a dispersion stabilizer for emulsion polymerization. . However, in the emulsion polymerization using the sulfonic acid group-modified polyvinyl alcohol disclosed herein, at present, it is not always possible to obtain an emulsion having high water resistance.
There is a strong demand for further improvement in water resistance.

【0005】[0005]

【発明が解決しようとする課題】本発明は、このような
事情のもとで、乳化重合時の安定性や粘度経時変化が少
なく、皮膜の耐水性が高いエマルジョンを得ることがで
きる乳化重合用分散安定剤を提供することを目的として
なされたものである。
SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an emulsion polymerization emulsion which is capable of obtaining an emulsion having a small stability with time and a low viscosity change during the emulsion polymerization and having a high water resistance of the film. The purpose of the present invention is to provide a dispersion stabilizer.

【0006】[0006]

【課題を解決するための手段】本発明者らは、上記の好
ましい性質を有する乳化重合用分散安定剤を開発すべく
鋭意研究を重ねた結果、特定のケン化度及びスルホン酸
基含有量を有するスルホン酸基変性ポリビニルアルコー
ルからなる乳化重合用分散安定剤が、目的とする性能を
備えたものであることを見出した。本発明はかかる知見
に基づいて完成したものである。すなわち、本発明は、
平均ケン化度が90モル%以下であり、カルボキシル基
含有量が0.1〜20モル%のスルホン酸基変性ポリビ
ニルアルコールからなる乳化重合用分散安定剤を提供す
るものである。
Means for Solving the Problems The present inventors have conducted intensive studies to develop a dispersion stabilizer for emulsion polymerization having the above-mentioned preferable properties, and as a result, a specific saponification degree and a sulfonic acid group content have been determined. It has been found that a dispersion stabilizer for emulsion polymerization comprising a sulfonic acid group-modified polyvinyl alcohol having the desired performance. The present invention has been completed based on such findings. That is, the present invention
The present invention provides a dispersion stabilizer for emulsion polymerization comprising a sulfonic acid group-modified polyvinyl alcohol having an average degree of saponification of 90 mol% or less and a carboxyl group content of 0.1 to 20 mol%.

【0007】本発明における乳化重合用分散安定剤であ
る平均ケン化度が90モル%以下であり、スルホン酸基
含有量が0.1〜20モル%のスルホン酸基変性ポリビ
ニルアルコールは、分子内にスルホン酸基あるいはスル
ホン酸アルカリ塩を有する変性ポリビニルアルコールで
あれば特に制限はないが、通常は、酢酸ビニルに代表さ
れるビニルエステル系単量体を、アリルスルホン酸、メ
タリルスルホン酸、ビニルスルホン酸、アクリルアミド
−2−メチルプロパンスルホン酸、メタクリルアミド−
2−メチルプロパンスルホン酸、アクリル酸スルホプロ
ピル、メタクリル酸スルホプロピル及びそれらのアルカ
リ塩等のスルホン酸基を有するエチレン性不飽和単量体
やN,N’−ジメチル(メタクリルアミドプロピル)ア
ンモニウムプロパンスルホネート等のスルホベタイン基
を有するエチレン性不飽和単量体と共重合した後、けん
化したもの(ランダム共重合体)か、末端にチオール基
を有するケン化度90モル%以下のポリビニルアルコー
ル系重合体の存在下、上記エチレン性不飽和スルホ酸を
ラジカル重合したもの(ブロック共重合体)が好適に用
いられる。なお、上記のビニルエステル系単量体として
は、酢酸ビニル以外に、ギ酸ビニル,プロピオン酸ビニ
ル,バーサチック酸ビニル,ピバリン酸ビニルなどを用
いることも可能である。
The sulfonic acid group-modified polyvinyl alcohol having an average degree of saponification of 90 mol% or less and a sulfonic acid group content of 0.1 to 20 mol%, which is a dispersion stabilizer for emulsion polymerization in the present invention, has There is no particular limitation as long as it is a modified polyvinyl alcohol having a sulfonic acid group or a sulfonic acid alkali salt, but usually, a vinyl ester monomer represented by vinyl acetate is converted to allyl sulfonic acid, methallyl sulfonic acid, vinyl Sulfonic acid, acrylamide-2-methylpropanesulfonic acid, methacrylamide-
Ethylenically unsaturated monomers having a sulfonic acid group, such as 2-methylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, and alkali salts thereof, and N, N'-dimethyl (methacrylamidopropyl) ammonium propane sulfonate Or a saponified (random copolymer) copolymerized with an ethylenically unsaturated monomer having a sulfobetaine group or a polyvinyl alcohol-based polymer having a thiol group at the terminal and having a saponification degree of 90 mol% or less. A product obtained by radically polymerizing the above ethylenically unsaturated sulfonic acid in the presence of (block copolymer) is preferably used. In addition, as the above-mentioned vinyl ester monomer, in addition to vinyl acetate, vinyl formate, vinyl propionate, vinyl versatate, vinyl pivalate and the like can also be used.

【0008】本発明におけるスルホン酸基変性ポリビニ
ルアルコールの重合度については特に制限はないが、5
0〜8000の範囲が好ましく、100〜4000の範
囲がより好ましい。また、該スルホン酸基変性ポリビニ
ルアルコールのケン化度は90モル%以下である必要が
あり、得られるエマルジョンの耐水性の観点から85モ
ル%以下が好ましく、80モル%以下が特に好ましい。
ケン化度が90モル%を越える場合、目的とする耐水性
が発現しない。ケン化度の下限については、該変性ポリ
ビニルアルコールが水溶性であれば特に制限はないが、
10モル%以上が好ましく、30モル%以上がより好ま
しく、50モル%以上が特に好ましい。さらに、スルホ
ン酸基含有量については、0.1〜20モル%の範囲で
あることが必要であり、0.2〜15モル%の範囲がよ
り好ましく、0.5〜10モル%の範囲が特に好まし
い。スルホン酸基変性量が0.1モル%未満では、ポリビ
ニルアルコール系重合体の水溶性が低下する場合があ
り、重合安定性の確保が困難となる。一方、スルホン酸
基変性量が20モル%を超えると、安定なエマルジョン
を得ることが困難となる上、本発明の効果である耐水性
が発現しない。
The degree of polymerization of the sulfonic acid group-modified polyvinyl alcohol in the present invention is not particularly limited.
The range of 0 to 8000 is preferable, and the range of 100 to 4000 is more preferable. Further, the saponification degree of the sulfonic acid group-modified polyvinyl alcohol needs to be 90 mol% or less, and is preferably 85 mol% or less, particularly preferably 80 mol% or less from the viewpoint of the water resistance of the obtained emulsion.
If the saponification degree exceeds 90 mol%, the desired water resistance is not exhibited. The lower limit of the saponification degree is not particularly limited as long as the modified polyvinyl alcohol is water-soluble,
It is preferably at least 10 mol%, more preferably at least 30 mol%, particularly preferably at least 50 mol%. Further, the sulfonic acid group content needs to be in the range of 0.1 to 20 mol%, more preferably in the range of 0.2 to 15 mol%, and more preferably in the range of 0.5 to 10 mol%. Particularly preferred. If the sulfonic acid group modification amount is less than 0.1 mol%, the water solubility of the polyvinyl alcohol-based polymer may decrease, and it is difficult to secure polymerization stability. On the other hand, when the sulfonic acid group modification amount exceeds 20 mol%, it is difficult to obtain a stable emulsion, and the water resistance, which is an effect of the present invention, is not exhibited.

【0009】また、本発明におけるスルホン酸基変性ポ
リビニルアルコールは、本発明の効果を損なわない範囲
で、共重合可能なエチレン性不飽和単量体を共重合する
こともできる。このようなエチレン性不飽和単量体とし
ては、例えば、エチレン,イソブチレン,アクリロニト
リル,メタクリロニトリル,アクリル酸,メタクリル
酸,(無水)フマル酸,(無水)マレイン酸,(無水)
イタコン酸、アクリルアミド,メタクリルアミド,トリ
メチル−(3−アクリルアミド−3−ジメチルプロピ
ル)−アンモニウムクロリド,エチルビニルエーテル,
ブチルビニルエーテル,N−ビニルピロリドン,塩化ビ
ニル,臭化ビニル,フッ化ビニル,塩化ビニリデン,フ
ッ化ビニリデン,テトラフルオロエチレンなどが挙げら
れる。また、チオール酢酸,メルカプトプロピオン酸な
どのチオール化合物存在下で、酢酸ビニルなどのビニル
エステル系単量体を、スルホン酸基を有するエチレン性
不飽和単量体と共重合し、それをけん化することによっ
て得られる末端変性物も用いることができる。
The sulfonic acid group-modified polyvinyl alcohol of the present invention can be copolymerized with a copolymerizable ethylenically unsaturated monomer as long as the effects of the present invention are not impaired. Such ethylenically unsaturated monomers include, for example, ethylene, isobutylene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, (anhydrous) fumaric acid, (anhydrous) maleic acid, (anhydrous)
Itaconic acid, acrylamide, methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, ethyl vinyl ether,
Examples thereof include butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene. Further, in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid, a vinyl ester-based monomer such as vinyl acetate is copolymerized with an ethylenically unsaturated monomer having a sulfonic acid group, and saponified. Can also be used.

【0010】次に、本発明の乳化重合用分散安定剤を用
いて得られるの水性エマルジョンの分散質を構成する重
合体は、エチレン性不飽和単量体あるいはジエン系単量
体の重合体であり、各種のものがある。分散質を構成す
る重合体の原料であるエチレン性不飽和単量体の好まし
い例としては、エチレン,プロピレン,イソブチレンな
どのオレフィン、塩化ビニル,フッ化ビニル,ビニリデ
ンクロリド,ビニリデンフルオリドなどのハロゲン化オ
レフィン、ギ酸ビニル,酢酸ビニル,プロピオン酸ビニ
ル,バーサチック酸ビニルなどのビニルエステル、アク
リル酸、メタクリル酸、アクリル酸メチル,アクリル酸
エチル,アクリル酸ブチル,アクリル酸2−エチルヘキ
シル,アクリル酸ドデシル,アクリル酸2−ヒドロキシ
エチルなどのアクリル酸エステル、メタクリル酸メチ
ル,メタクリル酸エチル,メタクリル酸ブチル,メタク
リル酸2−エチルヘキシル,メタクリル酸ドデシル,メ
タクリル酸2−ヒドロキシエチルなどのメタクリル酸エ
ステル、アクリル酸ジメチルアミノエチル,メタクリル
酸ジメチルアミノエチルおよびこれらの四級化物、さら
には、アクリルアミド,メタクリルアミド,N−メチロ
ールアクリルアミド,N,N−ジメチルアクリルアミ
ド,アクリルアミド−2−メチルプロパンスルホン酸お
よびそのナトリウム塩などのアクリルアミド系単量体、
スチレン,α−メチルスチレン,p−スチレンスルホン
酸およびそのナトリウム,カリウム塩などのスチレン系
単量体、N−ビニルピロリドンなどが挙げられる。ま
た、分散質を構成する重合体の原料であるジエン系単量
体の好ましい例としては、ブタジエン,イソプレン,ク
ロロプレンなどが挙げられる。これらの単量体は単独あ
るいは、二種以上混合して用いられる。
Next, the polymer constituting the dispersoid of the aqueous emulsion obtained by using the dispersion stabilizer for emulsion polymerization of the present invention is a polymer of an ethylenically unsaturated monomer or a diene monomer. There are various types. Preferred examples of the ethylenically unsaturated monomer which is a raw material of the polymer constituting the dispersoid include olefins such as ethylene, propylene and isobutylene, and halogenated compounds such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride. Olefins, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, acrylic acid Acrylates such as 2-hydroxyethyl, methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate; Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and their quaternaries, furthermore, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acrylamido-2-methylpropanesulfonic acid and its sodium Acrylamide monomers such as salts,
Examples include styrene-based monomers such as styrene, α-methylstyrene, p-styrenesulfonic acid and sodium and potassium salts thereof, and N-vinylpyrrolidone. Preferred examples of the diene monomer which is a raw material of the polymer constituting the dispersoid include butadiene, isoprene, chloroprene and the like. These monomers are used alone or in combination of two or more.

【0011】上記の単量体の中でも、ビニルエステル,
(メタ)アクリル酸エステル,スチレンおよびジエン系
単量体が好ましく、特にビニルエステル単独、エチレン
とビニルエステルとの併用および(メタ)アクリル酸エ
ステルが好適である。本発明の乳化重合用分散安定剤を
用いた上記単量体の乳化重合方法は特に制限はないが、
前述したスルホン酸基変性ポリビニルアルコールの水溶
液(あるいは水分散液)を分散安定剤に用いて、従来公
知の重合開始剤の存在下に、上記単量体を一時又は連続
的に添加することにより行われる。また、単量体を、予
めスルホン酸基変性ポリビニルアルコール水溶液を用い
て乳化したものを、連続的に重合反応系に添加する乳化
重合法も採用できる。本発明の乳化重合用分散安定剤で
あるスルホン酸基変性ポリビニルアルコールの使用量
は、エチレン性不飽和単量体の重合体100重量部に対
して1〜25重量部、好ましくは2〜15重量部の範囲
である。該使用量が1重量部より少ない場合および20
重量部を超える場合には、重合安定性の低下や耐水性の
低下が起こる。なお、本発明の乳化重合用分散安定剤に
は、必要に応じて、従来公知のアニオン性、ノニオン性
あるいはカチオン性の界面活性剤や、ポリビニルアルコ
ール系重合体、ヒドロキシエチルセルロースなどを併用
することもできる。
Among the above monomers, vinyl esters,
(Meth) acrylic acid esters, styrene and diene monomers are preferred, and vinyl esters alone, combined use of ethylene and vinyl esters, and (meth) acrylic acid esters are particularly preferred. Emulsion polymerization method of the above monomer using the emulsion polymerization dispersion stabilizer of the present invention is not particularly limited,
An aqueous solution (or aqueous dispersion) of the above-mentioned sulfonic acid group-modified polyvinyl alcohol is used as a dispersion stabilizer, and the above monomer is temporarily or continuously added in the presence of a conventionally known polymerization initiator. Will be Further, an emulsion polymerization method in which a monomer previously emulsified using a sulfonic acid group-modified polyvinyl alcohol aqueous solution and continuously added to the polymerization reaction system can also be adopted. The amount of the sulfonic acid group-modified polyvinyl alcohol used as the dispersion stabilizer for emulsion polymerization of the present invention is 1 to 25 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the polymer of the ethylenically unsaturated monomer. Range of parts. When the amount is less than 1 part by weight and 20
If the amount is more than 10 parts by weight, the polymerization stability and the water resistance will decrease. The dispersion stabilizer for emulsion polymerization of the present invention, if necessary, may be used in combination with a conventionally known anionic, nonionic or cationic surfactant, a polyvinyl alcohol polymer, hydroxyethyl cellulose, or the like. it can.

【0012】また、該水性エマルジョンには、さらに必
要に応じて、でんぷん,変性でんぷん,酸化でんぷん,
アルギン酸ソーダ,カルボキシメチルセルロース,メチ
ルセルロース,ヒドロキシメチルセルロース,無水マレ
イン酸/イソブテン共重合体,無水マレイン酸/スチレ
ン共重合体,無水マレイン酸/メチルビニルエーテル共
重合体などの水溶性高分子化合物や、尿素/ホルマリン
樹脂,尿素/メラミン/ホルマリン樹脂,フェノール/
ホルマリン樹脂などの熱硬化性樹脂もそれぞれ併用する
ことができる。さらに、本発明の乳化重合用分散安定剤
を用いて得られる水性エマルジョンには、クレー,カオ
リン,タルク,炭酸カルシウム,木粉などの充填剤、小
麦粉などの増量剤、ホウ酸,硫酸アルミニウムなどの反
応促進剤、酸化チタンなどの顔料、防腐剤,防錆剤など
の各種添加剤をも適宜添加することができる。
The aqueous emulsion may further contain starch, modified starch, oxidized starch,
Water-soluble polymer compounds such as sodium alginate, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, maleic anhydride / isobutene copolymer, maleic anhydride / styrene copolymer, maleic anhydride / methylvinyl ether copolymer, and urea / formalin Resin, urea / melamine / formalin resin, phenol /
A thermosetting resin such as a formalin resin can also be used together. Further, the aqueous emulsion obtained by using the dispersion stabilizer for emulsion polymerization of the present invention includes fillers such as clay, kaolin, talc, calcium carbonate, and wood flour, fillers such as flour, boric acid, aluminum sulfate and the like. Various additives such as a reaction accelerator, a pigment such as titanium oxide, a preservative, and a rust preventive can also be appropriately added.

【0013】本発明の乳化重合用分散安定剤を用いて得
られる水性エマルジョンは、耐水性が高いという特徴を
生かして、木工用接着剤、紙工用接着剤、塗料、繊維処
理剤等の各種用途において用いられる。
The aqueous emulsion obtained by using the dispersion stabilizer for emulsion polymerization of the present invention takes advantage of its high water resistance to use in various applications such as woodworking adhesives, paperworking adhesives, paints, and fiber treatment agents. Used in

【0014】[0014]

【実施例】次に、実施例及び比較例により本発明をさら
に詳細に説明する。なお以下の実施例及び比較例におい
て「部」および「%」は、特に断りのない限り重量基準
を意味する。なお、耐水性は下記の要領で評価した。
Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, “parts” and “%” mean on a weight basis unless otherwise specified. The water resistance was evaluated in the following manner.

【0015】(耐水性の評価) (1)皮膜の耐水性 得られた水性エマルジョンを20℃,65%RH下で、
PET上に流延し、7日間乾燥させて500μmの乾燥
皮膜を得た。この皮膜を直径2.5cmに打ち抜き、そ
れを試料として20℃の水に24時間浸漬した場合の、
皮膜の吸水率および溶出率を求めた。 (2)耐水接着力 得られた水性エマルジョンをツガ材(柾目)に150g
/m2 塗布し、貼り合わせて7kg/cm2 の荷重で1
6時間圧締した。その後、解圧し、20℃,65%RH
下で5日間養生した後、60℃の温水に3時間浸漬した
後、濡れたままの状態で圧縮せん断強度を測定した。
(Evaluation of Water Resistance) (1) Water Resistance of Film The obtained aqueous emulsion was prepared at 20 ° C. and 65% RH.
It was cast on PET and dried for 7 days to obtain a dry film of 500 μm. When this film is punched into a diameter of 2.5 cm and immersed in water at 20 ° C. for 24 hours as a sample,
The water absorption and elution rate of the film were determined. (2) Water resistant adhesive strength 150 g of the obtained aqueous emulsion was applied to hemlock material (straight grain).
/ M 2 applied and bonded together with a load of 7 kg / cm 2
Pressing for 6 hours. After that, the pressure is released and the temperature is reduced to 20 ° C and 65% RH.
After curing for 5 days under the following conditions, the specimen was immersed in warm water at 60 ° C. for 3 hours, and the compressive shear strength was measured in a wet state.

【0016】実施例1 還流冷却器,滴下ロート,温度計,窒素吹込口を備えた
1リットルのガラス製重合容器に、水400g,スルホ
ン酸基変性ポリビニルアルコール(重合度1000,ケ
ン化度70.5モル%,アリルスルホン酸ナトリウム塩
1モル%ランダム共重合変性)30gを仕込み、95℃
で完全に溶解した。次に、このポリビニルアルコール水
溶液を冷却、窒素置換後、140rpmで攪拌しながら
酢酸ビニル400gを仕込み、60℃に上昇したのち、
過酸化水素/ロンガリットのレドックス開始剤系の存在
下で重合を行った。2時間で重合は終了し、重合率9
9.8%,固形分濃度50.3%,粘度5500mPa
・sの安定なポリ酢酸ビニルエマルジョンが得られた。
このエマルジョンの固形分100部に対して、可塑剤と
してジブチルフタレート10部を添加し、耐水性を評価
した。その結果を表2に示す。
Example 1 In a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet, 400 g of water, sulfonic acid group-modified polyvinyl alcohol (polymerization degree 1000, saponification degree 70. 30 g of 5 mol%, 1 mol% of allylsulfonic acid sodium salt modified by random copolymerization)
Completely dissolved. Next, after cooling this polyvinyl alcohol aqueous solution and replacing with nitrogen, 400 g of vinyl acetate was charged while stirring at 140 rpm, and the temperature was raised to 60 ° C.
The polymerization was carried out in the presence of a hydrogen peroxide / Rongalit redox initiator system. The polymerization was completed in 2 hours and the polymerization rate was 9
9.8%, solids concentration 50.3%, viscosity 5500mPa
-A stable polyvinyl acetate emulsion of s was obtained.
To 100 parts of the solid content of this emulsion, 10 parts of dibutyl phthalate was added as a plasticizer, and the water resistance was evaluated. Table 2 shows the results.

【0017】比較例1 実施例1におけるスルホン酸基変性ポリビニルアルコー
ルの代わりに、重合度1000、ケン化度91.0モル
%、アリルスルホン酸ナトリウム1モル%ランダム共重
合変性のスルホン酸基変性ポリビニルアルコールを用い
る以外は実施例1と同様にした。その結果を表2に示
す。
COMPARATIVE EXAMPLE 1 Instead of the sulfonic acid group-modified polyvinyl alcohol in Example 1, a sulfonic acid group-modified polyvinyl resin having a degree of polymerization of 1,000, a saponification degree of 91.0 mol%, and sodium mol of allyl sulfonate 1 mol% was modified by random copolymerization. Same as Example 1 except that alcohol was used. Table 2 shows the results.

【0018】比較例2 実施例1におけるスルホン酸基変性ポリビニルアルコー
ルの代わりに、重合度1000、ケン化度83.0モル
%の無変性ポリビニルアルコールを用いる以外は実施例
1と同様にした。その結果を表2に示す。
Comparative Example 2 The procedure of Example 1 was repeated, except that in place of the sulfonic acid group-modified polyvinyl alcohol in Example 1, unmodified polyvinyl alcohol having a polymerization degree of 1000 and a saponification degree of 83.0 mol% was used. Table 2 shows the results.

【0019】比較例3 実施例1におけるスルホン酸基変性ポリビニルアルコー
ルの代わりに、重合度1000、ケン化度70.5モル
%の無変性ポリビニルアルコールを用いる以外は実施例
1と同様にしたが、該ポリビニルアルコールの水溶性が
乏しく乳化重合の安定性が悪くなり水性エマルジョンが
得られなかった。
Comparative Example 3 The procedure of Example 1 was repeated except that, instead of the sulfonic acid group-modified polyvinyl alcohol in Example 1, unmodified polyvinyl alcohol having a polymerization degree of 1000 and a saponification degree of 70.5 mol% was used. The water solubility of the polyvinyl alcohol was poor, and the stability of emulsion polymerization became poor, so that an aqueous emulsion could not be obtained.

【0020】実施例2 実施例1におけるスルホン酸基変性ポリビニルアルコー
ルの代わりに、重合度1700、ケン化度65.0モル
%、アクリルアミド−2−メチルプロパンスルホン酸ナ
トリウム塩2.5モル%変性のスルホン酸基変性ポリビ
ニルアルコールを用いる以外は実施例1と同様にした。
その結果を表2に示す。
Example 2 Instead of the sulfonic acid group-modified polyvinyl alcohol in Example 1, the polymerization degree was 1700, the saponification degree was 65.0 mol%, and the acrylamido-2-methylpropanesulfonic acid sodium salt was modified by 2.5 mol%. The procedure was the same as in Example 1 except that a sulfonic acid group-modified polyvinyl alcohol was used.
Table 2 shows the results.

【0021】実施例3 還流冷却器,滴下ロート,温度計,窒素吹込口を備えた
1リットルのガラス製重合容器に、水400g,末端に
チオール基を有するスルホン酸基変性ポリビニルアルコ
ール(重合度500,けん化度80.7モル%,アクリ
ルアミド−2−メチルプロパンスルホン酸ナトリウム塩
0.5モル%ランダム共重合変性,〔SH〕濃度:5×
10-5モル/g−ポリビニルアルコール)24gを仕込
み、95℃で完全に溶解した。次に、このポリニルアル
コール水溶液を冷却後、希硫酸でpHを4.0に調整
し、窒素置換を行い、140rpmで攪拌しながら、メ
タクリル酸メチル80gとアクリル酸n−ブチル80g
を仕込み、70℃に上昇したのち、5%過硫酸アンモニ
ウム水溶液5gを添加して重合を開始した。その後、メ
タクリル酸メチル120gとアクリル酸n−ブチル12
0gを2時間かけて逐次添加した。4時間で重合は完了
し、重合率99.9%,固形分濃度51.5%,粘度7
50mPa・sの安定なポリ(メタクリル酸メチル/ア
クリル酸ブチル)共重合体エマルジンが得られた。この
エマルジョンを用いて、実施例1と同様(但し、可塑剤
であるジブチルフタレートは添加せず)に耐水性を評価
した。結果を表2に示す。
Example 3 In a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet, 400 g of water, a sulfonic acid group-modified polyvinyl alcohol having a thiol group at a terminal (polymerization degree 500 Degree of saponification, 80.7 mol%, acrylamide-2-methylpropanesulfonic acid sodium salt, 0.5 mol%, random copolymerization modification, [SH] concentration: 5 ×
24 g of (10 −5 mol / g-polyvinyl alcohol) were charged and completely dissolved at 95 ° C. Next, after cooling the aqueous solution of polynyl alcohol, the pH was adjusted to 4.0 with diluted sulfuric acid, and the atmosphere was replaced with nitrogen. While stirring at 140 rpm, 80 g of methyl methacrylate and 80 g of n-butyl acrylate were used.
After the temperature was raised to 70 ° C., 5 g of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. Thereafter, 120 g of methyl methacrylate and n-butyl acrylate 12
0 g was added sequentially over 2 hours. The polymerization was completed in 4 hours, the polymerization rate was 99.9%, the solid content concentration was 51.5%, and the viscosity was 7
A stable poly (methyl methacrylate / butyl acrylate) copolymer emulzine having a viscosity of 50 mPa · s was obtained. Using this emulsion, the water resistance was evaluated in the same manner as in Example 1 (except that dibutyl phthalate as a plasticizer was not added). Table 2 shows the results.

【0022】比較例4 実施例3におけるスルホン酸基変性ポリビニルアルコー
ルの代わりに、重合度500、ケン化度80.7モル
%、〔SH〕濃度:5×10-5モル/g−ポリビニルア
ルコールの末端にチオール基を有するポリビニルアルコ
ールを用いて実施例3と同様にした。結果を表2に示
す。
Comparative Example 4 Instead of the sulfonic acid group-modified polyvinyl alcohol in Example 3, the polymerization degree was 500, the saponification degree was 80.7 mol%, and the [SH] concentration was 5 × 10 -5 mol / g-polyvinyl alcohol. It carried out similarly to Example 3 using the polyvinyl alcohol which has a thiol group at the terminal. Table 2 shows the results.

【0023】実施例4 末端にチオール基を有するスルホン酸基変性ポリビニル
アルコール(重合度300,けん化度75.0モル%,
アリルスルホン酸ナトリウム塩1.0モル%ランダム共
重合変性,〔SH〕濃度:7×10-5モル/g−ポリビ
ニルアルコール)15gをイオン交換水290g中で加
熱溶解し、それを窒素吹込口および温度計を備えた耐圧
オートクレーブ中に仕込んだ。希硫酸でpH4.0に調整
した後、スチレン165gを仕込み、次いで耐圧計量器
よりブタジエン135gを仕込み、70℃に昇温後、2
%過硫酸カリウム水溶液10gを圧入して重合を開始し
た。内圧は4.8kg/cm2 Gから重合の進行ととも
に低下し、15時間後に0.4kg/cm2 Gに低下し
た。重合率を測定したところ99.4%であった。得ら
れたエマルジョンをアンモニア水でpH6.0とし、固
形分濃度49.3%および粘度1500mPa・sの安
定なポリ(スチレン−ブタジエン)共重合体エマルジョ
ンを得た。このエマルジョンを用いて、実施例1と同様
(但し、可塑剤であるジブチルフタレートは添加せず)
に耐水性を評価した。結果を表2に示す。
Example 4 Sulfonic acid group-modified polyvinyl alcohol having a thiol group at a terminal (polymerization degree: 300, saponification degree: 75.0 mol%,
Allylsulfonic acid sodium salt, 1.0 mol%, random copolymerized, 15 g of [SH] concentration: 7 × 10 −5 mol / g-polyvinyl alcohol) was heated and dissolved in 290 g of ion-exchanged water. It was charged in a pressure-resistant autoclave equipped with a thermometer. After adjusting the pH to 4.0 with dilute sulfuric acid, 165 g of styrene was charged, and then 135 g of butadiene was charged from a pressure-resistant meter.
10 g of a 10% aqueous solution of potassium persulfate was injected to initiate polymerization. The internal pressure decreased from 4.8 kg / cm 2 G with the progress of polymerization, and decreased to 0.4 kg / cm 2 G after 15 hours. The measured conversion was 99.4%. The resulting emulsion was adjusted to pH 6.0 with aqueous ammonia to obtain a stable poly (styrene-butadiene) copolymer emulsion having a solid content of 49.3% and a viscosity of 1500 mPa · s. Using this emulsion, the same as in Example 1 (however, dibutyl phthalate as a plasticizer was not added)
The water resistance was evaluated. Table 2 shows the results.

【0024】比較例5 実施例4におけるスルホン酸基変性ポリビニルアルコー
ルの代わりに、重合度300、ケン化度82.0モル
%、〔SH〕濃度:7×10-5モル/g−ポリビニルア
ルコールの末端にチオール基を有するポリビニルアルコ
ールを用いて実施例4と同様にした。結果を表2に示
す。
Comparative Example 5 Instead of the sulfonic acid group-modified polyvinyl alcohol in Example 4, the polymerization degree was 300, the saponification degree was 82.0 mol%, and the [SH] concentration was 7 × 10 −5 mol / g-polyvinyl alcohol. It carried out similarly to Example 4 using the polyvinyl alcohol which has a thiol group at the terminal. Table 2 shows the results.

【0025】実施例5 実施例1のスルホン酸基変性ポリビニルアルコール1
4.4gをイオン交換水290gに加熱溶解し、それを
窒素吹込口および温度計を備えた耐圧オートクレーブ中
に仕込んだ。希硫酸でpH4.0に調整後、酢酸ビニル
300gを仕込み、次いで、エチレンを45kg/cm
2 Gまで昇圧した(エチレンの仕込量は60gに相当す
る)。温度を60℃まで昇温後、過酸化水素−ロンガリ
ット系レドックス開始剤で重合を開始した。2時間後、
残存酢酸ビニル濃度が0.7%となったところで重合を
終了した。固形分濃度52.5%,粘度2100mPa
・sの安定なポリ(酢酸ビニル−エチレン)共重合体エ
マルジョンが得られた。このエマルジョンを用いて、実
施例1と同様(但し、可塑剤であるジブチルフタレート
は添加せず)に耐水性を評価した。結果を表2に示す。
Example 5 Sulfonic acid group-modified polyvinyl alcohol 1 of Example 1
4.4 g was heated and dissolved in 290 g of ion-exchanged water, and charged in a pressure-resistant autoclave equipped with a nitrogen inlet and a thermometer. After adjusting the pH to 4.0 with dilute sulfuric acid, 300 g of vinyl acetate was charged, and then ethylene was added at 45 kg / cm.
The pressure was increased to 2 G (the charged amount of ethylene was equivalent to 60 g). After raising the temperature to 60 ° C., polymerization was started with a hydrogen peroxide-Rongalit redox initiator. Two hours later,
The polymerization was terminated when the residual vinyl acetate concentration reached 0.7%. Solids concentration 52.5%, viscosity 2100mPa
A stable poly (vinyl acetate-ethylene) copolymer emulsion of s was obtained. Using this emulsion, the water resistance was evaluated in the same manner as in Example 1 (except that dibutyl phthalate as a plasticizer was not added). Table 2 shows the results.

【0026】比較例6 実施例5におけるスルホン酸基変性ポリビニルアルコー
ルの代わりに、重合度1000、ケン化度88.0モル
%の無変性ポリビニルアルコールを用いて実施例5と同
様にした。結果を表2に示す。
Comparative Example 6 The procedure of Example 5 was repeated, except that unmodified polyvinyl alcohol having a polymerization degree of 1000 and a saponification degree of 88.0 mol% was used instead of the sulfonic acid group-modified polyvinyl alcohol in Example 5. Table 2 shows the results.

【0027】[0027]

【表1】 [Table 1]

【0028】(表1の脚注) SAS :アリルスルホン酸ナトリウム塩 Amps-Na :アクリルアミド−2−メチルプロパンスルホ
ン酸ナトリウム塩
(Footnotes to Table 1) SAS: allylsulfonic acid sodium salt Amps-Na: acrylamido-2-methylpropanesulfonic acid sodium salt

【0029】[0029]

【表2】 [Table 2]

【0030】[0030]

【発明の効果】本発明の乳化重合用分散安定剤を用いる
と、耐水性の高い水性エマルジョンが得られる。該水性
エマルジョンはは、例えば、塗料,接着剤,繊維加工
剤,紙加工剤などに幅広く、かつ有効に利用できる。
By using the dispersion stabilizer for emulsion polymerization of the present invention, an aqueous emulsion having high water resistance can be obtained. The aqueous emulsion can be widely and effectively used for, for example, paints, adhesives, fiber processing agents, paper processing agents, and the like.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 平均ケン化度が90モル%以下であり、
スルホン酸基含有量が0.1〜20モル%の変性ポリビ
ニルアルコールからなる乳化重合用分散安定剤。
An average degree of saponification of 90 mol% or less,
A dispersion stabilizer for emulsion polymerization comprising a modified polyvinyl alcohol having a sulfonic acid group content of 0.1 to 20 mol%.
JP21843596A 1996-08-20 1996-08-20 Dispersion stabilizer for emulsion polymerization Pending JPH1060015A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21843596A JPH1060015A (en) 1996-08-20 1996-08-20 Dispersion stabilizer for emulsion polymerization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21843596A JPH1060015A (en) 1996-08-20 1996-08-20 Dispersion stabilizer for emulsion polymerization

Publications (1)

Publication Number Publication Date
JPH1060015A true JPH1060015A (en) 1998-03-03

Family

ID=16719875

Family Applications (1)

Application Number Title Priority Date Filing Date
JP21843596A Pending JPH1060015A (en) 1996-08-20 1996-08-20 Dispersion stabilizer for emulsion polymerization

Country Status (1)

Country Link
JP (1) JPH1060015A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005306745A (en) * 2004-04-19 2005-11-04 Chuo Rika Kogyo Corp Aqueous dispersion composition for cosmetics
JP2007254712A (en) * 2006-02-22 2007-10-04 Nippon Synthetic Chem Ind Co Ltd:The Aqueous emulsion and its use
WO2009011334A1 (en) 2007-07-18 2009-01-22 Nichigo-Mowinyl Co., Ltd. Aqueous synthetic resin emulsion, re-emulsifiable emulion powder, and adhesive composition containing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005306745A (en) * 2004-04-19 2005-11-04 Chuo Rika Kogyo Corp Aqueous dispersion composition for cosmetics
JP2007254712A (en) * 2006-02-22 2007-10-04 Nippon Synthetic Chem Ind Co Ltd:The Aqueous emulsion and its use
WO2009011334A1 (en) 2007-07-18 2009-01-22 Nichigo-Mowinyl Co., Ltd. Aqueous synthetic resin emulsion, re-emulsifiable emulion powder, and adhesive composition containing the same

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