JPS5863706A - Stabilizer for emulsion polymerization of styrene - Google Patents

Abstract

PURPOSE:To provide the titled stabilizer composed of a polyvinyl alcohol containing >=4C hydrocarbon group and sulfonic acid group or sulfate group at the side chain, and giving an emulsion suitable as an adhesive, pressure-sensitive adhesive, textile or paper processing agent, etc. CONSTITUTION:Vinyl acetate is copolymerized with an ethylenic unsaturated monomer having >=4C hydrocarbon group at the side chain (e.g. lauryl vinyl ether, isoamyl vinyl ether, etc.) to obtain a copolymer having a polymerization degree of 200-3,000, which is saponified in methanol containing NaOH. The resultant modified PVA containing 0.01-15mol% hydrocarbon group is made to react with chlorosulfonic acid in pyridine, and neutralized to obtain the objective stabilizer. In place of the reaction with chlorosulfonic acid, the PVA may be copolymerized with a sulfonic acid group-containing monomer (e.g. sodium allylsulfonate).

Description

【発明の詳細な説明】 本発’Ｊｉｍ祉疎水性基と親水性基とな有す特定の変性
ポリビニルアルコール（以下ポリビニルアルコール′ｋ
Ｐｖムと略記する）ｔＰらなるスチレンＯ乳化重合安定
剤に関する。DETAILED DESCRIPTION OF THE INVENTION A specific modified polyvinyl alcohol (hereinafter referred to as polyvinyl alcohol'k) having a hydrophobic group and a hydrophilic group according to the present invention
The present invention relates to a styrene O emulsion polymerization stabilizer consisting of tP (abbreviated as Pvm).

スチレンを乳化重合せしめるにあたっては従来ヨシアル
キルベンインスルホン酸塩、アルキルｆフタリンスルホ
ン酸塩、高級脂肪酸塩、不均化ロジ／＃塩等の低分子界
面活性剤の単独又は混合ｍ−・０ 会乳化重合安定剤として用いられている。しかしながら
、この様な低分子界面活性剤を用いる方法で祷られるエ
マルジョンを塗料、接着剤、紙加工剤等として使用する
にメｆｉｃって兼期間貯蔵するとか尿素樹脂や類ｌｌ１
ｒ等を麟加すると粗粒が発生するとか、機械的安２４に
とほしくポンプによる移送とかスプレッダ−ロールによ
る塗工時などにエマルジョンの凝ｒｋ、破壊がおこり易
いなどの欠点かめるのでその壜扱いには細心の注意をは
られなければならないという難点がある。ｉた接着剤と
して用い死時に、１低分子界面活性剤か皮膜０１１面に
移行し％装着不良をおこし易いなどの難点がある。In emulsion polymerization of styrene, conventionally low molecular weight surfactants such as yoshyalkyl bene sulfonates, alkyl f phthalene sulfonates, higher fatty acid salts, and disproportionated logi/# salts are used singly or in combination. It is used as an emulsion polymerization stabilizer. However, it is difficult to use emulsions produced by methods using such low-molecular-weight surfactants as paints, adhesives, paper processing agents, etc., and to store them for a long period of time.
If R is added too little, coarse particles will be generated, and for mechanical safety, the emulsion will be easily curdled or destroyed when transferred by a pump or applied with a spreader roll, so handle the bottle accordingly. has the disadvantage that it requires careful attention. When used as an adhesive, the low-molecular-weight surfactant migrates to the surface of the film and tends to cause poor adhesion.

かかる難点を解消するためにＰＶＡなどの高分子界面活
性期を使用することなどが提案されている。In order to overcome these difficulties, it has been proposed to use a polymeric surfactant such as PVA.

ＰＶＡは酢酸ビニルエステルの乳化重合安定剤とシテ有
用であり、赦エマルジ曹ンは機械的安定性、凍！ｉ！融
解安定性など各槓安定性にすぐれ、接着剤とか塗料など
として多く用いられてしる。しかしながらＰＶＡ）安定
剤として用いてスチレンの乳化重合を試みても重合の進
行がきわめて遍く又、重合時に粗粒が多発するとか全体
がゲル化してしオリなど円滑な重合はおこなえないもの
である。PVA is useful as an emulsion polymerization stabilizer of vinyl acetate ester, and emulsion carbonate is useful for mechanical stability, freezing! i! It has excellent melting stability and other types of stability, and is often used as adhesives and paints. However, even if emulsion polymerization of styrene is attempted using PVA (PVA) as a stabilizer, the polymerization progresses extremely unevenly, and smooth polymerization cannot be achieved as many coarse particles are produced during polymerization or the entire product gels.

低分子界面活性剤とＰＶＡを併用するならば乳化重合は
可能であるが前記の低分子界面活性剤０皮膜ａｍへの移
行による接着不良など種々の難点位解消しえない４ので
めっ次。Emulsion polymerization is possible if a low-molecular-weight surfactant and PVA are used in combination, but it is difficult to solve various problems such as poor adhesion due to the transfer of the low-molecular-weight surfactant to the am film.

（メタ）アリルスルホン鐵アルカリ塩と酢識ビニルエス
テルとＯ共重合による変性ＰＶＡを安定剤としてスチレ
／を乳化重合する試みは轡公紹５１−１＄８７１にて公
知である。しかしながら（メタ）乳化重合を試みても１
合速度はきわめて遅くｉ九組粒が多尭するなどの難点が
Ｔｏシ前述した変性しティないＰＶＡを用いて乳化重合
を試みた時のｓ点は殆んど解決されていないのが実情で
ある。An attempt to emulsion polymerize styrene using (meth)allylsulfone iron alkali salt, acetic acid vinyl ester, and O modified PVA as a stabilizer by copolymerization is known in 轡 Official Introduction 51-1, $871. However, even if (meta)emulsion polymerization is attempted, 1
In addition to the drawbacks such as extremely slow synthesis rate and large number of i9-group grains, the fact is that the above-mentioned point s when attempting emulsion polymerization using unmodified PVA has hardly been resolved. be.

本発明看らは、上述のごとき状況に−み、鋭意研究し友
結果単Ｓ蒙用によｐスチレンを円滑に重合せしめかつき
わめて安定化効果の＾いＰｖム系高分子界向活性剤を見
出すＫｌｊＮ）本発ＷＡＫＩＡＪ達したＯ すなわち側鎖に炭素数４以上の炭化水ｌＡ＆とスルホン
酸基もしくは硫酸エステル基とを含有する変性ＰＶＡを
乳化重合安定剤としてスチレンを乳化１合するならば良
好な重合速度ですみ中かに重合−ｂＸ進行しかつ粗粒の
発生とかゲル化などの因翔なく円滑な乳化１合がおこな
える本のである。この４ＩＩな効朱社匈−にに素数４以
上の炭化水素基とスルホン酸基もしくは硫猷エステル基
の両者を有する変性ＰＶＡによってのみ得られるもので
Ｔｏｌ）、炭化水素基のみもしくはスルホンｍ基又は置
数エステル基をのみを有する変性ＰＶＡからはおよびも
つかない顕著な性能が得られることはおどろくべきであ
る。In view of the above-mentioned situation, the inventors of the present invention have conducted extensive research and have developed a Pv-based polymeric surfactant that can smoothly polymerize p-styrene and has an extremely stabilizing effect. Found KljN) Original WAKIAJ Reached O In other words, it is good if styrene is emulsified using modified PVA containing hydrocarbon lA& with 4 or more carbon atoms in the side chain and a sulfonic acid group or sulfuric acid ester group as an emulsion polymerization stabilizer. This book allows the polymerization-bX to proceed quickly at a moderate polymerization rate, and allows smooth emulsification to be carried out without problems such as generation of coarse particles or gelation. This 4II effect can only be obtained by modified PVA having both a hydrocarbon group with a prime number of 4 or more and a sulfonic acid group or a sulfur ester group. It is surprising that remarkable performance is obtained that cannot be obtained from modified PVA having only a few ester groups.

本発明の炭化水素基は炭素数が４以上である事か必要で
ある。炭ｌＡ数が３以下であると、エマルジョン重合速
度が遅く変性の効果が嘴確でない。It is necessary that the hydrocarbon group of the present invention has 4 or more carbon atoms. When the number of carbon atoms is 3 or less, the emulsion polymerization rate is slow and the modification effect is not reliable.

導入される炭化水素基は０．０１から１５モル−〇範囲
である事が好ましい。０．０．１モル−未満であると乳
化重合速度がおそいとかエマルジョ／の安定性が不充分
であるなど本発明の効果があられれにくい。１５モル−
をこえる時紘１本発ｖ４０効釆は飽和してしｔ５ｃ）み
ならずスルホン数基又は硫讃基Ｏ導大量にもよるが、変
性ＰＶＡの水溶性の低下によシ水不溶性のものてらった
）、又ＰＶＡが本来壱している所の強い造膜性などの性
能が失なわれる為か良い！！来がえられない場合がある
。導入されるスルホン酸基又は硫酸基は０．０１モル−
からｌｒ１モルＩＧｃ）＠囲であることがのぞましい。The amount of hydrocarbon group introduced is preferably in the range of 0.01 to 15 moles. If it is less than 0.0.1 mol, the effects of the present invention may be difficult to achieve, such as slow emulsion polymerization rate or insufficient emulsion stability. 15 mol-
When more than 1 bottle of V40 is used, the potency becomes saturated (t5c), but it also depends on the number of sulfone groups or the amount of sulfone group O conduction. ), and PVA's original properties such as strong film-forming properties are lost, which is good! ! There are times when you may not be able to come. The amount of sulfonic acid group or sulfuric acid group introduced is 0.01 mol-
It is preferable that the range is from 1 mol IGc) to 1 mol IGc).

０．０１モル−未満であると炭化水素基の導入量にもよ
るが、変性ＰＶＡが水に溶解しないものであった）、又
乳化重合エマルジョンの安定性が充分でないなどのｍ慮
が生じるときがめる。１５モル−を越えて尋人してもも
はや効果は飽和してしまうばかｐでなくむしろＰＶＡが
本来有している強い進展性などの良い性能が失なわれて
しまうためかエマルジョンの性能が低下する傾向にある
。If the amount is less than 0.01 mol, depending on the amount of hydrocarbon groups introduced, the modified PVA may not dissolve in water), or the stability of the emulsion polymerization emulsion may not be sufficient. I'm worried. Even if the amount exceeds 15 mol, the effect will no longer be saturated, but rather the performance of the emulsion will deteriorate, probably because the good performance such as the strong propagation properties that PVA originally has will be lost. There is a tendency to

さらに最北水素系は＆鎖状の炭化水素基であるより１分
岐状炭化水素基であった方がエマルジョンの安定性、皮
膜性能にすぐれておシ好ましい。Further, it is preferable that the northernmost hydrogen group is a monobranched hydrocarbon group rather than a &chain hydrocarbon group because it provides superior emulsion stability and film performance.

この理由は明確ではないが炭化水素基中のメチル基、メ
チレン幕、メチン基の比が分岐状炭化水素基と直鎖状炭
化水素基とでは異なることや結晶性。The reasons for this are not clear, but include the fact that the ratio of methyl groups, methylene groups, and methine groups in the hydrocarbon group differs between branched and straight-chain hydrocarbon groups, and crystallinity.

配向性、会合性などの！ｌＫ起因するので線ないかと考
えられる。Orientation, association, etc! Since it is caused by lK, it is thought that there is a line.

本発明の変性ＰＶＡｏ＠鎖に炭化水素基を導入する方法
−とじては炭化水素基を有するエチレン性不飽和単量体
５例えばブチルビニルエーテル、ラウリルビニルエーテ
ル、ステアリルビニルエーテルなどのアルキルビニルエ
ーテル類、ヘプテノ−１、オクテン−１１ドデセン−１
などの１−オレフィン類、ラフリン酸ビニルエステル、
ステアリン敵ビニルエステルなどのビニルエステル類、
Ｎ−ターシャリ−ブチルアクリルアミドなとのＮ−アル
キル置換アクリルアイド類と酢酸ビニルエステルとを共
重合せしめケン化する方法かめるが、なかでもインアイ
ルビニルエーテル、Ｖａ　ｏｖａ　−１０（シェル社商
榛；平均炭素数が１０の分岐状脂肪鍍ビニルエステル）
２２：どの分岐状炭化水素基を有する単量体が好適に用
いられる。さらに脂肪族モノアルデヒドでアセタール化
する方法かめる。Method for introducing hydrocarbon groups into modified PVAo@ chains of the present invention - Ethylenically unsaturated monomers having hydrocarbon groups 5 For example, alkyl vinyl ethers such as butyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, hepteno-1 , octene-11 dodecene-1
1-olefins such as luffric acid vinyl ester,
Vinyl esters, such as stearin vinyl ester,
A method of copolymerizing N-alkyl-substituted acrylic ides such as N-tert-butylacrylamide and vinyl acetate and saponifying the copolymerized vinyl ether, Va ova-10 (Shell Co., Ltd.; average carbon (branched aliphatic vinyl ester with number 10)
22: Which monomer having a branched hydrocarbon group is preferably used. Furthermore, a method of acetalization with aliphatic monoaldehydes is proposed.

ＩＩｌ鎮にスルホン酸もし−〈は硫酸エステル基を導入
する方法としては例えばビニルスルホンＷｂ　’ｙリル
スルホン鐵、メタリルスルホン戚、Ｎ−７クリルアミド
プロパンスルホン戚等のスルホン賦型含有率量体と酢酸
ビニルとを共重合せしめケン化する方法とか、ＰＶ人に
硫酸、クロルスルホン峡などを反応させてエステル化す
る方法等がめげられる。Examples of methods for introducing a sulfonic acid ester group into a sulfonic acid group include a sulfone-imported polymer such as vinyl sulfone Wb'ylylsulfone iron, methallyl sulfone family, N-7 crylamide propane sulfone family, etc. Methods such as copolymerizing it with vinyl acetate and saponifying it, and reacting PV with sulfuric acid, chlorsulfone, etc. to esterify it have been unsuccessful.

ケン化度については轡に制限はなく水溶性の範囲内であ
ればよしが通常は６０モル嘔のケン化度であった方がエ
マルジョンから得られたＦｊＬｌｌＩの耐水性などの面
で良好である。重合度は妥求される工ｉルジ曹ンＯ粘ｆ
等によｐ適宜選択すべきでおるが通常！００〜５ｏｏｏ
の範囲が適当である。Regarding the degree of saponification, there is no limit as long as it is within the range of water solubility, but a degree of saponification of 60 mol is usually better in terms of water resistance of FjLllI obtained from the emulsion. . The degree of polymerization is acceptable.
etc., you should choose as appropriate, but usually! 00～5ooo
A range of is appropriate.

上記の変性ＰＶムを単独で安定剤として用い水相中でラ
ジカル重合開始剤の存在下にスチレンを公知の方法によ
り乳化重合を行い良好な乳化重合エマルジョンが得られ
る。乳化重合にあ九っては少飯成分としてジエン類、ア
クリル鐵エステル−、メタクリル鈑エステル類、塩化ビ
ニル、アクリルることも可能である。A good emulsion polymerization emulsion can be obtained by emulsion polymerizing styrene by a known method in an aqueous phase in the presence of a radical polymerization initiator using the above-mentioned modified PV film alone as a stabilizer. In emulsion polymerization, it is also possible to use dienes, acrylic iron esters, methacrylic iron esters, vinyl chloride, and acrylic esters as ingredients.

この発明の変性ＰＶＡの単独便用で安定に乳化重合をお
こなうことができるが％例えば粒子径の―節などのため
の補助的手段として低分子外向活性剤を併用することは
さしつがえない。さらに場合によって扛他の保表コロイ
ドたとえばＰｖム。Although emulsion polymerization can be carried out stably when the modified PVA of this invention is used alone, it is not a problem to use a low-molecular external active agent in combination as an auxiliary means, for example, to adjust the particle size. In addition, other protective colloids such as Pvum may be used as the case may be.

ポリアクリル鍍、ポリメタクリル綬、およびその塩類、
ポリビニルアルキルエーテル、酢酸ビニルとアクリル酸
またはメタクリル酸の共重合−，ｔたは酢酸ビニル−無
水マレイン鈑共菖合−およびそのケン化物、低級アルキ
ルビニルエーテル−無水マレイン酸基Ｘ合物、アルキル
セルロース、ヒドロキシアルキルセルロースなどのセル
ロース誘導体、アルキル殿粉、カルボキシメチル澱粉、
ｔｌｔ化デンプン、アラビアゴム、トラガントゴム、ポ
リアルキレングリコールなどを重合時に使用するか、も
しくは重合後に添加することもできる。このほか普通の
乳化重合の際に用いられる液性調節剤、１価又は多価の
アルコール類、可履剤、塩化ナトリウム、胃り化ナトリ
ウム、りン歇ナトリクム、ｉｌｌナナトリウムどの無機
塩類、アンモニア、水歇化ナトリクム、塩酸などＯＰＨ
調節剤、消泡剤などの助剤を重合時、ｔたは重合後に併
用することは何らさしつか見ない。Polyacrylic plates, polymethacrylic ribbons, and their salts,
Polyvinyl alkyl ether, copolymerization of vinyl acetate and acrylic acid or methacrylic acid, or vinyl acetate-maleic anhydride copolymerization, and its saponified product, lower alkyl vinyl ether-maleic anhydride group X compound, alkyl cellulose, Cellulose derivatives such as hydroxyalkyl cellulose, alkyl starch, carboxymethyl starch,
Tltized starch, gum arabic, gum tragacanth, polyalkylene glycol, etc. can be used during polymerization or can be added after polymerization. In addition, liquid regulators used in ordinary emulsion polymerization, monohydric or polyhydric alcohols, lubricants, inorganic salts such as sodium chloride, sodium chloride, sodium phosphate, sodium chloride, and ammonia. , sodium hydroxide, hydrochloric acid, etc. OPH
I have rarely seen the use of auxiliary agents such as regulators and antifoaming agents during or after polymerization.

本発明において使用される変性ＰＶＡはスチレンに対し
てＯ，Ｓ〜４０重を一２好ｔＬ＜は２〜２６重量−の量
を乳化重合完了までに使用することに１９充分−成する
ことがで龜る。The modified PVA used in the present invention can be used in an amount of 12 to 26% by weight of O, S to styrene until the emulsion polymerization is completed. It gets cloudy.

使用される重置開始剤は通常の乳化重合に用ｉられゐ水
溶性開始剤系１例えば過酸化水素単独または過酸化水素
とオキシカルボン酸、蓚＊、スルフィンｌＩおよびこれ
らの塩類、オ中Ｖアルデヒド類、水溶＋！１＃塩攻どと
の組合せ、過硫識塩−１過炭ａｌ塩＃Ａ、過硼慮塩類、
過酸化物などが通用できる０ このＩｌにして得られた乳化重合エマルジョンはすぐれ
た安定性を示しかつ濁度の粘性を有しており、廣看薊、
粘矯剤、繊維加工剤５紙加工剤、さらにはセメン）ＩＩ
和剤などにも有効であり工業的利用価値Ｆｉ極めて大き
い。The superposition initiators used are those used in conventional emulsion polymerizations, such as water-soluble initiator systems 1, such as hydrogen peroxide alone or hydrogen peroxide and oxycarboxylic acids; Aldehydes, water soluble+! 1# Combination with salt attack, supersulfurized salt-1 supercharcoal salt #A, supersulfated salts,
The emulsion polymerized emulsion obtained using this Il exhibits excellent stability and has a viscosity of turbidity.
Cohesive agent, fiber processing agent 5 paper processing agent, and even cement) II
It is also effective in Japanese preparations and has extremely high industrial utility value Fi.

次に実施例をあけて本＠明をさらに具体的に説明する。Next, the present invention will be explained in more detail with reference to Examples.

実施例において［一部」、「チ」とめるのは籍にことわ
シのない＠シ１量基準でるる。In the examples, "part" and "chi" are defined based on the amount of @shi, without exception.

実施例１ 酢酸ビニル７７０部、メタノール９７０ｓ、フワリルビ
ニルエーテル２５．１ｍを重合缶に仕込んで常法により
重合し未反応の酢酸ビニルを追出しついで苛性ソーダを
含むメタノール中でクン化した。Example 1 770 parts of vinyl acetate, 970 s of methanol, and 25.1 ml of fluorinated vinyl ether were charged into a polymerization reactor and polymerized in a conventional manner, unreacted vinyl acetate was expelled, and the mixture was cured in methanol containing caustic soda.

得られた変性ＰＶＡはラウリルエーテル基を０．９モル
−含有し、ケン化度は９９．０七ルーでめった。The obtained modified PVA contained 0.9 mol of lauryl ether groups and had a saponification degree of 99.07 Ru.

次いでこの変性ＰＶＡにピリジン媒体中でクロルスルホ
ン識を反応させた後中和して得られた変性ＰＶＡはラウ
リルエーテル基を０．９モル−含有し、スルホン歌エス
テル基ｔ−２，４モルｔｓ１に含有シケン化［９９，ｘ
モル−１２０℃における４チ水溶液粘度が１６センチボ
イズでめりた。Next, this modified PVA was reacted with chlorosulfone in a pyridine medium, and then neutralized. The resulting modified PVA contained 0.9 mol of lauryl ether groups and t-2.4 mol of sulfone ester groups. Containing silicenization [99,x
The viscosity of the 4-inch aqueous solution at mol-120°C decreased to 16 centivoise.

コノ変性ＰＶＡｌ０部を水２６０ｓに溶解し、Ｓアンモ
ニア水３ｓを添加し、６０℃に保つ。チッ素ガス雰凹気
下にスチレン１５０部を投入し５分間攪袢したのち過硫
酸アンモニクムの２ｇ６水溶液５部を投入し重合を開始
し丸。２時間後に冷却し、内容物をと９だした時は平均
粒＆０．１５μの粗粒のないきれいなエマルジョ／が得
られた。スチレンの重合率Ｆｉｅ８．４％でありこのも
のは三ケ月放置して４ｈｔつたく安定でめつ九。又Ｂ［
粘度針を用い温［３０℃、１転１！ｌ［ｌＯｒｐｍで測
定した粘度は９４０ｅｐ暴でめった。0 parts of Kono-modified PVAl is dissolved in 260 s of water, 3 s of S ammonia water is added, and the temperature is maintained at 60°C. After 150 parts of styrene was added in a nitrogen gas atmosphere and stirred for 5 minutes, 5 parts of a 2g6 aqueous solution of ammonium persulfate was added to start polymerization. After 2 hours, it was cooled and the contents were taken out to give a clean emulsion with no coarse particles of average size &0.15μ. The polymerization rate of styrene was 8.4%, and this product remained stable for 4 hours after being left for three months. Also B[
Using a viscosity needle, temperature [30℃, 1 turn 1! The viscosity measured at l[lOrpm failed at 940 ep.

比較例１ 実施例１において中間生成物として得たところのラクリ
ルエーテル基を０．９モル−含有し、ケン化度９９．０
モル囁Ｏ変性ＰＶＡを用いてスチレンの乳化重合を試み
九が、該変性Ｐｖムは冷水にも熱水にも溶解しないもの
であり％曳好なスチレンの乳化１合一はえられなかった
０ 実施例２ 酢酸ピ；ｈｇｔｏｏ部、平均嶽素数がｌＯの分岐状脂肪
ｍ歇ビニルエステルである■・ｏｖａ−１ｏ（Ｖエル社
商ｍ）５０部、メタノール２０００Ｉｓ　アリルスルホ
ン離ナトリウム８２部を重合缶に仕込んで迫られた重合
体溶液を常法により苛性ソーダを触媒としてケン化した
。得られた変性ＰＶＡは炭化水素Ｓ＜バーナチック販エ
ステル部）ｔｌ、１モル−、スルホン数基を２９モル−
會み、ケン化［９７，８モル−１２０℃における４ｓ水
溶液粘鼠が１２センチボイズの変性ＰＶＡでめった。Comparative Example 1 Contains 0.9 mol of the lacryl ether group obtained as an intermediate product in Example 1, and has a saponification degree of 99.0.
Attempts were made to emulsion polymerize styrene using modified PVA, but the modified PVA did not dissolve in either cold or hot water, and it was not possible to obtain an emulsion of styrene that was highly tractable. Example 2 Too many parts of pyroacetate, 50 parts of OV-1O (Vel Co., Ltd.), which is a branched fatty vinyl ester with an average molecular weight of 1O, and 82 parts of methanol 2000Is allylsulfonate sodium were polymerized in a can. The polymer solution was saponified by a conventional method using caustic soda as a catalyst. The obtained modified PVA contains hydrocarbon S<Vernatic ester part) tl, 1 mol, and several sulfone groups at 29 mol.
Meeting, saponification [97.8 mol - 4s aqueous solution viscous mouse at 120°C was heated with modified PVA of 12 centivoise.

この変性ＰＶＡを用いる以外は実施例１と同様にしてス
チレンの乳化重合を賦みた。２時間後の１合率は９９．
８％であり３０℃、１０ｒｐｍでのＢ型粘度１３４０ｃ
ｐｓの粒径０．１μの粗粒のないきれいなエマルジョン
が得られた０このものは六ケ月放置してもまったく安定
でめった。Emulsion polymerization of styrene was carried out in the same manner as in Example 1 except that this modified PVA was used. The 1 ratio after 2 hours was 99.
8%, type B viscosity 1340c at 30°C and 10 rpm
A clean emulsion free of coarse particles with a particle size of 0.1 μm was obtained. This emulsion remained completely stable even after being left for six months.

比較例２ 炭素数が３の層化水素基でめるプロピルビ；ルエーテル
を０．８モル−、アリルスルホン練ナトリ９ムを２．０
モル共重合して得九クン化［■１モル％、２０℃におけ
る４−水Ｓ液粘度が９センチボイズの変性ＰＶＡＩ用い
る以外祉実施例１と同様にしてスチレンの乳化重合をこ
ころみた。２時間後のスチレンの重合率は３．７−であ
４７１！わめて重合速度が遅いものでめった。Comparative Example 2 0.8 mol of propyl vinyl ether and 2.0 mol of allyl sulfone sodium trichloride formed by a layered hydrogen group having 3 carbon atoms.
Emulsion polymerization of styrene was attempted in the same manner as in Example 1, except that modified PVAI was used, which was obtained by molar copolymerization and had a viscosity of 1 mol % and a 4-water S liquid viscosity of 9 cm at 20°C. The polymerization rate of styrene after 2 hours was 3.7-471! The polymerization rate was extremely slow, so it was a failure.

比較例３ アリルスルホン龍ナトリウムを２．０モルチ共重合して
常法によ９作成し九ところＯケン化［９８，７モルー、
２０℃における４−水溶液粘度が１０センデボイズの変
性Ｐｖムを使用する以外は実施例１と同様にしてスチレ
ンの乳化重合をこころみた０２時間後のスチレンの重合
率は３．９−でめシきわめて重合速度が遅いものであっ
た０ 比較例４ 重合度１７００．ケン化ＩＩ　９　ｇ、　５七ルーの未
変性ＰＶＡ（／ツレ−ＰＶＡ１１フ、２０℃に＊ｆｆル
４−水＃！液粘度が２８センチボイズ）を使用する以外
は実施例１と同様にしてスチレンの乳化重合をこころみ
た。冨時間後のスチレンの重合率は４．０−でありきわ
めて重合速度がおそかった０実施例３ 実施例１に得られたところのう９リルエーテル基ｌＯ，
１１モル−、スルホン酸エステル基ヲ２．４モル−含有
する変性ｐｖム１０ｉ１ｉｔ−水２０Ｇ１１に加熱溶解
後冷却してから過懺叡カリウム１．５ｉ１Ｓ、エチレン
ジアミン四酢ＩＩ！　０．１部を添加溶解する。しかる
ｏ６スチレン９ＯＮＳ、ブタジェン６０部を添加して攪
拌下に６０℃に１２時間保ったのち、冷却して内容物を
とり出した。反応率は９８．５−でわ丸平均粒径０．２
μの凝集のないきれいな之テックスでおった◇とのも（
ｉＯｒｉｍ温に４ケ月放置しても凝集とか増粘すること
なく安定でめった。又３０℃、ｌＯｒｐｍでのＢ型精度
は８７０センチポイズでＴｏｎ、このラテックスを０．
５　ｆｉの厚さになる様にｆＩｔ嬌作製した皮膜はやや
白濁していた。Comparative Example 3 9 was prepared by copolymerizing 2.0 mol of sodium allyl sulfonyl by a conventional method, and the 9 parts were O-saponified [98.7 mol,
Emulsion polymerization of styrene was attempted in the same manner as in Example 1, except that a modified Pvm with a 4-aqueous solution viscosity of 10 Sendebois at 20°C was used.The polymerization rate of styrene after 2 hours was 3.9, which was extremely high. The polymerization rate was slow.0 Comparative Example 4 Polymerization degree was 1700. Styrene was prepared in the same manner as in Example 1, except that 9 g of saponified II, 57 l of unmodified PVA (/Tre-PVA11, 4-water at 20°C, liquid viscosity of 28 centiboise) was used. I tried to emulsion polymerize it. The polymerization rate of styrene after a certain amount of time was 4.0-, indicating that the polymerization rate was extremely slow.Example 3 The polymerization rate of styrene obtained in Example 1 was 9.
A modified pv film containing 11 moles of sulfonic acid ester group and 2.4 moles of sulfonic acid ester groups was heated and dissolved in 20 g of water and then cooled. Add and dissolve 0.1 part. After adding 9ONS of O6 styrene and 60 parts of butadiene, the mixture was kept at 60° C. for 12 hours with stirring, then cooled and the contents were taken out. The reaction rate is 98.5- and the round average particle size is 0.2.
It was covered with clean texture without μ aggregation (
Even if it was left at iOrim temperature for 4 months, it remained stable without agglomeration or thickening. Also, the B type accuracy at 30°C and lOrpm is 870 centipoise Ton, and this latex is 0.
The film prepared to a thickness of 5 fi was slightly cloudy.

実施例４ 分岐状炭化水素基であるバーサチック献エステル’１１
．１モルチ含み、スルホン数基ｔｚ、ｅモに−含みかつ
ケン化［９７，８七ルー、２０℃における４参水博液粘
度が１２センチボイズであるところの夷−例２において
皺造した変性Ｐ■ムを使用する以外は実施例３と同様に
して乳化重合を行なったところ、反応率は９９．１−で
６シ、平均粒径０．２μの凝集のない、龜れいなラテッ
クスであった。このも０Ｆｉ−温に六ケ月放置しても凝
集とか増粘をすることなく安定であつ九。又３０″Ｃ，
１０ｒｐｍでのＢ製粘Ｊ［ｔｉｌｌｊｌＯセンチポイズ
であ）、このラテックスを０．５ＭＯ厚さになる橡に流
嬌作成し九皮龜は透明性が良好でめった。Example 4 Versatic ester '11 which is a branched hydrocarbon group
．． The modified P wrinkled in Example 2 contains 1 mole, contains several sulfone groups, tz and emo, and is saponified [97,87 lu], and has a viscosity of 12 centiboise at 20°C. Emulsion polymerization was carried out in the same manner as in Example 3, except that the emulsion polymer was used. The reaction rate was 99.1-6cm, and a clean latex with no agglomeration and an average particle size of 0.2μ was obtained. This product remains stable without agglomeration or thickening even if left at 0 Fi-temperature for six months. Also 30″C,
This latex was made to flow to a thickness of 0.5 MO using a viscosity manufactured by B (till 0 centipoise) at 10 rpm, and the latex was found to have good transparency.

脣許出販人　株式金社　り　ラ　　し 代塩入弁理士本多　臘Licensed seller: Kinsha Co., Ltd. Yoshioiri Patent Attorney Rin Honda

Claims (1)

【特許請求の範囲】[Claims] （１）　　側鎖に炭素数４以上の炭化水嵩基とスルホン
酸基もしく妹硫畝エステル基とを含有する資性ポリビニ
ルアルコールからなるスチレンの乳化重合安定剤。 （至）フ　責化水嵩基が分岐状炭化水嵩基でめる脣許晴
求の範１１（１）　Ｋ記載の乳化重合安定剤。(1) A styrene emulsion polymerization stabilizer consisting of polyvinyl alcohol containing a hydrocarbon bulk group having 4 or more carbon atoms and a sulfonic acid group or a sulfonic ester group in its side chain. (To) The emulsion polymerization stabilizer according to Section 11 (1) K, wherein the hydrocarbon bulk group is a branched hydrocarbon bulk group.