JP2003171423A - Polyvinyl alcohol-based resin and use thereof - Google Patents
Polyvinyl alcohol-based resin and use thereofInfo
- Publication number
- JP2003171423A JP2003171423A JP2001375397A JP2001375397A JP2003171423A JP 2003171423 A JP2003171423 A JP 2003171423A JP 2001375397 A JP2001375397 A JP 2001375397A JP 2001375397 A JP2001375397 A JP 2001375397A JP 2003171423 A JP2003171423 A JP 2003171423A
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- JP
- Japan
- Prior art keywords
- polymerization
- chain transfer
- polyvinyl alcohol
- transfer agent
- mol
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なポリビニル
アルコール系樹脂およびその用途に関し、更に詳しく
は、低温保存安定性および形成皮膜の耐水性に優れたビ
ニル樹脂系エマルジョンを得ることができる乳化重合用
分散安定剤に有用なポリビニルアルコール系樹脂および
それを用いた乳化重合用分散剤、ビニル樹脂系エマルジ
ョンに関する。TECHNICAL FIELD The present invention relates to a novel polyvinyl alcohol-based resin and its use, and more specifically, emulsion polymerization capable of obtaining a vinyl resin-based emulsion excellent in low-temperature storage stability and water resistance of a formed film. TECHNICAL FIELD The present invention relates to a polyvinyl alcohol-based resin useful as a dispersion stabilizer for emulsions, a dispersant for emulsion polymerization using the same, and a vinyl resin-based emulsion.
【０００２】従来より、ポリビニルアルコール系樹脂
（以下、ＰＶＡと略記することがある）は、分散（安
定）剤、接着剤、糊剤、フィルム、紙加工剤等に多用さ
れており、かかる分散（安定）剤用途では、ポリ酢酸ビ
ニルエマルジョンのようなビニル樹脂系のエマルジョン
の乳化重合用分散（安定）剤として、従来から利用され
ている。[0002] Conventionally, polyvinyl alcohol resins (hereinafter sometimes abbreviated as PVA) have been widely used as dispersing (stabilizing) agents, adhesives, sizing agents, films, paper processing agents, and the like. In the use of stabilizers, it has been conventionally used as a dispersion (stabilizer) for emulsion polymerization of vinyl resin emulsions such as polyvinyl acetate emulsions.
【０００３】近年ではポリ酢酸ビニルエマルジョンの耐
水接着強度のレベル（ＪＡＳ１類、２類、３類等）に応
じて各種ＰＶＡが使用されており、ＪＡＳ３類向けに
は、未変性の完全ケン化ＰＶＡが使用されている。ま
た、耐水１液用途（ＪＡＳ１〜２類適用）には、各種変
性の反応型のＰＶＡが使用されている。In recent years, various types of PVA have been used according to the level of water-resistant adhesive strength of polyvinyl acetate emulsion (JAS 1, 2 and 3), and for JAS3, unmodified fully saponified PVA. Is used. Further, various modified reaction-type PVA are used for water resistant one-liquid applications (JAS1 and 2 applied).
【０００４】本出願人も、近年、得られるエマルジョン
の耐熱水接着力、流動安定性、低温安定性、放置安定性
等の改善を目的として、ブロックキャラクターが０．
６以下で平均重合度が５００〜１５００のアセト酢酸エ
ステル基含有ＰＶＡ（特開２０００−１７８３１６号公
報）やアセト酢酸エステル基含有ＰＶＡとヨード呈色
度が０．０５以下のＰＶＡのブレンド物（特開２００１
−１３９６１２号公報）を提案し、さらに、アセト酢酸
エステル基含有ＰＶＡ以外にも、ケン化度とヨード呈
色度が特定の関係式を満たすＰＶＡ（特開２００１−２
１３９０６号公報）を提案した。[0004] In recent years, the applicant of the present invention also aimed to improve the hot water adhesiveness, the flow stability, the low temperature stability, the leaving stability, etc. of the obtained emulsion with a block character of 0.
An acetoacetic acid ester group-containing PVA having an average polymerization degree of 6 or less and 500 to 1500 (Japanese Patent Laid-Open No. 2000-178316) or a blend of PVA having an acetoacetic acid ester group and an iodine coloration degree of 0.05 or less (special Open 2001
In addition to PVA containing an acetoacetic acid ester group, PVA (Japanese Unexamined Patent Publication No. 2001-2) in which saponification degree and iodine coloration degree satisfy a specific relational expression.
13906 publication).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
やのアセト酢酸エステル基含有ＰＶＡは、良好なエ
マルジョンが得られるものの、変性ＰＶＡであるために
経済的に不利であったり、用途によっては、耐水接着性
があまり要求されない場合もあり、また、のＰＶＡに
ついてもスルフォン酸等の親水性基がＰＶＡ内に導入さ
れている為に、得られる被膜が膨潤する等の問題があっ
た。また、完全ケン化ＰＶＡを使用して得られるエマル
ジョンは適度な耐水性を示すもののエマルジョンの低温
安定性が低いという問題点があり、比較的安価で、低温
保存安定性及び形成皮膜の耐水性（ＪＡＳ３類レベル）
に優れたビニル樹脂系エマルジョンの乳化重合用分散安
定剤として有用なＰＶＡが望まれるところである。However, although the above-mentioned PVA containing an acetoacetic ester group can give a good emulsion, it is economically disadvantageous because it is a modified PVA, and depending on the application, it is water resistant. Adhesiveness may not be required so much, and also in PVA, since a hydrophilic group such as sulfonic acid is introduced into PVA, there is a problem that the obtained coating film swells. Further, the emulsion obtained by using the completely saponified PVA has a problem that the emulsion has low water temperature stability but low temperature stability at low temperature, is relatively inexpensive, has low temperature storage stability and water resistance of the formed film ( JAS3 class level)
A PVA which is useful as a dispersion stabilizer for emulsion polymerization of a vinyl resin emulsion having excellent properties is desired.
【０００６】[0006]
【課題を解決するための手段】そこで、かかる現況に鑑
みて本発明者が鋭意検討した結果、ケン化度が９０モル
％以上で、末端に炭素数４以上の長鎖アルキル基を有
し、かつ分子量分布（Ｍｗ／Ｍｎ）が２．５〜３．５で
あるポリビニルアルコール系樹脂が、上記の目的を達成
できることを見出して本発明を完成するに至った。な
お、上記の分子量分布は、重量平均分子量（Ｍｗ）と数
平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）を表す。Therefore, as a result of diligent studies by the present inventors in view of the present situation, the saponification degree is 90 mol% or more, and the terminal has a long chain alkyl group having 4 or more carbon atoms, Moreover, the inventors have found that a polyvinyl alcohol-based resin having a molecular weight distribution (Mw / Mn) of 2.5 to 3.5 can achieve the above object, and completed the present invention. The above molecular weight distribution represents the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn).
【０００７】[0007]
【発明に実施の形態】以下、本発明について詳述する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
【０００８】本発明のポリビニルアルコール系樹脂は、
ケン化度が９０モル％以上で、末端に炭素数４以上の長
鎖アルキル基を有し、かつ分子量分布が２．５〜３．５
であるＰＶＡからなるもので、かかるＰＶＡを得るには
特に制限はないが、下記の方法により製造することが好
ましい。The polyvinyl alcohol resin of the present invention is
The degree of saponification is 90 mol% or more, the terminal has a long-chain alkyl group having 4 or more carbon atoms, and the molecular weight distribution is 2.5 to 3.5.
There is no particular limitation for obtaining such PVA, but it is preferably produced by the following method.
【０００９】すなわち、末端に炭素数４以上の長鎖アル
キル基を導入するために、特定の連鎖移動剤の存在下
で、ビニルエステル系化合物を重合して、得られたポリ
ビニルエステル系化合物をケン化するのである。That is, in order to introduce a long-chain alkyl group having 4 or more carbon atoms at the terminal, a vinyl ester compound is polymerized in the presence of a specific chain transfer agent, and the obtained polyvinyl ester compound is saponified. Will be transformed.
【００１０】かかる連鎖移動剤としては、炭素数が４以
上のアルキル基を有するアルデヒドあるいはメルカプタ
ンが用いられ、アルデヒドとしては、ｎ−オクチルアル
デヒド、２−エチル−ヘキシルアルデヒド、ｎ−カプリ
ンアルデヒド、ｎ−デシルアルデヒド、ｎ−ウンデシル
アルデヒド、ラウリルアルデヒド、ｎ−トリデシルアル
デヒド、セチルアルデヒド、パルミチルアルデヒド、ス
テアリルアルデヒド等のアルキルアルデヒドを挙げるこ
とができる。As the chain transfer agent, an aldehyde or mercaptan having an alkyl group having 4 or more carbon atoms is used, and as the aldehyde, n-octylaldehyde, 2-ethyl-hexylaldehyde, n-caprinaldehyde, n- Examples thereof include alkyl aldehydes such as decyl aldehyde, n-undecyl aldehyde, lauryl aldehyde, n-tridecyl aldehyde, cetyl aldehyde, palmityl aldehyde and stearyl aldehyde.
【００１１】また、メルカプタンとしては、ｎ−ブチル
メルカプタン、ｎ−ペンチルメルカプタン、tert−ブチ
ルメルカプタン、ｎ−アミルメルカプタン、tert−アミ
ルメルカプタン、ｎ−ヘキシルメルカプタン、シクロヘ
キシルメルカプタン、ｎ−オクチルメルカプタン、tert
−オクチルメルカプタン、tert−ノニルメルカプタン、
ｎ−ドデシルメルカプタン、tert−ドデシルメルカプタ
ン、ｎ−テトラデシルメルカプタン、ｎ−オクタデシル
メルカプタン等のアルキルメルカプタンを挙げることが
でき、好適にはアルキルメルカプタンが用いられる。The mercaptans include n-butyl mercaptan, n-pentyl mercaptan, tert-butyl mercaptan, n-amyl mercaptan, tert-amyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan, n-octyl mercaptan, tert.
-Octyl mercaptan, tert-nonyl mercaptan,
Alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-tetradecyl mercaptan and n-octadecyl mercaptan can be mentioned, and alkyl mercaptan is preferably used.
【００１２】上記の連鎖移動剤のアルキル基の炭素数の
上限は特に制限されないが、入手しやすさ及び作業性等
の点から２５以下（さらには２０以下、特には１８以
下）が好ましい。なお、本発明においては、該炭素数が
４未満のアルキル基を含有する連鎖移動剤を用いても、
乳化重合用分散安定剤として用いたときに得られるエマ
ルジョンの低温安定性が不充分となり不適である。The upper limit of the number of carbon atoms of the alkyl group of the chain transfer agent is not particularly limited, but is preferably 25 or less (more preferably 20 or less, particularly 18 or less) from the viewpoints of availability and workability. In the present invention, even if a chain transfer agent containing an alkyl group having less than 4 carbon atoms is used,
When used as a dispersion stabilizer for emulsion polymerization, the low temperature stability of the emulsion obtained is unsatisfactory and unsuitable.
【００１３】また、重合されるビニルエステル系化合物
としては、ギ酸ビニル、酢酸ビニル、トリフルオロ酢酸
ビニル、プロピオン酸ビニル、酪酸ビニル、カプリン酸
ビニル、ラウリル酸ビニル、バーサティック酸ビニル、
パルミチン酸ビニル、ステアリン酸ビニル等が単独又は
併用で用いられるが、実用上は酢酸ビニルが好適であ
る。The vinyl ester compounds to be polymerized include vinyl formate, vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate,
Although vinyl palmitate, vinyl stearate and the like are used alone or in combination, vinyl acetate is preferable in practical use.
【００１４】また、本発明においては、本発明の目的を
阻害しない範囲において、他の単量体を共重合させるこ
とも可能で、かかる単量体としては、例えばエチレン、
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、ビニレンカー
ボネート類、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
類あるいはその塩あるいはモノ又はジアルキルエステル
等、アクリロニトリル、メタアクリロニトリル等のニト
リル類、アクリルアミド、メタクリルアミド、ジアセト
ン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
ンスルホン酸あるいはその塩、アルキルビニルエーテル
類、Ｎ−アクリルアミドメチルトリメチルアンモニウム
クロライド、アリルトリメチルアンモニウムクロライ
ド、ジメチルジアリルアンモニウムクロリド、ジメチル
アリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニ
ル、塩化ビニリデン、ポリオキシエチレン（メタ）アリ
ルエーテル、ポリオキシプロピレン（メタ）アリルエー
テルなどのポリオキシアルキレン（メタ）アリルエーテ
ル、ポリオキシエチレン（メタ）アクリレート、ポリオ
キシプロピレン（メタ）アクリレート等のポリオキシア
ルキレン（メタ）アクリレート、ポリオキシエチレン
（メタ）アクリルアミド、ポリオキシプロピレン（メ
タ）アクリルアミド等のポリオキシアルキレン（メタ）
アクリルアミド、ポリオキシエチレン（１−（メタ）ア
クリルアミド−１，１−ジメチルプロピル）エステル、
ポリオキシエチレンビニルエーテル、ポリオキシプロピ
レンビニルエーテル、ポリオキシエチレンアリルアミ
ン、ポリオキシプロピレンアリルアミン、ポリオキシエ
チレンビニルアミン、ポリオキシプロピレンビニルアミ
ン等を挙げることができる。Further, in the present invention, other monomers may be copolymerized within the range not impairing the object of the present invention. Examples of such a monomer include ethylene,
Olefin such as propylene, isobutylene, α-octene, α-dodecene, α-octadecene, vinylene carbonates, acrylic acid, methacrylic acid, crotonic acid,
Maleic acid, maleic anhydride, unsaturated acids such as itaconic acid or salts or mono- or dialkyl esters thereof, acrylonitrile, nitriles such as methacrylonitrile, amides such as acrylamide, methacrylamide, diacetone acrylamide, ethylene sulfonic acid,
Olefin sulfonic acids such as allyl sulfonic acid and methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallylammonium chloride, dimethylallylvinylketone, N-vinylpyrrolidone, chloride Vinyl, vinylidene chloride, polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether and other polyoxyalkylene (meth) allyl ethers, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, etc. Polyoxyalkylene (meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, etc. Polyoxyalkylene (meth)
Acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester,
Examples thereof include polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine and polyoxypropylene vinylamine.
【００１５】ビニルエステル系化合物を重合（あるいは
共重合）するに当たっては、特に制限はなく、例えば塊
状重合、溶液重合、懸濁重合、分散重合、又はエマルジ
ョン重合等の公知の方法を採用することができるが、通
常は溶液重合が行われ、かかる重合方法について説明す
る。なお、重合温度を１００℃以上にすることで、ＰＶ
Ａ主鎖中に１，２−グリコールを導入したものを使用す
ることが可能である。There are no particular restrictions on the polymerization (or copolymerization) of the vinyl ester compound, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization or emulsion polymerization may be employed. However, solution polymerization is usually carried out, and the polymerization method will be described. By setting the polymerization temperature to 100 ° C or higher, PV
It is possible to use those in which 1,2-glycol is introduced into the A main chain.
【００１６】溶液重合を行うに当たっては、溶媒中で、
重合開始剤の共存下でビニルエステル系化合物を重合す
ればよい。In carrying out solution polymerization, in a solvent,
The vinyl ester compound may be polymerized in the presence of a polymerization initiator.
【００１７】かかる溶剤としては、メタノール、エタノ
ール、ｉ−プロパノール、ｎ−プロパノール等のアルコ
ール類、アセトン、メチルエチルケトン等のケトン類を
挙げることができるが、好適にはメタノールが用いられ
る。溶媒の使用量は、目的とする重合体の重合度に合わ
せて、適宜選択すれば良い。Examples of the solvent include alcohols such as methanol, ethanol, i-propanol and n-propanol, and ketones such as acetone and methyl ethyl ketone, but methanol is preferably used. The amount of the solvent used may be appropriately selected according to the degree of polymerization of the desired polymer.
【００１８】また、重合開始剤としては、例えば２，
２′−アゾビス−（２，４−ジメチルバレロニトリ
ル）、ジメチル−２，２′−アゾビスイソブチレイト、
２，２′−アゾビスイソブチロニトリル、２，２′−ア
ゾビス−（４−メトキシ−２，４−ジメチルバレロニト
リル）等のアゾ化合物、ｔ−ブチルパーオキシネオデカ
ノエート、ｔ−ブチルパーオキシピバレ−ト、ｔ−ヘキ
シルパーオキシピバレート等のパーオキシエステル類、
ビス−（４−ｔ−ブチルシクロヘキシル）パーオキシ−
ジ−カーボネート、ジ−２−エチルヘキシルパーオキシ
−ジ−カーボネート、ジ−イソプロピルパーオキシ−ジ
−カーボネート、ジ−ｎ−プロピルパーオキシジカーボ
ネート等のパーオキシ−ジ−カーボネート類、ラウロイ
ルパーオキサイド、アセチルパーオキサイド、ベンゾイ
ルパーオキサイド、イソブチラルパーオキサイド等のジ
アシルパーオキシド類などを挙げることができ、好適に
はアゾ化合物が用いられる。As the polymerization initiator, for example, 2,
2'-azobis- (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate,
Azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), t-butyl peroxyneodecanoate, t-butyl Peroxy esters such as peroxypivalate and t-hexyl peroxypivalate,
Bis- (4-t-butylcyclohexyl) peroxy-
Peroxy-di-carbonates such as di-carbonate, di-2-ethylhexylperoxy-dicarbonate, di-isopropylperoxy-dicarbonate, di-n-propylperoxydicarbonate, lauroyl peroxide, acetylperoxide Examples thereof include diacyl peroxides such as oxide, benzoyl peroxide, and isobutyral peroxide, and azo compounds are preferably used.
【００１９】また、重合温度は、３５〜１５０℃（さら
には３５〜７５℃、特には６０〜７５℃）の範囲から選
択することができる。The polymerization temperature can be selected from the range of 35 to 150 ° C. (further 35 to 75 ° C., especially 60 to 75 ° C.).
【００２０】本発明においては、かかる重合時に、上述
のように連鎖移動剤を共存させる必要があるが、単に共
存させるだけでは、分子量分布の狭いＰＶＡしか得るこ
とができない。In the present invention, it is necessary to allow the chain transfer agent to coexist as described above during such polymerization, but by simply coexisting it, only PVA having a narrow molecular weight distribution can be obtained.
【００２１】すなわち、従来のように連鎖移動剤の一括
仕込を行ったのでは、分子量分布が２．４以下程度のＰ
ＶＡしか得ることができず、本発明の如き分子量分布が
２．５〜３．５のＰＶＡを得るためには、下記のように
連鎖移動剤を重合系に添加する必要がある。That is, if the chain transfer agent was batch charged as in the prior art, P having a molecular weight distribution of about 2.4 or less was obtained.
In order to obtain only VA and to obtain PVA having a molecular weight distribution of 2.5 to 3.5 as in the present invention, it is necessary to add a chain transfer agent to the polymerization system as described below.
【００２２】つまり、ビニルエステル系化合物を炭素数
４以上の長鎖アルキル基を有する連鎖移動剤の共存下に
重合を開始し、その後炭素数４以上の長鎖アルキル基を
有する連鎖移動剤を断続的あるいは連続的に重合系内に
添加して目標とする重合率の２０〜８０％の間に該添加
を終了することが必要で、さらには、最終の目標分子量
を設定し、まず重合率２０〜８０％の間に生成させるＰ
を決め、その後に後重合を続けることによって行われ
る。かかる重合開始初期に、目標重合度Ｐを得るために
は、通常下記のＣｍ、Ｃｓ、［Ｓ］、［Ｍ］を決定した
上で、下記（１）式にしたがって炭素数４以上の長鎖ア
ルキル基を有する連鎖移動剤の共存量を決める。その後
ビニルエステル系化合物の重合開始と同時に、連鎖移動
剤の滴下仕込時間間隔を決定し、予め確認されているＲ
ｐを用いて、下記（２）式にしたがって炭素数４以上の
長鎖アルキル基を有する連鎖移動剤を２０〜８０％まで
の所定の重合率までの連鎖移動剤を仕込んで連鎖移動剤
の添加を止め、重合を継続することが好ましい。That is, polymerization of a vinyl ester compound is started in the presence of a chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms, and then the chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms is interrupted. It is necessary to complete the addition within a range of 20 to 80% of the target polymerization rate by dynamically or continuously adding to the polymerization system. Furthermore, the final target molecular weight is set, and the polymerization rate is set to 20%. P generated between ~ 80%
Is determined and then post-polymerization is continued. In order to obtain the target degree of polymerization P at the beginning of the polymerization, usually, the following Cm, Cs, [S] and [M] are determined, and then a long chain having 4 or more carbon atoms is calculated according to the following formula (1). The coexisting amount of the chain transfer agent having an alkyl group is determined. Then, at the same time as the initiation of the polymerization of the vinyl ester compound, the time interval for dropping the chain transfer agent was determined, and R was confirmed in advance.
Using p, a chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms is charged according to the following formula (2), a chain transfer agent having a predetermined polymerization rate of 20 to 80% is charged, and the chain transfer agent is added. It is preferable to stop the polymerization and continue the polymerization.
【００２３】
１／Ｐ＝Ｃｍ＋Ｃｓ（［Ｓ］／［Ｍ］）＋Ｃｘ（［Ｘ］／［Ｍ］）・・・（１）
仕込量＝Ｃｘ（［Ｘ］／［Ｍ］）×Ｒｐ×ｔ ・・・（２）
〔ここで、Ｐは目的とする瞬間重合度、Ｃｍはモノマー
の連鎖移動定数、Ｃｓは溶媒の連鎖移動定数、Ｃｘは連
鎖移動剤の連鎖移動定数、［Ｓ］は溶媒濃度（モル/リット
ル）、［Ｍ］はモノマー濃度（モル/リットル）、［Ｘ］は連鎖
移動剤の初期添加濃度（モル/リットル）、Ｒｐは重合速度（モ
ル/リットル/秒）をそれぞれ示す。〕1 / P = Cm + Cs ([S] / [M]) + Cx ([X] / [M]) (1) Charge amount = Cx ([X] / [M]) × Rp × t (2) [where P is the desired instantaneous degree of polymerization, Cm is the chain transfer constant of the monomer, Cs is the chain transfer constant of the solvent, Cx is the chain transfer constant of the chain transfer agent, and [S] is the solvent. Concentration (mol / liter), [M] indicates the monomer concentration (mol / liter), [X] indicates the initial addition concentration of the chain transfer agent (mol / liter), and Rp indicates the polymerization rate (mol / liter / second). . ]
【００２４】より具体的に説明すれば、連鎖移動剤共存
下で、ビニルエステル系化合物を重合するときに、上記
（１）式に従って、目的とする瞬間重合度に応じた連鎖
移動剤の初期仕込量を決めて重合を開始して、同時に連
鎖移動剤の消費速度に合わせて上記（２）式で算出され
る連鎖移動剤の仕込量を１〜２０００秒（ｔ）の間隔で
添加して、目標重合率の２０〜８０％の間に該添加を完
了し、その後連鎖移動剤を添加することなく重合するの
であって、たとえば、ビニルエステル系化合物が酢酸ビ
ニルで、重合溶媒がメタノールのときは、Ｃｍ＝４．８
×１０-3×ｅ(- 1096/T)〔Ｔは重合温度（Ｋ）〕、Ｃｓ
＝２．０×１０-4（６０℃）よりそれぞれを算出するこ
とができる。More specifically, when the vinyl ester compound is polymerized in the coexistence of a chain transfer agent, the initial charge of the chain transfer agent according to the desired instantaneous polymerization degree according to the above formula (1) is carried out. The amount is determined to start the polymerization, and at the same time, the charged amount of the chain transfer agent calculated by the above formula (2) is added according to the consumption rate of the chain transfer agent at an interval of 1 to 2000 seconds (t), The addition is completed within 20 to 80% of the target polymerization rate, and then the polymerization is carried out without adding a chain transfer agent. For example, when the vinyl ester compound is vinyl acetate and the polymerization solvent is methanol, , Cm = 4.8
× 10 -3 × e ( -1096 / T) [T is polymerization temperature (K)], Cs
= 2.0 × 10 −4 (60 ° C.).
【００２５】なお、上記において、上記（２）式で算出
される量の連鎖移動剤を添加するにあたっては、上記の
如く１〜２０００秒（さらには１〜１０００秒、特には
１〜６０秒）間隔で、断続的あるいは連続的に添加すれ
ばよく、２０００秒以上の間隔をあけると重合速度の制
御が困難となったり、又分子量分布の制御の効果が出が
たくなり好ましくない。In addition, in the above, when adding the amount of the chain transfer agent calculated by the above formula (2), it is 1 to 2000 seconds (further 1 to 1000 seconds, particularly 1 to 60 seconds) as described above. It may be added intermittently or continuously at intervals, and if the interval is 2000 seconds or more, the control of the polymerization rate becomes difficult, and the effect of controlling the molecular weight distribution becomes difficult to obtain, which is not preferable.
【００２６】また、かかる連鎖移動剤の添加は、目標重
合率の２０〜８０％（さらには４０〜６５％）の間に完
了する必要があり、重合率が２０％未満の時に添加する
と得られるＰＶＡを乳化重合用分散安定剤剤に用いたと
きに得られるエマルジョンの低温保存安定性が低下し、
逆に８０％を越えて添加すると得られるポリビニルアル
コール系樹脂の重合度を充分に上げることができず、乳
化重合用分散安定剤として充分に機能しないことがあ
る。すなわち、エマルジョンの高粘度のエマルジョンが
得られなかったり、保護コロイド性が低下してエマルジ
ョンの凝集を引き起こしたり、エマルジヨンの低温安定
性や希釈安定性が低下したりする。Further, the addition of such a chain transfer agent must be completed within 20 to 80% (further 40 to 65%) of the target polymerization rate, and it can be obtained when the polymerization rate is less than 20%. When PVA is used as a dispersion stabilizer agent for emulsion polymerization, the low temperature storage stability of the emulsion obtained decreases,
On the other hand, if it is added in an amount of more than 80%, the degree of polymerization of the obtained polyvinyl alcohol resin cannot be sufficiently increased, and it may not function sufficiently as a dispersion stabilizer for emulsion polymerization. That is, it is not possible to obtain a high-viscosity emulsion, the protective colloid property is lowered to cause aggregation of the emulsion, and the emulsion is deteriorated in low temperature stability and dilution stability.
【００２７】ついで、得られたビニルエステル系重合体
をケン化するにあたっては、該重合体をアルコールに溶
解してアルカリ触媒の存在下に行なわれる。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の濃度は、２０〜５
０重量％の範囲から選ばれる。Then, the saponification of the obtained vinyl ester polymer is carried out by dissolving the polymer in alcohol and in the presence of an alkali catalyst. Examples of alcohols include methanol, ethanol, butanol and the like. The concentration of the copolymer in alcohol is 20 to 5
It is selected from the range of 0% by weight.
【００２８】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如きアルカリ触媒を用いることが
できる。かかる触媒の使用量はビニルエステル系化合物
に対して１〜１００ミリモル当量にすればよい。好まし
くは、３〜３０ミリモル当量である。なお、場合によっ
ては、酸触媒によりケン化することも可能である。As the saponification catalyst, sodium hydroxide,
Alkali catalysts such as alkali metal hydroxides and alcoholates such as potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate can be used. The amount of such a catalyst to be used may be 1 to 100 millimole equivalent to the vinyl ester compound. Preferably, it is 3 to 30 mmol equivalent. In addition, depending on the case, it is also possible to saponify with an acid catalyst.
【００２９】かくして、末端に炭素数４以上の長鎖アル
キル基を有し、かつ分子量分布が２．５〜３．５のポリ
ビニルアルコール系樹脂が得られるのであるが、本発明
では、かかるポリビニルアルコール系樹脂のケン化度を
９０モル％以上（さらには９５モル％、特には９７．８
モル％以上、殊に９９モル％以上）にする必要があり、
かかるケン化度が９０モル％未満では、乳化重合用分散
安定剤に用いたときに得られるエマルジョンの皮膜の耐
水性が不充分で不適である。Thus, a polyvinyl alcohol resin having a long-chain alkyl group having 4 or more carbon atoms at the end and having a molecular weight distribution of 2.5 to 3.5 can be obtained. In the present invention, such polyvinyl alcohol is used. The saponification degree of the resin is 90 mol% or more (further 95 mol%, especially 97.8).
Mol% or more, especially 99 mol% or more),
When the degree of saponification is less than 90 mol%, the water resistance of the emulsion film obtained when used as a dispersion stabilizer for emulsion polymerization is insufficient and unsuitable.
【００３０】なお、ポリビニルアルコール系樹脂の分子
量分布が上記の範囲外では、乳化重合用分散安定剤に用
いたときに得られるエマルジョンの低温保存安定性が不
充分となって不適である。かかる分子量分布のさらに好
ましい範囲は２．６〜３．３で、本発明の分子量分布
は、ＰＶＡを完全ケン化し、再酢化して、ＴＨＦを展開
液とし、ＧＰＣで測定されるスチレン換算の分子量分布
値である。If the molecular weight distribution of the polyvinyl alcohol resin is outside the above range, the emulsion obtained when used as a dispersion stabilizer for emulsion polymerization has an insufficient low-temperature storage stability and is not suitable. The more preferable range of the molecular weight distribution is 2.6 to 3.3, and the molecular weight distribution of the present invention is that the PVA is completely saponified, reaceticated, and THF is used as a developing solution, and the molecular weight in terms of styrene is measured by GPC. It is a distributed value.
【００３１】また、得られるポリビニルアルコール系樹
脂の平均重合度は特に制限されないが、２５０〜３００
０（さらには８５０〜２８００、特には１０００〜２６
００）が好ましく、かかる平均重合度が２５０未満で
は、乳化重合用分散安定剤に用いたときに得られるエマ
ルジョンを接着剤用途等に供したときに接着力が充分に
発現できなかったり、エマルジョン粘度が低くなった
り、エマルジョンの凝集を引き起こしたりして好ましく
ない。逆に３０００を越えると該エマルジョンの粘度が
高くなりすぎたり、該エマルジョンを接着剤用途等に供
したときの作業性が低下したりして好ましくない。The average degree of polymerization of the obtained polyvinyl alcohol resin is not particularly limited, but it is 250 to 300.
0 (further 850-2800, especially 1000-26)
00) is preferable, and when the average degree of polymerization is less than 250, when the emulsion obtained when used as a dispersion stabilizer for emulsion polymerization is used for adhesives or the like, the adhesive force cannot be sufficiently expressed, or the emulsion viscosity is low. Is low or causes aggregation of the emulsion, which is not preferable. On the other hand, when it exceeds 3000, the viscosity of the emulsion becomes too high, and the workability when the emulsion is used for an adhesive or the like is deteriorated, which is not preferable.
【００３２】かくして、本発明のポリビニルアルコール
系樹脂が得られるのであるが、かかるポリビニルアルコ
ール系樹脂は上述のように、乳化重合用分散安定剤とし
て大変有用で、かかる分散安定剤用途について説明す
る。かかる分散安定剤を用いてエマルジョンを得るには
以下の要領で得ることができる。Thus, the polyvinyl alcohol-based resin of the present invention can be obtained. As described above, the polyvinyl alcohol-based resin is very useful as a dispersion stabilizer for emulsion polymerization, and the use of such a dispersion stabilizer will be described. To obtain an emulsion using such a dispersion stabilizer, the emulsion can be obtained as follows.
【００３３】乳化重合を行う際には、上記の乳化重合用
分散安定剤、水及び重合触媒の存在下に不飽和単量体を
一時又は連続的に添加して、加熱・撹拌するが如き通常
の乳化重合法が実施され得る。かかる乳化重合用分散安
定剤は、粉末のまま或いは水溶液にして水媒体に加えら
れる。使用量は、目的とするエマルジョンの粘度や要求
されるエマルジョンの樹脂分等によって多少異なるが、
通常は不飽和単量体に対して１〜３０重量％、好ましく
は４〜１５重量％程度の範囲から好適に選択される。When emulsion polymerization is carried out, the unsaturated monomer is added temporarily or continuously in the presence of the above dispersion stabilizer for emulsion polymerization, water and a polymerization catalyst, and the mixture is usually heated and stirred. The emulsion polymerization method of can be carried out. The dispersion stabilizer for emulsion polymerization is added to the aqueous medium as a powder or in the form of an aqueous solution. The amount used will vary slightly depending on the desired emulsion viscosity, required emulsion resin content, etc.
Usually, it is suitably selected from the range of about 1 to 30% by weight, preferably about 4 to 15% by weight, based on the unsaturated monomer.
【００３４】使用される触媒としては、ラジカル発生剤
なかんずく水溶性触媒が好適に用いられ、例えば過硫酸
カリウム、過硫酸アンモニウム等がそれぞれ単独又は酸
性亜硫酸ナトリウムと併用して用いられる。また、過酸
化水素−酒石酸、過酸化水素−鉄塩、過酸化水素−アス
コルビン酸−鉄塩、過酸化水素−ロンガリット、過酸化
水素−ロンガリット−鉄塩などのレドックス系触媒が用
いられ、さらには、化薬アクゾ社製『カヤブチルＢ』や
同社製『カヤブチルＡ−５０Ｃ』等の有機過酸化物とレ
ドッックス系からなる触媒が用いられる。必要に応じて
さらに各種界面活性剤（例えばドデシルベンゼンスルホ
ン酸、脂肪酸塩等のアニオン系界面活性剤、ノニオン系
界面活性剤など）あるいは乳化剤（例えばカルボキシメ
チルセルロース，ヒドロキシエチルセルロース，メチル
セルロース等のセルロース誘導体、ポリアクリル酸誘導
体、（無水）マレイン酸−ビニルエーテル共重合体、
（無水）マレイン酸−酢酸ビニル共重合体、酢酸ビニル
−（メタ）アリルスルホン酸（塩）共重合体ケン化物な
ど）、保護コロイドとして上記のＰＶＡ以外の公知の各
種ＰＶＡ及びＰＶＡ誘導体も適宜併用することもでき
る。As the catalyst to be used, a water-soluble catalyst such as a radical generator is preferably used. For example, potassium persulfate, ammonium persulfate and the like are used alone or in combination with sodium acid sulfite. Further, redox catalysts such as hydrogen peroxide-tartaric acid, hydrogen peroxide-iron salt, hydrogen peroxide-ascorbic acid-iron salt, hydrogen peroxide-Rongalit, hydrogen peroxide-Rongalit-iron salt are used. A catalyst composed of an organic peroxide such as "Kayabutyl B" manufactured by Kayaku Akzo Co., Ltd. and "Kayabutyl A-50C" manufactured by the same company and a redox system is used. If necessary, various surfactants (for example, anionic surfactants such as dodecylbenzenesulfonic acid and fatty acid salts, nonionic surfactants, etc.) or emulsifiers (for example, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, Acrylic acid derivative, (anhydrous) maleic acid-vinyl ether copolymer,
(Anhydrous) maleic acid-vinyl acetate copolymer, vinyl acetate- (meth) allyl sulfonic acid (salt) copolymer saponification product, etc.), and various known PVA and PVA derivatives other than the above-mentioned PVA as protective colloid are also appropriately used. You can also do it.
【００３５】さらに、フタル酸エステルや燐酸エステル
等の可塑剤、炭酸ナトリウム，酢酸ナトリウム，燐酸ナ
トリウム等のｐＨ調整剤等も併用され得る。Further, a plasticizer such as phthalic acid ester or phosphoric acid ester, a pH adjusting agent such as sodium carbonate, sodium acetate, sodium phosphate, etc. may be used in combination.
【００３６】乳化重合の対象となる不飽和単量体として
は、エチレン系不飽和単量体やブタジエン系単量体等が
挙げられ、エチレン系不飽和単量体としては、酢酸ビニ
ル、アクリル酸エステル、メタクリル酸エステル等のア
クリル系単量体、塩化ビニル、塩化ビニリデン、アクリ
ロニトリル、スチレン等が挙げられ、これらの単独重合
若しくは共重合が実施され、好適には酢酸ビニルモノマ
ーが使用される。The unsaturated monomers to be emulsion-polymerized include ethylenically unsaturated monomers and butadiene-based monomers, and the ethylenically unsaturated monomers include vinyl acetate and acrylic acid. Examples thereof include acrylic monomers such as esters and methacrylic acid esters, vinyl chloride, vinylidene chloride, acrylonitrile, styrene and the like, and homopolymerization or copolymerization of these is preferably carried out, and vinyl acetate monomer is preferably used.
【００３７】また、ブタジエン系単量体としては、ブタ
ジエン−１，３、２−メチルブタジエン、１，３又は
２，３−ジメチルブタジエン−１，３、２−クロロブタ
ジエン−１，３等があり、単独又はエチレン性不飽和単
量体と混合して用いられる。これらの中でもブタジエン
−１，３とスチレン、ブタジエン−１，３とスチレンと
（メタ）アクリル酸、ブタジエン−１，３とアクリロニ
トリル、ブタジエン−１，３とアクリロニトリルとスチ
レン、ブタジエン−１，３とアクリロニトリルと（メ
タ）アクリル酸、ブタジエン−１，３とメタクリル酸メ
チル、ブタジエン−１，３とメタクリル酸メチルと（メ
タ）アクリル酸等の組み合わせで重合を行うことも可能
である。Examples of the butadiene-based monomer include butadiene-1,3,2-methylbutadiene, 1,3 or 2,3-dimethylbutadiene-1,3, and 2-chlorobutadiene-1,3. , Alone or as a mixture with an ethylenically unsaturated monomer. Among these, butadiene-1,3 and styrene, butadiene-1,3 and styrene and (meth) acrylic acid, butadiene and 1,3 and acrylonitrile, butadiene and 1,3 and acrylonitrile and styrene, and butadiene and 1,3 and acrylonitrile. It is also possible to carry out the polymerization with a combination of and (meth) acrylic acid, butadiene-1,3 and methyl methacrylate, butadiene-1,3 and methyl methacrylate, and (meth) acrylic acid.
【００３８】上記の如きビニル樹脂系エマルジョンは、
接着剤、バインダー、コーティング剤、内装用塗料等に
用いることができ、特に接着剤として有用で、かかる接
着剤として用いるにあたっては、エマルジョンは通常固
形分濃度３０〜６０％程度で使用され、その固形分中の
添加剤量が１〜３０重量％程度で、充填剤、消泡剤（或
いは発泡剤）、着色剤、造膜助剤、防腐・防虫剤、防錆
剤等の添加物が配合されて接着剤用途に供される。ま
た、対象となる接着物（被着体）としては、木材、紙、
プラスチックス、繊維等が挙げられる。The vinyl resin emulsion as described above is
It can be used in adhesives, binders, coating agents, interior paints, etc., and is particularly useful as an adhesive. When used as such an adhesive, an emulsion is usually used at a solid content concentration of about 30 to 60%. Additives such as fillers, antifoaming agents (or foaming agents), coloring agents, film-forming aids, antiseptic / insecticides, and rust-preventive agents are compounded in the content of about 1 to 30% by weight. To be used for adhesives. In addition, as the target adhesive (adherend), wood, paper,
Examples include plastics and fibers.
【００３９】以上、本発明のポリビニルアルコール系樹
脂の乳化重合用分散安定剤用途について説明したが、本
発明のポリビニルアルコール系樹脂は、この用途以外に
も、以下の用途を挙げることができる。The application of the dispersion stabilizer for emulsion polymerization of the polyvinyl alcohol-based resin of the present invention has been described above, but the polyvinyl alcohol-based resin of the present invention can be used in the following applications in addition to this application.
【００４０】（１）接着剤関係
木材、紙、アルミ箔、プラスチック等の接着剤、粘着
剤、再湿剤、不織布用バインダー、石膏ボードや繊維板
等の各種建材用バインダー、各種粉体造粒用バインダ
ー、セメントやモルタル用添加剤、ホットメルト型接着
力、感圧接着剤、アニオン性塗料の固着剤、等。(1) Adhesives Adhesives for wood, paper, aluminum foil, plastics, etc., adhesives, rewetting agents, binders for non-woven fabrics, binders for various building materials such as gypsum board and fiber board, various powder granulations Binders, additives for cement and mortar, hot melt adhesives, pressure-sensitive adhesives, anionic paint fixing agents, etc.
【００４１】（２）成形物関係
繊維、フィルム（特に農薬、洗剤、洗濯用衣類、土木用
添加剤、殺菌剤、染料、顔料等の物品包装用の易水溶性
フィルム：ポリビニルアルコール系樹脂のケン化度とし
ては６５〜９８モル％が好ましい）、シート、パイプ、
チューブ、防漏膜、暫定皮膜、ケミカルレース用、水溶
性繊維、等。(2) Molded product-related fibers and films (especially agricultural chemicals, detergents, laundry clothes, additives for civil engineering, bactericides, dyes, pigments, etc.) The degree of chemical conversion is preferably 65 to 98 mol%), sheet, pipe,
Tube, leak-proof film, temporary film, for chemical lace, water-soluble fiber, etc.
【００４２】（３）被覆剤関係
紙のクリアーコーティング剤、紙の顔料コーティング
剤、紙のサイジング剤、繊維製品用サイズ剤、経糸糊
剤、繊維加工剤、皮革仕上げ剤、塗料、防曇剤、金属腐
食防止剤、亜鉛メッキ用光沢剤、帯電防止剤、導電剤、
暫定塗料、等。(3) Coating-related materials Clear coating agent for paper, pigment coating agent for paper, sizing agent for paper, sizing agent for textile products, warp sizing agent, textile processing agent, leather finishing agent, paint, anti-fog agent, Metal corrosion inhibitor, zinc plating brightener, antistatic agent, conductive agent,
Temporary paint, etc.
【００４３】（４）乳化剤関係
エチレン性不飽和化合物、ブタジエン性化合物、各種ア
クリル系モノマーの乳化重合用乳化剤、ポリオレフィ
ン、ポリエステル樹脂等の疎水性樹脂、エポキシ樹脂、
パラフィン、ビチューメン等の後乳化剤、等。(4) Emulsifier Relation Ethylenically unsaturated compounds, butadiene compounds, emulsifiers for emulsion polymerization of various acrylic monomers, hydrophobic resins such as polyolefins and polyester resins, epoxy resins,
Post-emulsifiers such as paraffin and bitumen, etc.
【００４４】（５）懸濁剤関係
塗料、墨汁、水性カラー、接着剤等の顔料分散安定剤、
塩化ビニル、塩化ビニリデン、スチレン、（メタ）アク
リレート、酢酸ビニル等の各種ビニル化合物の懸濁重合
用分散安定剤、等。(5) Suspension-related paint, pigment dispersion stabilizer such as India ink, aqueous color, adhesive,
Dispersion stabilizers for suspension polymerization of various vinyl compounds such as vinyl chloride, vinylidene chloride, styrene, (meth) acrylate and vinyl acetate.
【００４５】（６）疎水性樹脂用ブレンド剤関係
疎水性樹脂の帯電防止剤、及び親水性付与剤、複合繊
維、フィルムその他成形物用添加剤、等。(6) Hydrophobic resin blending agent-related agents: Antistatic agents for hydrophobic resins, hydrophilicity-imparting agents, additives for composite fibers, films and other molded articles.
【００４６】（７）増粘剤関係
各種水溶液やエマルジョンの増粘剤、等。
（８）凝集剤関係
水中懸濁物及び溶存物の凝集剤、パルプ、スラリーの濾
水性、等。(7) Thickener-related thickeners for various aqueous solutions and emulsions, etc. (8) Flocculant-related Flocculant for suspended solids and dissolved substances, pulp, drainage of slurry, and the like.
【００４７】（９）土壌改良剤関係
（10）感光剤、感電子関係、感光性レジスト樹脂、等。
（11）その他イオン交換樹脂、イオン交換膜関係、キレ
ート交換樹脂、糊剤、等。(9) Soil conditioner-related (10) Photosensitizer, electron-sensitive, photosensitive resist resin, etc. (11) Other ion exchange resins, ion exchange membranes, chelate exchange resins, sizing agents, etc.
【００４８】[0048]
【実施例】以下、本発明について実施例を挙げて更に詳
しく説明する。尚、例中に断りのない限り、「％」、
「部」とあるのは、重量基準を示す。EXAMPLES The present invention will be described in more detail below with reference to examples. Unless otherwise specified, "%",
The term "part" indicates a weight basis.
【００４９】実施例１
先ず、予備実験として、ラウリルメルカプタン（連鎖移
動剤）存在下での酢酸ビニルの重合を行いラウリルメル
カプタンの連鎖移動定数（Ｃｘ＝２２）を決定した。さ
らに、別の予備実験から、以下の重合条件での初期重合
速度（Ｒｐ＝２．７×１０-4モル/リットル/秒）を求めた。Example 1 First, as a preliminary experiment, vinyl acetate was polymerized in the presence of lauryl mercaptan (chain transfer agent) to determine the chain transfer constant (Cx = 22) of lauryl mercaptan. Further, from another preliminary experiment, the initial polymerization rate (Rp = 2.7 × 10 −4 mol / l / sec) under the following polymerization conditions was determined.
【００５０】酢酸ビニル（Ｓ）８００ｇおよびメタノー
ル（Ｍ）３６０ｇ（Ｓ／Ｍ＝０．４５）を反応缶に仕込
み、内部を十分に窒素置換した後、瞬間重合度を２２０
として本文中の（１）式より算出される量の初期ラウリ
ルメルカプタン０．３５ｇを反応缶内部に加えた。続い
て、重合開始剤ＡＩＢＮ（アゾビスイソブチロニトリ
ル）０．０２６モル％（仕込みモノマーに対して）を反
応液に加えて重合反応を開始した。800 g of vinyl acetate (S) and 360 g of methanol (M) (S / M = 0.45) were charged into a reaction vessel, and the interior was sufficiently replaced with nitrogen.
Then, 0.35 g of the initial lauryl mercaptan calculated in the formula (1) in the text was added to the inside of the reaction vessel. Then, the polymerization initiator AIBN (azobisisobutyronitrile) 0.026 mol% (relative to the charged monomer) was added to the reaction solution to start the polymerization reaction.
【００５１】ＡＩＢＮを仕込んだ後、ジャケット温度を
７０℃にした。反応缶の還流が始まると同時に、本文中
の（２）式で求められる仕込量（１．１×１０-6モル/リット
ル/秒）のラウリルメルカプタンを５００秒（ｔ）間隔で
重合率が６２％になるまで断続的に添加して、その後は
ラウリルメルカプタンの添加を止めて重合率が８７％に
なるまで重合を行った。続いて、残存モノマーを追い出
した後、得られたポリ酢酸ビニルのペースト１００部
（樹脂分４５％）に対して２％の水酸化ナトリウムのメ
タノール溶液を１０ミリモル当量（対酢酸ビニルユニッ
トに対して）加えてケン化化反応を行った後、中和、メ
タノールで洗浄後、十分に乾燥を行って、本発明のポリ
ビニルアルコール系樹脂を得た。After charging AIBN, the jacket temperature was raised to 70 ° C. At the same time when the reflux of the reaction vessel started, the polymerization amount of lauryl mercaptan of the charged amount (1.1 × 10 −6 mol / l / sec) calculated by the formula (2) in the text at the interval of 500 sec (t) was 62. % Until the polymerization rate reached 87% by stopping the addition of lauryl mercaptan. Subsequently, after the residual monomer was expelled, 10 mmol equivalent of a methanol solution of 2% sodium hydroxide was added to 100 parts of the obtained polyvinyl acetate paste (resin content: 45%) (based on the vinyl acetate unit). ) In addition, a saponification reaction was performed, followed by neutralization, washing with methanol, and sufficient drying to obtain a polyvinyl alcohol resin of the present invention.
【００５２】得られたポリビニルアルコール系樹脂のケ
ン化度は９９．７モル％、分子量分布は３．２１（Ｍｗ
＝１．６０×１０5、Ｍｎ＝４．９９×１０4）で、ま
た、末端にラウリル基を有することが1Ｈ−ＮＭＲによ
り確認された。The polyvinyl alcohol resin thus obtained has a saponification degree of 99.7 mol% and a molecular weight distribution of 3.21 (Mw).
= 1.60 × 10 5 , Mn = 4.99 × 10 4 ) and having a lauryl group at the terminal was confirmed by 1 H-NMR.
【００５３】得られたポリビニルアルコール系樹脂を乳
化重合用分散安定剤として用いて、以下の要領で酢酸ビ
ニル樹脂エマルジョンの製造を行って、該エマルジョン
の低温安定性および得られる皮膜の耐水性の評価を行っ
た。Using the obtained polyvinyl alcohol-based resin as a dispersion stabilizer for emulsion polymerization, a vinyl acetate resin emulsion was produced in the following manner to evaluate the low temperature stability of the emulsion and the water resistance of the obtained film. I went.
【００５４】（酢酸ビニル樹脂エマルジョンの製造）撹
拌器、還流冷却器、滴下ロート、温度計を備えたセパラ
ブルフラスコに水６０部、上記で得られたポリビニルア
ルコール系樹脂を乳化重合用分散安定剤として５部及び
ｐＨ調整剤として酢酸ナトリウム２％（対ＰＶＡ）、酢
酸ビニルモノマー４．５部を仕込み、撹拌しながらフラ
スコ内の温度を６５℃に上げた。その間窒素ガスでフラ
スコ内を置換しながら、酢酸ビニルモノマーに対して過
酸化水素を０．２％、酒石酸を０．１６％添加して重合
を開始した。初期重合を開始と同時に残りの酢酸ビニル
モノマー４０．５部を３時間かけて滴下し、更に総仕込
み予定の酢酸ビニルモノマーの総量に対して０．２％の
過酸化水素と０．１６％の酒石酸を１時間毎に４分割し
て仕込みながら重合を行った。その後、７５℃で１時間
熟成した後冷却して、固形分４４．５％、粘度２４９０
０ｍＰａ・ｓｅｃ（２５℃）の酢酸ビニルのエマルジョ
ンを得た。(Production of Vinyl Acetate Resin Emulsion) 60 parts of water was placed in a separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer. The polyvinyl alcohol resin obtained above was added as a dispersion stabilizer for emulsion polymerization. 5 parts, sodium acetate 2% (vs PVA) as a pH adjuster, and 4.5 parts of vinyl acetate monomer were charged, and the temperature in the flask was raised to 65 ° C. with stirring. During that time, while displacing the inside of the flask with nitrogen gas, 0.2% of hydrogen peroxide and 0.16% of tartaric acid were added to the vinyl acetate monomer to initiate polymerization. Simultaneously with the start of the initial polymerization, the remaining 40.5 parts of vinyl acetate monomer was added dropwise over 3 hours, and 0.2% hydrogen peroxide and 0.16% of the total amount of vinyl acetate monomer to be charged were added. Polymerization was carried out while charging tartaric acid in four portions every hour. Then, the mixture was aged at 75 ° C for 1 hour and then cooled to give a solid content of 44.5% and a viscosity of 2490.
An emulsion of vinyl acetate having 0 mPa · sec (25 ° C.) was obtained.
【００５５】（低温保存安定性）得られたエマルジョン
の粘度を室温（２５℃）で、Ｂ型粘度計を用いて測定
し、その後、同様に１日、２日、３日、６日放置後の粘
度を測定して、製造時の粘度との比を求めた。(Low-temperature storage stability) The viscosity of the obtained emulsion was measured at room temperature (25 ° C.) using a B-type viscometer, and then left for 1 day, 2 days, 3 days, 6 days in the same manner. Was measured to determine the ratio with the viscosity at the time of production.
【００５６】（皮膜の耐水性）得られたエマルジョンを
２０℃、６５％ＲＨの雰囲気下で、ＰＥＴフィルム上に
流延し、１０日間放置して、膜厚約１２０μｍの試験片
（皮膜）を作製後、該皮膜を透明の５ｍｍ厚のガラス板
上に置き、これを８ポイント文字を印字した紙の上に置
いて、皮膜上に水を一滴落として、該文字が見えなくな
るまでの時間を測定した（ＪＩＳ Ｋ６８２８に準
拠）。(Water resistance of film) The obtained emulsion was cast on a PET film in an atmosphere of 20 ° C. and 65% RH and left for 10 days to give a test piece (film) having a film thickness of about 120 μm. After preparation, the film was placed on a transparent glass plate with a thickness of 5 mm, placed on a paper on which 8-point characters were printed, and a drop of water was dropped on the film until the characters disappeared. It was measured (according to JIS K6828).
【００５７】実施例２
実施例１において、酢酸ビニル（Ｍ）およびメタノール
（Ｓ）の仕込量を８００ｇおよび２００ｇ（Ｓ／Ｍ＝
０．２５）とし、連鎖移動剤の添加終了時期を重合率４
９％の時点として、最終の重合率を６８％にした以外は
同様に行って、ケン化度はが９９．５モル％、分子量分
布が２．８１（Ｍｗ＝２．４９×１０5、Ｍｎ＝８．８
５×１０4）で末端にラウリル基を有するポリビニルア
ルコール系樹脂を得た。得られたポリビニルアルコール
系樹脂を乳化重合用分散安定剤として用いて、実施例１
と同様に評価を行った。Example 2 In Example 1, the charged amounts of vinyl acetate (M) and methanol (S) were 800 g and 200 g (S / M =
0.25), and when the addition of the chain transfer agent is completed, the polymerization rate is 4
At 9%, the same procedure was performed except that the final polymerization rate was set to 68%, the saponification degree was 99.5 mol%, and the molecular weight distribution was 2.81 (Mw = 2.49 × 10 5 , Mn). = 8.8
A polyvinyl alcohol resin having a lauryl group at the end was obtained at 5 × 10 4 ). Using the obtained polyvinyl alcohol resin as a dispersion stabilizer for emulsion polymerization, Example 1
It evaluated similarly to.
【００５８】実施例３
実施例１において、最終の重合率を７０％にした以外は
同様に行って、ケン化度が９９．２モル％、分子量分布
が２．９３（Ｍｗ＝１．７９×１０5、Ｍｎ＝６．１０
×１０4）で末端にラウリル基を有するポリビニルアル
コール系樹脂を得た。得られたポリビニルアルコール系
樹脂を乳化重合用分散安定剤として用いて、実施例１と
同様に評価を行った。Example 3 The same procedure as in Example 1 was repeated except that the final polymerization rate was 70%. The saponification degree was 99.2 mol% and the molecular weight distribution was 2.93 (Mw = 1.79 ×). 10 5 , Mn = 6.10
A polyvinyl alcohol-based resin having a lauryl group at the end was obtained at × 10 4 ). Using the obtained polyvinyl alcohol-based resin as a dispersion stabilizer for emulsion polymerization, evaluation was performed in the same manner as in Example 1.
【００５９】実施例４
実施例１において、ラウリルメルカプタンを１秒（ｔ）
間隔で重合率が４４％になるまで連続的に添加して、そ
の後はラウリルメルカプタンの添加を止めて重合率が９
０％になるまで重合を行った以外は同様に行って、ケン
化度が９９．５モル％、分子量分布が３．１（Ｍｗ＝
１．７１×１０5、Ｍｎ＝５．４８×１０4）で末端にラ
ウリル基を有するポリビニルアルコール系樹脂を得た。
得られたポリビニルアルコール系樹脂を乳化重合用分散
安定剤として用いて、実施例１と同様に評価を行った。Example 4 In Example 1, lauryl mercaptan was added for 1 second (t).
Continuously added at intervals until the rate of polymerization reached 44%, after which the addition of lauryl mercaptan was stopped and the rate of polymerization reached 9%.
The same procedure was carried out except that the polymerization was carried out to 0%, and the saponification degree was 99.5 mol% and the molecular weight distribution was 3.1 (Mw =
A polyvinyl alcohol resin having a lauryl group at the end was obtained at 1.71 × 10 5 , Mn = 5.48 × 10 4 ).
Using the obtained polyvinyl alcohol-based resin as a dispersion stabilizer for emulsion polymerization, evaluation was performed in the same manner as in Example 1.
【００６０】比較例１
実施例１において、重合率１５％まで連鎖移動剤の添加
を続けた以外は、同様に行って、ケン化度が９７．８モ
ル％、分子量分布が２．３８（Ｍｗ＝２．３８×１
０5、Ｍｎ＝１．００×１０4）で末端にラウリル基を有
するポリビニルアルコール系樹脂を得た。得られたポリ
ビニルアルコール系樹脂を乳化重合用分散安定剤として
用いて、実施例１と同様に評価を行った。Comparative Example 1 The procedure of Example 1 was repeated, except that the chain transfer agent was continuously added until the polymerization rate reached 15%. The saponification degree was 97.8 mol% and the molecular weight distribution was 2.38 (Mw). = 2.38 × 1
A polyvinyl alcohol-based resin having a lauryl group at the end was obtained with an Mn of 0 5 and Mn = 1.00 × 10 4 . Using the obtained polyvinyl alcohol-based resin as a dispersion stabilizer for emulsion polymerization, evaluation was performed in the same manner as in Example 1.
【００６１】比較例２
実施例１において、ケン化触媒量を減らした以外は同様
に行ってケン化度８８モル％のポリビニルアルコール系
樹脂を得た。得られたポリビニルアルコール系樹脂を乳
化重合用分散安定剤として用いて、実施例１と同様に評
価を行った。Comparative Example 2 A polyvinyl alcohol resin having a saponification degree of 88 mol% was obtained in the same manner as in Example 1 except that the amount of the saponification catalyst was reduced. Using the obtained polyvinyl alcohol-based resin as a dispersion stabilizer for emulsion polymerization, evaluation was performed in the same manner as in Example 1.
【００６２】比較例３
実施例１において、連鎖移動剤を使用せずに、ケン化が
９９．７モル％、分子量分布が２．１（Ｍｗ＝２．０３
×１０5、Ｍｎ＝９．２７×１０4）で末端にラウリル基
を有しないポリビニルアルコール系樹脂を得た。得られ
たポリビニルアルコール系樹脂を乳化重合用分散安定剤
として用いて、実施例１と同様に評価を行った。Comparative Example 3 In Example 1, without using a chain transfer agent, saponification was 99.7 mol%, and molecular weight distribution was 2.1 (Mw = 2.03).
A polyvinyl alcohol resin having a lauryl group at the terminal was obtained with a molecular weight of × 10 5 and Mn = 9.27 × 10 4 . Using the obtained polyvinyl alcohol-based resin as a dispersion stabilizer for emulsion polymerization, evaluation was performed in the same manner as in Example 1.
【００６３】実施例及び比較例の評価結果を表１に示
す。Table 1 shows the evaluation results of the examples and the comparative examples.
【００６４】 〔表１〕 低 温 保 存 安 定 性 皮膜の耐水性 製造時の粘度 経時粘度比 （mPa・s） １日 ２日 ３日 ６日 実施例１ ２４９００ 1.9 2.5 2.7 3.0 ７分１８秒 〃 ２ ３４０００ 2.2 2.9 3.5 4.0 ６分５５秒 〃 ３ ２２５００ 2.4 2.3 3.2 3.5 ６分４５秒 〃 ４ ２３９００ 2.0 2.4 2.6 2.8 ７分 ８秒 比較例１ １０５００ 1.9 2.5 2.7 3.0 ４分２５秒 〃 ２ ５２０００ 1.2 1.4 1.5 1.7 １分１０秒 〃 ３ １３５００ 5.0 6.8 ＊ ＊ ３分５６秒 ＊ゲル状で粘度測定不能[0064] Table 1 water resistance produced when the viscosity with time the viscosity ratio of the low temperature preserved STABILITY film (mPa · s) 2 days 3 days 6 days 1 day Example 1 24900 1.9 2.5 2.7 3.0 7 min 18 seconds 〃 2 34000 2.2 2.9 3.5 4.0 6 minutes 55 seconds 〃 3 22500 2.4 2.3 3.2 3.5 6 minutes 45 seconds 〃 4 23900 2.0 2.4 2.6 2.8 7 minutes 8 seconds Comparative Example 1 10500 1.9 2.5 2.7 3.0 4 minutes 25 seconds 〃 2 52000 1.2 1.4 1.5 1.7 1 minute 10 seconds 〃 3 13500 5.0 6.8 ** 3 minutes 56 seconds * Viscosity cannot be measured in gel form
【００６５】[0065]
【発明の効果】本発明のポリビニルアルコール系樹脂
は、ケン化度が９０モル％以上で、末端に炭素数４以上
の長鎖アルキル基を有し、かつ分子量分布が２．５〜
３．５であるため、特に乳化重合用分散安定剤に有用
で、低温保存安定性に優れ、かつ耐水性に優れた皮膜を
形成するエマルジョンを得ることができ、この用途以外
にも、懸濁重合用分散剤、接着剤、糊剤、フィルム、紙
加工剤等にも有用である。Industrial Applicability The polyvinyl alcohol resin of the present invention has a saponification degree of 90 mol% or more, has a long-chain alkyl group having 4 or more carbon atoms at the end, and has a molecular weight distribution of from 2.5 to 2.5.
Since it is 3.5, it is particularly useful as a dispersion stabilizer for emulsion polymerization, and it is possible to obtain an emulsion that forms a film having excellent low-temperature storage stability and excellent water resistance. It is also useful as a dispersant for polymerization, an adhesive, a sizing agent, a film, a paper processing agent and the like.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｆ 8/12 Ｃ０８Ｆ 8/12 Ｆターム(参考） 4D077 AA10 AB14 AC05 BA01 BA02 DC26Z DD15X 4J011 AA05 BB01 BB06 BB09 BB12 DA01 DA04 DB12 DB27 HA04 HB02 HB06 HB14 HB22 KA16 KA23 KB02 KB05 KB09 KB12 KB22 KB29 NA25 NA30 NB05 NC02 4J100 AA01R AA15R AC02R AC03R AE02R AE18R AG02P AG02Q AG03P AG03Q AG04P AG04Q AG05P AG05Q AG08P AG08Q AJ01R AJ02R AJ08R AL08R AM02R AM15R AM21R AN04R AP01R AQ08R BA03H BA03R BA08R BA32R BA56R BB18P BB18Q CA01 CA04 CA31 DA01 DA04 DA28 DA32 DA40 EA06 FA03 FA04 FA19 FA28 FA39 FA41 HA09 HB39 HC09 HC12 JA01 JA03 JA15 JA18 JA67 Front page continued (51) Int.Cl. 7 Identification code FI theme code (reference) C08F 8/12 C08F 8/12 F term (reference) 4D077 AA10 AB14 AC05 BA01 BA02 DC26Z DD15X 4J011 AA05 BB01 BB06 BB09 BB12 DA01 DA04 DB12 DB27 HA04 HB02 HB06 HB14 HB22 KA16 KA23 KB02 KB05 KB09 KB12 KB22 KB29 NA25 NA30 NB05 NC02 4J100 AA01R AA15R AC02R AC03R AE02R AE18R AG02P AG02QAPR AM08R08R APR AM05R AG08R APR AM05R AG08R APR AM05R AG08R APR AM05R BB18P BB18Q CA01 CA04 CA31 DA01 DA04 DA28 DA32 DA40 EA06 FA03 FA04 FA19 FA28 FA39 FA41 HA09 HB39 HC09 HC12 JA01 JA03 JA15 JA18 JA67
Claims (6)
素数４以上の長鎖アルキル基を有し、かつ分子量分布
（Ｍｗ／Ｍｎ）が２．５〜３．５であることを特徴とす
るポリビニルアルコール系樹脂。1. A saponification degree of 90 mol% or more, a long-chain alkyl group having 4 or more carbon atoms at the end, and a molecular weight distribution (Mw / Mn) of 2.5 to 3.5. Characteristic polyvinyl alcohol resin.
の長鎖アルキル基を有する連鎖移動剤の共存下に重合を
開始し、その後炭素数４以上の長鎖アルキル基を有する
連鎖移動剤を断続的あるいは連続的に重合系内に添加し
て目標とする重合率の２０〜８０％の間に該添加を終了
して重合されたビニルエステル系重合体をケン化して得
られた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。2. Polymerization of a vinyl ester compound is initiated in the presence of a chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms, and then the chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms is interrupted. It is obtained by saponifying a vinyl ester polymer which is polymerized after the addition is completed within 20 to 80% of a target polymerization rate by adding it to the polymerization system dynamically or continuously. The polyvinyl alcohol resin according to claim 1.
の長鎖アルキル基を有する連鎖移動剤の共存下に重合を
開始するにあたり、目標とする重合率の２０〜８０％ま
での間に生成させる目標重合度Ｐを得るために、炭素数
４以上の長鎖アルキル基を有する連鎖移動剤を下記
（１）式を満足するように重合開始前に共存させ、引き
続きビニルエステル系化合物の重合開始と同時に、下記
（２）式で示される量の炭素数４以上の長鎖アルキル基
を有する連鎖移動剤をｔ（秒）間隔で添加することを特
徴とする請求項２記載のポリビニルアルコール系樹脂。 １／Ｐ＝Ｃｍ＋Ｃｓ（［Ｓ］／［Ｍ］）＋Ｃｘ（［Ｘ］／［Ｍ］）・・・（１） 仕込量＝Ｃｘ（［Ｘ］／［Ｍ］）×Ｒｐ×ｔ ・・・（２） 〔ここで、Ｐは目的とする重合度、Ｃｍはモノマーの連
鎖移動定数、 Ｃｓは溶媒の連鎖移動定数、Ｃｘは連鎖移動剤の連鎖移
動定数、 ［Ｓ］は溶媒濃度（モル/リットル）、［Ｍ］はモノマー濃度
（モル/リットル）、 ［Ｘ］は連鎖移動剤の初期添加濃度（モル/リットル）、 Ｒｐは重合速度（モル/リットル/秒）をそれぞれ表す〕3. When a vinyl ester compound is polymerized in the coexistence of a chain transfer agent having a long chain alkyl group having 4 or more carbon atoms, the vinyl ester compound is produced within a target polymerization rate of 20 to 80%. In order to obtain the target degree of polymerization P, a chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms is allowed to coexist before the initiation of the polymerization so as to satisfy the following formula (1), and then the polymerization of the vinyl ester compound is initiated. At the same time, a chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms in an amount represented by the following formula (2) is added at t (second) intervals, and the polyvinyl alcohol-based resin according to claim 2. 1 / P = Cm + Cs ([S] / [M]) + Cx ([X] / [M]) ... (1) Charge amount = Cx ([X] / [M]) × Rp × t ... (2) [where P is the desired degree of polymerization, Cm is the chain transfer constant of the monomer, Cs is the chain transfer constant of the solvent, Cx is the chain transfer constant of the chain transfer agent, and [S] is the solvent concentration (mol / mol / Liter), [M] represents the monomer concentration (mol / liter), [X] represents the initial addition concentration of the chain transfer agent (mol / liter), and Rp represents the polymerization rate (mol / liter / second)].
連鎖移動剤がアルキルメルカプタンであることを特徴と
する請求項２または３記載のポリビニルアルコール系樹
脂。4. The polyvinyl alcohol resin according to claim 2, wherein the chain transfer agent having a long-chain alkyl group having 4 or more carbon atoms is alkyl mercaptan.
アルコール系樹脂を用いることを特徴とする乳化重合用
分散安定剤。5. A dispersion stabilizer for emulsion polymerization, which comprises the polyvinyl alcohol resin according to any one of claims 1 to 4.
用いたことを特徴とするビニル樹脂系エマルジョン。6. A vinyl resin emulsion characterized by using the dispersion stabilizer for emulsion polymerization according to claim 5.
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|---|---|---|---|
| JP2001375397A JP3943382B2 (en) | 2001-12-10 | 2001-12-10 | Polyvinyl alcohol resin and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001375397A JP3943382B2 (en) | 2001-12-10 | 2001-12-10 | Polyvinyl alcohol resin and use thereof |
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|---|---|
| JP2003171423A true JP2003171423A (en) | 2003-06-20 |
| JP3943382B2 JP3943382B2 (en) | 2007-07-11 |
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|---|---|---|---|
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