JPH1171434A - Production of aqueous emulsion - Google Patents
Production of aqueous emulsionInfo
- Publication number
- JPH1171434A JPH1171434A JP16536498A JP16536498A JPH1171434A JP H1171434 A JPH1171434 A JP H1171434A JP 16536498 A JP16536498 A JP 16536498A JP 16536498 A JP16536498 A JP 16536498A JP H1171434 A JPH1171434 A JP H1171434A
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- JP
- Japan
- Prior art keywords
- vinyl acetate
- weight
- polyvinyl alcohol
- copolymerization reaction
- parts
- 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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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水性エマルジョン
の製造方法に関するものである。更に詳しくは、本発明
は、固形分濃度が極めて高いエチレン−酢酸ビニル共重
合体系水性エマルジョンの製造方法であって、共重合反
応中における反応系の粘度の上昇を抑制し、かつ安定な
エマルジョンを得ることができるという特徴を有する水
性エマルジョンの製造方法に関するものである。本発明
によりえられる水性エマルジョンは、固形分の濃度が極
めて高く、乾燥効率に優れた接着剤として有用である。TECHNICAL FIELD The present invention relates to a method for producing an aqueous emulsion. More specifically, the present invention relates to a method for producing an ethylene-vinyl acetate copolymer-based aqueous emulsion having a very high solid content, which suppresses a rise in the viscosity of the reaction system during the copolymerization reaction, and provides a stable emulsion. The present invention relates to a method for producing an aqueous emulsion having the characteristic that it can be obtained. The aqueous emulsion obtained by the present invention has an extremely high solid content and is useful as an adhesive having excellent drying efficiency.
【０００２】[0002]
【従来の技術】エチレン−酢酸ビニル共重合体系水性エ
マルジョンは、接着剤として広く使用されている。とこ
ろで、接着剤用途の水性エマルジョンは、乾燥効率の観
点から、固形分の濃度が高いことが要求される。ところ
が、高固形分のエチレン−酢酸ビニル共重合体系水性エ
マルジョンを製造する従来の方法においては、共重合反
応中に反応系の粘度が上昇し、攪拌が不十分になった
り、反応熱の除熱が不十分になり、所望の共重合反応を
安定的に完遂することが困難になるという問題を有して
いた。2. Description of the Related Art Aqueous emulsions of ethylene-vinyl acetate copolymers are widely used as adhesives. By the way, the aqueous emulsion used for the adhesive is required to have a high solid content from the viewpoint of drying efficiency. However, in the conventional method for producing an ethylene-vinyl acetate copolymer-based aqueous emulsion having a high solid content, the viscosity of the reaction system increases during the copolymerization reaction, resulting in insufficient stirring or removal of heat of reaction. Was insufficient, and it was difficult to stably complete the desired copolymerization reaction.
【０００３】[0003]
【発明が解決しようとする課題】かかる状況に鑑み、本
発明が解決しようとする主たる課題は、固形分濃度が極
めて高いエチレン−酢酸ビニル共重合体系水性エマルジ
ョンの製造方法であって、共重合反応中における反応系
の粘度の上昇を抑制し、かつ安定なエマルジョンを得る
ことができるという特徴を有する水性エマルジョンの製
造方法を提供する点に存するものである。SUMMARY OF THE INVENTION In view of the above circumstances, a main problem to be solved by the present invention is a method for producing an ethylene-vinyl acetate copolymer-based aqueous emulsion having a very high solid content, which comprises a copolymerization reaction. An object of the present invention is to provide a method for producing an aqueous emulsion, which is characterized in that a rise in the viscosity of a reaction system in the solution can be suppressed and a stable emulsion can be obtained.
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明は、エ
チレン単位１０〜４０重量％及び酢酸ビニル単位９０〜
６０重量％からなるエチレン−酢酸ビニル共重合体を含
有し、固形分が７０重量％以上であり、かつ粘度が５０
００ｍＰａ・ｓ以下である水性エマルジョンの製造方法
であって、下記（１）〜（４）の特徴を有する水性エマ
ルジョンの製造方法に係るものである。 （１）共重合反応に供する全酢酸ビニルのうちの５０〜
９０％を予め共重合反応の反応系に存在せしめ、共重合
反応に供する全酢酸ビニルのうちの５０〜１０％を共重
合反応の開始後に反応系に供給すること （２）共重合反応に供する全酢酸ビニル１００重量部あ
たり２〜６重量部の乳化分散剤を用い、該乳化分散剤は
ケン化度が８０モル％以上であり、かつ平均重合度が２
００〜１０００であるポリビニルアルコール及びＨＬＢ
が１０〜２０であるポリオキシエチレン非イオン界面活
性剤を含有すること （３）上記のポリビニルアルコールの全使用量は、共重
合反応に供する全酢酸ビニル１００重量部あたり０．４
〜３重量部であり、該ポリビニルアルコールの全使用量
のうちの１０〜５０％を予め共重合反応の反応系に存在
せしめ、ポリビニルアルコールの全使用量のうちの５０
〜９０％を共重合反応の開始後に反応系に供給すること （４）前記のポリオキシエチレン非イオン界面活性剤の
全使用量は、共重合反応に供する全酢酸ビニル１００重
量部あたり１〜５重量部であり、該ポリオキシエチレン
非イオン界面活性剤の全使用量を予め共重合反応の反応
系に存在せしめることThat is, the present invention relates to a method for preparing 10 to 40% by weight of ethylene units and 90 to 90% of vinyl acetate units.
It contains an ethylene-vinyl acetate copolymer of 60% by weight, has a solid content of 70% by weight or more, and has a viscosity of 50%.
A method for producing an aqueous emulsion having a pressure of not more than 00 mPa · s, which relates to a method for producing an aqueous emulsion having the following features (1) to (4). (1) 50 to 50% of the total vinyl acetate subjected to the copolymerization reaction
90% is pre-existing in the reaction system of the copolymerization reaction, and 50 to 10% of the total vinyl acetate to be subjected to the copolymerization reaction is supplied to the reaction system after the start of the copolymerization reaction. 2 to 6 parts by weight of an emulsifying dispersant per 100 parts by weight of total vinyl acetate is used.
Polyvinyl alcohol and HLB which are 00 to 1000
Contains a polyoxyethylene nonionic surfactant having a molecular weight of 10 to 20. (3) The total amount of the polyvinyl alcohol used is 0.4 per 100 parts by weight of the total vinyl acetate used for the copolymerization reaction.
To 3 parts by weight, and 10 to 50% of the total amount of the polyvinyl alcohol is previously present in the reaction system of the copolymerization reaction, and 50% of the total amount of the polyvinyl alcohol is used.
(4) The total amount of the polyoxyethylene nonionic surfactant used is 1 to 5 per 100 parts by weight of the total vinyl acetate used in the copolymerization reaction. Parts by weight, and the total amount of the polyoxyethylene nonionic surfactant used must be present in the reaction system of the copolymerization reaction in advance.
【０００５】[0005]
【発明の実施の形態】本発明の水性エマルジョンは、エ
チレン単位１０〜４０重量％及び酢酸ビニル単位９０〜
６０重量％からなるエチレン−酢酸ビニル共重合体を含
有し、固形分が７０重量％以上であり、かつ粘度が５０
００ｍＰａ・ｓ以下である水性エマルジョンである。固
形分濃度が低くなると接着剤としての乾燥効率に劣る。
粘度が高すぎると接着剤としての塗工性に劣る。なお、
粘度はＢ型粘度計を用い、温度２５℃にて測定する。DETAILED DESCRIPTION OF THE INVENTION The aqueous emulsion of the present invention contains 10 to 40% by weight of ethylene units and 90 to 90% of vinyl acetate units.
It contains an ethylene-vinyl acetate copolymer of 60% by weight, has a solid content of 70% by weight or more, and has a viscosity of 50%.
It is an aqueous emulsion of not more than 00 mPa · s. When the solid content concentration is low, the drying efficiency as an adhesive is inferior.
If the viscosity is too high, the coatability as an adhesive is poor. In addition,
The viscosity is measured at a temperature of 25 ° C. using a B-type viscometer.
【０００６】本発明の製造方法は、前記の（１）〜
（４）の全ての条件を充足する必要がある。[0006] The production method of the present invention is characterized in that
It is necessary to satisfy all the conditions of (4).
【０００７】条件（１）は、共重合反応に供する全酢酸
ビニルのうちの５０〜９０％を予め共重合反応の反応系
に存在せしめ、共重合反応に供する全酢酸ビニルのうち
の５０〜１０％を共重合反応の開始後に反応系に供給す
ること、である。本発明において、予め共重合反応の反
応系に存在せしめる部分を「初期仕込み」と、また共重
合反応の開始後に反応系に供給する部分を「後添加」と
記すことがある。また、本発明において、共重合反応の
開始後とは、反応系に重合触媒を添加し、反応系の温度
が上昇し始めた後を意味する。酢酸ビニルの初期仕込み
の量が過少であっても、過多であっても、エマルジョン
の粘度が上昇する場合がある。本発明において、後添加
の方法としては、連続的添加又は間欠的添加をあげるこ
とができ、添加時間は通常２〜４時間程度である。The condition (1) is that 50 to 90% of the total vinyl acetate to be subjected to the copolymerization reaction is previously present in the reaction system of the copolymerization reaction, and 50 to 90% of the total vinyl acetate to be subjected to the copolymerization reaction. % To the reaction system after the start of the copolymerization reaction. In the present invention, a part which is previously present in the reaction system of the copolymerization reaction may be referred to as “initial preparation”, and a part supplied to the reaction system after the start of the copolymerization reaction may be referred to as “post-addition”. Further, in the present invention, after the start of the copolymerization reaction means after the polymerization catalyst has been added to the reaction system and the temperature of the reaction system has started to rise. Regardless of whether the amount of the initially charged vinyl acetate is too small or too large, the viscosity of the emulsion may increase. In the present invention, as a method of the post-addition, continuous addition or intermittent addition can be mentioned, and the addition time is usually about 2 to 4 hours.
【０００８】条件（２）は、共重合反応に供する全酢酸
ビニル１００重量部あたり２〜６重量部の乳化分散剤を
用い、該乳化分散剤はケン化度が８０モル％以上であ
り、かつ平均重合度が２００〜１０００であるポリビニ
ルアルコール及びＨＬＢが１０〜２０であるポリオキシ
エチレン非イオン界面活性剤を含有すること、である。
乳化分散剤の使用量が過少であるとエマルジョン中に多
くの粕を含むようになり、一方乳化分散剤の使用量が過
多であるとエマルジョンの粘度が上昇する。ポリビニル
アルコールのケン化度が過小であるエマルジョン中に多
くの粕を含むようになる。ポリビニルアルコールの平均
重合度が過小であると、エマルジョン中に多くの粕を含
むようになる。ポリビニルアルコール平均重合度が過大
であるとエマルジョンの粘度が上昇する。ポリオキシエ
チレン非イオン界面活性剤のＨＬＢが過小であるとエマ
ルジョン中に多くの粕を含むようになり、一方該ＨＬＢ
が過大であるとエマルジョンの粘度が上昇する。なお、
ＨＬＢとは界面活性剤の親水性と親油性の相対的なバラ
ンスを数量的に表したものである。The condition (2) is that the emulsifying dispersant is used in an amount of 2 to 6 parts by weight per 100 parts by weight of the total vinyl acetate to be subjected to the copolymerization reaction. It contains a polyvinyl alcohol having an average degree of polymerization of 200 to 1000 and a polyoxyethylene nonionic surfactant having an HLB of 10 to 20.
If the used amount of the emulsifying dispersant is too small, a large amount of the emulsified dispersant will be contained in the emulsion, while if the used amount of the emulsifying dispersant is too large, the viscosity of the emulsion will increase. The emulsion in which the degree of saponification of polyvinyl alcohol is too small contains a large amount of lees. If the average degree of polymerization of polyvinyl alcohol is too small, the emulsion will contain a large amount of lees. If the average degree of polymerization of polyvinyl alcohol is too large, the viscosity of the emulsion increases. If the HLB of the polyoxyethylene nonionic surfactant is too small, the emulsion will contain a large amount of lees, while the HLB
Is too large, the viscosity of the emulsion increases. In addition,
HLB numerically represents the relative balance between hydrophilicity and lipophilicity of a surfactant.
【０００９】ポリビニルアルコールとしては、通常の部
分ケン化ポリビニルアルコール、完全ケン化ポリビニル
アルコール及びスルホン酸変性ポリビニルアルコール、
カルボキシ変性ポリビニルアルコール、シラノール基変
性ポリビニルアルコール、アセトアセチル化ポリビニル
アルコールなどの変性タイプのポリビニルアルコールを
あげることができる。Examples of the polyvinyl alcohol include ordinary partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and sulfonic acid-modified polyvinyl alcohol.
Modified polyvinyl alcohols such as carboxy-modified polyvinyl alcohol, silanol group-modified polyvinyl alcohol, and acetoacetylated polyvinyl alcohol can be given.
【００１０】ポリオキシエチレン非イオン界面活性剤と
しては、ポリエチレンオキサイド・ポリプロピレンオキ
サイドブロック共重合体、ポリエチレンオキサイド・ア
ルキルフェノールエーテル、ポリエチレンオキサイド・
アルキルエーテル等をあげることができる。Examples of the polyoxyethylene nonionic surfactant include polyethylene oxide / polypropylene oxide block copolymer, polyethylene oxide / alkylphenol ether, polyethylene oxide /
Alkyl ethers and the like can be mentioned.
【００１１】条件（３）は、上記のポリビニルアルコー
ルの全使用量は、共重合反応に供する全酢酸ビニル１０
０重量部あたり０．４〜３重量部であり、該ポリビニル
アルコールの全使用量のうちの１０〜５０％を予め共重
合反応の反応系に存在せしめ、ポリビニルアルコールの
全使用量のうちの５０〜９０％を共重合反応の開始後に
反応系に供給すること、である。ポリビニルアルコール
の全使用量が過少であるとエマルジョン中に多くの粕を
含むようになり、一方該使用量が過多であるとエマルジ
ョンの粘度が上昇する。ポリビニルアルコールの初期仕
込みの量が過少であるとエマルジョン中に多くの粕を含
むようになり、一方該初期仕込みの量が過多であるとエ
マルジョンの粘度が上昇する。The condition (3) is that the total amount of the above-mentioned polyvinyl alcohol used is the total amount of vinyl acetate used for the copolymerization reaction.
The amount is 0.4 to 3 parts by weight per 0 parts by weight, and 10 to 50% of the total amount of the polyvinyl alcohol is previously present in the reaction system of the copolymerization reaction, and 50 to 50% of the total amount of the polyvinyl alcohol is used. ~ 90% to the reaction system after the start of the copolymerization reaction. If the total amount of polyvinyl alcohol is too small, the emulsion will contain a large amount of lees, while if the amount is too large, the viscosity of the emulsion will increase. If the amount of the initial charge of polyvinyl alcohol is too small, the emulsion will contain a large amount of lees, while if the amount of the initial charge is too large, the viscosity of the emulsion will increase.
【００１２】条件（４）は、前記のポリオキシエチレン
非イオン界面活性剤の全使用量は、共重合反応に供する
全酢酸ビニル１００重量部あたり１〜５重量部であり、
該ポリオキシエチレン非イオン界面活性剤の全使用量を
予め共重合反応の反応系に存在せしめること、である。
ポリオキシエチレン非イオン界面活性剤の全使用量が過
少であるとエマルジョン中に多くの粕を含むようにな
り、一方該使用量が過多であるとエマルジョンの粘度が
上昇する。The condition (4) is that the total amount of the polyoxyethylene nonionic surfactant used is 1 to 5 parts by weight per 100 parts by weight of the total vinyl acetate to be subjected to the copolymerization reaction.
That is, the total amount of the polyoxyethylene nonionic surfactant to be used is previously present in the reaction system of the copolymerization reaction.
If the total amount of the polyoxyethylene nonionic surfactant is too small, the emulsion will contain a large amount of lees, while if the amount is too large, the viscosity of the emulsion will increase.
【００１３】本発明を実施する好ましい具体例をあげる
と、次のとおりである。重合反応容器に水、初期仕込み
の酢酸ビニル、初期仕込みのポリビニルアルコール及ポ
リオキシエチレン非イオン界面活性剤の全量を仕込み、
次にエチレンを供給し、攪拌しながら重合温度まで加熱
昇温する。ここで、重合温度は、通常３０〜８０℃であ
る。次に、重合触媒を添加する。重合触媒としてはいわ
ゆるレドックス系のものをあげることができる。酸化剤
としては、過酸化水素、ｔ−ブチルパーオキサイド、過
硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム
な度をあげることができる。還元剤としては、ナトリウ
ム（又は亜鉛）ホルムアルデヒドスルホキシレート、グ
リオキザール重亜硫酸ソーダ、第一鉄塩、酒石酸ソーダ
などをあげることができる。重合の開始による温度の上
昇が観測されたら、後添加の酢酸ビニル及びポリビニル
アルコールの添加を開始する。後添加の酢酸ビニルとポ
リビニルアルコールの添加の順序は、同時とすることが
好ましい。後添加の酢酸ビニル及びポリビニルアルコー
ルの添加が完了した後、反応系内の酢酸ビニルの残留量
が、エマルジョンの全重量の１重量％以下程度になった
時点で重合反応を終了する。The preferred embodiments of the present invention are as follows. Into the polymerization reaction vessel, water, initially charged vinyl acetate, initially charged polyvinyl alcohol and the entire amount of polyoxyethylene nonionic surfactant,
Next, ethylene is supplied, and the temperature is raised to the polymerization temperature while stirring. Here, the polymerization temperature is usually 30 to 80 ° C. Next, a polymerization catalyst is added. As the polymerization catalyst, a so-called redox type catalyst can be used. Examples of the oxidizing agent include hydrogen peroxide, t-butyl peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate. Examples of the reducing agent include sodium (or zinc) formaldehyde sulfoxylate, glyoxal sodium bisulfite, ferrous salt, sodium tartrate and the like. When an increase in temperature due to the initiation of polymerization is observed, the addition of post-addition vinyl acetate and polyvinyl alcohol is started. The order of adding the vinyl acetate and polyvinyl alcohol added later is preferably simultaneous. After the addition of the post-added vinyl acetate and polyvinyl alcohol is completed, the polymerization reaction is terminated when the residual amount of vinyl acetate in the reaction system becomes about 1% by weight or less of the total weight of the emulsion.
【００１４】[0014]
【実施例】次に実施例により本発明を具体的に説明す
る。なお、「重量部」は、酢酸ビニルの全使用量を１０
０重量部とした。Next, the present invention will be described in detail with reference to examples. "Parts by weight" refers to a total amount of vinyl acetate of 10 parts.
0 parts by weight.
【００１５】実施例１ 初期仕込みとして、酢酸ビニル７５重量部、ポリビニル
アルコール（クラレ社製「ポバール２０３」、ケン化度
＝８８モル％、平均重合度＝３００）０．４５重量部
（ポリビニルアルコールの全使用量の３３．３％に相当
する。）、ポリオキシエチレン非イオン界面活性剤（花
王社製「エマルゲン９３１」、ＨＬＢ＝１７．２）１．
５０重量部、ポリオキシエチレン非イオン界面活性剤
（旭電化工業社製「プルロニックＬ６４」、ＨＬＢ＝１
０．２）２．２５重量部及び水３６重量部を用いた。Example 1 As an initial charge, 75 parts by weight of vinyl acetate, 0.45 part by weight of polyvinyl alcohol (“Poval 203” manufactured by Kuraray Co., Ltd., degree of saponification = 88 mol%, average degree of polymerization = 300) were used. 33.3% of the total amount used), a polyoxyethylene nonionic surfactant ("Emulgen 931" manufactured by Kao Corporation, HLB = 17.2).
50 parts by weight of a polyoxyethylene nonionic surfactant ("Pluronic L64" manufactured by Asahi Denka Kogyo KK, HLB = 1
0.2) 2.25 parts by weight and 36 parts by weight of water were used.
【００１６】攪拌しながらエチレンを供給し、重合を開
始した。重合は２５℃から開始し、段階的に６０℃まで
昇温し以後６０℃を重合完了まで保った。重合中はエチ
レンで６０℃、４５ｋｇ／ｃｍ2に保持した。重合触媒
としてはレドックス系のものを用いた。還元剤としては
ホルムアルデヒドスルホキシル酸ソーダを酢酸ビニルの
全量に対し０．２５重量部、酸化剤としては過酸化水素
を酢酸ビニルの全量に対し０．１２重量部を使用し、還
元剤はその４５％を初期仕込み時に一括添加し、残りの
還元剤及び酸化剤は重合中連続で添加した。Ethylene was supplied with stirring to initiate polymerization. The polymerization was started at 25 ° C., and the temperature was increased stepwise to 60 ° C., and then maintained at 60 ° C. until the completion of the polymerization. During the polymerization, the temperature was maintained at 60 ° C. and 45 kg / cm 2 with ethylene. A redox catalyst was used as the polymerization catalyst. As a reducing agent, sodium formaldehyde sulfoxylate is used in an amount of 0.25 parts by weight based on the total amount of vinyl acetate. As an oxidizing agent, hydrogen peroxide is used in an amount of 0.12 parts by weight based on the total amount of vinyl acetate. % Was added all at once during the initial preparation, and the remaining reducing agent and oxidizing agent were added continuously during the polymerization.
【００１７】重合開始後、後添加として、酢酸ビニル２
５重量部及びポリビニルアルコール（前記のものに同
じ。）０．９０重量部を連続的に添加した。後添加は重
合開始２時間後から始め、５時間後に終了した。反応系
内の酢酸ビニルの残存量が１％以下程度になったところ
で重合反応を終了した。得られた水性エマルジョンは、
エチレン／酢酸ビニル重量比が２２／７８でありガラス
転移温度が−６℃の共重合体を含み、固形分が７２．８
重量％であり、粘度が６１０ｍＰａ・ｓのものであっ
た。After the initiation of the polymerization, vinyl acetate 2
5 parts by weight and 0.90 parts by weight of polyvinyl alcohol (same as above) were added continuously. The post-addition was started 2 hours after the start of the polymerization and ended after 5 hours. The polymerization reaction was terminated when the residual amount of vinyl acetate in the reaction system became about 1% or less. The resulting aqueous emulsion is
It contains a copolymer having an ethylene / vinyl acetate weight ratio of 22/78 and a glass transition temperature of -6 ° C, and a solid content of 72.8.
% By weight and a viscosity of 610 mPa · s.
【００１８】実施例２ 酢酸ビニル及びポリビニルアルコールの後添加を重合開
始１時間後から始め、５時間後に終了した他は実施例１
と同様に行った。得られた水性エマルジョンは、エチレ
ン／酢酸ビニル重量比が２４／７６でありガラス転移温
度が−９℃の共重合体を含み、固形分が７４．０重量％
であり、粘度が９００ｍＰａ・ｓのものであった。Example 2 Example 1 was repeated except that the post-addition of vinyl acetate and polyvinyl alcohol was started 1 hour after the start of the polymerization and ended 5 hours later.
The same was done. The resulting aqueous emulsion contains a copolymer having an ethylene / vinyl acetate weight ratio of 24/76 and a glass transition temperature of -9 ° C, and a solid content of 74.0% by weight.
And the viscosity was 900 mPa · s.
【００１９】実施例３ 後添加を重合開始３時間後から始め、５時間後に終了し
た他は実施例１と同様に行った。得られた水性エマルジ
ョンは、エチレン／酢酸ビニル重量比が２３／７７であ
りガラス転移温度が−８℃の共重合体を含み、固形分が
７３．５重量％であり、粘度が５３０ｍＰａ・ｓのもの
であった。Example 3 The procedure of Example 1 was repeated, except that the post-addition was started 3 hours after the start of the polymerization and ended 5 hours later. The resulting aqueous emulsion contains a copolymer having an ethylene / vinyl acetate weight ratio of 23/77, a glass transition temperature of -8 ° C, a solid content of 73.5% by weight, and a viscosity of 530 mPa · s. Was something.
【００２０】比較例１ ポリビニルアルコールの全量を初期仕込みし、酢酸ビニ
ルの後添加を重合開始３時間後から５時間後まで行った
こと以外は実施例１と同様に行った。得られた水性エマ
ルジョンは、エチレン／酢酸ビニル重量比が２３／７７
でありガラス転移温度が−８℃の共重合体を含み、固形
分が７２．４重量％であり、粘度が１４０００ｍＰａ・
ｓのものであった。Comparative Example 1 The procedure of Example 1 was repeated except that the whole amount of polyvinyl alcohol was initially charged, and post-addition of vinyl acetate was performed from 3 hours to 5 hours after the start of polymerization. The resulting aqueous emulsion had an ethylene / vinyl acetate weight ratio of 23/77.
Containing a copolymer having a glass transition temperature of −8 ° C., a solid content of 72.4% by weight, and a viscosity of 14,000 mPa ·
s.
【００２１】比較例２ 実施例１で用いた平均重合度３００のポリビニルアルコ
ール１．３４重量部及び平均重合度１７００のポリビニ
ルアルコール（クラレ社製「ポバール２１７」、ケン化
度＝８８％）０．３４重量部を初期仕込みし、ポリビニ
ルアルコールの後添加を行わなかったこと以外は実施例
１と同様に行った。得られた水性エマルジョンは、エチ
レン／酢酸ビニル重量比が２１／７９でありガラス転移
温度が−４℃の共重合体を含み、固形分が７１．１重量
％であり、粘度が１７２５０ｍＰａ・ｓのものであっ
た。Comparative Example 2 1.34 parts by weight of polyvinyl alcohol having an average degree of polymerization of 300 used in Example 1 and polyvinyl alcohol having an average degree of polymerization of 1700 (“Poval 217” manufactured by Kuraray Co., Ltd., saponification degree = 88%) The same procedure as in Example 1 was carried out except that 34 parts by weight was initially charged, and no post-addition of polyvinyl alcohol was performed. The resulting aqueous emulsion contains a copolymer having an ethylene / vinyl acetate weight ratio of 21/79, a glass transition temperature of -4 ° C, a solid content of 71.1% by weight, and a viscosity of 17,250 mPa · s. Was something.
【００２２】[0022]
【発明の効果】以上説明したとおり、本発明により、固
形分濃度が極めて高いエチレン−酢酸ビニル共重合体系
水性エマルジョンの製造方法であって、共重合反応中に
おける反応系の粘度の上昇を抑制し、かつ安定なエマル
ジョンを得ることができるという特徴を有する水性エマ
ルジョンの製造方法を提供することができた。As described above, according to the present invention, there is provided a method for producing an ethylene-vinyl acetate copolymer-based aqueous emulsion having a very high solid content, which suppresses an increase in the viscosity of a reaction system during a copolymerization reaction. Thus, a method for producing an aqueous emulsion having the characteristic that a stable emulsion can be obtained can be provided.
Claims (1)
ビニル単位９０〜６０重量％からなるエチレン−酢酸ビ
ニル共重合体を含有し、固形分が７０重量％以上であ
り、かつ粘度が５０００ｍＰａ・ｓ以下である水性エマ
ルジョンの製造方法であって、下記（１）〜（４）の特
徴を有する水性エマルジョンの製造方法。 （１）共重合反応に供する全酢酸ビニルのうちの５０〜
９０％を予め共重合反応の反応系に存在せしめ、共重合
反応に供する全酢酸ビニルのうちの５０〜１０％を共重
合反応の開始後に反応系に供給すること （２）共重合反応に供する全酢酸ビニル１００重量部あ
たり２〜６重量部の乳化分散剤を用い、該乳化分散剤は
ケン化度が８０モル％以上であり、かつ平均重合度が２
００〜１０００であるポリビニルアルコール及びＨＬＢ
が１０〜２０であるポリオキシエチレン非イオン界面活
性剤を含有すること （３）上記のポリビニルアルコールの全使用量は、共重
合反応に供する全酢酸ビニル１００重量部あたり０．４
〜３重量部であり、該ポリビニルアルコールの全使用量
のうちの１０〜５０％を予め共重合反応の反応系に存在
せしめ、ポリビニルアルコールの全使用量のうちの５０
〜９０％を共重合反応の開始後に反応系に供給すること （４）前記のポリオキシエチレン非イオン界面活性剤の
全使用量は、共重合反応に供する全酢酸ビニル１００重
量部あたり１〜５重量部であり、該ポリオキシエチレン
非イオン界面活性剤の全使用量を予め共重合反応の反応
系に存在せしめること1. An ethylene-vinyl acetate copolymer comprising 10 to 40% by weight of ethylene units and 90 to 60% by weight of vinyl acetate units, having a solid content of 70% by weight or more and a viscosity of 5000 mPa · s. A method for producing an aqueous emulsion as described below, which comprises the following features (1) to (4): (1) 50 to 50% of the total vinyl acetate subjected to the copolymerization reaction
90% is pre-existing in the reaction system of the copolymerization reaction, and 50 to 10% of the total vinyl acetate to be used for the copolymerization reaction is supplied to the reaction system after the start of the copolymerization reaction. (2) Used for the copolymerization reaction 2 to 6 parts by weight of an emulsifying dispersant is used per 100 parts by weight of total vinyl acetate. The emulsifying and dispersing agent has a saponification degree of 80 mol% or more and an average degree of polymerization of 2%.
Polyvinyl alcohol and HLB which are 00 to 1000
Contains a polyoxyethylene nonionic surfactant having a molecular weight of 10 to 20. (3) The total amount of the polyvinyl alcohol used is 0.4 per 100 parts by weight of the total vinyl acetate used for the copolymerization reaction.
To 3 parts by weight, and 10 to 50% of the total amount of the polyvinyl alcohol is previously present in the reaction system of the copolymerization reaction, and 50% of the total amount of the polyvinyl alcohol is used.
(4) The total amount of the polyoxyethylene nonionic surfactant used is 1 to 5 per 100 parts by weight of the total vinyl acetate used in the copolymerization reaction. Parts by weight, and the total amount of the polyoxyethylene nonionic surfactant used must be present in the reaction system of the copolymerization reaction in advance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16536498A JP3622000B2 (en) | 1997-07-03 | 1998-06-12 | Method for producing aqueous emulsion |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17823897 | 1997-07-03 | ||
| JP9-178238 | 1997-07-03 | ||
| JP16536498A JP3622000B2 (en) | 1997-07-03 | 1998-06-12 | Method for producing aqueous emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1171434A true JPH1171434A (en) | 1999-03-16 |
| JP3622000B2 JP3622000B2 (en) | 2005-02-23 |
Family
ID=26490126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16536498A Expired - Fee Related JP3622000B2 (en) | 1997-07-03 | 1998-06-12 | Method for producing aqueous emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3622000B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003516300A (en) * | 1999-12-10 | 2003-05-13 | エムビーティー ホールディング アーゲー | Water-soluble air control agent for cementitious composition |
| JP2003516301A (en) * | 1999-12-10 | 2003-05-13 | エムビーティー ホールディング アーゲー | Solubilized defoamer for cement composition |
| JP2005306745A (en) * | 2004-04-19 | 2005-11-04 | Chuo Rika Kogyo Corp | Aqueous dispersion composition for cosmetic |
| US6989414B2 (en) | 2001-03-16 | 2006-01-24 | Sumitomo Chemical Company, Limited | Aqueous emulsion comprising ethylene-vinylester copolymer |
| JP2012172063A (en) * | 2011-02-22 | 2012-09-10 | Nagasaki Univ | Long chain (meth)acrylate-based emulsion and method for producing the same |
-
1998
- 1998-06-12 JP JP16536498A patent/JP3622000B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003516300A (en) * | 1999-12-10 | 2003-05-13 | エムビーティー ホールディング アーゲー | Water-soluble air control agent for cementitious composition |
| JP2003516301A (en) * | 1999-12-10 | 2003-05-13 | エムビーティー ホールディング アーゲー | Solubilized defoamer for cement composition |
| US6989414B2 (en) | 2001-03-16 | 2006-01-24 | Sumitomo Chemical Company, Limited | Aqueous emulsion comprising ethylene-vinylester copolymer |
| JP2005306745A (en) * | 2004-04-19 | 2005-11-04 | Chuo Rika Kogyo Corp | Aqueous dispersion composition for cosmetic |
| JP4522134B2 (en) * | 2004-04-19 | 2010-08-11 | 中央理化工業株式会社 | Aqueous dispersion composition for cosmetics |
| JP2012172063A (en) * | 2011-02-22 | 2012-09-10 | Nagasaki Univ | Long chain (meth)acrylate-based emulsion and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3622000B2 (en) | 2005-02-23 |
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