JP4306943B2 - Ethylene-vinyl acetate copolymer emulsion composition - Google Patents

Ethylene-vinyl acetate copolymer emulsion composition Download PDF

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Publication number
JP4306943B2
JP4306943B2 JP2000312865A JP2000312865A JP4306943B2 JP 4306943 B2 JP4306943 B2 JP 4306943B2 JP 2000312865 A JP2000312865 A JP 2000312865A JP 2000312865 A JP2000312865 A JP 2000312865A JP 4306943 B2 JP4306943 B2 JP 4306943B2
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Prior art keywords
vinyl acetate
mass
ethylene
eva emulsion
acetate copolymer
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JP2002121353A (en
Inventor
学 八箇
大輔 四宮
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は各種無機粉体やセメントと混合した際に、非常に良好な作業性と接着性を発現するエチレン−酢酸ビニル系共重合体エマルジョン(以下「EVAエマルジョン」という)に関するものである。
【0002】
【従来の技術】
EVAエマルジョンは接着剤分野や土木建材分野において広く使用され、また、塗料分野、製紙分野、繊維分野においても利用されている。これらいずれの分野においてもEVAエマルジョンの安定性や作業性は非常に重要である。EVAエマルジョンはエチレン−酢酸ビニル系共重合体(以下「EVA」という)の微小な粒子が水中に分散したものであるが、分散剤としてポリビニルアルコール(以下「PVA」という)やヒドロキシエチルセルロースといった水溶性高分子を使用している場合が多く、これら水溶性高分子の持つ接着性、粘着性等の特性が、各種無機粉体やセメントと混合してなるポリマーセメントモルタルに接着性、粘着性を付与している。しかし逆にこの高い粘着性がコテでの作業性を悪くし、特にポリマーセメントモルタルがコテに付着してしまうという問題点が多々見られる。
【0003】
作業性に優れたポリマーセメントモルタルを得るために、従来からポリマーエマルジョンに特定の界面活性剤を添加したり(特開昭56−129653)、重合時に特定の界面活性剤を使用してポリマーエマルジョンを製造する方法(特開平6−329455)などが行われてきた。ところが、この様な方法で十分な作業性を得るためには界面活性剤の添加量が多く必要であり、見かけのポリマーの平均分子量が低下する。その為、界面活性剤を多く含有するポリマーセメントモルタルの硬化物の各種モルタル物性、特にコンクリートやスレート板、ALCパネル等の被着体への接着性や長期耐久性能が著しく低下してしまう課題が残されていた。
【0004】
【発明が解決しようとする課題】
本発明は各種無機粉体やセメントと混合した際に、優れた作業性を発現し、且つ各種被着体との接着性に優れたエチレン−酢酸ビニル系共重合体エマルジョン組成物を提供するものである。
【0005】
【課題を解決するための手段】
本発明者らは、かかる目的を達成すべく鋭意検討した結果、EVAエマルジョンに少量の酢酸ビニルモノマーを添加し重合させて得られる変性EVAエマルジョンに消泡剤を含有させることによって、各種無機粉体やセメントと混合した後に良好な作業性、及び接着性を示すEVAエマルジョンを製造できることを見い出したのである。
【0006】
【発明の実施の形態】
本発明で使用されるEVAエマルジョンはエチレンと酢酸ビニル成分を必須成分とするEVAのエマルジョンであり、エチレンと酢酸ビニルモノマーを乳化重合したもの、あるいは市販品のいずれも使用することができる。EVAの組成はエチレン含有量が5〜35質量%、酢酸ビニル含有量が65〜95質量%でエチレンと酢酸ビニルの合計が80質量%以上であるEVAを好適に用いることができる。
【0007】
エチレンと酢酸ビニル以外に20質量%未満であればエチレン、酢酸ビニルと共重合するその他の成分を含んでいてもよい。その他の成分としては例えば塩化ビニル、プロピオン酸ビニル、バーサチック酸ビニル、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、2−エチルヘキシルアクリレート、エチルメタアクリレート、プロピルメタアクリレート、ブチルメタアクリレート、2−エチルヘキシルメタアクリレートがあるが、これらの成分を一種類以上含有させることができる。また、トリアリルシアヌレート、トリアリルイソシアヌレートを併用することができ、この場合耐アルカリを向上させる効果がある。その添加量は1質量%以下、好ましくは0.5質量%以下である。
【0008】
本発明ではPVAを含有するEVAエマルジョンを好適に用いることができる。PVAはEVAエマルジョンを乳化重合により製造する際に保護コロイドとして添加されてEVAエマルジョンに含有されるものであっても、あるいは乳化重合の際には全く用いず重合後にEVAエマルジョンに添加されて含有されるものであってもよい。
【0009】
PVAの含有量は、EVAエマルジョンの不揮発分に対して10質量%以下が好ましい。PVAの種類には特に限定なく市販のものを用いることができる。完全ケン化PVA、部分ケン化PVAやスルホン基、カルボキシル基、アミド基等により変性されたPVAを用いることができる。
【0010】
本発明によればEVAエマルジョンの不揮発分100質量部に対して1〜10質量部の酢酸ビニルモノマーを混合し重合させて得られる変性EVAエマルジョンの不揮発分100質量部に対して消泡剤0.005〜1.0質量部を含有させることで、各種無機粉体やセメントと混合しても十分な作業性を発現し、且つ各種被着体との接着性に優れたEVAエマルジョンが得られる。
【0011】
変性EVAエマルジョンを製造する際に、EVAエマルジョンに加えられる酢酸ビニルモノマーは、EVAエマルジョンをエチレンの圧力下で重合した後に、エチレンをパージしてEVAエマルジョンを常圧に戻した際に、EVAエマルジョンに未反応の酢酸ビニルモノマーとして残存したものであってもよい。あるいは、EVAエマルジョン製造後に残存する未反応の酢酸ビニルモノマーに更に新たに酢酸ビニルモノマーを添加してもよい。要は所定量の酢酸ビニルモノマーがEVAエマルジョンに含有されてあればよい。
【0012】
酢酸ビニルモノマーに対して少量であれば酢酸ビニルモノマーと共重合する他の単量体モノマーを併用することができる。 それらの単量体としては例えば、カルボン酸のビニルエステル類、アクリル酸、アクリル酸のアルキルエステル類、メタアクリル酸のアルキルエステル類、アルキルエーテル類、アルキルアリルエーテル類、その他(メタ)アクリルアミド、(メタ)アクリロニトリル、(メタ)アリルスルホン酸塩等がある。
【0013】
EVAエマルジョンに含まれる酢酸ビニルモノマーはラジカル開始剤を添加することにより重合される。ラジカル開始剤としてはEVAエマルジョンの重合に用いられるものは全て用いることができる。例えば、過酸化水素、t−ブチルハイドロパーオキサイド等の有機過酸化物、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩を使用することができる。また、ラジカル開始剤とナトリウムホルムアルデヒドスルホキシレート等の還元剤を併用するレドックス触媒を用いることもできる。なかでも過硫酸アンモニウムや過硫酸カリウムといった過硫酸塩を好適に用いることができる。
【0014】
重合方法には特に限定されず酢酸ビニルモノマーを含有したEVAエマルジョンにラジカル開始剤を添加し重合することができる。重合温度は使用するラジカル開始剤の種類により異なるが40〜80℃とすることができる。重合はEVAエマルジョンに含有される未反応の酢酸ビニルモノマーが1質量%以下となるまで行うことが好ましい。
【0015】
本発明で変性EVAエマルジョンに含有させる消泡剤は、一般に使用されているものであれば特に限定するものではなく、例えば必要ならば表面処理した微粉シリカをシリコーンオイルや有機変性シリコーンに分散させたシリカシリコーン系消泡剤、ステアリン酸アルミニウム、ステアリン酸カルシウム、オレイン酸カリウム及びパルミチン酸マグメシウム等の金属石鹸系消泡剤、ポリアルキレンアミド、アシレートポリアミン及びジオクタデカノイルピペラジン等のアマイド系消泡剤、二酸化チタンや酸化アルミニウム等をシリコーンオイルに分散させたシリコーンコンパウンド系消泡剤、オクチルアルコール、オレイルアルコール、ポリオキシアルキレングリコール等のアルコール系消泡剤、ポリプロピレングリコール脂肪族エステル、ポリオキシプロピレンポリオキシエチレン共重合体及びソルビタンモノラウレートの酸化エチレン付加物等のポリエーテル系消泡剤、ソルビタンモノ脂肪酸エステル、ソルビタントリ脂肪酸エステル、脂肪酸モノグリセリド、エチレングリコールジ脂肪酸エステル及びエチレングリコールジ脂肪酸エステル等の非イオン型消泡剤、流動パラフィンやスピンドル油等の鉱物油系消泡剤及びこれら消泡剤を乳化分散させたエマルション型消泡剤等を単独ないしは組み合わせて使用できる。
【0016】
本発明におけるEVAエマルジョン組成物に含有される消泡剤の量は、変性EVAエマルジョンの不揮発分100質量部に対して、好ましくは0.005〜1.0質量部、特に好ましくは0.01〜0.8質量部である。
【0017】
消泡剤の含有量が0.005質量部以下では、各種無機系粉体やセメントと混合した際の作業性の改善効果が低下し、1.0質量部以上では作業性は改善されるものの、できあがったポリマーセメントモルタルのコンクリートやスレート板、ALCパネルへの接着性が低下する傾向がある。
【0018】
また、この消泡剤の添加方法に関しては特に限定されるものではなく、EVAエマルジョンを重合する際に加えても良いし、重合が終了した後に加えても良い、更には変性EVAを重合する際に加えても良いし、変性EVAエマルジョンに加えても良い。要は所定量の消泡剤が変性EVAエマルジョンに含有されてあればよい。
【0019】
本発明で得られたEVAエマルジョン組成物を使用することによって、各種無機系粉体やセメントと混合して得られるポリマーセメントモルタルは、作業性が非常に優れ、且つコンクリートやスレート板、ALCパネル等の被着体との接着性に優れたものとなる。
【0020】
【実施例】
以下更に詳細に実施例をもって説明する。
(EVAエマルジョンの製造例1)
攪拌機付の高圧重合缶に酢酸ビニルモノマー100質量部、PVA(電気化学工業社製)B−05とB−17を各2質量部、酢酸ソーダ0.4質量部、ロンガリット(ナトリウムホルムアルデヒドスルホキシレート、住友精化社製)0.2重量部、硫酸第一鉄・七水和物0.005質量部を90質量部の水に溶解した水溶液を攪拌下仕込み、窒素で重合缶内部を置換した後、エチレン25質量部を充填した。温度を65℃とした後、5%の過硫酸カリウム水溶液を添加し重合を行った。未反応の酢酸ビニルモノマー量が2%となった時点で残存するエチレンをパージしEVAエマルジョンを得た。生成したEVAエマルジョン中の未反応の酢酸ビニルモノマーを減圧下除去し、未反応の酢酸ビニルモノマーが0.5質量%以下のEVAエマルジョンを得た。このEVAエマルジョンの不揮発分は55.0質量%、EVA中のエチレン含量は19質量%、粘度3900mPa・s、粗粒率180ppm、セメント混和安定性6秒であった。
【0021】
(変性EVAエマルジョンの製造例1)
同じく(EVAエマルジョンの製造例1)で得られたEVAエマルジョンに不揮発分に対して6質量%となるよう酢酸ビニルモノマーを添加した。また、ナトリウムホルムアルデヒドスルホキシレート(ロンガリット)0.001質量部、硫酸第一鉄・7水和物0.00005質量部を純水1質量部に溶解したものをし、30分間攪拌しながら、温度を55℃とした。5質量%の過硫酸カリウム水溶液2.64質量部を90分間に渡って添加し重合を行った。残存する未反応の酢酸ビニルモノマーがEVAエマルジョンに対して1質量%以下となるまで重合を行い、変性EVAエマルジョンを得た。得られたEVAエマルジョン中の未反応の酢酸ビニルモノマーを減圧下除去し、未反応の酢酸ビニルモノマーが0.5質量%以下の変性EVAエマルジョンを得た。
【0022】
(実施例1)
同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「SNデフォーマー777」(サンノプコ株式会社製、鉱物油,ポリエーテル,シリカシリコーン等の混合物)を0.1質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。
【0023】
(実施例2)
同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「クリレス P−666」(栗田工業株式会社製、高級アルコール系消泡剤)を0.2質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。
【0024】
(実施例3)
同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「アデカネート B−925」(旭電化工業株式会社製、非イオン型消泡剤)を0.05質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。
【0025】
(比較例1)
(EVAエマルジョンの製造例1)で得られたEVAエマルジョンに消泡剤を全く添加せず評価用サンプルとした。
【0026】
(比較例2)
(EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「SNデフォーマー777」(サンノプコ株式会社製、鉱物油,ポリエーテル,シリカシリコーン等の混合物)を0.1質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。
【0027】
(比較例3)
(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンに、消泡剤を全く添加せず評価用サンプルとした。
【0028】
(比較例4)
同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「SNデフォーマー777」(サンノプコ株式会社製、鉱物油,ポリエーテル,シリカシリコーン等の混合物)を0.003質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。
【0029】
(比較例5)
同じく(変性EVAエマルジョンの製造例1)で得られたEVAエマルジョンの不揮発分100質量部に対して、消泡剤「クリレス P−666」(栗田工業株式会社製、高級アルコール系消泡剤)を1.5質量部添加し、良く攪拌して均一なEVAエマルジョンを得た。
【0030】
(セメント混和安定性)
比較例1、実施例1で得られたEVAエマルジョンを用い、水48.5質量部、EVAエマルジョンを不揮発分として22.5質量部、普通ポルトランドセメント100質量部をよく混合しセメント組成物を得た。それを35℃で一時間放置した後、ガラス棒で再度攪拌し流動性をみた。EVAエマルジョンの安定性が悪い場合は短時間でセメント組成物は混合できないほど凝結したが、安定性のよい場合は相当時間攪拌混合することができた。混合可能な時間を測定しEVAエマルジョンのセメントに対する混合安定性を評価した。評価結果を表1に示す。
【0031】
【表1】
【0032】
(モルタル接着強さ)
JIS A 6203「セメント混和用ポリマーディスパージョンおよび再乳化形粉末樹脂」の9.6「接着強さ」の評価方法に準じ、接着強さを測定した。なお、接着強さの品質は1.0MPa以上である。評価結果を表1に示す。
(作業性)
JIS A 6203「セメント混和用ポリマーディスパージョンおよび再乳化形粉末樹脂」の9.2.3の「ポリマーセメントモルタルの練混ぜ」のa)機械練りによる方法に準じてポリマーセメントモルタルを作製し、これをJIS A 5403「木毛セメント板」に規定する厚さ4mmのフレキシブル板上に塗膜厚2mmとなるように金コテで塗りつけた際、コテさばき性の優劣を下記基準で判断した。評価結果を表1に示す。
○−作業性良好で、ポリマーセメントモルタルのコテへの付着が少ない。
△−作業性は○と比較して若干劣り、ポリマーセメントモルタルのコテへの付着が若干ある。
×−作業性が悪く、ポリマーセメントモルタルのコテへの付着が多い。
(不揮発分、粘度)
JIS K 6828に準じて評価した。評価結果を表1に示す。尚、表1中の粘度の値はBM型回転式粘度計を用い、30℃の30rpmの値。
(残存酢酸ビニルモノマー)
JIS K 6828の5.10残存モノマーの5.10.1直接滴定法で求めた。結果を表1に示す。
【0033】
表1に記載した様に、実施例1から3では変性EVAエマルジョンに消泡剤を添加することにより、これに骨材とセメントを混合して得られるポリマーセメントモルタルは非常に良好な作業性を発現し、更にはこれを用いたモルタル接着強さ試験でも十分な接着強さを発現した。
【0034】
それに対して比較例1と2では、セメント混和安定性と作業性が著しくに劣っていた。また、比較例3と4ではセメント混和安定性とモルタル接着強さは良好な値を示したものの、消泡剤の添加量が少なすぎたために作業性は良くなかった。また、比較例5では消泡剤の添加量が多すぎるために、セメント混和安定性と作業性は良好であったがモルタル接着強さが大幅に低下して、JIS A 6203の品質1.0MPa未満となった。
【0035】
【発明の効果】
エチレン−酢酸ビニル系共重合体エマルジョンの不揮発分100質量部に対し1〜10質量部の酢酸ビニルモノマーを混合し重合して得られる変性エチレン−酢酸ビニル系共重合体エマルジョンに、消泡剤を含有することを特徴とするエチレン−酢酸ビニル系共重合体エマルジョン組成物は、セメント混和安定性に優れ、各種無機粉体やセメントを混合して作製したポリマーセメントモルタルは良好な作業性、接着性を発現する。
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ethylene-vinyl acetate copolymer emulsion (hereinafter referred to as “EVA emulsion”) that exhibits very good workability and adhesion when mixed with various inorganic powders and cement.
[0002]
[Prior art]
EVA emulsion is widely used in the field of adhesives and civil engineering materials, and is also used in the fields of paint, papermaking and textiles. In any of these fields, the stability and workability of the EVA emulsion are very important. EVA emulsion is a fine particle of ethylene-vinyl acetate copolymer (hereinafter referred to as “EVA”) dispersed in water, but water-soluble such as polyvinyl alcohol (hereinafter referred to as “PVA”) or hydroxyethyl cellulose as a dispersant. Polymers are often used, and these water-soluble polymers have properties such as adhesiveness and tackiness that provide adhesion and tackiness to polymer cement mortars mixed with various inorganic powders and cement. is doing. However, on the contrary, this high adhesiveness deteriorates the workability of the iron, and in particular, there are many problems that the polymer cement mortar adheres to the iron.
[0003]
In order to obtain a polymer cement mortar with excellent workability, a specific surfactant is conventionally added to a polymer emulsion (Japanese Patent Laid-Open No. 56-129653), or a specific surfactant is used during polymerization to form a polymer emulsion. A manufacturing method (Japanese Patent Laid-Open No. 6-329455) has been performed. However, in order to obtain sufficient workability by such a method, it is necessary to add a large amount of surfactant, and the average molecular weight of the apparent polymer is lowered. Therefore, various mortar physical properties of cured products of polymer cement mortar containing a large amount of surfactant, especially adhesion to adherends such as concrete, slate plate, ALC panel and long-term durability performance are significantly reduced. It was left.
[0004]
[Problems to be solved by the invention]
The present invention provides an ethylene-vinyl acetate copolymer emulsion composition that exhibits excellent workability when mixed with various inorganic powders and cement and has excellent adhesion to various adherends. It is.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have made various inorganic powders by adding an antifoaming agent to a modified EVA emulsion obtained by adding a small amount of vinyl acetate monomer to an EVA emulsion and polymerizing it. It has been found that EVA emulsions exhibiting good workability and adhesion after mixing with or cement can be produced.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The EVA emulsion used in the present invention is an EVA emulsion containing ethylene and a vinyl acetate component as essential components. Either an emulsion obtained by emulsion polymerization of ethylene and a vinyl acetate monomer or a commercially available product can be used. EVA having an ethylene content of 5 to 35% by mass, a vinyl acetate content of 65 to 95% by mass and a total of ethylene and vinyl acetate of 80% by mass or more can be suitably used.
[0007]
If it is less than 20% by mass in addition to ethylene and vinyl acetate, it may contain other components copolymerized with ethylene and vinyl acetate. Examples of other components include vinyl chloride, vinyl propionate, vinyl versatate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, propyl meta There are acrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, but one or more of these components can be contained. Further, triallyl cyanurate and triallyl isocyanurate can be used in combination, and in this case, there is an effect of improving alkali resistance. The amount added is 1% by mass or less, preferably 0.5% by mass or less.
[0008]
In the present invention, EVA emulsion containing PVA can be preferably used. PVA may be added to the EVA emulsion as a protective colloid when the EVA emulsion is produced by emulsion polymerization, or may be added to the EVA emulsion after polymerization without being used at all during the emulsion polymerization. It may be a thing.
[0009]
The content of PVA is preferably 10% by mass or less based on the nonvolatile content of the EVA emulsion. A commercially available product can be used with no particular limitation on the type of PVA. PVA modified with completely saponified PVA, partially saponified PVA, sulfone group, carboxyl group, amide group or the like can be used.
[0010]
According to the present invention, 1 to 10 parts by mass of vinyl acetate monomer is mixed with 100 parts by mass of the nonvolatile content of the EVA emulsion and polymerized, and 100% by mass of the nonvolatile content of the modified EVA emulsion is obtained. By containing 005 to 1.0 part by mass, an EVA emulsion that exhibits sufficient workability even when mixed with various inorganic powders and cement and is excellent in adhesion to various adherends can be obtained.
[0011]
When producing the modified EVA emulsion, the vinyl acetate monomer added to the EVA emulsion is polymerized into the EVA emulsion when the EVA emulsion is polymerized under the pressure of ethylene and then purged with ethylene to return the EVA emulsion to normal pressure. What remained as an unreacted vinyl acetate monomer may be sufficient. Alternatively, a new vinyl acetate monomer may be added to the unreacted vinyl acetate monomer remaining after the production of the EVA emulsion. In short, a predetermined amount of vinyl acetate monomer may be contained in the EVA emulsion.
[0012]
If the amount is small relative to the vinyl acetate monomer, another monomer monomer copolymerized with the vinyl acetate monomer can be used in combination. Examples of these monomers include vinyl esters of carboxylic acid, acrylic acid, alkyl esters of acrylic acid, alkyl esters of methacrylic acid, alkyl ethers, alkyl allyl ethers, other (meth) acrylamides, ( Examples include (meth) acrylonitrile and (meth) allyl sulfonate.
[0013]
The vinyl acetate monomer contained in the EVA emulsion is polymerized by adding a radical initiator. Any radical initiator used for polymerization of EVA emulsions can be used. For example, organic peroxides such as hydrogen peroxide and t-butyl hydroperoxide, and persulfates such as ammonium persulfate and potassium persulfate can be used. A redox catalyst using a radical initiator and a reducing agent such as sodium formaldehyde sulfoxylate in combination can also be used. Of these, persulfates such as ammonium persulfate and potassium persulfate can be preferably used.
[0014]
The polymerization method is not particularly limited, and polymerization can be performed by adding a radical initiator to an EVA emulsion containing a vinyl acetate monomer. Although superposition | polymerization temperature changes with kinds of radical initiator to be used, it can be 40-80 degreeC. The polymerization is preferably carried out until the unreacted vinyl acetate monomer contained in the EVA emulsion is 1% by mass or less.
[0015]
The antifoaming agent contained in the modified EVA emulsion in the present invention is not particularly limited as long as it is generally used. For example, if necessary, surface-treated fine silica is dispersed in silicone oil or organically modified silicone. Silica silicone antifoaming agents, metal soap antifoaming agents such as aluminum stearate, calcium stearate, potassium oleate and magmesium palmitate, and amide antifoaming agents such as polyalkyleneamide, acylate polyamine and dioctadecanoylpiperazine , Silicone compound defoamers in which titanium dioxide, aluminum oxide, etc. are dispersed in silicone oil, alcohol defoamers such as octyl alcohol, oleyl alcohol, polyoxyalkylene glycol, polypropylene glycol aliphatic esters, Polyether-based antifoaming agents such as reoxypropylene polyoxyethylene copolymer and ethylene oxide adduct of sorbitan monolaurate, sorbitan monofatty acid ester, sorbitan trifatty acid ester, fatty acid monoglyceride, ethylene glycol difatty acid ester and ethylene glycol di Nonionic antifoaming agents such as fatty acid esters, mineral oil-based antifoaming agents such as liquid paraffin and spindle oil, and emulsion type antifoaming agents obtained by emulsifying and dispersing these antifoaming agents can be used alone or in combination.
[0016]
The amount of the antifoaming agent contained in the EVA emulsion composition in the present invention is preferably 0.005 to 1.0 parts by mass, particularly preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the nonvolatile content of the modified EVA emulsion. 0.8 parts by mass.
[0017]
When the content of the antifoaming agent is 0.005 parts by mass or less, the workability improvement effect when mixed with various inorganic powders and cements is reduced, and when 1.0 part by mass or more, the workability is improved. There is a tendency that the adhesion of the resulting polymer cement mortar to concrete, a slate plate or an ALC panel is lowered.
[0018]
Further, the method for adding the antifoaming agent is not particularly limited, and may be added when polymerizing the EVA emulsion, may be added after the polymerization is completed, and further when polymerizing the modified EVA. It may be added to the modified EVA emulsion. In short, a predetermined amount of antifoaming agent may be contained in the modified EVA emulsion.
[0019]
By using the EVA emulsion composition obtained in the present invention, the polymer cement mortar obtained by mixing with various inorganic powders and cement has excellent workability, and concrete, slate plate, ALC panel, etc. It becomes excellent in adhesiveness to the adherend.
[0020]
【Example】
This will be described in more detail with reference to examples.
(Production example 1 of EVA emulsion)
In a high-pressure polymerization can equipped with a stirrer, 100 parts by weight of vinyl acetate monomer, 2 parts by weight of PVA (manufactured by Denki Kagaku Kogyo) B-05 and B-17, 0.4 parts by weight of sodium acetate, Rongalite (sodium formaldehyde sulfoxylate) (Manufactured by Sumitomo Seika Co., Ltd.) 0.2 parts by weight, an aqueous solution prepared by dissolving 0.005 parts by mass of ferrous sulfate heptahydrate in 90 parts by mass of water was added with stirring, and the inside of the polymerization vessel was replaced with nitrogen Thereafter, 25 parts by mass of ethylene was filled. After setting the temperature to 65 ° C., 5% potassium persulfate aqueous solution was added for polymerization. When the amount of the unreacted vinyl acetate monomer reached 2%, the remaining ethylene was purged to obtain an EVA emulsion. Unreacted vinyl acetate monomer in the produced EVA emulsion was removed under reduced pressure to obtain an EVA emulsion containing 0.5% by mass or less of unreacted vinyl acetate monomer. This EVA emulsion had a nonvolatile content of 55.0% by mass, an ethylene content in EVA of 19% by mass, a viscosity of 3900 mPa · s, a coarse particle ratio of 180 ppm, and a cement mixing stability of 6 seconds.
[0021]
(Production Example 1 of Modified EVA Emulsion)
Similarly, a vinyl acetate monomer was added to the EVA emulsion obtained in (Preparation Example 1 of EVA emulsion) so as to be 6% by mass based on the nonvolatile content. Further, 0.001 part by mass of sodium formaldehyde sulfoxylate (Longalite) and 0.00005 part by mass of ferrous sulfate heptahydrate were dissolved in 1 part by mass of pure water, and the temperature was maintained while stirring for 30 minutes. Was 55 ° C. Polymerization was carried out by adding 2.64 parts by mass of a 5% by mass aqueous potassium persulfate solution over 90 minutes. Polymerization was performed until the remaining unreacted vinyl acetate monomer was 1% by mass or less based on the EVA emulsion, to obtain a modified EVA emulsion. Unreacted vinyl acetate monomer in the obtained EVA emulsion was removed under reduced pressure to obtain a modified EVA emulsion containing 0.5% by mass or less of unreacted vinyl acetate monomer.
[0022]
Example 1
Similarly, with respect to 100 parts by mass of the nonvolatile content of the EVA emulsion obtained in (Production Example 1 of Modified EVA Emulsion), an antifoaming agent “SN Deformer 777” (manufactured by San Nopco Co., Ltd., mineral oil, polyether, silica silicone, etc.) 0.1 parts by mass of the mixture) was added and stirred well to obtain a uniform EVA emulsion.
[0023]
(Example 2)
Similarly, with respect to 100 parts by mass of the nonvolatile content of the EVA emulsion obtained in (Production Example 1 of Modified EVA Emulsion), an antifoaming agent “Krilles P-666” (manufactured by Kurita Kogyo Co., Ltd., a higher alcohol-based antifoaming agent) 0.2 parts by mass was added and stirred well to obtain a uniform EVA emulsion.
[0024]
(Example 3)
Similarly, with respect to 100 parts by mass of the nonvolatile content of the EVA emulsion obtained in (Production Example 1 of Modified EVA Emulsion), an antifoaming agent “Adecanate B-925” (manufactured by Asahi Denka Kogyo Co., Ltd., nonionic antifoaming agent) 0.05 parts by mass was added and stirred well to obtain a uniform EVA emulsion.
[0025]
(Comparative Example 1)
The EVA emulsion obtained in (Production Example 1 of EVA emulsion) was used as an evaluation sample without adding any antifoaming agent.
[0026]
(Comparative Example 2)
Antifoaming agent “SN Deformer 777” (mixed of Sannopco, mineral oil, polyether, silica silicone, etc.) with respect to 100 parts by mass of the nonvolatile content of the EVA emulsion obtained in Production Example 1 of EVA emulsion 0.1 parts by mass was added and stirred well to obtain a uniform EVA emulsion.
[0027]
(Comparative Example 3)
The EVA emulsion obtained in (Production Example 1 of Modified EVA Emulsion) was used as an evaluation sample without adding any antifoaming agent.
[0028]
(Comparative Example 4)
Similarly, with respect to 100 parts by mass of the nonvolatile content of the EVA emulsion obtained in (Production Example 1 of Modified EVA Emulsion), an antifoaming agent “SN Deformer 777” (manufactured by San Nopco Co., Ltd., mineral oil, polyether, silica silicone, etc.) 0.003 part by mass of the mixture) was added and stirred well to obtain a uniform EVA emulsion.
[0029]
(Comparative Example 5)
Similarly, with respect to 100 parts by mass of the nonvolatile content of the EVA emulsion obtained in (Production Example 1 of Modified EVA Emulsion), an antifoaming agent “Krilles P-666” (manufactured by Kurita Kogyo Co., Ltd., a higher alcohol-based antifoaming agent) 1.5 parts by mass was added and stirred well to obtain a uniform EVA emulsion.
[0030]
(Cement mixing stability)
Using the EVA emulsion obtained in Comparative Example 1 and Example 1, 48.5 parts by mass of water, 22.5 parts by mass of the EVA emulsion as a non-volatile content, and 100 parts by mass of ordinary Portland cement were mixed well to obtain a cement composition. It was. After leaving it at 35 ° C. for 1 hour, it was stirred again with a glass rod and fluidity was observed. When the stability of the EVA emulsion was poor, the cement composition coagulated so that it could not be mixed in a short time, but when the stability was good, it could be stirred and mixed for a considerable time. The mixing time was measured to evaluate the mixing stability of the EVA emulsion to the cement. The evaluation results are shown in Table 1.
[0031]
[Table 1]
[0032]
(Mortar bond strength)
The adhesive strength was measured in accordance with the evaluation method of 9.6 “Adhesive strength” of JIS A 6203 “Polymer dispersion for cement admixture and re-emulsified powder resin”. In addition, the quality of adhesive strength is 1.0 MPa or more. The evaluation results are shown in Table 1.
(Workability)
Prepare a polymer cement mortar according to the method of a) mechanical kneading in 9.2.3 “Mixing of polymer cement mortar” of JIS A 6203 “Polymer dispersion for cement admixture and re-emulsifying powder resin”. Was coated with a gold iron to a thickness of 2 mm on a 4 mm thick flexible board specified in JIS A 5403 “wooden cement board”, the superiority or inferiority of the iron separation was judged according to the following criteria. The evaluation results are shown in Table 1.
○-Good workability and little adhesion of polymer cement mortar to iron.
Δ—Workability is slightly inferior to that of ○, and polymer cement mortar is slightly adhered to the iron.
X—Workability is poor, and polymer cement mortar is often attached to the iron.
(Non-volatile content, viscosity)
Evaluation was performed according to JIS K 6828. The evaluation results are shown in Table 1. In addition, the value of the viscosity in Table 1 is a value of 30 rpm at 30 ° C. using a BM type rotary viscometer.
(Residual vinyl acetate monomer)
It was determined by 5.10.1 direct titration of 5.10 residual monomer of JIS K 6828. The results are shown in Table 1.
[0033]
As described in Table 1, in Examples 1 to 3, by adding an antifoaming agent to the modified EVA emulsion, the polymer cement mortar obtained by mixing the aggregate and the cement has very good workability. In addition, sufficient adhesion strength was exhibited in a mortar adhesion strength test using this.
[0034]
On the other hand, in Comparative Examples 1 and 2, cement mixing stability and workability were remarkably inferior. In Comparative Examples 3 and 4, although the cement mixing stability and the mortar adhesive strength showed good values, the workability was not good because the amount of antifoaming agent added was too small. In Comparative Example 5, the amount of antifoaming agent added was too large, so that the cement mixing stability and workability were good, but the mortar bond strength was greatly reduced, and the quality of JIS A 6203 was 1.0 MPa. It became less than.
[0035]
【The invention's effect】
An antifoaming agent is added to a modified ethylene-vinyl acetate copolymer emulsion obtained by mixing and polymerizing 1 to 10 parts by weight of a vinyl acetate monomer with respect to 100 parts by weight of a nonvolatile content of the ethylene-vinyl acetate copolymer emulsion. The ethylene-vinyl acetate copolymer emulsion composition characterized by containing is excellent in cement admixture stability, and polymer cement mortar prepared by mixing various inorganic powders and cement has good workability and adhesiveness. Is expressed.

Claims (3)

エチレン−酢酸ビニル系共重合体エマルジョンの不揮発分100質量部に対し1〜10質量部の酢酸ビニルモノマーを混合し重合して得られる変性エチレン−酢酸ビニル系共重合体エマルジョンに、該変性エチレン−酢酸ビニル系共重合体エマルジョンの不揮発分100質量部に対して0.005〜1.0質量部の消泡剤を含有することを特徴とする、ポリマーセメントモルタル用のエチレン−酢酸ビニル系共重合体エマルジョン組成物。The modified ethylene-vinyl acetate copolymer emulsion obtained by mixing and polymerizing 1 to 10 parts by mass of vinyl acetate monomer with respect to 100 parts by mass of the nonvolatile content of the ethylene-vinyl acetate copolymer emulsion is added to the modified ethylene- An ethylene-vinyl acetate copolymer for polymer cement mortar , comprising 0.005 to 1.0 part by mass of an antifoaming agent with respect to 100 parts by mass of a nonvolatile content of the vinyl acetate copolymer emulsion Combined emulsion composition. 請求項1において消泡剤が、シリカシリコーン系消泡剤、金属石鹸系消泡剤、アマイド系消泡剤、シリコーンコンパウンド系消泡剤、アルコール系消泡剤、ポリエーテル系消泡剤、非イオン型消泡剤、エマルション型消泡剤、鉱物油系消泡剤から選ばれる少なくとも1種類以上の消泡剤であることを特徴とするエチレン−酢酸ビニル系共重合体エマルジョン組成物。Oite defoamer in claim 1, silica silicone anti-foaming agents, metal soap-based antifoaming agents, amide-based defoaming agents, silicone compositions based defoaming agents, alcohol-based defoaming agents, polyether-based defoaming agent An ethylene-vinyl acetate copolymer emulsion composition comprising at least one antifoaming agent selected from a nonionic antifoaming agent, an emulsion defoaming agent, and a mineral oil-based antifoaming agent. 請求項のエチレン−酢酸ビニル系共重合体エマルジョン組成物を含有してなるセメント組成物。A cement composition comprising the ethylene-vinyl acetate copolymer emulsion composition of claim 2 .
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