JP3295116B2 - Re-emulsifiable synthetic resin emulsion powder composition with improved water resistance - Google Patents
Re-emulsifiable synthetic resin emulsion powder composition with improved water resistanceInfo
- Publication number
- JP3295116B2 JP3295116B2 JP36128091A JP36128091A JP3295116B2 JP 3295116 B2 JP3295116 B2 JP 3295116B2 JP 36128091 A JP36128091 A JP 36128091A JP 36128091 A JP36128091 A JP 36128091A JP 3295116 B2 JP3295116 B2 JP 3295116B2
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- resin emulsion
- emulsifiable
- emulsion powder
- weight
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は耐水性を向上した再乳化
性合成樹脂エマルジョン粉末組成物に関し、特にカルシ
ウムまたはマグネシウムの酸化物または水酸化物から選
ばれた１または２以上を配合した、再乳化性を低下する
ことなく耐水性を向上した再乳化性合成樹脂エマルジョ
ン粉末組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a re-emulsifiable synthetic resin emulsion powder composition having improved water resistance, and more particularly to a re-emulsifiable synthetic resin emulsion composition containing one or more oxides or hydroxides of calcium or magnesium. The present invention relates to a re-emulsifiable synthetic resin emulsion powder composition having improved water resistance without lowering emulsifiability.
【０００２】[0002]
【従来の技術】再乳化性合成樹脂エマルジョン粉末は、
一般的に水溶性高分子化合物を保護コロイドとした合成
樹脂水性エマルジョンを噴霧乾燥することによって得ら
れる粉末で、特に水に添加し撹拌すると再乳化する粉末
である。再乳化とは、水中に分散された再乳化性合成樹
脂エマルジョン粉末が粉末状態での粒子の大きさに単に
分散するのではなく、更に細かい元の合成樹脂エマルジ
ョンの樹脂粒子の大きさとほとんど同じ大きさの粒子と
なって乳化することであり、再乳化した液が、元の合成
樹脂エマルジョンとほぼ同様な性質を有することが必要
である。2. Description of the Related Art A re-emulsifiable synthetic resin emulsion powder is
Generally, this is a powder obtained by spray-drying a synthetic resin aqueous emulsion using a water-soluble polymer compound as a protective colloid, and particularly a powder that is re-emulsified when added to water and stirred. Re-emulsification means that the re-emulsifiable synthetic resin emulsion powder dispersed in water does not simply disperse in the size of the particles in the powder state, but has a finer particle size almost the same as the size of the resin particles of the original synthetic resin emulsion. The emulsification is performed as particles of the same size, and it is necessary that the re-emulsified liquid has substantially the same properties as the original synthetic resin emulsion.
【０００３】再乳化性合成樹脂エマルジョン粉末を水中
で再乳化した液が、元の合成樹脂エマルジョンとほぼ同
様な性質を有することにより合成樹脂エマルジョンが使
用されている広い用途、例えば接着剤、塗料バインダ
ー、繊維処理剤などに使用することが考えられている。
再乳化性合成樹脂エマルジョン粉末は実際に壁紙の接着
剤や繊維壁のバインダーとしても使用されている。冬場
の室内は壁面が結露しやすく、結露した水分により壁紙
の接着剤や繊維壁のバインダーの接着性が低下すれば、
壁紙や繊維壁が剥落してしまう可能性があり、壁紙の接
着剤や繊維壁のバインダーに使用される再乳化成合成樹
脂エマルジョン粉末から得られる皮膜の耐水性を向上す
ることが求められていた。[0003] The re-emulsifiable synthetic resin emulsion powder re-emulsified in water has almost the same properties as the original synthetic resin emulsion, so that it can be used in a wide range of applications where synthetic resin emulsions are used, such as adhesives and paint binders. It is considered to be used as a fiber treatment agent.
The re-emulsifiable synthetic resin emulsion powder is actually used as an adhesive for wallpaper or a binder for fiber walls. In winter, if the wall surface is easy to dew on the wall, and the dewed water reduces the adhesiveness of the wallpaper adhesive or the fiber wall binder,
There is a possibility that the wallpaper and the fiber wall may peel off, and it has been required to improve the water resistance of the film obtained from the re-emulsifying synthetic resin emulsion powder used for the adhesive of the wallpaper and the binder of the fiber wall. .
【０００４】[0004]
【発明が解決しようとする課題】従来の再乳化性合成樹
脂エマルジョン粉末は、単に水中で再乳化するだけでは
なく、再乳化した液が合成樹脂エマルジョンと同様に室
温で乾燥した時に均一で強靭な皮膜を形成することがで
きるが、一般の合成樹脂エマルジョンを室温乾燥して得
られた皮膜と比較すると耐水性が非常に悪いという欠点
を有していた。皮膜の耐水性が悪い理由としては、再乳
化性合成樹脂エマルジョン粉末中に保護コロイドである
水溶性高分子化合物が多量に含まれるためと考えられ
る。The conventional re-emulsifiable synthetic resin emulsion powder is not only re-emulsified in water, but also has a uniform and strong toughness when the re-emulsified liquid is dried at room temperature like a synthetic resin emulsion. Although a film can be formed, it has a drawback that its water resistance is very poor as compared with a film obtained by drying a general synthetic resin emulsion at room temperature. The reason why the water resistance of the film is poor is considered to be that a large amount of a water-soluble polymer compound as a protective colloid is contained in the re-emulsifiable synthetic resin emulsion powder.
【０００５】従来の再乳化性合成樹脂エマルジョン粉末
を再乳化した後に得られた皮膜は、例えば常態で強度７
０Ｋｇｆ／ｃｍ２、伸度４００％である皮膜でも、水中
に２日間浸漬すると強度０Ｋｇｆ／ｃｍ２、伸度０％と
なり、皮膜は全く耐水性を示さなかった。再乳化性合成
樹脂エマルジョン粉末を再乳化した後に得られた皮膜の
耐水性を向上することは、再乳化性との関係で非常に困
難であった。例えば、水溶性高分子化合物の使用量を少
なくして再乳化性合成樹脂エマルジョン粉末の親水性を
下げれば、再乳化性が得られなくなるか、著しく低下し
た。[0005] A film obtained after re-emulsifying a conventional re-emulsifiable synthetic resin emulsion powder has, for example, a strength of 7 under normal conditions.
Even a film having 0 kgf / cm 2 and an elongation of 400% had a strength of 0 kgf / cm 2 and an elongation of 0% when immersed in water for 2 days, and showed no water resistance at all. It has been very difficult to improve the water resistance of the film obtained after re-emulsifying the re-emulsifiable synthetic resin emulsion powder in relation to the re-emulsifiability. For example, if the hydrophilicity of the re-emulsifiable synthetic resin emulsion powder was reduced by reducing the amount of the water-soluble polymer compound used, re-emulsifiability could not be obtained or was significantly reduced.
【０００６】再乳化性合成樹脂エマルジョン粉末中の水
溶性高分子化合物としてはポリビニルアルコールを使用
していることが多い。この水溶性のポリビニルアルコー
ルを水不溶化する方法は古くから研究されており、例え
ば、グリオキザールや銅、硼素、アルミニウム、チタン
などのイオンと架橋すると耐水性が向上する。しかし、
これらの方法ではポリビニルアルコールが不溶化し再乳
化性が得られなくなるため再乳化性合成樹脂エマルジョ
ン粉末の耐水性の向上には利用出来なかった。As the water-soluble polymer compound in the re-emulsifiable synthetic resin emulsion powder, polyvinyl alcohol is often used. The method of insolubilizing this water-soluble polyvinyl alcohol with water has been studied for a long time. For example, when crosslinked with ions such as glyoxal, copper, boron, aluminum, and titanium, the water resistance is improved. But,
These methods cannot be used for improving the water resistance of the re-emulsifiable synthetic resin emulsion powder because polyvinyl alcohol is insoluble and re-emulsifiability cannot be obtained.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、再乳化性
合成樹脂エマルジョン粉末の再乳化性を低下することな
く再乳化性合成樹脂エマルジョン粉末より得られた皮膜
の耐水性を向上する方法について、鋭意研究を重ねた結
果、再乳化性合成樹脂エマルジョン粉末にカルシウムま
たはマグネシウムの酸化物または水酸化物から選ばれた
１または２以上を加えることにより再乳化性を損なうこ
となく、再乳化した後に得られた皮膜の耐水性が向上す
ることを見出し本発明を完成した。Means for Solving the Problems The present inventors have developed a method for improving the water resistance of a film obtained from a re-emulsifiable synthetic resin emulsion powder without reducing the re-emulsifiability of the re-emulsifiable synthetic resin emulsion powder. As a result of intensive studies, re-emulsification was performed without impairing the re-emulsifiability by adding one or more selected from oxides or hydroxides of calcium or magnesium to the re-emulsifiable synthetic resin emulsion powder. The inventors have found that the water resistance of the film obtained later is improved and completed the present invention.
【０００８】本発明は、 「（１） （ａ） 水酸基を持った水溶性高分子化合物
を保護コロイドとして含有するビニル系合成樹脂水性エ
マルジョンを噴霧乾燥して得た再乳化性合成樹脂エマル
ジョン粉末と、 １００重量部 （ｂ） カルシウムまたはマグネシウムの酸化物または
水酸化物から選ばれた１または２以上 ０．５〜１００
重量部とからなる耐水性を向上した再乳化性合成樹脂エ
マルジョン粉末組成物。 （２） （ａ） 水酸基を持った水溶性高分子化合物が
ポリビニルアルコールである１項に記載の耐水性を向上
した再乳化性合成樹脂エマルジョン粉末組成物。 （３） （ａ）の再乳化性合成樹脂エマルジョン粉末が
水酸基を持った水溶性高分子化合物を保護コロイドとし
て含有し、ガラス転移点が２０℃以下のビニル系合成樹
脂水性エマルジョンを抗粘結剤とともに噴霧乾燥して得
た再乳化性合成樹脂エマルジョン粉末である１項または
２に記載の耐水性を向上した再乳化性合成樹脂エマルジ
ョン粉末組成物。 （４） 抗粘結剤が無機粉末である３項に記載の耐水性
を向上した再乳化性合成樹脂エマルジョン粉末組成物。 （５） 抗粘結剤が、ガラス転移点が８０℃以上のビニ
ル系合成樹脂水性エマルジョンである３項に記載の耐水
性を向上した再乳化性合成樹脂エマルジョン粉末組成
物。 （６） （ｂ）が水酸化カルシウムである１項ないし５
のいずれか１項に記載の耐水性を向上した再乳化性合成
樹脂エマルジョン粉末組成物。」 に関する。The present invention relates to (1) (a) a re-emulsifiable synthetic resin emulsion powder obtained by spray-drying a vinyl synthetic resin aqueous emulsion containing a water-soluble polymer compound having a hydroxyl group as a protective colloid; 100 parts by weight (b) one or more selected from oxides or hydroxides of calcium or magnesium 0.5 to 100
A re-emulsifiable synthetic resin emulsion powder composition having improved water resistance comprising parts by weight. (2) The re-emulsifiable synthetic resin emulsion powder composition according to item 1, wherein the water-soluble polymer compound having a hydroxyl group is polyvinyl alcohol. (3) The re-emulsifiable synthetic resin emulsion powder (a) contains, as a protective colloid, a water-soluble polymer compound having a hydroxyl group, and an aqueous vinyl synthetic resin emulsion having a glass transition point of 20 ° C. or lower. 3. The re-emulsifiable synthetic resin emulsion powder composition having improved water resistance according to item 1 or 2, which is a re-emulsifiable synthetic resin emulsion powder obtained by spray drying. (4) The re-emulsifiable synthetic resin emulsion powder composition according to item 3, wherein the anti-binder is an inorganic powder. (5) The re-emulsifiable synthetic resin emulsion powder composition having improved water resistance according to item 3, wherein the anti-binder is an aqueous vinyl synthetic resin emulsion having a glass transition point of 80 ° C or higher. (6) Items 1 to 5 wherein (b) is calcium hydroxide.
The re-emulsifiable synthetic resin emulsion powder composition having improved water resistance according to any one of the above. About.
【０００９】[0009]
【作用】本発明に使用される再乳化性合成樹脂エマルジ
ョンとしては、水酸基を持った水溶性高分子化合物を保
護コロイドとして含有するビニル系合成樹脂水性エマル
ジョンを噴霧乾燥して得た再乳化性合成樹脂エマルジョ
ン粉末である。The re-emulsifiable synthetic resin emulsion used in the present invention is a re-emulsifiable synthetic resin emulsion obtained by spray-drying a vinyl synthetic resin aqueous emulsion containing a water-soluble polymer compound having a hydroxyl group as a protective colloid. It is a resin emulsion powder.
【００１０】水酸基を持った水溶性高分子化合物として
は、ポリビニルアルコール、メチルセルロース、ヒドロ
キシエチルセルロース、カルボキシメチルセルロースな
どであり、特にポリビニルアルコールは再乳化性が良
い。Examples of the water-soluble high molecular compound having a hydroxyl group include polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like. In particular, polyvinyl alcohol has good re-emulsifiability.
【００１１】本発明で使用するビニル系合成樹脂エマル
ジョンは、水酸基を持った水溶性高分子化合物を保護コ
ロイドとしてビニル系単量体を乳化重合したエマルジョ
ンである。ビニル系単量体としては特に限定されない
が、酢酸ビニル、バーサテイク酸ビニルエステル、アク
リル酸エステル、メタクリル酸エステル、スチレン、塩
化ビニルなどの単量体が使用される。本発明で使用する
これ等の単量体を重合した重合体としては特にエチレン
−酢酸ビニル共重合体および酢酸ビニル−バーサテイク
酸ビニルエステル共重合体、アクリル酸エステル−メタ
クリル酸エステル共重合体が好ましい。再乳化した液が
室温で乾燥することにより皮膜を形成するためには、再
乳化性粉末となるビニル系合成樹脂水性エマルジョンの
樹脂のガラス転移点は２０℃以下である必要が在り、特
に０℃以下であることが好ましい。The vinyl synthetic resin emulsion used in the present invention is an emulsion obtained by emulsion polymerization of a vinyl monomer using a water-soluble polymer compound having a hydroxyl group as a protective colloid. The vinyl monomer is not particularly limited, but monomers such as vinyl acetate, vinyl versatate, acrylate, methacrylate, styrene, and vinyl chloride are used. The polymer obtained by polymerizing these monomers used in the present invention is particularly preferably an ethylene-vinyl acetate copolymer and a vinyl acetate-vinyl versatate ester copolymer, and an acrylate-methacrylate ester copolymer. . In order to form a film by drying the re-emulsified liquid at room temperature, the glass transition point of the resin of the aqueous vinyl-based synthetic resin emulsion as a re-emulsifiable powder needs to be 20 ° C. or less, particularly 0 ° C. The following is preferred.
【００１２】ガラス転移点が２０℃を越えるビニル系合
成樹脂は再乳化した液をそのガラス転移点以上の温度で
乾燥しなければ皮膜を形成することができないので実用
的でない。つまりガラス転移点が２０℃以上の合成樹脂
は加熱乾燥する用途には使用できるが、一般に水性エマ
ルジョンは室温で乾燥することが多く、ガラス転移点２
０℃以下のものが好んで使用される。A vinyl-based synthetic resin having a glass transition point exceeding 20 ° C. is not practical because a re-emulsified liquid cannot be formed unless dried at a temperature not lower than the glass transition point. In other words, a synthetic resin having a glass transition point of 20 ° C. or higher can be used for drying by heating.
Those having a temperature of 0 ° C. or lower are preferably used.
【００１３】ガラス転移点が２０℃以下であるビニル系
水性合成樹脂のエマルジョンを単独で噴霧乾燥するとビ
ニル系合成樹脂粒子同士が粘結してブロック化し、粉末
が得られないため、抗粘結剤が必要である。抗粘結剤と
しては、シリカ、炭酸カルシウム、珪酸アルミニウムな
どの平均粒子径０．０１〜０．５μｍの無機微粉末が使
用される。When an emulsion of a vinyl-based aqueous synthetic resin having a glass transition point of 20 ° C. or lower is spray-dried alone, the vinyl-based synthetic resin particles are caking and blocked, and a powder cannot be obtained. is necessary. As the anti-binder, an inorganic fine powder having an average particle diameter of 0.01 to 0.5 μm, such as silica, calcium carbonate, and aluminum silicate, is used.
【００１４】ガラス転移点が２０℃以下のビニル系合成
樹脂のエマルジョン５０〜９５重量部にガラス転移点が
８０℃以上のビニル系合成樹脂の水性エマルジョン５０
〜５重量部（固形分換算）を使用すれば、この樹脂粉末
が抗粘結剤として作用するので無機微粉末を抗粘結剤と
して使用せずに再乳化性粉末を得ることができる。ガラ
ス転移点が８０℃以上のビニル系合成樹脂を用いた再乳
化性エマルジョン粉末は、無機微粉末を用いたものより
皮膜強度が高くなる利点がある。勿論無機粉末を併用し
てもよい。An aqueous emulsion 50 of a vinyl-based synthetic resin having a glass transition point of 80 ° C. or more is added to 50 to 95 parts by weight of an emulsion of a vinyl-based synthetic resin having a glass transition point of 20 ° C. or less.
When used in an amount of up to 5 parts by weight (in terms of solid content), this resin powder acts as an anti-binder, so that a re-emulsifiable powder can be obtained without using an inorganic fine powder as an anti-binder. A re-emulsifiable emulsion powder using a vinyl-based synthetic resin having a glass transition point of 80 ° C or higher has an advantage that the film strength is higher than that using an inorganic fine powder. Of course, inorganic powders may be used in combination.
【００１５】本発明に使用されるカルシウムまたはマグ
ネシウムの酸化物または水酸化物としては、酸化カルシ
ウム、過酸化カルシウム、生石灰、酸化マグネシウム、
焼成マグネシウム、水酸化カルシウム、消石灰、水酸化
マグネシウムから選ばれた１または２以上である。この
化合物は再乳化性樹脂エマルジョンが形成する皮膜の耐
水性を向上する作用を奏する。再乳化性合成樹脂エマル
ジョン粉末とカルシウムまたはマグネシウムの酸化物ま
たは水酸化物から選ばれた１または２以上との配合割合
は再乳化性合成樹脂エマルジョン粉末１００重量部に対
して０．５〜１００重量部であり、１〜２０重量部が好
ましい。０．５重量部以下では、耐水性を向上する効果
が少なく、１００重量部では再乳化性合成樹脂エマルジ
ョン粉末の効果が得られない。２０重量部以上加えても
それ以上の耐水性の向上は認められないので、耐水性を
向上する目的で加えるには２０重量部以下が好ましい。The calcium or magnesium oxide or hydroxide used in the present invention includes calcium oxide, calcium peroxide, quicklime, magnesium oxide,
One or more selected from calcined magnesium, calcium hydroxide, slaked lime, and magnesium hydroxide. This compound has the effect of improving the water resistance of the film formed by the re-emulsifiable resin emulsion. The mixing ratio of the re-emulsifiable synthetic resin emulsion powder and one or more selected from oxides or hydroxides of calcium or magnesium is 0.5 to 100 parts by weight based on 100 parts by weight of the re-emulsifiable synthetic resin emulsion powder. Parts by weight, preferably 1 to 20 parts by weight. If the amount is less than 0.5 part by weight, the effect of improving the water resistance is small, and if it is 100 parts by weight, the effect of the re-emulsifiable synthetic resin emulsion powder cannot be obtained. Even if it is added in an amount of 20 parts by weight or more, no further improvement in water resistance is recognized. Therefore, in order to improve the water resistance, the addition is preferably 20 parts by weight or less.
【００１６】カルシウムまたはマグネシウムの酸化物ま
たは水酸化物から選ばれた１または２以上の効果につい
ては、消石灰の主成分は水酸化カルシウムであり、酸化
カルシウムや生石灰は水と反応して水酸化カルシウムを
生成する。また過酸化カルシウム、酸化マグネシウム、
焼成マグネシウム、水酸化マグネシウムなどもまた水酸
化カルシウムと同様の効果が奏されるものと考えられる
ので、以下水酸化カルシウムについて効果を述べる。水
酸化カルシウムは難溶性であって、水溶解度は水１００
ｇに対しわずか０．１４ｇにすぎない。そのため再乳化
性合成樹脂エマルジョン粉末に水酸化カルシウムを混在
していても粉末組成物の再乳化性を阻害しない。しか
も、水酸化カルシウムを混在する粉末組成物を水に再乳
化した再乳化液が乾燥して皮膜が形成する時に、水酸基
を持った水溶性高分子化合物が水酸化カルシウムとコン
プレックスを形成し不溶化することで、皮膜の耐水性が
向上する。カルシウムの化合物でも、炭酸カルシウムな
どは水酸基を持った水溶性高分子化合物とコンプレック
スを形成しないため皮膜の耐水性の向上は認められな
い。Regarding one or more effects selected from oxides or hydroxides of calcium or magnesium, the main component of slaked lime is calcium hydroxide, and calcium oxide and quick lime react with water to form calcium hydroxide. Generate In addition, calcium peroxide, magnesium oxide,
Since it is considered that calcined magnesium, magnesium hydroxide and the like also exert the same effect as calcium hydroxide, the effect of calcium hydroxide will be described below. Calcium hydroxide is poorly soluble and has a water solubility of 100
Only 0.14 g per g. Therefore, even if calcium hydroxide is mixed in the re-emulsifiable synthetic resin emulsion powder, the re-emulsifiability of the powder composition is not hindered. In addition, when the re-emulsified liquid obtained by re-emulsifying the powder composition containing calcium hydroxide in water is dried to form a film, the water-soluble polymer compound having a hydroxyl group forms a complex with calcium hydroxide and becomes insoluble. This improves the water resistance of the film. Even with calcium compounds, calcium carbonate and the like do not form a complex with a water-soluble polymer compound having a hydroxyl group, and therefore, improvement in water resistance of the film is not recognized.
【００１７】[0017]
【実施例】以下、実施例を挙げて本願発明を説明する。The present invention will be described below with reference to examples.
【００１８】実施例１ ポリビニルアルコール（日本合成化学工業株式会社製
「ゴーセノールＧＬ０５」（商品名））を保護コロイド
としてエマルジョン固形分中に１０重量％含有する酢酸
ビニル−バーサテイク酸ビニル共重合体（ガラス転移点
は１５℃）水性エマルジョン（固形分濃度５０重量％）
１００重量部（固形分換算）と、平均粒子径０．０２μ
ｍの珪酸微粉末（株式会社トクヤマ製「トクシール」
（商品名））１０重量部と、別々のノズルから噴霧し、
同時に乾燥した再乳化性合成樹脂エマルジョン粉末１０
０重量部に、水酸化カルシウム粉末を０．５重量部、１
重量部、２重量部、５重量部、１０重量部、を加えて均
一に混合して、耐水性を向上した再乳化性合成樹脂エマ
ルジョン粉末組成物を得た。Example 1 A vinyl acetate-vinyl versatate copolymer (glass) containing polyvinyl alcohol ("Gohsenol GL05" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a protective colloid in an emulsion solid content of 10% by weight. Transition point: 15 ° C) aqueous emulsion (solids concentration 50% by weight)
100 parts by weight (in terms of solid content) and an average particle diameter of 0.02 μm
m silica powder (“Tokuseal” manufactured by Tokuyama Corporation)
(Product name)) 10 parts by weight and sprayed from separate nozzles,
Simultaneously dried re-emulsifiable synthetic resin emulsion powder 10
0 parts by weight, 0.5 parts by weight of calcium hydroxide powder, 1 part by weight
Parts by weight, 2 parts by weight, 5 parts by weight, and 10 parts by weight were added and uniformly mixed to obtain a re-emulsifiable synthetic resin emulsion powder composition having improved water resistance.
【００１９】比較例１ 実施例１で使用した、ポリビニルアルコールを保護コロ
イドとしてエマルジョン固形分中に１０重量％含有する
酢酸ビニル−バーサテイク酸ビニル共重合体（ガラス転
移点は１５℃）水性エマルジョン（固形分濃度５０重量
％）１００重量部（固形分換算）と、平均粒子径０．０
２μｍの珪酸微粉末１０重量部と、別々のノズルから噴
霧し、同時に乾燥した再乳化性合成樹脂エマルジョン粉
末をそのまま合成樹脂粉末として使用した。Comparative Example 1 A vinyl acetate-vinyl versatate copolymer (glass transition point: 15 ° C.) containing 10% by weight of polyvinyl alcohol as a protective colloid in the emulsion solid used in Example 1 100 parts by weight (in terms of solid content) and an average particle diameter of 0.0
A re-emulsifiable synthetic resin emulsion powder sprayed from a separate nozzle and dried simultaneously with 10 parts by weight of a 2 μm silicic acid fine powder was used as a synthetic resin powder.
【００２０】比較例２ 実施例１で使用した再乳化性合成樹脂エマルジョン粉末
１００重量部に炭酸カルシウム５重量部を加え均一に混
合して合成樹脂粉末組成物とした。Comparative Example 2 5 parts by weight of calcium carbonate was added to 100 parts by weight of the re-emulsifiable synthetic resin emulsion powder used in Example 1 and uniformly mixed to obtain a synthetic resin powder composition.
【００２１】比較例３ 実施例１で使用した再乳化性合成樹脂エマルジョン粉末
１００重量部に硼砂５重量部を加え均一に混合して合成
樹脂粉末組成物とした。Comparative Example 3 To 100 parts by weight of the re-emulsifiable synthetic resin emulsion powder used in Example 1, 5 parts by weight of borax was added and uniformly mixed to obtain a synthetic resin powder composition.
【００２２】試験例 実施例１で得た耐水性を向上した再乳化性合成樹脂エマ
ルジョン粉末組成物と比較例１〜３で得た合成樹脂粉末
について再分散性、標準時の皮膜の強度および伸度、水
中時の皮膜の強度および伸度を測定した。Test Example Redispersibility of the re-emulsifiable synthetic resin emulsion powder composition having improved water resistance obtained in Example 1 and the synthetic resin powder obtained in Comparative Examples 1 to 3, and the strength and elongation of the film at the standard time The strength and elongation of the film in water were measured.
【００２３】再分散性試験 合成樹脂エマルジョン粉末組成物１００重量部を水１０
０重量部に加え、撹拌機で充分撹拌し、再乳化性を観察
した。 ○ ： 合成樹脂粉末は再乳化し、安定な乳化液が得れ
れた。 × ： 合成樹脂粉末は再乳化せず、安定な乳化液は得
られなかった。 試験結果は表１の通りであった。Redispersibility test 100 parts by weight of the synthetic resin emulsion powder composition was added to water 10
In addition to 0 parts by weight, the mixture was sufficiently stirred with a stirrer, and the re-emulsifiability was observed. : The synthetic resin powder was re-emulsified, and a stable emulsion was obtained. ×: The synthetic resin powder was not re-emulsified, and a stable emulsion was not obtained. Table 1 shows the test results.
【００２４】標準時の皮膜の強度および伸度試験 再分散性試験で得られた乳化液を水で２０重量％まで希
釈し、ポリエチレンフイルム上に均一に流し込み４０℃
の恒温機中で乾燥して皮膜を形成し、温度２０℃、湿度
６５％ＲＨの条件下に２４時間放置した皮膜について、
引張り速度３００ｍｍ／ｍｉｎでオートグラフにより強
伸度を測定した。試験結果は表１の通りであった。 水中時の皮膜の強度および伸度試験 標準時の皮膜と同様にして得られた皮膜を２０℃の水中
に４８時間浸漬し、含水状態で皮膜の強伸度を標準時と
同様にして測定した。試験結果は表１の通りであった。Film strength and elongation test at standard time The emulsion obtained in the redispersibility test was diluted to 20% by weight with water and poured uniformly on a polyethylene film at 40 ° C.
A film was formed by drying in a thermostat at a temperature of 20 ° C. and a humidity of 65% RH for 24 hours.
The strength and elongation were measured by an autograph at a tensile speed of 300 mm / min. Table 1 shows the test results. Test of Strength and Elongation of Film in Water The film obtained in the same manner as the film in the standard condition was immersed in water at 20 ° C. for 48 hours, and the strength and elongation of the film in a water-containing state were measured in the same manner as in the standard condition. Table 1 shows the test results.
【００２５】[0025]
【表１】 [Table 1]
【００２６】実施例２ ポリビニルアルコール（日本合成化学工業株式会社製
「ゴーセノールＧＬ０５」（商品名））を保護コロイド
としてエマルジョン固形分中に１０重量％含有するエチ
レン−酢酸ビニル共重合体（ガラス転移点は０℃）水性
エマルジョン（固形分濃度５０重量％）１００重量部
（固形分換算）と、平均粒子径０．１μｍの炭酸カルシ
ウム微粉末（丸尾カルシウム株式会社製「ナノックス」
（商品名））２０重量部と、別々のノズルから噴霧し、
同時に乾燥した再乳化性合成樹脂エマルジョン粉末１０
０重量部に、消石灰５重量部、を加えて均一に混合し
て、耐水性を向上した再乳化性合成樹脂エマルジョン粉
末組成物を得た。実施例２で得た耐水性を向上した再乳
化性合成樹脂エマルジョン粉末組成物と消石灰を加えな
かったものについて、前記の試験例と同様に皮膜の強度
および伸度を試験した。結果を表２に示す。Example 2 An ethylene-vinyl acetate copolymer (glass transition point) containing polyvinyl alcohol ("Gohsenol GL05" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a protective colloid in an emulsion solid content of 10% by weight. Is 0 ° C.) 100 parts by weight of an aqueous emulsion (solid content concentration: 50% by weight) (calculated as solid content) and fine calcium carbonate powder having an average particle diameter of 0.1 μm (“Nanox” manufactured by Maruo Calcium Co., Ltd.)
(Product name)) Sprayed from 20 parts by weight and separate nozzle,
Simultaneously dried re-emulsifiable synthetic resin emulsion powder 10
To 0 part by weight, 5 parts by weight of slaked lime were added and uniformly mixed to obtain a re-emulsifiable synthetic resin emulsion powder composition having improved water resistance. With respect to the re-emulsifiable synthetic resin emulsion powder composition obtained in Example 2 having improved water resistance and a composition to which slaked lime was not added, the strength and elongation of the film were tested in the same manner as in the above-mentioned test examples. Table 2 shows the results.
【００２７】実施例３ ポリビニルアルコール（日本合成化学工業株式会社製
「ゴーセノールＧＬ０５」（商品名））を保護コロイド
としてエマルジョン固形分中に２０重量％含有するメタ
クリル酸メチル−アクリル酸ブチル共重合体（ガラス転
移点は０℃）水性エマルジョン（固形分濃度３５重量
％）１００重量部（固形分換算）と、平均粒子径０．２
μｍの珪酸微粉末１０重量部（株式会社トクヤマ製「ト
クシール」（商品名））と、別々のノズルから噴霧し、
同時に乾燥した再乳化性合成樹脂エマルジョン粉末１０
０重量部に、消石灰１０重量部、を加えて均一に混合し
て、耐水性を向上した再乳化性合成樹脂エマルジョン粉
末組成物を得た。実施例２で得た耐水性を向上した再乳
化性合成樹脂エマルジョン粉末組成物と消石灰を加えな
かったものについて、前記の試験例と同様に皮膜の強度
および伸度を試験した。結果を表２に示す。Example 3 Methyl methacrylate-butyl acrylate copolymer containing polyvinyl alcohol ("Gohsenol GL05" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a protective colloid in an emulsion solid content of 20% by weight ( Glass transition point: 0 ° C.) 100 parts by weight (solid content conversion) of an aqueous emulsion (solid content concentration: 35% by weight) and an average particle size of 0.2
Sprayed from a separate nozzle with 10 parts by weight of a fine silica powder of 10 μm (“Tokuseal” (trade name) manufactured by Tokuyama Corporation)
Simultaneously dried re-emulsifiable synthetic resin emulsion powder 10
0 parts by weight and 10 parts by weight of slaked lime were added and mixed uniformly to obtain a re-emulsifiable synthetic resin emulsion powder composition having improved water resistance. With respect to the re-emulsifiable synthetic resin emulsion powder composition obtained in Example 2 having improved water resistance and a composition to which slaked lime was not added, the strength and elongation of the film were tested in the same manner as in the above-mentioned test examples. Table 2 shows the results.
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【発明の効果】本発明はカルシウムまたはマグネシウム
の酸化物または水酸化物から選んだ１または２以上を配
合することにより再乳化性合成樹脂エマルジョンにより
形成される被膜等の耐水性を著しく向上した優れた効果
を奏する。According to the present invention, the water resistance of a coating formed by a re-emulsifiable synthetic resin emulsion is remarkably improved by blending one or more selected from oxides or hydroxides of calcium or magnesium. It has the effect.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 米国特許3879335（ＵＳ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 3/12 101 ────────────────────────────────────────────────── (5) References US Patent 3,879,335 (US, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08J 3/12 101
Claims (6)
合物を保護コロイドとして含有するビニル系合成樹脂水
性エマルジョンを噴霧乾燥して得た再乳化性合成樹脂エ
マルジョン粉末と、 １００重量部 （ｂ） カルシウムまたはマグネシウムの酸化物または
水酸化物から選ばれた１または２以上 ０．５〜１００
重量部とからなる耐水性を向上した再乳化性合成樹脂エ
マルジョン粉末組成物。1. A re-emulsifiable synthetic resin emulsion powder obtained by spray-drying a vinyl synthetic resin aqueous emulsion containing a water-soluble polymer compound having a hydroxyl group as a protective colloid, and 100 parts by weight (b) 1) one or more selected from oxides or hydroxides of calcium or magnesium 0.5 to 100
A re-emulsifiable synthetic resin emulsion powder composition having improved water resistance comprising parts by weight.
合物がポリビニルアルコールである請求項１に記載の耐
水性を向上した再乳化性合成樹脂エマルジョン粉末組成
物。2. The re-emulsifiable synthetic resin emulsion powder composition having improved water resistance according to claim 1, wherein (a) the water-soluble polymer compound having a hydroxyl group is polyvinyl alcohol.
粉末が水酸基を持った水溶性高分子化合物を保護コロイ
ドとして含有し、ガラス転移点が２０℃以下のビニル系
合成樹脂水性エマルジョンを抗粘結剤とともに噴霧乾燥
して得た再乳化性合成樹脂エマルジョン粉末である請求
項１または２に記載の耐水性を向上した再乳化性合成樹
脂エマルジョン粉末組成物。3. The re-emulsifiable synthetic resin emulsion powder of (a) contains a water-soluble polymer compound having a hydroxyl group as a protective colloid, and has a glass transition point of 20 ° C. or lower, which is an aqueous emulsion of a vinyl synthetic resin. The re-emulsifiable synthetic resin emulsion powder composition according to claim 1 or 2, which is a re-emulsifiable synthetic resin emulsion powder obtained by spray drying with a binder.
載の耐水性を向上した再乳化性合成樹脂エマルジョン粉
末組成物。4. The re-emulsifiable synthetic resin emulsion powder composition according to claim 3, wherein the anti-binder is an inorganic powder.
のビニル系合成樹脂水性エマルジョンである請求項３に
記載の耐水性を向上した再乳化性合成樹脂エマルジョン
粉末組成物。5. The re-emulsifiable synthetic resin emulsion powder composition having improved water resistance according to claim 3, wherein the anti-binder is an aqueous emulsion of a vinyl synthetic resin having a glass transition point of 80 ° C. or higher.
１ないし５のいずれか１項に記載の耐水性を向上した再
乳化性合成樹脂エマルジョン粉末組成物。6. The re-emulsifiable synthetic resin emulsion powder composition according to any one of claims 1 to 5, wherein (b) is calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36128091A JP3295116B2 (en) | 1991-12-26 | 1991-12-26 | Re-emulsifiable synthetic resin emulsion powder composition with improved water resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36128091A JP3295116B2 (en) | 1991-12-26 | 1991-12-26 | Re-emulsifiable synthetic resin emulsion powder composition with improved water resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05179008A JPH05179008A (en) | 1993-07-20 |
| JP3295116B2 true JP3295116B2 (en) | 2002-06-24 |
Family
ID=18472927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36128091A Expired - Fee Related JP3295116B2 (en) | 1991-12-26 | 1991-12-26 | Re-emulsifiable synthetic resin emulsion powder composition with improved water resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3295116B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2411266C2 (en) | 2005-11-24 | 2011-02-10 | Зе Ниппон Синтетик Кемикал Индастри Ко., Лтд. | Re-emulsifiable powdered resin, aqueous emulsion and adhesive composition based on said emulsion |
| JP4979494B2 (en) * | 2006-07-26 | 2012-07-18 | 日本合成化学工業株式会社 | Re-emulsifiable resin powder composition for hydraulic material, aqueous emulsion for hydraulic material, and building finish coating material using them |
| UA109282C2 (en) | 2010-07-09 | 2015-08-10 | WATER-BASED PESTICIDAL SUSPENSION |
-
1991
- 1991-12-26 JP JP36128091A patent/JP3295116B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05179008A (en) | 1993-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5534585A (en) | Polymer-modified particulate titanium dioxide | |
| JP2831317B2 (en) | Chemical composition redispersible in an aqueous medium comprising a copolymer and a protective colloid, an aqueous polymer dispersion thereof, a method for its production and a method for its use | |
| US5519084A (en) | Redispersible acrylic polymer powder for cementitious compositions | |
| KR100275289B1 (en) | Re-dispersible polymer powder and aqueous polymer dispersions obtained from it | |
| KR100197342B1 (en) | Redispersible dispersion powder composition, method of manufacturing it and its use | |
| EP0123927B1 (en) | Water resistant compositions | |
| RU2638984C2 (en) | Water-soluble powder polymers having improved dispersibility | |
| JPH07165843A (en) | Water-base latex polymer composition | |
| GB1569637A (en) | Preparation of dispersible dispersion powders | |
| EP0576844A1 (en) | Redispersible polymer powders using polyvinyl pyrrolidone as a dispersing aid | |
| JP3506453B2 (en) | Polychloroprene latex composition | |
| CN114181607A (en) | Waterborne polyurethane waterproof coating and cold preparation process thereof | |
| US6531538B1 (en) | Fast-drying rendering and coating composition | |
| JPH11263849A (en) | Preparation of synthetic resin emulsion powder | |
| JP3295116B2 (en) | Re-emulsifiable synthetic resin emulsion powder composition with improved water resistance | |
| US3092600A (en) | Modified polyvinyl acetate powders and compositions | |
| JP3342883B2 (en) | Re-emulsifiable synthetic resin emulsion powder composition and method for producing the same | |
| KR102006822B1 (en) | Polyvinyl chloride resin latex composition and method for preparing the same | |
| JPH0242397B2 (en) | ||
| JPS5874724A (en) | Redispersible powder composition | |
| JPH0657753B2 (en) | Manufacturing method of aqueous dispersion | |
| CN115516047A (en) | Powder coating composition | |
| JP3357710B2 (en) | Emulsion composition | |
| JP3519119B2 (en) | Aqueous coating composition and method for producing the same | |
| JP3332097B2 (en) | Aqueous thickened latex composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080405 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090405 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090405 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20100405 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20100405 |
|
| LAPS | Cancellation because of no payment of annual fees |