JP4316055B2 - Acrylic resin composition - Google Patents

Description

【００２０】
【化２】

【００２１】
【化３】

【００２２】
【化４】

【００２３】
上記非イオン系界面活性剤は、多段階重合体（Ｉ）のラテックスを塩析あるいは凍結−融解してなる多段階重合体（Ｉ）の凝固物のスラリー状態で加える。この際、上記非イオン系界面活性剤は単独であるいは併用して用いることができる。添加量は、多段階重合体（Ｉ）１００重量部に対し０．００５〜１重量部、好ましくは０．０１〜０．６重量部、更に好ましくは０．０５〜０．４重量部である。非イオン性界面活性剤の添加量が１重量部を越えると、非イオン性界面活性剤が最終的に得られる樹脂改質剤に多く残存し、着色や基材となる熱可塑性樹脂の特性低下を招く場合が多く好ましくない。一方、添加量が０．００５重量部未満では、添加効果が少なく凝固物同士のブロッキングや、スラリー輸送配管の閉塞、スラリーの泡立ちなどを起こしやすく好ましくない。
【００２４】
本発明において消泡作用のある非イオン系界面活性剤（ＩＩ）は、アクリル系樹脂組成物の製造において、凝固物のスラリーを脱水する前に添加する。この添加方法によれば、スラリーの安定性を増し、スラリー輸送配管の詰まりなどが著しく低減できるばかりでなく、凝固粒子の粒径も安定したものが得られる。
【００２５】
また、本発明で用いる脂肪酸の塩もしくはエステル、多価アルコールのエステル、無機塩、無機酸化物の群から選ばれる少なくとも１種の化合物（III）は、一般的に膠着防止効果の大きいものが好ましい。その具体例としては、ステアリン酸カルシウム、炭酸カルシウム、硫酸カルシウム、硫酸マグネシウム、硫酸バリウム、二酸化ケイ素などが挙げられる。これらの化合物は、上記消泡作用のある非イオン系界面活性剤（II）と組み合わせることにより多段階重合体（Ｉ）との分散性が向上し、それによって耐衝撃性の改善をより効果的にすることができる。その使用量は、多段階重合体（Ｉ）１００重量部に対して、通常０．０１〜１重量部、好ましくは０．１〜０．５重量部である。添加量が０．０１重量部未満では、膠着防止効果が少ないため好ましくなく、一方１重量部を越える場合は、膠着防止に更なる改善が見られず耐衝撃性改善効果の低下、成形加工時の金型汚れ、ブリードアウトなどが生じ易くなるため好ましくない。
【００２６】
多段階重合体（Ｉ）の凝固物スラリーの脱水は、公知のバケット型やデカンター型の遠心分離器等により行うことができ、乾燥は公知の流動乾燥機、振動乾燥機、熱風乾燥機などにより乾燥することができる。
【００２７】
本発明のアクリル系樹脂組成物には、必要に応じ紫外線吸収剤、滑剤、酸化防止剤、染料などの添加剤を含有していることができる。
得られたアクリル系樹脂組成物は、ポリ塩化ビニル樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリフッ化ビニリデン樹脂、ポリアミド樹脂、スチレン樹脂、アクリロニトリル−スチレン（ＡＳ）樹脂、ＡＢＳ樹脂、メタクリル樹脂等の耐衝撃性、耐溶剤性などの付与に有効に用いられる。
【００２８】
【実施例】
以下に具体的な実施例および比較例を挙げて説明するが、本発明はこれらに制限されるものではない。実施例および比較例で用いた「部」および「％」は全て「重量部」および「重量％」である。また、実施例および比較例の評価は以下の方法により行った。
（１）粒子径測定
大塚電子（株）製光散乱光度計ＤＬＳ−６００を用い測定した。
（２）粒度測定
２００ｇのアクリル系樹脂組成物の粉体を標準ふるいにより、分級し、重量平均粒径を平均粒度とした。
（３）アイゾット衝撃強度
ＡＳＴＭ Ｄ２５６に準じエッジワイズ、ノッチ有りの条件で３０ｋｇハンマーを使用し測定した。１０本評価しこのうち破断（ＮＢ）しなかった試験片の数（ＮＢ／試験数）で耐衝撃性改善効果を評価した。
（４）落球衝撃試験
水平に固定した試験板（１００ｍｍ×１００ｍｍ×１ｍｍｔ）の中心に鉛直に４０ｃｍの高さから、２ｋｇの鋼球を落下させ割れ発生の有無を確認した。１サンプル当たりの試験数を１０とし、耐衝撃性改良効果は割れが発生しなかった発生数をＮＢとし、ＮＢ／試験数で評価した。
【００２９】
実施例１
コンデンサー、温度計、攪拌機を備えたグラスライニング製７５リットル反応槽に、イオン交換水３３．４ｋｇを投入し、ニッコールＯＴＰ−１００（日光ケミカル製：ジオクチルスルホコハク酸ナトリウム）４０ｇおよび炭酸ナトリウム１０ｇを溶解して、攪拌しながら８０℃に昇温した。これとは別に３０リットルのステンレス容器にアクリル酸ブチル８．８７ｋｇ、メタクリル酸アリル１３５ｇ、ニッコールＯＴＰ−１００ ９０ｇを溶解し乳化剤溶解単量体混合物（１）を調製する。重合開始剤として過硫酸カリウム９ｇを投入した後、乳化剤溶解単量体混合物（１）を１．７重量％／分の供給速度で連続的に供給し重合を行った。乳化剤溶解単量体混合物（１）の供給が終了したら、撹拌しながら８０℃に３０分保持した後、過硫酸カリウム９ｇを投入した後アクリル酸ブチル８．８７ｋｇ、メタクリル酸アリル１３５ｇおよびニッコールＯＴＰ−１００ ４５ｇから成る乳化剤溶解単量体混合物（２）を２．０重量％／分の供給速度で連続的に供給し重合する。乳化剤溶解単量体混合物（２）の供給が終了したら、撹拌しながら８０℃に６０分保持し、過硫酸カリウム２．０ｇを投入した後、メタクリル酸メチル１．８８ｋｇ、アクリル酸メチル１２０ｇおよびニッコールＯＴＰ−１００ １０ｇから成る単量体混合物を５．０重量％／分の供給速度で連続的に供給して重合する。単量体混合物の供給が終了したら、撹拌しながら８０℃に６０分保持し、重合を完結させた。重合終了後４０℃まで冷却した後、３２５メッシュの金網で濾過して取り出し粒子径０．１４μｍの２段階重合体を３７％含有するエマルジョンを得た。
【００３０】
撹拌機、温度計およびジャケット付きの１００リットルのステンレス製タンクにイオン交換水を３３ｋｇ投入し、撹拌しながらデフォマックス７０２（東邦化学工業（株）製：プロピレンオキサイド主成分とする重合体のノニオン系界面活性剤、ＨＬＢ＝７）８．６ｇを投入し、３０℃に昇温した。−３０℃で凍結した２段階重合体の凍結エマルジョン１０ｋｇを砕きながら投入する。全ての凍結エマルジョンが全て融解し温度が一定となるのを確認し凝集重合体スラリーを得た。次いで凝集重合体スラリーを遠心分離器にフィードして洗浄、脱水した後、ステアリン酸カルシウム１１．１ｇを添加した後振動乾燥機にて乾燥して平均粒度２３５μｍで粒度の揃ったアクリル系樹脂組成物の粉体を得た。凝集体スラリーの性状を表１に示すが、凝集体の浮上もなく極めて安定に遠心分離器にフィードすることができ、また凝集重合体の合着による粗大粒子の生成も無かった。
得られたアクリル系樹脂組成物１０重量部を１００重量部のポリ塩化ビニル樹脂（ＰＶＣ）とミキサーにてブレンドし、スクリュー径３０ｍｍの二軸押出機にて溶融混練し、耐衝撃性改良ＰＶＣのペレットを得た。このペレットを住友重機（株）製ＳＧ−１００型射出成形機にてシリンダ−温度１８０℃、金型温度４０℃の条件でＩｚｏｄ試験片を成形し評価した。評価結果を表１に示す。
【００３１】
比較例１
撹拌機、温度計およびジャケット付きの１００リットルのステンレス製タンクにイオン交換水を３３ｋｇ投入し３０℃に昇温した。−３０℃で凍結した実施例１の２段階重合体の凍結エマルジョン１０ｋｇを砕きながら投入する。全ての凍結エマルジョンが全て融解し温度が一定となるのを確認し凝集重合体スラリーを得た。しかしながら凝集体スラリーの大部分が浮上し、スラリー移送時に配管の詰まりも発生したため洗浄、脱水のために遠心分離器にフィードできた凝集体量は乾燥した状態で全仕込量の１／４であった。また乾燥して得られた重合体は１０００μｍ以上の粗大粒子の粉体が混在した不均一な粉体であった。
得られた重合体は実施例１と同様の方法により評価を行ったが、実施例１に比べ耐衝撃性改良効果は低いものであった。粗大粒子が混在したため耐衝撃改良剤の分散不良が発生したものと考えられる。
【００３２】
比較例２
比較例１の凝集重合体スラリーを遠心分離器にフィードして洗浄、脱水した後、ステアリン酸カルシウム１１．１ｇ添加した後振動乾燥機にて乾燥して重合体の平均粒径３９５μｍの粉体を得た。これを実施例１と同様の操作で評価した。ステアリン酸カルシウムの添加によりある程度の粗大粒子生成の抑制効果があったが十分では無く、耐衝撃性改善効果は実施例１に比較して低いものであった。
【００３３】
実施例２
撹拌機、温度計およびジャケット付きの１００リットルのステンレス製タンクにイオン交換水を３３ｋｇ投入し、硫酸マグネシウム４０ｇを投入し４０℃に昇温した。実施例１の２段階重合体エマルジョン１０ｋｇ連続的にフィードして塩析を行った。ついで、撹拌しながらデフォマックス７０２を８．６ｇ投入したのち、８０℃に昇温して６０分保持して凝集重合体スラリーを得た。次いで凝集重合体スラリーを遠心分離器にフィードして洗浄、脱水した後、ステアリン酸カルシウム５．６ｇを添加して振動乾燥機にて乾燥することにより平均粒度２７２μｍで粒度の揃ったアクリル系樹脂組成物の粉体を得た。凝集体スラリーの性状を表１に示すが、凝集体の浮上もなく極めて安定に遠心分離器にフィードすることができ、また凝集重合体の合着による粗大粒子の生成も無かった。
得られたアクリル系樹脂組成物は実施例１と同様の操作でＩｚｏｄ試験片を成形し評価した。評価結果を表１に示す。
【００３４】
比較例３
撹拌機、温度計およびジャケット付きの１００リットルのステンレス製タンクにイオン交換水を３３ｋｇ投入し、硫酸マグネシウム４０ｇを投入し４０℃に昇温した。実施例１の２段階重合体エマルジョン１０ｋｇ連続的にフィードして塩析を行った後、８０℃に昇温して６０分保持して凝集重合体スラリーを得た。しかしながら凝集体スラリーの合着による粗大粒子が生成し、スラリー移送時に配管の詰まりも発生したため洗浄、脱水のために遠心分離器にフィードできた凝集体量は乾燥した状態で全仕込量の１／２であった。また乾燥して得られた樹脂改質剤は１０００μｍ以上の粗大粒子の粉体が混在した不均一な粉体であった。
得られた耐衝撃改良剤は実施例１と同様の方法により評価を行ったが、実施例２に比べ耐衝撃性改良効果は低いものであった。
【００３５】
実施例３
コンデンサー、温度計、攪拌機を備えたグラスライニング製７５リットルの反応槽に、イオン交換水３３．４ｋｇを投入し、ニッコールＯＴＰ−１００（日光ケミカル製：ジオクチルスルホコハク酸ナトリウム）２ｇおよび炭酸ナトリウム１０ｇを溶解して、攪拌しながら８０℃に昇温した。これとは別に３０リットルのステンレス容器にアクリル酸ブチル８．９ｋｇ、メタクリル酸アリル９０ｇ、１，６−ヘキサンジオールジアクリレート３６ｇおよびニッコールＯＴＰ−１００ ４５ｇを溶解し乳化剤溶解単量体混合物（３）を調製する。重合開始剤として過硫酸カリウム９ｇを投入した後、乳化剤溶解単量体混合物（３）を１．７重量％／分の供給速度で連続的に供給し重合を行った。乳化剤溶解単量体混合物（３）の供給が終了したら、撹拌しながら８０℃に３０分保持した後、過硫酸カリウム８．８ｇを投入した後アクリル酸ブチル８．９ｋｇ、メタクリル酸アリル９０ｇ、１，６−ヘキサンジオールジアクリレート３６ｇおよびニッコールＯＴＰ−１００ ２７ｇから成る乳化剤溶解単量体混合物（４）を２．０重量％／分の供給速度で連続的に供給し重合する。乳化剤溶解単量体混合物（４）の供給が終了したら、撹拌しながら８０℃に６０分保持し、過硫酸カリウム２．０ｇを投入した後、メタクリル酸メチル１．９ｋｇ、アクリル酸メチル１００ｇおよびニッコールＯＴＰ−１００ ４ｇから成る単量体混合物を５．０重量％／分の供給速度で連続的に供給して重合する。単量体混合物の供給が終了したら、撹拌しながら８０℃に６０分保持し、重合を完結させた。重合終了後４０℃まで冷却した後、３２５メッシュの金網で濾過して取り出し粒子径０．３５μｍの２段階重合体を３７％含有するエマルジョンを得た。
【００３６】
撹拌機、温度計およびジャケット付きの１００リットルのステンレス製タンクにイオン交換水を３３ｋｇ投入し、撹拌しながらデフォマックス７０２を８．６ｇ投入し、３０℃に昇温した。−３０℃で凍結した２段階重合体の凍結エマルジョン１０ｋｇを砕きながら投入する。全ての凍結エマルジョンが全て融解し温度が一定となるのを確認し凝集重合体スラリーを得た。次いで凝集重合体スラリーを遠心分離器にフィードして洗浄、脱水した後、エアロジル（二酸化ケイ素粉体）を１０ｇ添加し振動乾燥機にて乾燥することにより平均粒度２０５μｍで粒度の揃ったアクリル系樹脂組成物の粉体を得た。凝集体スラリーの性状を表１に示すが、凝集体の浮上もなく極めて安定に遠心分離器にフィードすることができ、また凝集重合体の合着による粗大粒子の生成も無かった。
得られた耐衝撃改良剤１０重量部を１００重量部のポリエチレンテレフタレート樹脂（ＰＥＴ：（株）クラレ製 ＫＳ７５０ＲＣ）とミキサーにてブレンドし、スクリュー径３０ｍｍの二軸押出機にてシリンダー温度２８０℃で溶融混練し、耐衝撃性改良ＰＥＴのマスターペレットを得た。このマスターペレット５部と９５重量部のポリエチレンテレフタレート樹脂ペレット均一に混合した後、住友重機（株）製ＳＧ−１００型射出成形機にてシリンダ−温度２７０℃、金型温度４０℃の条件で落球衝撃試験片（１００ｍｍ×１００ｍｍ×１ｍｍｔ）を成形し評価した。評価結果を表１に示す。
【００３７】
比較例４
撹拌機、温度計およびジャケット付きの１００リットルのステンレス製タンクにイオン交換水を３３ｋｇ投入し３０℃に昇温した。−３０℃で凍結した実施例１の２段階重合体の凍結エマルジョン１０ｋｇを砕きながら投入する。全ての凍結エマルジョンが全て融解し温度が一定となるのを確認し凝集重合体スラリーを得た。しかしながら凝集体スラリーの大部分が浮上し、スラリー移送時に配管の詰まりも発生したため洗浄、脱水のために遠心分離器にフィードできた凝集体量は乾燥した状態で全仕込量の１／４であった。また乾燥して得られた樹脂改質剤は１０００μｍ以上の粗大粒子の粉体が混在した不均一な粉体であった。
得られた耐衝撃改良剤は実施例３と同様の方法により評価を行ったが、実施例３に比べ耐衝撃性改良効果は低いものであった。
【００３８】
比較例５
凝集重合体スラリーを作製する際に添加する非イオン系界面活性剤であるデフォマックス７０２の添加量を３２．３ｇとした以外は実施例３と同様の操作で樹脂改質剤を作製し評価した。凝集重合体スラリーの性状および粉体粒度はは良好であったが、耐衝撃性改良効果は実施例３に比べ低いものであった。
【００３９】
実施例４
凝集重合体スラリーを作製する際に添加する非イオン系界面活性剤としてデフォマックス７０２の替わりにノナール２０４（東邦化学工業（株）製：ポリオキシエチレンノニルフェニールエーテル、ＨＬＢ＝８．９）を用いた以外は、実施例３と同様の操作を行った。
【００４０】
実施例５
凝集重合体スラリーを作製する際に添加する非イオン系界面活性剤としてデフォマックス７０２の替わりにソルボンＳ−６０（東邦化学工業（株）製：ソルビタンモノステアレート、ＨＬＢ＝４．７）１０ｇ添加した以外は、実施例３と同様の操作を行った。
【００４１】
実施例６
凝集重合体スラリーを作製する際に添加する非イオン系界面活性剤としてデフォマックス７０２の替わりにペグノールＯ−６（東邦化学工業（株）製：ポリオキシエチレンオレイルエーテル、ＨＬＢ＝９．６）８ｇ添加した以外は、実施例３と同様の操作を行った。
【００４２】
【表１】

【００４３】
【発明の効果】
本発明のアクリル系樹脂組成物は、改質する熱可塑性樹脂の物性低下を招かず耐衝撃性を向上に有用な樹脂改質剤として極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an acrylic resin composition, and more particularly to an acrylic resin composition useful for improving impact resistance without causing deterioration in physical properties of a thermoplastic resin to be modified.
[0002]
[Prior art]
Conventionally, polybutadiene, methyl methacrylate-butadiene-styrene (MBS) resin (US Pat. No. 3,985,704) and the like have been used for improving impact resistance of vinyl chloride resin and the like. Further, an impact resistance improver using acrylic rubber having excellent weather resistance has been developed, and acrylic resin (Japanese Patent Publication No. 55-27576), polyvinyl chloride resin (US Pat. No. 4,145,380) and polyalkylene terephthalate. It is known that there is an effect in improving the impact resistance of a resin such as a resin (Japanese Patent Publication No. 60-3101). The impact resistance improver using acrylic rubber disclosed in Japanese Patent Publication No. 55-27576, US Pat. No. 4,145,380 and Japanese Patent Publication No. 60-3101 is a submicron produced by emulsion polymerization. The multistage polymer is usually supplied as an agglomerated powder having a size of several tens to several hundreds of μm. The production is generally performed by agglomerating the polymer from a multistage polymer emulsion obtained by emulsion polymerization into several tens to several hundreds of μm, and washing and drying to form a powder. It is.
[0003]
In such a production method, when the resin is taken out from the emulsion polymerization emulsion, a slurry of the aggregate polymer is formed in the aggregation process. Agglomerated polymer slurries can coalesce depending on the temperature conditions and agitation conditions after agglomeration to produce coarse particles, or settle at a relatively low flow rate in the transfer line and cause clogging of the pipes. In the aqueous phase, a part of the emulsifier component used at the time of polymerization is present, so that the agglomerated polymer may float due to foaming by stirring. In particular, the formation of coarse particles and floating polymer is not preferable because the cleaning effect of the polymer is low and impurities are easily contained.
Further, the obtained impact resistance improver may cause blocking when temperature or pressure is applied. Therefore, it is known to add an inorganic salt or a lubricant as a method for improving the powder characteristics. Such an antiblocking agent is preferably mixed uniformly, and therefore, it is necessary to devise an addition method.
[0004]
[Problems to be solved by the invention]
The present invention provides an acrylic resin composition that is useful for resin modifier applications that impart impact resistance without impairing the properties of a thermoplastic resin that is a base material with less coarse particles and impurities. It is.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by a specific acrylic resin composition, and have achieved the present invention.
That is, the present invention provides a methacrylic acid ester having an alkyl group having 1 to 8 carbon atoms in the presence of an elastic body (A) layer mainly composed of an acrylate monomer unit having an alkyl group having 1 to 8 carbon atoms. In a latex coagulated slurry containing 100 parts by weight of a multi-stage polymer (I) obtained by polymerizing a resin (B) comprising 40% by weight or less of another monomer copolymerizable with 60% by weight or more of a monomer, Non-ionic surfactant (II) having defoaming action and dehydrated coagulum by adding 0.005 to 1 part by weight, fatty acid salt or ester, polyhydric alcohol ester, inorganic salt, inorganic oxide Acrylic resin composition comprising 0.01 to 1 part by weight of one kind of compound (III) An acrylic resin characterized in that the nonionic surfactant (II) having an antifoaming action is an adduct of a nonionic surfactant having an HLB of 10 or less and / or propylene oxide Composition It is.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the multistage polymer (I) used in the present invention, an elastic layer mainly composed of an acrylate monomer having an alkyl group having 1 to 8 carbon atoms is “soft”, and this is crosslinked and / or graft-bonded. When a resin layer comprising 40% by weight or less of another monomer copolymerizable with 60% by weight or more of a methacrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms is defined as “hard”, -Hard or hard-soft two-stage polymer, soft-hard-soft or hard-soft-hard three-stage polymer, soft-hard-soft-hard four-stage polymer.
[0007]
Hereinafter, the present invention will be described in more detail by taking a soft-hard two-stage polymer as an example.
In the two-stage polymer, the elastic body (A) is first emulsion polymerized. The elastic body (A) can be copolymerized with 70 to 99.95% by weight of an acrylate monomer having an alkyl group having 1 to 8 carbon atoms and 0.05 to 5% by weight of a graft-bonding monomer. It is preferable that it is obtained by emulsion polymerization of 29.95% by weight or less of such monomer units. Here, the alkyl group may be any of a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group. Specific examples of the acrylate monomer having an alkyl group having 1 to 8 carbon atoms in the present invention include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. The graft-bonding monomer is continuously polymerized in the presence of the cross-linked structure in the elastic body (A) of the multistage polymer (I) and in the presence of the elastic body (A) layer. resin (B) Used for the purpose of graft bonding to the layer. Examples of the graft-bonding monomer include allyl esters and crotyl esters of α and β unsaturated carboxylic acids. Specific examples thereof include allyl methacrylate and diallyl maleate.
[0008]
In the polymerization of the elastic body (A), if the ratio of the acrylate monomer having an alkyl group having 1 to 8 carbon atoms is less than 70% by weight, the impact resistance improving effect as a resin modifier is small, which is not preferable. On the other hand, when the proportion of the acrylate monomer exceeds 99.95% by weight, the proportion of the graft-bonding monomer is less than 0.05% by weight, and the crosslinking structure is too small or in the next stage. Since the graft bond with the thermoplastic resin to be polymerized becomes insufficient, the elasticity is lowered, which is not preferable. On the other hand, when the ratio of the graft-bonding monomer exceeds 5% by weight, the cross-linked structure increases, so that it becomes hard and the effect of improving impact resistance as a resin modifier is reduced, which is not preferable.
[0009]
Specific examples of the copolymerizable monomer in the polymerization of the elastic body (A) include methacrylate monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, styrene, and p-methylstyrene. , Aromatic vinyl monomers such as o-methylstyrene, maleimide monomers such as N-propylmaleimide, N-cyclohexylmaleimide, N-o-chlorophenylmaleimide, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate tri Polyfunctional monomers such as Lil isocyanurate.
[0010]
The emulsion polymerization of the elastic body (A) is generally carried out using an aqueous medium in a nitrogen atmosphere. Emulsifiers used in emulsion polymerization are carboxylate salts such as sodium stearate as anionic emulsifiers, dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dilauryl sulfosuccinate, and alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate. And alkyl sulfates such as sodium dodecyl sulfate, and examples of nonionic emulsifiers include polyoxyethylene alkyl ether and polyoxyethylene nonylphenyl ether. Examples of nonionic and anionic emulsifiers include polyoxyethylene nonylphenyl ether sulfate such as polyoxyethylene nonylphenyl ether sodium sulfate, polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene And alkyl ether carboxylates such as sodium tridecyl ether acetate. If the number of moles of ethylene oxide added in the nonionic emulsifier and the nonionic anionic emulsifier is too large, foaming properties increase, which is not preferable. The added mole number of ethylene oxide is 30 mol or less, preferably 20 mol or less, more preferably 10 mol or less. Two or more of these emulsifiers can be used in combination.
[0011]
The polymerization initiator may be any of persulfate initiators such as potassium persulfate and ammonium persulfate, and redox initiators such as persulfoxylate / organic peroxide and persulfate / sulfite. May be used.
The polymerization temperature is usually within a range of 40 to 95 ° C. The monomer mixture of the elastic body (A) is supplied to the polymerization system by a method such as divided addition or continuous dropping.
[0012]
When the polymerization of the elastic body (A) is completed, the resin (B) is emulsion-polymerized in the presence of the elastic body (A) as the next step. In this case, after replenishing the polymerization initiator to the polymerization system and adding an emulsifier if necessary, other copolymerizable with 60 to 100% by weight of a methacrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms. A monomer mixture comprising 40% by weight or less of monomer is continuously added to the polymerization system to polymerize the resin (B).
[0013]
Here, the alkyl group in the methacrylic acid ester monomer may be any of a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group as long as it has 1 to 8 carbon atoms. Examples of the methacrylic acid ester having an alkyl group having 1 to 8 carbon atoms include methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, and cyclohexyl methacrylate. Among them, methyl methacrylate is preferably used.
[0014]
Examples of other monomers copolymerizable in the polymerization of the resin (B) include methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-acrylic acid 2- Acrylic ester monomers such as ethylhexyl, phenyl acrylate and benzyl acrylate, aromatic vinyl such as vinyl acetate, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, vinylnaphthalene Monomers, nitriles such as acrylonitrile and methacrylonitrile, α and β unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, maleimide compounds such as N-ethylmaleimide and N-cyclohexylmaleimide, etc. Two or more of these can be used in combination. Further, a chain transfer agent such as octyl mercaptan or lauryl mercaptan can be added as necessary.
[0015]
resin (B) The polymerization of the multi-stage polymer (I) is completed by the completion of the polymerization. The latex of the multistage polymer (I) is cooled and taken out, filtered through a metal mesh of 100 mesh or more, preferably 200 mesh or more to remove aggregates generated during polymerization, and then subjected to salting out or freeze-thawing. A slurry containing aggregates of the multistage polymer (I) is prepared. The solid content of the slurry is usually 5 to 40% by weight, preferably 10 to 30% by weight.
[0016]
Salting-out can be performed by a known salting-out agent and method. Specific examples of the salting-out agent include magnesium sulfate, aluminum sulfate, aluminum chloride and the like, and the salting-out temperature is about 20 to 60 ° C.
Freezing-thawing can also be performed by a known method. The latex is frozen at a temperature of −5 ° C. or lower, preferably −20 ° C. or lower, and melted at a temperature of 5-60 ° C.
[0017]
The resin composition of the present invention is a multi-stage polymer (I) obtained by the above-described method. Of latex containing coagulation slurry Nonionic surfactant with defoaming action (II) Added dehydrated coagulum, And fatty acid salts or esters, polyhydric alcohol esters, inorganic salts, inorganic oxidation Thing At least one compound (III) is blended.
[0018]
The nonionic surfactant (II) used in the present invention is a nonionic surfactant having an antifoaming action, and as such a nonionic surfactant, a low HLB nonionic surfactant or Propylene oxide adducts Adopted .
The low HLB nonionic surfactant is a nonionic surfactant having an HLB of 10 or less, preferably 5 or less. Specific examples thereof include sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan Examples include trioleate, polyoxyethylene alkyl ether and polyoxyethylene nonyl phenyl ether having 5 to 10 moles of addition of ethylene oxide, and alkylene oxide adducts. Examples of adducts of alkylene oxide include polyoxypropylene ether and polyoxypropylene polyoxyethylene ether obtained by adding ethylene oxide to propylene oxide and derivatives thereof, and polyoxypropyleneoxyethylene alkyl ether. Represent.
[0019]
[Chemical 1]

[0020]
[Chemical formula 2]

[0021]
[Chemical 3]

[0022]
[Formula 4]

[0023]
The nonionic surfactant is added in a slurry state of a coagulated product of the multistage polymer (I) obtained by salting out or freezing-thawing the latex of the multistage polymer (I). In this case, the nonionic surfactant can be used alone or in combination. The addition amount is 0.005 to 1 part by weight, preferably 0.01 to 0.6 part by weight, more preferably 0.05 to 0.4 part by weight, based on 100 parts by weight of the multistage polymer (I). . If the added amount of the nonionic surfactant exceeds 1 part by weight, a large amount of the nonionic surfactant remains in the finally obtained resin modifier, and the properties of the thermoplastic resin used as a base material are deteriorated. Is often undesirable. On the other hand, if the addition amount is less than 0.005 parts by weight, the effect of addition is small, and it is not preferable because it tends to cause blocking between solidified products, clogging of the slurry transport pipe, foaming of the slurry, and the like.
[0024]
In the present invention, the nonionic surfactant (II) having an antifoaming action is used in the production of an acrylic resin composition. , Add coagulated slurry before dehydrating The According to this addition method, not only the stability of the slurry can be increased and the clogging of the slurry transport pipe can be remarkably reduced, but also the solidified particles having a stable particle size can be obtained.
[0025]
In addition, at least one compound (III) selected from the group of fatty acid salts or esters, polyhydric alcohol esters, inorganic salts, and inorganic oxides used in the present invention is generally preferred to have a large anti-sticking effect. . Specific examples thereof include calcium stearate, calcium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, and silicon dioxide. These compounds, when combined with the non-ionic surfactant (II) having the antifoaming effect, improve the dispersibility with the multistage polymer (I), thereby improving the impact resistance more effectively. Can be. The amount of its use is 0.01-1 weight part normally with respect to 100 weight part of multistage polymer (I), Preferably it is 0.1-0.5 weight part. If the amount added is less than 0.01 parts by weight, the effect of preventing sticking is small, which is not preferable. On the other hand, if it exceeds 1 part by weight, no further improvement is observed in the prevention of sticking, and the effect of improving impact resistance is reduced. Mold dirt, Bleed This is not preferable because out-out easily occurs.
[0026]
The dewatering of the coagulated slurry of the multi-stage polymer (I) can be performed by a known bucket type or decanter type centrifuge, and the drying is performed by a known fluid dryer, vibration dryer, hot air dryer or the like. Can be dried.
[0027]
The acrylic resin composition of the present invention may contain additives such as ultraviolet absorbers, lubricants, antioxidants, and dyes as necessary.
The obtained acrylic resin composition is composed of polyvinyl chloride resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyvinylidene fluoride resin, polyamide resin, styrene resin, acrylonitrile-styrene (AS) resin, ABS. Effectively used for imparting impact resistance, solvent resistance, etc., such as resin and methacrylic resin.
[0028]
【Example】
Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited thereto. “Parts” and “%” used in Examples and Comparative Examples are all “parts by weight” and “% by weight”. In addition, evaluation of Examples and Comparative Examples was performed by the following methods.
(1) Particle size measurement
It measured using Otsuka Electronics Co., Ltd. product light scattering photometer DLS-600.
(2) Particle size measurement
200 g of the acrylic resin composition powder was classified with a standard sieve, and the weight average particle size was defined as the average particle size.
(3) Izod impact strength
Measurement was performed using a 30 kg hammer according to ASTM D256 under conditions of edgewise and notched. The impact resistance improving effect was evaluated by the number of test pieces (NB / number of tests) which were evaluated and 10 pieces were not broken (NB).
(4) Falling ball impact test
A 2 kg steel ball was dropped from a height of 40 cm vertically to the center of a horizontally fixed test plate (100 mm × 100 mm × 1 mmt) to confirm whether cracks occurred. The number of tests per sample was 10, and the impact resistance improvement effect was evaluated as NB / number of tests, where NB was the number of cracks that did not occur.
[0029]
Example 1
Into a glass-lined 75 liter reaction vessel equipped with a condenser, thermometer and stirrer, 33.4 kg of ion-exchanged water is added, and 40 g of Nikkor OTP-100 (Nikko Chemical: sodium dioctylsulfosuccinate) and 10 g of sodium carbonate are dissolved. The temperature was raised to 80 ° C. with stirring. Separately, 8.87 kg of butyl acrylate, 135 g of allyl methacrylate and 90 g of Nikkor OTP-100 are dissolved in a 30 liter stainless steel container to prepare an emulsifier-dissolved monomer mixture (1). After 9 g of potassium persulfate was added as a polymerization initiator, polymerization was carried out by continuously supplying the emulsifier-dissolved monomer mixture (1) at a supply rate of 1.7 wt% / min. After the supply of the emulsifier-dissolved monomer mixture (1) was completed, the mixture was kept at 80 ° C. for 30 minutes with stirring, and 9 g of potassium persulfate was added, and then 8.87 kg of butyl acrylate, 135 g of allyl methacrylate and Nikkor OTP- 100 45 g of the emulsifier-dissolved monomer mixture (2) is continuously fed at a feed rate of 2.0% by weight / min for polymerization. When the supply of the emulsifier-dissolved monomer mixture (2) is completed, the mixture is kept at 80 ° C. for 60 minutes with stirring, and 2.0 g of potassium persulfate is added, and then 1.88 kg of methyl methacrylate, 120 g of methyl acrylate and Nikkor A monomer mixture consisting of 10 g of OTP-100 is continuously fed at a feed rate of 5.0 wt% / min for polymerization. When the supply of the monomer mixture was completed, the polymerization was completed by maintaining at 80 ° C. for 60 minutes with stirring. After completion of the polymerization, the mixture was cooled to 40 ° C. and filtered through a 325 mesh wire net to obtain an emulsion containing 37% of a two-stage polymer having a particle size of 0.14 μm.
[0030]
33 kg of ion-exchanged water was put into a 100 liter stainless steel tank equipped with a stirrer, thermometer and jacket, and while stirring, Defmax 702 (manufactured by Toho Chemical Industry Co., Ltd .: nonionic polymer based on propylene oxide) 8.6 g of a surfactant, HLB = 7) was added, and the temperature was raised to 30 ° C. 10 kg of a frozen emulsion of a two-stage polymer frozen at −30 ° C. is charged while being crushed. It was confirmed that all the frozen emulsions were melted and the temperature was constant, and an agglomerated polymer slurry was obtained. Next, the aggregated polymer slurry is fed to a centrifugal separator for washing and dehydration, and then 11.1 g of calcium stearate is added, followed by drying with a vibration dryer to obtain an acrylic resin composition having an average particle size of 235 μm and a uniform particle size. A powder was obtained. The properties of the agglomerate slurry are shown in Table 1. The agglomerate was not floated and could be fed to the centrifuge very stably, and there was no generation of coarse particles due to coalescence of the agglomerated polymer.
10 parts by weight of the resulting acrylic resin composition was blended with 100 parts by weight of polyvinyl chloride resin (PVC) with a mixer, melt-kneaded with a twin screw extruder with a screw diameter of 30 mm, and the impact resistance improved PVC Pellets were obtained. The pellets were evaluated by molding Izod test pieces using a SG-100 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. under conditions of a cylinder temperature of 180 ° C. and a mold temperature of 40 ° C. The evaluation results are shown in Table 1.
[0031]
Comparative Example 1
Into a 100 liter stainless steel tank equipped with a stirrer, a thermometer and a jacket, 33 kg of ion exchange water was added and the temperature was raised to 30 ° C. 10 kg of the frozen emulsion of the two-stage polymer of Example 1 frozen at −30 ° C. is charged while being crushed. It was confirmed that all the frozen emulsions were melted and the temperature was constant, and an agglomerated polymer slurry was obtained. However, most of the agglomerate slurry surfaced and clogging of the piping occurred during the slurry transfer, so the amount of agglomerate that could be fed to the centrifuge for cleaning and dehydration was 1/4 of the total charge in the dry state. It was. Further, the polymer obtained by drying was a non-uniform powder in which powders of coarse particles of 1000 μm or more were mixed.
The obtained polymer was evaluated by the same method as in Example 1, but the impact resistance improving effect was lower than that in Example 1. It is thought that poor dispersion of the impact resistance improver occurred due to the presence of coarse particles.
[0032]
Comparative Example 2
The agglomerated polymer slurry of Comparative Example 1 was fed to a centrifugal separator for washing and dehydration, and then 11.1 g of calcium stearate was added, followed by drying with a vibration drier to obtain a powder having an average particle size of 395 μm. It was. This was evaluated by the same operation as in Example 1. The addition of calcium stearate had a certain effect of suppressing the formation of coarse particles, but it was not sufficient, and the impact resistance improving effect was lower than that of Example 1.
[0033]
Example 2
Into a 100 liter stainless steel tank equipped with a stirrer, a thermometer and a jacket, 33 kg of ion-exchanged water was added, 40 g of magnesium sulfate was added, and the temperature was raised to 40 ° C. Salting out was carried out by continuously feeding 10 kg of the two-stage polymer emulsion of Example 1. Next, 8.6 g of Defomax 702 was added while stirring, and then the temperature was raised to 80 ° C. and held for 60 minutes to obtain an agglomerated polymer slurry. Next, the aggregated polymer slurry is fed to a centrifuge to be washed and dehydrated, and then 5.6 g of calcium stearate is added and dried with a vibration drier to obtain an acrylic resin composition having an average particle size of 272 μm and a uniform particle size. Of powder was obtained. The properties of the agglomerate slurry are shown in Table 1. The agglomerate was not floated and could be fed to the centrifuge very stably, and there was no generation of coarse particles due to coalescence of the agglomerated polymer.
The obtained acrylic resin composition was evaluated by molding an Izod test piece in the same manner as in Example 1. The evaluation results are shown in Table 1.
[0034]
Comparative Example 3
Into a 100 liter stainless steel tank equipped with a stirrer, a thermometer and a jacket, 33 kg of ion-exchanged water was added, 40 g of magnesium sulfate was added, and the temperature was raised to 40 ° C. After 10 kg of the two-stage polymer emulsion of Example 1 was continuously fed and salted out, the temperature was raised to 80 ° C. and held for 60 minutes to obtain an agglomerated polymer slurry. However, coarse particles are generated due to the coalescence of the aggregate slurry, and clogging of the piping also occurs during the slurry transfer, so the amount of aggregate that can be fed to the centrifuge for cleaning and dehydration is 1 / of the total charge in the dry state. 2. The resin modifier obtained by drying was a non-uniform powder in which coarse particles of 1000 μm or more were mixed.
The obtained impact resistance improver was evaluated by the same method as in Example 1, but the impact resistance improvement effect was lower than that in Example 2.
[0035]
Example 3
Into a glass-lined 75 liter reaction vessel equipped with a condenser, thermometer, and stirrer, 33.4 kg of ion exchange water is added, and 2 g of Nikkor OTP-100 (Nikko Chemical: sodium dioctylsulfosuccinate) and 10 g of sodium carbonate are dissolved. The temperature was raised to 80 ° C. with stirring. Separately, 8.9 kg of butyl acrylate, 90 g of allyl methacrylate, 36 g of 1,6-hexanediol diacrylate and 45 g of Nikkor OTP-100 were dissolved in a 30 liter stainless steel container to obtain an emulsifier-dissolved monomer mixture (3). Prepare. After 9 g of potassium persulfate was added as a polymerization initiator, polymerization was carried out by continuously supplying the emulsifier-dissolved monomer mixture (3) at a supply rate of 1.7 wt% / min. When the supply of the emulsifier-dissolved monomer mixture (3) is completed, the mixture is kept at 80 ° C. for 30 minutes with stirring, and then 8.8 g of potassium persulfate is added, and then 8.9 kg of butyl acrylate, 90 g of allyl methacrylate, 1 An emulsifier-dissolved monomer mixture (4) composed of 36 g of 1,6-hexanediol diacrylate and 27 g of Nikkor OTP-100 is continuously fed at a feed rate of 2.0 wt% / min for polymerization. When the supply of the emulsifier-dissolved monomer mixture (4) is completed, the mixture is kept at 80 ° C. for 60 minutes with stirring, and after adding 2.0 g of potassium persulfate, 1.9 kg of methyl methacrylate, 100 g of methyl acrylate and Nikkor A monomer mixture consisting of 4 g of OTP-100 is continuously fed at a feed rate of 5.0 wt% / min for polymerization. When the supply of the monomer mixture was completed, the polymerization was completed by maintaining at 80 ° C. for 60 minutes with stirring. After completion of the polymerization, the mixture was cooled to 40 ° C. and filtered through a 325 mesh wire net to obtain an emulsion containing 37% of a two-stage polymer having a particle size of 0.35 μm.
[0036]
Into a 100 liter stainless steel tank equipped with a stirrer, a thermometer and a jacket, 33 kg of ion exchange water was added, 8.6 g of Defomax 702 was added while stirring, and the temperature was raised to 30 ° C. 10 kg of a frozen emulsion of a two-stage polymer frozen at −30 ° C. is charged while being crushed. It was confirmed that all the frozen emulsions were melted and the temperature was constant, and an agglomerated polymer slurry was obtained. Next, the aggregated polymer slurry is fed to a centrifuge to be washed and dehydrated, and then 10 g of aerosil (silicon dioxide powder) is added and dried in a vibration drier to obtain an acrylic resin having an average particle size of 205 μm and a uniform particle size. A powder of the composition was obtained. The properties of the agglomerate slurry are shown in Table 1. The agglomerate was not floated and could be fed to the centrifuge very stably, and there was no generation of coarse particles due to coalescence of the agglomerated polymer.
10 parts by weight of the resulting impact resistance improver was blended with 100 parts by weight of a polyethylene terephthalate resin (PET: KS750RC manufactured by Kuraray Co., Ltd.) using a mixer, and the cylinder temperature was 280 ° C. using a twin screw extruder with a screw diameter of 30 mm. The mixture was melt-kneaded to obtain a master pellet of improved impact resistance PET. After 5 parts of the master pellets and 95 parts by weight of polyethylene terephthalate resin pellets were uniformly mixed, the balls dropped on a SG-100 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. under conditions of a cylinder temperature of 270 ° C. and a mold temperature of 40 ° C. An impact test piece (100 mm × 100 mm × 1 mmt) was molded and evaluated. The evaluation results are shown in Table 1.
[0037]
Comparative Example 4
Into a 100 liter stainless steel tank equipped with a stirrer, a thermometer and a jacket, 33 kg of ion exchange water was added and the temperature was raised to 30 ° C. 10 kg of the frozen emulsion of the two-stage polymer of Example 1 frozen at −30 ° C. is charged while being crushed. It was confirmed that all the frozen emulsions were melted and the temperature was constant, and an agglomerated polymer slurry was obtained. However, most of the agglomerate slurry surfaced and clogging of the piping occurred during the slurry transfer, so the amount of agglomerate that could be fed to the centrifuge for cleaning and dehydration was 1/4 of the total charge in the dry state. It was. The resin modifier obtained by drying was a non-uniform powder in which coarse particles of 1000 μm or more were mixed.
The obtained impact resistance improver was evaluated by the same method as in Example 3, but the impact resistance improving effect was lower than that in Example 3.
[0038]
Comparative Example 5
A resin modifier was prepared and evaluated in the same manner as in Example 3 except that the amount of Defomax 702, which is a nonionic surfactant added when preparing the agglomerated polymer slurry, was changed to 32.3 g. . The properties and powder particle size of the agglomerated polymer slurry were good, but the impact resistance improving effect was lower than that of Example 3.
[0039]
Example 4
Nonal 204 (manufactured by Toho Chemical Industry Co., Ltd .: polyoxyethylene nonyl phenyl ether, HLB = 8.9) is used instead of Defomax 702 as a nonionic surfactant to be added when preparing an agglomerated polymer slurry. The same operation as in Example 3 was carried out except that.
[0040]
Example 5
10 g of sorbon S-60 (manufactured by Toho Chemical Industry Co., Ltd .: sorbitan monostearate, HLB = 4.7) is added in place of Defomax 702 as a nonionic surfactant to be added when preparing an agglomerated polymer slurry. Except that, the same operation as in Example 3 was performed.
[0041]
Example 6
Pegnol O-6 (manufactured by Toho Chemical Co., Ltd .: polyoxyethylene oleyl ether, HLB = 9.6) 8 g instead of Defomax 702 as a nonionic surfactant to be added when preparing an agglomerated polymer slurry The same operation as in Example 3 was performed except for the addition.
[0042]
[Table 1]

[0043]
【The invention's effect】
The acrylic resin composition of the present invention is extremely useful as a resin modifier useful for improving impact resistance without causing deterioration of the physical properties of the thermoplastic resin to be modified.

Claims (2)

60% by weight of a methacrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms in the presence of an elastic body (A) layer mainly composed of an acrylate monomer unit having an alkyl group having 1 to 8 carbon atoms. The latex coagulated slurry containing 100 parts by weight of the multistage polymer (I) obtained by polymerizing the resin (B) composed of 40% by weight or less of other monomers copolymerizable with the above has a defoaming action. Nonionic surfactant (II) coagulated dehydrated by adding 0.005 to 1 part by weight, and at least one compound of fatty acid salt or ester, polyhydric alcohol ester, inorganic salt, inorganic oxide ( III) An acrylic resin composition comprising 0.01 to 1 part by weight , wherein the non-ionic surfactant (II) having an antifoaming action is a nonionic surfactant having an HLB of 10 or less and / or Or propi Acrylic resin composition characterized in that an adduct of emissions oxide.   The elastic body (A) can be copolymerized with 70 to 99.95% by weight of an acrylate monomer having an alkyl group having 1 to 8 carbon atoms and 0.05 to 5% by weight of a graft-bonding monomer. The acrylic resin composition according to claim 1, which is obtained by emulsion polymerization of 0 to 29.95% by weight of a monomer.