JP3928447B2 - Aqueous emulsion of polyolefin derivative, method for producing the same, and surface treatment method for olefin polymer using the same - Google Patents

Description

（式（Ｉ）及び式（ II ）中、Ｒは水素原子又はメチル基を示す。）
本発明の別の要旨は、水不溶性の有機溶剤が、水に対する溶解度が２０℃で１重量％以下である有機溶剤である前記水性エマルジョンに存する。
【００１２】
本発明の別の要旨は、水酸基含有共役ジエン系重合体が、１，３−ブタジエンの１，２−付加体と１，４−付加体との構成繰返し単位を、前者０〜４０モル％、後者１００〜６０モル％の割合で含むものである前記水性エマルジョンに存する。
【００１３】
本発明の別の要旨は、水酸基含有共役ジエン系重合体の水素添加誘導体、水不溶性の有機溶剤を０．２重量％以上５重量％以下、乳化剤、及び水を含む溶液を、６０℃以上で剪断混合することにより乳化させることを特徴とする水性エマルジョンの製造方法に存する。
【００１４】
本発明の別の要旨は、オレフィン系重合体表面に前記水性エマルジョンを塗布することを特徴とするオレフィン系重合体の表面処理方法に存する。
【００１６】
【発明の実施の形態】
ポリオレフィン誘導体として水酸基含有共役ジエン系重合体の水素添加誘導体を用いた本発明の水性エマルジョンは、ポリオレフィンに対するプライマーとして使用するのに好適である。中でも主として末端に水酸基を有する共役ジエン系重合体の水素添加誘導体であって、例えば、ブタジエン又はイソプレンを、過酸化水素等の水酸基含有ラジカル重合開始剤を用いてラジカル重合させることによって、直接に、末端に水酸基を有する共役ジエン系重合体とするか、或いは、アルカリ金属等のアニオン重合触媒を用いて末端にアルカリ金属が結合したリビングポリマーを製造し、次いでエポキシ化合物やホルムアルデヒド等を反応させることによって、末端に水酸基を有する共役ジエン系重合体とし、得られた水酸基含有共役ジエン系重合体を常法により水素添加することにより製造されたものが適している。
【００１７】
前記共役ジエンは２種以上が併用されてもく、スチレン、アクリロニトリル、メチル（メタ）アクリレート、酢酸ビニル等のビニル系単量体、或いはエチレン、プロピレン、イソブチレン等のα−オレフィンが、３０重量％以下の量で共重合されていてもよい。又、これらのビニル系単量体やα−オレフィンを含む共重合体においては、例えば、共重合体をオゾン等で酸化分解処理し、次いでリチウムアルミニウムハイドライド等で還元処理することによって、末端に水酸基を付加した共重合体とし、得られた共重合体を常法により水素添加することによっても製造することができる。
【００１８】
又、水酸基含有共役ジエン系重合体としては、その一部が、例えば、ポリエチレングリコール、ポリプロピレンエーテルグリコール、ポリトリメチレンエーテルグリコール、ポリテトラメチレンエーテルグリコール、ポリヘキサメチレンエーテルグリコール、エチレンオキサイドとプロピレンオキサイドのブロック又はランダム共重合体、エチレンオキサイドとテトラヒドロフランのブロック又はランダム共重合体等のポリエーテル系、ポリカプロラクトンポリオール、ポリエチレンアジペートポリオール、ポリブチレンアジペートポリオール等のポリエステル系、１，６−ヘキサンポリカーボネートポリオール等のポリカーボネート系等のジオール化合物で置き換えられたものでもよい。
【００２１】
水酸基含有共役ジエン系重合体の共役ジエンとしては、１，３−ブタジエンが好ましく、その共役ジエン系重合体としては、１，３−ブタジエンの１，２−付加体と１，４−付加体との構成繰り返し単位を、前者０〜４０モル％、後者１００〜６０モル％の割合で含むものであるのが好ましく、前者１０〜３５モル％、後者９０〜６５モル％の割合で含むものであるのが更に好ましく、前者１５〜３０モル％、後者８５〜７０モル％の割合で含むものであるのが特に好ましい。１，２−付加体が前記範囲超過で１，４−付加体が前記範囲未満では、プライマー等としての材料強度が低下する傾向となる。
【００２２】
尚、本発明において、前記水酸基含有共役ジエン系重合体の水素添加誘導体は、プライマー等としての耐熱性、耐湿性等の面から、その水添率が９８％以上であるのが好ましく、１００％であるのが更に好ましい。
又、前記水酸基含有共役ジエン系重合体の水素添加誘導体は、プライマー等としての材料強度等の面から、その数平均分子量が５００〜１０，０００であるのが好ましく、８００〜８，０００であるのが更に好ましく、１，０００〜５，０００であるのが特に好ましい。
【００２３】
又、プライマー等としての材料強度等の面から、その数平均分子量と水酸基含有割合（重量％）との乗数に基づいて求められる１分子当たりの水酸基の平均結合数が１個以上であるのが好ましく、１．５個以上であるのが更に好ましく、１．８個以上であるのが特に好ましい。又、接着性等の面から、８以下であるのが好ましく、２．５以下であるのが更に好ましい。
［有機溶剤］
本発明において添加される有機溶剤は、水不溶性であり、好ましくは水に対する溶解度が２０℃で１重量％以下（２０℃の水１００ｇに対して溶解する量が１ｇ以下）である。水に対する溶解度は小さい方が好ましく、好ましくは０．１重量％以下、更に好ましくは０．０５重量％以下である。
【００２４】
この有機溶剤は、水と水酸基含有共役ジエン系重合体の水素添加誘導体の界面に作用して、この水素添加誘導体からなる油滴を球形にして油滴表面積を最少にし、エマルジョンを安定化する働きを有すると考えられる。この働きにより、乳化処理前のプレ乳化においてエマルジョンが形成され易くなり、常温で高粘度液体が固体である水酸基含有共役ジエン系重合体の水素添加誘導体の粘度を低下させることができるので、その後の乳化処理で分散効果がかかりやすくなると考えられる。更に、乳化処理後のエマルジョンにおいても、これらの有機溶剤が、上述の働きによりエマルジョンを安定化させると考えられる。
【００２５】
これに対し、水に対する溶解度が高い有機溶剤及び炭化水素化合物は、水と溶け合うための上述の働きをすることができないので、プレ乳化でエマルジョンが形成されず、その後の乳化処理で分散効果がかかり難くなると共に、乳化処理後もエマルジョンの安定化効果が得られないと考えられる。又、水に対する溶解度が２０℃で数重量％のものを使用すると、水と油滴の境界面が乱れ易くエマルジョンの寿命を短くするし、更には水に微量の有機溶剤が溶け込むことにより水酸基含有共役ジエン系重合体の水素添加誘導体が油滴から水中へ溶けだし、この水素添加誘導体が析出しやすくなると考えられる。
【００２６】
また、有機溶剤は、エマルジョンの保存温度で液体であることが好ましい。４０℃で液体であることが好ましく、更には２０℃で液体であることが好ましい。エマルジョンの保存温度で液体でない場合は、保存時にエマルジョンの油滴を球形に保つ役割を果たし難くなる。また、乳化処理温度でも液体であることが好ましい。乳化処理時に沸点を越えると、乳化処理中に揮発してしまい、エマルジョンの油滴中に存在できなくなってしまうからである。
【００２７】
更に、常温から乳化処理温度の温度範囲（例えば２０〜１００℃）で、水酸基含有共役ジエン系重合体の水素添加誘導体と有機溶剤の混合物が均一溶液（透明溶液であることが好ましいが、懸濁溶液でも均一状態を保つことができればよい）であることが好ましい。この混合物が均一溶液でないと乳化機の分散効果がかかり難くなるからである。従って、有機溶剤は、その温度範囲で均一溶液を形成する様な、水酸基含有共役ジエン系重合体の水素添加誘導体と相溶性の高いものを選択して使用することが好ましい。尚、乳化処理温度は水の沸点以下であるが、本発明では６０℃以上で乳化することが好ましいので、すくなくとも２０〜６０℃以下で均一溶液であることが好ましい。
【００２８】
有機溶剤は、水不溶性であれば、炭化水素、ハロゲン化炭化水素、非炭化水素のいずれでもよく、炭化水素は脂肪族炭化水素、芳香族炭化水素、脂環式炭化水素のいずれでもよい。有機溶剤の例としては、トルエン、シクロヘキサン、ｎ−ヘキサン等が挙げられるが、中でもトルエンが好ましい。又、有機溶剤として、例えばエマルションを安定化させると同時に香りを付ける目的としてテルピノレン、リモネン等のイソプレン骨格を有するものが挙げられるが、中でもテルピノレンが好ましい。有機溶剤は２種以上併用してもよい。
【００２９】
有機溶剤の添加量は、水性エマルジョンの全体量に対して０．２重量％以上５重量％以下である。好ましくは１重量％以上、３重量％以下、更に好ましくは、２重量％以下である。０．２重量％未満だと、４０℃以上で保存した場合にクリーミング現象を起こしやすくなる。また、５重量％を越える場合には、使用する乳化剤の量が増え、プライマーとして使用する際に接着力を低下させてしまう。更に、トルエン等の有機溶剤を５重量％を越えて添加すると、有機溶剤の臭いがきつくなって実用的ではない。有機溶剤を２種以上併用する場合には、合計で０．２〜５重量％である。
［乳化剤］
本発明で使用する乳化剤は、公知の乳化剤が使用できるが、通常、アルキル硫酸ナトリウム及びアルキルベンゼンスルホン酸ナトリウムからなる群から選択された１種以上である。特に、ポリオレフィン誘導体として水酸基含有共役ジエン系重合体の水素添加体を用いる本発明では特にこれらの乳化剤を使用することが好ましい。これらの界面活性剤を用いた水性エマルジョンは、保存安定性に優れると共に、高接着性、低粘度となる。
【００３０】
アルキル硫酸ナトリウムにおけるアルキル基としては、炭素数が１０〜３０のものが好ましく、炭素数が１２〜１８のものが更に好ましい。このアルキル基は、直鎖状、分岐状のいずれであってもよい。これらのアルキル基は２種以上併用してもよい。
アルキルベンゼンスルホン酸ナトリウムにおけるアルキル基としては、炭素数が１０〜２０のものが好ましく、炭素数が１０〜１６のものが更に好ましい。このアルキル基は、直鎖状、分岐状のいずれであってもよい。これらのアルキル基は２種以上併用してもよい。
【００３１】
乳化剤の添加量は、水性エマルジョンの保存安定性及びプライマーとしての粘度等の面から、水酸基含有共役ジエン系重合体の水素添加誘導体１００重量部に対して、５〜４０重量部であるのが好ましく、１０〜２０重量部であるのが更に好ましい。また、本発明の水性エマルジョンとしては、本発明の効果を損なわない範囲で、他のアニオン系、カチオン系、ノニオン系等の乳化剤または高分子界面活性剤が併用されてもよく、更に、粘度調整剤、増粘剤、消泡剤等を含有していてもよく、又、エマルジョン又は／及び前記水酸基含有共役ジエン系重合体の水素添加誘導体に、酸化防止剤、熱安定剤、紫外線吸収剤、光安定剤、帯電防止剤、難燃剤、着色剤、充填材等を含有していてもよい。
［水性エマルジョンの製造方法］
本発明の水性エマルジョンは、水酸基含有共役ジエン系重合体の水素添加誘導体、前記有機溶剤、乳化剤、及び水とを混合し、乳化させることにより製造される。通常、乳化処理前に有機溶剤と水酸基含有共役ジエン系重合体の水素添加誘導体とを混合して均一溶液（透明溶液が好ましいが、懸濁溶液でも均一であれば良い）を調製し、これに乳化剤水溶液を混合しプレ乳化した後、乳化機で乳化する。有機溶剤を乳化後に添加したのでは、有機溶剤がエマルジョンの油滴中に取り込まれず、エマルジョンの上部に浮遊し、高温でのクリーミング現象を抑えないばかりか、プライマーとして塗布した際に、平滑性、透明性を損なう原因となってしまう。
【００３２】
その際、水酸基含有共役ジエン系重合体の水素添加誘導体の仕込量は、水とこの水素添加誘導体の合計量に対して通常１〜５０重量％程度とする。乳化剤の使用量は、水酸基含有共役ジエン系重合体の水素添加誘導体１００重量部に対して、通常５〜４０重量部、好ましくは１０〜２０重量部とする。プレ乳化は、乳化できれば手振とうでもよいが、必要に応じて攪拌方式の乳化機等を使用してもよい。
【００３３】
乳化は、通常、水酸基含有共役ジエン系重合体の水素添加誘導体、有機溶剤、乳化剤、及び水の混合液を、剪断混合することにより行うが、必要に応じて、更にキャビテーション作用又は／及び衝突を負荷して行う。例えば、高速回転翼で攪拌する方式の乳化機（例えば、スリーワンモーター等の攪拌機、特殊化工機社製ホモミキサー、エムテクニック社製クレアミックス等）により剪断力を負荷し、剪断混合し乳化させる。或いは、高圧ポンプを使用して流出させ、流路を急激に狭めて高流速化した後、物体に衝突させる（例えばＧａｕｒｉｎ社製バルブホモジナイザー）か、流路を二分割し再度合流させて衝突させ低圧部に噴出させる方式の乳化機（例えばスギノマシン社製アルティマイザー、特殊化工機社製ウルトラミクロマイザー等）により乳化させる。通常、１０〜１００ＭＰａ程度の圧力下、１００〜３００ｍ／秒程度の流速で、剪断力、キャビテーション作用、又は／及び衝突を負荷し乳化させる。これらの乳化法は、２種以上を併用してもよく、又、本発明においては、これらの乳化法の中で、特に後者の方法によるのが好ましい。又、その際の温度としては、水酸基含有共役ジエン系重合体の水素添加誘導体を軟化させるために、６０℃以上とするのが好ましく、８０℃以上とするのが更に好ましい。
［積層体の製造］
本発明の水性エマルジョンは、オレフィン系重合体表面に他材料を積層して積層体を製造する際の接着剤、或いは接着剤の下塗り剤、としてのプライマーとして好適である。従って本発明の水性エマルジョンをポリオレフィン系重合体の表面処理剤として用いた積層体は、オレフィン系重合体表面に前記水性エマルジョンによる塗膜層が形成されている。
【００３４】
ここで、オレフィン系重合体としては、具体的には、例えば、エチレン、プロピレン、１−ブテン、３−メチル−１−ブテン、４−メチル−１−ペンテン等の炭素数２〜８程度のα−オレフィンの単独重合体、それらのα−オレフィンと、エチレン、プロピレン、１−ブテン、３−メチル−１−ブテン、１−ペンテン、４−メチル−１−ペンテン、４，４−ジメチル−１−ペンテン、１−ヘキセン、４−メチル−１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−オクタデセン等の炭素数２〜１８程度の他のα−オレフィンや、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸エステル等との共重合体等の樹脂、具体的には、例えば、分岐状低密度ポリエチレン、直鎖状高密度ポリエチレン等のエチレン単独重合体、エチレン−プロピレン共重合体、エチレン−１−ブテン共重合体、エチレン−プロピレン−１−ブテン共重合体、エチレン−４−メチル−１−ペンテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−１−ヘプテン共重合体、エチレン−１−オクテン共重合体、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸共重合体、エチレン−（メタ）アクリル酸メチル共重合体、エチレン−（メタ）アクリル酸エチル共重合体、エチレン−（メタ）アクリル酸−（メタ）アクリル酸メチル共重合体等のエチレン系樹脂、プロピレン単独重合体、プロピレン−エチレン共重合体、プロピレン−エチレン−１−ブテン共重合体等のプロピレン系樹脂、及び、１−ブテン単独重合体、１−ブテン−エチレン共重合体、１−ブテン−プロピレン共重合体等の１−ブテン系樹脂等が挙げられる。
【００３５】
尚、本発明におけるこれらのオレフィン系樹脂としては、密度が０．８５０〜０．９６０ｇ／ｃｍ³ であるのが好ましく、０．８９０〜０．９３０ｇ／ｃｍ³ であるのが更に好ましい。又、ＪＩＳ Ｋ７２１０に準拠して２１．１８Ｎ荷重で測定したメルトフローレートが、エチレン系樹脂等においては１９０℃で、プロピレン系樹脂においては２３０℃で、０．０１〜２００ｇ／１０分であるのが好ましく、０．１〜１００ｇ／１０分であるのが更に好ましい。
【００３６】
又、本発明におけるオレフィン系重合体としては、エチレンと、プロピレン、１−ブテン、３−メチル−１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、４−メチル−１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン等の炭素数３〜１０程度のα−オレフィンとの二元又は三元以上の共重合体、及び、更に、１，４−ヘキサジエン、４−メチル−１，４−ヘキサジエン、５−メチル−１，４−ヘキサジエン、６−メチル−１，５−ヘプタジエン、１，４−オクタジエン、７−メチル−１，６−オクタジエン、シクロヘキサジエン、シクロオクタジエン、ジシクロペンタジエン、５−メチレン−２−ノルボルネン、５−エチリデン−２−ノルボルネン、５−ブチリデン−２−ノルボルネン、５−イソプロペニル−２−ノルボルネン等の非共役ジエンを共重合した三元又は四元以上の共重合体等のゴム、具体的には、例えば、エチレン−プロピレン共重合体、エチレン−１−ブテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−１−オクテン共重合体、エチレン−プロピレン−非共役ジエン共重合体、エチレン−１−ブテン−非共役ジエン共重合体等のゴムが挙げられる。
【００３７】
本発明において、前記エチレン−α−オレフィン系共重合体ゴムは、エチレン含有量が５０〜９０重量％であるのが好ましく、５５〜７５重量％であるのが更に好ましい。又、ＡＳＴＭ Ｄ１６４６に準拠して１００℃で測定したムーニー粘度〔ＭＬ₁₊₄ （１００℃）〕が３０〜２５０であるのが好ましく、５０〜１５０であるのが更に好ましい。
【００３８】
本発明におけるオレフィン系重合体としては、前記オレフィン系重合体樹脂と前記オレフィン系重合体ゴムとの混合物等であるのが好ましく、前記オレフィン系重合体樹脂０〜７０重量％と前記オレフィン系重合体ゴム１００〜３０重量％とからなるものが好ましく、前者樹脂１０〜６０重量％と後者ゴム９０〜４０重量％とからなるものが更に好ましく、前者樹脂２０〜５０重量％と後者ゴム８０〜５０重量％とからなるものが特に好ましい。
【００３９】
又、本発明におけるオレフィン系重合体としては、他の熱可塑性樹脂やゴム等が混合されたものであってもよく、更に、必要に応じて、酸化防止剤、熱安定剤、紫外線吸収剤、光安定剤、ブロッキング防止剤、滑剤、帯電防止剤、防曇剤、中和剤、分散剤、難燃剤、着色剤、架橋剤、軟化剤、防菌剤、防黴剤、導電性付与剤、充填材等を含有していてもよい。
【００４０】
本発明の水性エマルジョンを用いて積層体を製造する際のオレフィン系重合体表面とは、前記オレフィン系重合体の押出成形体、圧縮成形体、射出成形体、中空成形体等、更に、それらに熱成形、延伸、架橋、発泡等の二次成形を施した各種成形体の表面を言い、それらの表面に、前記水性エマルジョンを塗布し、乾燥させて塗膜層を形成する。
【００４１】
ここで、その塗布法としては、ナイフコータ、ロールコータ、スプレー、刷毛塗り、及びディップ等の方法が挙げられ、その塗布量としては、接着性の面等から、固形分換算で、０．０２〜２５ｇ／ｍ² とするのが好ましく、０．５〜５ｇ／ｍ² とするのが更に好ましい。尚、前記水性エマルジョンに水酸基含有共役ジエン系重合体の水素添加誘導体の硬化剤を含有させ、オレフィン系重合体表面の塗膜層を硬化させる場合には、前記塗布後、通常、５０〜２００℃の温度に加熱する。
【００４２】
このようにして形成された塗膜層に直接に、或いは、その上に設けられる接着剤層を介して、例えば、ポリアミド系樹脂、エチレン−酢酸ビニル共重合体鹸化物、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリスチレン系樹脂、アクリル系樹脂等の各種熱可塑性樹脂のフィルム或いはシート、織布或いは不織布、及び他の成形体等、並びに各種熱硬化性樹脂のシート等、及び、アルミニウム等の金属箔或いはシート、紙等が圧着等により積層され、所望の積層物が形成される。
【００４３】
【実施例】
以下、本発明を実施例により更に具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。尚、以下の実施例及び比較例で用いた水酸基含有共役ジエン系重合体の水素添加誘導体、乳化剤、乳化機、及び平均粒子径の測定機を以下に示す。
＜水酸基含有共役ジエン系重合体の水素添加誘導体＞
Ｐ−１；数平均分子量２，８００、水酸基含有量１．４重量％、数平均分子量と水酸基含有量との乗数に基づいて求められる１分子当たりの水酸基の平均結合数２．３個、１，２−付加体／１，４−付加体＝２０モル％／８０モル％の水酸基含有１，３−ポリブタジエンの水添率９８％以上の水素添加誘導体（三菱化学（株）社製「ポリテールＨ」）。
Ｐ−２；数平均分子量４，０００、水酸基含有量１．５重量％、数平均分子量と水酸基含有量との乗数に基づいて求められる１分子当たりの水酸基の平均結合数３．７個の水酸基含有ポリイソプレンの水添率９８％以上の水素添加誘導体（出光石油化学（株）社製「エポール」）。
＜乳化剤＞
ドデシルベンゼンスルホン酸ナトリウム（東京化成社製 有効成分９９％）
＜乳化機＞
エムテクニック社製クレアミックス
Ｇａｕｒｉｎ社製バルブホモジナイザー
＜平均粒子径＞
日機装社製「Ｍｉｃｒｏｔｒａｃ ＵＰＡ」を用いて測定した。
実施例１
ポリテールＨ３０重量部とトルエン２重量部を７０℃で混合し、Ａ液を調製した。脱塩水７０重量部とドデシルベンゼンスルフォン酸ナトリウム３重量部を７０℃で混合し、Ｂ液を調製した。Ａ液とＢ液を７０℃で混合し、エムテクニック社製クレアミックスにて、２００００回転で２分間処理した後、Ｇａｕｒｉｎ社製バルブホモジナイザーにて、２５ＭＰａの圧力下で１０分間処理し、冷却して水性エマルジョンを得た（処理温度６０℃以上）。調製直後の水性エマルジョンの平均（５０％）粒子径を測定した。また、高温保存安定性試験として、水性エマルジョンを４０℃の恒温層に入れ、目視にてクリーミング、及び層分離等を観察した。その結果を、表−１に示す。
（Ａ液）
ポリエーテルＨ ３０重量部
トルエン ２重量部
（Ｂ液）
脱塩水 ７０重量部
ドデシルベンゼンスルフォン酸ナトリウム ３重量部
実施例２〜３、比較例１〜４
上記トルエンに変えて表−１に示す有機溶剤の各添加量に変えた以外は、実施例１と同様にして水性エマルジョン調製、評価を行った。その結果を表−１に示す。尚、実施例、比較例で使用した有機溶剤の水に対する溶解度（２０℃）を、表−２に示す。
【００４４】
【表１】

【００４５】
【表２】

【００４６】
【発明の効果】
本発明は、高温安定性に優れ、特にプライマー用途に適した水性エマルジョン、その製造方法、及びこの水性エマルジョンを用いるオレフィン系重合体の表面処理方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous emulsion of a polyolefin derivative excellent in high-temperature storage stability, a method for producing the same, and a laminate using the same.
[0002]
[Prior art]
Polyolefin resins are relatively inexpensive and have excellent performance, such as molding processability, mechanical properties, electrical properties, water vapor barrier properties, chemical resistance, water resistance, heat resistance, etc., automotive parts, home appliance parts, Widely used as building materials. However, since the polyolefin-based resin does not have a functional group rich in crystallinity and reactivity on the surface while having such characteristics, it is difficult to bond or coat the polyolefin-based resin substrate.
[0003]
In order to improve this, it is widely known that these olefin polymers are subjected to a surface treatment in terms of adhesion to other materials, paintability, printability, and the like. Especially for non-polar olefin polymers, the surface of the olefin polymer molded body is chemically and electrically treated such as solvent treatment, flame treatment, corona discharge treatment, and plasma treatment. A method of oxidizing by the method of forming a primer layer by applying a primer treatment to the surface of the molded body is performed.
[0004]
Above all, the primer treatment method does not require complicated processes and equipment, has little variation in treatment effect, and has the advantage that it can be applied to molded products with complicated shapes. Various polyolefin derivatives are used as primers. It has been. At present, modified polyolefins such as chlorination are widely used, but in recent years, hydrogenated derivatives of conjugated diene polymers such as hydroxyl-containing polybutadiene and polyisoprene have been attracting attention in the course of dechlorination.
[0005]
However, in the primer treatment method, generally, a solution obtained by dissolving a polyolefin derivative in an organic solvent such as toluene, xylene and / or esters is applied to the surface of the molded body as a primer. Therefore, a large amount of organic solvent is released into the atmosphere when the primer is applied, which causes environmental pollution problems and health problems for workers.
[0006]
In order to solve this problem, various methods of using a primer as an aqueous emulsion have been studied, but all have problems in storage stability as an emulsion. In particular, there are some aqueous emulsions prepared by conventional methods that are stable at room temperature. However, when storage tests are conducted at 40 ° C. in consideration of storage stability in summer, the upper part of the emulsion is peeled off within one month. It has the disadvantage of causing a phenomenon such as so-called creaming. The emulsion that causes the creaming phenomenon is a major cause of losing the smoothness and transparency of the coating film when used as a primer.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to improve the high-temperature storage stability of aqueous emulsions of polyolefin derivatives, particularly hydrogenated derivatives of hydroxyl group-containing conjugated diene polymers, and has excellent high-temperature storage stability with less environmental pollution problems. It is an object to provide an aqueous emulsion suitable for the above.
[0008]
[Means for Solving the Problems]
  Therefore, the researcher of the present invention has intensively studied to solve the above problems,Hydrogenation of hydroxyl group-containing conjugated diene polymersThe inventors have found that the high-temperature storage stability of the aqueous emulsion is greatly improved by containing a predetermined amount of a water-insoluble organic solvent in the aqueous emulsion of the derivative, and the present invention has been achieved.
[0009]
  That is, the gist of the present invention is as follows.The following formula (I) and / or ( II Hydrogenated derivatives of hydroxyl group-containing conjugated diene polymers having structural repeating units represented byAn aqueous emulsion of an emulsifierAnd 0.2 to 5% by weight of a water-insoluble organic solventIt exists in the aqueous emulsion characterized by this.

(Formula (I) and Formula ( II R) represents a hydrogen atom or a methyl group. )
  Another gist of the present invention resides in the aqueous emulsion, wherein the water-insoluble organic solvent is an organic solvent having a solubility in water of 1% by weight or less at 20 ° C..
[0012]
  BookAnother gist of the invention is that the hydroxyl group-containing conjugated diene polymer is composed of 1,3-butadiene 1,2-adducts and 1,4-adducts in repeating units of 0-40 mol% in the former and the latter It exists in the said aqueous emulsion which is contained in the ratio of 100-60 mol%.
[0013]
  BookAnother gist of the invention is:Hydrogenation of hydroxyl group-containing conjugated diene polymersA method for producing an aqueous emulsion comprising emulsifying a solution containing 0.2% by weight to 5% by weight of a derivative, a water-insoluble organic solvent, an emulsifier, and water by shear mixing at 60 ° C. or higher. Exist.
[0014]
  Another aspect of the present invention is to provide the aqueous emulsion on the surface of the olefin polymer.The present invention resides in a method for treating the surface of an olefin polymer, which is characterized in that the above is applied.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
  The aqueous emulsion of the present invention using a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer as a polyolefin derivative is suitable for use as a primer for polyolefin.Among them, hydrogenated derivatives of conjugated diene polymers mainly having a hydroxyl group at the terminal, such as butadieneorIsopreneThe, By radical polymerization using a hydroxyl group-containing radical polymerization initiator such as hydrogen peroxide, directly to a conjugated diene polymer having a hydroxyl group at the terminal, or using an anionic polymerization catalyst such as an alkali metal A living polymer having an end bonded with an alkali metal is produced, and then reacted with an epoxy compound, formaldehyde, or the like to obtain a conjugated diene polymer having a hydroxyl group at the end, and the obtained hydroxyl group-containing conjugated diene polymer is a conventional method. Those produced by hydrogenation with are suitable.
[0017]
Two or more kinds of the conjugated dienes may be used in combination, and 30% by weight of vinyl monomers such as styrene, acrylonitrile, methyl (meth) acrylate, vinyl acetate, or α-olefins such as ethylene, propylene, and isobutylene. It may be copolymerized in the following amounts. Moreover, in the copolymer containing these vinyl monomers and α-olefins, for example, the copolymer is subjected to oxidative decomposition treatment with ozone or the like and then reduced with lithium aluminum hydride or the like, so that a hydroxyl group is formed at the terminal. It can also be produced by adding a copolymer to the obtained copolymer and hydrogenating the obtained copolymer by a conventional method.
[0018]
Moreover, as the hydroxyl group-containing conjugated diene polymer, a part thereof is, for example, polyethylene glycol, polypropylene ether glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, ethylene oxide and propylene oxide. Blocks or random copolymers, polyethers such as ethylene oxide and tetrahydrofuran block or random copolymers, polyesters such as polycaprolactone polyol, polyethylene adipate polyol, polybutylene adipate polyol, 1,6-hexane polycarbonate polyol, etc. It may be replaced with a diol compound such as polycarbonate.
[0021]
  waterThe conjugated diene of the acid group-containing conjugated diene polymer is 1,3-butadiene.PreferPreferably, the conjugated diene polymer is composed of 1,3-butadiene 1,2-adduct and 1,4-adduct as a repeating unit of 0-40 mol% in the former and 100-60 mol in the latter. %, Preferably 10 to 35 mol% of the former and 90 to 65 mol% of the latter, more preferably 15 to 30 mol% of the former and 85 to 70 mol% of the latter. It is particularly preferable. When the 1,2-adduct exceeds the above range and the 1,4-adduct exceeds the above range, the material strength as a primer or the like tends to decrease.
[0022]
In the present invention, the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer preferably has a hydrogenation rate of 98% or more from the viewpoint of heat resistance, moisture resistance, etc. as a primer, etc. More preferably.
In addition, the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer preferably has a number average molecular weight of 500 to 10,000, preferably 800 to 8,000, from the viewpoint of material strength as a primer or the like. Is more preferable, and it is especially preferable that it is 1,000-5,000.
[0023]
In addition, from the viewpoint of material strength as a primer or the like, the average number of hydroxyl group bonds per molecule determined on the basis of the multiplier of the number average molecular weight and the hydroxyl group content (% by weight) is 1 or more. The number is preferably 1.5 or more, and more preferably 1.8 or more. Further, in terms of adhesiveness and the like, it is preferably 8 or less, and more preferably 2.5 or less.
[Organic solvent]
The organic solvent added in the present invention is water-insoluble, and preferably has a solubility in water of 1% by weight or less at 20 ° C. (the amount dissolved in 100 g of water at 20 ° C. is 1 g or less). The solubility in water is preferably small, preferably 0.1% by weight or less, more preferably 0.05% by weight or less.
[0024]
  This organic solvent is water andHydrogenation of hydroxyl group-containing conjugated diene polymersActing on the interface of the derivative,This hydrogenated derivativeIt is considered that the oil droplets made of spheres have a spherical shape to minimize the surface area of the oil droplets and stabilize the emulsion. By this function, an emulsion is easily formed in pre-emulsification before the emulsification treatment, and the high-viscosity liquid is solid at room temperature.Hydrogenation of hydroxyl group-containing conjugated diene polymersSince the viscosity of the derivative can be lowered, it is considered that a dispersion effect is easily applied in the subsequent emulsification treatment. Furthermore, even in the emulsion after the emulsification treatment, these organic solvents are considered to stabilize the emulsion by the above-described action.
[0025]
  In contrast, organic solvents and hydrocarbon compounds having high solubility in water cannot perform the above-described function for dissolving with water, so an emulsion is not formed by pre-emulsification, and a dispersion effect is applied in the subsequent emulsification treatment. It becomes difficult, and it is considered that the effect of stabilizing the emulsion cannot be obtained even after the emulsification treatment. Also, if water solubility of several weight percent is used at 20 ° C, the interface between water and oil droplets tends to be disturbed, shortening the life of the emulsion, and further, a trace amount of organic solvent dissolves in water.Hydrogenation of hydroxyl group-containing conjugated diene polymersThe derivative begins to dissolve from the oil droplets into the water,This hydrogenationIt is considered that the derivative is easily precipitated.
[0026]
The organic solvent is preferably liquid at the storage temperature of the emulsion. It is preferably liquid at 40 ° C., and more preferably liquid at 20 ° C. If it is not liquid at the storage temperature of the emulsion, it will be difficult to keep the oil droplets of the emulsion spherical during storage. Moreover, it is preferable that it is a liquid also at the emulsification processing temperature. This is because if the boiling point is exceeded during the emulsification process, it will volatilize during the emulsification process and cannot be present in the oil droplets of the emulsion.
[0027]
  Furthermore, in the temperature range (for example, 20-100 degreeC) of the emulsification processing temperature from normal temperature,Hydrogenation of hydroxyl group-containing conjugated diene polymersIt is preferable that the mixture of the derivative and the organic solvent is a uniform solution (a transparent solution is preferable, but it is sufficient that a uniform state can be maintained even in a suspension solution). This is because the dispersion effect of the emulsifier is difficult to be applied unless this mixture is a uniform solution. Therefore, the organic solvent forms a uniform solution in that temperature range,Hydrogenation of hydroxyl group-containing conjugated diene polymersIt is preferable to select and use one having high compatibility with the derivative. The emulsification treatment temperature is not higher than the boiling point of water, but in the present invention, it is preferable to emulsify at 60 ° C. or higher, so that it is preferably a homogeneous solution at least at 20 to 60 ° C. or lower.
[0028]
The organic solvent may be any of hydrocarbon, halogenated hydrocarbon, and non-hydrocarbon as long as it is water-insoluble, and the hydrocarbon may be any of aliphatic hydrocarbon, aromatic hydrocarbon, and alicyclic hydrocarbon. Examples of the organic solvent include toluene, cyclohexane, n-hexane and the like, and among them, toluene is preferable. Examples of the organic solvent include those having an isoprene skeleton such as terpinolene and limonene for the purpose of stabilizing the emulsion and imparting a scent, but terpinolene is preferred. Two or more organic solvents may be used in combination.
[0029]
  The addition amount of the organic solvent is 0.2 wt% or more and 5 wt% or less with respect to the total amount of the aqueous emulsion. Preferably it is 1 weight% or more and 3 weight% or less, More preferably, it is 2 weight% or less. If it is less than 0.2% by weight, a creaming phenomenon is likely to occur when stored at 40 ° C. or higher. On the other hand, when the amount exceeds 5% by weight, the amount of the emulsifier used is increased, and the adhesive force is lowered when used as a primer. Furthermore, when an organic solvent such as toluene is added in an amount exceeding 5% by weight, the odor of the organic solvent becomes so strong that it is not practical. When using 2 or more types of organic solvents together, it is 0.2 to 5 weight% in total.
[emulsifier]
  Although the well-known emulsifier can be used for the emulsifier used by this invention, Usually, it is 1 or more types selected from the group which consists of sodium alkyl sulfate and sodium alkylbenzenesulfonate. In particular, a hydrogenated product of a hydroxyl group-containing conjugated diene polymer is used as a polyolefin derivative.In the present inventionIt is particularly preferable to use these emulsifiers. Aqueous emulsions using these surfactants are excellent in storage stability, and have high adhesion and low viscosity.
[0030]
The alkyl group in sodium alkyl sulfate preferably has 10 to 30 carbon atoms, and more preferably has 12 to 18 carbon atoms. This alkyl group may be linear or branched. Two or more of these alkyl groups may be used in combination.
The alkyl group in sodium alkylbenzene sulfonate preferably has 10 to 20 carbon atoms, and more preferably has 10 to 16 carbon atoms. This alkyl group may be linear or branched. Two or more of these alkyl groups may be used in combination.
[0031]
  The amount of emulsifier added is from the viewpoint of the storage stability of the aqueous emulsion and the viscosity as a primer.Hydrogenation of hydroxyl group-containing conjugated diene polymersThe amount is preferably 5 to 40 parts by weight, more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the derivative. Further, as the aqueous emulsion of the present invention, other anionic, cationic and nonionic emulsifiers or polymer surfactants may be used in combination as long as the effects of the present invention are not impaired. Agents, thickeners, antifoaming agents, etc., and emulsions and / or hydrogenated derivatives of the hydroxyl group-containing conjugated diene polymers, antioxidants, heat stabilizers, ultraviolet absorbers, It may contain a light stabilizer, an antistatic agent, a flame retardant, a colorant, a filler and the like.
[Method for producing aqueous emulsion]
  The aqueous emulsion of the present invention isHydrogenation of hydroxyl group-containing conjugated diene polymersIt is produced by mixing and emulsifying a derivative, the organic solvent, an emulsifier, and water. Usually with organic solvent before emulsificationHydrogenation of hydroxyl group-containing conjugated diene polymersThe derivative is mixed to prepare a uniform solution (a transparent solution is preferable, but a suspension solution may be uniform), and an aqueous emulsifier solution is mixed and pre-emulsified, followed by emulsification with an emulsifier. When an organic solvent is added after emulsification, the organic solvent is not taken into the oil droplets of the emulsion and floats on top of the emulsion, not only suppressing the creaming phenomenon at high temperature, but also when applied as a primer, It will cause the loss of transparency.
[0032]
  that time,Hydrogenation of hydroxyl group-containing conjugated diene polymersThe derivative charge is water andThis hydrogenationThe amount is usually about 1 to 50% by weight based on the total amount of the derivatives. The amount of emulsifier used isHydrogenation of hydroxyl group-containing conjugated diene polymersThe amount is usually 5 to 40 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the derivative. The pre-emulsification may be shaken as long as it can be emulsified, but if necessary, an agitation type emulsifier may be used.
[0033]
  Emulsification is usuallyHydrogenation of hydroxyl group-containing conjugated diene polymersThe mixture of the derivative, the organic solvent, the emulsifier, and water is carried out by shear mixing. If necessary, the mixture is further loaded with a cavitation action or / and collision. For example, a shearing force is applied by an emulsifier using a method of stirring with a high-speed rotary blade (for example, a stirrer such as a three-one motor, a homomixer manufactured by Kokusai Koki Co., Ltd., a clear mix manufactured by Mtechnic Co., Ltd.), and the mixture is sheared and mixed to emulsify. Alternatively, use a high-pressure pump to flow out, rapidly narrow the flow path to increase the flow velocity, and then collide with the object (for example, a Gaurin valve homogenizer), or split the flow path into two and rejoin to collide. Emulsification is carried out using an emulsifier of a type that is ejected to the low pressure part (for example, an optimizer manufactured by Sugino Machine Co., Ltd., an ultra micromizer manufactured by Kokusai Koki Co., Ltd.). Usually, under a pressure of about 10 to 100 MPa, a shearing force, a cavitation action, or / and a collision are applied and emulsified at a flow rate of about 100 to 300 m / sec. These emulsification methods may be used in combination of two or more, and in the present invention, among these emulsification methods, the latter method is particularly preferable. Also, as the temperature at that timeThe waterAcid groupContainsIn order to soften the hydrogenated derivative of the conjugated diene polymer, the temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher.
[Manufacture of laminates]
  The aqueous emulsion of the present invention is laminated with other materials on the olefin polymer surface.To produce a laminateSuitable as a primer for adhesives or adhesive primeris there. Therefore, the aqueous emulsion of the present invention was used as a surface treatment agent for polyolefin polymers.In the laminate, a coating layer of the aqueous emulsion is formed on the surface of the olefin polymer.NoThe
[0034]
Here, as the olefin polymer, specifically, for example, α having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. Homopolymers of olefins, α-olefins thereof, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1- Other α-olefins having about 2 to 18 carbon atoms such as pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene and 1-octadecene, vinyl acetate, (meta ) Resins such as copolymers with acrylic acid, (meth) acrylic acid esters, etc., specifically, ethylene homopolymers such as branched low-density polyethylene and linear high-density polyethylene, ethylene -Propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene- 1-heptene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid methyl copolymer, ethylene- ( Ethylene resins such as (meth) ethyl acrylate copolymer, ethylene- (meth) acrylic acid-methyl (meth) acrylate copolymer, propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1- Propylene resins such as butene copolymer, 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene Copolymers of 1-butene resins.
[0035]
In addition, as these olefin resin in this invention, a density is 0.850-0.960g / cm.^ThreePreferably, 0.890-0.930 g / cm^ThreeMore preferably. Also, the melt flow rate measured at 21.18N load in accordance with JIS K7210 is 190 ° C for ethylene resins and 230 ° C for propylene resins, and is 0.01 to 200 g / 10 min. It is more preferable that it is 0.1-100 g / 10min.
[0036]
Examples of the olefin polymer in the present invention include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 4-methyl-1. A binary or ternary copolymer with an α-olefin having about 3 to 10 carbon atoms such as hexene, 1-heptene, 1-octene, 1-decene, and 1,4-hexadiene, 4 -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,5-heptadiene, 1,4-octadiene, 7-methyl-1,6-octadiene, cyclohexadiene, cycloocta Diene, dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 5-isopropenyl Rubbers such as ternary or quaternary copolymers obtained by copolymerizing non-conjugated dienes such as 2-norbornene, specifically, for example, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene Examples thereof include rubbers such as a -1-hexene copolymer, an ethylene-1-octene copolymer, an ethylene-propylene-nonconjugated diene copolymer, and an ethylene-1-butene-nonconjugated diene copolymer.
[0037]
In the present invention, the ethylene-α-olefin copolymer rubber preferably has an ethylene content of 50 to 90% by weight, more preferably 55 to 75% by weight. Also, Mooney viscosity [ML measured at 100 ° C. according to ASTM D1646]_{1 + 4}(100 ° C.)] is preferably 30 to 250, more preferably 50 to 150.
[0038]
The olefin polymer in the present invention is preferably a mixture of the olefin polymer resin and the olefin polymer rubber, and the olefin polymer resin is 0 to 70% by weight and the olefin polymer. Those composed of 100 to 30% by weight of rubber are preferred, those composed of 10 to 60% by weight of the former resin and 90 to 40% by weight of the latter rubber are more preferred, and 20 to 50% by weight of the former resin and 80 to 50% by weight of the latter rubber. % Is particularly preferred.
[0039]
Further, the olefin polymer in the present invention may be a mixture of other thermoplastic resins or rubbers, and if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, Light stabilizer, antiblocking agent, lubricant, antistatic agent, antifogging agent, neutralizing agent, dispersant, flame retardant, colorant, crosslinking agent, softener, antibacterial agent, antifungal agent, conductivity imparting agent, It may contain a filler or the like.
[0040]
  The present inventionWhen manufacturing a laminate using an aqueous emulsion ofThe olefin polymer surface refers to an extrusion molded body, compression molded body, injection molded body, hollow molded body, etc. of the olefin polymer, and further subjected to secondary molding such as thermoforming, stretching, cross-linking and foaming. The surfaces of various molded products are applied, and the aqueous emulsion is applied to the surfaces and dried to form a coating layer.TheFormationTo do.
[0041]
Here, examples of the coating method include methods such as knife coater, roll coater, spray, brush coating, and dip, and the coating amount is 0.02 to 0.02 in terms of solid content in terms of adhesiveness. 25 g / m²Preferably, 0.5 to 5 g / m²Is more preferable. When the aqueous emulsion contains a curing agent of a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer and the coating layer on the surface of the olefin polymer is cured, it is usually 50 to 200 ° C. after the coating. Heat to the temperature of.
[0042]
  Formed in this wayFor example, polyamide-based resin, saponified ethylene-vinyl acetate copolymer, polyester-based resin, polycarbonate-based resin, polystyrene-based resin, acrylic resin, directly or through an adhesive layer provided on the coating layer. Various thermoplastic resin films or sheets such as resin, woven or non-woven fabrics, and other molded articles, various thermosetting resin sheets, and metal foils or sheets such as aluminum, paper, etc. To form a desired laminate.
[0043]
【Example】
  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. It was used in the following examples and comparative examples.Hydrogenation of hydroxyl group-containing conjugated diene polymersDerivatives, emulsifiers, emulsifiers, and average particle diameter measuring machines are shown below.
<Hydrogenation of hydroxyl group-containing conjugated diene polymersDerivative>
  P-1: Number average molecular weight 2,800, hydroxyl group content 1.4% by weight, average number of hydroxyl group bonds per molecule 2.3 determined based on multiplier of number average molecular weight and hydroxyl group content, , 2-Adduct / 1,4-Adduct = 20 mol% / 80 mol% of a hydroxylated 1,3-polybutadiene hydrogenated derivative having a hydrogenation rate of 98% or more (“Polytail H” manufactured by Mitsubishi Chemical Corporation) ").
  P-2: number average molecular weight 4,000, hydroxyl group content 1.5% by weight, hydroxyl group having an average number of hydroxyl bonds of 3.7 per molecule determined based on the multiplier of the number average molecular weight and the hydroxyl group content Hydrogenated derivative of polyisoprene containing hydrogenated at 98% or more (“Epol” manufactured by Idemitsu Petrochemical Co., Ltd.).
<Emulsifier>
  Sodium dodecylbenzenesulfonate (99% active ingredient manufactured by Tokyo Chemical Industry Co., Ltd.)
<Emulsifier>
  Mtechnic's Clare mix
  Gaurin valve homogenizer
<Average particle size>
  Measurement was performed using “Microtrac UPA” manufactured by Nikkiso Co., Ltd.
Example 1
  30 parts by weight of polytail H and 2 parts by weight of toluene were mixed at 70 ° C. to prepare solution A. 70 parts by weight of demineralized water and 3 parts by weight of sodium dodecylbenzenesulfonate were mixed at 70 ° C. to prepare solution B. Liquid A and liquid B were mixed at 70 ° C, treated with MtTechnic's Claremix at 20000 rpm for 2 minutes, then treated with Gaurin's valve homogenizer for 10 minutes under a pressure of 25 MPa and cooled. To obtain an aqueous emulsion (treatment temperature of 60 ° C. or higher). The average (50%) particle size of the aqueous emulsion immediately after preparation was measured. As a high temperature storage stability test, the aqueous emulsion was placed in a constant temperature layer at 40 ° C., and creaming, layer separation, and the like were observed visually. The results are shown in Table-1.
(Liquid A)
  Polyether H 30 parts by weight
  2 parts by weight of toluene
(Liquid B)
  70 parts by weight of demineralized water
  Sodium dodecylbenzenesulfonate 3 parts by weight
Examples 2-3, Comparative Examples 1-4
  An aqueous emulsion was prepared and evaluated in the same manner as in Example 1 except that the addition amount of the organic solvent shown in Table 1 was changed to the toluene. The results are shown in Table-1. In addition, the solubility (20 degreeC) with respect to the water of the organic solvent used by the Example and the comparative example is shown in Table-2.
[0044]
[Table 1]

[0045]
[Table 2]

[0046]
【The invention's effect】
  The present invention is an aqueous emulsion excellent in high temperature stability and particularly suitable for primer use, ThatManufacturing method,And an olefin polymer surface treatment method using the aqueous emulsionCan be provided.

Claims (12)

An aqueous emulsion of a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer having a constitutional repeating unit represented by the following formula (I) and / or ( II ), comprising an emulsifier and 0.2 wt% or more and 5 wt% or less An aqueous emulsion comprising a water-insoluble organic solvent .

(In formula (I) and formula ( II ), R represents a hydrogen atom or a methyl group.) The aqueous emulsion according to claim 1, wherein the water-insoluble organic solvent has a solubility in water of 1% by weight or less at 20 ° C. The hydroxyl group-containing conjugated diene polymer is composed of 1,3-butadiene 1,2-adduct and 1,4-adduct as repeating units of 0-40 mol% in the former and 100-60 mol% in the latter.
The aqueous emulsion according to claim 1 , wherein the aqueous emulsion is contained at a ratio of The hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer has a hydrogenation rate of 98% or more and a number average molecular weight of 500 to 10,000, according to any one of claims 1 to 3. Aqueous emulsion. The hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer has an average number of hydroxyl group bonds per molecule of 1 or more and 8 or less determined based on the multiplier of the number average molecular weight and the hydroxyl group content (% by weight). The aqueous emulsion according to claim 1, wherein the aqueous emulsion is present. Emulsifier, an aqueous emulsion according to any one of claims 1 to 5, characterized in that one selected from the group consisting of sodium alkyl sulfate and sodium alkylbenzenesulfonate. The aqueous emulsion according to any one of claims 1 to 6, wherein the content of the emulsifier is 5 to 40 parts by weight with respect to 100 parts by weight of the hydrogenated derivative of the hydroxyl group-containing conjugated diene polymer. The aqueous emulsion according to any one of claims 1 to 7, wherein the organic solvent is liquid at 20 ° C. A method for surface treatment of an olefin polymer, comprising applying the aqueous emulsion according to any one of claims 1 to 8 to the surface of the olefin polymer. A raw material mixture containing a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer having a constitutional repeating unit represented by the following formula (I) and / or ( II ), an emulsifier, a water-insoluble organic solvent and water, 9. The aqueous solution according to claim 1, wherein the water-insoluble organic solvent is emulsified at a temperature of 60 ° C. or higher at a ratio of 0.2% to 5% by weight. Method for producing emulsion.

(In formula (I) and formula ( II ), R represents a hydrogen atom or a methyl group.) The method for producing an aqueous emulsion according to claim 10, wherein the raw material mixture is prepared using a mixture of a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer and a water-insoluble organic solvent in advance. The method for producing an aqueous emulsion according to claim 10 or 11, wherein the emulsification is carried out through a step of stirring and mixing with a high-speed rotary blade.