JP3620671B2 - Method for producing coating polymer aqueous dispersion and dispersion - Google Patents
Method for producing coating polymer aqueous dispersion and dispersion Download PDFInfo
- Publication number
- JP3620671B2 JP3620671B2 JP34961695A JP34961695A JP3620671B2 JP 3620671 B2 JP3620671 B2 JP 3620671B2 JP 34961695 A JP34961695 A JP 34961695A JP 34961695 A JP34961695 A JP 34961695A JP 3620671 B2 JP3620671 B2 JP 3620671B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- copolymer
- aqueous
- polymer
- dispersion
- 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 - Lifetime
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、被覆用重合体水性分散液の製造法及び該分散液に関する。さらに詳しくは、紙の表面処理剤、水性オーバープリントコート用バインダー、水性塗料用バインダー、フレキソインキ等の水性インキ用バインダーなどに好適な被覆用重合体水性分散液の製造法及び該分散液に関する。
【０００２】
【従来の技術】
従来、前記用途には各種の水性重合体被覆剤が使用されているが、これらは水可溶型と水分散型に大別できる。水可溶性被覆剤は、光沢、透明性などの塗膜外観や塗工性に優れたものが多いが、耐水性が悪く、乾燥が著しく遅いという欠点があるため、今日では水分散型被覆剤が主流となっている。一方、水分散型被覆剤では、光沢、透明性、耐水性、耐摩擦性等を向上させるために、各種高分子系乳化剤が用いられてはいるが、該乳化剤の親水性が高く、またその使用量も多いため、乾燥性を必ずしも満足しうるものではない。
【０００３】
【発明が解決しようとする課題】
本発明は、前記実情に鑑み、水性重合体被覆剤としての諸性能である、乾燥性、光沢、透明性、耐水性、耐摩擦性、水分散安定性などに優れた被覆用重合体水性分散液を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明者は、上記課題を解決すべく、特に高分子系乳化剤の種類とその使用量に着目して鋭意研究を行った結果、特定の酸価とガラス転移温度を有するアクリル系共重合体水溶性塩を比較的少量使用してビニルモノマーを乳化重合することにより、前記課題を悉く解決しうる被覆用重合体水性分散液を収得できることを見出した。本発明はかかる知見に基づき完成したものである。
【０００５】
すなわち、本発明は、酸価５０〜８０ｍｇＫＯＨ／ｇ 、ガラス転移温度９０〜１３０℃のアクリル系共重合体水溶性塩（Ａ）の存在下、ビニルモノマー（Ｂ）を乳化重合することを特徴とする被覆用重合体水性分散液の製造法に関わり、更には該製造法に基づき得られる被覆用重合体水性分散液に関わる。
【０００６】
【発明の実施の形態】
本発明においては、一種以上のビニルモノマー（Ｂ）を乳化重合せしめるに際し、高分子系乳化剤として機能する、アクリル系共重合体水溶性塩（Ａ）を使用することが必須とされる。該共重合体水溶性塩（Ａ）に用いられるモノマーは、特に限定されず各種公知のビニルモノマーが使用でき、特に（メタ）アクリル酸エステル、マレイン酸半エステル、（メタ）アクリル酸などが好適である。
【０００７】
該（メタ）アクリル酸エステルとしては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｎ−アミル、アクリル酸イソアミル、アクリル酸ｎ−ヘキシル、アクリル酸２−エチルヘキシル、アクリル酸ｎ−オクチル、アクリル酸ｎ−デシル、アクリル酸ｎ−ラウリル、アクリル酸ｎ−ステアリル、アクリル酸メトキシエチル、アクリル酸エトキシエチル、アクリル酸イソプロポキシエチル、アクリル酸ｎ−ブトキシエチル、アクリル酸ステアロキシエチル、アクリル酸メトキシエトキシエチル、アクリル酸エトキシエトキシエチル、アクリル酸ブトキシエトキシエチル、アクリル酸ステアロキシエトキシエチル等の、炭素数１〜１８の脂肪族モノアルコールとアクリル酸とのエステル化物、炭素数３〜２０のエチレングリコールモノアルキルエーテルもしくは炭素数５〜２２のジエチレングリコールモノアルキルエーテルとアクリル酸とのエステル化物、並びにこれらに対応するメタクリル酸エステル類を例示できる。該（メタ）アクリル酸エステルは単独使用または適宜に併用できる。その他、（メタ）アクリル酸グリシジル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸ジエチルアミノエチルなども使用できる。
【０００８】
該マレイン酸半エステルとしては、たとえばマレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノ（ｎ−プロピル）、マレイン酸モノ（イソプロピル）、マレイン酸モノ（ｎ−ブチル）、マレイン酸モノ（イソブチル）、マレイン酸モノ（ｎ−アミル）、マレイン酸モノ（ｎ−ヘキシル）、マレイン酸モノ（２−エチルヘキシル）、マレイン酸モノ（ｎ−オクチル）、マレイン酸モノ（ｎ−デシル）、マレイン酸モノ（イソデシル）、マレイン酸モノ（ｎ−ラウリル）、マレイン酸モノ（トリデシル）、マレイン酸モノ（ｎ−ステアリル）、マレイン酸モノ（メトキシエチル）、マレイン酸モノ（エトキシエチル）、マレイン酸モノ（イソプロポキシエチル）、マレイン酸モノ（ｎ−ブトキシエチル）、マレイン酸モノ（ステアロキシエチル）、マレイン酸モノ（メトキシエトキシエチル）、マレイン酸モノ（エトキシエトキシエチル）、マレイン酸モノ（イソプロポキシエトキシエチル）、マレイン酸モノ（ブトキシエトキシエチル）、マレイン酸モノ（ステアロキシエトキシエチル）等の、炭素数１〜１８の脂肪族モノアルコールと無水マレイン酸とのエステル化物、炭素数３〜２０のエチレングリコールモノアルキルエーテルもしくは炭素数５〜２２のジエチレングリコールモノアルキルエーテルと無水マレイン酸とのエステル化物を例示できる。該マレイン酸半エステルは単独使用または適宜に併用できる。
【０００９】
前記（メタ）アクリル酸エステルやマレイン酸半エステル以外のモノマーとしては、例えば（メタ）アクリルアミド、ジアセトンアクリルアミド、ジエチルアクリルアミド、（メタ）アクリルニトリル、スチレン、酢酸ビニルなどを例示できる。
【００１０】
該共重合体水性塩（Ａ）の中和前の固形分酸価は、乳化重合時の安定性、並びに、得られるバインダーの乾燥性を考慮して慎重に決定され、通常５０〜８０ｍｇＫＯＨ／ｇ 程度、より好ましくは６０〜８０ｍｇＫＯＨ／ｇ である。５０ｍｇＫＯＨ／ｇ 未満では重合安定性が著しく低下し、８０ｍｇＫＯＨ／ｇ を越える場合は得られるバインダ−の乾燥性が著しく低下する。かかる範囲の酸価に調整するには、前記ビニルモノマーのうちカルボキシル基を含有するものの使用量を調節すれば足り、通常は含カルボキシル基ビニルモノマーの使用量は高分子乳化剤の製造に用いるビニルモノマーの全量のうち通常５〜１５重量％程度、好ましくは７〜１２重量％である。
【００１１】
また、共重合体水性塩（Ａ）の固形分のガラス転移温度（以下、Ｔｇという）は、得られるバインダーの乾燥性を考慮して慎重に決定され、通常９０〜１３０℃程度、より好ましくは９０〜１１０℃である。なお、本発明においてＴｇとは、ＦｏＸの近似式による計算値をいう。Ｔｇが９０℃未満の場合には、得られる被覆用重合体水性分散液の乾燥性が著しく低下し、また１３０℃を越える場合には、得られる被覆用重合体皮膜の耐摩耗性が著しく低下する。
【００１２】
なお、共重合体水性塩（Ａ）の固形分の平均分子量については、特に限定はされないが、重量平均分子量が２０００〜２０００００程度のものが好ましい。
【００１３】
本発明で用いる前記高分子乳化剤である共重合体水性塩（Ａ）の製造方法は、特に限定されず、塊状重合、溶液重合、乳化重合法などの各種公知の重合方法により容易に製造できる。例えば、溶液重合法を採用する場合は、前記所定量のビニルモノマーおよび炭化水素などの溶剤を反応容器に仕込み、過酸化ベンゾイル、過酸化ジ−ｔ− ブチル等の過酸化物系ラジカル重合開始剤、またはアゾビスイソブチロニトリル、アゾビスイソ酪酸ニトリル等のアゾ系ラジカル重合開始剤の存在下に、通常７０〜１５０℃程度に加熱して重合を行い、所望のアクリル系共重合体を得る。次いで、水酸化ナトリウムなどのアルカリ金属水酸化物、アンモニア、トリエチルアミン、モノエタノールアミン、２−ジメチルエタノールアミンなどの有機アミンのいずれか少なくとも一種を用いて該共重合体中和することにより、目的とする高分子乳化剤が得られる。なお、中和度は特に制限されないが、通常１００〜１８０％程度、好ましくは１３０〜１７０％程度である。また、使用溶剤の留去が必要な場合には、中和前または中和後に減圧留去、水蒸気蒸留などの操作を行えば良い。
【００１４】
前記の高分子乳化剤である共重合体水性塩（Ａ）を用いて本発明の被覆用重合体水性分散液を得るには、例えば以下の製造方法に従えばよい。即ち、該共重合体水溶性塩（Ａ）の存在下、以下のようなビニルモノマー（Ｂ）を乳化重合させればよい。該重合に際しては、ビニルモノマー（Ｂ）およびラジカル重合開始剤の全量を一括仕込、連続滴下、分割仕込などの方法により反応系に供給し、３０〜９０℃、反応時間１〜８時間程度の条件下で重合反応を完結させる。用いるラジカル重合開始剤は、特に制限はされず、過硫酸アンモニウム、過硫酸カリウム等の公知の水溶性のものを適宜に選択でき、その使用量はビニルモノマー（Ｂ）の全量１００部に対して通常０．１〜５部である。なお、ラジカル重合開始剤の他に還元剤を併用して反応系をレドックス系としてもよい。
【００１５】
乳化重合に供せられるビニルモノマー（Ｂ）は、得られる被覆用重合体水性分散液の性能を考慮して適宜決定される。具体的には、アルキル基の炭素数が１〜２２の（メタ）アクリル酸エステル； 水酸基、アミノ基、グリシジル基等を有する（メタ）アクリル酸エステル； （メタ）アクリルアミド、（メタ）アクリロニトリル、スチレン、メチルスチレン、ビニルトルエン、（メタ）アクリル酸、無水マレイン酸、マレイン酸半エステル、イタコン酸、イタコン酸半エステル等を例示しうる。なかでもスチレン、アルキル基の炭素数が１〜２２の（メタ）アクリル酸エステル、アミノ基含有（メタ）アクリル酸エステルが好ましい。該ビニルモノマーは単独使用または適宜に併用できる。
【００１６】
本発明では、ビニルモノマー（Ｂ）を２段階で乳化重合することもできる。２段階乳化重合法を採用した場合には、通常の１段階乳化重合法に比し、得られる被覆用重合体水性分散液の造膜性や該皮膜の光沢の点で一層良好となる。２段階乳化重合法の具体例としては、共重合体水性塩（Ａ）の存在下、まずビニルモノマー（Ｂ）の所定量とラジカル重合開始剤を一括仕込、連続滴下、分割仕込などの方法により反応系に供給し、第１段階の乳化重合を行い重合体水性分散液を得る。次いで、該重合体固形分１００重量部に対し、残余のモノマー（Ｂ）５〜１００重量部、好ましくは５〜７０重量部と、ラジカル重合開始剤とを反応系に供給して、第２段階の重合を完結させる。第１段階の乳化重合に供するモノマー（Ｂ）のＴｇは、通常５０〜１３０℃、好ましくは８０〜１１０℃である。第１段階で得られる重合体のＴｇが５０℃未満の場合には、得られる被覆用重合体水性分散液の乾燥性が低下し、また１３０℃を越える場合には、得られる重合体皮膜の耐摩耗性が低下する。また第２段階の乳化重合に供するモノマー（Ｂ）は、得られる被覆用重合体皮膜の造膜性を考慮して、該ホモポリマーのＴｇが０℃以下となるモノマー種を選択するのが好ましく、該モノマーは単独使用であってもよく、また共重合体としてのＴｇが０℃以下である限り２種以上の併用も可能である。また、第１段階で得られる重合体１００重量部に対し、第２段階に供するモノマー（Ｂ）の使用量が５重量部未満の場合には、得られる被覆用重合体皮膜の光沢が低下し、一方１００重量部を越える場合には、得られる被覆用重合体水性分散液の乾燥性が低下する。
【００１７】
前記乳化重合に際しては、乳化重合安定性や得られる被覆用重合体水性分散液の性能を考慮して、アクリル系共重合体水溶性塩（Ａ）と乳化重合に供するビニルモノマー（Ｂ）との使用割合を慎重に決定することが重要である。すなわち、該共重合体水溶性塩（Ａ）の固形分使用量は、ビニルモノマー（Ｂ）１００重量部に対し、通常５〜１５重量部であるのが好ましく、５重量％未満では重合安定性が著しく低下し、１５重量％を超える場合には得られる重合体水性分散液の乾燥性が著しく低下する。
【００１８】
本発明においては、前記共重合体水性塩（Ａ）を使用する限り、乳化重合に際し界面活性剤を使用せずとも、安定に被覆用重合体の水性分散液を収得しうるが、界面活性剤の併用を積極排除するものではない。また、ポリビニルアルコールなどの保護コロイドも、本発明の性能を逸脱しない範囲内であれば使用してもよい。
【００１９】
得られる被覆用重合体水性分散液の不揮発分や粘度は、特に限定されないが、作業性などを考慮すれば、通常は不揮発分３０〜７０重量％程度、粘度は５〜６０００ｃＰ程度であるのが好ましい。また被覆用重合体水性分散液の粒子径は、機械的安定性などを考慮すれば０．１μｍ以下であるのが好ましい。なお、被覆用重合体のＴｇについては、その用途に応じて決定されるため、格別の限定はないが、例えば塗料、インキ用の水性バインダーに使用する場合には、通常１５〜５０℃程度が好ましい。
【００２０】
こうして得られた本発明の被覆用重合体水性分散液は、単独使用できることはもとよりであるが、用途に応じて次のような添加剤を適宜に併用できる。すなわち、アクリル樹脂、ロジン変性マレイン酸樹脂、スチレンーマレイン酸樹脂、シェラック等のアルカリ可溶型樹脂、ポリエチレン系等のワックス類などが挙げられる。また、有色の光沢皮膜を得たい場合には、染料、顔料等の着色剤を添加すればよい。
【００２１】
【発明の効果】
本発明の被覆用重合体水性分散液は、高分子乳化剤として機能するアクリル系共重合体水性塩（Ａ）の使用量が少ないにも拘らず水分散安定性が良好であり、また該使用量が少ないため速乾性であり、しかも得られる皮膜の光沢、耐水性、透明性、耐摩擦性が良好である。そのため該水性分散液を用いて、とくに乾燥性に優れたオーバープリントコート用、塗料用、インキ用などの各種水性バインダーを提供できる。
【００２２】
【実施例】
以下、参考例、実施例により本発明を更に具体的に説明するが、本発明がこれら実施例に限定されるものではない。なお、以下「部」および「％」は、特記しない限り重量基準であり、ＴｇはＦｏｘの近似式による計算値である。
【００２３】
参考例１（アクリル系共重合体水性塩（Ａ）の製造）
撹拌装置、温度計、滴下ロート、窒素ガス導入管および還流冷却器を備えた反応容器に窒素気流下にキシレン４５０部を仕込み、内温が１２５〜１３０℃に達するまで昇温した。ついでメタクリル酸メチル２８６部、メタクリル酸イソプロピル２２０部、メタクリル酸４４部、およびジ−ｔ−ブチルパーオキシド１１部からなる混合液を滴下ロートより３時間を要して滴下した後、同温度で２時間保温して重合反応を完結させ、次いで減圧下でキシレンと未反応成分を除去し、酸価５２ｍｇＫＯＨ／ｇ 、Ｔｇ９７℃の共重合体を得た。別の反応容器に該共重合体１００部をとり、２８％アンモニア水１２部および脱イオン水２２１部を加え、８０℃にて２時間撹拌溶解させ、中和度１５０％、固形分濃度３０％の共重合体水溶液（以下、共重合体水溶性塩（１）という）を得た。
【００２４】
参考例２
参考例１と同様の反応容器にキシレン４５０部を仕込み、内温が１２５〜１３０℃に達するまで昇温した。ついでメタクリル酸メチル４４０部、メタクリル酸イソブチル５５部、メタクリル酸５５部およびジ−ｔ−ブチルパーオキシド１１部からなる混合液を滴下ロートより３時間を要して滴下した後、同温度で２時間保温して重合反応を完結させ、次いで減圧下でキシレンと未反応成分を除去し、酸価６５ｇＫＯＨ／ｇ、Ｔｇ１０３℃の共重合体を得た。該共重合体を用い、参考例１と同様に中和し、中和度１４５％、固形分濃度３０％の共重合体水溶液（以下、共重合体水溶性塩（２）という）を得た。
【００２５】
参考例３
参考例１と同様の反応容器にキシレン４５０部を仕込み、内温が１２５〜１３０℃に達するまで昇温した。ついでメタクリル酸メチル３８５部、メタクリル酸イソプロピル１１０部、アクリル酸５５部およびジ−ｔ−ブチルパーオキシド１１部からなる混合液を滴下ロートより３時間を要して滴下した後、同温度で２時間保温して重合反応を完結させ、次いで減圧下でキシレンと未反応成分を除去し、酸価７８ｍｇＫＯＨ／ｇ 、Ｔｇ１００℃の共重合体を得た。該共重合体を用い、参考例１と同様に中和し、中和度１５０％、固形分濃度３０％の共重合体水溶液（以下、共重合体水溶性塩（３）という）を得た。
【００２６】
参考例４（比較用の共重合体水性塩の製造）
参考例１と同様の反応容器にキシレン４５０部を仕込み、内温が１２５〜１３０℃に達するまで昇温した。ついでメタクリル酸メチル４１２．５部、アクリル酸ｎ−ブチル８２．５部、アクリル酸５５部およびジ−ｔ−ブチルパーオキシド１１部からなる混合液を滴下ロートより３時間を要して滴下した後、同温度で２時間保温して重合反応を完結させ、次いで減圧下でキシレンと未反応成分を除去し、酸価７８ｍｇＫＯＨ／ｇ 、Ｔｇ６７℃の共重合体を得た。該共重合体を用い、参考例１と同様に中和し、中和度１５０％、固形分濃度３０％の共重合体水溶液（以下、共重合体水溶性塩（４）という）を得た。
【００２７】
参考例５
参考例１と同様の反応容器にキシレン４５０部を仕込み、内温が１２５〜１３０℃に達するまで昇温した。ついでメタクリル酸メチル４４０部、メタクリル酸イソブチル３８．５部、アクリル酸７１．５部およびジ−ｔ−ブチルパーオキシド１１部からなる混合液を滴下ロートより３時間を要して滴下した後、同温度で２時間保温して重合反応を完結させ、次いで減圧下でキシレンと未反応成分を除去し、酸価１０１ｍｇＫＯＨ／ｇ 、Ｔｇ１０２℃の共重合体を得た。該共重合体を用い、参考例１と同様に中和し、中和度１５０％、固形分濃度３０％の共重合体水溶液（以下、共重合体水溶性塩（５）という）を得た。
【００２８】
参考例６
参考例１と同様の反応容器にキシレン４５０部を仕込み、内温が１２５〜１３０℃に達するまで昇温した。ついでメタクリル酸メチル４４０部、メタクリル酸イソブチル７７部、アクリル酸３３部およびジ−ｔ−ブチルパーオキシド１１部からなる混合液を滴下ロートより３時間を要して滴下した後、同温度で２時間保温して重合反応を完結させた。その後、減圧下でキシレンと未反応成分を除去した。得られた共重合体の酸価は４５ｍｇＫＯＨ／ｇ 、ガラス転移温度は９９℃であった。該共重合体を用い、参考例１と同様に中和し、中和度１５０％、固形分濃度３０％の共重合体水溶液（以下、共重合体水溶性塩（６）という）を得た。
【００２９】
実施例１（被覆用重合体水性分散液の製造）
参考例１と同様の反応容器に、脱イオン水１５８部及び共重合体水溶性塩（１）２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、共重合体水溶性塩（１）１２０部、スチレン３５０部、過硫酸アンモニウム３．１部及び脱イオン水１３９部からなる乳化混合物を４時間かけて滴下し、更に２時間保温することにより、固形分５０％の被覆用重合体水性分散液Ａを得た。
【００３０】
実施例２
参考例１と同様の反応容器に、脱イオン水２７０部及び共重合体水溶性塩（２）１２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、メタクリル酸メチル３２０部及びアクリル酸ｎ−ブチル１０部のモノマー混合液と、過硫酸アンモニウム２．９部を脱イオン水２２部に溶解した重合開始剤水溶液とを別々に３時間で滴下し、１時間保温して第１段階の乳化重合を完結した。次いで該反応系に、アクリル酸２−エチルヘキシル２０部（該ホモポリマーのＴｇは−８５℃）と、過硫酸アンモニウム０．２部を脱イオン水１０部に溶解した重合開始剤水溶液とを別々に３０分で滴下し、１時間保温することにより、第２段階の乳化重合を完結し、固形分５０％の被覆用重合体水性分散液Ｂを得た。なお、第１段階で得られる重合体のＴｇは９７℃である。
【００３１】
実施例３
参考例１と同様の反応容器に、脱イオン水２７０部及び共重合体水溶性塩（３）１２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、メタクリル酸メチル２８０部及びスチレン２０部のモノマー混合液と、過硫酸アンモニウム２．７部を脱イオン水２２部に溶解した重合開始剤水溶液とを別々に３時間で滴下し、１時間保温して第１段階の乳化重合を完結した。次いで該反応系に、アクリル酸エチル５０部（該ホモポリマーのＴｇは−２２℃）と、過硫酸アンモニウム０．４部を脱イオン水１０部に溶解した重合開始剤水溶液とを別々に３０分で滴下し、１時間保温することにより、第２段階の乳化重合を完結し、固形分５０％の被覆用重合体水性分散液Ｃを得た。なお、第１段階で得られる重合体のＴｇは１０５℃である。
【００３２】
実施例４
参考例１と同様の反応容器に、脱イオン水２７０部及び共重合体水溶性塩（３）１２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、メタクリル酸メチル２０部及びスチレン２８０部のモノマー混合液と、過硫酸アンモニウム２．７部を脱イオン水２２部に溶解した重合開始剤水溶液とを別々に３時間で滴下し、１時間保温して第１段階の乳化重合を完結した。次いで該反応系に、アクリル酸エチル５０部（該ホモポリマーのＴｇは−２２℃）と、過硫酸アンモニウム０．４部を脱イオン水１０部に溶解した重合開始剤水溶液とを別々に３０分で滴下し、１時間保温することにより、第２段階の乳化重合を完結し、固形分５０％の被覆用重合体水性分散液Ｄを得た。なお、第１段階で得られる重合体のＴｇは１０１℃である。
【００３３】
比較例１（比較用の重合体水性分散液の製造）
参考例１と同様の反応容器に、脱イオン水２７０部及び共重合体水溶性塩（４）１２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、メタクリル酸メチル２８０部及びスチレン２０部のモノマー混合液と、過硫酸アンモニウム２．７部を脱イオン水２２部に溶解した重合開始剤水溶液とを別々に３時間で滴下し、１時間保温して第１段階の乳化重合を完結した。次いで該反応系に、アクリル酸エチル５０部（該ホモポリマーのＴｇは−２２℃）と、過硫酸アンモニウム０．４部を脱イオン水１０部に溶解した重合開始剤水溶液とを別々に３０分で滴下し、１時間保温することにより、第２段階の乳化重合を完結し、固形分５０％の被覆用重合体水性分散液Ｅを得た。なお、第１段階で得られる重合体のＴｇは１０５℃である。
【００３４】
比較例２
参考例１と同様の反応容器に、脱イオン水２７０部及び共重合体水溶性塩（５）１２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、メタクリル酸メチル２８０部及びスチレン２０部のモノマー混合液と、過硫酸アンモニウム２．７部を脱イオン水２２部に溶解した重合開始剤水溶液とを別々に３時間で滴下し、１時間保温して第１段階の乳化重合を完結した。次いで該反応系に、アクリル酸エチル５０部（該ホモポリマーのＴｇは−２２℃）と、過硫酸アンモニウム０．４部を脱イオン水１０部に溶解した重合開始剤水溶液とを別々に３０分で滴下し、１時間保温することにより、第２段階の乳化重合を完結し、固形分５０％の被覆用重合体水性分散液Ｆを得た。なお、第１段階で得られる重合体のＴｇは１０５℃である。
【００３５】
比較例３
参考例１と同様の反応容器に、脱イオン水２７０部及び共重合体水溶性塩（６）１２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、メタクリル酸メチル２８０部及びスチレン２０部のモノマー混合液と、過硫酸アンモニウム２．７部を脱イオン水２２部に溶解した重合開始剤水溶液とを別々に３時間で滴下した。しかしながら、滴下終了時に、凝集物の発生量が多く、分散液が分離状態を呈したため、第２段階の乳化重合への移行を断念した。
【００３６】
比較例４
参考例１と同様の反応容器に、脱イオン水２７０部及び共重合体水溶性塩（５）１２０部を仕込み、窒素雰囲気下に撹拌しながら、８０℃まで加熱した。次いで、メタクリル酸メチル２２８部及びメタクリル酸２−エチルヘキシル７２部のモノマー混合液と、過硫酸アンモニウム２．７部を脱イオン水２２部に溶解した重合開始剤水溶液とを別々に３時間で滴下し、１時間保温して第１段階の乳化重合を完結した。次いで該反応系に、メタクリル酸メチル５０部（該ホモポリマーのＴｇは１０５℃）と、過硫酸アンモニウム０．４部を脱イオン水１０部に溶解した重合開始剤水溶液とを別々に３０分で滴下し、１時間保温することにより、第２段階の乳化重合を完結し、固形分５０％の被覆用重合体水性分散液Ｇを得た。なお、第１段階で得られる重合体のＴｇは３１℃である。
【００３７】
（性能評価）
水性墨インキを印刷したコート紙に、ザーンカップ＃４で１５秒の粘度に調製した重合体水性分散液（Ａ〜Ｇ）をそれぞれバーコーター＃８で塗工後、１時間放置し、以下の方法により性能を評価した。これらの結果を表１に示す。
光沢及び透明性：目視により５段階評価（５が最良）
乾燥性：塗工後指触により５段階評価（５が最良）
耐水性：キャラコ布に水５滴を落としこれを塗布面にあて、学振型摩擦堅牢度試験機で２００ｇ×１０往復の条件でテストし、キャラコ布に移ったインキ跡を目視により５段階評価（５が最良）
耐摩擦性：上質紙を塗布面にあて、学振型摩擦堅牢度試験機で２００ｇ×５００往復の条件でテストし、上質紙に移ったインキ跡を目視により５段階評価（５が最良）
【００３８】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a coating aqueous polymer dispersion and the dispersion. More specifically, the present invention relates to a method for producing a coating polymer aqueous dispersion suitable for paper surface treatment agents, aqueous overprint coating binders, aqueous paint binders, aqueous ink binders such as flexographic inks, and the like.
[0002]
[Prior art]
Conventionally, various types of aqueous polymer coatings have been used for the above applications, and these can be roughly classified into a water-soluble type and a water-dispersed type. Many water-soluble coatings have excellent appearance and coating properties such as gloss and transparency, but they have the disadvantages of poor water resistance and extremely slow drying. It has become mainstream. On the other hand, in the water-dispersed coating agent, various polymer emulsifiers are used in order to improve gloss, transparency, water resistance, friction resistance, etc., but the emulsifier has high hydrophilicity. Since the amount used is also large, the drying property is not always satisfactory.
[0003]
[Problems to be solved by the invention]
In view of the above circumstances, the present invention provides a coating polymer aqueous dispersion excellent in drying performance, gloss, transparency, water resistance, friction resistance, water dispersion stability, etc., which are various performances as an aqueous polymer coating agent. The purpose is to provide a liquid.
[0004]
[Means for Solving the Problems]
In order to solve the above problems, the present inventor has conducted intensive research focusing on the type of polymer emulsifier and the amount of the emulsifier used, and as a result, an acrylic copolymer water solution having a specific acid value and glass transition temperature has been obtained. It has been found that an aqueous dispersion of a coating polymer that can solve the above-mentioned problems can be obtained by emulsion polymerization of a vinyl monomer using a relatively small amount of a functional salt. The present invention has been completed based on such findings.
[0005]
That is, the present invention is characterized in that the vinyl monomer (B) is emulsion-polymerized in the presence of an acrylic copolymer water-soluble salt (A) having an acid value of 50 to 80 mg KOH / g and a glass transition temperature of 90 to 130 ° C. The present invention relates to a method for producing an aqueous coating polymer dispersion, and further relates to an aqueous coating polymer dispersion obtained based on the production method.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, when one or more vinyl monomers (B) are emulsion-polymerized, it is essential to use an acrylic copolymer water-soluble salt (A) that functions as a polymer emulsifier. The monomer used in the copolymer water-soluble salt (A) is not particularly limited, and various known vinyl monomers can be used, and (meth) acrylic acid ester, maleic acid half ester, (meth) acrylic acid and the like are particularly preferable. It is.
[0007]
Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate and acrylic. 2-ethylhexyl acid, n-octyl acrylate, n-decyl acrylate, n-lauryl acrylate, n-stearyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, isopropoxyethyl acrylate, n-butoxy acrylate Aliphatic monoalcohol having 1 to 18 carbon atoms such as ethyl, stearoxyethyl acrylate, methoxyethoxyethyl acrylate, ethoxyethoxyethyl acrylate, butoxyethoxyethyl acrylate, stearoxyethoxyethyl acrylate, etc. Ester of acrylic acid, esters of diethylene glycol monoalkyl ether and acrylic acid ethylene glycol monoalkyl ether or 5 to 22 carbon atoms having 3 to 20 carbon atoms, as well as methacrylic acid esters corresponding to these can be exemplified. These (meth) acrylic acid esters can be used alone or in appropriate combination. In addition, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like can also be used.
[0008]
Examples of the maleic acid half ester include monomethyl maleate, monoethyl maleate, mono (n-propyl) maleate, mono (isopropyl) maleate, mono (n-butyl) maleate, mono (isobutyl) maleate, and maleate. Mono (n-amyl) acid, mono (n-hexyl) maleate, mono (2-ethylhexyl) maleate, mono (n-octyl) maleate, mono (n-decyl) maleate, mono (isodecyl) maleate , Mono (n-lauryl) maleate, mono (tridecyl) maleate, mono (n-stearyl) maleate, mono (methoxyethyl) maleate, mono (ethoxyethyl) maleate, mono (isopropoxyethyl) maleate , Mono (n-butoxyethyl) maleate, mono (maleate stearate) Ciethyl), mono (methoxyethoxyethyl) maleate, mono (ethoxyethoxyethyl) maleate, mono (isopropoxyethoxyethyl) maleate, mono (butoxyethoxyethyl) maleate, mono (stearoxyethoxyethyl) maleate, etc. Esterified product of aliphatic monoalcohol having 1 to 18 carbon atoms and maleic anhydride, ester of ethylene glycol monoalkyl ether having 3 to 20 carbon atoms or diethylene glycol monoalkyl ether having 5 to 22 carbon atoms and maleic anhydride A compound can be exemplified. These maleic acid half esters can be used alone or in appropriate combination.
[0009]
Examples of monomers other than the (meth) acrylic acid ester and maleic acid half ester include (meth) acrylamide, diacetone acrylamide, diethyl acrylamide, (meth) acrylonitrile, styrene, vinyl acetate and the like.
[0010]
The solid content acid value before neutralization of the aqueous copolymer salt (A) is carefully determined in consideration of the stability during emulsion polymerization and the drying property of the obtained binder, and is usually 50 to 80 mgKOH / g. Degree, more preferably 60-80 mg KOH / g. When it is less than 50 mgKOH / g, the polymerization stability is remarkably lowered, and when it exceeds 80 mgKOH / g, the drying property of the obtained binder is remarkably lowered. In order to adjust the acid value within such a range, it is sufficient to adjust the amount of the vinyl monomer containing a carboxyl group. Usually, the amount of the carboxyl-containing vinyl monomer used is the vinyl monomer used for the production of the polymer emulsifier. Is generally about 5 to 15% by weight, preferably 7 to 12% by weight.
[0011]
Further, the glass transition temperature (hereinafter referred to as Tg) of the solid content of the copolymer aqueous salt (A) is carefully determined in consideration of the drying property of the obtained binder, and is usually about 90 to 130 ° C., more preferably 90-110 ° C. In the present invention, Tg means a calculated value based on an approximate expression of FoX. When the Tg is less than 90 ° C., the drying property of the resulting coating polymer aqueous dispersion is remarkably reduced. When the Tg is higher than 130 ° C., the wear resistance of the resulting coating polymer film is significantly reduced. To do.
[0012]
In addition, although it does not specifically limit about the average molecular weight of solid content of copolymer aqueous salt (A), A thing with a weight average molecular weight of about 2000-200000 is preferable.
[0013]
The method for producing the copolymer aqueous salt (A), which is the polymer emulsifier used in the present invention, is not particularly limited, and can be easily produced by various known polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization. For example, when employing a solution polymerization method, a predetermined amount of a solvent such as vinyl monomer and hydrocarbon is charged into a reaction vessel, and a peroxide radical polymerization initiator such as benzoyl peroxide or di-t-butyl peroxide is introduced. Or, in the presence of an azo radical polymerization initiator such as azobisisobutyronitrile or azobisisobutyronitrile, the polymerization is usually carried out by heating to about 70 to 150 ° C. to obtain a desired acrylic copolymer. Next, the copolymer is neutralized with at least one of alkali metal hydroxides such as sodium hydroxide, organic amines such as ammonia, triethylamine, monoethanolamine, 2-dimethylethanolamine, and the like. To obtain a polymer emulsifier. The neutralization degree is not particularly limited, but is usually about 100 to 180%, preferably about 130 to 170%. In addition, when the solvent used needs to be distilled off, operations such as distillation under reduced pressure and steam distillation may be performed before or after neutralization.
[0014]
In order to obtain the coating polymer aqueous dispersion of the present invention using the copolymer aqueous salt (A) as the polymer emulsifier, for example, the following production method may be followed. That is, the following vinyl monomer (B) may be emulsion polymerized in the presence of the copolymer water-soluble salt (A). In the polymerization, the total amount of the vinyl monomer (B) and the radical polymerization initiator is supplied to the reaction system by a method such as batch charging, continuous dropping, or divided charging, and the conditions are 30 to 90 ° C. and the reaction time is about 1 to 8 hours. The polymerization reaction is completed under The radical polymerization initiator to be used is not particularly limited, and known water-soluble ones such as ammonium persulfate and potassium persulfate can be appropriately selected. The amount used is usually based on 100 parts of the total amount of the vinyl monomer (B). 0.1 to 5 parts. In addition to the radical polymerization initiator, a reducing agent may be used in combination to make the reaction system a redox system.
[0015]
The vinyl monomer (B) to be subjected to emulsion polymerization is appropriately determined in consideration of the performance of the resulting coating polymer aqueous dispersion. Specifically, (meth) acrylic acid ester having 1 to 22 carbon atoms of alkyl group; (meth) acrylic acid ester having hydroxyl group, amino group, glycidyl group, etc .; (meth) acrylamide, (meth) acrylonitrile, styrene , Methylstyrene, vinyltoluene, (meth) acrylic acid, maleic anhydride, maleic acid half ester, itaconic acid, itaconic acid half ester, and the like. Of these, styrene, (meth) acrylic acid ester having 1 to 22 carbon atoms in the alkyl group, and amino group-containing (meth) acrylic acid ester are preferable. These vinyl monomers can be used alone or in appropriate combination.
[0016]
In the present invention, the vinyl monomer (B) can be emulsion-polymerized in two stages. When the two-stage emulsion polymerization method is employed, the resulting coating polymer aqueous dispersion is more excellent in film-forming properties and gloss of the film than the usual one-stage emulsion polymerization method. As a specific example of the two-stage emulsion polymerization method, in the presence of the copolymer aqueous salt (A), first, a predetermined amount of the vinyl monomer (B) and a radical polymerization initiator are collectively charged, continuously dropped, or dividedly charged. Supply to the reaction system and perform the first stage emulsion polymerization to obtain an aqueous polymer dispersion. Next, the remaining monomer (B) 5 to 100 parts by weight, preferably 5 to 70 parts by weight, and a radical polymerization initiator are supplied to the reaction system with respect to 100 parts by weight of the polymer solid content, and the second stage. To complete the polymerization. The Tg of the monomer (B) to be subjected to the first stage emulsion polymerization is usually 50 to 130 ° C, preferably 80 to 110 ° C. When the Tg of the polymer obtained in the first step is less than 50 ° C., the drying property of the resulting coating polymer aqueous dispersion decreases, and when it exceeds 130 ° C., Wear resistance is reduced. The monomer (B) to be used for the emulsion polymerization in the second stage is preferably selected from monomer types in which the Tg of the homopolymer is 0 ° C. or less in consideration of the film forming property of the resulting coating polymer film. These monomers may be used alone or in combination of two or more as long as the Tg as a copolymer is 0 ° C. or lower. Further, when the amount of the monomer (B) used in the second stage is less than 5 parts by weight with respect to 100 parts by weight of the polymer obtained in the first stage, the gloss of the resulting coating polymer film decreases. On the other hand, when it exceeds 100 parts by weight, the drying property of the resulting coating polymer aqueous dispersion is lowered.
[0017]
In the emulsion polymerization, in consideration of the stability of the emulsion polymerization and the performance of the resulting coating polymer aqueous dispersion, the acrylic copolymer water-soluble salt (A) and the vinyl monomer (B) to be subjected to the emulsion polymerization are used. It is important to carefully determine the usage rate. That is, the amount of the solid content of the copolymer water-soluble salt (A) is preferably 5 to 15 parts by weight with respect to 100 parts by weight of the vinyl monomer (B), and the polymerization stability is less than 5% by weight. When the amount exceeds 15% by weight, the drying property of the resulting aqueous polymer dispersion is significantly reduced.
[0018]
In the present invention, as long as the aqueous copolymer salt (A) is used, an aqueous dispersion of the coating polymer can be stably obtained without using a surfactant during emulsion polymerization. It is not intended to eliminate the combined use. Further, a protective colloid such as polyvinyl alcohol may be used as long as it does not deviate from the performance of the present invention.
[0019]
The non-volatile content and viscosity of the resulting coating polymer aqueous dispersion are not particularly limited, but considering workability and the like, the non-volatile content is usually about 30 to 70% by weight, and the viscosity is about 5 to 6000 cP. preferable. The particle diameter of the coating polymer aqueous dispersion is preferably 0.1 μm or less in view of mechanical stability and the like. The Tg of the coating polymer is determined according to its use and is not particularly limited. However, for example, when used for an aqueous binder for paints and inks, it is usually about 15 to 50 ° C. preferable.
[0020]
The coating polymer aqueous dispersion of the present invention thus obtained can be used alone, but the following additives can be used in combination depending on the application. That is, acrylic resins, rosin-modified maleic resins, styrene-maleic resins, alkali-soluble resins such as shellac, polyethylene-based waxes, and the like. In addition, when it is desired to obtain a colored glossy film, a colorant such as a dye or pigment may be added.
[0021]
【The invention's effect】
The aqueous coating polymer dispersion of the present invention has good water dispersion stability despite the small amount of the acrylic copolymer aqueous salt (A) that functions as a polymer emulsifier. Therefore, it is quick-drying and has good gloss, water resistance, transparency and friction resistance. Therefore, various aqueous binders for overprint coats, paints, inks and the like, which are particularly excellent in drying properties, can be provided using the aqueous dispersion.
[0022]
【Example】
Hereinafter, the present invention will be described more specifically with reference examples and examples, but the present invention is not limited to these examples. In the following description, “part” and “%” are based on weight unless otherwise specified, and Tg is a value calculated by an approximate formula of Fox.
[0023]
Reference Example 1 (Production of Acrylic Copolymer Aqueous Salt (A))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen gas inlet tube and a reflux condenser, 450 parts of xylene was charged under a nitrogen stream, and the temperature was raised until the internal temperature reached 125 to 130 ° C. Then, a mixed solution consisting of 286 parts of methyl methacrylate, 220 parts of isopropyl methacrylate, 44 parts of methacrylic acid, and 11 parts of di-t-butyl peroxide was dropped over 3 hours from the dropping funnel, The polymerization reaction was completed by incubating for a period of time, and then xylene and unreacted components were removed under reduced pressure to obtain a copolymer having an acid value of 52 mgKOH / g and Tg of 97 ° C. In a separate reaction vessel, 100 parts of the copolymer is added, 12 parts of 28% ammonia water and 221 parts of deionized water are added and dissolved by stirring at 80 ° C. for 2 hours, the degree of neutralization is 150%, and the solid content is 30%. A copolymer aqueous solution (hereinafter referred to as copolymer water-soluble salt (1)) was obtained.
[0024]
Reference example 2
450 parts of xylene was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised until the internal temperature reached 125 to 130 ° C. Next, a mixture of 440 parts of methyl methacrylate, 55 parts of isobutyl methacrylate, 55 parts of methacrylic acid and 11 parts of di-t-butyl peroxide was dropped from the dropping funnel over 3 hours, and then at the same temperature for 2 hours. The temperature was maintained to complete the polymerization reaction, and then xylene and unreacted components were removed under reduced pressure to obtain a copolymer having an acid value of 65 gKOH / g and Tg of 103 ° C. Using this copolymer, neutralization was performed in the same manner as in Reference Example 1 to obtain a copolymer aqueous solution (hereinafter referred to as copolymer water-soluble salt (2)) having a neutralization degree of 145% and a solid content concentration of 30%. .
[0025]
Reference example 3
450 parts of xylene was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised until the internal temperature reached 125 to 130 ° C. Next, a mixture of 385 parts of methyl methacrylate, 110 parts of isopropyl methacrylate, 55 parts of acrylic acid and 11 parts of di-t-butyl peroxide was dropped from the dropping funnel over 3 hours, and then at the same temperature for 2 hours. The temperature was maintained to complete the polymerization reaction, and then xylene and unreacted components were removed under reduced pressure to obtain a copolymer having an acid value of 78 mgKOH / g and Tg of 100 ° C. The copolymer was neutralized in the same manner as in Reference Example 1 to obtain a copolymer aqueous solution (hereinafter referred to as copolymer water-soluble salt (3)) having a neutralization degree of 150% and a solid content concentration of 30%. .
[0026]
Reference Example 4 (Production of Comparative Copolymer Aqueous Salt)
450 parts of xylene was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised until the internal temperature reached 125 to 130 ° C. Next, after dropping a mixed liquid consisting of 412.5 parts of methyl methacrylate, 82.5 parts of n-butyl acrylate, 55 parts of acrylic acid and 11 parts of di-t-butyl peroxide, taking 3 hours from the dropping funnel. The mixture was kept at the same temperature for 2 hours to complete the polymerization reaction, and then xylene and unreacted components were removed under reduced pressure to obtain a copolymer having an acid value of 78 mgKOH / g and Tg of 67 ° C. The copolymer was neutralized in the same manner as in Reference Example 1 to obtain a copolymer aqueous solution (hereinafter referred to as copolymer water-soluble salt (4)) having a neutralization degree of 150% and a solid content concentration of 30%. .
[0027]
Reference Example 5
450 parts of xylene was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised until the internal temperature reached 125 to 130 ° C. Next, a mixture of 440 parts of methyl methacrylate, 38.5 parts of isobutyl methacrylate, 71.5 parts of acrylic acid and 11 parts of di-t-butyl peroxide was dropped from the dropping funnel over 3 hours, The temperature was maintained for 2 hours to complete the polymerization reaction, and then xylene and unreacted components were removed under reduced pressure to obtain a copolymer having an acid value of 101 mgKOH / g and Tg of 102 ° C. The copolymer was used for neutralization in the same manner as in Reference Example 1 to obtain a copolymer aqueous solution (hereinafter referred to as copolymer water-soluble salt (5)) having a neutralization degree of 150% and a solid content concentration of 30%. .
[0028]
Reference Example 6
450 parts of xylene was charged into the same reaction vessel as in Reference Example 1, and the temperature was raised until the internal temperature reached 125 to 130 ° C. Next, a mixture of 440 parts of methyl methacrylate, 77 parts of isobutyl methacrylate, 33 parts of acrylic acid and 11 parts of di-t-butyl peroxide was dropped from the dropping funnel over 3 hours, and then at the same temperature for 2 hours. The polymerization reaction was completed by keeping the temperature. Thereafter, xylene and unreacted components were removed under reduced pressure. The acid value of the obtained copolymer was 45 mgKOH / g and the glass transition temperature was 99 ° C. Using this copolymer, neutralization was performed in the same manner as in Reference Example 1 to obtain a copolymer aqueous solution (hereinafter referred to as copolymer water-soluble salt (6)) having a neutralization degree of 150% and a solid content concentration of 30%. .
[0029]
Example 1 (Production of aqueous polymer dispersion for coating)
In a reaction vessel similar to that of Reference Example 1, 158 parts of deionized water and 20 parts of copolymer water-soluble salt (1) were charged and heated to 80 ° C. while stirring in a nitrogen atmosphere. Next, an emulsion mixture composed of 120 parts of the copolymer water-soluble salt (1), 350 parts of styrene, 3.1 parts of ammonium persulfate and 139 parts of deionized water was dropped over 4 hours, and the mixture was further kept warm for 2 hours. A coating polymer aqueous dispersion A having a solid content of 50% was obtained.
[0030]
Example 2
In a reaction vessel similar to Reference Example 1, 270 parts of deionized water and 120 parts of the copolymer water-soluble salt (2) were charged and heated to 80 ° C. with stirring in a nitrogen atmosphere. Next, a monomer mixed solution of 320 parts of methyl methacrylate and 10 parts of n-butyl acrylate and an aqueous polymerization initiator solution in which 2.9 parts of ammonium persulfate was dissolved in 22 parts of deionized water were separately added dropwise over 3 hours. The first stage emulsion polymerization was completed by incubating for 1 hour. Subsequently, 20 parts of 2-ethylhexyl acrylate (Tg of the homopolymer is −85 ° C.) and an aqueous polymerization initiator solution in which 0.2 part of ammonium persulfate is dissolved in 10 parts of deionized water are separately added to the reaction system. By dropping the solution for 1 minute and keeping it warm for 1 hour, the second stage emulsion polymerization was completed to obtain a coating polymer aqueous dispersion B having a solid content of 50%. The Tg of the polymer obtained in the first stage is 97 ° C.
[0031]
Example 3
In a reaction vessel similar to Reference Example 1, 270 parts of deionized water and 120 parts of the copolymer water-soluble salt (3) were charged and heated to 80 ° C. with stirring in a nitrogen atmosphere. Next, a monomer mixture of 280 parts of methyl methacrylate and 20 parts of styrene and an aqueous polymerization initiator solution in which 2.7 parts of ammonium persulfate was dissolved in 22 parts of deionized water were separately added dropwise over 3 hours and kept warm for 1 hour. Thus, the first stage emulsion polymerization was completed. Next, 50 parts of ethyl acrylate (Tg of the homopolymer is −22 ° C.) and an aqueous polymerization initiator solution in which 0.4 part of ammonium persulfate is dissolved in 10 parts of deionized water are separately added to the reaction system in 30 minutes. By dropping and incubating for 1 hour, the second-stage emulsion polymerization was completed, and a coating polymer aqueous dispersion C having a solid content of 50% was obtained. The Tg of the polymer obtained in the first stage is 105 ° C.
[0032]
Example 4
In a reaction vessel similar to Reference Example 1, 270 parts of deionized water and 120 parts of the copolymer water-soluble salt (3) were charged and heated to 80 ° C. with stirring in a nitrogen atmosphere. Next, a monomer mixture of 20 parts of methyl methacrylate and 280 parts of styrene and an aqueous polymerization initiator solution in which 2.7 parts of ammonium persulfate was dissolved in 22 parts of deionized water were separately added dropwise over 3 hours and kept warm for 1 hour. Thus, the first stage emulsion polymerization was completed. Next, 50 parts of ethyl acrylate (Tg of the homopolymer is −22 ° C.) and an aqueous polymerization initiator solution in which 0.4 part of ammonium persulfate is dissolved in 10 parts of deionized water are separately added to the reaction system in 30 minutes. By dropping and incubating for 1 hour, the second stage emulsion polymerization was completed, and a coating polymer aqueous dispersion D having a solid content of 50% was obtained. The Tg of the polymer obtained in the first stage is 101 ° C.
[0033]
Comparative Example 1 (Production of Comparative Polymer Aqueous Dispersion)
In a reaction vessel similar to that of Reference Example 1, 270 parts of deionized water and 120 parts of the copolymer water-soluble salt (4) were charged and heated to 80 ° C. with stirring in a nitrogen atmosphere. Next, a monomer mixture of 280 parts of methyl methacrylate and 20 parts of styrene and an aqueous polymerization initiator solution in which 2.7 parts of ammonium persulfate was dissolved in 22 parts of deionized water were separately added dropwise over 3 hours and kept warm for 1 hour. Thus, the first stage emulsion polymerization was completed. Next, 50 parts of ethyl acrylate (Tg of the homopolymer is −22 ° C.) and an aqueous polymerization initiator solution in which 0.4 part of ammonium persulfate is dissolved in 10 parts of deionized water are separately added to the reaction system in 30 minutes. By dropping and incubating for 1 hour, the second-stage emulsion polymerization was completed, and a coating polymer aqueous dispersion E having a solid content of 50% was obtained. The Tg of the polymer obtained in the first stage is 105 ° C.
[0034]
Comparative Example 2
In a reaction vessel similar to that of Reference Example 1, 270 parts of deionized water and 120 parts of the copolymer water-soluble salt (5) were charged and heated to 80 ° C. with stirring in a nitrogen atmosphere. Next, a monomer mixture of 280 parts of methyl methacrylate and 20 parts of styrene and an aqueous polymerization initiator solution in which 2.7 parts of ammonium persulfate was dissolved in 22 parts of deionized water were separately added dropwise over 3 hours and kept warm for 1 hour. Thus, the first stage emulsion polymerization was completed. Next, 50 parts of ethyl acrylate (Tg of the homopolymer is −22 ° C.) and an aqueous polymerization initiator solution in which 0.4 part of ammonium persulfate is dissolved in 10 parts of deionized water are separately added to the reaction system in 30 minutes. By dropping and incubating for 1 hour, the second stage emulsion polymerization was completed, and a coating aqueous polymer dispersion F having a solid content of 50% was obtained. The Tg of the polymer obtained in the first stage is 105 ° C.
[0035]
Comparative Example 3
In a reaction vessel similar to that of Reference Example 1, 270 parts of deionized water and 120 parts of the copolymer water-soluble salt (6) were charged and heated to 80 ° C. with stirring in a nitrogen atmosphere. Next, a monomer mixture of 280 parts of methyl methacrylate and 20 parts of styrene and an aqueous polymerization initiator solution in which 2.7 parts of ammonium persulfate was dissolved in 22 parts of deionized water were separately added dropwise over 3 hours. However, at the end of dropping, a large amount of aggregate was generated and the dispersion was in a separated state, so the shift to the second stage emulsion polymerization was abandoned.
[0036]
Comparative Example 4
In a reaction vessel similar to Reference Example 1, 270 parts of deionized water and a water-soluble salt of the copolymer (5) 120 parts were charged and heated to 80 ° C. with stirring in a nitrogen atmosphere. Next, a monomer mixture of 228 parts of methyl methacrylate and 72 parts of 2-ethylhexyl methacrylate and an aqueous polymerization initiator solution in which 2.7 parts of ammonium persulfate was dissolved in 22 parts of deionized water were separately added dropwise over 3 hours. The first stage emulsion polymerization was completed by incubating for 1 hour. Next, 50 parts of methyl methacrylate (Tg of the homopolymer is 105 ° C.) and an aqueous polymerization initiator solution in which 0.4 part of ammonium persulfate is dissolved in 10 parts of deionized water are dropped into the reaction system separately in 30 minutes. Then, by keeping the temperature for 1 hour, the second stage emulsion polymerization was completed, and a coating polymer aqueous dispersion G having a solid content of 50% was obtained. The Tg of the polymer obtained in the first stage is 31 ° C.
[0037]
(Performance evaluation)
A polymer aqueous dispersion (A to G) prepared with a Zahn cup # 4 to a viscosity of 15 seconds is coated on a coated paper printed with water-based black ink with a bar coater # 8, and left for 1 hour. The performance was evaluated by the method. These results are shown in Table 1.
Gloss and transparency: 5 grades visually (5 is best)
Drying: 5 grades by touch after coating (5 is best)
Water resistance: Drop 5 drops of water on a caraco cloth, apply it to the coated surface, test it with a Gakushin type friction fastness tester under conditions of 200g x 10 reciprocations, and visually evaluate the ink marks transferred to the caraco cloth in 5 levels (5 is the best)
Friction resistance: High-quality paper is applied to the coated surface, tested with a Gakushin type friction fastness tester at 200 g x 500 reciprocating conditions, and the ink marks transferred to the high-quality paper are visually evaluated in five stages (5 is the best)
[0038]
[Table 1]
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34961695A JP3620671B2 (en) | 1995-12-20 | 1995-12-20 | Method for producing coating polymer aqueous dispersion and dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34961695A JP3620671B2 (en) | 1995-12-20 | 1995-12-20 | Method for producing coating polymer aqueous dispersion and dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09169806A JPH09169806A (en) | 1997-06-30 |
| JP3620671B2 true JP3620671B2 (en) | 2005-02-16 |
Family
ID=18404942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34961695A Expired - Lifetime JP3620671B2 (en) | 1995-12-20 | 1995-12-20 | Method for producing coating polymer aqueous dispersion and dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3620671B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8216666B2 (en) | 2008-02-29 | 2012-07-10 | The Procter & Gamble Company | Substrates having improved crockfastness |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427875A (en) * | 2000-05-12 | 2003-07-02 | 东亚合成株式会社 | Water-based sealer composition |
| JP3599677B2 (en) | 2001-03-19 | 2004-12-08 | クラリアントポリマー株式会社 | Coating composition for inkjet recording medium and inkjet recording medium |
| JP3640921B2 (en) * | 2001-12-28 | 2005-04-20 | クラリアントポリマー株式会社 | Synthetic resin emulsion, easily water-swellable pressure-sensitive adhesive composition comprising the same, and method for producing synthetic resin emulsion |
| JP5564342B2 (en) * | 2010-06-28 | 2014-07-30 | 昭和電工株式会社 | Water-based quick-drying composition and quick-drying coating composition |
| JP6220185B2 (en) * | 2013-08-09 | 2017-10-25 | サカタインクス株式会社 | Water-based inkjet ink composition and inkjet recording method |
-
1995
- 1995-12-20 JP JP34961695A patent/JP3620671B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8216666B2 (en) | 2008-02-29 | 2012-07-10 | The Procter & Gamble Company | Substrates having improved crockfastness |
| US8673430B2 (en) | 2008-02-29 | 2014-03-18 | Alrick Vincent Warner | Substrates having improved crockfastness |
| US9283794B2 (en) | 2008-02-29 | 2016-03-15 | The Procter & Gamble Company | Substrates having improved crockfastness |
| US9770373B2 (en) | 2008-02-29 | 2017-09-26 | The Procter & Gamble Company | Substrates having improved crockfastness |
| US10836196B2 (en) | 2008-02-29 | 2020-11-17 | The Procter & Gamble Company | Substrates having improved crockfastness |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09169806A (en) | 1997-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5227083B2 (en) | Pigment dispersant, method for producing the same, and use thereof | |
| US5708095A (en) | Graft copolymers containing sulfonate and phosphonate groups having particular utility as pigmented ink dispersants | |
| CN101597355B (en) | Water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof | |
| US4289678A (en) | Acrylic thickener for publication gravure inks, method of preparing said thickener, ink containing the same and method of printing | |
| WO2009127127A1 (en) | Ink resin used for intaglio printing and its preparing method | |
| US20060167135A1 (en) | Inkjet ink binder and inkjet ink composition | |
| CN107513124B (en) | A kind of polyester acrylic ester aqueous dispersion and preparation method thereof | |
| JP3394828B2 (en) | Aqueous printing ink composition for paper | |
| US4388434A (en) | Lithographic ink vehicle containing addition polymer and aliphatic hydrocarbon solvent | |
| JP3620671B2 (en) | Method for producing coating polymer aqueous dispersion and dispersion | |
| WO2002032971A1 (en) | Water-soluble resin, process for its production and water-soluble resin composition | |
| CN113105576A (en) | Resin modified acrylic emulsion with core-shell structure and preparation method and application thereof | |
| CN114276495B (en) | Polyolefin/acrylic ester hybridized water dispersion, preparation method and application thereof | |
| JP3111542B2 (en) | Resin emulsion for aqueous overprint varnish | |
| CA1120641A (en) | Acrylic thickener for publication gravure inks, method of preparing said thickener, ink containing the same and method of printing | |
| JPH0774242B2 (en) | Method for producing resin binder for water-based flexo ink | |
| JPS607643B2 (en) | Vehicle for water-based gravure or flexographic printing inks | |
| JP2004115750A (en) | Pigment dispersant and water-based ink | |
| AU626406B2 (en) | Aqueous resin composition | |
| CN111285953A (en) | Acrylic emulsion and preparation method thereof | |
| JP4132573B2 (en) | Method for producing aqueous dispersion and aqueous dispersion thereof | |
| JP2004224866A (en) | Redispersible resin powder, powder composition containing the same, and use of them | |
| EP0972783B1 (en) | Method for producing amphoteric resin having dispersing function | |
| JP2005002172A (en) | Organic fluorescent pigment and water-based fluorescent composition | |
| JP2000264927A (en) | Aqueous dispersion of alkali-soluble resin and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040802 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040826 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040906 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041029 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041111 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081126 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091126 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091126 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101126 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101126 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111126 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111126 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121126 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121126 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121126 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121126 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131126 Year of fee payment: 9 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |