JP4045827B2 - Aqueous resin composition - Google Patents

Description

【化２】

【００７０】
上記構造式［１］及び［２］中、Ｒ₁は任意のアルキル基、Ｒ₂は任意のアルキレン基、Ｒ₃、Ｒ₄は何れか一方がエチレン残基で、他方が炭素原子数が３〜８のアルキレン残基であり、Ｒ₅はアルキル基、アセチル基もしくは水素を示し、ａ及びｂは各々１以上の整数を示し、ｍ及びｎは各々任意の整数を示す。
【００７１】
これらの感熱ゲル化剤［Ｙ］の量は、特に制限されるものではないが、重合体水性分散液の長期保存性の面から、重合体粒子［Ｘ］１００重量部に対して、通常、０．０５〜３０重量部の範囲で使用することが好ましい。
【００７２】
重合体粒子［Ｘ］のカルボキシル基と反応性を有する架橋剤［Ｚ］（以下架橋剤［Ｚ］という）としては、カルボキシル基と反応性を有する架橋剤であれば、特に制限を受けるものではない。架橋剤［Ｚ］の態様は、水溶性、或いは水希釈性または水分散性等が挙げられる。
【００７３】
架橋剤［Ｚ］としては、具体的には、例えば多官能性メラミン化合物、多官能性ポリエチレンイミン化合物、多官能性（ブロック）イソシアネート化合物、多官能性アジリジン化合物、多官能性グリシジル化合物、多官能性カルボジイミド化合物、多官能性オキサゾリン化合物等が挙げられる。
【００７４】
これらの中でも、多官能性グリシジル化合物、多官能性カルボジイミド化合物、多官能性オキサゾリン化合物が、得られる被膜の架橋密度を向上させることができ、被膜の耐衝撃性や硬度が向上するため好ましい。
【００７５】
さらにこれらの架橋剤の中で、被膜の耐衝撃性の点で特に優れるため、多官能性オキサゾリン化合物が好ましい。
【００７６】
多官能性グリシジル化合物の具体例としては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ヘキサメチレングリコールジグリシジルエーテル、シクロヘキサンジオールジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル等の脂肪族多価アルコールのグリシジルエーテル類；ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル等のポリアルキレングリコールのグリシジルエーテル類；多価アルコール［エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサメチレングリコール、ビス（ヒドロキシメチル）ベンゼン等］と多価カルボン酸［蓚酸、アジピン酸、ブタントリカルボン酸、マレイン酸、フタル酸、テレフタル酸、イソフタル酸、ベンゼントリカルボン酸等］とのポリエステルのポリグリシジル化物、ポリカプロラクトンのポリグリシジル化物等のポリエステルのポリグリシジル化物；多価アミン［エチレンジアミン、ジエチレントリアミン、１，４−シクロヘキサンジアミン、イソホロンジアミン、トリレンジアミン等］と多価カルボン酸［蓚酸、アジピン酸、ブタントリカルボン酸、マレイン酸、フタル酸、テレフタル酸、イソフタル酸、ベンゼントリカルボン酸等］とのポリアミドのポリグリシジル化物；ビスフェノールＡとエピクロルヒドリンの縮合物、ビスフェノールＡとエピクロルヒドリンの縮合物のエチレンオキシド付加物、ビスフェノールＡとエピクロルヒドリンの縮合物のプロピレンオキシド付加物等のビスフェノールＡ系エポキシ樹脂；フェノールノボラック樹脂、フェノールノボラック樹脂のエチレンオキシド付加物、フェノールノボラック樹脂のプロピレンオキシド付加物等のフェノールノボラック系エポキシ樹脂；エポキシ樹脂をウレタン変性したエポキシウレタン樹脂；側鎖にエポキシ基を有する各種ビニル系（共）重合体；グリシジル変性シリコーンオイル；γ−グリシドキシプロピルトリメトキシシラン等のグリシジル基含有アルコキシシランの部分加水分解物；グリシジル基含有アクリル樹脂等の１分子中にグリシジル基を２個以上有する化合物が挙げられる。
【００７７】
この様なグリシジル基含有化合物の中でも、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル類、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル類、グリセロールポリグリシジルエーテル類、ジグリセロルポリグリシジルエーテル類、ポリグリセロールポリグリシジルエーテル類、ソルビトールポリグリシジルエーテル類等の水溶性グリシジル基含有化合物、または、「デナコールＥＭ−１２５」［ナガセ化成工業（株）製］、「ディックファインＥＭ−１００」［大日本インキ化学工業（株）製］、「アデカレジンＥＰＥ−０４１０、ＥＰＥＳ−０４２５Ｗ」［旭電化工業（株）製］等の自己分散性のグリシジル基含有化合物をエマルジョン化したもの、或いは水不溶性のグリシジル基含有化合物（液状、固型状）を乳化剤でエマルジョン化したものが、重合体粒子［Ｘ］との相溶性や硬化性の点から好ましい。
【００７８】
また多官能性グリシジル化合物としては、１分子中にグリシジル基と、グリシジル基以外の反応性官能基（ここで反応性官能基とは、重合体粒子［Ｘ］中の反応基と反応し得る反応性官能基、もしくは該反応基同士で反応し得る反応性官能基をいう）を有していることが好ましい。かかる化合物としては、具体的には、１分子中にグリシジル基と、加水分解性シリル基もしくはシラノール基を含有するグリシジル基含有シラン化合物が挙げられる。
【００７９】
このグリシジル基含有シラン化合物を用いた場合、被膜の耐水性や耐衝撃性等の諸物性、特に耐衝撃性が著しく向上し、更に、架橋性が良好であり、例えば常温乾燥のみで所望とする性能の架橋被膜が得られるため好ましい。
【００８０】
グリシジル基含有シラン化合物としては、これらの両種の反応性基を併有するエチレン性重合体や、グリシジル基を有するシランカップリング剤、あるいはグリシジル基を有するシリコーン樹脂などが特に代表的なものとして挙げられる。
【００８１】
ここにおいて、加水分解性シリル基とは、たとえばアルコキシ基、置換アルコキシ基、フェノキシ基、ハロゲン原子、イソプロペニルオキシ基、アシロキシ基またはイミノオキシなどが結合した珪素原子を含む原子団であって、容易に加水分解が進行し、シラノール基を生成する官能基を指称するものである。かかる加水分解性シリル基としては、例えばアルコキシシリル基、フェノキシシリル基、ハロシリル基、イソプロペニルオキシシリル基、アシロキシシリル基またはイミノオキシシリル基などが挙げられる。
【００８２】
上記したグリシジル基と加水分解性シリル基もしくはシラノール基を併有するエチレン性重合体を調製するには、公知の各種の方法がいずれも適用できる。これらのうち、推奨し得る方法としては、▲１▼各種の加水分解性シリル基含有重合性単量体類と各種のグリシジル基含有重合性単量体類とをラジカル共重合する方法、▲２▼加水分解性シリル基含有重合性単量体類と、各種のグリシジル基含有重合性単量体類と、これらと共重合可能なるその他の重合性単量体とをラジカル共重合する方法、▲３▼γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシランまたはγ−メルカプトプロピルトリイソプロペニルオキシシランの如き、加水分解性シリル基を含有する各種の連鎖移動剤の存在下に、前述した各種のグリシジル基含有重合性単量体類を必須の単量体成分とする単量体混合物をラジカル（共）重合せしめるか、あるいは、▲４▼上記▲１▼もしくは▲２▼の方法と上記▲３▼の方法を組み合わせた方法等の種々の方法が挙げられる。
【００８３】
また、上記したグリシジル基含有シランカップリング剤として、特に代表的なものとしては、例えば、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルメチルジエトキシシランもしくはγ−グリシドキシプロピルトリイソプロぺニルオキシシランの如き、各種のグリシジル基含有シラン化合物；γ−イソシアネ−トプロピルトリイソプロぺニルオキシシランもしくはγ−イソシアネ−トプロピルトリメトキシシランの如き、各種のイソシアネートシラン化合物と、グリシド−ルとの付加物；またはγ−アミノプロピルトリメトキシシランの如き、各種のアミノシラン化合物と、ジグリシジル化合物との付加物；あるいは、上掲の如き各種のグリシジル基含有シラン化合物を部分加水分解縮合せしめて得られる、一分子中に２個以上のグリシジル基と加水分解性シリル基とを併有する化合物等が挙げられる。
【００８４】
架橋剤［Ｚ］として、多官能性グリシジル化合物を使用する場合は、硬化触媒を併用することが、被膜の架橋性をより一層向上することができる点から好ましい。
【００８５】
かかる硬化触媒として特に代表的なものとしては、例えば水酸化リチウム、水酸化ナトリウム、水酸カリウム、ナトリウム・メチラート等の各種の塩基性化合物類；テトライソプロピルチタネート、テトラ−ｎ−ブチルチタネート、オクチル酸錫、オクチル酸鉛、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸カルシウム、ナフテン酸亜鉛、ナフテン酸コバルト、ジ−ｎ−ブチル錫ジアセテート、ジ−ｎ−ブチル錫ジオクトエート、ジ−ｎ−ブチル錫ジラウレート、ジ−ｎ−ブチル錫マレエート等の各種の含金属化合物類；ｐ−トルエンスルホン酸、トリクロル酢酸、燐酸、モノアルキル燐酸、ジアルキル燐酸、モノアルキル亜燐酸、ジアルキル亜燐酸等の各種の酸性化合物などが挙げられる。
【００８６】
次に、架橋剤［Ｚ］として使用する多官能性カルボジイミド化合物としては、２個以上のカルボジイミド基を含有する化合物であり、例えば、有機ジイソシアネートの脱二酸化炭素を伴う縮合反応によりイソシアネート末端多価カルボジイミドを合成することにより製造できる。
【００８７】
２個以上のカルボジイミド基を含有する化合物を合成する際の原料である有機ジイソシアネートとしては、脂肪族、脂環式或いは芳香族のジイソシアネートが挙げられ、これらを単独或いは二種以上の混合物として使用することができる。具体的には、１，５−ナフチレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、４，４−ジフェニルメチルメタンジイソシアネート、１，４−トリレンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ヘキサメチレンジイソシアネート、シクロヘキサン−１，４−ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン−４，４−ジイソシアネート、メチルシクロヘキサンジイソシアネート、テトラメチルキシリレンジイソシアネート等が挙げられる。
【００８８】
上記した有機ジイソシアネートとともにモノイソシアネート等の末端イソシアネート基と反応する化合物を用いて、分子を適当な重合度に制御することもできる。
【００８９】
上記した有機ジイソシアネートの脱二酸化炭素を伴う縮合反応は、カルボジイミド化触媒の存在下に進行する。このカルボジイミド化触媒としては、例えば、１−フェニル−２−ホスホレン−１−オキシド、３−メチル−２−ホスホレン−１−オキシド、１−エチル−２−ホスホレン−１−オキシドや、これらの３−ホスホレン異性体等のホスホレンオキシド等を使用することができる。
【００９０】
また多官能性カルボジイミド化合物は、水溶性、或いは水希釈性または水分散性であることが、重合体粒子［Ｘ］との相溶性の点から好ましい。
【００９１】
多官能性カルボジイミド化合物を自己乳化或いは水溶液の形態にするには、適当な乳化剤や分散安定剤を用いて水に分散させたり、或いは多官能性カルボジイミド化合物の分子構造内に親水性のセグメントを付加することにより行うことができる。
【００９２】
上記親水性セグメントとしては、ジアルキルアミノアルコールの四級アンミニウム塩（例えば２−ジメチルアミノエタノールの四級塩等）、ジアルキルアミノアルキルアミンの四級塩（例えば３−ジメチルアミノ−ｎ−プロピルアミンの四級塩等）、反応性ヒドロキシル基を少なくとも１個以上有するアルキルスルホン酸塩（例えばヒドロキシプロパンスルホン酸塩等）、アルコキシ基で末端封鎖されたポリエチレンオキサイドまたはポリエチレンオキサイドとポリプロピレンオキサイドとの混合物（例えばメトキシ基またはエトキシ基で末端封鎖されたポリエチレンオキサイド等）等が挙げられる。
【００９３】
多官能性カルボジイミド化合物としては、製品として、例えば、カルボジライトＶ−０１、Ｖ−０２、Ｖ−０３、Ｖ−０４、Ｖ−０５、Ｖ−０６［日清紡（株）製］、ＵＣＡＲＬＩＮＫ ＸＬ−２９ＳＥ、ＸＬ−２９ＭＰ［ユニオンカーバイド（株）製］を挙げることができる。
【００９４】
次に、架橋剤［Ｚ］として使用する多官能性オキサゾリン化合物は、２個以上のオキサゾリン基を含有する化合物である。かかる多官能性オキサゾリン化合物は、低分子量化合物であっても重合体であってもよいが、被膜の架橋密度を向上し、被膜の耐衝撃性等に優れる点から、重合体であることが好ましい。
【００９５】
上記多官能性オキサゾリン化合物の低分子量化合物としては、例えば、２，２’−ビス−（２−オキサゾリン）、２，２’−メチレン−ビス−（２−オキサゾリン）、２，２’−エチレン−ビス−（２−オキサゾリン）、２，２’−トリメチレン−ビス−（２−オキサゾリン）、２，２’−テトラメチレン−ビス−（２−オキサゾリン）、２，２’−ヘキサメチレン−ビス−（２−オキサゾリン）、２，２’−オクタメチレン−ビス−（２−オキサゾリン）、２，２’−エチレン−ビス−（４，４’−ジメチル−２−オキサゾリン）、２，２’−ｐ−フェニレン−ビス−（２−オキサゾリン）、２，２’−ｍ−フェニレン−ビス−（２−オキサゾリン）、２，２’−ｍ−フェニレン−ビス−（４，４’−ジメチル−２−オキサゾリン）、ビス−（２−オキサゾリニルシクロヘキサン）スルフィド、ビス−（２−オキサゾリニルノルボルナン）スルフィド等を挙げることができる。
【００９６】
また多官能性オキサゾリン化合物の重合体としては、下記一般式［１］（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄はそれぞれ独立に水素、ハロゲン原子、アルキル基、アラルキル基、アリール基または置換アリール基であり、Ｒ₅は付加重合性不飽和結合を有する非環状有機基である）で表される付加重合性オキサゾリンと、共重合可能な単量体を含むモノマー成分を重合したオキサゾリン基含有重合体が挙げられる。
【化３】

【００９７】
上記付加重合性オキサゾリンとして、具体的には、例えば、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−ビニル−５−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリン、２−イソプロペニル−５−メチル−２−オキサゾリン、２−イソプロペニル−５−エチル−２−オキサゾリン等を挙げることができる。これらのうち、２−イソプロペニル−２−オキサゾリンが、工業的に入手し易いため、好ましい。
【００９８】
付加重合性オキサゾリンの使用量は、特に制限を受けるものではないが、単量体成分中の５重量％以上含有することが好ましく、更に好ましくは、３０〜６０重量％の範囲である。
【００９９】
付加重合性オキサゾリンの使用量がかかる範囲であれば、得られる被膜に優れた耐衝撃性、耐水性などを付与することができる。
【０１００】
付加重合性オキサゾリンの使用量が５重量％未満では、重合体粒子［Ｘ］のカルボキシル基との架橋反応の程度が不十分となり、得られる被膜の耐衝撃性等が低下することがある。
【０１０１】
また６０重量％を越える場合には、多官能オキサゾリン化合物自体の親水性が強くなり、得られる被膜の耐水性が低下することがある。
【０１０２】
本発明に使用する付加重合性オキサゾリンと共重合可能な単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸メトキシポリエチレングリコール、（メタ）アクリル酸とポリエチレングリコールとのモノエステル化合物等の（メタ）アクリル酸エステル類；２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−ペンタフルオロプロピル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３，−テトラフルオロプロピル（メタ）アクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレート等のフッ素含有エチレン性不飽和単量体；（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−（２−ヒドロキシエチル）（メタ）アクリルアミド等の不飽和アミド類；酢酸ビニル、プロピオン酸ビニル、ビニルブチラート、バーサチック酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、ヘキシルビニルエーテル等のビニルエーテル類；（メタ）アクリロニトリル等のニトリル基含有エチレン性不飽和単量体；スチレン、α−メチルスチレン、ビニルトルエン、ビニルアニソール、α−ハロスチレン、ビニルナフタリン、ジビニルスチレン等の芳香族環を有するビニル化合物；イソプレン、クロロプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、Ｎ−ビニルピロリドン等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【０１０３】
また、多官能性オキサゾリン化合物は、水溶性、或いは水希釈性または水分散性であることが、重合体粒子［Ｘ］との相溶性の点から好ましい。
【０１０４】
多官能性オキサゾリン化合物の重合体は、上記単量体成分を、従来公知の溶液重合法や乳化重合法等の方法で製造することができる。
【０１０５】
多官能性オキサゾリン化合物の重合体としては、市販品として、例えばエポクロスＫ−１０１０Ｅ、Ｋ−１０２０Ｅ、Ｋ−１０３０Ｅ、Ｋ−２０１０Ｅ、Ｋ−２０２０Ｅ、Ｋ−２０３０Ｅ［(株)日本触媒製：エマルジョンタイプ］、エポクロスＷＳ−５００、ＷＳ−７００［(株)日本触媒製：水溶性タイプ］を挙げることができる。
【０１０６】
これらの多官能性オキサゾリン化合物の市販品のうち、水溶性のエポクロスＷＳ−５００、ＷＳ−７００が、前述の如く被膜の架橋密度を向上することができ、耐衝撃性に優れるため、好ましい。
【０１０７】
これらの架橋剤［Ｚ］の量は、特に制限されるものではないが、水性分散液の架橋性、架橋被膜の性能及び水性分散液の貯蔵安定性の面から、重合体粒子［Ｘ］中に含まれるカルボキシル基１モルに対して、通常、０．１〜２．０モルの範囲で使用することが好ましい。
【０１０８】
本発明の水性樹脂組成物は、それ自体、常温もしくは加熱乾燥により、耐衝撃性に優れ、柔軟性や屈曲性に優れ、且つ硬度に優れた被膜を形成するものであるが、本発明の奏する効果を損なわない範囲において、架橋剤［Ｚ］以外の架橋剤を使用することができる。かかる架橋剤としては、例えば、多官能性ポリアミン化合物、多官能ポリエチレンイミン化合物、金属塩化合物等が挙げられ、これらの１種または２種以上の混合物として使用することができる。
【０１０９】
本発明の水性樹脂組成物は、被膜形成時のブリスタの発生を防止するという点で、さらに無機充填剤［Ｗ］を併用するものである。
この無機充填剤［Ｗ］としては、特に限定されるものでないが、例えば炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、水酸化アルミニウム、タルク、珪藻土、マイカ、カオリン、酸化チタン、アルミナ、シリカ、ケイ酸カルシウム、カーボンブラック、アタパルジャイト、シラスバルーン、パーライト等が挙げられ、これらは単独又は２種以上を混合使用してもよい。
【０１１０】
本発明において、上記の無機充填剤［Ｗ］の含有量は、重合体粒子［Ｘ］１００重量部に対して５〜５０重量部の範囲であることが好ましい。無機充填剤［Ｗ］の含有量がかかる範囲であれば強度の優れた被膜が得られる。
【０１１１】
また、無機充填剤［Ｗ］の平均粒子径は、特に制限されるものではないが、好ましくは０．１〜１００μｍの範囲である。
【０１１２】
無機充填剤［Ｗ］の混和安定性及び貯蔵安定性を向上させる目的で分散安定剤を使用することができる。分散安定剤としては、例えば水溶性高分子物質を使用することができる。この水溶性高分子物質としては、例えば、ポリビニルアルコール、繊維素エーテル、澱粉、マレイン化ポリブタジエン、マレイン化アルキッド樹脂、ポリアクリル酸（塩）、ポリアクリルアミド、水溶性アクリル樹脂等の合成或いは天然の水溶性高分子物質が挙げられ、これらの１種又は２種以上の混合物を使用することができる。
【０１１３】
上記分散安定剤は、被膜の耐水性等の面からその使用量を極力少なくすることが好ましい。分散安定剤の使用量は、重合体粒子［Ｘ］１００重量部に対して２重量部以下とすることが好ましい。
【０１１４】
本発明の水性樹脂組成物は、さらに増粘剤［Ｖ］を含むことが好ましい。増粘剤［Ｖ］は、従来公知の増粘剤を用いることができる。従来公知の増粘剤としては、例えばカルボキシルメチルセルロース（ＣＭＣ）水溶液、ヒドロキシルエチルセルロース水溶液、デンプン、ポリビニルアルコール、親水性基含有合成樹脂エマルジョン等が挙げられるが、ブリスタの発生を防止する点で、親水性基含有合成樹脂エマルジョンが好ましく、この中でもカルボキシル基含有アクリル系共重合体エマルジョンであることが特に好ましい。
【０１１５】
カルボキシル基含有アクリル系共重合体エマルジョンを製造する方法としては、水性媒体中で単量体を乳化重合することにより上記重合体［Ａ］を製造する方法と同様の方法を用いることができる。
この場合、アンモニア水溶液や水酸化ナトリウム水溶液を添加したときのアルカリ増粘性の点で、単量体のうちカルボキシル基含有単量体を１５〜６０重量％用いるのが好ましい。
【０１１６】
本発明で使用するカルボキシル基含有アクリル系共重合体の分子量を調整する必要がある場合は、分子量調整剤として連鎖移動能を有する化合物を添加してもよい。
【０１１７】
また本発明で使用するカルボキシル基含有アクリル系共重合体エマルジョンのカルボキシル基は、必要に応じて塩基性物質等の中和剤で中和させることができる。
【０１１８】
本発明において、上記の増粘剤［Ｖ］の含有量は、特に制限されるものではないが、重合体粒子［Ｘ］１００重量部に対して５重量部以下の範囲であることが好ましい。増粘剤［Ｖ］の含有量がかかる範囲であれば水性樹脂組成物の粘度の経時安定性に優れる。
【０１１９】
本発明の水性樹脂組成物により形成された被膜の測定温度２５℃での引張試験でのヤング率は、特に制限されないが、被覆された繊維の保護に優れる点で５０ＭＰａ以上であることが好ましい。
【０１２０】
本発明の水性樹脂組成物により形成された被膜の測定温度２５℃での引張試験での破断点伸度は、特に制限されないが、塗膜の屈曲性に優れる点で、２００％以上であることが好ましい。
【０１２１】
この測定温度２５℃での引張試験でのヤング率及び破断点伸度は、後記実施例で得られる試験片を、引張試験機を用いて、温度２５℃でクロスヘッドスピード２００ｍｍ／分の条件で軸方向に引っ張ったときの軸方向の伸びを測定した数値に基づくものである。
【０１２２】
本発明の水性樹脂組成物には、更に必要に応じて、水溶性或いは水分散性の熱硬化性樹脂、例えばフェノール樹脂、尿素樹脂、メラミン樹脂、或いは熱可塑性樹脂、例えばポリウレタン樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリエチレン樹脂等を混和して使用することもできる。
【０１２３】
更に、必要に応じて、本発明の所望の効果を阻害しない範囲で、顔料、ｐＨ調整剤、被膜形成助剤、レベリング剤、撥水剤、消泡剤、酸化防止剤、耐光安定剤等公知のものを適宜添加して使用することができる。
【０１２４】
本発明の水性樹脂組成物は、優れた低温特性を有し、且つ、常温での硬度に優れ、耐水性の良好な被膜を与えるものであり、その用途は多岐にわたる。特に、耐衝撃性と柔軟性や屈曲性を有し、且つ硬度の要求される分野において有用なものであり、例えば塗料、プライマー処理剤、接着剤、フィルムコーティング剤、繊維加工用樹脂（織編物や不織布用バインダー・被覆剤、植毛加工用バインダー等）、紙加工（含浸、塗工）用樹脂、ガラス繊維加工用樹脂（ガラス繊維集束剤、ガラスペーパー用バインダー、ガラス繊維被覆剤等）、モルタル改質用樹脂等として利用できる。特に、塗料、インキ、ニス、フィルムコーティング、接着、繊維加工用樹脂、紙加工用樹脂等の応用分野で利用される場合、既述の通り極めて優れた効果を発現する。
【０１２５】
尚、本発明の態様は、上述したように、分子中にカルボキシル基を有する重合体粒子［Ｘ］と感熱ゲル化剤［Ｙ］とカルボキシル基と反応性を有する架橋剤［Ｚ］と無機充填剤［Ｗ］が水性媒体中に分散してなる水性樹脂組成物であって、該分子中にカルボキシル基を有する重合体粒子［Ｘ］として、分子中にカルボキシル基を有する合成ゴムラテックス（ｘ１）、該合成ゴムラテックス及び分子中にカルボキシル基を有するアクリル酸エステル共重合体エマルジョン（ｘ２）、又は分子中にカルボキシル基を有するポリウレタン樹脂エマルジョン及び該アクリル酸エステル共重合体エマルジョン（ｘ３）のいずれか１種を用いることを特徴とする水性樹脂組成物にかかるものである。
【０１２６】
本発明の他の態様の一つとしては、前記水性樹脂組成物により形成される被膜の測定温度２５℃での破断点伸度が２００％以上である水性樹脂組成物にかかるものである。
【０１２７】
本発明の他の態様の一つとして、前記水性樹脂組成物により形成される被膜の測定温度２５℃での引張試験におけるヤング率が５０ＭＰａ以上である水性樹脂組成物にかかるものである。
【０１２８】
本発明の他の態様の一つとして、前記感熱ゲル化剤［Ｙ］が、ポリエーテル変性シリコーンである水性樹脂組成物にかかるものである。
【０１２９】
また本発明の他の態様の一つとして、前記ポリエーテル変性シリコーンの１重量％水溶液の曇点が３０〜５５℃である水性樹脂組成物にかかるものである。
さらに本発明の他の態様の一つとして、前記カルボキシル基と反応性を有する架橋剤［Ｚ］が、多官能性グリシジル化合物、多官能性カルボジイミド化合物及び多官能性オキサゾリン化合物からなる群から選ばれる１種以上の架橋剤である水性樹脂組成物にかかるものである。
【０１３０】
本発明の他の態様の一つとして、さらに増粘剤［Ｖ］を含有する水性樹脂組成物にかかるものである。
また本発明の他の態様の一つとして、前記水性樹脂組成物中の固形分が５０重量％以上である水性樹脂組成物にかかるものである。
【０１３１】
【実施例】
以下、本発明を実施例及び比較例により、一層、具体的に説明するが、本発明の範囲はこれら実施例に限定されるものではない。以下において、特に断らない限り、「％」は重量％、「部」は重量部をそれぞれ示すものとする。
【０１３２】
まず本発明で用いた測定方法及び評価方法について以下に述べる。
【０１３３】
［平均粒子径の測定方法］
平均粒子径は、動的光散乱法により、日機装(株)製マイクロトラックＵＰＡ型粒度分布測定装置にて測定した平均粒子径（５０％メジアン径）の値を求めた。
【０１３４】
［測定温度２５℃での引張試験でのヤング率の測定方法］
実施例で得られた本発明の水性樹脂組成物を乾燥後の膜厚が０．５ｍｍとなるようにガラス板に塗工し、４０℃で８時間乾燥した後、ガラス板から剥離し、更に１４０℃で５分間乾燥したものを２号ダンベルで打ち抜き、これを試料とした。この試料を用いて、オリエンテック社製テンシロンＲＴＭ−１００型引張試験機にて、２５℃の雰囲気下で、クロスヘッドスピード２００ｍｍ／分で引張試験を実施した時の０〜２．５％のひずみΔεと応力Δσから次式を用いて表した値をヤング率Ｅとした。
【０１３５】
【式１】
Ｅ＝Δσ／Δε
【０１３６】
［測定温度２５℃での引張試験での破断点伸度及び破断点強度の測定方法］
実施例で得られた本発明の水性樹脂組成物を乾燥後の膜厚が０．５ｍｍとなるようにガラス板に塗工し、４０℃で８時間乾燥した後、ガラス板から剥離し、更に１４０℃で５分間乾燥したものを２号ダンベルで打ち抜き、これを試料とした。この試料を用いて、オリエンテック社製テンシロンＲＴＭ−１００型引張試験機にて、２５℃の雰囲気下で、クロスヘッドスピード２００ｍｍ／分で引張試験を実施した時の破断点伸度を測定した。
【０１３７】
［曇点の測定方法］
実施例で使用した感熱ゲル化剤の１重量％水溶液を室温より徐々に攪拌しながら加熱し、目視観察で該水溶液が濁った時点の温度を曇点とした。
【０１３８】
［ブリスタ（被膜のふくれ）の評価方法］
実施例で得られた本発明の水性樹脂組成物を内径１４ｍｍ、高さ３０ｍｍ、厚さ１ｍｍのガラス製容器に充填剤未添加品の場合は０．７ｇ、充填剤添加品の場合は１．５ｇ入れ、９０℃に設定したタバイ社製熱風乾燥機に６分間入れた後、すぐに１５０℃に設定したタバイ社製熱風乾燥機に３分間入れてブリスタの有無を目視で観察し、以下の基準に従い判定した。
○：変化無し
△：少し膨らむ
×：ブリスタ発生もしくは破裂
【０１３９】
［耐衝撃性の測定方法］
実施例で得られた本発明の水性樹脂組成物を乾燥後の膜厚が０．７ｍｍとなるようにガラス板に塗工し、４０℃で８時間乾燥した後、ガラス板から剥離し、更に１４０℃で５分間乾燥したものを３０ｍｍ×３０ｍｍに切り出したものを試料とし、２５℃の雰囲気下で、ＪＩＳ Ｋ−５４００に準じたデュポン式衝撃変形試験器を用いて測定した。
【０１４０】
操作は半径６．３５±０．０３ｍｍの撃ち型と受け台とを取り付け、被膜をその間に挟み、質量５００ｇ±１ｇのおもりを試料から１００ｍｍの高さから撃ち型の上に落とした後、被膜に余分の損傷を与えないように注意しながら試験片を取り出し、目視によって被膜の損傷を調べた。
試験数を１０枚とし、評価結果は、以下の基準にしたがって判定した。
×：６０％以上の破損もしくは亀裂が発生
△：２０以上６０％未満の破損もしくは亀裂が発生
○：２０％未満の破損もしくは亀裂が発生
【０１４１】
《合成例１》（増粘剤［Ｖ］の合成）
撹拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に脱イオン水６９０部とノイゲンＥＴ−１７０［第一工業製薬(株)製］２４部を入れ、窒素を吹き込みながら７５℃まで昇温した。撹拌下、１０％過硫酸アンモニウム水溶液１０部とエチルアクリレート２０３部、メタクリル酸８７部からなる単量体混合物に、脱イオン水１００部とノイゲンＥＴ−１７０［第一工業製薬(株)製］３部を加えて乳化させたモノマープレエマルジョン（前記単量体混合物と乳化剤と水でモノマーを乳化状態にしたものを云う）をそれぞれ滴下漏斗を使用して、反応容器内温度を７５℃に保ちながら１２０分間かけて滴下して重合せしめた。
【０１４２】
《合成例２》（アクリル酸エステル共重合体エマルジョンの合成）
撹拌装置を備えた重合容器にイオン交換水２１０部を仕込み、窒素ガスを送入しつつ攪拌しながら反応容器内を８０℃に昇温した。昇温後、下記の▲１▼モノマー乳化液の内４部を反応容器に添加し、その後過硫酸アンモニウム０．６部を添加し重合を開始した。反応容器内温度８０℃で１時間保持した後、残りのモノマー乳化液７２６部と下記の▲２▼重合開始剤水溶液をそれぞれ反応容器内に同時に滴下し重合を行った。滴下時間はモノマー乳化液が４時間、重合開始剤水溶液が４．５時間であり、反応容器内温度を８０℃に保持しながら重合を完結させた。重合終了後、アンモニア水でｐＨを調整し、固形分６０％、ｐＨ８．０、平均粒子径３５０ｎｍのアクリル酸エステル共重合体エマルジョンを得た。
▲１▼モノマー乳化液の組成
ｎ−ブチルアクリレート ３５０部
メチルメタクリレート ２２５部
メタクリル酸 １５部
ニューコール７０７ＳＦ（花王(株)製） ４０部
イオン交換水 １００部
▲２▼重合開始剤水溶液の組成
過硫酸アンモニウム １．５部
イオン交換水 ７５部
【０１４３】
《合成例３》（合成ゴムラテックスの合成）
撹拌装置を備えた耐圧重合容器に、水１２０部、水酸化ナトリウム０．１部、反応性乳化剤Ｓ−１８０〔花王(株)製不飽和アルキル硫酸塩〕１．２部、エチレンジアミン四酢酸０．１部、ブタジエン３０部、メタクリル酸メチル６８部、アクリル酸２部およびｔ−ドデシルメルカプタン０．１部を仕込み、撹拌を開始し、反応温度を６０℃に昇温し、重合容器内温度が６０℃に達したとき、過硫酸アンモニウム０．１部を添加して反応を開始させた。７時間後、重合率が９８％に達したとき冷却を行なって合成樹脂ラテックスを得た。得られた合成樹脂ラテックスは、重合率９８．６％であった。次いで、２５％アンモニア水でｐＨを９．０に調整し、その後水蒸気蒸留によって固形分５０．１％の合成ゴムラテックスを得た。
【０１４４】
《合成例４》（ポリウレタン樹脂エマルジョンの合成）
ポリテトラメチレンエーテルグリコール（分子量２,０００）５００部、２,２−ジメチロ−ルプロピオン酸３６部、ネオペンチルグリコール１８部、イソホロンジイソシアネ−ト２０６部、８０％水加ヒドラジン１３部、トリエチルアミン２７部を反応させることにより、不揮発分（％）＝３５、酸価＝２０、粒子径＝５０ｎｍ、流動開始温度＝１００℃のポリウレタン樹脂エマルジョンを得た。
【０１４５】
《実施例１》（本発明の水性樹脂組成物の製造）
前述の合成例２で得られたアクリル酸エステル共重合体エマルジョン２００部と合成例３で得られた合成ゴムラテックス２００部に、感熱ゲル化剤としてＦＺ−２１６４［オルガノポリシロキサンポリオキシアルキレングリコール：有効成分１００重量％：日本ユニカー（株）製］１０部を添加し、無機充填剤としてＮＳ−２００［炭酸カルシウム：日東紛化（株）製］１００部を添加し、増粘剤として合成例１で得られた１０部を添加し、架橋剤としてエポクロスＷＳ−５００［オキサゾリン基含有水溶性架橋剤：有効成分４０重量％：（株）日本触媒製］２０部を添加して、固形分濃度が５５．０％になるように脱イオン水で調整した後、１００メッシュ金網で濾過し、本発明の水性樹脂組成物を得た。
【０１４６】
この本発明の水性樹脂組成物を用いて得た被膜の評価結果を第１表に示したが、測定温度２５℃での引張試験での破断点伸度は２６５％であり、測定温度２５℃での引張試験での破断点応力は１１ＭＰａであり、ヤング率は１２７ＭＰａであった。また、この水性樹脂組成物から得られた被膜の耐衝撃性は良好であった。
【０１４７】
《実施例２〜３》単量体混合物及び感熱ゲル化剤、架橋剤、増粘剤として第１表に示したものを用いた以外は、実施例１と全く同様にして本発明の水性樹脂組成物を得た。この固形分濃度は第１表に記載した通りであった。また、この水性樹脂組成物から得られた被膜の測定温度２５℃での引張試験でのヤング率と破断点伸度と破断点応力、耐衝撃性、ブリスタは第１表に記載した通りであった。
【０１４８】
《比較例１〜３》
単量体混合物として第２表に示したものを用いた以外は、実施例１と全く同様にして水性樹脂組成物を得た。この水性樹脂組成物の粒子径、固形分濃度は第２表に記載した通りであった。また、この水性樹脂組成物から得られた被膜の測定温度２５℃での引張試験でのヤング率と破断点伸度と破断点応力、耐衝撃性、ブリスタは第２表に記載した通りであった。
【０１４９】
【表１】

【０１５０】
【表２】

【０１５１】
第１表及び第２表中の略号の正式名称を下記に示す。
ＦＺ−２１６４；
日本ユニカー（株）製：シリコーン型感熱ゲル化剤 有効成分１００％
ＦＺ−２１０１；
日本ユニカー（株）製：シリコーン型感熱ゲル化剤 有効成分１００％
エポクロス ＷＳ−５００；
（株）日本触媒製：オキサゾリン基含有架橋剤 有効成分４０％
ＵＣＡＲＬＩＮＫ ＸＬ−２９ＳＥ；
ユニオンカーバイド（株）製：カルボジイミド基含有架橋剤 有効成分５０％
ＮＳ−２００；
日東紛化工業（株）製：炭酸カルシウム 有効成分１００％
ハイジライトＨ−３１；
昭和電工（株）製：水酸化アルミニウム 有効成分１００％
【０１５２】
第１表及び第２表中の部数は固形分とする。
【０１５３】
【発明の効果】
本発明の水性樹脂組成物は、被覆剤（表面コーティング剤）として使用した場合に、耐衝撃性に優れ、柔軟性や屈曲性を有し、且つ、硬度の高い被膜を形成する。特に、低温特性と常温での高硬度の要求される分野において有用なものであり、塗料、インキ、ニス、フィルムコーティング、接着、繊維加工用樹脂、紙加工用樹脂等の分野で、極めて優れた効果を発揮する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous resin composition in which polymer particles having a carboxyl group in a molecule, a heat-sensitive gelling agent, and a crosslinking agent having reactivity with a carboxyl group are dispersed in an aqueous medium. And an aqueous resin composition useful as a coating agent for forming a film having flexibility and flexibility.
[0002]
[Prior art]
Conventionally, aqueous resin compositions obtained by polymerizing various ethylenically unsaturated monomers are used as emulsion binders in a wide range of applications such as paints, adhesives, and fiber processing.
The polymer emulsions used as these emulsion binders usually exist as polymer particles, and are formed into a film through a film forming process by fusion between the polymer particles at the time of film formation. For this reason, when trying to obtain a relatively hard coating, the polymer particles themselves are hard, so the fusion between the polymer particles at the time of coating formation is not sufficient, and only the hard and brittle coating is formed In addition, in applications that require flexibility, particularly in applications that require flexibility, there is a disadvantage that the coating is cracked and cannot be used.
[0003]
On the other hand, when the polymer particles are made soft and the fusion between the polymer particles is facilitated, the hardness of the resulting coating becomes insufficient, which is a problem in use.
[0004]
In order to improve these disadvantages, (1) a plasticizer for plasticizing the polymer (hereinafter referred to as “film-forming aid”) is added to the hard polymer particles, so that the fusion between the polymer particles can be improved. And (2) improving the fusion between polymer particles by making the particle shape of the polymer particles “multi-layer structure particles” composed of a hard polymer and a soft polymer. The method of making it etc. is proposed.
[0005]
However, in the method (1), the fusion property between the polymer particles is improved, but the polymer itself is plasticized immediately after the coating, so that it is difficult to express the hardness. In particular, since the plasticizer flows out, the hardness of the coating changes over time.
[0006]
In the case of method {circle around (2)}, for example, JP-A-7-70215 discloses a multistage polymerization latex having water whitening resistance, film formation characteristics, and properties suitable for applications requiring flexibility. However, the impact resistance and hardness of the coating are still insufficient, which is a practical problem.
On the other hand, a method for improving impact resistance by adding a crosslinking agent to an aqueous resin composition to crosslink between polymer particles is disclosed in, for example, JP-A-11-256006. The impact resistance, flexibility, and flexibility of the film obtained in (1) are still insufficient.
[0007]
JP-A-10-110135 discloses an overprint varnish composition crosslinked with a resin obtained from a starting material containing a carboxyl group-containing resin having a core / shell structure (that is, a multilayer structure) and an addition-polymerizable oxazoline. Although disclosed, the impact resistance of the coating is insufficient, and a coating excellent in flexibility and flexibility cannot be obtained.
[0008]
These emulsions are used in various coating and impregnation processes, but blisters (film blisters) are generally generated during film formation, particularly in coating applications that form a thick film such as carpet backing. It has the disadvantage of degrading the quality and physical properties of processed products.
[0009]
In general, the blister is generated when the water-based coating agent is dried with hot air, and the vicinity of the surface that is in direct contact with the hot air proceeds first. It is considered that the water is evaporated later and the surface film is expanded from the inside.
[0010]
It is known that it is likely to occur particularly when the film thickness is thick, when the drying temperature is high, or when the airflow is strong. As a method for suppressing the blister, a method of adding a filler to JP-B-5-6593 and a method of adding a silicone oil-based heat-sensitive gelling agent have been proposed in JP-B-6-4935. In the former method of adding a filler, a large amount of filler is required to suppress blistering, and there is a drawback that the film forming property of the coating is lowered and various physical properties such as coating strength are deteriorated. Further, the latter method of adding a silicone oil-based heat-sensitive gelling agent is still insufficient to suppress the generation of blisters.
[0011]
For the above reasons, development of an aqueous resin composition for coatings that can obtain a film having impact resistance, flexibility, flexibility and excellent hardness without generating blisters is eagerly desired. It was.
[0012]
[Problems to be solved by the invention]
Therefore, the object of the present invention is to provide a film with excellent impact resistance, flexibility and flexibility, and excellent hardness, especially when used as a coating agent (ie, surface coating agent). An object of the present invention is to provide an aqueous resin composition that can be formed without being generated.
[0013]
[Means for Solving the Problems]
The inventors have prepared an aqueous resin composition in which specific polymer particles containing a carboxyl group, an inorganic filler, a heat-sensitive gelling agent, and a crosslinking agent having reactivity with a carboxyl group are dispersed in an aqueous medium. By using it, it discovered that the said subject could be solved and came to complete this invention.
[0014]
That is, the present invention provides a polymer particle [X] having a carboxyl group in the molecule and a heat-sensitive gelling agent [Y].With polyether modified silicone asAn aqueous resin composition in which a crosslinking agent [Z] having reactivity with a carboxyl group and an inorganic filler [W] are dispersed in an aqueous medium, and the polymer particles [X] having a carboxyl group in the molecule AsHas a carboxyl group in the moleculeAny one of a synthetic rubber latex and an acrylate copolymer emulsion (x2) having a carboxyl group in the molecule, or a polyurethane resin emulsion having a carboxyl group in the molecule and the acrylate copolymer emulsion (x3) An aqueous resin composition characterized by usingBecause
The (x2) is a weight ratio of the synthetic rubber latex and the acrylate copolymer emulsion of 30:70 to 95: 5, and the (x3) is the polyurethane resin emulsion and the acrylic acid copolymer. The weight ratio with the combined emulsion is 30:70 to 95: 5,
The content of the heat-sensitive gelling agent [Y] is 0.05 to 30 parts by weight with respect to 100 parts by weight of the polymer particles [X], and the content of the crosslinking agent [Z] is the polymer particles [ X] is 0.1 to 2.0 mol with respect to 1 mol of the carboxyl group, and the content of the inorganic filler [W] is 5 to 50 parts by weight with respect to 100 parts by weight of the polymer particles. An aqueous resin compositionIs to provide.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in further detail below.
[0016]
First, the polymer particles [X] having a carboxyl group in the molecule used in the present invention will be described. The polymer particle [X] having a carboxyl group (hereinafter referred to as polymer particle [X]) has a carboxyl group in the molecule.,Either a synthetic rubber latex and an acrylate copolymer emulsion (x2), or a polyurethane resin emulsion and an acrylate copolymer emulsion (x3).
[0017]
Synthetic rubber latex (x1) [hereinafter referred to as synthetic rubber latex (x1)] having a carboxyl group in the molecule constituting the aqueous resin composition of the present invention includes, for example, an aliphatic conjugated diene monomer (a), (Meth) acrylic acid alkyl ester monomer (b) having 1 to 10 carbon atoms in the alkyl group, carboxyl group-containing vinyl monomer (c), and other copolymerizable if necessary It can be obtained by emulsion polymerization of the vinyl monomer (d). The weight ratio of these monomers is such that the monomer (a) / monomer (b) / monomer (c) is 5-50 / 30-80 / in terms of the hardness of the resulting resin film. It is preferable that it is 1-10.
[0018]
Examples of the aliphatic conjugated diene monomer (a) used here include 1,2-butadiene, 1,3-butadiene, isoprene, chloroprene and the like.
[0019]
Examples of the (meth) acrylic acid alkyl ester monomer (b) having 1 to 10 carbon atoms in the alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic. Propyl acid, butyl (meth) allylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, octadecyl (meth) acrylate, etc., among others, the number of carbon atoms of the alkyl group 1 to 4 (meth) acrylic acid alkyl ester monomers are preferred, and methyl methacrylate is particularly preferred from the viewpoint of obtaining a high Young's modulus.
[0020]
Furthermore, examples of the carboxyl group-containing vinyl monomer (c) include (meth) acrylic acid, crotonic acid, maleic acid and anhydrides thereof, fumaric acid, itaconic acid, unsaturated dicarboxylic acid monoalkyl esters (for example, maleic acid). Acid monomethyl, monoethyl fumarate, mononormal butyl itaconate) and the like.
[0021]
Furthermore, examples of other copolymerizable vinyl monomers (d) include methyl (meth) acrylate, ethyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, 2, Ethylenically unsaturated aromatic monomers such as 4-dibromostyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; vinylidene halides such as vinylidene chloride and vinylidene bromide; ) Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as acrylic acid-2-hydroxyethyleryl and (meth) acrylic acid-2-hydroxypropyl; Glycidyl esters of ethylenically unsaturated carboxylic acids such as glycidyl (meth) acrylate ; (Meth) acrylamide, N-methylol (meth) a Riruamido, butoxymethyl (meth) acrylamide, diacetone acryl bromide and the like.
[0022]
The synthetic rubber latex (x1) constituting the aqueous resin composition of the present invention can be obtained by emulsion polymerization of the above monomers in an aqueous medium in the presence of an emulsifier, a free radical generating catalyst and the like. In this case, a two-stage polymerization method can also be employed.
As an emulsifier, various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used.
[0023]
Examples of the anionic surfactant include sulfates of higher alcohols, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, etc., and examples of nonionic surfactants include polyoxyethylene alkyls. Examples include ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, and the like. Examples of the cationic surfactant include alkyl ammonium chloride (Arcard 12-50 manufactured by Lion Corporation). Furthermore, examples of amphoteric surfactants include polyethylene alkyl sulfates and polyoxyethylene alkylphenyl sulfates, and one or a mixture of two or more thereof can be used.
[0024]
As a free radical generating catalyst, for example, potassium persulfate (K₂S₂O₈), Ammonium persulfate [(NH_Four)₂S₂O₈], Aqueous catalysts such as hydrogen peroxide, and oily catalysts such as tert-butyl hydroxide and cumene hydroperoxide.
[0025]
In addition, other additives can be usually used in the polymerization. Examples of such additives include chain transfer agents, ethylenediaminetetraacetic acid, alkaline substances for pH adjustment, and the like.
[0026]
The synthetic rubber latex (x1) constituting the aqueous resin composition of the present invention is concentrated to the required solid content by a method such as stripping, for example, to reduce the odor of the unreacted monomer. It is preferable to use it.
[0027]
The synthetic rubber latex and the acrylate copolymer emulsion (x2) constituting the aqueous resin composition of the present invention can be obtained by mixing the synthetic rubber latex and the acrylate copolymer emulsion.
Examples of the mixing method include mechanical stirring using a homomixer and mixing using a static mixer.
[0028]
The ratio of the synthetic rubber latex to the acrylate copolymer emulsion is synthetic rubber latex: acrylate copolymer emulsion = 30: 70 to 95: 5 in terms of impact resistance, flexibility and flexibility. Is preferred.
As the synthetic rubber latex, the above synthetic rubber latex (x1) can be used as it is.
[0029]
An acrylic ester copolymer emulsion having a carboxyl group in the molecule [hereinafter referred to as an acrylic ester copolymer emulsion] is a (meth) acrylic compound in the presence of a polymerization initiator, and if necessary, an emulsifier and a dispersion stabilizer. It is obtained by using acid ester and (meth) acrylic acid as essential polymerizable monomer components and further copolymerizing a mixture of other polymerizable monomers copolymerizable with these monomers as necessary. be able to.
As a polymerization method, for example, (1) a method in which water, a polymerizable monomer, a polymerization initiator, and the like are mixed together for polymerization, and (2) a mixture in which water, a polymerizable monomer, and an emulsifier are previously mixed are dropped. And so-called pre-emulsion method and (3) monomer dropping method.
[0030]
Examples of (meth) acrylic acid and (meth) acrylic acid ester used for the production of an acrylic ester copolymer emulsion include acrylic acid, methacrylic acid, β-carboxyethyl (meth) acrylate, and 2- (meth) acryloylpropion. Acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) hydroxy Ethyl hydrogen phthalate and salts thereof, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) Acry Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylates such as (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl Fluorine-containing ethylenic unsaturation such as (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate single Glycidyl group-containing polymerizable monomers such as glycidyl (meth) acrylate and allyl glycidyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono Hydroxyl group-containing polymerizable monomers such as (meth) acrylate; amino group-containing polymerizability such as aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, and N, N-dialkylaminoalkyl (meth) acrylate Monomers; 2-aziridinylethyl (meth) acrylate-containing polymerizable monomers; aziridinyl group-containing polymerizable monomers; allyl (meth) acrylate-containing polymerizable monomers; dicyclopentenyl (meth) acrylate, etc. Cyclopentenyl group-containing polymerizable monomer Body: ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol Examples include di (meth) acrylate, diallyl phthalate, divinylbenzene, allyl (meth) acrylate, and the like.
[0031]
Furthermore, as other polymerizable monomers, for example, N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, etc. A methylolamide group or an alkoxylated product-containing polymerizable monomer; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ -(Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, -Β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and silyl group-containing polymerizable monomers such as hydrochloride thereof; (meth) acryloyl isocyanate, phenol of (meth) acryloyl isocyanate ethyl Alternatively, an isocyanate group and / or a blocked isocyanate group-containing polymerizable monomer such as methyl ethyl ketoxime adduct; an oxazoline group-containing polymerizable monomer such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline Amide group-containing polymerizable monomers such as (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; carbonyl group-containing polymerizable such as acrolein and diacetone (meth) acrylamide Monomer; acetoacetoxyethyl (meth) Ethylene containing acetoacetyl group-containing polymerizable monomer such as acrylate, sulfonic acid group and / or sulfate group (and / or salt thereof), phosphoric acid group and / or phosphate ester group (and / or salt thereof) Unsaturated monomers, vinyl sulfonic acids such as vinyl sulfonic acid and styrene sulfonic acid or salts thereof, allyl group-containing sulfonic acids such as allyl sulfonic acid and 2-methylallyl sulfonic acid or salts thereof, (meth) acrylic acid 2 -(Meth) acryloyl group-containing sulfonic acids such as sulfoethyl, 2-sulfopropyl (meth) acrylate or salts thereof, (meth) acrylamide group-containing sulfonic acids such as (meth) acrylamide-t-butylsulfonic acid or salts thereof, "Adekaria soap PP-70, PPE-710" having a phosphate group [Asahi Denka Kogyo Co., Ltd.]; , Vinyl esters such as vinyl propionate, vinyl butyrate, vinyl versatate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether; nitrile groups such as (meth) acrylonitrile Ethylenically unsaturated monomers: vinyl compounds having an aromatic ring such as styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene, divinylstyrene; isoprene, chloroprene, butadiene, ethylene, tetrafluoro Examples include monomers capable of radical polymerization such as ethylene, vinylidene fluoride, and N-vinylpyrrolidone. These 1 type, or 2 or more types of mixtures can be used.
[0032]
The above-mentioned emulsifiers can be used as they are as the emulsifiers used in the production of the acrylate copolymer emulsion.
[0033]
Furthermore, if necessary, an emulsifier having a polymerizable unsaturated group in the molecule generally called “reactive emulsifier” may be used. As such a reactive emulsifier, for example, “Latemul S-180” (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, “Eleminol JS-2, RS-30” [Sanyo Chemical Industries, Ltd. [Aqualon HS-10, HS-20] [Daiichi Kogyo Seiyaku Co., Ltd.], “Adekaria Soap SE-10, SE-20” [Asahi Denka Kogyo Co., Ltd.] "New Frontier A-229E" having a phosphate group [Daiichi Kogyo Seiyaku Co., Ltd.], etc .; "Aqualon RN-10, RN-20, RN-30 having nonionic hydrophilic groups" , RN-50 ”[Daiichi Kogyo Seiyaku Co., Ltd.] and the like, and one or a mixture of two or more thereof can be used.
[0034]
Other dispersion stabilizers other than emulsifiers that can be used in the production of acrylate copolymer emulsions include, for example, polyvinyl alcohol, fiber ether, starch, maleated polybutadiene, maleated alkyd resin, and polyacrylic acid. (Salt), polyacrylamide, water-based acrylic resin, water-based polyester resin, water-based polyamide resin, water-based polyurethane resin, and the like include synthetic or natural water-soluble polymer substances, and one or a mixture of two or more of these is used. be able to.
[0035]
Further, the aqueous medium for producing the acrylic ester copolymer emulsion is not particularly limited, but only water may be used, or a mixed solvent of water and a water-soluble solvent is used. May be. Examples of the water-soluble solvent used here include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone. A mixture of two or more can be used.
[0036]
Moreover, a radical polymerization initiator is used as a polymerization initiator used when manufacturing the acrylic ester copolymer emulsion constituting the aqueous resin composition of the present invention. Examples of such radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, and t-butylcumylper Dialkyl peroxides such as oxide and dicumyl peroxide, peroxyesters such as t-butyl peroxylaurate and t-butyl peroxybenzoate, cumene hydroperoxide, paramentane hydroperoxide, t-butyl hydroper Examples thereof include organic peroxides such as hydroperoxides such as oxide, hydrogen peroxide, and the like.
[0037]
Moreover, the redox polymerization initiator which used the said peroxide and the reducing agent together can also be used. Examples of the reducing agent include ascorbic acid and its salt, erythorbic acid and its salt, tartaric acid and its salt, citric acid and its salt, metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite, ferric chloride, etc. Is mentioned. It is also possible to use an azo initiator such as 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride. One or a mixture of two or more of the above polymerization initiators can be used.
[0038]
Moreover, when it is necessary to adjust the molecular weight of the polymer of the acrylate copolymer emulsion constituting the aqueous resin composition of the present invention, a compound having chain transfer ability may be added as a molecular weight modifier. Examples of such molecular weight regulators include mercaptans such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, thioglycerin, or α-methylstyrene dimer. Is mentioned.
[0039]
Moreover, in order to neutralize the carboxyl group of the acrylate copolymer emulsion constituting the aqueous resin composition of the present invention, a neutralizing agent can be used. A basic substance can be used as such a neutralizing agent, for example, alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia; monomethylamine and dimethyl Examples include water-soluble organic amines such as amine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine. As the basic substance, one or a mixture of two or more of the above compounds can be used. Among these, in particular, in order to further improve the water resistance of the resulting coating, it is preferable to use ammonia that is easily scattered by normal temperature or heating.
[0040]
In addition, the polymerization temperature at the time of producing the acrylate copolymer emulsion varies depending on the type of monomer used, the type of polymerization initiator, etc., but when polymerizing in an aqueous medium, it is usually 30 to 90 ° C. It is preferable to carry out within a range.
[0041]
The average particle diameter (50% median diameter) of the copolymer of the acrylate copolymer emulsion is preferably 250 to 1500 nm because it has excellent drying properties during film formation.
[0042]
In addition, a water-soluble or water-dispersible thermosetting resin such as a phenol resin, a urea resin, a melamine resin, a polyester resin, a polyamide resin, or the like can be mixed with the acrylic ester copolymer emulsion.
[0043]
Furthermore, if necessary, known substances such as pigments, pH adjusters, film forming aids, leveling agents, thickeners, water repellents, antifoaming agents, etc., are appropriately used within the range not impairing the desired effects of the present invention. It can be used by adding.
[0044]
The polyurethane resin emulsion having a carboxyl group in the molecule constituting the aqueous resin composition of the present invention [hereinafter referred to as polyurethane resin emulsion] and the acrylate copolymer emulsion (x3) are a polyurethane resin emulsion and an acrylate copolymer. It can be obtained by mixing with an emulsion.
[0045]
The ratio of the polyurethane resin emulsion to the acrylate copolymer emulsion is polyurethane resin emulsion: acrylate copolymer emulsion = 30: 70 to 95: 5 in terms of impact resistance, flexibility and flexibility. Is preferred.
As the acrylate copolymer emulsion, the above acrylate copolymer emulsion can be used as it is.
As a method for producing a polyurethane resin emulsion, any of the conventionally well-known methods may be used. That is, for example, the following methods may be mentioned.
[0046]
1) An organic solvent solution or an organic solvent dispersion of a hydrophilic group-containing polyurethane resin obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with a polyisocyanate contains a neutralizer as necessary. A method of obtaining an emulsion by mixing aqueous solutions. 2) A hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with a polyisocyanate is mixed with an aqueous solution containing a neutralizing agent, or in advance A method in which a neutralizing agent is added to a prepolymer, water is mixed and dispersed in water, and then reacted with a polyamine to obtain an emulsion.
3) A hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with a polyisocyanate is mixed with an aqueous solution containing a neutralizing agent and a polyamine, Alternatively, a method in which a neutralizing agent is previously added to a prepolymer and then mixed with an aqueous solution containing a polyamine to obtain an emulsion.
[0047]
In addition to the above method, there is a method in which a polyurethane resin having no hydrophilic group is forcibly dispersed in an aqueous medium with an external emulsifier, but what is obtained by such a method is not so preferable.
[0048]
Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2 , 2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4 ' -Biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate Trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane Examples include diisocyanate and 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate.
[0049]
Other active hydrogen-containing compounds that can react with isocyanate groups are divided into high molecular weight compounds having an average molecular weight of 300 to 10,000, preferably 500 to 5,000, and low molecular weight compounds having a molecular weight of 300 or less for convenience.
[0050]
Examples of the high molecular weight compound include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, polythioether polyols, polybutadiene-based polyolefin polyols, and the like.
[0051]
Examples of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexane Glycol components such as dimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, succinic acid, adipic acid, azelaic acid, seba Acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, and anhydrides or ester-forming derivatives of these dicarboxylic acids In addition to polyesters obtained by dehydration condensation reaction from acid components such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydryloxycarboxylic acids, ε-caprolactone, etc. Polyester obtained by ring-opening polymerization reaction of cyclic ester compound Examples include stealth and copolyesters thereof.
[0052]
Polyether polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, triethylene glycol, Methylolethane, trimethylolpropane, sorbitol, sucrose, aconite sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propane Ethylene oxide, propylene oxide, butylene oxalate using one or more of compounds having at least two active hydrogen atoms such as trithiol as an initiator De, styrene oxide, epichlorohydrin, tetrahydrofuran, and the like obtained by addition polymerization in a conventional manner one or more of such cyclohexylene.
[0053]
Examples of the polycarbonate polyol include compounds obtained by reacting glycols such as 1,4-butanediol, 1,6-hexanediol, and diethylene glycol with diphenyl carbonate and phosgene.
[0054]
Examples of the low molecular weight compound include compounds containing at least two active hydrogens in a molecule having a molecular weight of 300 or less. For example, a glycol component used as a raw material for a polyester polyol; glycerin, trimethylolethane, trimethylolpropane, Polyhydroxy compounds such as sorbitol and pentaerythritol; ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4, Examples include amine compounds such as 4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, hydrazine, diethylenetriamine, and triethylenetetramine.
[0055]
A polyurethane resin emulsion can introduce | transduce a hydrophilic group into a polyurethane resin by using the terminal isocyanate group containing urethane prepolymer which has a hydrophilic group.
Examples of the raw material of the terminal isocyanate group-containing urethane prepolymer having a hydrophilic group include a hydrophilic group-containing compound, for example, a salt of a carboxyl group or a sulfonic acid having at least one active hydrogen atom in the molecule. A basically ionic compound containing at least one functional group selected from the group consisting of a salt, a salt of phosphoric acid, a quaternary ammonium salt, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a tertiary amino group, Alternatively, a nonionic compound having at least one active hydrogen atom in the molecule and containing a group consisting of an ethylene oxide repeating unit or an ethylene oxide repeating unit and another alkylene oxide repeating unit can be mentioned. .
Of these hydrophilic groups, a nonionic group containing an anionic group comprising a carboxyl group and a carboxyl base and / or a repeating unit of ethylene oxide is preferred in that it can be a reaction point with the crosslinking agent [Z].
[0056]
Specific examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, and 1,3-phenylenediamine-4. , 6-disulfonic acid, sulfonic acid-containing compounds such as 2,4-diaminotoluene-5-sulfonic acid and their derivatives or polyester polyols obtained by copolymerization thereof; 2,2-dimethylolpropionic acid, 2, Carboxylic acid-containing compounds such as 2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-diaminobenzoic acid, and their derivatives or copolymers thereof Polyester polyol obtained; methyldiethanolamine, butyldiethanolamine, Tertiary amino group-containing compounds such as alkyl diisopropanolamine and their derivatives or polyester polyols or polyether polyols obtained by copolymerization thereof; the tertiary amino group-containing compounds and their derivatives or their copolymers; Polyester polyols or polyether polyols obtained in this manner and quaternizing agents such as methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, bromobutane, etc. A polyoxyethylene glycol or polyoxyethylene-poly having a molecular weight of 300 to 20,000 containing at least 30% by weight of ethylene oxide repeating units and containing at least one active hydrogen in the polymer Nonionic group-containing compounds such as xylene-propylene copolymer glycol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or monoalkyl ether thereof, or obtained by copolymerization thereof Examples thereof include polyester polyether polyols, which are used alone or in combination.
[0057]
The content of the hydrophilic group in the polyurethane resin emulsion used in the present invention is as follows. When the hydrophilic group is an ionic group such as a carboxyl group or a sulfonic acid group, the polyurethane resin emulsion is finally obtained per 100 parts by weight of the solid content of the polyurethane resin. It is at least 0.005 to 0.2 equivalent, preferably 0.01 to 0.1 equivalent. Among the above, a carboxyl group is particularly preferable as the hydrophilic group.
[0058]
When a nonionic compound is used, it is at least 20 parts by weight per 100 parts by weight of the finally obtained polyurethane resin solid content, and preferably 10 parts by weight or less.
[0059]
In the present invention, the hydrophilic group-containing compound and an external emulsifier may be used in combination.
As such an emulsifier, the above-mentioned emulsifier can be used as it is.
[0060]
The polyurethane resin and the terminal isocyanate group-containing urethane prepolymer according to the present invention are produced by a conventionally known method. As a known production method, for example, in the case of a polyurethane resin, the polyisocyanate and the active hydrogen-containing compound (including a hydrophilic group-containing compound) are used. The reaction is carried out at a ratio of 0.8: 1 to 1.2: 1, preferably 0.9: 1 to 1.1: 1. In the case of a terminal isocyanate group-containing urethane prepolymer, the reaction is carried out at a ratio of 1.1: 1 to 3: 1, preferably 1.2: 1 to 2: 1, and 20 to 120 ° C., preferably 30 to 100 ° C. It is something to be made.
[0061]
These reactions can be carried out in the absence of a solvent, but organic solvents can also be used for the purpose of reaction control of the reaction system or viscosity reduction. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; acetate esters such as ethyl acetate and butyl acetate; dimethylformamide, N -Amides such as methylpyrrolidone. In the case where such an organic solvent is distilled off from the finally obtained polyurethane resin aqueous dispersion, it is preferable to use a solvent having a relatively low boiling point that can be easily removed by distillation. Even when it is unavoidable to use an organic solvent having a boiling point of 100 ° C. or higher, the amount used is preferably minimized.
[0062]
Examples of neutralizing agents for neutralizing carboxyl groups that can be used in the production of polyurethane resin emulsions include non-volatile bases such as sodium hydroxide and potassium hydroxide; trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, Examples include tertiary amines such as triethanolamine, and volatile bases such as ammonia. These neutralizing agents may be added before, during or after the polymerization of the carboxyl group-containing unsaturated monomer, or during or after the urethanization reaction.
[0063]
Examples of the polyamine that can be used in the production of the polyurethane resin emulsion include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4 , 4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexyl Diamines such as ethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, aminohexylpropanolamine; diethylenetriamine, dipropylenetriamine, trie Polyamines such as Rentetoramin; hydrazines; acid hydrazides, water and the like, are used these singly or in combination.
[0064]
The polyurethane resin emulsion thus obtained may be used as it is, but it can also be used after removing the organic solvent by distillation if necessary.
Various distillation apparatuses can be used for distilling off the organic solvent, but a distillation apparatus in which the distillation efficiency and the organic solvent removed by distillation are not released into the atmosphere is preferable, and a thin film evaporation apparatus is particularly preferable.
[0065]
The polyurethane resin emulsion obtained by removing the organic solvent is an emulsion having a resin solid content of 10 to 60% by weight, preferably 15 to 50% by weight. Even if an organic solvent having a boiling point of 100 ° C. or more must be used, the amount of such an organic solvent should be stopped by 20% by weight based on the total weight of the aqueous dispersion.
[0066]
Next, as the heat-sensitive gelling agent [Y] used in the aqueous resin composition of the present invention, polyether-modified silicone, alkylene oxide adduct of alkylphenol-formalin condensate, zinc ammonium salt, nonionic surfactant, inorganic metal Examples thereof include salts, polypropylene glycol, and polyvinyl methyl ether. Of these, polyether-modified silicones, alkylene oxide adducts of alkylphenol-formalin condensates, nonionic surfactants, and polyvinyl methyl ether are preferred from the viewpoint of water resistance, and polyether modification is preferred from the viewpoint of suppressing blistering. Silicone is preferred. Moreover, it is preferable that the cloud point of 1 weight% aqueous solution of polyether modified silicone is 30-55 degreeC at the point of the effect which suppresses a blister.
[0067]
Here, the cloud point of the heat-sensitive gelling agent [Y] means a temperature at which a 1% by weight aqueous solution of a transparent polyether-modified silicone is gradually heated from room temperature, and the aqueous solution becomes turbid by visual observation. The cloud point in this invention is based on the numerical value measured by the method shown in the below-mentioned Example.
[0068]
More specifically, the polyether-modified silicone is represented by Structural Formula [1] or Structural Formula [2]. Examples of the polyoxyalkylene glycol unit in Structural Formula [1] and Structural Formula [2] include ethylene oxide and alkylene oxides other than ethylene oxide.
[0069]
[Chemical 1]

[Chemical formula 2]

[0070]
In the structural formulas [1] and [2], R₁Is any alkyl group, R₂Is any alkylene group, R_Three, R_FourIs one of ethylene residues and the other is an alkylene residue having 3 to 8 carbon atoms, R_FiveRepresents an alkyl group, an acetyl group or hydrogen, a and b each represent an integer of 1 or more, and m and n each represent an arbitrary integer.
[0071]
The amount of these heat-sensitive gelling agents [Y] is not particularly limited, but from the viewpoint of long-term storage stability of the polymer aqueous dispersion, usually, with respect to 100 parts by weight of the polymer particles [X], It is preferable to use in the range of 0.05 to 30 parts by weight.
[0072]
The crosslinking agent [Z] having reactivity with the carboxyl group of the polymer particle [X] (hereinafter referred to as crosslinking agent [Z]) is not particularly limited as long as it is a crosslinking agent having reactivity with the carboxyl group. Absent. Examples of the crosslinking agent [Z] include water solubility, water dilutability, and water dispersibility.
[0073]
Specific examples of the crosslinking agent [Z] include a polyfunctional melamine compound, a polyfunctional polyethylenimine compound, a polyfunctional (block) isocyanate compound, a polyfunctional aziridine compound, a polyfunctional glycidyl compound, and a polyfunctional compound. Carbodiimide compounds, polyfunctional oxazoline compounds and the like.
[0074]
Among these, a polyfunctional glycidyl compound, a polyfunctional carbodiimide compound, and a polyfunctional oxazoline compound are preferable because they can improve the crosslinking density of the resulting film and improve the impact resistance and hardness of the film.
[0075]
Furthermore, among these crosslinking agents, polyfunctional oxazoline compounds are preferred because they are particularly excellent in terms of impact resistance of the coating.
[0076]
Specific examples of the polyfunctional glycidyl compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol. Glycidyl ethers of aliphatic polyhydric alcohols such as tetraglycidyl ether; glycidyl ethers of polyalkylene glycols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether; polyhydric alcohol [ethylene glycol , Propylene glycol, butylene glycol, hexamethyle Glycol, bis (hydroxymethyl) benzene, etc.] and a polyglycidylated polyester of polyvalent carboxylic acid [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] Polyglycidylated polyester such as polyglycidylated polycaprolactone; polyvalent amine [ethylenediamine, diethylenetriamine, 1,4-cyclohexanediamine, isophoronediamine, tolylenediamine, etc.] and polyvalent carboxylic acid [succinic acid, adipic acid, butanetricarboxylic acid] Acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] polyamide polyglycidylated product; condensate of bisphenol A and epichlorohydrin, bisphenol A and epichloro Ethylene oxide adduct of condensate of drin, bisphenol A epoxy resin such as propylene oxide adduct of condensate of bisphenol A and epichlorohydrin; phenol novolac resin, ethylene oxide adduct of phenol novolac resin, propylene oxide adduct of phenol novolac resin, etc. Phenol novolac epoxy resins; epoxy urethane resins obtained by urethane modification of epoxy resins; various vinyl (co) polymers having an epoxy group in the side chain; glycidyl-modified silicone oils; glycidyl such as γ-glycidoxypropyltrimethoxysilane Examples include partial hydrolysates of group-containing alkoxysilanes; compounds having two or more glycidyl groups in one molecule such as glycidyl group-containing acrylic resins.
[0077]
Among such glycidyl group-containing compounds, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ethers, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, glycerol polyglycidyl ethers, diglycerol polyglycidyl ethers, Water-soluble glycidyl group-containing compounds such as polyglycerol polyglycidyl ethers and sorbitol polyglycidyl ethers, or “Denacol EM-125” [manufactured by Nagase Kasei Kogyo Co., Ltd.], “Dick Fine EM-100” [Dainippon Ink Chemical Industry Co., Ltd.], “Adeka Resin EPE-0410, EPES-0425W” [Asahi Denka Kogyo Co., Ltd.] and other self-dispersing glycidyl group-containing compounds were emulsified. Of, or glycidyl group-containing water-insoluble compounds (liquid, solid form) what was emulsified with an emulsifier, from the viewpoint of compatibility and curability with polymer particles [X].
[0078]
The polyfunctional glycidyl compound includes a glycidyl group in one molecule and a reactive functional group other than the glycidyl group (where the reactive functional group is a reaction that can react with a reactive group in the polymer particle [X]. A reactive functional group, or a reactive functional group capable of reacting with each other). Specific examples of such compounds include glycidyl group-containing silane compounds containing a glycidyl group and a hydrolyzable silyl group or silanol group in one molecule.
[0079]
When this glycidyl group-containing silane compound is used, various physical properties such as water resistance and impact resistance of the coating, particularly impact resistance are remarkably improved, and further, the cross-linking property is good, for example, it is desired only by drying at room temperature. It is preferable because a crosslinked film having high performance can be obtained.
[0080]
Typical examples of the glycidyl group-containing silane compound include an ethylenic polymer having both of these reactive groups, a silane coupling agent having a glycidyl group, or a silicone resin having a glycidyl group. It is done.
[0081]
Here, the hydrolyzable silyl group is an atomic group containing a silicon atom to which, for example, an alkoxy group, a substituted alkoxy group, a phenoxy group, a halogen atom, an isopropenyloxy group, an acyloxy group, or iminooxy is bonded. It refers to a functional group that undergoes hydrolysis and generates a silanol group. Examples of such hydrolyzable silyl groups include alkoxysilyl groups, phenoxysilyl groups, halosilyl groups, isopropenyloxysilyl groups, acyloxysilyl groups, and iminooxysilyl groups.
[0082]
In order to prepare the ethylenic polymer having both the glycidyl group and the hydrolyzable silyl group or silanol group, any of various known methods can be applied. Among these, the methods that can be recommended include (1) radical copolymerization of various hydrolyzable silyl group-containing polymerizable monomers and various glycidyl group-containing polymerizable monomers, and (2) ▼ Method of radical copolymerizing hydrolyzable silyl group-containing polymerizable monomers, various glycidyl group-containing polymerizable monomers, and other polymerizable monomers copolymerizable therewith, ▲ 3 ▼ Various chain transfers containing hydrolyzable silyl groups such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane or γ-mercaptopropyltriisopropenyloxysilane In the presence of an agent, radical (co) polymerization of a monomer mixture containing the above-mentioned various glycidyl group-containing polymerizable monomers as essential monomer components was performed. Luke, or, ▲ 4 ▼ the ▲ 1 ▼ or ▲ 2 ▼ manner as above ▲ 3 ▼ various methods methods such as a combination of methods thereof.
[0083]
Further, as the above-mentioned glycidyl group-containing silane coupling agents, particularly typical ones include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyl. Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4 -Epoxycyclohexyl) various glycidyl group-containing silane compounds such as ethylmethyldiethoxysilane or γ-glycidoxypropyltriisopropenyloxysilane; γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanate- Topropyltrime Adducts of various isocyanate silane compounds such as xylsilane and glycidyl; or adducts of various aminosilane compounds such as γ-aminopropyltrimethoxysilane and diglycidyl compounds; or various as described above And a compound having two or more glycidyl groups and a hydrolyzable silyl group in one molecule, obtained by partial hydrolytic condensation of the glycidyl group-containing silane compound.
[0084]
When a polyfunctional glycidyl compound is used as the crosslinking agent [Z], it is preferable to use a curing catalyst in combination because the crosslinkability of the coating can be further improved.
[0085]
Typical examples of such curing catalysts include various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, etc .; tetraisopropyl titanate, tetra-n-butyl titanate, octylic acid Tin, lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate Various metal-containing compounds such as di-n-butyltin maleate; various acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid, dialkylphosphorous acid, etc. Is mentioned.
[0086]
Next, the polyfunctional carbodiimide compound used as the crosslinking agent [Z] is a compound containing two or more carbodiimide groups, for example, an isocyanate-terminated polyvalent carbodiimide by a condensation reaction involving decarbonization of organic diisocyanate. Can be produced by synthesizing.
[0087]
The organic diisocyanate that is a raw material for synthesizing a compound containing two or more carbodiimide groups includes aliphatic, alicyclic or aromatic diisocyanates, and these are used alone or as a mixture of two or more. be able to. Specifically, 1,5-naphthylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-diphenylmethylmethane diisocyanate, 1,4-tolylene diisocyanate, 2,4-tolylene diisocyanate Isocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, etc. It is done.
[0088]
By using a compound that reacts with a terminal isocyanate group such as monoisocyanate together with the above organic diisocyanate, the molecule can be controlled to an appropriate degree of polymerization.
[0089]
The condensation reaction accompanied by decarbonization of the organic diisocyanate proceeds in the presence of a carbodiimidization catalyst. Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3- Phosphorene oxides such as phospholene isomers can be used.
[0090]
In addition, the polyfunctional carbodiimide compound is preferably water-soluble, water-dilutable or water-dispersible from the viewpoint of compatibility with the polymer particles [X].
[0091]
To make the polyfunctional carbodiimide compound into a self-emulsified or aqueous solution form, disperse it in water using an appropriate emulsifier or dispersion stabilizer, or add a hydrophilic segment in the molecular structure of the polyfunctional carbodiimide compound. This can be done.
[0092]
Examples of the hydrophilic segment include a quaternary ammonium salt of a dialkylamino alcohol (for example, a quaternary salt of 2-dimethylaminoethanol), a quaternary salt of a dialkylaminoalkylamine (for example, a quaternary salt of 3-dimethylamino-n-propylamine). Grade salts), alkyl sulfonates having at least one reactive hydroxyl group (for example, hydroxypropane sulfonate), polyethylene oxide end-capped with alkoxy groups, or a mixture of polyethylene oxide and polypropylene oxide (for example, methoxy) And polyethylene oxide end-capped with a group or an ethoxy group).
[0093]
Examples of the multifunctional carbodiimide compound include carbodilite V-01, V-02, V-03, V-04, V-05, V-06 [manufactured by Nisshinbo Co., Ltd.], UCALINK XL-29SE, XL-29MP [Union Carbide Co., Ltd.] can be mentioned.
[0094]
Next, the polyfunctional oxazoline compound used as the crosslinking agent [Z] is a compound containing two or more oxazoline groups. Such a polyfunctional oxazoline compound may be a low molecular weight compound or a polymer, but is preferably a polymer from the viewpoint of improving the cross-linking density of the film and excellent impact resistance of the film. .
[0095]
Examples of the low molecular weight compound of the polyfunctional oxazoline compound include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), and 2,2′-ethylene- Bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline), 2,2′-hexamethylene-bis- ( 2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2,2'-p- Phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'-dimethyl-2-oxazoline) ,Screw (2-oxazolinyl sulfonyl cyclohexane) sulfide, bis - (2-oxazolinyl sulfonyl norbornane) can be mentioned sulfides.
[0096]
Moreover, as a polymer of a polyfunctional oxazoline compound, the following general formula [1] (in the formula, R₁, R₂, R_Three, R_FourAre each independently hydrogen, a halogen atom, an alkyl group, an aralkyl group, an aryl group or a substituted aryl group, and R_FiveIs an acyclic organic group having an addition polymerizable unsaturated bond), and an oxazoline group-containing polymer obtained by polymerizing a monomer component containing a copolymerizable monomer.
[Chemical Formula 3]

[0097]
Specific examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl. -2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. Among these, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially.
[0098]
The amount of addition polymerizable oxazoline used is not particularly limited, but it is preferably 5% by weight or more in the monomer component, and more preferably in the range of 30 to 60% by weight.
[0099]
If the amount of addition polymerizable oxazoline used is within such a range, excellent impact resistance, water resistance and the like can be imparted to the resulting coating.
[0100]
When the amount of addition polymerizable oxazoline used is less than 5% by weight, the degree of crosslinking reaction with the carboxyl groups of the polymer particles [X] becomes insufficient, and the impact resistance and the like of the resulting coating film may be lowered.
[0101]
On the other hand, when it exceeds 60% by weight, the hydrophilicity of the polyfunctional oxazoline compound itself becomes strong, and the water resistance of the resulting film may be lowered.
[0102]
Examples of the monomer copolymerizable with the addition polymerizable oxazoline used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) Acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid methoxypolyethylene (Meth) acrylic acid esters such as glycol and monoester compounds of (meth) acrylic acid and polyethylene glycol; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl Fluorine-containing ethylenic unsaturation such as (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate Monomers; Unsaturated amides such as (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate Vinyl esters such as methyl vinyl ether , Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether and other vinyl ethers; (meth) acrylonitrile and other nitrile group-containing ethylenically unsaturated monomers; styrene, α-methylstyrene, vinyl toluene, vinyl anisole , Α-halostyrene, vinyl naphthalene, divinylstyrene, and other vinyl compounds having an aromatic ring; isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone, and the like, A mixture of two or more can be used.
[0103]
In addition, the polyfunctional oxazoline compound is preferably water-soluble, water-dilutable or water-dispersible from the viewpoint of compatibility with the polymer particles [X].
[0104]
The polymer of a polyfunctional oxazoline compound can produce the above monomer component by a conventionally known method such as a solution polymerization method or an emulsion polymerization method.
[0105]
As a polymer of a polyfunctional oxazoline compound, for example, Epocross K-1010E, K-1020E, K-1030E, K-2010E, K-2020E, K-2030E [manufactured by Nippon Shokubai Co., Ltd .: emulsion type ], Epocross WS-500, WS-700 [manufactured by Nippon Shokubai Co., Ltd .: water-soluble type].
[0106]
Of these commercially available products of polyfunctional oxazoline compounds, water-soluble Epocros WS-500 and WS-700 are preferable because they can improve the cross-linking density of the coating as described above and are excellent in impact resistance.
[0107]
The amount of these cross-linking agents [Z] is not particularly limited, but in the polymer particles [X] from the viewpoint of the crosslinkability of the aqueous dispersion, the performance of the cross-linked coating, and the storage stability of the aqueous dispersion. In general, it is preferably used in the range of 0.1 to 2.0 mol with respect to 1 mol of the carboxyl group contained in.
[0108]
The aqueous resin composition of the present invention itself forms a film having excellent impact resistance, flexibility and flexibility, and excellent hardness by room temperature or heat drying. As long as the effect is not impaired, a crosslinking agent other than the crosslinking agent [Z] can be used. Examples of such cross-linking agents include polyfunctional polyamine compounds, polyfunctional polyethylenimine compounds, metal salt compounds, and the like, and these can be used as one or a mixture of two or more thereof.
[0109]
The aqueous resin composition of the present invention further uses an inorganic filler [W] in combination in terms of preventing the generation of blisters during film formation.
The inorganic filler [W] is not particularly limited. For example, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, talc, diatomaceous earth, mica, kaolin, titanium oxide, alumina, silica, calcium silicate. , Carbon black, attapulgite, shirasu balloon, pearlite, and the like. These may be used alone or in combination of two or more.
[0110]
In this invention, it is preferable that content of said inorganic filler [W] is the range of 5-50 weight part with respect to 100 weight part of polymer particles [X]. If the content of the inorganic filler [W] is within such a range, a film having excellent strength can be obtained.
[0111]
The average particle size of the inorganic filler [W] is not particularly limited, but is preferably in the range of 0.1 to 100 μm.
[0112]
A dispersion stabilizer can be used for the purpose of improving the mixing stability and storage stability of the inorganic filler [W]. As the dispersion stabilizer, for example, a water-soluble polymer substance can be used. Examples of the water-soluble polymer substance include synthetic or natural water-soluble substances such as polyvinyl alcohol, cellulose ether, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt), polyacrylamide, and water-soluble acrylic resin. , And one or a mixture of two or more of these can be used.
[0113]
It is preferable to reduce the amount of the dispersion stabilizer used as much as possible from the viewpoint of water resistance of the coating. The amount of the dispersion stabilizer used is preferably 2 parts by weight or less with respect to 100 parts by weight of the polymer particles [X].
[0114]
The aqueous resin composition of the present invention preferably further contains a thickener [V]. As the thickener [V], a conventionally known thickener can be used. Conventionally known thickeners include, for example, carboxymethyl cellulose (CMC) aqueous solution, hydroxylethyl cellulose aqueous solution, starch, polyvinyl alcohol, hydrophilic group-containing synthetic resin emulsion, etc., but hydrophilic in terms of preventing the occurrence of blisters. A group-containing synthetic resin emulsion is preferable, and among them, a carboxyl group-containing acrylic copolymer emulsion is particularly preferable.
[0115]
As a method for producing the carboxyl group-containing acrylic copolymer emulsion, a method similar to the method for producing the polymer [A] by emulsion polymerization of a monomer in an aqueous medium can be used.
In this case, it is preferable to use 15 to 60% by weight of a carboxyl group-containing monomer among the monomers in terms of alkali thickening when an aqueous ammonia solution or an aqueous sodium hydroxide solution is added.
[0116]
When it is necessary to adjust the molecular weight of the carboxyl group-containing acrylic copolymer used in the present invention, a compound having chain transfer ability may be added as a molecular weight modifier.
[0117]
Moreover, the carboxyl group of the carboxyl group-containing acrylic copolymer emulsion used in the present invention can be neutralized with a neutralizing agent such as a basic substance, if necessary.
[0118]
In the present invention, the content of the thickener [V] is not particularly limited, but is preferably in the range of 5 parts by weight or less with respect to 100 parts by weight of the polymer particles [X]. When the content of the thickener [V] is within such a range, the aqueous resin composition has excellent viscosity stability over time.
[0119]
The Young's modulus in the tensile test at a measurement temperature of 25 ° C. of the film formed from the aqueous resin composition of the present invention is not particularly limited, but is preferably 50 MPa or more from the viewpoint of excellent protection of the coated fiber.
[0120]
The elongation at break in the tensile test at a measurement temperature of 25 ° C. of the coating formed with the aqueous resin composition of the present invention is not particularly limited, but is 200% or more in terms of excellent coating flexibility. Is preferred.
[0121]
The Young's modulus and elongation at break in the tensile test at a measurement temperature of 25 ° C. were determined by using the test piece obtained in the examples described later on a condition of a crosshead speed of 200 mm / min at a temperature of 25 ° C. using a tensile tester. This is based on numerical values obtained by measuring the axial elongation when pulled in the axial direction.
[0122]
In the aqueous resin composition of the present invention, if necessary, a water-soluble or water-dispersible thermosetting resin such as phenol resin, urea resin, melamine resin, or thermoplastic resin such as polyurethane resin, polyester resin, A polyamide resin, a polyethylene resin, or the like can also be mixed and used.
[0123]
Further, if necessary, pigments, pH adjusters, film forming aids, leveling agents, water repellents, antifoaming agents, antioxidants, light stabilizers and the like are known as long as the desired effects of the present invention are not impaired. Can be used as appropriate.
[0124]
The aqueous resin composition of the present invention has excellent low-temperature properties, is excellent in hardness at normal temperature, and gives a coating film with good water resistance. In particular, it has impact resistance, flexibility and flexibility, and is useful in fields requiring hardness, such as paints, primer treatment agents, adhesives, film coating agents, textile processing resins (woven and knitted fabrics) And binders for non-woven fabrics, binders for flocking, etc.), resins for paper processing (impregnation, coating), resins for glass fiber processing (glass fiber sizing agents, binders for glass paper, glass fiber coatings, etc.), mortar It can be used as a modifying resin. In particular, when used in application fields such as paints, inks, varnishes, film coatings, adhesions, fiber processing resins, paper processing resins, etc., extremely excellent effects are exhibited as described above.
[0125]
In addition, as described above, the aspect of the present invention includes the polymer particles [X] having a carboxyl group in the molecule, the heat-sensitive gelling agent [Y], the crosslinking agent [Z] having reactivity with the carboxyl group, and inorganic filling. Synthetic rubber latex (x1) having a carboxyl group in the molecule as polymer particles [X] having a carboxyl group in the molecule, wherein the agent [W] is dispersed in an aqueous medium Any of the synthetic rubber latex and an acrylate copolymer emulsion (x2) having a carboxyl group in the molecule, or a polyurethane resin emulsion having a carboxyl group in the molecule and the acrylate copolymer emulsion (x3) The present invention relates to an aqueous resin composition characterized by using one kind.
[0126]
Another aspect of the present invention relates to an aqueous resin composition having an elongation at break of 200% or more at a measurement temperature of 25 ° C. of a film formed from the aqueous resin composition.
[0127]
As another aspect of the present invention, the present invention relates to an aqueous resin composition having a Young's modulus of 50 MPa or more in a tensile test at a measurement temperature of 25 ° C. of a film formed from the aqueous resin composition.
[0128]
As another aspect of the present invention, the heat-sensitive gelling agent [Y] is applied to an aqueous resin composition which is a polyether-modified silicone.
[0129]
Another aspect of the present invention relates to an aqueous resin composition in which the cloud point of a 1% by weight aqueous solution of the polyether-modified silicone is 30 to 55 ° C.
Furthermore, as another aspect of the present invention, the crosslinking agent [Z] having reactivity with the carboxyl group is selected from the group consisting of a polyfunctional glycidyl compound, a polyfunctional carbodiimide compound, and a polyfunctional oxazoline compound. The present invention relates to an aqueous resin composition that is one or more crosslinking agents.
[0130]
Another aspect of the present invention is an aqueous resin composition further containing a thickener [V].
Another aspect of the present invention relates to an aqueous resin composition having a solid content of 50% by weight or more in the aqueous resin composition.
[0131]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples. In the following, unless otherwise specified, “%” represents “% by weight”, and “part” represents “part by weight”.
[0132]
First, the measurement method and evaluation method used in the present invention will be described below.
[0133]
[Measurement method of average particle size]
For the average particle size, the value of the average particle size (50% median size) measured with a Microtrac UPA type particle size distribution analyzer manufactured by Nikkiso Co., Ltd. was determined by a dynamic light scattering method.
[0134]
[Measurement method of Young's modulus in tensile test at a measurement temperature of 25 ° C.]
The aqueous resin composition of the present invention obtained in Examples was applied to a glass plate so that the film thickness after drying was 0.5 mm, dried at 40 ° C. for 8 hours, then peeled off from the glass plate, and What was dried at 140 ° C. for 5 minutes was punched with a No. 2 dumbbell and used as a sample. Using this sample, a strain of 0 to 2.5% when a tensile test was performed at a crosshead speed of 200 mm / min in an atmosphere of 25 ° C. in a Tensilon RTM-100 type tensile tester manufactured by Orientec Co., Ltd. A value represented by the following equation from Δε and stress Δσ was defined as Young's modulus E.
[0135]
[Formula 1]
E = Δσ / Δε
[0136]
[Method of measuring elongation at break and strength at break in a tensile test at a measurement temperature of 25 ° C.]
The aqueous resin composition of the present invention obtained in Examples was applied to a glass plate so that the film thickness after drying was 0.5 mm, dried at 40 ° C. for 8 hours, then peeled off from the glass plate, and What was dried at 140 ° C. for 5 minutes was punched with a No. 2 dumbbell and used as a sample. Using this sample, the elongation at break when a tensile test was carried out at a crosshead speed of 200 mm / min in an atmosphere of 25 ° C. in a Tensilon RTM-100 type tensile tester manufactured by Orientec Corp. was measured.
[0137]
[Method of measuring cloud point]
The 1% by weight aqueous solution of the heat-sensitive gelling agent used in the examples was heated while gradually stirring from room temperature, and the temperature at which the aqueous solution became cloudy by visual observation was defined as the cloud point.
[0138]
[Blister (film blister) evaluation method]
The aqueous resin composition of the present invention obtained in the Examples was added to a glass container having an inner diameter of 14 mm, a height of 30 mm, and a thickness of 1 mm in the case of an additive-free product of 0.7 g, and in the case of a filler-added product. Put 5g and put into Tabai hot air dryer set to 90 ° C for 6 minutes, then immediately put into Tabai hot air dryer set to 150 ° C for 3 minutes and visually observe the presence or absence of blister, Judgment was made according to criteria.
○: No change
Δ: Swells a little
×: Blister occurrence or rupture
[0139]
[Measurement method of impact resistance]
The aqueous resin composition of the present invention obtained in Examples was applied to a glass plate so that the film thickness after drying was 0.7 mm, dried at 40 ° C. for 8 hours, then peeled off from the glass plate, and What was dried at 140 ° C. for 5 minutes and cut into 30 mm × 30 mm was used as a sample, and measured under a 25 ° C. atmosphere using a DuPont impact deformation tester according to JIS K-5400.
[0140]
For operation, attach a shooting die with a radius of 6.35 ± 0.03 mm and a cradle, sandwich the coating between them, drop a weight of 500 g ± 1 g from the sample onto the shooting die from a height of 100 mm, and then coat The test piece was taken out while taking care not to give extra damage to the film, and the damage of the coating film was examined visually.
The number of tests was 10 and the evaluation results were determined according to the following criteria.
×: Breakage or crack of 60% or more occurred
Δ: Breakage or crack of 20% or more and less than 60%
○: Less than 20% breakage or crack occurred
[0141]
<< Synthesis Example 1 >> (Synthesis of thickener [V])
690 parts of deionized water and 24 parts of Neugen ET-170 [Daiichi Kogyo Seiyaku Co., Ltd.] were put into a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, and nitrogen was blown into the reaction vessel. The temperature was raised to 75 ° C. Under stirring, a monomer mixture consisting of 10 parts of a 10% aqueous ammonium persulfate solution, 203 parts of ethyl acrylate and 87 parts of methacrylic acid, 100 parts of deionized water and 3 parts of Neugen ET-170 [Daiichi Kogyo Seiyaku Co., Ltd.] A monomer pre-emulsion emulsified by adding (referred to the monomer mixture, the emulsifier and water emulsified with water), respectively, using a dropping funnel while maintaining the temperature in the reaction vessel at 75 ° C. The polymerization was carried out dropwise over a period of minutes.
[0142]
<< Synthesis Example 2 >> (Synthesis of acrylic ester copolymer emulsion)
In a polymerization vessel equipped with a stirrer, 210 parts of ion-exchanged water was charged, and the temperature in the reaction vessel was raised to 80 ° C. while stirring while feeding nitrogen gas. After raising the temperature, 4 parts of the following (1) monomer emulsion was added to the reaction vessel, and then 0.6 parts of ammonium persulfate was added to initiate polymerization. After maintaining the temperature in the reaction vessel at 80 ° C. for 1 hour, 726 parts of the remaining monomer emulsion and the following aqueous solution (2) of polymerization initiator were simultaneously dropped into the reaction vessel for polymerization. The dropping time was 4 hours for the monomer emulsion and 4.5 hours for the polymerization initiator aqueous solution, and the polymerization was completed while maintaining the temperature in the reaction vessel at 80 ° C. After completion of the polymerization, the pH was adjusted with aqueous ammonia to obtain an acrylate copolymer emulsion having a solid content of 60%, a pH of 8.0, and an average particle size of 350 nm.
(1) Composition of monomer emulsion
350 parts of n-butyl acrylate
225 parts of methyl methacrylate
Methacrylic acid 15 parts
40 parts of New Call 707SF (manufactured by Kao Corporation)
100 parts of ion exchange water
(2) Composition of polymerization initiator aqueous solution
1.5 parts ammonium persulfate
75 parts of ion exchange water
[0143]
<< Synthesis Example 3 >> (Synthesis of synthetic rubber latex)
In a pressure-resistant polymerization vessel equipped with a stirrer, 120 parts of water, 0.1 part of sodium hydroxide, 1.2 parts of reactive emulsifier S-180 (unsaturated alkyl sulfate produced by Kao Corporation), 0. 1 part, 30 parts of butadiene, 68 parts of methyl methacrylate, 2 parts of acrylic acid and 0.1 part of t-dodecyl mercaptan are charged, stirring is started, the reaction temperature is raised to 60 ° C., and the temperature in the polymerization vessel is 60 When the temperature reached, 0.1 part of ammonium persulfate was added to initiate the reaction. Seven hours later, when the polymerization rate reached 98%, cooling was performed to obtain a synthetic resin latex. The obtained synthetic resin latex had a polymerization rate of 98.6%. Next, the pH was adjusted to 9.0 with 25% aqueous ammonia, and then a synthetic rubber latex having a solid content of 50.1% was obtained by steam distillation.
[0144]
<< Synthesis Example 4 >> (Synthesis of polyurethane resin emulsion)
Polytetramethylene ether glycol (molecular weight: 2,000) 500 parts, 2,2-dimethylolpropionic acid 36 parts, neopentyl glycol 18 parts, isophorone diisocyanate 206 parts, 80% hydrazine 13 parts, triethylamine By reacting 27 parts, a polyurethane resin emulsion having a nonvolatile content (%) = 35, an acid value = 20, a particle diameter = 50 nm, and a flow start temperature = 100 ° C. was obtained.
[0145]
<< Example 1 >> (Production of aqueous resin composition of the present invention)
FZ-2164 [organopolysiloxane polyoxyalkylene glycol: heat-sensitive gelling agent was added to 200 parts of the acrylic ester copolymer emulsion obtained in Synthesis Example 2 and 200 parts of the synthetic rubber latex obtained in Synthesis Example 3. 100% by weight of active ingredient: Nihon Unicar Co., Ltd.] 10 parts are added, NS-200 [calcium carbonate: manufactured by Nitto Fukasei Co., Ltd.] 100 parts is added as an inorganic filler, and a synthetic example is used as a thickener. 10 parts obtained in 1 were added, and Epocross WS-500 [Oxazoline group-containing water-soluble crosslinking agent: active ingredient 40% by weight: manufactured by Nippon Shokubai Co., Ltd.] was added as a crosslinking agent to obtain a solid content concentration. Was adjusted with deionized water so as to be 55.0%, followed by filtration with a 100 mesh wire net to obtain an aqueous resin composition of the present invention.
[0146]
The evaluation results of the coating obtained using the aqueous resin composition of the present invention are shown in Table 1. The elongation at break in a tensile test at a measurement temperature of 25 ° C. is 265%, and the measurement temperature is 25 ° C. The stress at break in the tensile test was 11 MPa, and the Young's modulus was 127 MPa. Moreover, the impact resistance of the film obtained from this aqueous resin composition was good.
[0147]
<< Example 23>> The aqueous resin composition of the present invention was obtained in exactly the same manner as in Example 1 except that the monomer mixture, the heat-sensitive gelling agent, the crosslinking agent, and the thickener shown in Table 1 were used. This solid content concentration was as described in Table 1. Further, the Young's modulus, elongation at break, stress at break, impact resistance, and blister of the film obtained from this aqueous resin composition in the tensile test at a measurement temperature of 25 ° C. are as described in Table 1. It was.
[0148]
<< Comparative Examples 1-3 >>
An aqueous resin composition was obtained in exactly the same manner as in Example 1 except that the monomer mixture shown in Table 2 was used. The particle diameter and solid content concentration of this aqueous resin composition were as described in Table 2. Further, the Young's modulus, elongation at break, stress at break, impact resistance, and blister of the film obtained from this aqueous resin composition in the tensile test at a measurement temperature of 25 ° C. are as described in Table 2. It was.
[0149]
[Table 1]

[0150]
[Table 2]

[0151]
The official names of the abbreviations in Tables 1 and 2 are shown below.
FZ-2164;
Nippon Unicar Co., Ltd .: Silicone-type thermosensitive gelling agent 100% active ingredient
FZ-2101;
Nippon Unicar Co., Ltd .: Silicone-type thermosensitive gelling agent 100% active ingredient
Epocross WS-500;
Nippon Shokubai Co., Ltd .: Oxazoline group-containing crosslinking agent 40% active ingredient
UCALINK XL-29SE;
Union Carbide Co., Ltd .: Carbodiimide group-containing crosslinking agent 50% active ingredient
NS-200;
Nitto Powder Industries, Ltd .: 100% calcium carbonate active ingredient
Heidilite H-31;
Showa Denko KK: Aluminum hydroxide 100% active ingredient
[0152]
The parts in Tables 1 and 2 are solid contents.
[0153]
【The invention's effect】
When used as a coating agent (surface coating agent), the aqueous resin composition of the present invention is excellent in impact resistance, has flexibility and flexibility, and forms a film with high hardness. In particular, it is useful in fields that require low temperature characteristics and high hardness at room temperature, and is extremely excellent in fields such as paint, ink, varnish, film coating, adhesion, resin for fiber processing, and resin for paper processing. Demonstrate the effect.

Claims (7)

Polymer medium [X] having carboxyl group in molecule, polyether-modified silicone as heat-sensitive gelling agent [Y] , crosslinking agent [Z] having reactivity with carboxyl group, and inorganic filler [W] are aqueous media An aqueous resin composition dispersed therein, and polymer particles [X] having a carboxyl group in the molecule, a synthetic rubber latex having a carboxyl group in the molecule, and an acrylic acid having a carboxyl group in the molecule ester copolymer emulsion (x2), or in the molecule encounters aqueous resin composition is characterized by using any one of a polyurethane resin emulsion and the acrylic acid ester copolymer emulsion having a carboxyl group (x3) And
The (x2) is a weight ratio of the synthetic rubber latex and the acrylate copolymer emulsion of 30:70 to 95: 5, and the (x3) is the polyurethane resin emulsion and the acrylic acid copolymer. The weight ratio with the combined emulsion is 30:70 to 95: 5,
The content of the heat-sensitive gelling agent [Y] is 0.05 to 30 parts by weight with respect to 100 parts by weight of the polymer particles [X], and the content of the crosslinking agent [Z] is the polymer particles [ X] is 0.1 to 2.0 mol with respect to 1 mol of the carboxyl group, and the content of the inorganic filler [W] is 5 to 50 parts by weight with respect to 100 parts by weight of the polymer particles. An aqueous resin composition. The aqueous resin composition according to claim 1, wherein the elongation at break at a measurement temperature of 25 ° C. of the film formed from the aqueous resin composition is 200% or more. 3. The aqueous resin composition according to claim 1, wherein a Young's modulus in a tensile test at a measurement temperature of 25 ° C. of the film formed of the aqueous resin composition is 50 MPa or more. The cloud point of 1% by weight aqueous solution of the polyether-modified silicone aqueous resin composition according to claim 1, wherein a 30 to 55 ° C.. 2. The crosslinking agent [Z] having reactivity with a carboxyl group is at least one crosslinking agent selected from the group consisting of a multifunctional glycidyl compound, a multifunctional carbodiimide compound, and a multifunctional oxazoline compound. An aqueous resin composition. The aqueous resin composition according to claim 1, further comprising a thickener [V]. The solid content in the said aqueous resin composition is 50 weight% or more, The aqueous resin composition of any one of Claims 1-6.