JP5031947B2 - Aqueous hard surface protective polish - Google Patents

Description

（式中、Ｒ⁴，Ｒ⁵は互いに同一であるか又は異なって、水素原子又は炭素数が１〜３０、好ましくは８〜３０、特に１０〜２６のアルキル基であり、Ｒ⁶，Ｒ⁷，Ｒ⁸，Ｒ⁹は少なくとも１つは水素原子であって、かつ互いに同一であるか又は異なって、水素原子又は炭素数が１〜３０、好ましくは８〜３０、特に１０〜２６のアルキル基であり、ｎ、ｎ′、ｍ、ｍ′及びｌはこの一般式全体として適当な高分子量となるような任意の数であり、ｋは１〜１０である）
で表わされる架橋型ポリマーなどが挙げられる。
【００３６】
また、両親媒性カルボキシビニル系ポリマーは平均分子量１０万〜５００万、中でも３０万〜３００万、特に５０万〜２００万をもつものが好ましい。
【００３７】
両親媒性カルボキシビニル系ポリマーとしては適当な市販品をそのまま用いることもできる。
この市販品としては、例えばＢ．Ｆ．Ｇｏｏｄｒｉｃｈ社のＰＥＭＵＬＥＮ各種（例えばＴＲ−１、ＴＲ−２、１６２１、１６２２等）、Ｃａｒｂｏｐｏｌ各種（例えば、１６１０、１６２３、１３８２、１３４２、ＥＴＤ２０２０等）、ＳＥＰＰＩＣ社のＳＯＬＡＧＡＭ（例えばＳＦ３０６、ＳＨ２１０、ＳＪ１０８等）、東亜合成工業社のＢ−３００やＢ−５００等、ロームアンドハース社のＡＣＵＳＯＬ各種（例えば、８２０、８８０、８８２等）や、ＡＣＵＬＹＮ各種（例えば２２等）等が挙げられ、中でもＰＥＭＵＬＥＮ ＴＲ−１、ＰＥＭＵＬＥＮ ＴＲ−２、ＰＥＭＵＬＥＮ １６２１、ＰＥＭＵＬＥＮ １６２２、ＳＯＬＡＧＡＭ ＳＦ３０６、ＳＯＬＡＧＡＭ ＳＨ２１０、ＳＯＬＡＧＡＭ ＳＪ１０８、ＡＣＵＬＹＮ ２２が好ましい。
なお、アルキル基で変性されていない、ポリアクリル酸、ポリアクリル酸塩（例えばナトリウム塩等）、アクリル酸−メタクリル酸共重合体等の親水性ポリマーには、油性保護艶出し成分、中でもオルガノポリシロキサンに対する親和性がほとんどなく、上記微分散状態の持続効果もほとんどない。
【００３８】
両親媒性高分子増粘剤については、それを単に配合するだけで増粘効果を示すものでもよいが、例えばｐＨ調節剤で中和等ｐＨを適切に調節することにより増粘効果を示すものなどであってもよく、このようなものとしては上記の各種両親媒性カルボキシビニル系ポリマーが挙げられ、該ポリマーはカルボキシル基を塩基性物質により中和させることにより増粘する。
【００３９】
この際に中和剤として用いられる塩基性物質については特に制限されないが、安全性、素材表面への影響、取り扱い性等の点からみて、一般的には水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、塩基性アミノ酸（例えばヒスチジン、リジン、アルギニン等）、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、２‐アミノ‐２‐メチル‐１‐プロパノール、２‐アミノ‐２‐メチル‐１，３‐プロパンジオール、２‐アミノ‐２‐ヒドロキシメチル‐１，３‐プロパンジオール、ポリオキシエチレントリエタノールアミン等が挙げられ、中でも水酸化ナトリウム、水酸化カリウム、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、ポリオキシエチレントリエタノールアミンが好ましく、特にポリオキシエチレントリエタノールアミンは界面活性剤の使用量を減少させることができるので好ましい。
これら塩基性物質を用いるに当たっては、所望保護艶出し剤のｐＨが５〜９になるように添加すればよく、素材や人体に対する影響や安全性、油性保護艶出し成分、中でもオルガノポリシロキサンの微分散安定化効果等を考慮するとｐＨ６〜８に調整されるように添加するのがより好ましい。
【００４０】
本発明の保護艶出し剤において、両親媒性高分子増粘剤の含有割合は０．０１〜０．２質量％、中でも０．０２〜０．１５質量％の範囲とするのが好ましい。この割合が０．０１質量％未満では増粘効果が発揮され難くなるし、また０．２質量％を超えると粘度が上がりすぎ取り扱いにくくなる。
【００４１】
本発明の保護艶出し剤はこのように両親媒性高分子増粘剤により増粘され、１００〜３０００ｃＳｔ、好ましくは１５０〜２０００ｃＳｔの範囲の粘度に調整されていることが肝要である。粘度が１００ｃＳｔ未満では微分散安定性が低下するし、また３０００ｃＳｔを超えると高粘度となるため取り扱いにくく、素材表面に塗布或いはスプレーした際に速やかには均一性が得られにくくなる。
【００４２】
本発明の保護艶出し剤に用いられる紫外線吸収剤により素材表面は日光から保護される。
紫外線吸収剤については特に制限されず、例えば安息香酸系、サリチル酸系、ケイ皮酸系、ウロカニン酸系、ベンゾフェノン系、ベンゾトリアゾール系のものの他、オクチルトリアゾン、アントラニン酸メンチル、エチル ２‐シアノ‐３，３‐ジフェニルアクリレート、オクチル ２‐シアノ‐３，３‐ジフェニルアクリレートなどが挙げられる。
【００４３】
安息香酸系紫外線吸収剤としては、例えばパラアミノ安息香酸、パラアミノ安息香酸エチル、パラアミノ安息香酸グリセリル、パラジメチルアミノ安息香酸アミル、パラジメチルアミノ安息香酸オクチル、４‐［Ｎ，Ｎ‐ジ（２‐ヒドロキシプロピル）アミノ］安息香酸エチルなどが挙げられる。
サリチル酸系紫外線吸収剤としては、例えばサリチル酸エチレングリコール、サリチル酸フェニル、サリチル酸オクチル、サリチル酸ベンジル、サリチル酸ｐ‐ｔｅｒｔ‐ブチルフェニル、サリチル酸ホモメンチルなどが挙げられる。
ケイ皮酸系紫外線吸収剤としては、例えばケイ皮酸ベンジル、パラメトキシケイ皮酸２‐エトキシエチル、パラメトキシケイ皮酸オクチル、ジパラメトキシケイ皮酸モノ‐２‐エチルヘキサン酸グリセリル、パラメトキシケイ皮酸イソプロピル・ジイソプロピルケイ皮酸混合物などが挙げられる。
ウロカニン酸系紫外線吸収剤としては、例えばウロカニン酸、ウロカニン酸エチルなどが挙げられる。
【００４４】
ベンゾフェノン系紫外線吸収剤としては、例えばヒドロキシメトキシベンゾフェノン、ヒドロキシメトキシベンゾフェノンスルホン酸、ヒドロキシメトキシベンゾフェノンスルホン酸ナトリウム、ヒドロキシジメトキシベンゾフェノン、ジヒドロキシジメトキシベンゾフェノンスルホン酸ナトリウム、ジヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、ヒドロキシオクチルベンゾフェノンなどが挙げられる。
【００４５】
ベンゾトリアゾール系紫外線吸収剤としては、例えば２‐（２′‐ヒドロキシ‐５′‐メチルフェニル）ベンゾトリアゾール、２‐（２′‐ヒドロキシ‐３′‐ｔ‐ブチル‐５′‐メチルフェニル）‐５‐クロロベンゾトリアゾール、２‐［２′‐ヒドロキシ‐３′，５′‐ジ（ｔ‐ブチル）フェニル］‐５‐クロロベンゾトリアゾール、２‐［２′‐ヒドロキシ‐３′，５′‐ジ（ｔ‐ブチル）フェニル］ベンゾトリアゾール、２‐［２′‐ヒドロキシ‐３′，５′‐ジ（ｔ‐オクチル）フェニル］ベンゾトリアゾール、２‐［２′‐ヒドロキシ‐３′‐（３″，４″，５″，６″‐テトラヒドロフタルイミドメチル）‐５′‐メチルフェニル］ベンゾトリアゾール、２‐［２′‐ヒドロキシ‐３′，５′‐ジ（ｔ‐アミル）フェニル］ベンゾトリアゾール、メチル‐３‐［３‐（２Ｈ‐ベンゾトリアゾール‐２‐イル）‐５‐ｔ‐ブチル‐４‐ヒドロキシフェニル］プロピオネートとポリエチレングリコール３００の反応生成物（チバスペシャリティケミカルズ社製、商品名「チヌビン１１３０」）などが挙げられる。
【００４６】
これらの紫外線吸収剤は、通常、本発明の保護艶出し剤の他の成分と同時に処方すればよく、また非水溶性の紫外線吸収剤についてはあらかじめ前記の界面活性剤に溶解してから用いてもよい。
上記紫外線吸収剤のうち、素材表面を紫外線から強力に保護するためにはベンゾフェノン系やベンゾトリアゾール系紫外線吸収剤を用いるのが好ましい。
また、チヌビン１１３０のような、ポリエーテル基が付加された紫外線吸収剤は、界面活性作用も示すため界面活性剤量を低減することができるので好ましい。
【００４７】
本発明の保護艶出し剤において、紫外線吸収剤の含有割合は０．０１〜０．５質量％、中でも０．０２〜０．３質量％の範囲とするのが好ましい。この割合が０．０１質量％未満では本来の効果が発揮され難いし、また０．５質量％を超えるとその量に見合う効果の向上が得られにくくなり、むしろ経済的にも不利となる。
【００４８】
本発明の保護艶出し剤としてより好ましいのは、オルガノポリシロキサン５〜５０質量％、界面活性剤０．０１〜２質量％、両親媒性カルボキシビニル系ポリマー０．０１〜０．２質量％、紫外線吸収剤０．０１〜０．５質量％を含有してなり、かつ粘度が１００〜３０００ｃＳｔである水性エマルション型硬表面保護艶出し剤であり、中でも油滴粒子径が１００μｍ未満、中でも５０μｍ未満であるのが好ましく、さらに加えて０．５μｍ以上であるのがより一層好ましい。このような油滴粒子径とすると、油滴の微分散状態を均一に長期間維持しうるし、またエマルションの安定性を高めうるので好ましい。
この好適保護艶出し剤の中でも好ましいのは、オルガノポリシロキサンとしてジメチルポリシロキサン及び／又は変性ジメチルポリシロキサンを用いるか、或いはジメチルポリシロキサン及び／又は変性ジメチルポリシロキサンを主とし、シリコーンレジン及び／又はシリコーンゴムを併用し、かつ両親媒性カルボキシビニル系ポリマーとして一般式
ＣＨ₂＝ＣＲ¹ＣＯＯＲ³
（式中、Ｒ¹は水素原子、ハロゲン原子又は炭素数１〜４のアルキル基を、Ｒ³は炭素数１〜３０のアルキル基をそれぞれ示す）
で表わされるコモノマーと一般式
ＣＨ₂＝ＣＲ²ＣＯＯＨ
（式中、Ｒ²は水素原子、ハロゲン原子又は炭素数１〜４のアルキル基を示す）で表わされるコモノマーとのコポリマーからなるもの、中でもアルキル基が炭素数８〜３０、好ましくは１０〜２６の長鎖であるものや、（メタ）アクリル酸とアルキル基の炭素数が１〜３０、好ましくは８〜３０、特に１０〜２６の（メタ）アクリル酸アルキルの共重合体であって、かつその主鎖同士が架橋された構造を持つものや、（メタ）アクリル酸とアルキル基の炭素数が１〜３０、好ましくは８〜３０、特に１０〜２６の（メタ）アクリル酸アルキルからなるかあるいはこれらを主とするモノマーを、架橋剤の存在下に重合するとともに架橋することにより得られる架橋ポリマーを用いたものであり、中でも特に上記オルガノポリシロキサンのうちジメチルポリシロキサンを用いるか或いはそれを主とし、これにシリコーンレジンや、シリコーンゴムや、変性ジメチルポリシロキサン、中でもアミノ変性ジメチルポリシロキサンやフルオロアルキル変性ジメチルポリシロキサンを組み合わせたものを用いた場合である。
両親媒性カルボキシビニル系ポリマーについては、さらに平均分子量１０万〜５００万、中でも３０万〜３００万、特に５０万〜２００万をもつものが好ましい。
【００４９】
本発明の保護艶出し剤には、その目的をそこなわない範囲で必要に応じて通常保護艶出し剤に用いられる添加成分、例えば熱安定剤、酸化防止剤、防腐剤、顔料、染料、香料、水溶性溶剤等を適宜添加することができる。
【００５０】
本発明の保護艶出し剤は、ディスパ等の撹拌装置を備えた溶解槽に所定の各成分を添加し、撹拌、混合することにより容易に調製することができる。
調製方法として好ましくは、まず、溶媒たる水に両親媒性高分子増粘剤をあらかじめ溶解させる。この際、あらかじめ両親媒性高分子増粘剤の高濃度液を調製しておき、単に水で希釈するだけにしてもよい。次いで、中和剤以外の各配合成分を一緒に或いは順次に添加し、撹拌、混合する。順次に添加する際には、添加順序は特に問わない。配合成分が均一に微分散されたことを確認したのち、中和剤を添加し系を増粘させ微分散状態を安定化させる。このとき、適当な時間、例えば２０分間程度を限度として撹拌を継続すれば、更に均一性に優れたものとすることができる。
また、本発明における高分子増粘剤は両親媒性であるため、最初に溶解させる媒体を油性の保護艶出し剤成分としても何ら差し支えない。この場合は、中和剤を除く他の成分を前記したように添加していき、最後に中和増粘させれば良い。前記と同様、中和後適当な時間撹拌を継続すれば、更に均一性に優れたものとすることができる。
【００５１】
本発明の保護艶出し剤で素材表面を処理するには特に制限はなく、ハンドスプレー等でスプレーすることもできるし、直接あるいはスポンジや布等につけて塗布し塗り広げることもできる。いかなる処理の場合においても、保護艶出し成分が速やかに放出されるため単に塗布するか或いは塗布後軽く拭き上げるだけで非常に優れた光沢を素材表面に付与することができ、形成された保護艶出し膜は長期間にわたり優れた光沢を保ったまま雨水等により流亡することなく保持することができる。
【００５２】
【実施例】
以下実施例により本発明をさらに詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。
なお、分析手段として、ＩＲスペクトルは島津製作所製ＦＴＩＲ−８２００ＰＣ型（ＫＢｒ法で測定）を、また平均分子量は島津製作所製高速液体クロマトグラフィーＬＣ−６ＡＤ（示差屈折率検出器：同ＲＩＤ−６Ａ、カラムＳＨＯＤＥＸ製ＧＰＣ ＫＦ８０５、ポリスチレンの標準曲線使用、溶媒テトラヒドロフラン）をそれぞれ用いて測定した。
【００５３】
合成例１（両親媒性カルボキシビニル系ポリマーの合成）
撹拌器、冷却器、温度制御装置を備えた３００ｍｌ反応容器にメタクリル酸ベヘニル１１．８２ｇ（３０ｍｍｏｌ）、アクリル酸０．２２ｇ（３ｍｍｏｌ）をベンゼン１００ｇと共に仕込み窒素気流下で７０℃まで昇温させた。次いで、２０ｇのベンゼンに溶解させた２，２′‐アゾビス（イソブチロニトリル）（東京化成製試薬）０．０３ｇ（０．１８ｍｍｏｌ）を、窒素気流下、撹拌しながら２０分間かけて滴下した後、８０℃まで更に昇温し１２時間反応を継続させた。反応終了後、反応系を１０℃にまで冷却し、１０倍容量の水を加え撹拌した後、分液ロートにより水相を分取した。分取した水相をエバポレーターにより濃縮後、さらに恒温真空乾燥機にて４０℃で２４時間乾燥させて白色粉末のアクリル酸・メタクリル酸ベヘニル共重合体（平均分子量８０万）９．７４ｇ（収率８２％）を得た。
ＦＴ−ＩＲ（ｃｍ^-1）：２４００〜３４００（−ＣＯＯＨ）、１７２５（−ＣＯＯＲ³）
この共重合体を合成物１と称する。
【００５４】
合成例２（両親媒性カルボキシビニル系ポリマーの合成）
撹拌器、冷却器、温度制御装置を備えた３００ｍｌ反応容器にアクリル酸ステアリル５．１１ｇ（１６ｍｍｏｌ）、アクリル酸ベヘニル３．６７ｇ（１０ｍｍｏｌ）、アクリル酸０．１４ｇ（２ｍｍｏｌ）、ポリエチレン（４ｍｏｌ）グリコールジアクリレート（新中村化学製ＮＫエステルＡ−２００）０．０３ｇ（０．０９ｍｍｏｌ）をベンゼン１００ｇと共に仕込み窒素気流下で６０℃まで昇温させた。次いで、２０ｇのベンゼンに溶解させた２，２′‐アゾビス（イソブチロニトリル）０．０３ｇ（０．１８ｍｍｏｌ）を、窒素気流下、撹拌しながら２０分間かけて滴下した後、８０℃まで更に昇温し２０時間反応を継続させた。反応終了後、反応系を１０℃まで冷却し、１０倍容量の水を加え撹拌した後、分液ロートにより水相を分取した。分取した水相をエバポレーターにより濃縮後、さらに恒温真空乾燥機にて４０℃で２４時間乾燥させて白色粉末のアクリル酸・アクリル酸アルキル架橋型共重合体（平均分子量１８０万）６．３５ｇ（収率７１％）を得た。
ＦＴ−ＩＲ（ｃｍ^-1）：２３００〜３５００（−ＣＯＯＨ）、１７４０（−ＣＯＯＲ³）
この共重合体を合成物２と称する。
【００５５】
実施例１〜２５（ただし実施例１２及び１８〜２０は参考例）、比較例１〜６
上記合成例１、２及び下記に示す各成分の中から表１〜３に示す処方で、同表に示す粘度を有する各種硬表面保護艶出し剤を試料として調製した。
【００５６】
【表１】

【００５７】
【表２】

【００５８】
【表３】

【００５９】
調製方法については次のとおり。
撹拌装置を備えた溶解槽に所定量のイオン交換水を入れ、これに所定高分子増粘剤又は高分子乳化剤を加えて溶解させ、撹拌しながら中和剤を除く他の成分を加えて均一に分散させたのち、中和剤を加えて所定のｐＨに調整し、２０分間撹拌した。これらの操作は全て室温条件下で行った。
なお、高分子増粘剤又は高分子乳化剤があらかじめアルカリ塩等で中和されている場合は、ｐＨ調整操作を省いてもよい。又、各種アルキル変性カルボキシビニル系ポリマーについては、その有効成分に基づいて配合した。
ｐＨは堀場製作所製ガラス電極ｐＨメーター「Ｆ−１３型」で、また粘度は東京科学製Ｂ型粘度計「Ｂ６Ｈ型」でそれぞれ測定した。
【００６０】
各成分については以下のとおり。
・ ＫＦ−９６−１００：信越化学製ストレートジメチルシリコーンオイル、１００ｃＳｔ
・ ＫＦ−９６−３５０：同、３５０ｃＳｔ
・ ＫＦ−９６−１０００：同、１０００ｃＳｔ
・ ＫＦ−９６−３０００：同、３０００ｃＳｔ
・ ＫＦ−９６−６０００：同、６０００ｃＳｔ
・ ＴＳＦ４７０２：ＧＥ東芝シリコーン製側鎖アミノ基変性シリコーン、５００ｃＳｔ
・ ＦＳ１２６５―１０００：東レダウコーニングシリコーン製側鎖フルオロアルキル基変性シリコーン、１０００ｃＳｔ
・ Ｒ．Ａ １０３８：旭化成ワッカーシリコーン製シリコーンレジンの「Ｒｅｌｅａｓｅ Ａｇｅｎｔ １０３８（２０００ｃＳｔ）」の略
・ ノイゲンＥＴ−９５：第一工業製薬製ノニオン系界面活性剤、ポリオキシエチレンアルキルエーテル（合成アルコール系）、ＨＬＢ＝１０．５
・ ノイゲンＥＴ−１０２：同、ポリオキシエチレンラウリルエーテル（天然アルコール系）、ＨＬＢ＝１０．８
・ ノイゲンＥＳ−１６９：同、ポリオキシエチレンオレイン酸エステル、ＨＬＢ＝１３．５
・ プルロニックＬ−６２：旭電化製ノニオン系界面活性剤、ポリオキシエチレンポリオキシプロピレンブロック共重合体
・ テイカライトＮ２０３０：テイカ製アニオン系界面活性剤、ナトリウム高級アルコール硫酸塩
・ ＫＦ−３５１：信越化学製側鎖ポリエーテル基変性シリコーン活性剤、ＨＬＢ＝１４．５
・ ＫＦ−３５４：同、ＨＬＢ＝１８
・ ＫＦ−３５５：同、ＨＬＢ＝１４．４
・ ＳＩＬＷＥＴ ＦＺ−２１６１：日本ユニカー製側鎖ポリエーテル変性シリコーン界面活性剤、ＨＬＢ＝１８
・ ＳＩＬＷＥＴ Ｌ−７６０４：同、ＨＬＢ＝１３
・ ＰＥＭＵＬＥＮ ＴＲ−１：Ｂ．Ｆ．Ｇｏｏｄｒｉｃｈ製アルキル変性カルボキシビニル系ポリマー、粧配基名「アクリル酸・メタクリル酸アルキル共重合体」、ＣＴＦＡ名「Ａｃｒｙｌａｔｅｓ／Ｃ１０−３０ Ａｌｋｙｌ Ａｃｒｙｌａｔｅ Ｃｒｏｓｓｐｏｌｙｍｅｒ」
・ ＰＥＭＵＬＥＮ ＴＲ−２：同
・ ＰＥＭＵＬＥＮ １６２１：同、工業グレード品
・ ＰＥＭＵＬＥＮ １６２２：同、工業グレード品
・ アロン Ａ−１０Ｈ：東亞合成製高分子増粘剤、ポリアクリル酸、有効成分２６％
・ アロン Ａ−７１００：東亞合成製高分子増粘剤、ポリアクリル酸ナトリウム、有効成分２１％
・ アロン Ｂ−５００：東亞合成製高分子増粘剤、アクリル酸メタクリル酸共重合体、有効成分３５％
・ ＳＯＬＡＧＡＭ ＳＦ３０６：ＳＥＰＰＩＣ製アルキル変性カルボキシビニル系ポリマー、有効成分４３％
・ ＳＯＬＡＧＡＭ ＳＨ２１０：同、有効成分５５％
・ ＳＯＬＡＧＡＭ ＳＪ１０８：同、有効成分３５％
・ ＡＣＵＬＹＮ ２２：ロームアンドハース（Ｒｏｈｍ ａｎｄ Ｈａａｓ）製アルキル変性カルボキシビニル系ポリマー、ＣＴＦＡ名「Ａｃｒｙｌａｔｅｓ／Ｓｔｅａｒｅｔｈ−２０ Ｍｅｔｈａｃｒｙｌａｔｅ Ｃｏｐｏｌｙｍｅｒ」、有効成分３０％
・ Ｕｖｉｎｕｌ ＭＳ−４０：ＢＡＳＦ製ベンゾフェノン系紫外線吸収剤、ＣＴＦＡ名「ベンゾフェノン‐４」
・ ＶＩＯＳＯＲＢ ５８３：共同薬品製ベンゾトリアゾール系紫外線吸収剤、化学名「２‐（２′‐ヒドロキシ‐５′‐オクチルフェニル）ベンゾトリアゾール」
・ ＴＩＮＵＶＩＮ（チヌビン） １１３０：チバスペシャリティーケミカルズ製ベンゾトリアゾール系紫外線吸収剤、メチル‐３‐〔３‐（２Ｈ‐ベンゾトリアゾール‐２‐イル）‐５‐ｔ‐ブチル‐４‐ヒドロキシフェニル〕プロピオネートとポリエチレングリコール３００との反応生成物
・ トリエタノールアミン：高分子増粘剤の中和剤
・ 水酸化ナトリウム：高分子増粘剤の中和剤、但し２０％水溶液として使用
【００６１】
各試料の諸性質について以下の試験又は測定方法で調べ、必要に応じ評価した。その結果を、表４及び表５に示す。
【００６２】
（１）油滴粒度分布
試料について、（Ａ）調製直後、（Ｂ）ヤマト科学製低温乾燥器「ＤＫ−６３」で５０℃で１ヶ月間放置後、（Ｃ）長野科学機械製作所製サイクリング試験器「ＬＨ−４０−１３Ｐ型」で１ヶ月放置後、それぞれ油滴粒度分布状態を堀場製作所製レーザ回折／散乱式粒子径分布測定装置「ＬＡ−９２０」で測定し、次の基準で評価した。
◎：５０μｍ以上の油滴が存在しない。
○：１００μｍ以上の油滴が存在しない。
△：１００μｍ以上の油滴が油滴全体の２０％を超えない範囲で存在する。
×：１００μｍ以上の油滴が油滴全体の２０％を超える範囲で存在する。
【００６３】
（２）安定性
試料について、（Ａ）調製直後、（Ｂ）ヤマト科学製低温乾燥器「ＤＫ−６３」で５０℃で１ヶ月間放置後、（Ｃ）長野科学機械製作所製サイクリング試験器「ＬＨ−４０−１３Ｐ型」で１ヶ月放置後、それぞれ乳化状態やその推移を目視で観察した。
◎：完全な乳化状態である。
○：視認可能な油滴がわずかに生じるが水相の分離は認められない。
△：視認可能な油滴がかなり生じるが水相の分離は認められない。
×：油相或いは水相の分離層が生じる。
【００６４】
（３）レベリング性
試料をハンドスプレーガンでタイヤに吹きつけ、スポンジで円周状に３周拭き上げたのち、乾燥し、目視により以下の基準で評価した。
◎：完全な均一膜を形成し塗りむらが全くない。
○：全体に均一膜を形成しているが、至近距離からの目視ではごく一部に濃淡がある。
△：タイヤの一部に明らかな塗りむらがある。
×：タイヤ全面に明らかな塗りむらがある。
【００６５】
（４）光沢
試料をハンドスプレーガンでタイヤに吹きつけ、スポンジで円周状に３周拭き上げ、光沢及びタイヤ面における５×５ｍｍ大の文字の写り込み具合を目視により以下の基準で評価した。
◎：優れた光沢があり、写り込んだ文字がはっきり読みとれる。
○：光沢は明らかにあるが、写り込んだ文字は識別できるもののややぼやけている。
△：光沢はあるものの、写り込んだ文字は輪郭程度しか識別できない。
×：光沢も劣り、写り込んだ文字も識別できない。
【００６６】
（５）撥水性
試料を、あらかじめ中性洗剤で洗浄した天然ゴム試験片（日本テストパネル製、２×３０×１２０ｍｍ）に５０μｌ滴下し、スポンジで均一に塗り広げたのち、１時間乾燥させ、水に対する静止接触角を測定した。
なお、この接触角の測定には、協和界面化学製自動接触角測定装置ＣＡ−Ｚ型を使用した。また、試料塗布前の天然ゴム試験片に対する水の静止接触角は７５°であった。
【００６７】
（６）耐久性（Ｉ）及び（ＩＩ）
試料を、天然ゴム試験片（日本テストパネル大阪製、２×７０×１５０ｍｍ）に１ｍｌ滴下し、スポンジで均一に塗り広げ、乾燥したのち、ＪＩＳ−Ｄ−０２０５に規定される「自動車部品の耐候性試験方法」による屋外直接暴露試験（標準：ＷＯＮ−Ｓ）に従い、２週間、屋外暴露試験を行った。試験期間中、雨は４日間、曇りは１日間、晴れは９日間、平均気温２４℃であった。この試験にはＪＩＳ−Ｚ−２３８１に規定される直接暴露装置を使用し、試料当り３枚の評価試験片と１枚の対比用保存試験片を作成した。
次いで、水流のみで軽く水洗した試験後の試験片について、耐久性（Ｉ）として試験前の試験片に対する光沢及び撥水性の維持の程度を、耐久性（ＩＩ）として耐汚染性を汚れの度合いでそれぞれ目視により観察し、評価した。
評価時には３枚の評価試験片と対比用保存試験片を比較して評価を平均化した。
評価基準は以下のとおりである。
（光沢及び撥水性）
◎：光沢、撥水性共にほぼ変化がない。
○：光沢、撥水性のいずれかで多少劣化する。
△：光沢、撥水性のいずれかで明らかに劣化する。
×：光沢、撥水性共に明らかに劣化する。
（耐汚染性）
◎：ほとんど汚れが付着していない。
○：汚れがあるものの目立たない。
△：汚れがかなり目立つ。
×：よごれがひどい。
【００６８】
（７）保護性
上記耐久性試験と同様にして暴露試験を行ったのち、水流のみで軽く水洗した試験後の試験片のひび割れの発生状態について目視により観察し、以下の基準で評価した。
◎：ひび割れが全く発生していない。
○：視認しにくい微細なひび割れが発生している。
△：試験片の一部に明らかなひび割れが発生している。
×：試験片全面に明らかなひび割れが発生している。
【００６９】
【表４】

【００７０】
【表５】

【００７１】
これより、各実施例の硬表面保護つや出し剤は、界面活性剤をごく少量しか用いていないにも拘わらず、安定性に優れ、また、簡単な操作で基材に塗布するのみで、レベリング性、光沢、撥水性にすぐれた被膜を基材表面に付与することができ、かつこの被膜は耐久性に優れ、しかもこの被膜は基材表面の外観や美観を向上させるだけでなく、基材を十分に保護することも分る。
【００７２】
【発明の効果】
本発明の硬表面保護つや出し剤は、硬表面、中でもゴム‐、レザー‐又は樹脂系表面、特に車両のそれ、例えばタイヤ、バンパー、車室内装部材等の表面に対し、光沢性、安定性、レベリング性、耐久性、保護性に優れた被膜を形成し、この被膜形成処理を塗布するか或いは塗布後簡単に拭き上げるだけで可能とするなど作業性が良好であるという顕著な効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous hard surface protective polish such as an aqueous emulsion type, and more particularly to an aqueous hard surface protective polish having an organopolysiloxane such as dimethylsiloxane as a protective polish component.
[0002]
[Prior art]
Until now, rubber and synthetic resin materials such as automobile tires, vehicle interior front panels, unpainted bumpers, etc. have become extremely aesthetically pleasing due to adhesion of dust, dirt, mud, soot, pitch, etc. Various protective polishes have been used because the appearance is damaged and the surface is cracked due to deterioration due to oxidation or ultraviolet rays, resulting in loss of gloss.
[0003]
As the protective polish, a composition having an organopolysiloxane as an active ingredient is frequently used, which is roughly classified into a solvent type and an aqueous type.
First, the solvent type is one in which an organic solvent is mainly blended with an organopolysiloxane.
Examples of the solvent type include those in which an organopolysiloxane such as dimethyl silicone is dissolved in an organic solvent (JP-A-62-236876, JP-A-8-73815, etc.). Since it invades or swells rubber and synthetic resin materials, and usually uses volatile organic solvents, the working environment is inevitably deteriorated.
[0004]
Some dimethylpolysiloxanes and cyclic dimethylpolysiloxanes are the only active ingredients and are injected with dimethyl ether (JP-A-6-192575, etc.). However, since dimethyl ether evaporates rapidly, dimethylpolysiloxanes Insufficient leveling is required, and it is necessary to carry out the injection operation several times toward the same location. Further, dimethyl ether as a propellant has a problem from the work environment.
[0005]
In addition, some amino-modified silicone oils and water-reactive silicones react with each other in the presence of water to form a rubber film, but there is a risk of gelation due to water mixing during storage.
In any of these solvent types, the organic solvent contained in the blending composition causes the deterioration of the material surface or the working environment.
[0006]
Next, as an example of the aqueous type, there is one obtained by dispersing or emulsifying organopolysiloxane, which is a protective polishing component, in water or an aqueous solvent with a surfactant.
As such an aqueous type, an oil-in-water emulsion, for example, dimethylpolysiloxane as a main component, and a hydrocarbon solvent, various waxes, etc., are blended (Japanese Patent Laid-Open No. 64-90275). JP-A-1-207369, JP-A-8-199199, etc.), a mixed system of fatty acid alkylolamide and sorbitan fatty acid ester as a surfactant, and further water-insoluble or self-emulsifiable polyether-modified silicone oil (For example, Japanese Patent No. 2091515).
[0007]
In these oil-in-water types, it is presumed that the surfactant is adsorbed at the interface between the oily component and the aqueous component to form a kind of liquid crystal state, but it is stabilized, but applied or sprayed on the material. In this case, the organopolysiloxane, which is an active ingredient, is quickly released on the surface of the material and is not easily developed, and may be washed away with the aqueous medium component, and the surfactant is used in a relatively large amount. Protective glazing components on the surface of the material are re-emulsified during washing such as a car wash or when it rains, resulting in inferior durability.If the material is rubber or resin, the remaining surfactant is contained in the interior. In order to bleed out the anti-aging agent, stabilizer, plasticizer and the like that have penetrated and blended into the material, the surface of the material may be deteriorated.
[0008]
Therefore, in order to improve the durability, there are those using amino-modified silicone as the modified organopolysiloxane (Japanese Patent No. 2137896, Japanese Patent Laid-Open No. 11-264000, etc.). In addition, the emulsion becomes unstable and separates during storage, and since the amino group, which is a modified functional group, is a hydrophilic group, an emulsion is formed on the surface of the material, which peels off. May be a difficult soiling material.
In order to prevent this, some amino-modified silicones are acylated with acetic anhydride and the like to protect the amino group (Patent No. 2106166 etc.), but due to destabilization of the formed amide bond by ultraviolet rays in sunlight, etc. Deteriorated and inferior in light resistance and weather resistance.
[0009]
Various types of aqueous emulsions for automobile tires using resins are known (Japanese Patent No. 2509116, Japanese Patent Laid-Open No. 64-171, Japanese Patent Laid-Open No. 7-242857, and Japanese Patent Laid-Open No. 8-239629). However, they cannot follow the expansion and contraction of the tire and may cause peeling or cracking, thereby deteriorating the appearance.
In addition, there are some which use an organopolysiloxane having a silanol group to form a protective glazing film on the surface of a material such as a tire (JP-A-7-305033, JP-A-8-34970, etc.). May be regelled during storage due to the self-condensation of silanol groups, and if it contains an organic solvent to improve storage stability, leveling and emulsifying properties, it will cause problems on the surface of the material and work environment .
[0010]
In addition, there are some which use an emulsified silicone emulsion as an active ingredient and use it together with a cleaning component to polish the surface of a material, particularly the surface of an automobile tire, at the same time as cleaning (Japanese Patent Laid-Open Nos. 63-248897 and 6) No. 192700, etc.), since the cleaning component foams, the uniform adhesion of the silicone component to the material is hindered, and it is difficult to form a silicone film having an excellent appearance.
[0011]
Furthermore, since such an aqueous type is usually emulsified and dispersed using a surfactant as an emulsifier in a large amount of 20 to 40% by mass with respect to the organopolysiloxane, release of the active ingredient into the material, It has the disadvantage that deployment is not quick.
In view of this, a solution in which organopolysiloxane is emulsified in water using a polymer emulsifier has been proposed (Japanese Patent Application Laid-Open No. 10-120981).
In this material, polyacrylic acid, polyacrylic acid salt, acrylic acid-methacrylic acid copolymer or the like is used as a polymer emulsifier. However, these polymer emulsifiers are unlikely to have a high affinity between the acrylic main chain and the organopolysiloxane, and are likely to easily separate the organopolysiloxane phase and the aqueous phase due to aging, It is inferior in heat resistance, and this is also one of the causes of deteriorating storage stability. Furthermore, in the emulsification system using only the polymer emulsifier, those having an oil droplet particle diameter of 100 μm or more are usually included, which causes coalescence of the oil droplets during storage and decreases stability.
[0012]
[Problems to be solved by the invention]
The object of the present invention is to provide gloss, stability, leveling and durability for hard surfaces, especially rubber-, leather- or resin-based surfaces, especially those of vehicles, such as tires, bumpers, interior compartments, etc. To provide an aqueous hard surface protective polish that has good workability, such as forming a film with excellent workability and protection, and applying this film formation treatment or simply wiping it off after application. It is in.
[0013]
[Means for Solving the Problems]
As a result of intensive studies on the aqueous hard surface protective polish having the above-mentioned preferable properties, the present inventors have obtained a state in which an oily protective polish component, particularly an organopolysiloxane, is finely dispersed in water using a surfactant. The polymer thickener having a good affinity (also referred to as amphiphilic) to the polishing component and the medium is suitable for maintaining the oil-based protective polishing component and surfactant. The present inventors have found that a composition containing an ultraviolet absorber together with a predetermined thickener and having a predetermined viscosity can meet the purpose, and based on these findings, the present invention has been made.
[0014]
  That is, the present invention
  (1) Oily protective glazing component 5-50% by weight, nonionic surfactant 0.01-2% by weight, amphiphilic polymer thickener 0.01-0.2% by weight, UV absorber 0.01 ~ 0.5% by mass,
Organopolysiloxane is the oil-based protective polish, and general formula is an amphiphilic polymer thickener.
  CH₂= CR¹COOR^Three
  (Wherein R¹Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, R^ThreeRepresents an alkyl group having 1 to 30 carbon atoms)
Comonomers and general formula
  CH₂= CR²COOH
  (Wherein R²Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms)
The main chain is an alkyl-modified carboxyvinyl polymer composed of a copolymer with a comonomer represented by formula (1) and / or a copolymer structure of (meth) acrylic acid and an alkyl (meth) acrylate having 1 to 30 carbon atoms in the alkyl group. The main chain is cross-linked, or the (meth) acrylic acid and the alkyl group are composed of an alkyl (meth) acrylate having 1 to 30 carbon atoms, or a monomer mainly composed of these is present in the presence of a cross-linking agent. An alkyl-modified carboxyvinyl-based cross-linked polymer that is polymerized and cross-linked underneath,
Furthermore, it contains 0.01 to 0.6% by mass of a hydrophilic silicone surfactant,
And an aqueous hard surface protective polish, characterized in that the viscosity is 100 to 3000 cSt,
Is to provide.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
  As a preferred embodiment of the present invention,
  (2) The hard surface protective polishing agent according to (1), which is an aqueous emulsion type,
  (3) The hard surface protective polishing agent according to (2), wherein the oil droplet particle diameter is less than 100 μm,
  (4) The hard surface protective polish according to any one of (1) to (3), wherein the blending ratio of the surfactant is 0.02 to 10% by mass with respect to the oily protective polish component,
  (5) The hard surface protective polish according to any one of (1) to (4), wherein the viscosity of the organopolysiloxane is 100 to 10000 cSt,
  (6) The hard surface protective polish according to any one of (1) to (5), wherein the organopolysiloxane is dimethylpolysiloxane and / or modified dimethylpolysiloxane.
  (7) The hard surface protective glazing according to any one of (1) to (5), wherein dimethylpolysiloxane and / or modified dimethylpolysiloxane is mainly used as the organopolysiloxane, and the silicone resin and / or silicone rubber is used in combination. Agent,
  (8) The hard surface protective polish according to any one of (1) to (7), wherein the surfactant has an HLB of 8 to 20.
  (9) Organopolysiloxane 5-50% by mass, nonionic surfactant 0.01-2% by mass, amphiphilic carboxyvinyl polymer 0.01-0.2% by mass, ultraviolet absorber 0.01-0. Containing 5% by weight,
Amphiphilic carboxyvinyl polymer is a general formula
  CH₂= CR¹COOR^Three
  (Wherein R¹Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, R^ThreeRepresents an alkyl group having 1 to 30 carbon atoms)
Comonomers and general formula
  CH₂= CR²COOH
  (Wherein R²Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms)
The main chain is an alkyl-modified carboxyvinyl polymer composed of a copolymer with a comonomer represented by formula (1) and / or a copolymer structure of (meth) acrylic acid and an alkyl (meth) acrylate having 1 to 30 carbon atoms in the alkyl group. The main chain is cross-linked, or the (meth) acrylic acid and the alkyl group are composed of an alkyl (meth) acrylate having 1 to 30 carbon atoms, or a monomer mainly composed of these is present in the presence of a cross-linking agent. An alkyl-modified carboxyvinyl-based cross-linked polymer that is polymerized and cross-linked underneath,
Furthermore, it contains 0.01 to 0.6% by mass of a hydrophilic silicone surfactant,
And an aqueous emulsion type hard surface-protecting glazing agent having a viscosity of 100 to 3000 cSt.
  (10) The hard surface protective polishing agent according to (9), wherein the organopolysiloxane is dimethylpolysiloxane and / or modified dimethylpolysiloxane,
  (11) The hard surface protective polishing agent according to the above (9), which mainly comprises dimethylpolysiloxane and / or modified dimethylpolysiloxane as the organopolysiloxane, and a silicone resin and / or silicone rubber.
  (12) The hard surface protective polish according to any one of (9) to (11), wherein the oil droplet particle size is less than 100 μm,
  (13) The hard surface protective polish according to any one of the above (1) to (12), which is for rubber, leather or resin-based surfaces,
  (14) The hard surface protective polish according to any one of (1) to (13), which is for vehicles.
Is mentioned.
[0016]
The hard surface protective polish of the present invention is basically an oily component which is a surface protective polish component, a surfactant for uniformly and finely dispersing this in water, and maintaining this uniform and finely dispersed state for a long period of time. These are amphiphilic polymer thickeners and ultraviolet absorbers that protect the surface of the material, and those of the aqueous emulsion type are preferred.
In the case of the aqueous emulsion type, the oil droplet particle size is preferably less than 100 μm, more preferably less than 50 μm, and even more preferably 0.5 μm or more. Such oil droplet particle diameter is preferable because the finely dispersed state of the oil droplets can be maintained uniformly over a long period of time, and the stability of the emulsion can be improved.
The oil-based protective glazing component used in the present invention is not particularly limited as long as it can protect the hard surface to prevent or suppress defects such as deterioration and impart gloss to the surface.
Hard surfaces are usually hard materials, especially rubber-, leather- or resin surfaces (also referred to as rubber resin-based surfaces), especially vehicle tires, bumpers, interior interior parts, and car body coatings. The entire article may be composed of a single material or a composite material, and the base material is coated with a hard material, especially rubber, leather or resin. It may be coated with an appropriate means such as adhesion.
[0017]
Examples of such oil-based protective glazing components include various synthetic and natural waxes, polymer paraffin, polyethylene glycol (carbowax), organopolysiloxane, and the like. It is desirable to use an organopolysiloxane to provide gloss to the surface and to be able to protect the surface over a long period of time.
[0018]
Although it does not specifically limit about organopolysiloxane, The viscosity in 25 degreeC is 100-10000 cSt, Especially what is 350-6000 cSt is preferable. If the viscosity is less than 100 cSt, the gloss and durability are inferior, and if it exceeds 10000 cSt, the viscosity increases excessively, making it difficult to handle, and it is difficult to form a uniform film by a simple operation.
For dimethylpolysiloxane, this viscosity is A.I. J. et al. Those having an average molecular weight of 6,000 to 60,000, particularly 10,000 to 50,000, as converted by the Barry formula are preferred.
Examples of the organopolysiloxane include those having no functional group, as well as various modified organopolysiloxanes having a functional group, and any of silicone oil, silicone resin, and silicone rubber can be used. It is preferable to use silicone oil mainly and use one or both of silicone resin and silicone rubber. The silicone resin may be used as a silicone varnish.
[0019]
The modified organopolysiloxane has a side chain type, a both-end type, a one-end type, a side-chain both-end type, and the like depending on the form of introduction of the functional group. Functional groups include amino groups, epoxy groups, carboxyl groups, carbinol groups, methacryl groups, mercapto groups, phenol groups, alkoxyl groups, vinyl groups, polyether groups, methylstyryl groups, long chain alkyl groups, higher fatty acids. An ester group, a fluoroalkyl group, a fluoropolyether group, and the like can be mentioned. The modified organopolysiloxane may have one of these functional groups, or may have two or more. Good.
Among these modified organopolysiloxanes, amino-modified organopolysiloxanes, epoxy-modified organopolysiloxanes, mercapto-modified organopolysiloxanes, vinyl-modified organopolysiloxanes, hydroxy-modified organopolysiloxanes, halogen-modified organopolysiloxanes can be used to improve durability. In order to improve water resistance and water repellency, higher fatty acid ester-modified organopolysiloxane, long-chain alkyl-modified organopolysiloxane, fluoroalkyl-modified organopolysiloxane, fluoropolyether-modified organopolysiloxane and the like are preferable.
[0020]
Examples of the silicone oil include straight silicone oil such as dimethylpolysiloxane and various modified silicone oils having functional groups such as amino-modified silicone oil. Among them, dimethylpolysiloxane and various modified products thereof such as amino-modified And fluoroalkyl-modified products are preferred, and those having a viscosity at 25 ° C. of 100 to 10000 cSt, particularly 350 to 6000 cSt are preferred.
These may be used alone or in combination of two or more. As the combination of two or more, a combination of straight silicone oil and amino-modified silicone oil is preferable, and a combination of dimethylpolysiloxane and amino-modified dimethylpolysiloxane or fluoroalkyl-modified dimethylpolysiloxane is particularly preferable. The modified organopolysiloxanes used in such a combination are preferably used in an amount of 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the organopolysiloxane, from the viewpoint of cost effectiveness.
A straight silicone oil such as dimethylpolysiloxane alone can provide a sufficient protective glazing effect, but in order to further improve this effect, various modified organopolysiloxanes such as amino-modified dimethylpolysiloxane are used. It is good.
As for straight dimethyl silicone oil, which is a typical straight silicone oil, commercially available TSF451 series manufactured by GE Toshiba Silicone, KF-96 series manufactured by Shin-Etsu Silicone, SH-200 series manufactured by Toray Dow Corning, L-45 manufactured by Nihon Unicar Series, AK series manufactured by Asahi Kasei Wacker Silicone Co., Ltd., among which dimethylpolysiloxane that falls within the above-mentioned viscosity or average molecular weight range is preferable.
Preferably, dimethylpolysiloxane and / or modified dimethylpolysiloxane is used as the organopolysiloxane, or dimethylpolysiloxane and / or modified dimethylpolysiloxane is mainly used, and a silicone resin and / or silicone rubber is used in combination.
[0021]
In the protective polish of the present invention, the oily protective polish component, especially the organopolysiloxane which may contain a modified product, particularly dimethylpolysiloxane which may contain a modified product, is usually 5 to 50% by mass, preferably Is preferably contained in an amount of 10 to 40% by mass, more preferably 10 to 30% by mass. If the content of the organopolysiloxane is less than 5% by mass, it is difficult to sufficiently obtain a protective glazing effect, and if the content exceeds 50% by mass, no improvement in the effect can be expected, which is preferable from the viewpoint of emulsion stability. Absent.
[0022]
In the present invention, it is necessary to use a surfactant in order to uniformly disperse the oil component, which is a protective polishing component on the material surface, in water. The dispersion at this time is preferably liquid / liquid fine dispersion.
The surfactant is not particularly limited, but generally, a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant can be used.
[0023]
Nonionic surfactants include, for example, polyhydric alcohol fatty acid esters, polyhydric alcohol alkyl ethers, polyoxyethylene ethers, ether esters, nitrogen-containing derivatives, polymers, fluorine-containing derivatives, silicones, poly Peptide type, natural type and the like can be mentioned.
Examples of the polyhydric alcohol fatty acid ester nonionic surfactant include propylene glycol monofatty acid ester, ethylene glycol monofatty acid ester, glycerin monofatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, and methylglucoside fatty acid ester.
Examples of the polyhydric alcohol alkyl ether nonionic surfactant include alkyl polyglucoside.
Examples of the polyoxyethylene ether nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene phytostanol, polyoxyethylene cholesterol, polyoxyethylene cholestanol, polyoxyethylene polyoxypropylene alkyl ether, Examples include polyoxyethylene lanolin alcohol ether, polyoxyethylene glycol, polyoxypropylene glycol and the like.
Examples of the ether ester-based nonionic surfactant include polyoxyethylene mono fatty acid ester, polyethylene glycol difatty acid ester, polyoxyethylene fatty acid diester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitol fatty acid ester, orioxyethylene methyl glucoside fatty acid. Esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene animal and vegetable oils, polyoxyethylene alkyl ether fatty acid ester, polyoxyethylene polyoxypropylene glycol, special polyoxyalkylene fatty acid ester, polyoxyethylene lanolin fatty acid ester, etc. Can be mentioned.
Examples of the nitrogen-containing derivative nonionic surfactant include polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, alkyl diethanolamide, alkyl alkanolamide, alkylamine oxide and the like.
Examples of the polymer nonionic surfactant include polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene random polymer, polyoxyethylene rosin ester, condensate of ethylenediamine and polyoxyethylene polyoxypropylene block polymer, etc. Is mentioned.
[0024]
Examples of the anionic surfactant include carboxylate, sulfonate, sulfate, phosphate, and the like.
Examples of carboxylate anionic surfactants include fatty acid salts, alkyl ether carboxylates, fatty acid amide ether carboxylates, acyl lactates, N-acyl glutamates, N-acyl alanine salts, N-acyl sarcosine salts, And N-acyl-ω-amino acid salts.
Examples of the sulfonate anionic surfactant include alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid methyl ester salt, acyl isethionate, alkyl glycidyl ether sulfonate, alkyl sulfosuccinate, and dialkyl sulfosuccinate. Acid ester salts, alkyl sulfoacetates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, N-acyl methyl taurates, formalin condensed sulfonates, and the like can be used.
Examples of sulfate anionic surfactants include alkyl sulfates, alkyl ether sulfates, alkyl aryl ether sulfates, fatty acid alkanolamide sulfates, fatty acid monoglyceride sulfates, and the like.
Examples of the phosphate anionic surfactant include alkyl phosphates, polyoxyethylene alkyl ether phosphates, alkylaryl ether phosphates, fatty acid amide ether phosphates, and the like.
[0025]
Examples of amphoteric surfactants include alkylaminocarboxylic acid-based, alkylcarboxybetaine-based, alkylimidazoline-based, glycine-based, aminopropion-based, sulfobetaine-based, sulfonic acid-based, sulfuric acid-based and phosphoric acid-based agents. .
[0026]
Examples of the cationic surfactant include aliphatic amine salts, quaternary ammonium salts thereof, cyclic quaternary ammonium salts, and the like.
Examples of aliphatic amine salt cationic surfactants include primary amine salts, secondary amine salts, tertiary amine salts, aliphatic amidoamine salts, alkyltrialkylene glycol amine salts, alkyl ether amine salts, amine oxide salts, and the like. Can be mentioned.
Examples of the cyclic quaternary ammonium salt cationic surfactant include benzaconium salts, benzethonium salts, pyrididium salts, imidazolium salts, and the like.
[0027]
These surfactants may be used singly or in combination of two or more, but it is desirable to use anionic surfactants and nonionic surfactants from the viewpoint of emulsion stability and handleability. .
Further, the surfactant preferably has an HLB of 8 to 20, more preferably 10 to 18, particularly in the case of a nonionic surfactant.
[0028]
In the protective polish of the present invention, the surfactant content is in the range of 0.01 to 2% by mass, preferably 0.1 to 1% by mass, so that the amount of the surfactant is extremely small in view of safety and the environment. This is preferable from the viewpoint of reducing the load. If this ratio is less than 0.01% by mass, the oily protective polishing component is not sufficiently finely dispersed in water. If it exceeds 2% by mass, the finely dispersed state is too stabilized and effective on the surface of the material. Rapid release development of components is less likely to occur.
[0029]
In the protective polish of the present invention, it is preferable to use hydrophilic silicone in order to more uniformly and finely disperse the oily protective polish component in water more effectively. Examples of the hydrophilic silicone include silicones having hydrophilic functional groups such as polyether groups (polyoxyethylene groups, polyoxyethylene polyoxypropylene groups, etc.), amino groups, etc., and particularly hydrophilic silicones having surface active ability. Of these surfactants, polyether-modified surfactants are preferred. As for the hydrophilic silicone, examples of the functional group introduction type include a side chain introduction type, a one-end introduction type, and a both-end introduction type.
[0030]
In particular, in the case of hydrophilic silicone surfactants, particularly those modified with polyether, when the organopolysiloxane is used as the oily protective polish component, the polysiloxane main chain of the hydrophilic silicone surfactant is the protective polish. In order to show a good affinity with the taking-out component, it exhibits good miscibility even with a high HLB such as HLB 10 or more, and can be used in an extremely small amount compared to general surfactants. For this reason, it is particularly preferable because the active ingredient can be promptly released and developed when the protective polish is applied to the target material.
In addition, hydrophilic silicone surfactants, especially those modified with polyethers, are water-soluble when organopolysiloxane is used as an oily protective glazing component in order to liquid / liquid finely disperse it in the medium water. It is desirable that Therefore, it is preferable that the HLB is 10 or more, especially 12 or more.
[0031]
As such hydrophilic silicones, for example, polyether-modified silicones, those generally marketed as “silicone surfactants” can be used.
Typical examples include KF-351, KF-354, and KF-355 manufactured by Shin-Etsu Silicone, SH3771, SH3772, SH3773, SH3775, SH3746, etc. manufactured by Toray Dow Corning, and TSF-4440 manufactured by GE Toshiba Silicone. , TSF-4441, TSF-4452, etc., SILWET series manufactured by Nihon Unicar, FZ-2104, FZ-2105, FZ-2118, FZ-2123, FZ-2161, FZ-2162, FZ-2163, FZ-2164 FZ-2165, L-7604 and the like, L-03, L-051 and the like manufactured by Asahi Kasei Wacker Silicone. Of these, there is no problem even if any of them is used. However, when organopolysiloxane is used as a protective polish component, it takes into consideration its affinity, solubility in water, its fine dispersion ability and handling properties. Then, KF-351, KF-354, KF-355, SH3771, SH3772, TSF-4440, FZ-2104, FZ-2105, FZ-2118, FZ-2161, FZ-2162, FZ-2163, L-7604, It is preferable to use L-051 or the like.
[0032]
These silicone surfactants may be used alone without using the other surfactants described above, or may be used in combination with other surfactants.
Moreover, when using hydrophilic silicone including a hydrophilic silicone type surfactant in the protective polish of this invention, the content rate is 0.01-0.6 mass%, especially 0.05-0.3. It is preferable to set it as the range of the mass%. When this ratio is 0.01% by mass, the fine dispersion ability is hardly exhibited, and when it exceeds 0.6% by mass, the finely dispersed state is too stabilized and the active ingredient is rapidly released onto the surface of the material. Is less likely to occur.
[0033]
In the protective polish of the present invention, it is preferable to prepare such that the blending ratio of the surfactant to the oily protective polish component is 0.02 to 10% by mass. If this proportion is less than 0.02% by mass, it is difficult to obtain a fine dispersion effect sufficiently, and if it exceeds 10% by mass, the fine dispersion state is too stabilized, and the active ingredient is rapidly released and developed on the surface of the material. Less likely to occur.
[0034]
In the protective polish of the present invention, the rheology of the aqueous phase as a medium is changed, and the oily protective polish component as an active ingredient is maintained in a liquid / liquid finely dispersed state in water for a long period of time by a surfactant. Amphiphilic polymer thickeners are used.
As described above, the amphiphilic polymer thickener is a polymer thickener having a good affinity for water, which is an amphiphilic or oily protective polishing component and a medium.
[0035]
The amphiphilic polymer thickener is preferably an amphiphilic carboxyvinyl polymer.
As the amphiphilic carboxyvinyl polymer, an alkyl-modified carboxyvinyl polymer, in which an alkyl group is a long chain having 8 or more carbon atoms, preferably 8 to 30, particularly 10 to 26, is preferable. Examples thereof include crosslinkable polymers obtained by polymerizing an acid, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc., or by polymerizing and crosslinking a monomer mainly composed of an unsaturated carboxylic acid in the presence of a crosslinking agent. It is done. Examples of the crosslinking agent include ethylene glycol diacrylate, divinylbenzene, polyallyl compounds (for example, polyallyl sucrose), polyepoxide, and the like.
The alkyl-modified carboxyvinyl polymer is preferably a general formula.
CH₂= CR¹COOR^Three
(Wherein R¹Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, R^ThreeRepresents an alkyl group having 1 to 30 carbon atoms)
Comonomers and general formula
CH₂= CR²COOH
(Wherein R²Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms)
Comprising a copolymer with a comonomer represented by^ThreeIn which the alkyl group is a long chain having 8 to 30, preferably 10 to 26 carbon atoms, or (meth) acrylic acid and the alkyl group have 1 to 30 carbon atoms, preferably 8 to 30 carbon atoms, particularly 10 to 26 carbon atoms. The main chain is a copolymer structure with (meth) alkyl acrylate and the main chain is cross-linked, or (meth) acrylic acid and the alkyl group have 1 to 30 carbon atoms, preferably 8 To 30 and especially 10 to 26 alkyl (meth) acrylates or a crosslinkable polymer obtained by polymerizing and crosslinking a monomer mainly composed of these in the presence of a crosslinking agent, for example, a general formula
[Chemical 1]

(Wherein R^Four, R^FiveAre the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 30, preferably 8 to 30, particularly 10 to 26 carbon atoms, and R⁶, R⁷, R⁸, R⁹Are at least one hydrogen atom and are the same as or different from each other, and are a hydrogen atom or an alkyl group having 1 to 30, preferably 8 to 30, particularly 10 to 26 carbon atoms, n, n ′, M, m ′ and l are any numbers that give a suitable high molecular weight as a whole of this general formula, and k is 1 to 10)
And a crosslinkable polymer represented by the formula:
[0036]
The amphiphilic carboxyvinyl polymer is preferably one having an average molecular weight of 100,000 to 5,000,000, particularly 300,000 to 3,000,000, particularly 500,000 to 2,000,000.
[0037]
As the amphiphilic carboxyvinyl polymer, a suitable commercial product can be used as it is.
As this commercial item, for example, B.I. F. Goodrich PEMULEN (eg TR-1, TR-2, 1621, 1622, etc.), Carbopol (eg 1610, 1623, 1382, 1342, ETD2020 etc.), SEPPIC SOLAGAM (eg SF306, SH210, SJ108 etc.) ), Toa Gosei Kogyo B-300, B-500, etc., Rohm and Haas ACUSOL (for example, 820, 880, 882, etc.), ACULYN (for example, 22), etc., among others PEMULEN TR -1, PEMULEN TR-2, PEMULEN 1621, PEMULEN 1622, SOLAGAM SF306, SOLAGAM SH210, SOLAGAM SJ108, and ACULYN22 are preferable.
In addition, hydrophilic polymers such as polyacrylic acid, polyacrylic acid salt (for example, sodium salt), and acrylic acid-methacrylic acid copolymer that are not modified with an alkyl group include an oily protective polish component, especially organopoly There is almost no affinity for siloxane, and there is almost no effect of sustaining the fine dispersion state.
[0038]
The amphiphilic polymer thickener may show a thickening effect simply by blending it, but it shows a thickening effect by appropriately adjusting the pH such as neutralization with a pH adjuster, for example. Such examples include the above-mentioned various amphiphilic carboxyvinyl polymers, and the polymer is thickened by neutralizing the carboxyl group with a basic substance.
[0039]
In this case, the basic substance used as a neutralizing agent is not particularly limited. However, in view of safety, influence on the material surface, handling property, etc., in general, sodium hydroxide, potassium hydroxide, hydroxide Ammonium, monoethanolamine, diethanolamine, triethanolamine, basic amino acids (eg histidine, lysine, arginine, etc.), monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, 2 -Amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, polyoxyethylenetriethanolamine, etc., among others, sodium hydroxide, potassium hydroxide, Monoethanolamine, diethano Amines, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, polyoxyethylene triethanolamine are preferred, particularly polyoxyethylene triethanolamine can reduce the amount of the surfactant used preferably.
When these basic substances are used, they may be added so that the pH of the desired protective polishing agent is 5 to 9, and the influence and safety on the material and the human body, oily protective polishing components, especially organopolysiloxane In view of the dispersion stabilizing effect and the like, it is more preferable to add so that the pH is adjusted to 6-8.
[0040]
In the protective polish of the present invention, the content of the amphiphilic polymer thickener is preferably 0.01 to 0.2% by mass, and more preferably 0.02 to 0.15% by mass. If this ratio is less than 0.01% by mass, the thickening effect is hardly exhibited, and if it exceeds 0.2% by mass, the viscosity increases so that it becomes difficult to handle.
[0041]
It is important that the protective polish of the present invention is thus thickened with an amphiphilic polymer thickener and adjusted to a viscosity in the range of 100 to 3000 cSt, preferably 150 to 2000 cSt. If the viscosity is less than 100 cSt, the fine dispersion stability decreases, and if it exceeds 3000 cSt, it becomes difficult to handle because of high viscosity, and it is difficult to obtain uniformity quickly when applied or sprayed on the material surface.
[0042]
The surface of the material is protected from sunlight by the ultraviolet absorbent used in the protective polish of the present invention.
The ultraviolet absorber is not particularly limited, and examples thereof include benzoic acid-based, salicylic acid-based, cinnamic acid-based, urocanic acid-based, benzophenone-based, and benzotriazole-based materials, octyl triazone, anthranic acid menthyl, ethyl 2-cyano- Examples include 3,3-diphenyl acrylate and octyl 2-cyano-3,3-diphenyl acrylate.
[0043]
Examples of the benzoic acid ultraviolet absorber include paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N-di (2-hydroxy). Propyl) amino] ethyl benzoate and the like.
Examples of the salicylic acid ultraviolet absorber include ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, homomenthyl salicylate, and the like.
Examples of the cinnamic acid UV absorber include benzyl cinnamate, 2-ethoxyethyl paramethoxycinnamate, octyl paramethoxycinnamate, di-2-methoxycinnamate mono-2-ethylhexanoate glyceryl, paramethoxy Examples thereof include isopropyl cinnamate / diisopropyl cinnamate mixture.
Examples of urocanic acid-based ultraviolet absorbers include urocanic acid and ethyl urocanate.
[0044]
Examples of the benzophenone-based ultraviolet absorber include hydroxymethoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, hydroxydimethoxybenzophenone, dihydroxydimethoxybenzophenone sodium sulfonate, dihydroxybenzophenone, tetrahydroxybenzophenone, hydroxyoctylbenzophenone, and the like. It is done.
[0045]
Examples of the benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 -Chlorobenzotriazole, 2- [2'-hydroxy-3 ', 5'-di (t-butyl) phenyl] -5-chlorobenzotriazole, 2- [2'-hydroxy-3', 5'-di ( t-butyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-di (t-octyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-di (t-amyl) phenyl] base Reaction product of zotriazole, methyl-3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and polyethylene glycol 300 (trade name, manufactured by Ciba Specialty Chemicals) “Tinubin 1130”) and the like.
[0046]
These ultraviolet absorbers are usually formulated at the same time as other components of the protective polish of the present invention. In addition, water-insoluble ultraviolet absorbers are used after being dissolved in the surfactant in advance. Also good.
Among the ultraviolet absorbers, it is preferable to use a benzophenone-based or benzotriazole-based ultraviolet absorber in order to strongly protect the material surface from ultraviolet rays.
In addition, an ultraviolet absorber to which a polyether group is added, such as tinuvin 1130, is preferable because it also exhibits a surface-active action and can reduce the amount of the surface-active agent.
[0047]
In the protective polish of the present invention, the content of the ultraviolet absorber is preferably 0.01 to 0.5% by mass, and more preferably 0.02 to 0.3% by mass. If this ratio is less than 0.01% by mass, the original effect is hardly exhibited, and if it exceeds 0.5% by mass, it is difficult to improve the effect commensurate with the amount, which is disadvantageous economically.
[0048]
More preferable as the protective polish of the present invention is 5 to 50% by weight of organopolysiloxane, 0.01 to 2% by weight of a surfactant, 0.01 to 0.2% by weight of an amphiphilic carboxyvinyl polymer, It is an aqueous emulsion type hard surface protective polish that contains 0.01 to 0.5% by weight of an ultraviolet absorber and has a viscosity of 100 to 3000 cSt. In particular, the oil droplet particle size is less than 100 μm, especially less than 50 μm. It is preferable that the thickness is 0.5 μm or more. Such oil droplet particle diameter is preferable because the finely dispersed state of the oil droplets can be maintained uniformly over a long period of time, and the stability of the emulsion can be improved.
Among these preferred protective polishes, dimethylpolysiloxane and / or modified dimethylpolysiloxane is used as the organopolysiloxane, or dimethylpolysiloxane and / or modified dimethylpolysiloxane is mainly used as a silicone resin and / or General formula as amphiphilic carboxyvinyl polymer with silicone rubber
CH₂= CR¹COOR^Three
(Wherein R¹Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, R^ThreeRepresents an alkyl group having 1 to 30 carbon atoms)
Comonomers and general formula
CH₂= CR²COOH
(Wherein R²Represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms), and among them, the alkyl group is a long chain having 8 to 30 carbon atoms, preferably 10 to 26 carbon atoms. Or a copolymer of (meth) acrylic acid and an alkyl group having 1 to 30 carbon atoms, preferably 8 to 30 carbon atoms, especially 10 to 26 (meth) acrylic acid alkyl chains, and their main chains are cross-linked. Or a (meth) acrylic acid and an alkyl group having 1 to 30, preferably 8 to 30, particularly 10 to 26 alkyl (meth) acrylate, or mainly composed of these. A monomer is used in the presence of a crosslinking agent and a crosslinked polymer obtained by crosslinking is used. Hexane was used or it mainly, to which, silicone resin, silicone rubber, modified dimethylpolysiloxane, a case of using a combination of inter alia amino-modified dimethylpolysiloxane and fluoroalkyl-modified dimethylpolysiloxane.
As for the amphiphilic carboxyvinyl polymer, those having an average molecular weight of 100,000 to 5,000,000, particularly 300,000 to 3,000,000, particularly 500,000 to 2,000,000 are preferable.
[0049]
In the protective polish of the present invention, additives that are usually used in the protective polish, as necessary, such as heat stabilizers, antioxidants, preservatives, pigments, dyes, fragrances, as long as the purpose is not lost. A water-soluble solvent or the like can be appropriately added.
[0050]
The protective polish of the present invention can be easily prepared by adding predetermined components to a dissolution tank equipped with a stirring device such as a disperser, stirring and mixing.
Preferably as a preparation method, first, an amphiphilic polymer thickener is first dissolved in water as a solvent. At this time, a high concentration solution of the amphiphilic polymer thickener may be prepared in advance and simply diluted with water. Subsequently, each compounding component other than the neutralizing agent is added together or sequentially, and stirred and mixed. When adding sequentially, the addition order is not particularly limited. After confirming that the compounding ingredients are uniformly finely dispersed, a neutralizing agent is added to thicken the system and stabilize the finely dispersed state. At this time, if stirring is continued for an appropriate time, for example, about 20 minutes, the uniformity can be further improved.
Moreover, since the polymer thickener in the present invention is amphiphilic, the medium to be dissolved first can be used as an oily protective polish component. In this case, other components except for the neutralizing agent may be added as described above, and finally neutralized and thickened. Similarly to the above, if the stirring is continued for an appropriate time after neutralization, the uniformity can be further improved.
[0051]
There is no restriction | limiting in particular in processing the raw material surface with the protective polishing agent of this invention, It can spray by hand spray etc., and can also apply | coat and spread directly, or it attaches to sponge or cloth. In any treatment, the protective glazing component is released quickly, so it can be applied to the surface of the material by simply applying it or by wiping it lightly. The discharge film can be held without being washed away by rainwater or the like while maintaining an excellent gloss over a long period of time.
[0052]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
As an analysis means, IR spectrum is FTIR-8200PC type (measured by KBr method) manufactured by Shimadzu Corporation, and average molecular weight is high performance liquid chromatography LC-6AD (differential refractive index detector: RID-6A, manufactured by Shimadzu Corporation) Columns were measured using GPC KF805 manufactured by SHODEX, standard polystyrene curve, solvent tetrahydrofuran).
[0053]
Synthesis Example 1 (Synthesis of amphiphilic carboxyvinyl polymer)
A 300 ml reaction vessel equipped with a stirrer, a cooler and a temperature controller was charged with 11.82 g (30 mmol) of behenyl methacrylate and 0.22 g (3 mmol) of acrylic acid together with 100 g of benzene, and the temperature was raised to 70 ° C. under a nitrogen stream. . Next, 0.03 g (0.18 mmol) of 2,2′-azobis (isobutyronitrile) (a reagent made by Tokyo Chemical Industry) dissolved in 20 g of benzene was added dropwise over 20 minutes with stirring under a nitrogen stream. Thereafter, the temperature was further raised to 80 ° C., and the reaction was continued for 12 hours. After completion of the reaction, the reaction system was cooled to 10 ° C., 10 volumes of water was added and stirred, and then the aqueous phase was separated using a separatory funnel. The separated aqueous phase is concentrated by an evaporator, and further dried by a constant temperature vacuum dryer at 40 ° C. for 24 hours to obtain 9.74 g of a white powdery acrylic acid / behenyl methacrylate copolymer (average molecular weight 800,000) (yield) 82%).
FT-IR (cm^-1): 2400-3400 (-COOH), 1725 (-COOR)^Three)
This copolymer is referred to as “Composite 1”.
[0054]
Synthesis Example 2 (Synthesis of amphiphilic carboxyvinyl polymer)
Stearate acrylate 5.11 g (16 mmol), behenyl acrylate 3.67 g (10 mmol), acrylic acid 0.14 g (2 mmol), polyethylene (4 mol) glycol in a 300 ml reaction vessel equipped with stirrer, cooler and temperature controller 0.03 g (0.09 mmol) of diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-200) was charged together with 100 g of benzene and heated to 60 ° C. under a nitrogen stream. Next, 0.02 g (0.18 mmol) of 2,2′-azobis (isobutyronitrile) dissolved in 20 g of benzene was added dropwise over 20 minutes with stirring under a nitrogen stream, and further to 80 ° C. The temperature was raised and the reaction was continued for 20 hours. After completion of the reaction, the reaction system was cooled to 10 ° C., 10 volumes of water was added and stirred, and then the aqueous phase was separated with a separatory funnel. The separated aqueous phase is concentrated by an evaporator, and further dried at 40 ° C. for 24 hours by a constant temperature vacuum dryer to obtain 6.35 g of a white powdery acrylic acid / alkyl acrylate cross-linked copolymer (average molecular weight 1.8 million) ( Yield 71%).
FT-IR (cm^-1): 2300-3500 (-COOH), 1740 (-COOR)^Three)
This copolymer is referred to as a composite 2.
[0055]
Examples 1 to 25 (Examples 12 and 18 to 20 are reference examples), Comparative Examples 1 to 6
  Various hard surface protective polishes having the viscosities shown in Table 1 to 3 were prepared as samples from the synthesis examples 1 and 2 and the components shown below.
[0056]
[Table 1]

[0057]
[Table 2]

[0058]
[Table 3]

[0059]
The preparation method is as follows.
Put a predetermined amount of ion-exchanged water in a dissolution tank equipped with a stirrer, add a predetermined polymer thickener or polymer emulsifier to dissolve it, and add the other ingredients except the neutralizer while stirring. After the dispersion, a neutralizing agent was added to adjust to a predetermined pH, and the mixture was stirred for 20 minutes. All these operations were performed at room temperature.
In addition, when the polymer thickener or the polymer emulsifier is previously neutralized with an alkali salt or the like, the pH adjustment operation may be omitted. Various alkyl-modified carboxyvinyl polymers were blended based on their active ingredients.
The pH was measured with a glass electrode pH meter “F-13” manufactured by HORIBA, Ltd., and the viscosity was measured with a B-type viscometer “B6H type” manufactured by Tokyo Scientific.
[0060]
Each component is as follows.
・ KF-96-100: Shin-Etsu Chemical straight dimethyl silicone oil, 100 cSt
・ KF-96-350: 350 cSt
・ KF-96-1000: Same as above, 1000 cSt
・ KF-96-3000: 3000cSt
・ KF-96-6000: Same as above, 6000 cSt
TSF4702: GE Toshiba Silicone side chain amino group-modified silicone, 500 cSt
FS 1265-1000: Toray Dow Corning silicone side chain fluoroalkyl group-modified silicone, 1000 cSt
・ R. A 1038: Abbreviation of “Release Agent 1038 (2000 cSt)” of silicone resin made by Asahi Kasei Wacker Silicone
-Neugen ET-95: Daiichi Kogyo Seiyaku nonionic surfactant, polyoxyethylene alkyl ether (synthetic alcohol), HLB = 10.5
Neugen ET-102: Same as above, polyoxyethylene lauryl ether (natural alcohol type), HLB = 10.8
Neugen ES-169: Same as above, polyoxyethylene oleate, HLB = 13.5
Pluronic L-62: Nonionic surfactant produced by Asahi Denka, polyoxyethylene polyoxypropylene block copolymer
・ Taikalite N2030: Anionic surfactant made by Taika, sodium higher alcohol sulfate
KF-351: Shin-Etsu Chemical side chain polyether group-modified silicone activator, HLB = 14.5
・ KF-354: HLB = 18
・ KF-355: Same as above, HLB = 14.4
SILWET FZ-2161: side chain polyether modified silicone surfactant manufactured by Nihon Unicar, HLB = 18
・ SILWET L-7604: Same as HLB = 13
PEMULEN TR-1: B. F. Goodrich's alkyl-modified carboxyvinyl polymer, makeup group name "acrylic acid / alkyl methacrylate copolymer", CTFA name "Acrylates / C10-30 Alkyl Acrylate Crosspolymer"
・ PEMULEN TR-2: Same
・ PEMULEN 1621: Industrial grade product
・ PEMULEN 1622: Industrial grade product
-Aron A-10H: Toagosei high molecular thickener, polyacrylic acid, 26% active ingredient
-Aron A-7100: Polymer thickener manufactured by Toagosei, sodium polyacrylate, 21% active ingredient
Aron B-500: Toagosei Co., Ltd. polymer thickener, acrylic acid / methacrylic acid copolymer, 35% active ingredient
SOLAGAM SF306: SEPPIC alkyl-modified carboxyvinyl polymer, active ingredient 43%
・ SOLAGAM SH210: Same as above, 55% active ingredient
・ SOLAGAM SJ108: Same as above, 35% active ingredient
ACULYN 22: Rohm and Haas alkyl-modified carboxyvinyl polymer, CTFA name “Acrylates / Steareth-20 Methacrylate Copolymer”, active ingredient 30%
Uvinul MS-40: a benzophenone UV absorber manufactured by BASF, CTFA name “benzophenone-4”
VIOSORB 583: Benzotriazole UV absorber manufactured by Kyodo Pharmaceutical, chemical name “2- (2′-hydroxy-5′-octylphenyl) benzotriazole”
TINUVIN 1130: Benzotriazole UV absorber from Ciba Specialty Chemicals, methyl-3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate Reaction product with polyethylene glycol 300
・ Triethanolamine: Neutralizing agent for polymer thickener
・ Sodium hydroxide: Neutralizing agent for polymer thickener, but used as 20% aqueous solution
[0061]
Various properties of each sample were examined by the following test or measurement method, and evaluated as necessary. The results are shown in Tables 4 and 5.
[0062]
(1) Oil droplet size distribution
Samples were (A) immediately after preparation, (B) left at 50 ° C. for 1 month in a low temperature dryer “DK-63” manufactured by Yamato Scientific, and (C) a cycling tester “LH-40-13P manufactured by Nagano Scientific Machinery Co., Ltd.” After being allowed to stand for 1 month in the “type”, the particle size distribution state of the oil droplets was measured with a laser diffraction / scattering particle size distribution measuring device “LA-920” manufactured by Horiba, Ltd., and evaluated according to the following criteria.
A: There are no oil droplets of 50 μm or more.
○: There are no oil droplets of 100 μm or more.
(Triangle | delta): The oil droplet of 100 micrometers or more exists in the range which does not exceed 20% of the whole oil droplet.
X: Oil droplets of 100 μm or more exist in a range exceeding 20% of the whole oil droplets.
[0063]
(2) Stability
Samples were (A) immediately after preparation, (B) left at 50 ° C. for 1 month in a low temperature dryer “DK-63” manufactured by Yamato Scientific, and (C) a cycling tester “LH-40-13P manufactured by Nagano Scientific Machinery Co., Ltd.” After standing for 1 month in the “mold”, the emulsified state and its transition were visually observed.
A: Completely emulsified state.
○: Visible oil droplets are slightly generated, but separation of the aqueous phase is not recognized.
Δ: Visible oil droplets are considerably generated, but separation of the aqueous phase is not recognized.
X: Separation layer of oil phase or water phase occurs.
[0064]
(3) Leveling properties
The sample was sprayed on the tire with a hand spray gun, wiped with a sponge three times in a circumferential manner, dried, and visually evaluated according to the following criteria.
A: A completely uniform film is formed and there is no uneven coating.
◯: A uniform film is formed on the entire surface, but there is only a slight shade when visually observed from a close distance.
(Triangle | delta): There exists clear coating nonuniformity in a part of tire.
X: There is clear coating unevenness on the entire surface of the tire.
[0065]
(4) Gloss
The sample was sprayed on the tire with a hand spray gun, wiped with a sponge three times in a circumferential manner, and gloss and the appearance of a 5 × 5 mm large letter on the tire surface were visually evaluated according to the following criteria.
A: Excellent gloss, and the reflected characters can be read clearly.
○: The gloss is clear, but the reflected characters are slightly blurred although they can be identified.
Δ: Although glossy, the reflected characters can be distinguished only by the outline.
X: The gloss is inferior and the reflected characters cannot be identified.
[0066]
(5) Water repellency
50 μl of the sample was dropped onto a natural rubber test piece (manufactured by Nippon Test Panel, 2 × 30 × 120 mm) previously washed with a neutral detergent, spread evenly with a sponge, dried for 1 hour, and static contact angle with water Was measured.
For the measurement of the contact angle, an automatic contact angle measuring device CA-Z type manufactured by Kyowa Interface Chemical was used. Moreover, the static contact angle of water with respect to the natural rubber test piece before the sample application was 75 °.
[0067]
(6) Durability (I) and (II)
1 ml of a sample is dropped on a natural rubber test piece (manufactured by Nippon Test Panel Osaka, 2 × 70 × 150 mm), spread evenly with a sponge, dried, and then, according to JIS-D-0205, “Weather resistance of automobile parts” The outdoor exposure test was conducted for 2 weeks according to the outdoor direct exposure test (standard: WON-S) according to the “Testing method”. During the test period, rain was 4 days, cloudy was 1 day, clear was 9 days, and average temperature was 24 ° C. In this test, a direct exposure apparatus specified in JIS-Z-2381 was used, and three evaluation test pieces and one comparison storage test piece were prepared per sample.
Next, with respect to the test piece after the test which was washed lightly with only a water flow, the degree of maintenance of gloss and water repellency with respect to the test piece before the test as durability (I), and the stain resistance as the degree of durability (II) Each was visually observed and evaluated.
At the time of evaluation, three evaluation test pieces and a comparison storage test piece were compared and averaged.
The evaluation criteria are as follows.
(Gloss and water repellency)
A: There is almost no change in both gloss and water repellency.
○: Slightly deteriorated in either gloss or water repellency.
Δ: Clearly deteriorated in either gloss or water repellency.
X: Both gloss and water repellency are clearly deteriorated.
(Contamination resistance)
A: Almost no dirt is attached.
○: Dirt is not noticeable.
Δ: Dirt is quite noticeable.
X: The dirt is terrible.
[0068]
(7) Protection
After performing an exposure test in the same manner as the above durability test, the occurrence of cracks in the test piece after the test that was lightly washed with only a water flow was visually observed and evaluated according to the following criteria.
A: No cracks are generated.
○: Fine cracks that are difficult to visually recognize have occurred.
(Triangle | delta): The clear crack has generate | occur | produced in a part of test piece.
X: Clear cracks are generated on the entire surface of the test piece.
[0069]
[Table 4]

[0070]
[Table 5]

[0071]
As a result, the hard surface protecting polish of each example is excellent in stability despite the fact that only a small amount of surfactant is used, and leveling properties can be achieved by simply applying it to a substrate with a simple operation. It is possible to apply a coating with excellent gloss and water repellency to the substrate surface, and this coating is excellent in durability, and this coating not only improves the appearance and aesthetics of the substrate surface, but also You can see that it is well protected.
[0072]
【The invention's effect】
The hard surface-protecting polish of the present invention is glossy, stable on hard surfaces, especially rubber-, leather- or resin-based surfaces, especially those of vehicles such as tires, bumpers, interior compartment members, A film having excellent leveling properties, durability, and protective properties is formed, and this film forming treatment can be applied, or it can be simply wiped off after application, and the workability is excellent.

Claims (14)

Oil-based protective polishing component 5-50 % by mass , nonionic surfactant 0.01-2% by mass , amphiphilic polymer thickener 0.01-0.2% by mass , UV absorber 0.01-0. Containing 5% by weight ,
Organopolysiloxane is the oil-based protective polish, and general formula is an amphiphilic polymer thickener.
CH ₂ = CR ¹ COOR ³
(Wherein R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents an alkyl group having 1 to 30 carbon atoms)
Comonomers and general formula
CH ₂ = CR ² COOH
(Wherein R ² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms)
The main chain is an alkyl-modified carboxyvinyl polymer composed of a copolymer with a comonomer represented by formula (1) and / or a copolymer structure of (meth) acrylic acid and an alkyl (meth) acrylate having 1 to 30 carbon atoms in the alkyl group. The main chain is cross-linked, or the (meth) acrylic acid and the alkyl group are composed of an alkyl (meth) acrylate having 1 to 30 carbon atoms, or a monomer mainly composed of these is present in the presence of a cross-linking agent. An alkyl-modified carboxyvinyl-based cross-linked polymer that is polymerized and cross-linked underneath,
Furthermore, it contains 0.01 to 0.6% by mass of a hydrophilic silicone surfactant,
And an aqueous hard surface protective polish having a viscosity of 100 to 3000 cSt.   The hard surface protective polish according to claim 1 which is an aqueous emulsion type.   The hard surface protective polish according to claim 2, wherein the oil droplet particle diameter is less than 100 µm. The hard surface protective polishing agent according to any one of claims 1 to 3 , wherein a blending ratio of the surfactant is 0.02 to 10% by mass with respect to the oily protective polishing component. The hard surface protective polish according to any one of claims 1 to 4, wherein the viscosity of the organopolysiloxane is 100 to 10,000 cSt. The hard surface protective polish according to any one of claims 1 to 5, wherein the organopolysiloxane is dimethylpolysiloxane and / or modified dimethylpolysiloxane. The hard surface protective polish according to any one of claims 1 to 5, wherein dimethylpolysiloxane and / or modified dimethylpolysiloxane is mainly used as organopolysiloxane, and silicone resin and / or silicone rubber is used in combination. The hard surface protective polish according to any one of claims 1 to 7 , wherein the surfactant has an HLB of 8 to 20. Organopolysiloxane 5-50% by mass, nonionic surfactant 0.01-2% by mass, amphiphilic carboxyvinyl polymer 0.01-0.2% by mass, UV absorber 0.01-0.5% by mass Containing
Amphiphilic carboxyvinyl polymer is a general formula
CH ₂ = CR ¹ COOR ³
(Wherein R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents an alkyl group having 1 to 30 carbon atoms)
Comonomers and general formula
CH ₂ = CR ² COOH
(Wherein R ² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms)
The main chain is an alkyl-modified carboxyvinyl polymer composed of a copolymer with a comonomer represented by formula (1) and / or a copolymer structure of (meth) acrylic acid and an alkyl (meth) acrylate having 1 to 30 carbon atoms in the alkyl group. The main chain is cross-linked, or the (meth) acrylic acid and the alkyl group are composed of an alkyl (meth) acrylate having 1 to 30 carbon atoms, or a monomer mainly composed of these is present in the presence of a cross-linking agent. An alkyl-modified carboxyvinyl-based cross-linked polymer that is polymerized and cross-linked underneath,
Furthermore, it contains 0.01 to 0.6% by mass of a hydrophilic silicone surfactant,
And an aqueous emulsion type hard surface-protecting glazing agent having a viscosity of 100 to 3000 cSt. The hard surface protective polish according to claim 9 , wherein the organopolysiloxane is dimethylpolysiloxane and / or modified dimethylpolysiloxane. The hard surface protective polish according to claim 9 , wherein dimethylpolysiloxane and / or modified dimethylpolysiloxane is mainly used as organopolysiloxane, and silicone resin and / or silicone rubber is used in combination. The hard surface protective polish according to any one of claims 9 to 11 , wherein the oil droplet particle diameter is less than 100 µm. The hard surface protective polish according to any one of claims 1 to 12 , which is used for rubber-, leather-, or resin-based surfaces. The hard surface protective polish according to any one of claims 1 to 13 , which is for vehicles.