201018701 六、發明說明： 【發明所屬之技術領域】 本發明涉及硬質塗層用組成物和形成了硬質塗層的成 形品，更具體地說，涉及耐久性和密合性良好的硬質塗層 用組成物以及形成了硬質塗層的成形品。 【先前技術】 一直以來，各種塑料被應用於家電和汽車行業等很多 領域。塑料除加工性、透明性等以外，還具有質輕、價廉 0 等各種優點，不過，與玻璃等材料相比，其存在柔軟、表 面容易受傷等缺點。 為了改進這些缺點，現採用在塑料表面上塗敷硬質塗 層材料，以在不損害塑料所具有的透明性和輕質性等的前 題下改善表面的耐擦傷性等的技術。 作為這種硬質塗層材料，使甩的是例如碎類、丙嫦酸 類、三聚氰胺類樹脂等熱固化型硬質塗層材料。其中，紫 外線等光可使其固化的丙烯酸類樹脂，從固化時間、原料 ® 成本等角度考慮是有利的，因而曰益成為主流。 然而，丙烯酸類樹脂，與通常的矽類塗料相比，其耐 擦傷性和耐磨損性較差。為此，提出了採用分子中具有至 少2個以上（甲基）丙烯醯基的多官能（甲基）丙烯酸酯等的 方法等（例如，日本特開平9-48934號公報等）。 【發明内容】 但是，多官能（甲基）丙烯酸酯等，存在著固化收縮率 大，特別是當形成薄的膜狀時，捲曲性變的明顯的問題。 3 321527 201018701 本發明是為了解決上述問題而作出的，其目的是提供 可以使其最大程度地發揮所用成分的透明性、耐擦傷性， 同時，可將捲曲性抑制到最小程度的硬質塗層用組成物以 及成形品。 本發明的硬質塗層用組成物特徵在於，含有（A)聚胺酯 (甲基）丙烯酸酯樹脂、（B)多官能（甲基）丙烯酸酯樹脂和（c) 金屬氧化物微粒。[Technical Field] The present invention relates to a composition for a hard coat layer and a molded article formed with a hard coat layer, and more particularly to a hard coat layer having good durability and adhesion. A composition and a molded article in which a hard coat layer is formed. [Prior Art] Various plastics have been used in many fields such as the home appliance and automobile industries. In addition to workability and transparency, plastics have various advantages such as light weight and low cost. However, compared with materials such as glass, they are soft and have surface defects. In order to improve these disadvantages, a technique of applying a hard coating material to a plastic surface to improve the scratch resistance of the surface or the like without impairing the transparency and lightness of the plastic is now employed. As such a hard coat material, a heat-curable hard coat material such as a pulverized, a propionic acid or a melamine-based resin is used. Among them, an acrylic resin which can be cured by ultraviolet light, etc., is advantageous from the viewpoints of curing time, raw material cost, and the like, and thus the benefit becomes mainstream. However, acrylic resins are inferior in scratch resistance and abrasion resistance as compared with conventional enamel paints. For this reason, a method of using a polyfunctional (meth) acrylate having at least two (meth) acrylonitrile groups in the molecule or the like has been proposed (for example, JP-A-9-48934, etc.). DISCLOSURE OF THE INVENTION However, polyfunctional (meth) acrylate or the like has a large curing shrinkage ratio, and particularly when a thin film is formed, curling property is remarkably problematic. 3 321527 201018701 The present invention has been made to solve the above problems, and an object thereof is to provide a hard coat layer which can exhibit the transparency and scratch resistance of a component to be used to the utmost extent while suppressing the curling property to a minimum. Composition and molded article. The composition for a hard coat layer of the present invention is characterized by comprising (A) a polyurethane (meth) acrylate resin, (B) a polyfunctional (meth) acrylate resin, and (c) metal oxide fine particles.
這種硬質塗層用組成物係（A)聚胺酯（曱基）丙烯酸酯 樹脂為經由使異氰酸酯化合物、含羥基的（甲 化合物、以聚鱗多元醇為主鏈的化合物反應而製得：： 脂’或進-步地，（A)聚胺醋（曱基）丙稀_樹腊以含有下 述式（1)表示的聚胺酯（曱基）丙烯酸酯低聚 (R10-C0NH-)m-R2-(-NHC0-0R3)n (1)為佳 (式中’ fO-為以聚醚多元醇為主鏈的化合在 卜、 „ ^ 0守勿的脫氳殘基， -R2-為異氰酸酯化合物的脫異氰酸酯基的殘為人一 基的（甲基）丙烯酸酯化合物的脫氫殘基，" 3 至50的整 ❹ 數）。 尤其’異氰酸酯化合物之較佳者為二潘、 一'^聚*酸S旨類或者The composition for a hard coat layer (A) a polyurethane (mercapto) acrylate resin is obtained by reacting an isocyanate compound, a hydroxyl group-containing compound (a compound, a compound having a polyquaternary polyol as a main chain): 'Or step-by-step, (A) polyamine vinegar (mercapto) propylene _ tree wax is oligo(R10-C0NH-)m-R2 containing a polyurethane (mercapto) acrylate represented by the following formula (1) -(-NHC0-0R3)n (1) is preferred (wherein fO- is a polyether polyol as the main chain of the compound, „ ^ 守 的 的 氲 氲 , , , , , , , , , , - - - The deisocyanate-based residue is a dehydrogenation residue of a human-based (meth) acrylate compound, "3 to 50 ❹.) In particular, the preferred isocyanate compound is dipan, a '^ Polyacid S
二異氰酸酯單體縮聚的多異氰酸酯類，或者具有在異氛西A 酉旨基上加成醇化合物的聚胺醋結構及/式+ 、 ' 4加成胺化合物的 脲結構。 另外，以聚鱗多元醇為主鏈的化合物之教户者θ 一末 端具有經基的聚核二醇化合物或（甲基的:烧 加成化合物，或者-末端具錢基的聚伸$4化合物為 321527 4 201018701 烷氧基聚伸烷二醇類，或（曱基）丙烯酸的環氧烷加成化合 物為將（曱基）丙烯酸加成環氧烷或者聚伸烷二醇的單（甲 基）丙嫦酸酯化而得到的化合物。 另外，含經基的（曱基）丙浠酸醋化合物之較佳者為（甲 基）丙稀酸經基炫基酯類、多元醇（曱基）丙婦酸酯類或環氧 炫加成的多元醇（甲基）丙烯酸酯類。 多官能（曱基）丙烯酸醋樹脂之較佳者為1分子中具有 至少2個（甲基）丙烯醯基的化合物。 ~ ❹ 另外，本發明的成形品特徵在於开 用組成物的固化聚合物作為硬質塗層。 根據本發明的硬質塗層用組成物，可以提供能夠達到 所用成分的量與㈣所帶㈣性能的平衡，衫 地發揮這些成分原本具有的透明性、紛 '、 又 耐擦傷性，同時，將 -直以來成為問題的捲曲性抑制到最切 組成物以及成形品。 【實施方式】 本發明的硬質塗層用組成物，主要含有（A)聚胺醋（甲 基)丙_樹脂、⑻多官能(甲基)兩埽酸醋樹脂和⑹ 金屬氧化物微粒。 另外，在本說明書中，（甲基）丙埽酸表示（甲基）丙稀 酸或者丙稀酸的含義。 (A)聚胺酯（甲基）丙烯酸酯樹脂為例如具有1個以上 親水性基團（例如祕、缓基、乙二醇基團、;二醇等） 的即可，具體地可以列舉經由使⑴以聚鍵多元醇為主鏈的 321527 5 201018701 化合物、（2)異氰酸酯化合物、（3)含羥基的（甲基）丙烯酸 酯化合物的反應所製得的樹脂。 例如，作為聚胺酯（甲基）丙烯酸酯樹脂的一個例子， 可以列舉下述式（1)表示的化合物， (R10-C0NH-)m-R2-(-NHC0-0R3)n (1) (式中，fO-為以聚醚多元醇為主鏈的化合物的脫氫殘基， -R2-為異氰酸酯化合物的脫異氰酸酯基的殘基，R3〇-為含羥 基的（曱基）丙稀酸酯化合物的脫氫殘基，m+n=l至50的整 數）。 ❿ 式（1)中，m也可以為0，但構成R1的取代基的分子量 為100至2000左右的範圍較合適，宜為100至1000左右 的範圍。因為若聚醚多元醇鏈的分子量過大，則存在硬度 下降的傾向。 構成R2的取代基的分子量為150至5000左右的範圍較 合適，宜為500至3000左右的範圍。因為若該分子量過大， 則硬度會下降。 η也可以為0，但適合為大於0的整數。特別是構成 ® R3的取代基的分子量，為150至2000左右是合適的，宜為 100至1000左右。該分子量太大的話，硬度會下降。 作為（1)以聚醚多元醇為主鏈的化合物，只要是主鏈上 具有聚醚基團，且具有羥基的化合物（包括一末端具有羥基 的化合物）即可，可以列舉例如聚伸烷二醇類、烷氧基聚伸 烷二醇類、（曱基）丙烯醯氧基聚伸烷二醇類、聚伸烷與聚 丁二醇的反應產物、具有環氧乙烷環的環氧基化合物與（甲 6 321527 201018701 基）丙烯酸加成反應而得到的含經基的（曱基）内缔於，生 物與環氧乙烷、環氧丙烷等環氧烷反應而得到的含 丙:基的聚喊多元醇類、（甲基）两缚酸的環氣产 、 合物等。 几加成化 其中，較佳者為聚伸烷二醇類、一末端具有羥基的聚 伸烷二醇類、烷氧基聚伸烷二醇類、含（曱基）丙烯^基的 聚醚多元醇類、（甲基）丙烯酸的環氧烷加成化合物，進一 步宜為一末端具有經基的聚伸燒二醇化合物或者（甲基）丙 ❹稀酸的環氧烧加成化合物。 尤其’ 一末具有經基的聚伸燒二醇化合物宜為炫氧 基聚伸院·一酵類，另外’（甲基）丙稀酸的環氧烧加成化合 物宜為使（甲基）丙烯酸加成環氧院所得的化合物或使聚伸 烷二醇進行單（曱基）丙烯酸酯化所得的化合物。 另外，這些化合物的伸烧基和燒氧基的碳原子數，可 以列舉1至6左右的範圍。 聚伸炫二醇類可以列舉例如聚乙二酵、聚丙二醇、聚 ❹ 丁二醇。 烷氧基聚伸烷二醇類可以列舉姐m威屎子.數為j 至6範圍的烷氧基的聚伸烧二醇類（伸炫基的碳原子數為 例如1至6的範圍），具體可以列舉甲氧基聚乙二醇、甲氧 基聚丙二醇、甲氧基聚丁二醇。烷氧基聚伸烷二醇類的分 子量可以任意選擇，以100至2000為佳。 (曱基）丙烯醯氧基聚伸烧二醇類可以列舉例如（甲基） 丙烯醯氧基聚乙二醇、（甲基）丙烯醯氧基聚丙二醇。 7 321527 201018701 聚伸烷與聚丁二醇的反應產物，可以列舉例如聚乙烯 與聚丁二醇的反應產物、甲氧基聚乙稀與聚丁二醇的反應 產物:（甲基）丙稀酿氧基聚乙締與聚丁二醇的反應產物。 含（甲基）丙烯醯基的聚醚多元醇類可以列舉含有被羥 基取代的碳原子數為1至6範圍的烧基的丙烯酸g旨，例如 丙婦酸2經基乙酯的環氧乙烧加成物（例如，加 為1至20的範圍）。 、 (甲基）丙烯酸的環氧烷加成化合物可以列舉例如使以 衣氧乙烧％氧丙燒、環氧丁院為代表的環氧燒（例如，碳 原子數為2至6的範圍）加成到（甲基）丙稀酸而得到的化合 物。 作為（2)異氰酸g旨化合物’可以列舉二異氰酸醋類、二 異氰酸酯早體縮聚的多異氰酸酯類、具有在異氰酸酯基上 加成醇化合物的聚裝結構及/或加成胺化合物的腺結構 的化合物等。其中’以後兩種（即多異氰酸醋類、具有聚胺 酯結構及/或脲結構的化合物）為佳。 ❹ '異氰酸酯類可以列舉例如2, 4-甲苯二異氰酸酯、 2, 6-甲^二異氰酸酯、異佛_二異氰酸醋、己二異氛酸 酯、二苯基甲烧二異氰酸酯 '(鄰、㈤、對）二甲苯二 酸醋、亞甲基二（環己基異氰酸醋）、三甲基己二異氰酸醋、 環己炫-U-二亞甲基二異氰酸醋、環己烧心—二 一異氰酸=、1,5-萘二異氰酸g旨、降冰片院二異氰酸醋等。 -異氰酸^單體縮聚的多異氰酸g旨類，例如 異氣酸醋化合物，可以列舉異佛爾闕二異氰酸醋、己：二 321527 8 201018701 氰酸酯、降冰片烷二異氰酸酯、曱苯二異氰酸酯、苯二甲 基二異氰酸酯、二苯基曱烷二異氰酸酯、三曱基己二異氰 酸酯、氫化苯二甲基二異氰酸酯以及氫化二苯基甲烷二異 氰酸酯等2官能異氰酸酯、作為它們的雙縮脲物或異氰脲 酸酯化物的3官能以上的異氰酸酯。其中，1分子中具有 3個以上異氰酸酯基的多異氰酸酯化合物係例如，含鏈狀 或環狀烷基或芳基（例如碳原子數為6至12的範圍）的多異 氰酸酯化合物，特別以己二異氰酸酯、異佛爾酮二異氰酸 ❹ 酯、甲苯二異氰酸酯等的異氰脲酸酯化物為佳。 醇化合物可以列舉例如碳原子數為2至10範圍的2至 4元醇類，具體地，可以列舉乙二醇、丙二醇、丁二醇、 甘油、三經曱基丙烧、季戊四醇。 胺化合物可以列舉例如二胺基乙烷、二胺基丙烷、丁 二胺。 若加成了醇化合物或胺化合物，可以增大異氰酸S旨化 ©合物每分子的官能基數。另外，從提高固化聚合物的耐擦 傷性的角度考慮，這些醇化合物和胺化合物宜使用每個官 能基的分子量小的化合物。 作為（3)含羥基的（曱基）丙烯酸酯化合物，可以列舉 (甲基）丙烯酸羥基烷基酯類、多元醇（甲基）丙烯酸酯類或 環氧烷加成的多元醇（曱基）丙烯酸酯類以及由環氧樹脂與 碳酸衍生的化合物等。其中，以前3種為佳。 (甲基）丙烯酸羥基烷基酯類可以列舉例如（曱基）丙烯 酸羥基乙酯、（曱基）丙烯酸羥基丙酯、（甲基）丙烯酸羥基 9 321527 201018701 丁酯、（曱基）丙烯酸羥基苯氧基丙酯。 多元醇（甲基）丙烯酸酯類可以列舉例如碳原子數為2 至10範圍的2至4元的多元醇（甲基）丙烯酸酯類，具體 地，可以列舉甘油二（曱基）丙烯酸酯、三羥甲基丙烷二（甲 基）丙烯酸酯、二-三羥曱基丙烷三（曱基）丙烯酸酯、季戊 四醇三（甲基）丙烯酸醋、二季戊四醇五（甲基）丙稀酸醋。 環氧烧加成的多元醇（甲基）丙稀酸酯可以列舉例如環 氧烷加成的三羥甲基丙烷二（甲基）丙烯酸酯、環氧烷加成 的季戊四醇三（甲基）丙烯酸酯、環氧烷加成的二季戊四醇 五（曱基）丙稀酸g旨。 作為由環氧樹脂與叛酸衍生的化合物，可以列舉（曱基） 丙烯酸縮水甘油基酯的（曱基）丙烯酸加成物。 另外’聚胺醋（甲基）丙烯酸酯樹脂可以單獨使用，也 可以兩種以上聯用。 本發明的聚胺酯（曱基）丙烯酸酯，在式（1)中，特別以 下列組合為佳：作為以聚醚多元醇為主鏈的化合物的聚 伸烷二醇類、烷氧基聚伸烷二醇類、含（曱基）丙烯醯基的 © 聚醚多元醇類、（甲基）丙烯酸的環氧烷加成化合物與作為 (2)異氰酸酯化合物的多異氰酸酯類、具有在異氰酸酯上加 成醇化合物的聚胺酯結構的化合物以及作為（3)含經基的 (甲基）丙烯酸酯化合物的（甲基）丙烯酸羥基烷基酯類、多 元醇（甲基）丙烯酸醋類的組合。 本發明的聚胺酯（曱基）丙烯酸酯’例如分子量為500 至5000範圍的較佳。若分子量過大，則存在硬度下降的傾 321527 10 201018701 向。攻種聚胺酯（甲基）丙烯酸酯，可以通過例如日本特開 2000-264936號中記載的方法製備。 另外，在（A)聚胺酯（甲基）丙烯酸酯中，（1)以聚醚多 元醇為主鏈的化合物’例如一末端具有經基的聚伸院二醇 化合物的莫耳比，宜為⑶含祕的（甲基）丙烯㈣化合物 的莫耳比以下。聚醚多元醇鏈的分子量越大，在使其交聯 聚合時硬度就越下降。含經基的（甲基）丙稀_化合物的 官能基數越多’使其交聯聚合時的硬度就越增大，相反， ©越少則硬度就越下降。因此，通過對其進行調整，可以獲 得適當硬度的固化聚合物。 (B)夕（甲基）丙烯酸醋樹脂宜為1分子中具有兩 個以上（甲基）丙稀酿基的化合物。可以列舉例如季戊四醇 (四）三（甲基）丙稀酸酯、二季戊四醇六（甲基）丙婦酸醋、 二經甲基三環魏二（甲基）㈣酸醋、三經甲基丙烧（環氧 乙烧加成物）三（甲基）丙烯酸醋、聚醋二（甲基）丙婦酸醋、 ❹四甘醇二（甲基）丙稀酸醋、甘油二（甲基）丙婦酸醋、甘油 的環氧乙烧加成物的（甲基）丙、甘油的環氧丙院加 成物的（甲基）丙烯酸酯、乙二醇、二甘醇、三甘醇、四甘 醇、丙二醇、二丙二醇、三丙二醇、四丙二醇等聚伸烷二 醇的二丙烯酸醋、多元醇與多元酸縮合所得的化合物的^ 基）丙烯酸酯以及上述多異氰酸酯與含羥基的（ 酸醋反應所得的化合物。它們可以單獨使用，也可土以 以上聯用。 多官能（曱基）丙烯酸酯樹脂，相對於1〇〇重量份上述 321527 11 201018701 (A)聚胺S旨（甲基）丙婦酸g旨樹脂，宜使用1()至5⑽重量份， 更宜使S 20至300重量份。通過在這種範圍内使用，與其 他成分相結合，可以調整固化收縮率。 (C)金屬氧化物微粒，對其沒有特別的限制，使用粒徑 為5mn至50nm的較佳，特別以⑺⑽至2〇nm為佳。這樣， 可以增大組成物膜的硬度。另外，還可以調節塗膜的折射 率。 作為金屬氧化物微粒，可以列舉氧化石夕、氧化錯 '氧 化鈦、氧化鋅、五氧化綈、氧化錫、氧化紹、氧化鋼、鋼 錫氧化物、氧化鐵、氧化鈽、氧化釔、氧化錳 '氧化鈥' 氧化銅 '氧⑽、氧⑽、四氧化三銘、四氧化三鐵 ，鎂、氧化、氧化镨、氧化鈹、氧切、氧化销、氧化 氧化試、氧化銷、氧化铒、氧化链、氧化镱、氧化縳、 乳化知、五氧化组、五氧化銳、氧化銀 ' 以及使它們結合的複合氧化物。 乳⑽乳化舒 的氧2較t有下述式⑵表示_化合物或其部分水解物 R5aR6bSi(〇R7)4.a.b (2) =中’R5為可具有環氧基、曱基兩稀醯基 基、醯脲基或疏基的碳原子數為U12的有胺 至8舰基、碳原子數為 碳原子數為1至8的嫌美、方基、 婦 數為1至8的酿基，R7 料子數為1至1G的絲或碳原子數為^ 、土 ’a為 〇或 i，b為 〇、1 或2)〇 321527 12 201018701 這晨’作為有機基團’可以例不烧基、稀基、_芳基等。 作為烷基，可以列舉曱基、乙基、丙基、正丁基、第 三丁基、第二丁基、異丁基、戊基、己基、庚基、辛基等。 作為芳基，可以列舉苯基、曱苯基、二曱苯基等。 作為烯基，可以列舉乙烯基、烯丙基、2-丙烯基、丙 _2_稀_1_基等。 作為醯基，可以列舉曱醯基、乙醯基、丙醯基、丁醯 基、戊醯基、乙二醯基、丙二醯基、琥珀醯基、苯曱醯基、 © 曱苯曱醯基、鄰苯二曱醯基等。 作為具體的化合物，可以例示例如三甲基曱氧基矽 烷、三苯基曱氧基矽烷、二苯基曱基曱氧基矽烷、苯基二 曱基曱氧基矽烷、乙烯基二曱基乙氧基矽烷、二曱基二甲 氧基梦烧、苯基甲基二乙氧基碎院、T _疏基丙基三甲氧基 矽烷、r-環氧丙氧基丙基三乙氧基矽烷、原矽酸四乙酯、 原矽酸四曱酯等，特別是日本特開2006-70120號中例示的 已知石夕化合物或其部分水解物。 ◎ 為了進一步提高膜的硬度，特別以R5為甲基丙烯醯 基、丙烯醯基的矽化合物為佳。作為這種矽化.佥„物，如有. 3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯 氧基丙基三曱氧基矽烷、3-曱基丙烯醯氧基丙基曱基二乙 氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯 醯氧基丙基三甲氧基矽烷等。 另外，金屬氧化物微粒可以單獨使用，也可以兩種以 上聯用。 13 321527 201018701 金屬氧化物微粒，相對於1〇〇重晋 (甲基)丙烯酸醋’換算為固體成分 ’至 用一重量份。通過在這種範至圍： 〃、其他成分相結合，可以調整固化收縮率。 另外，金屬氧化物微粒可以分散於有 溶膠的形式使用。 中以有機 該溶劑種類，作為醇類，可以列舉例如甲醇、乙醇、 卜丙酵、2-丙醇、卜甲氧基_2_丙醇、異丙醇等。 矿:為二醇類’可以列舉例如乙二醇單甲鱗乙酸醋、乙 -醇早乙鱗乙酸醋、乙二醇單_乙酸g|、乙二醇單丁醚 乙丙二醇單甲驗乙酸醋、丙二醇單乙鱗乙酸酯、丙 -醇早㈣乙酸醋、丙二醇單獨乙酸醋、乙二醇二甲鱗、 乙二醇二乙醚、乙二醇二_、乙二醇二丁醚、二甘醇二 甲醚、二甘醇二乙輕、二甘醇二㈣、二甘醇二獨、丙 一醇一甲醚、丙二醇二乙醚、丙二醇單甲醚、乙二醇單乙 醚、乙二醇單丁醚。 作為脂肪族環狀酮類’可以列舉例如環己酮、鄰、間、 對-甲基環己酮等。 作為乙酸醋類，可以列舉例如乙酸乙酯、乙酸正丙g旨、 乙酸正丁酯。 另外，還可以使用溶劑石腦油、甲基乙基闕等。 膠可財損這些溶劑配成固體成分為$至1〇〇% 濃度範圍的有機溶膠而使用。 本發明的组成物還可以進一步含有（甲基）丙稀酸化合 321527 14 201018701 物或含乙烯基的化合物。此時，相對於全部組成物100重 量份’宜含有0. 1至50重量份。這些化合物可以單獨使用， 也可以兩種以上聯用。 (甲基）丙烯酸化合物可以列舉例如丙烯醯胺類、（曱基） 丙烯酸烷基酯類、（曱基）丙烯酸胺基烷基酯類、（曱基）丙 烯酸胺基烧基酯的四級銨鹽類、烷氧基聚伸烷二醇（甲基） 丙稀酸醋類、（甲基）丙烯酸羥基烷基酯類、（曱基）丙烯酸 輕基院基醋的酸酐加成物類、聚伸烷二醇二（甲基）丙烯酸 ❺酯類、烷二醇二（甲基）丙烯酸酯類、多元醇聚（甲基）丙烯 酸ga類、％氧烷加成的多元醇聚（甲基）丙烯酸酯類。這些 化合物可以例示日本特開2〇〇〇_264939號中記載的化合 物0 含乙烯基化合物可以列舉例如醋酸乙烯醋、N-乙稀基 乙‘胺:乙烯基料㈣、乙烯基燒基簡、乙稀基確酸、 乙烯基續酸鹽類等。 ❹平劑本：：二：成物還可以混合聚合起始劑、稀釋劑、整 千劑、> 聞滑性賦予劑、其他添加劑等。 苯基酮 -2-苯基乙酿基苯 聚合起始劑，沒有特別生 而產生自由基的光聚合起^限制，且為通過活化能射線 苯基™:甲劑 &基苯、二笨鲷、2、 ，2~一甲氧基 嗎淋基-1-丙酮、2-羥基〜2〜曱義土—（甲硫基）笨基] 異丙基苯基）~2-羥基-2-甲基苯基丙烷〜1—鲖、1~(4〜 苯基-(2-經基-2—丙基）明 燒一1_陶、4'(2,基乙氧基. (2'丙稀酿氧基乙氧基)笨基」 321527 15 201018701 (2-羥基-2-丙基）酮、4-(2-甲基丙烯醯氧基乙氧基）苯基-(2-羥基-2-丙基）酮、2, 4, 6-三甲基苯甲醯基二笨基膦氧化 物等。 作為稀釋劑，可以列舉烷二醇的單烷基醚類、烷二醇 類、烷二醇單烷基醇的烷基羧酸酯類、酮類、烷基醇的烷 基羧酸酯類等。其可以例示例如日本特開2004-43790號中 記載的稀釋劑。 本發明的硬質塗層用組成物，根據需要還可以含有溶 劑。作為溶劑，可以使用上述的醇類、二醇類、脂肪族環 0 狀酮類、醋酸酯類、其他溶劑等。 作為整平劑和潤滑性賦予劑，可以列舉例如聚氧化烯 與聚二甲基矽氧烷等的共聚物、聚氧化烯與碳氟化合物的 共聚物等。 本發明的硬質塗層用組成物，可以通過照射紫外線、 射線、紅外線、X射線、電子束的活化能射線而使其固化， 該固化聚合物在成形品的表面構成硬質塗層。 這裏的成形品，並不限於由聚苯乙烯樹脂、聚烯烴樹 脂、ABS樹脂、AS樹脂、AN樹脂等通用樹脂構成的塑料成 形品，還包括由木材、玻璃、金屬、陶瓷、紙、水泥、它 們的複合品等各種材料形成的成形品。較佳者係指其表面 上形成了本發明硬質塗層用組成物作為硬質塗層的成形品 的含義。另外，作為該成形品，還可以是本發明的硬質塗 層用組成物處於構成硬質塗層的薄膜、轉印箔等的形態。 因此，可以是例如在透明基材上用本發明的硬質塗層 16 321527 201018701 用組成物製成薄膜形狀，製作成硬質塗層用轉印箔或硬質 塗層用薄膜’也可以將這些轉印箱或薄膜貼合到成形品的 表面上。 另外，當成形品由塑料製得時，在不影響該塑料成形 品的目的性能的情況下，還可以將本發明的硬質塗層用組 成物混在構成成形品的塑料中作為硬質塗層。 ❹ 例如，在透明基材的一側或兩侧表面上塗敷硬質塗層 用組成物，將該塗膜通過光照射等形成硬質塗層。 作為透明基材，可以列舉由聚細旨樹脂、聚環硫樹脂、 如聚甲基丙烯酸甲醋（簡）等（甲基）丙婦酸類聚合物、烯 丙基類聚口物、—甘醇二碳酸婦丙基酯、聚碳酸醋、奶樹 2、環狀聚稀烴等各種合成樹脂製的基材。基材可以為平 板狀、彎曲板狀、薄膜狀等各種形狀。 塗敷可以採用例如浸漬塗敷法、流塗法、喷塗法、凹 法、：塗法、旋塗法、糙塗法、柔版印刷法、絲網 ❹印刷法、刷塗法等而進行。 塗敷厚度，固化後為0.01至範圍較好。A polyisocyanate in which a diisocyanate monomer is polycondensed, or a polyamine structure having an alcohol compound added to an isomeric group, and a urea structure of a ++, '4 addition amine compound. In addition, a nucleus diol having a polystyrene polyol as a main chain has a transnuclear polynuclear diol compound or a methyl group: a calcined addition compound, or a terminally occluded compound having a valence group of $4 Is 321527 4 201018701 alkoxy polyalkylene glycols, or alkylene oxide addition compounds of (mercapto)acrylic acid are mono(methyl) groups of (mercapto)acrylic acid added to alkylene oxide or polyalkylene glycol a compound obtained by esterification of a propionate. Further, a perylene group-containing (mercapto) propionate vinegar compound is preferably a (meth)acrylic acid via a leucoyl ester or a polyhydric alcohol. a polyglycol (meth) acrylate having a polyglycolic acid ester or an epoxy resin. The polyfunctional (fluorenyl) acryl vine resin preferably has at least two (meth) acrylonitriles in one molecule. The compound of the present invention is characterized in that the molded article of the present invention is characterized in that the cured polymer of the composition is used as a hard coat layer. According to the composition for a hard coat layer of the present invention, it is possible to provide an amount capable of achieving the components used and (4) With the balance of performance (4), the shirts play these ingredients In the present invention, the composition of the hard coat layer of the present invention is mainly composed of the composition of the hard coat layer of the present invention. Containing (A) polyamine vinegar (meth) propylene resin, (8) polyfunctional (methyl) bismuth citrate resin, and (6) metal oxide fine particles. In addition, in the present specification, (meth)propionic acid is indicated ( The meaning of methyl)acrylic acid or acrylic acid. (A) The polyurethane (meth) acrylate resin has, for example, one or more hydrophilic groups (for example, a secret group, a slow group, an ethylene glycol group, a diol). Specifically, it may be exemplified by a reaction of (1) a compound having a poly-bond polyol as a main chain of 321527 5 201018701, (2) an isocyanate compound, and (3) a hydroxyl group-containing (meth) acrylate compound. For example, as an example of the polyurethane (meth) acrylate resin, a compound represented by the following formula (1), (R10-C0NH-)m-R2-(-NHC0-0R3)n (1) (wherein fO- is a compound with a polyether polyol as the main chain Hydrogen residue, -R2- is the residue of the isocyanate group of the isocyanate compound, R3〇- is the dehydrogenation residue of the hydroxyl group-containing (mercapto) acrylate compound, m+n=l to 50) In the formula (1), m may be 0, but the molecular weight of the substituent constituting R1 is preferably in the range of about 100 to 2,000, preferably in the range of about 100 to 1,000, because if the molecular weight of the polyether polyol chain is When the content is too large, the molecular weight of the substituent constituting R2 is preferably in the range of about 150 to 5,000, preferably in the range of about 500 to 3,000. If the molecular weight is too large, the hardness may be lowered. 0, but suitable as an integer greater than 0. In particular, the molecular weight of the substituent constituting the ? R3 is suitably from about 150 to about 2,000, preferably from about 100 to about 1,000. If the molecular weight is too large, the hardness will decrease. (1) The compound having a polyether polyol as a main chain is not particularly limited as long as it is a compound having a polyether group in the main chain and having a hydroxyl group (including a compound having a hydroxyl group at one terminal). Alcohols, alkoxy polyalkylene glycols, (mercapto) propylene decyloxypolyalkylene glycols, reaction products of polyalkylenes and polytetramethylene glycols, epoxy groups having an oxirane ring a C-containing group containing a trans group-containing (fluorenyl) group obtained by an addition reaction of a compound with (A6 321527 201018701-based) acrylic acid and reacting with an alkylene oxide such as ethylene oxide or propylene oxide The poly-alcohols, (meth)-bonded acid ring gas products, and the like. Among them, preferred are polyalkylene glycols, polyalkylene glycols having a hydroxyl group at one terminal, alkoxy polyalkylene glycols, polyethers containing (fluorenyl) propylene groups. The alkylene oxide-based (meth)acrylic acid alkylene oxide addition compound is more preferably an epoxy-fired addition compound having a transcondensed diol compound having a trans group at one end or a (meth) propylene dicarboxylic acid. In particular, the polyglycol diol compound having a mercapto group is preferably a oxy-oxyl condensing compound and a yeast, and the epoxy-based addition compound of '(meth) acrylic acid is preferably (methyl) A compound obtained by adding acrylic acid to an epoxy compound or a compound obtained by subjecting a polyalkylene glycol to mono(mercapto)acrylation. Further, the number of carbon atoms of the alkylene group and the alkoxy group of these compounds may be in the range of about 1 to 6. Examples of the polyglycol diols include polyethylene glycol, polypropylene glycol, and polybutylene glycol. Examples of the alkoxy-polyalkylene glycols include agglomerated diols having a number of alkoxy groups in the range of j to 6 (the number of carbon atoms in the exudyl group is, for example, in the range of 1 to 6). Specific examples thereof include methoxypolyethylene glycol, methoxypolypropylene glycol, and methoxypolybutylene glycol. The molecular weight of the alkoxypolyalkylene glycols can be arbitrarily selected, preferably from 100 to 2,000. Examples of the (fluorenyl) propylene oxime-based polycondensation diol include (meth) propylene oxime polyethylene glycol and (meth) propylene decyloxy polypropylene glycol. 7 321527 201018701 The reaction product of polyalkylene and polytetramethylene glycol, for example, the reaction product of polyethylene and polytetramethylene glycol, the reaction product of methoxypolyethylene and polytetramethylene glycol: (meth) propylene The reaction product of brewing oxypolyethylene and polytetramethylene glycol. The polyether polyol containing a (meth) acrylonitrile group may, for example, be an acrylic acid containing a group having a carbon number of 1 to 6 substituted by a hydroxy group, for example, an epoxy group of ethyl acetoacetate Burn the adduct (for example, add a range of 1 to 20). The alkylene oxide addition compound of (meth)acrylic acid, for example, is an epoxy-burning represented by oxypropylene, oxypropylidene or epoxidizer (for example, a range of 2 to 6 carbon atoms). A compound obtained by addition to (meth)acrylic acid. Examples of the (2) isocyanate g-based compound 'polyisocyanate of diisocyanate, diisocyanate early polycondensation, polyaddition structure having an alcohol compound added to an isocyanate group, and/or an amine compound The structure of the glandular structure, etc. Among them, the latter two (i.e., polyisocyanate, a compound having a polyurethane structure and/or a urea structure) are preferred. ❹ 'Isocyanates may, for example, be 2,4-toluene diisocyanate, 2,6-methyl diisocyanate, isophora-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate' (o. , (5), p), xylene diacetate, methylene di(cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexyl-U-dimethylene diisocyanate, Cyclohexene heart-diisocyanate = 1,5-naphthalene diisocyanate g, norbornene diisocyanate vinegar. - Isocyanic acid monomer polycondensed polyisocyanate g, such as isogastric acid vinegar compound, may be exemplified by isophora diisocyanate vine, hexane: two 32327 8 201018701 cyanate ester, norbornane II a bifunctional isocyanate such as isocyanate, toluene diisocyanate, benzodimethyl diisocyanate, diphenyldecane diisocyanate, tridecyl hexamethylene diisocyanate, hydrogenated dimethyl diisocyanate, and hydrogenated diphenylmethane diisocyanate, Their biuret or isocyanurate is a trifunctional or higher isocyanate. Among them, a polyisocyanate compound having three or more isocyanate groups in one molecule is, for example, a polyisocyanate compound containing a chain or a cyclic alkyl group or an aryl group (for example, a range of from 6 to 12 carbon atoms), particularly An isocyanurate such as isocyanate, isophorone diisocyanate or toluene diisocyanate is preferred. The alcohol compound may, for example, be a 2- to 4-membered alcohol having a carbon number of 2 to 10, and specific examples thereof include ethylene glycol, propylene glycol, butylene glycol, glycerin, tri-propyl mercapto-propene, and pentaerythritol. The amine compound may, for example, be diaminoethane, diaminopropane or butane. When an alcohol compound or an amine compound is added, the number of functional groups per molecule of the isocyanate can be increased. Further, from the viewpoint of improving the scratch resistance of the cured polymer, it is preferred to use a compound having a small molecular weight per functional group for these alcohol compounds and amine compounds. Examples of the (3) hydroxyl group-containing (fluorenyl) acrylate compound include hydroxyalkyl (meth) acrylates, polyol (meth) acrylates, and alkylene oxide-added polyols (fluorenyl groups). Acrylates and compounds derived from epoxy resins and carbonic acid. Among them, the previous three are preferred. The hydroxyalkyl (meth) acrylate may, for example, be hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy 9 321527 201018701 butyl acrylate, hydroxy benzene (mercapto) acrylate Oxypropyl propyl ester. The polyhydric alcohol (meth) acrylate may, for example, be a 2 to 4 membered polyol (meth) acrylate having a carbon number of 2 to 10, and specific examples thereof include glycerol bis(indenyl) acrylate. Trimethylolpropane di(meth)acrylate, di-trihydroxydecylpropane tri(mercapto) acrylate, pentaerythritol tris(meth)acrylate vinegar, dipentaerythritol penta(methyl) acrylate vinegar. The poly(ol) (meth) acrylate which is added by epoxy burning may, for example, be an alkylene oxide-added trimethylolpropane di(meth)acrylate or an alkylene oxide-added pentaerythritol tris(methyl). An acrylate or alkylene oxide-added dipentaerythritol penta(indenyl) acrylate acid. As the compound derived from the epoxy resin and the oxo acid, a (mercapto)acrylic acid adduct of (mercapto)glycidyl acrylate may be mentioned. Further, the polyamine vinegar (meth) acrylate resin may be used singly or in combination of two or more. The polyurethane (mercapto) acrylate of the present invention is preferably the following combination in the formula (1): a polyalkylene glycol or alkoxypolyalkylene as a compound having a polyether polyol as a main chain. Glycols, polyether polyols containing (fluorenyl) acrylonitrile groups, alkylene oxide addition compounds of (meth)acrylic acid, and polyisocyanates as (2) isocyanate compounds, having an addition to isocyanate A compound of a polyurethane structure of an alcohol compound and a combination of a (meth)acrylic acid hydroxyalkyl ester and a polyol (meth)acrylic acid vinegar as (3) a transbasic (meth)acrylate compound. The polyurethane (mercapto) acrylate of the present invention has a molecular weight of, for example, preferably in the range of 500 to 5,000. If the molecular weight is too large, there is a tendency to decrease the hardness of 321527 10 201018701. The attack of the polyurethane (meth) acrylate can be carried out, for example, by the method described in JP-A-2000-264936. Further, in the (A) polyurethane (meth) acrylate, (1) a compound having a polyether polyol as a main chain, for example, a molar ratio of a polycondensation diol compound having a trans group at the end, preferably (3) The molar ratio of the secret (meth) propylene (iv) compound is below. The larger the molecular weight of the polyether polyol chain, the lower the hardness when it is crosslinked and polymerized. The more the number of functional groups of the (meth)acryl-containing compound having a mercapto group, the greater the hardness at the time of crosslinking polymerization, and the smaller the thickness of ©, the lower the hardness. Therefore, by adjusting it, a cured polymer of an appropriate hardness can be obtained. (B) The (meth)acrylic acid vinegar resin is preferably a compound having two or more (meth)acrylic groups in one molecule. For example, pentaerythritol (tetra)tri(methyl) acrylate, dipentaerythritol hexa(methyl) acetoacetate, di-methyltricyclo-di(methyl) (tetra) vinegar, tri-methyl propyl acrylate Burning (epoxy Ethylene Additive) Tris(meth)acrylic acid vinegar, poly(ethylene) acetonate vinegar, ❹tetraethylene glycol di(meth) acrylate vinegar, glycerol di(methyl) (meth) acrylate of ethylene acetoacetate, glycerin ethylene oxide addition product, (meth) acrylate of ethylene glycol glycerin, ethylene glycol, diethylene glycol, triethylene glycol, a diacrylate acrylate of a polyalkylene glycol such as tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol or tetrapropylene glycol; a acrylate of a compound obtained by condensing a polyhydric alcohol with a polybasic acid; and the above polyisocyanate and a hydroxyl group-containing (acid) The compound obtained by the reaction of vinegar may be used singly or in combination with the above. Polyfunctional (fluorenyl) acrylate resin, the above-mentioned 321527 11 201018701 (A) polyamine S (methyl) ) B-glycolic acid, preferably 1 () to 5 (10) parts by weight, more preferably S 20 300 parts by weight. By using in this range, the curing shrinkage ratio can be adjusted in combination with other components. (C) Metal oxide fine particles are not particularly limited, and a particle diameter of 5 nm to 50 nm is preferably used. In particular, it is preferable to use (7) (10) to 2 〇 nm. In this way, the hardness of the composition film can be increased. Further, the refractive index of the coating film can be adjusted. Examples of the metal oxide fine particles include oxidized oxide and oxidized titanium oxide. Zinc oxide, antimony pentoxide, antimony oxide, antimony oxide, oxidized steel, steel tin oxide, iron oxide, antimony oxide, antimony oxide, manganese oxide 'yttria', copper oxide 'oxygen (10), oxygen (10), tetraoxide, Ferric oxide, magnesium, oxidation, cerium oxide, cerium oxide, oxygen cutting, oxidation pin, oxidative oxidation test, oxidation pin, cerium oxide, oxidized chain, cerium oxide, oxidation binding, emulsification, pentoxide, pentoxide , silver oxide 'and composite oxides that bind them. Milk (10) emulsified oxygen 2 has the following formula (2) compared with t. _ compound or its partial hydrolysate R5aR6bSi (〇R7) 4.ab (2) = medium 'R5 It can have an epoxy group and a sulfhydryl group. The rare earthy group, the uretido group or the sulfhydryl group has an amine to 8 ship base having a U12 carbon number, a carbon atom number of 1 to 8 carbon atoms, a square base, and a number of women 1 to 8. Brewing base, R7 material number is 1 to 1G wire or carbon number is ^, soil 'a is 〇 or i, b is 〇, 1 or 2) 〇321527 12 201018701 This morning 'as an organic group' can be Burning base, dilute base, _aryl group, and the like. The alkyl group may, for example, be a mercapto group, an ethyl group, a propyl group, a n-butyl group, a tributyl group, a second butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. Examples of the aryl group include a phenyl group, a fluorenylphenyl group, and a diphenylene group. The alkenyl group may, for example, be a vinyl group, an allyl group, a 2-propenyl group or a propylene group. Examples of the fluorenyl group include a mercapto group, an ethyl group, a propyl group, a butyl group, a butyl group, a pentyl group, a ethanediyl group, a propylene group, an amber fluorenyl group, a benzoinyl group, a fluorenyl fluorenyl group, and O-phthalic acid and the like. Specific examples of the compound include, for example, trimethyl decyl decane, triphenyl decyl decane, diphenyl decyl decyl decane, phenyl decyl decyl decane, and vinyl di decyl Oxydecane, dimercaptodimethoxymethane, phenylmethyldiethoxymethane, T-sulfopropyltrimethoxydecane, r-glycidoxypropyltriethoxydecane And tetraethyl orthophthalic acid, tetradecyl ortho-decanoate, and the like, and the known Schisandra compound or a partial hydrolyzate thereof, which is exemplified in JP-A-2006-70120. ◎ In order to further increase the hardness of the film, a ruthenium compound in which R5 is a methacryl oxime group or an acryl oxime group is particularly preferable. As such a deuterium, such as: 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercapto Propylene methoxypropyl decyl diethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3-propenyl methoxy propyl trimethoxy decane, etc. In addition, metal oxide particles It can be used singly or in combination of two or more. 13 321527 201018701 Metal oxide fine particles, in terms of 1% by weight of heavy (meth)acrylic acid vinegar 'to solid content' to one part by weight.至 : 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Propylene, 2-propanol, bromo-2-propanol, isopropanol, etc. Mineral: is a diol type, for example, ethylene glycol monomethyl squaternine acetate, ethyl alcohol early squamous acetate vinegar , ethylene glycol mono-acetic acid g|, ethylene glycol monobutyl ether ethylene glycol monoacetate acetic acid vinegar , propylene glycol monoethyl sulphate acetate, propanol early (four) acetic acid vinegar, propylene glycol alone acetic acid vinegar, ethylene glycol dimethyl scale, ethylene glycol diethyl ether, ethylene glycol di-, ethylene glycol dibutyl ether, digan Alcohol dimethyl ether, diethylene glycol diethylene light, diethylene glycol di(tetra), diethylene glycol diiso, propanol monomethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Examples of the aliphatic cyclic ketones include, for example, cyclohexanone, o-, m-, p-methylcyclohexanone, etc. Examples of the acetic acid vinegar include ethyl acetate, acetic acid, and acetic acid. In addition, a solvent naphtha, methyl ethyl hydrazine, etc. may be used. The gel may be used to form an organosol having a solid content of a concentration ranging from $1 to 1% by weight. The compound may further contain (meth)acrylic acid compound 321527 14 201018701 or a vinyl group-containing compound. In this case, it is preferably contained in an amount of from 0.1 to 50 parts by weight based on 100 parts by weight of the total composition. It can also be used in combination of two or more. (Meth)Acrylic The compound may, for example, be a acrylamide, a (mercapto)alkyl acrylate, an alkylaminoalkyl (mercapto) acrylate, a quaternary ammonium salt of a (mercapto) acryloyl methacrylate, or an alkane. Oxyalkyl polyalkylene glycol (meth) acrylic acid vinegar, hydroxyalkyl (meth) acrylate, acid anhydride addition of (meth) acryl light base vinegar, polyalkylene glycol Poly(meth)acrylates of bis(meth)acrylate, alkanediol di(meth)acrylates, polyol poly(meth)acrylic acid ga, and %oxyxane addition. These compounds can be exemplified by the compound 0 described in JP-A No. 2,264,939, and examples of the vinyl group-containing compound include vinyl acetate vinegar, N-ethylene ethylene amine: vinyl material (tetra), and vinyl group. Ethyl acid, vinyl acid salt and the like. ❹平剂本::二: The product may also be mixed with a polymerization initiator, a diluent, a whole thousand agent, > a slipperiness imparting agent, other additives, and the like. Phenyl ketone-2-phenylethyl benzene polymerization initiator, which is not limited by photopolymerization which generates radicals, and is activated by energy ray phenyl TM: methylating agent &benzene;鲷, 2, 2~-methoxy methoxy linyl-1-propanone, 2-hydroxy~2~ 曱--(methylthio) phenyl] isopropyl phenyl)~2-hydroxy-2- Methylphenylpropane~1—anthracene, 1~(4~phenyl-(2-yl-2-yl)-pyrene- 1_teron, 4'(2,ylethoxy. (2'-C Thin oxyethoxy) stupid 321527 15 201018701 (2-hydroxy-2-propyl) ketone, 4-(2-methylpropenyloxyethoxy)phenyl-(2-hydroxy-2 -propyl)ketone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, etc. Examples of the diluent include monoalkyl ethers, alkanediols, and alkanes of alkanediols. An alkyl carboxylic acid ester of an alcohol monoalkyl alcohol, a ketone, an alkyl carboxylic acid ester of an alkyl alcohol, etc., which may, for example, be a diluent as described in JP-A-2004-43790. The layer composition may further contain a solvent as needed. As the solvent, the above alcohols, glycols, and fats may be used. Examples of the leveling agent and the lubricity imparting agent include a copolymer of polyoxyalkylene and polydimethyl siloxane, a polyoxyalkylene and carbon. A copolymer of a fluorine compound, etc. The composition for a hard coat layer of the present invention can be cured by irradiation with an active energy ray of ultraviolet rays, rays, infrared rays, X-rays, and electron beams, and the cured polymer is formed on the surface of the molded article. Hard-coated layer. The molded article here is not limited to a plastic molded article composed of a general-purpose resin such as a polystyrene resin, a polyolefin resin, an ABS resin, an AS resin, or an AN resin, and includes wood, glass, metal, ceramics, and the like. A molded article formed of various materials such as paper, cement, and a composite thereof is preferably a molded article in which a composition for a hard coat layer of the present invention is formed as a hard coat layer on the surface thereof. Further, the composition for a hard coat layer of the present invention may be in the form of a film constituting a hard coat layer, a transfer foil, or the like. Therefore, for example, the present invention may be used on a transparent substrate. A hard coating of 16 321527 201018701 is formed into a film shape from a composition to form a transfer foil for hard coating or a film for hard coating. These transfer cases or films can also be attached to the surface of a molded article. Further, when the molded article is made of plastic, the composition for a hard coat layer of the present invention may be mixed in a plastic constituting the molded article as a hard coat layer without affecting the intended properties of the plastic molded article. For example, a composition for a hard coat layer is applied to one surface or both side surfaces of a transparent substrate, and the coating film is formed into a hard coat layer by light irradiation or the like. Examples of the transparent substrate include a fine resin and a poly ring. Sulfur resin, such as polymethyl methacrylate (M) vinegar (methyl) propyl acrylate polymer, allyl sulphate, glycerol dicarboxylate, polycarbonate, milk tree 2, ring A substrate made of various synthetic resins such as a polybasic hydrocarbon. The substrate may have various shapes such as a flat plate shape, a curved plate shape, and a film shape. The coating can be carried out, for example, by dip coating, flow coating, spray coating, concave coating, coating, spin coating, rough coating, flexographic printing, screen printing, brushing, and the like. . The coating thickness is preferably from 0.01 to the range after curing.
的水^射可以列舉採用紫外線照射約刚至鳥J/W 明成硬質塗層的密合性’還可以預先在透 基=的表面上設置底塗層，進行驗處理、酸處 等離子處理、電暈處理、火_理等前處理。 底塗 至5〇而的乾圍較好。底塗層可以通過將 321527 17 201018701 這些樹脂溶液通過浸潰法、喷塗法、流塗法、輥塗法、旋 塗法等任一方法進行塗敷而形成。 以下，對本發明硬質塗層用組成物的實施例進行詳細 說明。 合成例1(聚胺酯（甲基）丙烯酸酯樹脂A-1的合成） 在四頸燒瓶上安裝攪拌裝置、溫度計和冷卻裝置，加 入己二異氰酸酯的聚異氰脲酸酯化物（日本聚胺酯工業（股） 生產的商品名：CORONATE HK，210. Og/當量）415. 8重量份 作為構成聚胺酯（甲基）丙烯酸酯樹脂的異氰酸酯化合物、 0 季戊四醇三丙烯酸酯（共榮社化學（股）生產的商品名： LIGHT-ACRYLATE PE-3A，498. 3g/當量）288. 2 重量份和丙 烯酸2-羥基乙酯（共榮社化學（股）生產的商品名：LIGHT-ACRYLATE Η0Α ， 498. 3g/當量 ）190. 8 重量份作為含羥基的 (甲基）丙烯酸酯化合物、對曱氧基苯酚0. 17重量份、BHT 0. 17重量份，在58至62°C下反應3小時後，加入1滴二 月桂酸二丁基錫，再在58至62°C下使其反應6小時，合 ❹ 成得到聚胺酯丙烯酸酯樹脂。 測定所得聚胺酯丙烯酸酯的紅外吸收光譜’ 2250CHT1 處的異氰酸酯基的峰已消失，確認反應完成，生成了聚胺 酉旨丙稀酸醋樹脂。 合成例2(聚胺酯（曱基）丙烯酸酯樹脂A-2的合成） 在四頸燒瓶上安裝攪拌裝置、溫度計和冷卻裝置，加 入己二異氰酸酯的異氰脲酸酯化物（日本聚胺酯工業（股） 生產的商品名：CORONATE HK ’ 210· 0g/當量）73.4重量份 18 321527 201018701 作為構成聚胺i旨（甲基）丙稀酸g旨樹脂的異氰酸醋化合物、 丙烯酸2-羥基乙酯的環氧乙烷加成物（8莫耳環氧乙烷的 加成物，575. 5g/當量）78. 0重量份作為以聚醚多元醇為主 鏈的化合物、對甲氧基苯酚0. 15重量份，在78至82°C下 反應3小時後，加入季戊四醇三丙烯酸酯（共榮社化學（股） 生產的商品名：LIGHT-ACRYLATE PE-3A，498. 3g/ 當量） 148. 7重量份作為含羥基的（甲基）丙烯酸酯化合物以及二 月桂酸二丁基錫1滴，再在78至82°C下使其反應6小時， © 合成得到聚胺酯丙烯酸酯樹脂。 測定所得聚胺酯丙烯酸酯的紅外吸收光譜，2250〇11-1 處的異氰酸酯基的峰已消失，確認反應完成，生成了聚胺 酯丙稀酸酯樹脂。 實施例1 將合成例1中合成的樹脂3重量份、有機矽酸膠溶液（扶桑 化學工業公司生產的商品名：PL-1-IPA，粒徑10nm，異丙 ❹醇溶液，固體成分含量12. 5%)24重量份、季戊四醇六丙烯The water spray can be exemplified by the adhesion of ultraviolet rays to the hard coating of the bird J/W. It is also possible to provide an undercoat layer on the surface of the permeation base in advance, and perform the treatment, acid treatment, and electricity. Halo treatment, fire treatment and other pre-treatment. It is better to apply the primer to 5 inches. The undercoat layer can be formed by applying any of the resin solutions of 321527 17 201018701 by a dipping method, a spray coating method, a flow coating method, a roll coating method, a spin coating method, or the like. Hereinafter, examples of the composition for a hard coat layer of the present invention will be described in detail. Synthesis Example 1 (Synthesis of Polyurethane (meth)acrylate Resin A-1) A stirrer, a thermometer, and a cooling device were attached to a four-necked flask, and polyisocyanurate of hexamethylene diisocyanate was added (Japan Polyurethane Industry) ) Product name: CORONATE HK, 210. Og/eq.) 415. 8 parts by weight of an isocyanate compound constituting a polyurethane (meth) acrylate resin, and 0 pentaerythritol triacrylate (product of Kyoritsu Chemical Co., Ltd.) Name: LIGHT-ACRYLATE PE-3A, 498. 3g/eq.) 288. 2 parts by weight and 2-hydroxyethyl acrylate (trade name: LIGHT-ACRYLATE Η0Α, 498. 3g/eq. 190. 8 parts by weight as a hydroxyl group-containing (meth) acrylate compound, p-methoxyphenol 0. 17 parts by weight, BHT 0.17 parts by weight, after reacting at 58 to 62 ° C for 3 hours, add 1 Dibutyltin dilaurate was added dropwise and reacted at 58 to 62 ° C for 6 hours to obtain a polyurethane acrylate resin. The infrared absorption spectrum of the obtained polyurethane acrylate was measured, and the peak of the isocyanate group at 2250 CHT1 disappeared, and it was confirmed that the reaction was completed, and a polyamine acetal acetal resin was produced. Synthesis Example 2 (Synthesis of Polyurethane (Mercapto) Acrylate Resin A-2) A stirrer, a thermometer, and a cooling device were attached to a four-necked flask, and isocyanurate of hexamethylene diisocyanate was added (Japan Polyurethane Industry Co., Ltd.) Product name of the product: CORONATE HK '210·0g/eq.) 73.4 parts by weight 18 321527 201018701 As an isocyanate compound or 2-hydroxyethyl acrylate which constitutes a resin of (meth)acrylic acid 0重量。 The ethylene oxide adduct (8 moles of ethylene oxide adduct, 575. 5g / equivalent) 78.0 parts by weight of the polyether polyol as the main chain of the compound, p-methoxyphenol 0. 15 After weight reaction, after reacting at 78 to 82 ° C for 3 hours, pentaerythritol triacrylate (trade name: LIGHT-ACRYLATE PE-3A, 498. 3 g / equivalent) produced by Kyoeisha Chemical Co., Ltd. was added. The fraction was used as a hydroxyl group-containing (meth) acrylate compound and 1 part of dibutyltin dilaurate, and further reacted at 78 to 82 ° C for 6 hours to obtain a polyurethane acrylate resin. The infrared absorption spectrum of the obtained polyurethane acrylate was measured, and the peak of the isocyanate group at 2250 〇 11-1 disappeared, and it was confirmed that the reaction was completed, and a polyurethane acrylate resin was produced. Example 1 3 parts by weight of a resin synthesized in Synthesis Example 1 and an organic phthalic acid gum solution (trade name: PL-1-IPA manufactured by Fuso Chemical Industry Co., Ltd., particle size 10 nm, isopropyl alcohol solution, solid content 12 5%) 24 parts by weight of pentaerythritol hexapropylene
酸醋（共榮社化學（股）生產的商品名：LIGHT-ACRYLATE PE-3A)4重量份、羥基環己基苯基酮（汽巴精化（股）生產 的：IRGACURE 184)0. 5重量份、異丙醇3. 5重量份進行混 練’得到含重量比約為3〇%的樹脂成分的硬質塗層用组成 物。 實施例2至8和比較例1至4 除了各成分的組成為表1中所示的以外，與實施例1 同樣地製得硬質塗層用組成物。 19 321527 201018701 表1 實施例 | 比較例 1 2 3 4 5 6 7 8 9 10 2 3 4 樹脂 ⑷-1 3 3 3 5 5 3 2 2 2 10 樹脂 (A)-2 5 樹脂 (BM 4 2 2 2 2 2 2 2 10 8 7 樹脂 ⑻-2 4 樹脂4 (B)-3 10 有機矽酸| 24 膠溶液1 24 24 24 24 24 7 有機矽酸 膠溶液2 15 30 有機矽酸 膠溶液3 30 有機矽酸 膠溶液4 | 30 IRGACURE 0.5 184 jr^ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 IPA 3.5 3.5 3,5 3.5 3.5 3.5 0.5 0.5 24.5 24.5 19.5 17.5 MEK 12.5 0.5 初期評價 塗膜狀態 (透明性） ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 鉛筆硬度 3H 4H 4H 4H 4H 4H 4H 4H 4H 4H Η 2Η 2Η 3Η 耐鋼絲性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ 捲曲性| ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ X X Δ 密合性| ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 另外，表1的成分如下。 樹脂（B)-l商品名：UA-306H(共榮社化學工業（股）生 20 321527 201018701 樹脂（B)-2 商品名：LIGHT-ACRYLATE DPE-6AC共榮社 化學工業（股）生產，二季戊四醇六丙烯酸酯） 樹脂（B)-3商品名：LIGHT-ACRYLATE PE-3A(共榮社化 學工業（股）生產，季戊四醇丙烯酸酯） 有機矽酸膠溶液1 商品名：PL-；l-IPA(扶桑化學工業 (股）生產，粒徑l〇nm，固體成分含量12. 5%) 有機矽酸膠溶液2 商品名：PL-2L-MEK(扶桑化學工 業（股）生產，粒徑20nm，固體成分含量20. 0%) 〇 有機矽酸膠溶液3 商品名：PL-；l-IPA(扶桑化學工業 (股）生產）的微粒上引入甲基丙烯基的產品（相當於式（2) 中R5為甲基丙烯基的產品） 有機矽酸膠溶液4 商品名：PL-1-IPAC扶桑化學工業 (股）生產）的微粒上引入丙烯基的產品（相當於式（2)中R5 為丙坤基的產品） IPA :異丙醇 MEK :甲基乙基酮 ® 塗敷基材：100/zm的PET(未處理） 將實施例1至8和比較例1至4中製得的硬質塗層用 組成物塗敷於基材上，乾燥溶劑。將其裝入6m/分鐘速度 的傳送帶上，用80W/cm的高壓汞燈從高度為10cm的位置 照射2次紫外線，使其交聯聚合，形成含固化聚合物的約 5#m厚度的塗層。 對所得塗層進行塗膜狀態（透明性）、鉛筆硬度、耐鋼 絲性、捲曲性和密合性的評價。 21 321527 201018701 塗膜狀態通過目視觀察，按4個等級進行評價，完全 沒有白化的評價為◎，幾乎沒有白化的評價為〇，部分存 在白化的評價為△，整體上都存在白化的評價為X。 鉛筆硬度在鉛筆硬度計負載500g重量下進行試驗，顯 示為沒有受損的鉛筆的硬度。 耐鋼絲性通過用負載約lkg負重的鋼絲（#0000)對所 得塗層進行10次往返摩擦而進行。按4個等級進行評價， 目視觀察時，沒有受損的評價為◎，幾乎沒有受損的評價 為〇，稍微受損的評價為△，受損的評價為X。 © 捲曲性，將塗膜剪切成10cm的正方形，測定其四角的 翹起高度的平均值。按4個等級進行評價，翹起高度的平 均值為10mm以下的評價為◎，10至20mm的評價為〇，20 至30mm的評價為△，30mm以上的評價為X。 密合性進行劃格試驗，按4個等級進行評價，100/100 的評價為©，9(V100以上的評價為〇，50/100以上的評價 為△，不到50/100的評價為X。 由表1可知，在實施例1至8中，通過向聚胺酯丙烯 ® 酸酯樹脂中配入其他官能基的（甲基）丙烯酸酯樹脂和有機 矽酸膠，在塗膜狀態、鉛筆硬度、耐鋼絲性、捲曲性和密 合性的所有方面均可獲得令人滿意的結果。 相比之下，在比較例1至4中，在塗膜狀態、錯筆硬 度、财鋼絲性、捲曲性和密合性的所有方面均無法獲得令 人滿意的結果。 實施例9 22 321527 201018701 將實施例1所得硬質塗層用組成物，與上述之塗膜狀 態（透明性）、錯筆硬度、财鋼絲性、捲曲性和密合性之評 價用相同，在基材上塗佈而形成塗佈層，製得硬質塗膜。 將所得塗膜夾在射出成型模具中，以成形同時射出之 成形法射出丙烯酸樹脂。冷卻後，得到具有硬質塗層之成 形品。 這樣，本發明的組成物可以使其最大程度地發揮丙烯 酸樹脂的透明性、耐擦傷性和耐久性，同時，使其降低捲 〇 曲性。另外，通過含有金屬氧化物微粒，可以進一步賦予 其更加良好的硬質塗層性。 產業上的可應用性 本發明的硬質塗層用組成物，可適用於由塑料、玻璃、 紙、木材等製作的成形品，可以對這些成形品長期、穩定 地形成在密合性、透明性、财擦傷性、财濕性等的耐久性 等方面優良的硬質塗層，可以降低硬質塗層用組成物的捲 曲性，即固化收縮率，從而獲得良好的塗層。因此，可以 〇 應用於需要這些性能的地方、成形品中。 【圖式簡單說明】 . 益〇 【主要元件符號說明】 Αί 〇 23 3215275重量份, 酸- hydroxy hexyl phenyl ketone (produced by Ciba Specialty Chemicals Co., Ltd.: IRGACURE 184) 0. 5 weight 5 parts by weight of isopropyl alcohol and kneading were carried out to obtain a composition for a hard coat layer containing a resin component in a weight ratio of about 3% by weight. Examples 2 to 8 and Comparative Examples 1 to 4 A composition for a hard coat layer was obtained in the same manner as in Example 1 except that the composition of each component was as shown in Table 1. 19 321527 201018701 Table 1 Examples | Comparative Example 1 2 3 4 5 6 7 8 9 10 2 3 4 Resin (4)-1 3 3 3 5 5 3 2 2 2 10 Resin (A)-2 5 Resin (BM 4 2 2 2 2 2 2 2 10 8 7 Resin (8)-2 4 Resin 4 (B)-3 10 Organic decanoic acid | 24 Glue solution 1 24 24 24 24 24 7 Organic citric acid solution 2 15 30 Organic bismuth solution 3 30 Organic bismuth solution 4 | 30 IRGACURE 0.5 184 jr^ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 IPA 3.5 3.5 3,5 3.5 3.5 3.5 0.5 0.5 24.5 24.5 19.5 17.5 MEK 12.5 0.5 Initial evaluation of the film state ( ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Pencil hardness 3H 4H 4H 4H 4H 4H 4H 4H 4H 4H Η 2Η 2Η 3Η Steel resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ XX Δ Adhesive| ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ In addition, the components of Table 1 are as follows. Resin (B)-l :UA-306H (Kyoeisha Chemical Industry Co., Ltd.) 20 321527 201018701 Resin (B)-2 Product Name: LIGHT-ACRYLATE DPE-6AC Co., Ltd. Chemical Industry Co., Ltd., Dipentaerythritol Hexaacrylate) Resin (B)-3 Product Name: LIGHT-ACRYLATE PE-3A (produced by Kyoeisha Chemical Industry Co., Ltd., pentaerythritol acrylate) Organic phthalic acid syrup solution 1 Trade name: PL-; l-IPA (Fusang Chemical Industry Co., Ltd. production, particle size L〇nm, solid content of 12.5%) 矽 矽 矽 商品 商品 商品 商品 商品 商品 商品 商品 商品 商品 商品 商品 商品 PL PL PL PL PL PL PL PL PL PL PL PL PL PL PL 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Acid Glue Solution 3 Trade name: PL-; l-IPA (product produced by Fuso Chemical Industry Co., Ltd.) Introduces a methacryl-based product (equivalent to a product in which R5 is a methacryl group in formula (2)) Organic矽 胶 溶液 4 商品 商品 商品 商品 商品 PL -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- IP IP IP IP IP IP IP IP IP IP IP IP IP IP IP IP IP IP IP MEK: methyl ethyl ketone® coated substrate: 100/zm PET (untreated) Examples 1 to 8 and Comparative Examples 1 to 4 The hard coat layer prepared in the composition is applied onto a substrate to dry the solvent. It was placed on a conveyor belt at a speed of 6 m/min, and irradiated with ultraviolet light twice from a height of 10 cm with a high-pressure mercury lamp of 80 W/cm to cross-link and polymerize to form a coating having a thickness of about 5 #m containing the cured polymer. Floor. The obtained coating layer was evaluated for coating state (transparency), pencil hardness, steel resistance, curling property, and adhesion. 21 321527 201018701 The film state was evaluated by visual observation and evaluated in four grades. The evaluation of no whitening was ◎, the evaluation of almost no whitening was 〇, the evaluation of partial whitening was △, and the evaluation of whitening as a whole was evaluated as X. . The pencil hardness was tested under a pencil hardness tester load of 500 g, which showed the hardness of the pencil without damage. The steel wire resistance was carried out by performing 10 round-trip rubbing of the obtained coating layer with a steel wire (#0000) carrying a load of about lkg. The evaluation was carried out in four levels. When visually observed, the evaluation without damage was ◎, the evaluation with little damage was 〇, the evaluation with slight damage was Δ, and the evaluation for damage was X. © Curlability, the film was cut into a square of 10 cm, and the average value of the lift height of the four corners was measured. The evaluation was carried out in four grades, and the evaluation of the average height of the lift height was 10 mm or less, the evaluation of 10 to 20 mm was 〇, the evaluation of 20 to 30 mm was Δ, and the evaluation of 30 mm or more was X. The adhesion test was carried out in four levels, and the evaluation of 100/100 was ©, 9 (the evaluation of V100 or more was 〇, the evaluation of 50/100 or more was △, and the evaluation of less than 50/100 was X). As can be seen from Table 1, in Examples 1 to 8, by adding a functional group (meth) acrylate resin and an organic phthalic acid gel to a polyurethane acrylate resin, the coating state, pencil hardness, Satisfactory results were obtained in all aspects of the steel wire resistance, curling property, and adhesion. In contrast, in Comparative Examples 1 to 4, the film state, the pen hardness, the profitability, and the curl property were observed. Satisfactory results were not obtained in all aspects of adhesion and adhesion. Example 9 22 321527 201018701 The composition for a hard coat layer obtained in Example 1 and the above-mentioned film state (transparency), wrong pen hardness, and wealth The steel wire, curling property, and adhesion were evaluated in the same manner, and a coating layer was formed by coating on a substrate to obtain a hard coating film. The obtained coating film was sandwiched in an injection molding die to form a simultaneous injection molding method. Eject the acrylic resin. After cooling, it has Thus, the composition of the present invention can maximize the transparency, scratch resistance and durability of the acrylic resin, and at the same time reduce the curling property of the acrylic resin. Further, the fine particles can be further imparted with a hard coating property. INDUSTRIAL APPLICABILITY The composition for a hard coat layer of the present invention can be applied to a molded article made of plastic, glass, paper, wood, or the like, and can be used. These molded articles are formed into a hard coat layer excellent in durability such as adhesion, transparency, scratch resistance, and moisture resistance for a long period of time, and can reduce the curling property of the composition for a hard coat layer, that is, cure shrinkage. Rate, so as to obtain a good coating. Therefore, it can be applied to places where there is a need for these properties, and molded articles. [Simple description of the diagram] . 〇 [Main component symbol description] Αί 〇23 321527