201038683 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種在表面上具有鉻層及/或氧化鉻層 之含鉻體之表面上形成塗膜之塗膜形成材料，及表面上具 有鉻層及/或氧化鉻層之含銘體上形成塗膜之層合體，及 該層合體之製造方法’本發明尤其關於可獲得與含鉻體之 接著性優異之塗膜之塗膜形成材料，及形成有與含鉻體之 0 接著性優異之塗膜之層合體’及該層合體之製造方法。 【先前技術】 通常，印刷電路板係藉由在基材材料表面上層合乾膜 等光阻劑，在光阻劑之表面上密著光罩之形成有曝光用圖 型之面，透過光罩使光阻劑曝光後，將光罩剝離，使光阻 劑顯像，並施以蝕刻處理而製造。此時剝離之光罩係重複 使用於下一次的印刷電路板之製作。 Q 近年來，對於印刷電路板等高密度化之要求顯著，對 於提高其中所使用之光罩之尺寸精準度成爲有其必要。因 此，使用以玻璃作爲支撐體，於其上設置由感光乳劑所構 成之層之使用玻璃乾板之光罩，進而高精密者係使用形成 鉻層及/或氧化鉻層替代由該感光乳劑所構成之層。 鉻層及/或氧化鉻層通常爲表面硬度高、不易刮傷者 ，但形成此等鉻層及/或氧化鉻層之光罩於重複曝光時， 會有因爲靜電火花使蒸鍍之鉻層及/或氧化鉻層斷線，而 產生發生針孔之問題。 -5- 201038683 另一方面，設置有由感光乳劑所構成之層之光罩爲了 重複使用而防止光阻劑之附著等之目的，而有在形成曝光 用圖型之面上貼合透明保護薄膜之情況（專利文獻1 )。 因此，認爲在形成該等鉻層及/或氧化鉻層之光罩之 表面上藉由貼合如上述之透明保護薄膜，可避免光阻劑之 附著及鉻層及/或氧化鉻層之斷線，但蒸鍍鉻層及/或氧化 鉻層之光罩由於光罩本身爲高精密，因此若如上述貼合透 明保護薄膜，則會發生曝光精密度下降之問題。 又，亦認爲藉由將塗膜形成用塗佈液塗佈於形成鉻層 及/或氧化鉻層之光罩之表面上形成塗膜（塗膜），可避 免光阻劑之附著及鉻層及/或氧化鉻層之斷線，但通常由 於鉻層及/或氧化鉻層與有機物之接著性低，導致鉻層及/ 或氧化鉻層與塗膜之接著性不充分，使塗膜自鉻層及/或 氧化鉻層剝離而無法進行重複曝光。 因此，考慮有可在如形成鉻層及/或氧化鉻層之光罩 般之於表面具有絡層及/或氧化鉻層之含鉻體之表面上， 藉由比較低溫且短時間硬化進行易接著處理，同時與含鉻 體之接著性良好且可形成均句美麗之塗膜之塗膜形成材用 ’以及含有鉻層及/或氧化鉻層之層合體（專利文獻2 )。 [先前技術文獻] [專利文獻] [專利文獻1]實登25 8 9276號公報（申請專利範圍第1 項） [專利文獻2 ]特開2 0 0 6 -2 3 2 9 0 8號公報（申請專利範 201038683 圍第1項） 【發明內容】 [發明欲解決之課題] 然而，近年來，爲了削減生產成本，而要求可在更短 時間內製造光罩，藉由如上述專利文獻2之熱硬化形成之 塗膜並無法滿足與被塗佈物之接著性良好，且在更短時間 0 內形成均勻且美麗之塗膜之要求。 因此，本發明之目的係提供一種可在短時間內形成塗 膜、表面具有鉻層及/或氧化鉻層之含鉻體之表面與塗膜 之接著性優異且塗膜之表面硬度優異之塗膜形成材料。 又，本發明之目的係提供一種形成有可在短時間內形 成塗膜、與表面具有鉻層及/或氧化鉻層之含鉻體之接著 性優異且塗膜之表面硬度優異之塗膜之含有鉻層及/或氧 化鉻層之層合體，及含有鉻層及/或氧化鉻層之層合體之 Q 製造方法。 [爲解決課題之手段] 爲解決上述課題而積極硏究之結果，已了解塗膜之形 成時間與塗膜中所含熱硬化型樹脂之硬化時間有關，爲了 在短時間內形成塗膜，藉由不使用硬化時間長的熱硬化型 樹脂，而使用硬化時間爲短時間之電離輻射線硬化型樹脂 可以解決上述課題。然而，已知僅藉由將塗膜形成材料之 塗膜形成用塗佈液中之熱硬化型樹脂變更成電離輻射線硬 201038683 化型樹脂’則具有鉻層及/或氧化鉻層之含鉻體與塗膜之 接著性不足’使塗膜之耐久性變差。因此，發現利用含有 具有胺基之有機矽烷水解縮合物者作爲易接著處理液，可 提闻含鉻體與塗膜之接著性及提高塗膜之表面硬度，因而 得以解決該問題。 亦即’本發明之塗膜形成材料之特徵爲由包含具有胺 基之有機矽烷水解縮合物之易接著處理液與包含電離輻射 線硬化型樹脂之塗膜形成用塗佈液之兩種塗佈液所構成。 又’本發明之層合體之特徵爲在表面上具有鉻層及/ 或氧化鉻層之含鉻體上依序具有由具有胺基之有機矽烷水 解縮合物所形成之易接著層、由電離輻射線硬化型樹脂所 形成之塗膜。 又’本發明之層合體之製造方法其特徵爲在表面上具 有鉻層及/或氧化鉻層之含鉻體上塗佈包含具有胺基之有 機矽烷水解縮合物之易接著處理液，於其上塗佈包含電離 輕射線硬化型樹脂之塗膜形成用塗佈液後，照射電離輻射 線使塗膜硬化而成。 [發明效果] 本發明之塗膜形成材料可在短時間內形成塗膜，且可 獲得表面具有鉻層及/或氧化鉻層之含鉻體之表面與塗膜 之接著性優異’塗膜之表面硬度優異之含鉻層及/或氧化 鉻層之層合體。 本發明之層合體可成爲表面具有鉻層及/或氧化鉻層 -8 - 201038683 之含鉻體與塗膜之接著性優異、塗膜之表面硬度 本發明之層合體之製造方法可製造可在短時 塗膜，且在表面上具有絡層及/或氧化鉻層之含 成與表面上具有鉻層及/或氧化鉻層之含鉻體之 異且塗膜之表面硬度優異之塗膜之含鉻層及/或 之層合體。 q 【實施方式】 就本發明之塗膜形成材料之實施型態加以說 明之塗膜形成材料爲由包含具有胺基之有機矽烷 物之易接著處理液與包含電離輻射線硬化型樹脂 成用塗佈液之兩種塗佈液所構成者。 首先，針對易接著處理液加以說明。易接著 用以提高表面具有鉻層及/或氧化鉻層（以下亦 鉻層等」之情況）之含鉻體與爲有機物之塗膜之 Q 用者，本發明中爲包含具有胺基之有機矽烷水解 〇 具有胺基之有機矽烷爲具有至少一個胺基者 表面具有鉻層及/或氧化鉻層之含鉻體與由後述 用塗佈液所形成之塗膜之接著性。至於該等具有 機矽烷可使用例如γ-胺基丙基三甲氧基矽烷、γ-三乙氧基矽烷、Ν-β (胺基乙基）γ-胺基丙基三 烷、Ν-β (胺基乙基）胺基丙基甲基二甲氧基紀 (胺基乙基）γ-胺基丙基三甲氧基矽烷、γ-[雙（ 優異者。 間內形成 鉻體上形 接著性優 氧化鉻層 明。本發 水解縮合 之塗膜形 處理液係 有稱爲「 接著性所 縮合物者 ，可提高 塗膜形成 胺基之有 胺基丙基 甲氧基矽 > 烷、Ν-β β-羥基乙 -9 - 201038683 基）]-胺基丙基三乙氧基矽烷、（2-胺基乙基）胺基 三烷氧基矽烷、3 -胺基丙基三甲氧基矽烷、3 -胺基丙 乙氧基矽烷、3 -胺基丙基二甲基乙氧基矽烷、3 -胺基 甲基二乙氧基矽烷、N-(2-胺基乙基）-3-胺基丙基甲 氧基矽烷、N- (2-胺基乙基）-3-胺基丙基三甲氧基矽 〇 該等具有胺基之有機矽烷有必要成爲水解縮合物 中，本發明中所謂的具有胺基之有機矽烷水解縮合物 使具有胺基之有機矽烷水解，並經縮合獲得之縮合物 /或經縮合所得之部份縮合物。藉由使該等具有胺基 機矽烷水解縮合，可產生矽烷醇基而提高對含鉻體之 性。基於該等理由，可提高與以未經水解者之因接著 足而未接著之含鉻體之接著性。 又，將此種含有具有該等胺基之有機矽烷水解縮 之易接著處理液使用於光罩時，與未形成鉻層之玻璃 接著，由於亦可產生矽烷醇基而提高接著性’因而較 具有該等胺基之有機矽烷水解縮合物於易接著處 中之下限爲0.01重量％以上’進而以0.1重量％以上 ，上限爲1 0重量％以下，進而以5重量％以下較佳。 成爲〇 · 〇 1重量％以上，可獲得必要的與含鉻體之接著 藉由成爲10重量％以下，可防止因干涉不均等造成之 不良之發生。 又，具有胺基之有機矽烷水解縮合物以佔易接著 液之總固形成分之90重量％以上爲佳。藉由使之成ί 丙基 基三 丙基 基甲 烷等 。其 係指 ，及 之有 反應 性不 合物 面之 圭。 理液 較佳 藉由 力， 外觀 處理 I 90 -10- 201038683 重量％以上，可使與含鉻體之接著性變好’亦可使與使用 後述之塗膜形成用塗佈液之塗膜之接著性變良好。 如上述之本發明易接著處理液通常以甲醇、乙醇、及 異丙醇等之醇系溶劑稀釋具有胺基之有機矽烷，且可藉由 使用鹽酸等酸或氫氧化鈉等鹼作爲觸媒進行水解，在恆溫 下攪拌任意時間而成爲所需之水解縮合物。又，亦可以與 上述同樣之醇系溶劑進一步稀釋水解縮合物，成爲易接著 處理液。 接著，對塗膜形成用塗佈液加以說明。塗膜形成用塗 佈液係使用於表面上具有鉻層及/或氧化鉻層之含鉻體上 形成塗膜者，本發明中爲含有電離輻射線硬化型樹脂者。 藉由使用該等塗膜形成用塗佈液，可於短時間在表面上具 有絡層及/或氧化鉻層之含鉻體表面上形成塗膜。 電離輻射線硬化型樹脂爲至少可藉由電離輻射線（紫 外線或電子束）之照射而交聯硬化者。至於該等電離輻射 〇 ，線硬化型樹脂可使用混合陽離子光可聚合之光陽離子聚合 性樹脂’或自由基光可聚合之光聚合性預聚物，或光聚合 性單體等之一種或兩種以上而成者。 力其’具有不飽和性雙鍵者由於與藉由前述之易接著 液形成之易接著層之接著性良好故而較佳。具有不飽 m ft 胃之電離輻射線硬化型樹脂可使用（甲基）丙烯酸 醋寡聚物或（甲基）丙烯酸系單體等。 (甲基）丙烯酸酯寡聚物，可使用酯（甲基）丙 (甲基）丙烯酸酯、胺基甲酸酯（甲基）丙烯酸 -11 - 201038683 酯 '環氧（甲基）丙烯酸酯、胺基樹脂（甲基）丙烯酸醋 、丙烯酸樹脂（甲基）丙烯酸酯、三聚氰胺（甲基）丙燒 酸酯、多氟烷基（甲基）丙烯酸酯、聚矽氧（甲基）丙烯 酸酯等。又，該等（甲基）丙烯酸酯寡聚物可單獨使用， 但爲了賦予提高交聯硬化性、調整硬化收縮等各種性能， 較好混合兩種以上使用。 又’（甲基）丙烯酸系單體係使用1,6-己二醇二（甲 基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、二乙二醇 二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、羥 基特戊酸酯新戊二醇二（甲基）丙烯酸酯等二官能基（甲 基）丙烯酸單體，二季戊四醇六（甲基）丙烯酸酯、三甲 基丙烷三（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸 酯等多官能基（甲基）丙烯酸單體等之一種或兩種以上。 (甲基）丙烯酸酯寡聚物及（甲基）丙烯酸系單體較 好佔塗膜形成用塗佈液之總固形成分之5 0〜8 9重量％。藉 由成爲5 0重量％以上，可防止塗膜之表面硬度降低，藉由 成爲89重量％以下，可充分發揮易接著層與塗膜之接著性 〇 又，藉由紫外線照射硬化而使用本發明之塗膜形成用 塗佈液時，除（甲基）丙烯酸酯寡聚物及（甲基）丙烯酸 系單體以外’較好使用光聚合起始劑或光聚合促進劑等添 加劑。 至於光聚合起始劑，舉例有苯乙酮、二苯甲酮、米契 爾酮（Michler ketone ) '苯偶因、苄基甲基縮酮、苯偶 -12- 201038683 因苯甲酸酯、α-醯基肟酯、噻噸酮類等。 又，光聚合促進劑爲可減輕硬化時因空氣造成之聚合 障礙以加速硬化速度者，例如，對·二甲基胺基苯甲酸異 戊酯、對-二甲基胺基苯甲酸乙酯等。 又’爲了提高與由易接著處理液形成之易接著層之接 著性’亦可添加反應性親水性物質。該等反應性親水性物 質爲可與（甲基）丙烯酸酯寡聚物及/或（甲基）丙烯酸 0 系單體共聚合者。藉由與（甲基）丙烯酸酯寡聚物及/或 (甲基）丙儲酸系單體共聚合，不會自塗膜滲出，且可防 止易接著層與塗膜之接著性之經時變化，可提高塗膜之耐 久性。再者’由於可與（甲基）丙烯酸酯寡聚物及/或（ 甲基）丙烯酸系單體共聚合，可增加塗膜中之交聯密度充 分’且藉由添加反應性親水性物質可防止塗膜之硬度降低 〇 該等反應性親水物質可使用具有例如羥基、（甲基） Q 丙烯醯基、乙烯基、環氧基、苯乙烯基、（甲基）丙烯醯 氧基、胺基、锍基、異氰酸酯基等之親水性物質。尤其， 具有（甲基）丙烯醯基之（甲基）丙烯酸改質之親水性物 質由於容易與前述之（甲基）丙烯酸酯寡聚物及/或（甲 基）丙烯酸系單體共聚合，同時與前述（甲基）丙烯酸酯 寡聚物及/或（甲基）丙烯酸系單體之相溶性良好故而較 佳。 至於（甲基）丙烯酸改質之親水性物質，爲了使與乳 化光罩之接著性良好，可使用（甲基）丙烯酸改質之磷酸 -13- 201038683 酯、（甲基）丙烯酸改質之四級銨鹽等，尤其，爲了使塗 膜形成用塗佈液之儲存安定性良好，更好使用（甲基）丙 烯酸改質之四級銨鹽。 至於（甲基）丙烯酸改質之磷酸酯可使用三硬脂醯氧 基乙基磷酸酯、2-丙烯醯氧基乙基酸性磷酸酯、2-甲基丙 烯醯氧基乙基酸性磷酸酯等，至於（甲基）丙烯酸改質之 四級銨鹽可使用二甲胺基乙基丙烯酸酯氯化甲基四級鹽、 二甲胺基丙基丙烯醯胺氯化甲基四級鹽、二甲胺基乙基甲 基丙烯酸酯氯化甲基四級鹽等。 反應性親水性物質較好佔塗膜形成用塗佈液之總固形 成分之10〜30重量％，最好爲10-20重量％，成爲10重量 %以上係因爲可獲得易接著層與塗膜之接著性，成爲30重 量％以下係因爲不會使塗膜之表面硬度降低之故。 又，該等塗膜形成用塗佈液亦可適當的添加賦予脫模 性之脫模劑，或賦予抗靜電性之抗靜電劑等。 此等脫模劑可使用二甲基矽氧油、甲基氫化矽氧油、 甲基苯基矽氧油、環狀二甲基矽氧油等矽氧油或於矽氧油 中導入有機基而成之改質矽氧油。 至於改質之矽氧油可使用烷基改質、聚醚改質、氟改 質、锍基改質、環氧基改質、羧基改質、高級脂肪酸酯改 質、（甲基）丙烯酸改質、卡必醇改質等之改質矽氧油。 尤其，使用具有與（甲基）丙烯酸酯寡聚物及（甲基 )丙烯酸系單體或反應性親水性物質反應之基之反應性矽 氧油由於可持續脫模性或防污性故而較佳。據此，如此可 -14- 201038683 容易地去除塗膜表面之光阻劑等之附著物。 至於該等反應性矽氧油可使用具有例如羥基、（甲基 )丙烯醯基、乙烯基、環氧基、苯乙烯基、（甲基）丙烯 醯氧基、胺基、锍基、異氰酸酯基等者。尤其，較好爲可 與（甲基）丙烯酸酯寡聚物及（甲基）丙烯酸系單體或反 應性親水性物質輕易地共聚合，且與前述（甲基）丙烯酸 酯寡聚物及（甲基）丙烯酸系單體相溶性佳之具有（甲基 q )丙烯酸酯基者。 脫模劑較好爲塗膜形成用塗佈液之總固形成分之 0.5〜2〇重量％ ’成爲0.5重量％以上之原因係爲了獲得足 夠之脫模性、防污性，成爲2 0重量％以下之原因係爲了不 使表面硬度降低。 本發明之塗膜形成用塗佈液可調配以上說明之電離輻 射線硬化型樹脂或依據需要調配之其他成分、溶解於適當 溶劑中而調製。再者’使各成分彼此相溶由於可防止塗膜 Q 之白化等故而較好。 接著’針對本發明之包含鉻層及/或氧化鉻層之層合 體之製造法之實施形態加以說明。本發明之包含鉻層及/ 或氧化鉻層之層合體製造方法係將包含具有胺基之有機矽 院水解縮合物之易接著處理液塗佈於表面具有鉻層等之含 銘體上’於其上塗佈包含電離輻射線硬化型樹脂之塗膜形 成用塗佈液後，照射電離輻射線使塗膜硬化者。 本發明中使用之表面上具有鉻層等之含鉻體爲於成形 體上層合鉻層等而成者’例如，可舉出用以在印刷電路板 -15- 201038683 或樹脂凸版上形成細微圖型之於形成有圖型之玻璃基板上 塗佈鉻層等而成之鉻光罩等。又’不僅爲於成形體表面之 整面上具有鉻層等者，亦包含一部份具有鉻層者。 首先，於該等之表面上具有鉻層等之含鉻體上塗布包 含具有胺基之有機矽烷水解縮合物之易接著處理液，並經 乾燥。乾燥溫度爲80~ 100 °C左右，乾燥時間爲1〜3分鐘左 右之使易接著處理液中所含溶劑蒸發程度之乾燥溫度、乾 燥時間即可。 易接著層厚度變厚時容易產生干涉不均，若於易接著 層上產生干涉不均勻，則塗佈塗膜後亦無法消除干涉不均 ，造成外觀之不良，因此較好成爲2 μηι以下。 該等易接著層可在表面上具有鉻層等之成形體之一部 份上形成，在未形成有鉻層及/或氧化鉻層之部分上形成 亦無妨。 接著，在設有易接著層之含鉻體之易接著層上塗佈包 含電離輻射線硬化型樹脂之塗膜形成用塗佈液，且視需要 乾燥後，以電離輻射線照射使塗膜交聯硬化。如此於本發 明中，藉由包含電離輻射線硬化型樹脂之塗膜形成用塗佈 液形成塗膜，比使用熱硬化型樹脂時可以更短的時間形成 塗膜。 由本發明之塗膜形成用塗佈液獲得之塗膜厚度爲2〜4 μηι’較好爲2〜3μιη。成爲2μηι以上之原因係爲了獲得塗 膜表面硬度，成爲4μηι以下之原因係爲了避免產生龜裂或 塗膜白化、透明性降低。 -16- 201038683 至於塗佈該等易接著處理液及塗膜形成用塗佈液之方 法可使用旋轉塗佈法或模具塗佈法（Die coat)、蓋塗佈 法（Cap coat)、棒塗佈法等習知之方法。 利用上述之本發明之含鉻層及/或氧化鉻層之層合體 之製造方法，可在本發明之表面上具有鉻層及/或氧化鉻 層之含鉻體上獲得依序具有由具有胺基之有機矽烷水解縮 合物形成之易接著層、由電離輻射線硬化型樹脂形成之塗 膜之包含鉻層及/或氧化鉻層之層合體。 由塗膜形成用塗佈液獲得之塗膜，其硬化後之塗膜表 面以lkg荷重之鋼絲絨#〇〇〇〇在表面摩擦來回十次後，塗 膜之表面上並無傷痕者爲佳。 如此藉由使用由具有胺基之有機矽烷水解縮合物形成 之易接著層，可在短時間內於表面上具有鉻層及/或氧化 鉻層之含鉻體上形成接著性優異之塗膜。 [實施例] 以下以實施例進一步說明本發明。又，「份」、^ % 」若無特別顯示則爲重量基準。 [實施例1] 以旋轉塗佈將下列組成之易接著處理液塗佈於表面上 具有絡層及/或氧化絡層之含絡體（形成圖型之絡光罩） 上，在80 °C乾燥2分鐘’形成厚度5 Onm之易接著層。 -17- 201038683 <易接著處理液> •具有胺基之有機矽烷水解縮合物 〇.3份 (KBP-90:信越聚砂氧公司，固形成分32%) •稀釋溶劑 3 1.9份 接著，利用旋轉塗佈將下列組成之塗膜形成用塗佈 '液 塗佈在易接著層上，在80°C乾燥2分鐘，照射紫外線1〇 秒鐘（1 000mJ/cm2 )，形成厚度約3μπι之塗膜，製備實施 例1之包含鉻層及/或氧化鉻層之層合體。 <塗膜形成用塗佈液> •丙烯酸胺基甲酸酯寡聚物 3 (ART RESIN UN904 ：根上工業公司） •丙烯酸胺基甲酸酯單體 丨 (NK ESTER A-TMMT :新中村工業公司） •丙烯酸改質之四級銨鹽 j (DMAEA-Q:興人公司，固形成分79%) •脫検劑 〇 · 3 5份 (末端基帶有不飽和鍵之聚矽氧烷改質之聚合_ %@ 形成分7 0 % ) *光自由基聚合起始劑 (Irgacure 184 : Ciba Japan 公司） •稀釋溶劑 ^ //x [實施例2] -18 - 201038683 除以下述之易接著處理液取代實施例1之易接著處理 液以外，餘如實施例1般製備實施例2之含有鉻層及/或 氧化鉻層之層合體。易接著層之厚度爲2 nm。 <易接著處理液> .具有胺基之有機矽烷水解縮合物 0.1份 (KBP-90 :信越聚矽氧公司，固形成分32%) 0 ·稀釋溶劑 319份 [實施例3] 除以下述之易接著處理液取代實施例1之易接著處理 液以外，餘如實施例1般製備實施例3之含有鉻層及/或 氧化鉻層之層合體。易接著層之厚度爲15 nm。 <易接著處理液> Q .具有胺基之有機矽烷水解縮合物 ο. 1份 (KBP-90:信越聚矽氧公司，固形成分32%) •稀釋溶劑 3 1 . 9份 [實施例4] 除以下述之易接著處理液取代實施例1之易接著處理 液以外，餘如實施例1般製備實施例4之含有鉻層及/或 氧化鉻層之層合體。易接著層之厚度爲1.6 μηι。 -19- 201038683 <易接著處理液> •具有胺基之有機砂垸水解縮合物 4份 (KBP-90:信越聚砂氧烷公司，固形成分32%) •稀釋溶劑 9份 [實施例5] 除以下述之塗膜形成用塗佈液取代實施例丨之塗膜形 成用塗佈液以外，餘如實施例1般製備實施例5之含有鉻 層及/或氧化鉻層之層合體。 <塗膜形成用塗佈液> •丙烯酸胺基甲酸酯單體 4份 (NKESTERA-DPH:新中村工業公司） •丙烯酸改質之四級銨鹽 1份 (DMAEA-Q:興人公司，固形成分79%) •脫模劑 0.3 5份 (末端基帶有不飽和鍵之聚砂氧院改質之聚合物，固 形成分7 0 % ) •光自由基聚合起始劑 0.3 5份 (Irgacure 184 ·· Ciba Japan 公司） •稀釋溶劑 1 5份 [實施例6] 除以下述之易接著處理液取代實施例1之易接著處理 -20 - 201038683 液，再以下述之塗膜形成用塗佈液取代實施例1之塗膜形 成用塗佈液以外’餘如實施例1般製備實施例6之含有路 層及/或氧化鉻層之層合體。易接著層之厚度爲15nm。易 接著層上之塗膜厚度約爲3 μηι。 <實施例6之易接著處理液之調製> 將1.54份之0.2mo 1/1鹽酸、2.14份純水、16.33份乙 q 醇加於容器中充分冷卻攪拌，製作稀釋之鹽酸溶液。 於另一容器中添加4份乙醇、1份具有胺基之有機矽 烷（KBM-903，信越聚矽氧公司），且調溫至25°C。隨後 ，添加5份上述稀釋鹽酸溶液作爲觸媒，在25°C之恆溫下 攪拌24小時’獲得具有胺基之有機矽烷水解縮合物。接 著添加990份之異丙醇稀釋，獲得實施例6之易接著處理 液。 Q 〈塗膜形成用塗佈液> •丙烯酸胺基甲酸酯寡聚物 5份 (UNIDIC 1 7-8 06 ： DIC 公司） •光自由基聚合起始劑 0.1 2份· (Irgacure 18 4： Ciba Japan 公司） .稀釋溶劑 i 5份 [比較例1 ] 除以下述之塗膜形成用塗佈液取代實施例1之塗膜形 -21 - 201038683 成用塗佈液，以旋轉塗佈於易接著層上進行塗佈’且在 8 0。(：乾燥3 0分鐘’形成塗膜以外，餘如實施例1般製作 比較例1之含有鉻層及/或氧化鉻層之餍合體。 <塗膜形成用塗佈液> •丙烯酸多元醇 5份 .脫模劑 0 · 3 5份 (末端基帶有不飽和鍵之聚矽氧烷改質之聚合物’固 形成分70% ) .硬化劑 1份 (TAKENATE D1 10Ν :三井化學聚胺基甲酸酯公司， 固形成分60% ) •稀釋溶劑 1 5份 [比較例2] 利用旋轉塗佈在表面上具有鉻層及/或氧化鉻層之含 鉻體（形成圖型之鉻光罩）上塗佈下述組成之塗膜形成用 塗佈液，在 80°C乾燥2分鐘，經紫外線照射1 0秒（ 1 000mJ/cm2 )，形成厚度約3 μπι之塗膜，製作比較例2之 包含鉻層及/或氧化鉻層之層合體。 <塗膜形成用塗佈液> •丙烯酸胺基甲酸酯寡聚物 3份 (ART RESIN UN90 4 ··根上工業公司） -22- 201038683 •丙烯酸胺基甲酸酯單體 1份 (NK ESTER A-TMMT :新中村工業公司） •丙烯酸改質之四級銨鹽 1份 (DMAEA-Q:興人公司’固形成分79%) •脫模劑 0.35份 (末端基帶有不飽和鍵之聚矽氧烷改質之聚合物，固 形成分70%) 0.3 5 份 15份201038683 6. Technical Field of the Invention The present invention relates to a coating film forming material for forming a coating film on a surface of a chromium-containing body having a chromium layer and/or a chromium oxide layer on a surface thereof, and having a surface thereon. A laminate for forming a coating film on a chrome layer and/or a chromium oxide layer, and a method for producing the laminate. The present invention relates in particular to a coating film forming material which can obtain a coating film excellent in adhesion to a chromium-containing body. And a laminate in which a coating film having excellent adhesion to a chromium-containing body is formed, and a method of producing the laminate. [Prior Art] Generally, a printed circuit board is formed by laminating a photoresist such as a dry film on the surface of a substrate material, and a surface of the photoresist is formed with a mask formed on the surface of the photoresist, and the mask is formed through the mask. After exposing the photoresist, the photomask is peeled off, the photoresist is developed, and an etching treatment is performed. The mask that was peeled off at this time was reused for the production of the next printed circuit board. Q In recent years, there has been a significant demand for high density of printed circuit boards, etc., and it has become necessary to improve the dimensional accuracy of the reticle used therein. Therefore, a glass mask using a glass as a support and a layer made of an emulsion is provided thereon, and a high-precision person uses a chromium layer and/or a chromium oxide layer instead of the emulsion. Layer. The chrome layer and/or chrome oxide layer usually has a high surface hardness and is not easily scratched. However, when the reticle forming the chrome layer and/or the chrome oxide layer is repeatedly exposed, the chrome layer deposited by the static spark may be / or the chrome oxide layer is broken, causing pinhole problems. -5- 201038683 On the other hand, a photomask provided with a layer composed of an emulsion is used for the purpose of preventing the adhesion of the photoresist for repeated use, and the transparent protective film is bonded to the surface on which the exposure pattern is formed. (PTL 1). Therefore, it is considered that the adhesion of the photoresist and the chromium layer and/or the chromium oxide layer can be avoided by laminating the transparent protective film as described above on the surface of the photomask forming the chromium layer and/or the chromium oxide layer. Since the mask of the vapor-deposited chrome layer and/or the chrome oxide layer is highly precise, if the transparent protective film is bonded as described above, the exposure precision is lowered. Further, it is also considered that a coating film (coating film) is formed by applying a coating liquid for forming a coating film onto the surface of a photomask which forms a chromium layer and/or a chromium oxide layer, thereby preventing adhesion of the photoresist and chromium. The layer and/or the chromium oxide layer are broken, but usually the adhesion between the chromium layer and/or the chromium oxide layer and the organic layer is low, and the adhesion between the chromium layer and/or the chromium oxide layer and the coating film is insufficient, so that the coating film is formed. The chrome layer and/or the chromium oxide layer are peeled off and repeated exposure is not possible. Therefore, it is considered that the surface of the chromium-containing body having a layer of a layer and/or a chromium oxide layer on the surface such as a reticle forming a chromium layer and/or a chromium oxide layer is easily cooled by a relatively low temperature and a short time hardening. Then, it is treated with a coating film forming material which is excellent in adhesion to a chromium-containing body and which can form a uniform coating film, and a laminate containing a chromium layer and/or a chromium oxide layer (Patent Document 2). [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Publication No. 25 8 9276 (Patent Document No. 1) [Patent Document 2] Japanese Patent Publication No. 2 0 0 6 - 2 3 2 9 0 8 ( [Patent No. 201038683, the first item of the invention] [Problem to be Solved by the Invention] However, in recent years, in order to reduce the production cost, it is required to manufacture a photomask in a shorter time, as in Patent Document 2 described above. The coating film formed by heat hardening does not satisfy the requirement that the adhesion to the object to be coated is good, and a uniform and beautiful coating film is formed in a shorter time. Accordingly, an object of the present invention is to provide a coating which is capable of forming a coating film in a short period of time, has a surface of a chromium-containing body having a chromium layer and/or a chromium oxide layer, and has excellent adhesion to a coating film and excellent surface hardness of the coating film. Film forming material. Moreover, an object of the present invention is to provide a coating film which is excellent in adhesion to a chromium-containing body which can form a coating film in a short time and has a chromium layer and/or a chromium oxide layer on the surface, and which is excellent in surface hardness of a coating film. A Q manufacturing method comprising a laminate of a chromium layer and/or a chromium oxide layer, and a laminate comprising a chromium layer and/or a chromium oxide layer. [Means for Solving the Problem] In order to solve the above problems, it is known that the formation time of the coating film is related to the curing time of the thermosetting resin contained in the coating film, and in order to form the coating film in a short time, The above problem can be solved by using an ionizing radiation-curable resin having a hardening time of a short period of time without using a thermosetting resin having a long hardening time. However, it is known that the thermosetting resin in the coating liquid for coating film formation of the coating film forming material is changed to ionizing radiation hard 201038683, and the chrome layer and/or the chromium oxide layer are chrome-containing. Insufficient adhesion between the body and the coating film makes the durability of the coating film worse. Therefore, it has been found that the use of an organic decane hydrolyzed condensate having an amine group as an easy-to-handle treatment liquid can improve the adhesion between the chromium-containing body and the coating film and increase the surface hardness of the coating film, thereby solving the problem. That is, the coating film forming material of the present invention is characterized by two coatings of an easy-to-treat treatment liquid containing an organic decane hydrolysis-condensation product having an amine group and a coating liquid for forming a coating film containing an ionizing radiation-curable resin. The liquid is composed. Further, the laminate of the present invention is characterized in that the chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface sequentially has an easily-adhesive layer formed of an organic decane hydrolyzed condensate having an amine group, and is ionized radiation. A coating film formed by a wire-curable resin. Further, the method for producing a laminate of the present invention is characterized in that an easy-to-treat liquid containing an organic decane hydrolyzed condensate having an amine group is coated on a chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface thereof. After coating a coating liquid for forming a coating film containing an ionizing light ray-curable resin, the coating film is cured by irradiation with ionizing radiation. [Effect of the Invention] The coating film forming material of the present invention can form a coating film in a short time, and the surface of the chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface can be excellent in adhesion to the coating film. A laminate of a chromium-containing layer and/or a chromium oxide layer having excellent surface hardness. The laminate of the present invention can be made to have a chromium layer and/or a chromium oxide layer on the surface of the layer -8 - 201038683. The chromium-containing body is excellent in adhesion to the coating film, and the surface hardness of the coating film can be produced. a short-time coating film having a coating layer having a complex layer and/or a chromium oxide layer on the surface and having a chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface thereof, and having a surface hardness of the coating film is excellent. a chromium-containing layer and/or a laminate. [Embodiment] The coating film forming material described in the embodiment of the coating film forming material of the present invention is an easy-to-treat liquid containing an organic decane having an amine group and a coating comprising an ionizing radiation curing resin. The composition of the two coating liquids of the cloth liquid. First, the description will be given for the easy-to-handle treatment liquid. It is easy to use a Q-containing body having a chromium layer and/or a chromium oxide layer (hereinafter also referred to as a chromium layer or the like) and a coating film for an organic substance, and the present invention includes an organic group having an amine group. The decane hydrolyzed hydrazine-containing organic decane is an adhesion of a chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface of at least one amine group to a coating film formed of a coating liquid to be described later. As the above-mentioned organic decane, for example, γ-aminopropyltrimethoxydecane, γ-triethoxydecane, Ν-β(aminoethyl)γ-aminopropyltrioxane, Ν-β (for example) can be used. Aminoethyl)aminopropylmethyldimethoxy(aminoethyl)γ-aminopropyltrimethoxydecane, γ-[double (excellent. The chromium oxide layer is formed. The coating film-shaped treatment liquid of the present hydrolysis condensation system has an amine propyl methoxy hydrazine which can be used to form an amine group in the coating film. β β-hydroxyethyl-9 - 201038683 base)]-aminopropyltriethoxydecane, (2-aminoethyl)aminotrialkoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropylethoxy decane, 3-aminopropyldimethylethoxy decane, 3-aminomethyldiethoxydecane, N-(2-aminoethyl)-3-amine Propyl methoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxy fluorene, etc. These organic decanes having an amine group are necessary to be hydrolyzed condensates, which are referred to in the present invention. Amino-based organic decane The condensate is obtained by hydrolyzing an organic decane having an amine group and obtaining a condensate obtained by condensation/or a partial condensate obtained by condensation. By hydrolytic condensation of the amine-based organic decane, a stanol group can be produced to increase For the above-mentioned reasons, the adhesion to the chromium-containing body which is not followed by the unhydrolyzed person can be increased. Further, the organic decane containing the amine group is hydrolyzed. When the treatment liquid is used in the reticle, the glass which does not form the chrome layer is followed by the sterol group to increase the adhesion, and thus the organic decane hydrolysis condensate having the amine group is easily attached. The lower limit is 0.01% by weight or more and further 0.1% by weight or more, the upper limit is 10% by weight or less, and more preferably 5% by weight or less. 〇·〇1% by weight or more, and the necessary chromium-containing body can be obtained. Then, by making it 10% by weight or less, it is possible to prevent the occurrence of defects due to unevenness in interference. Further, the organic decane hydrolyzed condensate having an amine group accounts for 90% by weight of the total solid content of the easy-to-attach liquid. It is preferred to make it into propylpropyltripropylmethane, etc. It refers to the reaction of the compound. It is better to use force, appearance treatment I 90 -10- 201038683% by weight or more, the adhesion to the chromium-containing body can be improved, and the adhesion to the coating film using the coating liquid for coating film formation described later can be improved. The organic decane having an amine group is diluted with an alcohol solvent such as methanol, ethanol or isopropyl alcohol, and can be hydrolyzed by using an acid such as hydrochloric acid or an alkali such as sodium hydroxide as a catalyst, and stirred at a constant temperature for any time. Further, the hydrolysis condensate may be further diluted with the same alcohol solvent as described above to form an easy-to-treat treatment liquid. Next, the coating liquid for forming a coating film will be described. The coating liquid for forming a coating film is used for forming a coating film on a chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface thereof, and is a material containing an ionizing radiation curing resin in the present invention. By using the coating liquid for forming a coating film, a coating film can be formed on the surface of the chromium-containing body having a complex layer and/or a chromium oxide layer on the surface in a short time. The ionizing radiation-curable resin is a cross-linking hardener which can be at least irradiated by ionizing radiation (ultraviolet rays or electron beams). As the ionizing radiation, the linear curing resin may be one or both of a mixed cationic photopolymerizable photocationic polymer resin or a radical photopolymerizable photopolymerizable prepolymer or a photopolymerizable monomer. More than one species. It is preferred that the person having an unsaturated double bond has good adhesion to an easy-to-adhere layer formed by the above-mentioned easy-to-contact liquid. As the ionizing radiation-curable resin having an insufficient m ft stomach, a (meth)acrylic acid vinegar oligomer or a (meth)acrylic monomer can be used. As the (meth) acrylate oligomer, ester (meth) propyl (meth) acrylate, urethane (meth) acrylate-11 - 201038683 ester 'epoxy (meth) acrylate, Amine-based resin (meth)acrylic acid vinegar, acrylic resin (meth) acrylate, melamine (meth) propionate, polyfluoroalkyl (meth) acrylate, poly methoxy (meth) acrylate, etc. . In addition, these (meth) acrylate oligomers can be used singly, but in order to provide various properties such as improvement of crosslinking hardenability and adjustment of curing shrinkage, it is preferred to use two or more kinds. Also, '(meth)acrylic single system uses 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate a difunctional (meth)acrylic monomer such as polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate One or two or more kinds of polyfunctional (meth)acrylic monomers such as trimethylpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate. The (meth) acrylate oligomer and the (meth)acrylic monomer are preferably from 50 to 89% by weight based on the total solid content of the coating liquid for forming a coating film. When it is 50% by weight or more, the surface hardness of the coating film can be prevented from being lowered, and when it is 89% by weight or less, the adhesion between the easy-adhesion layer and the coating film can be sufficiently exhibited, and the present invention can be used by ultraviolet irradiation curing. In the case of the coating liquid for forming a coating film, an additive such as a photopolymerization initiator or a photopolymerization accelerator is preferably used in addition to the (meth) acrylate oligomer and the (meth)acrylic monomer. As the photopolymerization initiator, acetophenone, benzophenone, Michler ketone 'benzoin, benzyl methyl ketal, benzo-12-201038683 benzoate, Α-mercapto oxime ester, thioxanthone, and the like. Further, the photopolymerization accelerator is one which can reduce the polymerization failure due to air during hardening to accelerate the curing speed, for example, p-amyl dimethylaminobenzoate or ethyl p-dimethylaminobenzoate. . Further, a reactive hydrophilic substance may be added in order to improve the adhesion to the easy-adhesion layer formed by the easy-to-handle treatment liquid. These reactive hydrophilic materials are copolymerizable with (meth) acrylate oligomers and/or (meth)acrylic acid 0 monomers. By copolymerizing with a (meth) acrylate oligomer and/or a (meth) propylene storage acid monomer, it does not bleed out from the coating film, and the adhesion of the adhesive layer to the coating film can be prevented. Changes can improve the durability of the film. Furthermore, 'copolymerization with a (meth) acrylate oligomer and/or a (meth) acryl monomer can increase the crosslinking density in the coating film sufficiently ' and by adding a reactive hydrophilic substance The hardness of the coating film is prevented from being lowered. The reactive hydrophilic substances may be, for example, a hydroxyl group, a (meth) Q propylene group, a vinyl group, an epoxy group, a styryl group, a (meth) acryloxy group, an amine group. A hydrophilic substance such as a mercapto group or an isocyanate group. In particular, a hydrophilic substance modified with a (meth)acrylonitrile group (meth)acrylic acid is easily copolymerized with the above-mentioned (meth) acrylate oligomer and/or (meth)acrylic monomer. It is preferable because it has good compatibility with the above (meth) acrylate oligomer and/or (meth)acrylic monomer. As for the (meth)acrylic acid-modified hydrophilic substance, in order to improve the adhesion to the emulsion mask, a (meth)acrylic acid-modified phosphoric acid-13-201038683 ester or a (meth)acrylic acid modified fourth can be used. In particular, in order to improve the storage stability of the coating liquid for coating film formation, a quaternary ammonium salt modified with (meth)acrylic acid is more preferably used. As the (meth)acrylic acid modified phosphate, tristearyloxyethyl phosphate, 2-propenyloxyethyl acid phosphate, 2-methylpropenyloxyethyl acid phosphate, etc. can be used. As for the (meth)acrylic acid modified quaternary ammonium salt, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminopropyl acrylamide methyl chloride quaternary salt, two Methylaminoethyl methacrylate chlorinated methyl quaternary salt and the like. The reactive hydrophilic substance is preferably from 10 to 30% by weight, preferably from 10 to 20% by weight, based on the total solid content of the coating liquid for forming a coating film, to be 10% by weight or more because an easy-adhesion layer and a coating film are obtained. The adhesiveness is 30% by weight or less because the surface hardness of the coating film is not lowered. Further, the coating liquid for forming a coating film may be appropriately added with a release agent which imparts mold release property, or an antistatic agent which imparts antistatic property. These mold release agents may use an oxime oil such as dimethyl sulfonium oil, methyl hydrogen hydride oil, methyl phenyl sulfonium oil or cyclic dimethyl sulfonium oil or an organic group introduced into a fluorinated oil. It is a modified oxime oil. As for the modified oxime oil, alkyl modification, polyether modification, fluorine modification, sulfhydryl modification, epoxy modification, carboxyl modification, higher fatty acid ester modification, (meth)acrylic acid can be used. Modification of hydrazine, modified by carbamide, etc. In particular, a reactive oxime oil having a group reactive with a (meth) acrylate oligomer and a (meth) acryl monomer or a reactive hydrophilic substance is used because of sustainable mold release property or antifouling property. good. According to this, it is possible to easily remove the deposit of the photoresist or the like on the surface of the coating film by -14-201038683. As the reactive oxygenated oil, for example, a hydroxyl group, a (meth) acrylonitrile group, a vinyl group, an epoxy group, a styryl group, a (meth) acryloxy group, an amine group, a fluorenyl group, an isocyanate group can be used. And so on. In particular, it is preferred to easily copolymerize with a (meth) acrylate oligomer and a (meth) acryl monomer or a reactive hydrophilic substance, and with the aforementioned (meth) acrylate oligomer and A (meth) acrylate group having a good compatibility with a methyl group-acrylic monomer. The release agent is preferably 0.5 to 2% by weight of the total solid content of the coating liquid for forming a coating film. The reason for becoming 0.5% by weight or more is to obtain sufficient mold release property and antifouling property to become 20% by weight. The reason for the following is to not lower the surface hardness. The coating liquid for forming a coating film of the present invention can be prepared by dispersing the ionizing radiation-curable resin described above or other components blended as needed, and dissolving in an appropriate solvent. Further, it is preferable to make each component compatible with each other because it can prevent whitening of the coating film Q. Next, an embodiment of a method for producing a laminate comprising a chromium layer and/or a chromium oxide layer of the present invention will be described. The method for producing a laminate comprising a chromium layer and/or a chromium oxide layer according to the present invention is to apply an easy-to-handle treatment liquid containing an organic broth hydrolyzed condensate having an amine group to a surface containing a chromium layer or the like. After coating a coating liquid for forming a coating film containing an ionizing radiation curing resin thereon, the coating film is cured by irradiation with ionizing radiation. The chromium-containing body having a chromium layer or the like on the surface used in the present invention is a laminate of a chromium layer or the like on a molded body. For example, a fine pattern can be formed on a printed circuit board-15-201038683 or a resin relief. A chrome mask or the like which is formed by coating a chrome layer or the like on a glass substrate on which a pattern is formed. Further, it is not only a layer having a chrome layer on the entire surface of the formed body but also a part having a chrome layer. First, an easy-to-process liquid containing an organic decane hydrolyzed condensate having an amine group is coated on a chromium-containing body having a chromium layer or the like on the surface, and dried. The drying temperature is about 80 to 100 °C, and the drying time is about 1 to 3 minutes, so that the drying temperature and the drying time of the solvent contained in the treatment liquid can be easily followed. When the thickness of the adhesive layer is increased, interference unevenness is likely to occur. If the interference unevenness occurs on the easily-adhesive layer, the unevenness of the interference cannot be eliminated after the application of the coating film, and the appearance is poor. Therefore, it is preferably 2 μηι or less. These easy-adhesion layers may be formed on one portion of a molded body having a chromium layer or the like on the surface, and may be formed on a portion where the chromium layer and/or the chromium oxide layer are not formed. Next, a coating liquid for forming a coating film containing an ionizing radiation curing resin is applied onto an easy-adhesion layer containing a chromium-containing body which is easy to adhere, and if necessary, dried to irradiate the coating film with ionizing radiation. Joint hardening. In the present invention, the coating film is formed by the coating liquid for coating film formation containing the ionizing radiation-curable resin, and the coating film can be formed in a shorter time than when the thermosetting resin is used. The coating film obtained from the coating liquid for forming a coating film of the present invention has a thickness of 2 to 4 μηι', preferably 2 to 3 μm. The reason for the reason of 2 μηι or more is to obtain a surface hardness of the coating film and to be 4 μm or less in order to prevent cracking or whitening of the coating film and to lower the transparency. -16-201038683 As a method of applying the coating liquid for the easy-to-treat processing liquid and the coating film formation, a spin coating method, a die coating method, a cap coating method, and a bar coating method can be used. Known methods such as cloth. The method for producing a laminate of the chromium-containing layer and/or the chromium oxide layer of the present invention can be obtained by having an amine on the chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface of the present invention. The easy-to-layer layer formed of the organodecane hydrolysis condensate, and the laminate comprising the chromium layer and/or the chromium oxide layer of the coating film formed of the ionizing radiation-curable resin. The coating film obtained by the coating liquid for forming a coating film, after the surface of the coating film after hardening is rubbed back and forth ten times on the surface with a lkg load, it is preferable that there is no scratch on the surface of the coating film. . By using an easy-adhesion layer formed by hydrolyzing a condensate of an organic decane having an amine group, a coating film excellent in adhesion can be formed on a chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface in a short time. [Examples] Hereinafter, the present invention will be further described by way of examples. In addition, "parts" and "%" are weight references unless otherwise indicated. [Example 1] An easy-to-handle treatment liquid having the following composition was applied by spin coating to a complex containing a complex layer and/or an oxide layer on the surface (a patterned photomask) at 80 ° C Drying for 2 minutes 'forms an easy-to-layer layer with a thickness of 5 Onm. -17- 201038683 <Easy to process liquid> • Organic decane hydrolyzed condensate having an amine group 3.3 parts (KBP-90: Shin-Etsu Chemical Co., Ltd., solid content 32%) • Dilution solvent 3 1.9 parts Next, The coating liquid for coating film formation of the following composition was applied onto the easy-adhesive layer by spin coating, dried at 80 ° C for 2 minutes, and irradiated with ultraviolet rays for 1 〇 second (1 000 mJ/cm 2 ) to form a thickness of about 3 μm. A film comprising the layer of the chromium layer and/or the chromium oxide layer of Example 1 was prepared by coating. <Coating liquid for coating film formation> •Acrylic urethane oligomer 3 (ART RESIN UN904: Roots Industrial Co., Ltd.) • Acrylic urethane monomer NK (NK ESTER A-TMMT: Shin-Nakamura Industrial company) • Acrylic modified quaternary ammonium salt j (DMAEA-Q: Xingren Company, 79% solids) • Deodorizer 〇 · 3 5 parts (polyoxyalkylene with terminally unsaturated bonds) Polymerization_%@ formation of 70%) * Photoradical polymerization initiator (Irgacure 184: Ciba Japan) • Dilution solvent ^ //x [Example 2] -18 - 201038683 Divided by the following A laminate containing the chromium layer and/or the chromium oxide layer of Example 2 was prepared as in Example 1 except that the liquid was replaced by the easy-to-handle treatment liquid of Example 1. The easy adhesion layer has a thickness of 2 nm. <Easy to carry out the treatment liquid> 0.1 part of the organic decane hydrolysis condensate having an amine group (KBP-90: Shin-Etsu Chemical Co., Ltd., solid content 32%) 0 - 319 parts of the dilution solvent [Example 3] A laminate containing the chromium layer and/or the chromium oxide layer of Example 3 was prepared as in Example 1 except that the treatment liquid was replaced by the easy-to-treat treatment liquid of Example 1. The easy adhesion layer has a thickness of 15 nm. <Easy to process liquid> Q. Organic decane hydrolyzed condensate having an amine group ο. 1 part (KBP-90: Shin-Etsu Chemical Co., Ltd., solid content 32%) • Dilution solvent 3 1. 9 parts [Examples 4] A laminate comprising the chromium layer and/or the chromium oxide layer of Example 4 was prepared as in Example 1 except that the following easy-to-handle treatment liquid was used instead of the easy-to-handle treatment liquid of Example 1. The thickness of the easy-adhesion layer is 1.6 μηι. -19- 201038683 <Easy to process liquid> • 4 parts of organic sand hydrazine hydrolysis condensate having an amine group (KBP-90: Shin-Etsu Polysiloxane, 32% solid content) • 9 parts of dilution solvent [Examples] 5) A laminate containing a chromium layer and/or a chromium oxide layer of Example 5 was prepared as in Example 1 except that the coating liquid for forming a coating film described below was used instead of the coating liquid for forming a coating film of Example . <Coating liquid for coating film formation> • 4 parts of urethane urethane monomer (NKESTERA-DPH: Shin-Nakamura Industrial Co., Ltd.) • 1 part of quaternary ammonium salt modified with acrylic acid (DMAEA-Q: Xingren Company, solid content 79%) • Release agent 0.3 5 parts (polymer modified with polysulfonate with unsaturated bond at the end, solid content of 70%) • Photo radical polymerization initiator 0.3 5 parts ( Irgacure 184 ··Ciba Japan Co., Ltd.) • 1 part of the dilution solvent [Example 6] The following easy-to-treat treatment liquid of Example 1 was replaced by the following easy-to-treat liquid, and the coating film was formed by the following coating film. A laminate containing the road layer and/or the chromium oxide layer of Example 6 was prepared as in Example 1 except that the cloth liquid was used instead of the coating liquid for forming a coating film of Example 1. The thickness of the easy adhesion layer is 15 nm. Easy The film thickness on the next layer is about 3 μηι. <Preparation of the easy-to-handle treatment liquid of Example 6> 1.54 parts of 0.2 mol of 1/1 hydrochloric acid, 2.14 parts of pure water, and 16.33 parts of ethylene glycol were placed in a container and sufficiently cooled and stirred to prepare a diluted hydrochloric acid solution. To another vessel were added 4 parts of ethanol, 1 part of an organic decane having an amine group (KBM-903, Shin-Etsu Chemical Co., Ltd.), and the temperature was adjusted to 25 °C. Subsequently, 5 parts of the above diluted hydrochloric acid solution was added as a catalyst, and stirred at a constant temperature of 25 ° C for 24 hours to obtain an organodecane hydrolyzed condensate having an amine group. Subsequently, 990 parts of isopropyl alcohol was added and diluted to obtain an easy-to-substrate solution of Example 6. Q <coating liquid for coating film formation> 5 parts of urethane acrylate oligomer (UNIDIC 1 7-8 06 : DIC Corporation) • Photo radical polymerization initiator 0.1 2 parts · (Irgacure 18 4 : Ciba Japan Co., Ltd.. Dilution solvent i 5 parts [Comparative Example 1] The coating liquid for forming a coating film of the following Example 1 was replaced by the coating liquid for forming a coating film of the following Example 1 to be applied by spin coating. It is easy to apply the coating on the layer 'and at 80. (: drying for 30 minutes', except that a coating film was formed, and a composite containing a chromium layer and/or a chromium oxide layer of Comparative Example 1 was produced as in Example 1. <Coating liquid for coating film formation> Alcohol 5 parts. Release agent 0 · 3 5 parts (Polyoxyalkylene modified polymer with terminal bond with unsaturated bond 'solid content 70%). Hardener 1 part (TAKENATE D1 10Ν: Mitsui Chemical Polyamine Formate company, solid content 60%) • Dilute solvent 1 5 parts [Comparative Example 2] Rotating coated chromium-containing body with chromium layer and/or chromium oxide layer on the surface (formation of chrome mask) The coating liquid for forming a coating film having the following composition was applied, dried at 80 ° C for 2 minutes, and irradiated with ultraviolet rays for 10 seconds (1 000 mJ/cm 2 ) to form a coating film having a thickness of about 3 μm to prepare Comparative Example 2. A laminate comprising a chromium layer and/or a chromium oxide layer. <Coating liquid for coating film formation> • Three parts of urethane acrylate oligomer (ART RESIN UN90 4 · Roots Industrial Co., Ltd.) -22- 201038683 • 1 part of urethane acrylate monomer (NK ESTER A-TMMT: Xinzhongcun Industrial Co., Ltd.) • Acrylic modified quaternary ammonium salt 1 part (DMAEA-Q: Xingren Company's solid content of 79%) • Mold release agent 0.35 parts (Polysiloxane modified with a terminal with an unsaturated bond, 70% solids) 0.3 5 parts 15 parts
.光自由基聚合起始劑 (Irgacure 184 ·· Ciba Japan 公司） •稀釋溶劑 [比較例3 ] 除以下述之易接著處理液取代實施例1之易接著處理 液以外，餘如實施例1般製備比較例3之含有鉻層及/或 氧化鉻層之層合體。易接著層之厚度爲Ιμηι。 <易接著處理液> •具有胺基之有機矽烷 5份 (ΚΒΜ-903:信越聚矽氧公司，有效成分100%) •稀釋溶劑 9 5份 [比較例4 ] 除以下述之易接著處理液取代實施例1之易接著處理 液以外，餘如實施例1般製備比較例4之含有鉻層及/或 -23- 201038683 氧化鉻層之層合體。易接著層之厚度爲1μπ1。 <易接著處理液> •具有锍基之有機矽烷 5份 (ΚΒΜ-8 03 :信越聚矽氧公司，固形成分1〇0% ) •稀釋 '丨谷劑 9 5份 [比較例5 ] 除以下述之易接著處理液取代實施例1之易接著處理 液以外’餘如實施例1般製備比較例5之含有鉻層及/或 氧化鉻層之層合體。易接著層之厚度爲15 〇nm。 <比較例5之易接著處理液之調製> 將50份之〇.2mol/l鹽酸、70份純水、1 26 1份乙醇添 加於容器中充分冷卻攪拌，製作稀釋鹽酸溶液。 於另一容器中添加1242份乙醇、138份作爲具有環氧 基之有機矽烷之γ -縮水甘油氧基丙基三甲氧基矽烷（ KB Μ - 4 0 3，信越聚矽氧公司），調溫至2 5 °C。隨後，添加 1 3 8 1份上述稀釋鹽酸溶液作爲觸媒，在2 5 °C之恆溫攪拌 24小時，獲得具有環氧基之有機矽烷水解縮合物。接著添 加8 2 8 0份之異丙醇並稀釋，獲得比較例5之易接著處理 液。 對所得之實施例1〜6及比較例1〜5之包含銘層及/或 氧化鉻層之層合體進行下述項目之評價。結果示於表1。 -24- 201038683 〔易接著層對含鉻體（形成圖型之鉻光罩）之接著性〕 利用棋盤格膠帶法（JIS Κ5600-5-6:1 999 )評價實施 例卜6及比較例1~5之鉻層及/或氧化鉻層（形成圖型之 鉻光罩之圖型部分）與易接著層之接著性。由棋盤格膠帶 法獲得之剝離試驗結果，棋盤格部份之易接著層全部剝離 者判定爲「X」，棋盤格部份之易接著層少許剝離者判定 0 爲「△」，棋盤格部份之易接著層完全未剝離者判定爲「 〇」。結果示於表1。 [塗膜之接著性] 利用棋盤格膠帶法（JIS Κ5600-5 -6:1 999 )評價實施 例1 ~6及比較例1〜5之塗膜之接著性。由棋盤格膠帶法獲 得之剝離試驗結果，棋盤格部份之塗膜全部剝離者判定爲 「X」，棋盤格部份之塗膜少許剝離者判定爲「△」，棋 Q 盤格部份之塗膜完全未剝離者判定爲「〇」。結果示於表 [塗膜之表面硬度] 以lkg荷重之鋼絲絨#0000在實施例1〜6及比較例 1〜5之包含鉻層及/或氧化鉻層之層合體之塗膜表面來回摩 擦十次後，以目視觀察塗膜表面有無傷痕。有傷痕者判定 爲「X」，沒有傷痕者判定爲「〇」。結果示於表1。 -25- 201038683 [塗膜外觀] 以目視觀察實施例1〜6及比較例之包含鉻層及/ 或氧化鉻層之層合體之塗膜。明顯白化或塗佈不均者判定 爲「X」’有少許白化或塗佈不均者判定爲「△」，完全 沒有不均之塗膜判定爲「〇」。結果示於表卜 [表1] 易接著層之接著性 塗膜之接著怖 塗膜之表面硬度 塗膜之外觀 實施例1 〇 ----土 〇 〇 〇 實施例2 Δ -- —— 〇 〇 實施例3 〇 — 〇 〇 實施例4 Δ △ 〇 Δ 實施例5 〇 -- _〇 〇 〇 實施例6 〇 --- _〇 〇 〇 比較例1 〇 ---X— _〇 X 〇 比較例2 — X X X 比較例3 X X X 〇 比較例4 X — X X X 比較例5 〇 X X Δ '----. 實施例1〜6之塗膜形成材料由於係由包含具有胺基之 有機砂院水解縮合物之易接著處理液及包含電離福射線硬 化型樹脂之塗膜形成用塗佈液兩種塗佈液所構成者，因此 爲可縮短自塗佈至塗膜之製膜爲止之時間者。又，爲塗膜 表面硬度亦優異者。 實施例1、3、5、0之塗膜形成材料由於係由包含具 有胺基之有機矽烷水解縮合物之易接著處理液及包含電離 輻射線硬化型樹脂之塗膜形成用塗佈液兩種塗佈液所構成 ，且易接著處理液中之具有胺基之有機矽烷水解縮合物在 -26- 201038683 0.1重量％至5重量％之範圍，因此表面具有鉻層等之含鉻 體之表面與塗膜之接著性優異，且塗膜之外觀亦良好者。 實施例2之塗膜形成材料由於係由包含具有胺基之有 機矽垸水解縮合物之易接著處理液及包含電離輻射線硬化 型樹脂之塗膜形成用塗佈液兩種塗佈液所構成，且易接著 處理液中之具有胺基之有機矽烷水解縮合物接近〇. 〇 i重 量％之下限値，因此表面具有鉻層等之含鉻體之表面與塗 0 膜之接著性相較於實施例1之塗膜形成材料梢差，但塗膜 之外觀良好者。 實施例4之塗膜形成材料由於係由包含具有胺基之有 機矽烷水解縮合物之易接著處理液及包含電離輻射線硬化 型樹脂之塗膜形成用塗佈液兩種塗佈液所構成，且易接著 處理液中之具有胺基之有機矽烷水解縮合物接近10重量％ 之上限値，因此表面具有鉻層等之含鉻體之表面與塗膜之 接著性比實施例1之塗膜形成材料差，且塗膜之外觀亦稍 〇 差者。 比較例1之塗膜形成材料由於係由包含具有胺基之有 機矽烷水解縮合物之易接著處理液及包含熱硬化型樹脂之 塗膜形成用塗佈液兩種塗佈液所構成，因此成爲無法縮短 自塗佈至塗膜之製膜爲止之時間者。又’塗膜之硬度不足 ，以鋼絲絨會產生傷痕者。 比較例2之塗膜形成材料由於係由包含電離輻射線硬 化型樹脂之塗膜形成用塗佈液所構成者’因此爲無法獲得 表面具有鉻層等之含鉻體表面與塗膜之接著性者’且以鋼 -27- 201038683 絲絨會有傷痕。另外’於塗膜上看到白化者。 比較例3之塗膜形成材料爲具有胺基之有機矽烷，但 由於並非水解縮合物’因此爲無法獲得表面具有鉻層等之 含鉻體表面與易接著層之接著性，爲無法獲得塗膜接著性 者，且以鋼絲絨會產生傷痕者。 比較例4之塗膜形成材料由於使用不具胺基之有機矽 烷，因此爲無法獲得表面具有鉻層等之含鉻體表面與易接 著層之接著性，及無法獲得與塗膜之接著性者，以鋼絲絨 會產生傷痕者。又，爲塗膜上看到有白化者。 比較例5之塗膜形成材料由於使用不具有胺基之有機 矽烷水解縮合物，因此爲無法獲得表面具有鉻層等之含絡 體表面上形成之易接著層與塗膜之接著性者，且藉鋼絲絨 會有傷痕者。 又’實施例1~6之含鉻層等之層合體爲在表面上具有 鉻層及/或氧化鉻層之含鉻體上依序具有由具有胺基之有 機矽烷水解縮合物所形成之易接著層、由電離輻射線硬化 型樹脂所形成之塗膜者。 實施例I、3、5、6之含有鉻層等之層合體爲表面具 有鉻層之含鉻體表面與塗膜之接著性優異，且塗膜之外觀 亦良好者。另外，爲塗膜之表面硬度亦優異者。 實施例2之含有鉻層等之層合體爲表面具有鉻層等之 含鉻體表面與塗膜之接著性比實施例1之塗膜形成材料稍 差者’但爲塗膜外觀良好者。又’爲塗膜之表面硬度亦優 異者。 -28- 201038683 實施例4之含有鉻層等之層合體爲表面具有鉻層等之 含鉻體表面與塗膜之接著性比實施例1之塗膜形成材料差 ，且塗膜外觀亦稍差者。然而，爲塗膜之表面硬度優異者 〇 由實施例I、3、5、6之含有鉻層等之層合體製造方 法製造之層合體爲表面具有鉻層等之含鉻體表面與塗膜之 接著性優異’塗膜之外觀亦良好者。又，爲塗膜之表面硬 0 度亦優異者。 由實施例2之含有鉻層等之層合體之製造方法製造之 層合體爲表面具有鉻層等之含鉻體表面與塗膜之接著性比 實施例1之塗膜形成材料梢差者，但塗膜之外觀爲良好者 。又，爲塗膜之表面硬度亦優異者。 由實施例4之含有鉻層等之層合體之製造方法製造之 層合體爲表面具有鉻層等之含鉻體表面與塗膜之接著性比 實施例1之塗膜形成材料差，且塗膜之外觀亦稍差者。然 Q 而，爲塗膜之表面硬度優異者。 -29-Photoradical polymerization initiator (Irgacure 184 · Ciba Japan Co., Ltd.) • Dilution solvent [Comparative Example 3] Except that the following easy-to-handle treatment liquid was used in place of the easy-to-treat treatment liquid of Example 1, the remainder was as in Example 1. A laminate containing the chromium layer and/or the chromium oxide layer of Comparative Example 3 was prepared. The thickness of the easy-adhesion layer is Ιμηι. <Easy to process liquid> • 5 parts of organic decane having an amine group (ΚΒΜ-903: Shin-Etsu Chemical Co., Ltd., active ingredient 100%) • 9 parts of diluent solvent [Comparative Example 4] Divided by the following A laminate containing the chromium layer and/or the -23-201038683 chromium oxide layer of Comparative Example 4 was prepared as in Example 1 except that the treatment liquid was used in place of the easy-to-handle treatment liquid of Example 1. The thickness of the easy-adhesion layer is 1 μπ1. <Easy to process liquid> • 5 parts of organic decane having a mercapto group (ΚΒΜ-8 03: Shin-Etsu Polyoxane Co., Ltd., solid content of 1〇0%) • Dilution of 'Kiwan agent 9 5 parts [Comparative Example 5] A laminate containing the chromium layer and/or the chromium oxide layer of Comparative Example 5 was prepared as in Example 1 except that the following easy-to-handle treatment liquid was used instead of the easy-to-handle treatment liquid of Example 1. The thickness of the easy adhesion layer is 15 〇 nm. <Preparation of the easy-to-handle treatment liquid of Comparative Example 5> 50 parts of 〇. 2 mol/l hydrochloric acid, 70 parts of pure water, and 261 parts of ethanol were added to the vessel, and the mixture was sufficiently cooled and stirred to prepare a diluted hydrochloric acid solution. Adding 1242 parts of ethanol and 138 parts of γ-glycidoxypropyltrimethoxydecane (KB Μ - 4 0 3, Shin-Etsu Chemical Co., Ltd.) as an organic decane having an epoxy group in another container, and adjusting the temperature To 2 5 °C. Subsequently, 1 3 8 1 of the above diluted hydrochloric acid solution was added as a catalyst, and the mixture was stirred at a constant temperature of 25 ° C for 24 hours to obtain an organodecane hydrolyzed condensate having an epoxy group. Then, 8 2 80 parts of isopropyl alcohol was added and diluted to obtain an easy-to-substrate solution of Comparative Example 5. The laminates of the obtained examples 1 to 6 and the comparative examples 1 to 5 containing the underlayer and/or the chromium oxide layer were evaluated for the following items. The results are shown in Table 1. -24- 201038683 [Adhesiveness of the easy-adhesion layer to the chromium-containing body (chrome mask forming the pattern)] Example 6 and Comparative Example 1 were evaluated by the checkerboard tape method (JIS Κ5600-5-6:1 999) The adhesion of the chrome layer and/or the chromia layer of ~5 (the pattern portion of the chrome mask forming the pattern) to the easy adhesion layer. The result of the peeling test obtained by the checkerboard tape method is that the all-peel layer of the checkerboard portion is judged as "X", and the easy-to-layer layer of the checkerboard portion is judged to be "△", and the checkerboard portion is determined. The easy-to-back layer is not peeled off at all and is judged as "〇". The results are shown in Table 1. [Adhesiveness of Coating Film] The adhesion of the coating films of Examples 1 to 6 and Comparative Examples 1 to 5 was evaluated by a checkerboard tape method (JIS Κ 5600-5 -6:1 999). The peeling test result obtained by the checkerboard tape method was judged as "X" by the peeling of all the coating films of the checkerboard portion, and "△" was determined by the little peeling of the coating film of the checkerboard portion, and the chess Q portion was If the coating film was not peeled off completely, it was judged as "〇". The results are shown in the table [surface hardness of the coating film]. The steel wool with the lkg load #0000 was rubbed back and forth on the surface of the coating film of the laminates comprising the chromium layer and/or the chromium oxide layer of Examples 1 to 6 and Comparative Examples 1 to 5. After ten times, the surface of the coating film was visually observed for scratches. Those who have a flaw are judged as "X", and those who have no scar are judged as "〇". The results are shown in Table 1. -25-201038683 [Appearance of Coating Film] The coating films of the laminates comprising the chromium layer and/or the chromium oxide layer of Examples 1 to 6 and Comparative Examples were visually observed. When the whitening or uneven coating was judged to be "X", a slight whitening or uneven coating was judged as "△", and the coating film having no unevenness was judged as "〇". The results are shown in the table [Table 1] Appearance of the surface hardness coating film of the adhesive film of the adhesive film of the easy-adhesive layer. Example 1 〇---- soil 〇〇〇 Example 2 Δ -- —— 〇 〇 Example 3 〇 - 〇〇 Example 4 Δ Δ 〇 Δ Example 5 〇-- _ 〇〇〇 Example 6 〇--- _ 〇〇〇 Comparative Example 1 〇---X- _〇X 〇Comparative Example 2 - XXX Comparative Example 3 XXX 〇 Comparative Example 4 X - XXX Comparative Example 5 〇 XX Δ '----. The coating film forming materials of Examples 1 to 6 were hydrolyzed by an organic sand containing organic amines. Since the material is easily formed by the treatment liquid and the coating liquid for coating film formation containing the ionizing radiation hardening resin, the time from the application to the film formation of the coating film can be shortened. Further, the surface hardness of the coating film is also excellent. The coating film forming materials of Examples 1, 3, 5, and 0 are two kinds of coating liquids for forming a coating film comprising an organic decane hydrolyzed condensate having an amine group and a coating liquid for forming a coating film containing an ionizing radiation curing resin. The organic decane hydrolyzed condensate having an amine group in the treatment liquid is easily in the range of from -26 to 201038683 in the range of from 0.1% by weight to 5% by weight, so that the surface has a chromium-containing surface such as a chromium layer and The coating film is excellent in adhesion and the appearance of the coating film is also good. The coating film forming material of Example 2 is composed of two coating liquids which are an easy-to-treat treatment liquid containing an organic hydrazine hydrolysis-condensation product having an amine group and a coating liquid for forming a coating film containing an ionizing radiation-curable resin. And the organic decane hydrolyzed condensate having an amine group in the subsequent treatment liquid is close to the lower limit 重量 of 重量i 重量i, so the surface of the chrome-containing surface having a chromium layer or the like is compared with the adhesion of the etched film. The coating film of Example 1 had a poor material tip, but the appearance of the coating film was good. The coating film forming material of Example 4 is composed of two coating liquids, which are an easy-to-treat treatment liquid containing an organic decane hydrolysis-condensation product having an amine group, and a coating liquid for coating film formation containing an ionizing radiation-curable resin. And the organic decane hydrolyzed condensate having an amine group in the treatment liquid is likely to be close to the upper limit of 10% by weight of the amine group, so that the surface of the chromium-containing body having a chromium layer or the like on the surface and the coating film are more adhesive than the coating film of Example 1. The material is poor and the appearance of the film is slightly worse. The coating film forming material of Comparative Example 1 is composed of two coating liquids including an easy-to-treat liquid containing an organic decane hydrolyzed condensate having an amine group and a coating liquid for forming a coating film containing a thermosetting resin. It is not possible to shorten the time from the application to the film formation of the coating film. In addition, the hardness of the coating film is insufficient, and the steel wool may cause scars. The coating film forming material of Comparative Example 2 is composed of a coating liquid for forming a coating film containing an ionizing radiation curable resin. Therefore, it is impossible to obtain the adhesion between the surface of the chromium-containing body having a chromium layer or the like on the surface and the coating film. 'And steel -27- 201038683 velvet will have scars. In addition, whites were seen on the film. The coating film forming material of Comparative Example 3 is an organic decane having an amine group, but since it is not a hydrolysis condensate, it is impossible to obtain a coating film having a surface of a chromium-containing body having a chromium layer or the like and an adhesion layer. Then the sex, and the steel wool will cause scars. In the coating film forming material of Comparative Example 4, since the organic decane having no amine group is used, the adhesion between the surface of the chromium-containing body having a chromium layer or the like and the easy-adhesion layer cannot be obtained, and the adhesion to the coating film cannot be obtained. Steel wool can cause scars. Also, there is an albino on the coating film. In the coating film forming material of the comparative example 5, since the organic decane hydrolyzed condensate having no amine group is used, it is impossible to obtain an adhesive layer formed on the surface of the complex having a chromium layer or the like on the surface and the coating film. There are scars in steel wool. Further, the laminate of the chromium-containing layer or the like of Examples 1 to 6 is formed by sequentially having an organic decane hydrolyzed condensate having an amine group on a chromium-containing body having a chromium layer and/or a chromium oxide layer on the surface. Next, the film is formed by an ionizing radiation-curable resin. The laminate containing the chromium layer or the like of Examples I, 3, 5, and 6 is excellent in the adhesion between the surface of the chromium-containing body having a chromium layer and the coating film, and the appearance of the coating film is also good. In addition, the surface hardness of the coating film is also excellent. The laminate containing the chromium layer or the like of Example 2 has a surface having a chromium layer or the like and the surface of the coating film is slightly inferior to that of the coating film forming material of Example 1 but is excellent in the appearance of the coating film. Also, the surface hardness of the coating film is also excellent. -28-201038683 The laminate containing a chromium layer or the like of Example 4 is such that the surface of the chromium-containing body having a chromium layer or the like on the surface and the coating film are inferior to those of the coating film of Example 1, and the appearance of the coating film is also slightly poor. By. However, in the case where the surface hardness of the coating film is excellent, the laminate produced by the method for producing a laminate containing the chromium layer or the like of Examples I, 3, 5, and 6 is a chromium-containing surface having a chromium layer or the like and a coating film. Excellent in the following. The appearance of the coating film is also good. Further, the surface of the coating film is also hard to be 0 degree. The laminate produced by the method for producing a laminate containing a chromium layer or the like of Example 2 is such that the surface of the chromium-containing body having a chromium layer or the like on the surface and the coating film are superior to those of the coating film forming material of Example 1, but The appearance of the coating film is good. Further, the surface hardness of the coating film is also excellent. The laminate produced by the method for producing a laminate containing a chromium layer or the like of Example 4 is such that the surface of the chromium-containing body having a chromium layer or the like on the surface and the coating film are inferior to those of the coating film of Example 1, and the coating film is formed. The appearance is also slightly worse. However, Q is the surface hardness of the coating film. -29-