TW201038686A - Ultraviolet ray shielding layered coating, substrate with said layered coating, and production method therefor - Google Patents

Ultraviolet ray shielding layered coating, substrate with said layered coating, and production method therefor Download PDF

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TW201038686A
TW201038686A TW099105370A TW99105370A TW201038686A TW 201038686 A TW201038686 A TW 201038686A TW 099105370 A TW099105370 A TW 099105370A TW 99105370 A TW99105370 A TW 99105370A TW 201038686 A TW201038686 A TW 201038686A
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Taiwan
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mass
parts
substrate
undercoat layer
ultraviolet
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TW099105370A
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Chinese (zh)
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Ikutaro Morikawa
Toru Masatomi
Motoshi Sasaki
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Dow Corning Toray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Abstract

A primer layer with a thickness at time of application of 10 to 200 [μ]m which contains a curing resin and an ultraviolet ray absorption agent, and is characterized by [amount of ultraviolet ray absorption agent contained per 100 parts source monomer of curing resin (by mass)] [thickness of primer layer at time of application ([μ]m)] being in the range of 100 to 1000. An ultraviolet ray shielding layered coating formed on the surface of the abovementioned primer layer, and characterized by being provided with a cured layer comprising a silicone photocurable resin composition containing colloidal silica that has been photocured by high energy irradiation.

Description

201038686 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種形成耐候性及紫外線遮蔽性優異之硬 . 化皮膜的紫外線遮蔽性積層塗膜，詳細而言，本發明係關 於一種藉由紫外線可容易地使其硬化，且硬化後3〇〇 nmw 近之紫外線吸收效果、物理強度、耐污染性、塗膜之均勻 性、塗臈之密著性優異的耐候性紫外線遮蔽性積層塗膜。 x ’本發明係關於一種表面上具有該紫外線遮蔽性積層塗 〇 膜之基材及其製造方法。 【先前技術】 可藉由紫外線進行硬化之高能量線硬化性塗佈劑特別適 合於包含耐熱性較低之熱塑性樹脂之基材的表面被覆、基 材保護，具有無損該等基材之物理強度，而對其賦予耐污 染性、耐擦傷性、平滑性等優異之物理特性的優點。 此種高能量線硬化性塗佈劑已眾所周知，例如已知有包 〇 ㈣矽烷化丙烯酸酯、膠體二氧化矽、丙烯醯氧基官能性 石夕烧以及光聚合起始劑之耐磨耗性紫外線硬化性被覆用組 . 合物（專利文獻D。&，已知有：以含有含燒氧基之有機聚 . _氧烧類、及多官能性丙烯酸酯為特徵之高能量線硬化性 、组合物（專利文獻2)，或者物理強度獲得提昇的包含多官能 性丙婦酸醋、膠體二氧化石夕、有機燒氧基石夕炫以及胺基改 質有機聚石夕氧燒或其麥可（Michaei)加成反應產物的高能量 線硬化性丙烯醯氧基聚石夕氧組合物（專利文獻3)。又，該等 文獻中記载有，藉由紫外線使上述組合物硬化之情形時， 146540.doc 201038686 可較好地使用公知之光聚合起始劑。但是，包含聚碳酸酯 樹脂等熱塑性樹脂之基材容易因波長300 nm附近之紫外線 而發生光分解’在室外等長時間曝露於太陽光下之環境中 使用’或者照射上述波長300 nm附近之紫外線以使塗佈層 硬化時，存在所塗佈之基材自身劣化之問題。 為了防止因紫外線而引起之熱塑性樹脂基材之劣化、改 善耐候性，眾所周知可調配紫外線吸收劑（例如專利文獻3 之[0019]段落）。但是’由於該紫外線吸收劑亦會吸收硬化 塗佈劑所需之紫外線’故而若為了改善耐候性而大量調配 塗佈劑’則會阻礙塗佈劑利用紫外線而進行之硬化。該硬 化阻礙直接導致硬化皮膜之物理強度、财污染性、塗膜強 度及密著性降低’以及硬化所需之紫外線照射時間變長， 因此公知之光硬化性樹脂組合物尤其不具備可滿足作為容 易藉由波長300 nm附近之紫外線而發生光分解之聚碳酸酯 樹脂等塗佈劑之性能。 另一方面，為改善包含如上所述之聚矽氧系之硬化覆膜 的保護膜（亦稱為硬塗層）與基材之密著性而使用丙烯酸系 树月曰底塗劑的方法已廣為人知（例如，專利文獻4)。進而， 於專利文獻5中，揭示有如下之耐磨耗性聚碳酸酯物品， 即該耐磨耗性聚碳酸酯物品係使用含有約25〜85%之熱硬 化丙烯酸系聚合物以及15〜75°/。之紫外線吸收劑的接著促 進性底塗劑被覆聚碳酸酯樹脂，然後利用填充有膠體二氧 化矽之熱硬化有機聚矽氧烷形成表塗層而成。又，提出 有：將於基材上以1〜10 μιη&右之膜厚塗佈含有紫外線吸 146540.doc 201038686 收劑之丙烯酸系樹脂底塗劑而成的底塗層形成在聚碳酸酿 等基材上，且於該底塗層上形成聚矽氧系之硬化覆膜，藉 此獲得紫外線遮蔽性優異之基材（專利文獻6〜9)。 * 例如’專利文獻6中提出有一種聚碳酸酯成型物，其特 徵在於.於聚碳酸酯基材上設置含有紫外線吸收劑的膜厚 為2〜5 μηι之底塗層，並於該底塗劑上塗佈含有含膠體二氧 化石夕之有機聚石夕氧炫組合物的組合物，使其半硬化後進行 ❹ 成型（專利文獻6之請求項及[0011]段落等^又，專利文獻 7〜9中提出有一種紫外線吸收性透明體，其係於透明基材 上依序被覆含有紫外線吸收劑等且膜厚為μιη、較好 的是3〜8 μηι之底塗層，以及聚矽氧系之硬塗層而成者（例 如’專利文獻7之請求項及[〇〇 16]段落）。 但是，即便該等包含聚矽氧系之硬化覆膜之基材，其耐 候性、物理強度及紫外線之遮蔽性亦尚不能令人滿意。 又’於專利文獻5〜9中所記載之使用底塗層之情形時，尤 Q 其是於嚴格之評價條件下聚矽氧系之硬塗層之密著性不充 刀特別疋對於用容易藉由波長3 00 nm附近之紫外線而發 生光分解之聚碳酸酯樹脂板等來代替用作建築材料或車窗 材料之玻璃基材而言’尚不能令人滿意。 . 為解決上述課題，本案發明者等人提出一種含有多官能 !·生丙烯酸酯、膠體二氧化矽、丙稀醯氧基官能性矽烧、於 220〜400 11„1具有吸收波長之紫外線吸收劑以及於3〇〇〜45〇 nm具有吸收波長之光聚合起始劑的光硬化性樹脂組合物， 進而提出在將該光硬化性樹脂組合物塗佈於聚碳酸酯樹脂 146540.doc 201038686 等基材上時，併用膜厚丨〜“ μιη之丙烯酸系樹脂系之底塗 層（專利文獻10)。包含將該光硬化性樹脂組合物硬化而成 之覆膜的基材不容易因紫外線而劣化，且該覆膜與基材之 密著性亦優異，因此尤其於耐候性、物理強度方面發揮出 令人非常滿意之性能。 另一方面，對於以聚碳酸酯樹脂板等來代替用作建築材 料或車窗材料之玻璃基材，理想的是包含聚碳酸酯樹脂之 基材即使於太％光下連續曝露十幾年以上亦不會因波長 3〇〇 nm附近之紫外線而劣化。因此，對於本案發明者等人 而言，尚存進一步嘗試研究一種紫外線遮蔽性優異，且於 耐候性、物理強度方面發揮出可令人非常滿意之性能的基 材保護層之餘地。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特表昭57-500984號公報 [專利文獻2]日本專利特開2〇〇2_ 12638號公報 [專利文獻3]曰本專利特開2〇〇4_269589號公報 [專利文獻4]曰本專利特開昭57_162730號公報 [專利文獻5]曰本專利特開昭56_92〇59號公報 [專利文獻6]曰本專利特開平〇8_3〇979〇號公報 [專利文獻7]曰本專利特開平〇6_145387號公報 [專利文獻8]曰本專利特開平〇7_187717號公報 [專利文獻9]曰本專利特開平〇8·133792號公報 [專利文獻1〇]w〇2009/〇28741國際公開手冊 146540.doc 201038686 【發明内容】 本發明之目的在於提供—種藉由紫外線可容易地獲得硬 化，且硬化後300 nm附近之紫外線吸收效果、物理強度、 耐污染性、塗膜之均勻性、塗膜之密著性優異的耐候性紫 外線遮蔽性積層塗膜。又，本發明之目的在於提供一種表 面上包含该紫外線遮蔽性積層塗膜之基材及其製造方法。 本發明之紫外線遮蔽性積層塗膜之特徵在於包含：⑴底 塗層，其特徵在於含有硬化性樹脂丨〇〇質量份、及紫外線 吸收劑5-100質量份，塗佈時之膜厚為1〇〜2〇〇 ，且[相 對於每1 00質量份硬化性樹脂原料單體之紫外線吸收劑之 含1 (質量份）]χ[底塗層於塗佈時之膜厚(^111)]在1〇〇〜1〇〇〇 之範圍内’及（II)硬化層’其係形成於上述底塗層表面， 藉由高能量線照射使包含下述成分（Α)〜成分（D)之光硬化 性樹脂組合物光硬化而成者·_ (Α)多官能性丙烯酸酯或多官能性甲基丙烯酸酯1 〇〇質量 份、 (Β)具有脂肪族不飽和鍵之有機烷氧基矽烷^^0質量 份、 (C) 膠體二氧化矽1〜3〇〇質量份、及 (D) 光聚合起始劑〇 〇1〜3〇質量份。 進而’於本發明之紫外線遮蔽性積層塗膜中，可較好地 使用上述硬化性樹脂為（a)丙烯酸系樹脂，且該硬化性樹脂 原料單體為（al)丙烯酸系樹脂原料單體之底塗層。 即’本發明之紫外線遮蔽性積層塗膜之較佳者為下述紫 146540.doc 201038686 外線遮蔽性積層塗膜，其特徵在於包含：（z)丙烯酸系底塗 層’其特徵在於含有（a)丙烯酸系樹脂丨〇〇質量份、及紫 外線吸收劑5〜1 〇〇質量份，塗佈時之膜厚為丨〇〜2〇〇 μιη，且 [相對於每體1 〇〇質量份（a丨）丙烯酸系樹脂原料之（b)紫外線 吸收劑之含量（質量份）]x [底塗層於塗佈時之膜厚（μιη)]在 100〜1000之範圍内；及 (II)硬化層，其係形成於上述底塗層表面，藉由高能量 線照射使包含下述成分（Α)〜成分（D)之光硬化性樹脂組合 物光硬化而成者： (Α)多官能性丙稀酸酯或多官能性曱基丙浠酸酯1 〇〇質量 份、 (Β)具有脂肪族不飽和鍵之有機烷氧基矽烷質量 份、 (C) 膠體二氧化矽1〜300質量份、及 (D) 光聚合起始劑〇.〇1~30質量份。 上述丙烯酸系底塗層（I)較好的是使包含下述成分 (a 1)〜(d)之底塗層塗佈組合物硬化而成者： (al)丙烯酸系樹脂原料單體100質量份、 (b) 紫外線吸收劑5〜100質量份、 (c) 受阻胺系光穩定劑0_1〜20質量份、及 (d) 具有脂肪族不飽和鍵之有機烷氧基矽烷1〜100質量 份。 此處，成分（al)丙烯酸系樹脂原料單體更具體為：丙烯 酸酯系單體、曱基丙烯酸酯系單體、或者包含該等單體及 146540.doc 201038686 可與忒4單體共聚合之含不飽和鍵之單體的自由基共聚合 性混合物。 本發明之紫外線遮蔽性積層塗膜之第一特徵在於：上述 • 底塗層中之紫外線吸收劑之量以及底塗層於塗佈時之膜厚 在特定範圍内，且兩者滿足[相對於每100質量份硬化性樹 脂原料單體之（b)紫外線吸收劑之含量（質量份）]x[底塗層於 塗佈時之膜厚（μηι)]在100〜1000之範圍内的特定關係。尤 ❹其是，[相對於每100質量份硬化性樹脂原料單體之（b)紫外 線吸收劑之含量（質量份）]x[底塗層於塗佈時之膜厚（pm)] 較好的是120〜600之範圍，特別好的是16〇〜4〇〇之範圍。進 而，本發明之紫外線遮蔽性積層塗膜之第二特徵在於：於 該底塗層上，具備由含有多官能性丙烯酸酯或多官能性曱 基丙烯酸酯、具有脂肪族不飽和鍵之有機烷氧基矽烷、膠 體二氧化矽以及光聚合起始劑而成的聚矽氧系之光硬化性 樹脂組合物所形成的外塗層。 〇 本發明之附著紫外線遮蔽性積層塗膜之基材係於基材表 面被覆上述紫外線遮蔽性積層塗膜而成，且該基材較好的 是厚度在0.005 m〜0.1 m之範圍内的透明板狀聚碳酸酯樹 脂。又，上述附著紫外線遮蔽性積層塗膜之基材可藉由如 • 下方式而獲得：將含有硬化性樹脂原料單體10〇質量份、 及紫外線吸收劑5〜100質量份之底塗層塗佈組合物，以塗 佈時之膜厚為10〜200 μιη，且[相對於每100質量份硬化性 樹脂原料單體之（b)紫外線吸收劑之含量（質量份）]χ[底塗層 於塗佈時之膜厚（μιη)]在100〜1000之範圍内的量而塗佈於 146540.doc 201038686 基材表面且使之硬化，從而於基材表面被覆底塗層，然後 於該底塗層上塗佈包含下述成分（A卜成分之光硬化性 樹脂組合物，並利用高能量線使其光硬化，藉此依序對該 基材進行被覆： (A) 多官能性丙烯酸酯或多官能性甲基丙烯酸酯1 〇〇質量 份、 (B) 具有脂肪族不飽和鍵之有機烷氧基矽烷質量 份、 (C) 膠體二氧化矽1〜300質量份、及 (D) 光聚合起始劑〇.〇1〜3〇質量份。 本發明之1外線遮蔽性積層塗膜由於包含下述硬化層作 為外塗層，即該硬化層係包含含有多官能性丙烯酸酯或多 官能性甲基丙烯酸酯、具有脂肪族不飽和鍵之有機烷氧基 矽烷、膠體二氧化矽以及光聚合起始劑的特定之聚矽氧系 之光硬化性樹脂組合物者’故而可利用藉由紫外線可容易 地硬化，且硬化後物理強度、耐污染性、塗膜之均句性優 異的硬化覆膜來被覆基材。進而，本㈣之紫㈣遮蔽性 積層塗膜藉由具備含有特^量之紫外線吸收劑而成，且塗 佈時之膜厚在特定範圍内的包含硬化性樹脂之底塗層，而 使上述外塗層經由該底塗層牢固地密著於基材表面且發 揮出優異之紫外線遮蔽性。因此，可提供—種塗膜之密著 性及耐候性、尤其是料線魏絲優異，並且特別是於 被覆有包含聚碳酸樹脂的基材之情形時，不會因波長 300哨近之紫外線㈣化，且塗㈣基材之密著性可^ 146540.doc 201038686 時間維持的紫外線遮蔽性積層塗膜。 【實施方式】 本發明之紫外線遮蔽性積層塗膜之第一特徵在於包含（工) • 底塗層，6亥底塗層之特徵在於：含有硬化性樹脂1 〇〇質量 份、及紫外線吸收劑5〜100質量份，塗佈時之膜厚為 10〜200 μηι，且[相對於每1〇〇質量份硬化性樹脂原料單體 之紫外線吸收劑之含量（質量份）]χ[底塗層於塗佈時之膜厚 ❹ （μίη)]在100〜1000之範圍内。由於該底塗層含有紫外線吸 收劑，故而可對本發明之積層塗膜賦予紫外線遮蔽性。進 而，該底塗層係以硬化性樹脂作為主成分者，其使下述特 定之聚矽氧系之光硬化性樹脂組合物牢固地密著於基材 上，從而改善本發明之積層塗膜與基材之密著性。另一方 面’於本發明之紫外線遮蔽性積層塗膜中，含有紫外線吸 收劑之底塗層係由使聚矽氧系之光硬化性樹脂組合物硬化 而成之外塗層所被覆，故而於長時間使用之情形時，可防 Q 止紫外線吸收劑溶出，可維持優異之紫外線遮蔽性。 若不使用上述底塗層，而於聚矽氧系之光硬化性樹脂組 合物中調配大量之紫外線吸收劑，則有可能出現高能量線 照射之硬化不良或塗膜與基材之密著不良。又，使用不含 ' 紫外線吸收劑之底塗層之情形時，則存在包含聚矽氧系之 光硬化性樹脂組合物的外塗層之密著性變得不充分的情 形，又，所獲得之積層塗膜之紫外線遮蔽性會變得不充 分。 硬化性樹脂係上述底塗層之主成分，其係使硬化性樹脂 146540.doc 201038686 原料早體聚合而成之合成樹脂系硬化性樹脂。此種硬化性 樹脂可用作改善與基材之密著性的底塗劑，該硬化性樹脂 只要與紫外線吸收劑之相容性優異則無特別限定，可為加 熱硬化型、或藉由高能量線照射之光硬化型中之任一種。 作為該硬化性樹脂，更具體可例示：丙烯酸系樹脂、胺基 甲酸酯系樹脂、氟系樹脂'&酯系樹脂、聚醯胺系樹脂、 聚醯亞胺系樹脂、環氧系樹脂或聚烯烴系樹脂。 上述硬化性樹脂原料單體中，作為丙烯酸系樹脂原料單 體可例示：丙烯酸酯系單體、甲基丙烯酸酯系單體、多官 能性丙烯酸酯或多官能性甲基丙烯酸酯。同樣地，作為胺 基甲酸酯系樹脂原料單體，可例示：二異氰酸酯等異氰酸 酯系單體、以及乙二醇等多元醇系單體。作為氟系樹脂原 料單體，可例示氟化烯煙系單體。作為聚醋系樹脂原料單 體，可例示：對苯二甲酸等多元羧酸、以及乙二醇等多元 醇系單體。作為聚醯胺系樹脂原料單體，可例示：ε_己内 醯胺等醯胺系單體、己二胺等二胺系單體、以及對苯二曱 酸等多元羧酸。作為聚醯亞胺系樹脂原料單體，例如可例 示：作為聚醯亞胺系樹脂之預聚物的聚醯胺酸（p〇lyamie acid)之原料即四羧酸二酐、以及二胺系單體。作為環氧系 樹脂原料單體，可例示：雙酚等芳香族系單體、以及表氣 醇等環氧官能性化合物。作為聚烯烴系樹脂原料單體，可 例示乙烯、丙烯等不飽和烴系單體。 該等硬化性樹脂可藉由利用公知之聚合方法，使上述硬 化性樹脂原料單體聚合或者共聚合而獲得。考慮到可於基 146540.doc -12- 201038686 材上谷易地使該硬化性樹脂加熱硬化或光硬化，構成本發 明之底塗層之硬化性樹脂適宜的是丙烯酸系樹月旨、胺基甲 酸酯系樹脂、聚酯系樹脂或聚醯胺系樹脂。 - 尤其疋於本發明之紫外線遮蔽性積層塗膜中，適宜之硬 化性樹脂為（a)丙烯酸系樹脂，作為該硬化性樹脂原料單 體’適宜的是（al)丙烯酸系樹脂原料單體。其原因在於， 藉由使用包含該（a)丙烯酸系樹脂之底塗層，容易調配紫外 線吸收劑，可容易地塗佈於基材上並藉由加熱或高能量線 照射而容易地使其硬化。 即，本發明之紫外線遮蔽性積層塗膜合適宜是以如下内 谷作為第一特徵：包含⑴丙烯酸系底塗層，該丙烯酸系底 塗層之特徵在於：含有（a)丙烯酸系樹脂i 〇〇質量份、（b)紫 外線吸收劑5〜1〇〇質量份，塗佈時之膜厚為1〇〜2〇〇 μπι，且 [相對於每體1 00質量份（al)丙烯酸系樹脂原料之（b)紫外線 吸收劑之含量（質量份）]x [底塗層於塗佈時之膜厚（μιη)]在 Q 100〜1000之範圍内。由於該底塗層含有紫外線吸收劑，故 而可對本發明之積層塗膜賦予紫外線遮蔽性。進而，由於 該底塗層含有丙烯酸系樹脂，故而使下述特定之聚矽氧系 之光硬化性樹脂組合物牢固地密著於基材上，而改善本發 明之積層塗膜與基材之密著性。 (a)成分係作為底塗層之主劑之丙烯酸系樹脂，其主成分 可例示：聚丙烯酸系樹脂、聚甲基丙烯酸系樹脂、多官能 !·生丙稀@欠g曰或多官能性甲基丙烯酸酯之聚合物。作為丙稀 酸系樹脂，適宜的是使用以聚丙烯酸系樹脂或聚甲基丙烯 146540.doc •13· 201038686 酸系樹脂作為主成分之丙烯酸系樹脂，特別適宜的是使用 以聚曱基丙烯酸系樹脂作為主成分之丙烯綾系樹脂。上述 丙烯酸系樹脂可藉由調配紫外線吸收劑而形成紫外線遮蔽 性優異之底塗層，而顯著改善與形成本案發明之外塗層的 聚石夕氧系之光硬化性樹脂組合物之密著性。 (a)成分之丙烯酸系樹脂係以（a丨）丙烯酸系樹脂原料單體 作為構成單元的聚合物，於本發明中，可藉由將包含（al) 丙烯酸系樹脂原料單體及公知之聚合起始劑之底塗層塗佈 組合物塗佈於基材上，進行加熱或者紫外線等高能量線之 光照射而獲得。 (al)丙烯酸系樹脂原料單體更具體而言係指丙烯酸酯系 單體、曱基丙烯酸酯系單體、含有多官能性丙烯酸酯或多 g月&性甲基丙烯酸酯之單體，可使用選自該等單體中之丄 種或2種以上之混合物。同樣地，本發明中可使用的（ai)丙 烯酸系樹脂原料單體包括包含該等單體、及可與該等單體 共聚合之含不飽和鍵之單體的單體混合物，可使用下述單 體混合物，s亥單體混合物包含：選自由丙烯酸酯系單體、 甲基丙烯酸S旨系單體、多官能性丙稀酸酷及多官能性甲基 丙烯酸酯所組成群中之丨種或2種以上單體7〇〜1〇〇質量％， 以及可與忒等單體共聚合之含不飽和鍵之單體〇〜3〇質量 %。 (al)丙烯酸系樹脂原料單體適宜的是丙烯酸酯系單體、 甲基丙烯酸Μ單體、或者包含該等單體及可與該等單體 共聚合之含不飽和鍵之單體的單體混合物。更具體而言， 146540.doc 14 201038686 可適宜地使用：丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙 酯、丙烯酸正丁酯、丙烯酸-2-乙基己酯等作為丙烯酸烷基 酯之丙烯酸酯系單體；曱基丙烯酸甲酯、曱基丙烯酸乙 • 酯、甲基丙稀酸異丙酯、甲基丙稀酸正丁酯等作為甲基丙 烯酸烷基酯之甲基丙烯酸酯系單體。又，作為可與該等單 體共聚合之含不飽和鍵之單體，可例示：苯乙稀、α_甲基 苯乙烯、乙烯基甲苯等芳香族乙烯化合物。 ^ 於本發明中，就所獲得之紫外線遮蔽性積層塗膜與基材 之後、著性、以及藉由調配紫外線吸收劑而賦予紫外線遮蔽 性方面而言，（a)成分之丙烯酸系樹脂適宜的是其主成分為 以上述甲基丙烯酸酯系單體作為主要構成要素之聚甲基丙 烯酸系樹脂。特別好的是使用以作為（al)成分之曱基丙烯 酸曱酯作為主要構成要素的聚曱基丙烯酸甲酯樹脂。特別 好的是（al)成分之75〜100質量％為曱基丙烯酸甲酯，且將 該（a 1)成分聚合而成之聚甲基丙烯酸曱酯樹脂。 Q (b)紫外線吸收劑係對本發明之積層塗膜賦予紫外線遮 蔽性之成分，該（b)成分之調配量相對於硬化性樹脂、適宜 的是相對於（a)丙烯酸系樹脂100質量份，而為$〜1〇〇質量 份。再者，於本發明中，形成底塗層之底塗層塗佈劑組合 . 物，於硬化前之階段含有硬化性樹脂原料單體、適宜的是 01)丙烯酸系樹脂原料單體以及（b)紫外線吸收劑。因此， 上述（b)成分之調配量係於將丙烯酸系樹脂硬化而形成底塗 層之前之階段中，相對於100質量份之（al)丙烯酸系樹脂原 料單體的調配量。 146540.doc -15· 201038686 (b)紫外線吸收劑之調配量相對於硬化性樹脂、適宜的 是相對於（a)丙烯酸系樹脂100質量份而在5〜1〇〇質量份之範 圍内，適宜的是7〜60質量份，更適宜的是75〜4〇質量份，& 最適宜的是8〜20質量份。若（b)紫外線吸收劑之調配量未 達上述下限，則本發明之積層塗膜之紫外線遮蔽性會=得 不充分。又，若（b)紫外線吸收劑之調配量超過上述上限， 則即使於使用有上述底塗層之情形時，包含聚矽氧系之光 硬化性樹脂組合物之硬化皮膜與基材的密著性亦不充分， 會出現本發明之積層塗膜剝落等密著不良之情況。 於將本發明之紫外線遮蔽性積層塗膜，用作被覆藉由波 長300 nm附近之紫外線容易發生光分解之聚碳酸酯樹脂等 基材的基材保護層時，（b)紫外線吸收劑較好的是（b ”於 260〜400 nm具有吸收波長之紫外線吸收劑。又，成分 特別好的是選自由羥基苯基三畊系化合物、二苯曱酮系化 合物以及氰基丙烯酸酯系化合物所組成群中的於22〇〜4〇〇 nm具有吸收波長之紫外線吸收劑，該等可單獨使用一種， 亦可併用兩種以上。 更具體而言’成分（b)為選自以下化合物中之1種以上之 1外線吸收劑：2-[4-[(2-經基-3-十二烧氧基丙基）氧基卜 4,6-雙（2,4-一曱基苯基）-1,3,5-三p井及2-[4-[(2-經基_3-十三 烧氧基丙基）氧基]_4,6-雙（2,4-二甲基苯基）-1，3,5-三$之1-曱氧基-2-丙醇溶液、2_[4_[(2_羥基乙基）己基）氧基卜 2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1，3,5-三哺、2_(2-羥 基-4-[l-辛基羰基乙氧基]苯基）_4,6_雙（4_苯基苯基 146540.doc •16- 201038686 三畊等羥基苯基三畊系化合物；2,4-二羥基二苯甲酮、2-羥基-4-正十二烷氧基二苯甲酮、2-羥基-4-曱氧基二苯曱 酮等二苯甲酮系化合物；2-氰基-3,3’-二苯基丙烯酸2-乙基 己基酯、2-氰基-3，3^二苯基丙烯酸乙酯等氰基丙烯酸酯系 化合物。最好的是羥基苯基三畊系化合物。 該等紫外線吸收劑於市場上有售，作為羥基苯基三畊系 化合物之紫外線吸收劑，可適宜地使用由汽巴精化（Ciba Specialty Chemicals)股份有限公司所提供之產品編號（註冊 商標：TINUVIN) :「TINUVIN 400」、「TINUVIN 405」、 「TINUVIN 479」，特別好地可使用「TINUVIN 400」（註 冊商標：TINUVIN)。 以下，例示適宜之羥基苯基三畊系化合物之紫外線吸收 劑的結構式。 [化1][Technical Field] The present invention relates to an ultraviolet shielding multilayer coating film which forms a hard coating film excellent in weather resistance and ultraviolet shielding property, and more particularly, the present invention relates to Ultraviolet light can be easily hardened, and the UV-absorbing effect, physical strength, stain resistance, uniformity of the coating film, and adhesion of the coating film are excellent. . The present invention relates to a substrate having the ultraviolet shielding layer coated film on its surface and a method for producing the same. [Prior Art] A high-energy-line-curable coating agent which can be cured by ultraviolet rays is particularly suitable for surface coating of a substrate containing a thermoplastic resin having low heat resistance, substrate protection, and physical strength of the substrate without damage Further, it has an advantage of imparting excellent physical properties such as stain resistance, scratch resistance, and smoothness. Such high-energy linear curable coating agents are well known, for example, abrasion resistance of yttrium (iv) decylated acrylate, colloidal cerium oxide, acryloxy-functional cerium oxide, and photopolymerization initiator are known. The ultraviolet curable coating composition (Patent Document D. & is known to have high energy ray curability characterized by containing an alkoxy group-containing organic poly--oxygen-based and polyfunctional acrylate) Composition (Patent Document 2), or an increase in physical strength including polyfunctional acetoacetate, colloidal silica, organic alkaloids, and amine-modified organic polyoxo or its wheat A high-energy linearly curable acrylonitrile-polyoxylate composition which can be a reaction product of Michaei (Patent Document 3). Further, these documents describe a case where the composition is hardened by ultraviolet rays. 146540.doc 201038686 A well-known photopolymerization initiator can be preferably used. However, a substrate containing a thermoplastic resin such as a polycarbonate resin is liable to undergo photodecomposition due to ultraviolet rays having a wavelength of around 300 nm. Exposure When using the ultraviolet light in the vicinity of the wavelength of 300 nm to illuminate the coating layer in the environment under sunlight, there is a problem that the coated substrate itself is deteriorated. In order to prevent the thermoplastic resin substrate from being caused by ultraviolet rays It is known that the ultraviolet absorber can be adjusted and deteriorated (for example, paragraph [0019] of Patent Document 3). However, "the ultraviolet absorber absorbs the ultraviolet rays required for the hardening coating agent", so that the weather resistance is improved. A large amount of the coating agent' will hinder the curing of the coating agent by ultraviolet rays, which hinders the physical strength, chemical contamination, film strength and adhesion of the hardened film directly, and the ultraviolet irradiation required for hardening. In particular, the known photocurable resin composition does not have the performance of a coating agent such as a polycarbonate resin which is easily photodegraded by ultraviolet rays having a wavelength of around 300 nm. A protective film (also referred to as a hard coat layer) comprising a polysulfonated hardened film as described above is densely bonded to a substrate A method of using an acrylic tree ruthenium primer is widely known (for example, Patent Document 4). Further, Patent Document 5 discloses the following abrasion resistant polycarbonate article, that is, the abrasion resistance. The polycarbonate article is coated with a polycarbonate resin using a post-accelerating primer containing about 25 to 85% of a thermosetting acrylic polymer and a UV absorber of 15 to 75°, and then filled with colloidal dioxide. The thermosetting hardened organopolyoxane is formed into a top coat. Further, it is proposed to apply an acrylic system containing a UV-absorbing 146540.doc 201038686 to a film thickness of 1 to 10 μm at the right side of the substrate. A primer layer made of a resin primer is formed on a substrate such as polycarbonate or the like, and a hardened film of a polysiloxane is formed on the undercoat layer, thereby obtaining a substrate excellent in ultraviolet shielding properties (Patent Literature) 6~9). * For example, 'Patent Document 6 proposes a polycarbonate molded article characterized in that an undercoat layer having a film thickness of 2 to 5 μηι containing an ultraviolet absorber is provided on a polycarbonate substrate, and the primer is applied to the primer. A composition containing a colloidal silica dioxide-containing organic polyoxime composition is applied to the agent to be semi-hardened and then subjected to bismuth molding (Patent Document 6 and [0011] paragraph, etc., Patent Literature 7 to 9, there is proposed an ultraviolet absorbing transparent body which is sequentially coated on a transparent substrate with an undercoat layer containing an ultraviolet absorber or the like and having a film thickness of μιη, preferably 3 to 8 μηι, and polyfluorene. An oxygen-based hard coat layer is formed (for example, in the 'Request of Patent Document 7 and paragraph [〇〇16]). However, the weather resistance and physical properties of the substrate containing the polyoxyl-based hardened film are The strength and the shielding property of ultraviolet rays are also unsatisfactory. In the case of using the undercoat layer described in Patent Documents 5 to 9, U is a hard coat of polyoxynized oxygen under strict evaluation conditions. The adhesion of the layer is not full of knives, especially for easy use. A polycarbonate resin sheet which is photo-decomposed by ultraviolet rays having a length of about 300 nm in place of a glass substrate for use as a building material or a window material is not satisfactory. In order to solve the above problems, the inventor of the present invention Et al. propose a UV-absorbing agent containing polyfunctional acid acrylate, colloidal cerium oxide, acryloxy-functional lanthanum, having an absorption wavelength of 220 to 400 11 „1 and 3 〇〇 to 45 〇 The photocurable resin composition having a photopolymerization initiator which absorbs a wavelength, and further, when the photocurable resin composition is applied onto a substrate such as polycarbonate resin 146540.doc 201038686, the film thickness is used in combination. ~ ""acrylic resin-based undercoat layer (Patent Document 10). The substrate containing the film obtained by curing the photocurable resin composition is not easily deteriorated by ultraviolet rays, and the film and the substrate are not easily deteriorated by ultraviolet rays. The adhesion is also excellent, so it is very satisfactory in terms of weather resistance and physical strength. On the other hand, it is used as a building material or window material instead of a polycarbonate resin sheet or the like. For the glass substrate of the material, it is desirable that the substrate containing the polycarbonate resin is not deteriorated by ultraviolet rays in the vicinity of 3 〇〇 nm even if it is continuously exposed to too much light for more than ten years. Therefore, the inventor of the present invention In addition, there is still room for further research on a substrate protective layer which is excellent in ultraviolet shielding properties and exhibits a very satisfactory performance in terms of weather resistance and physical strength. [Prior Art Literature] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] [Patent Document 5] [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 56-92-59 (Patent Document 6). Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 28741 International Open Handbook 146540. Doc 201038686 SUMMARY OF THE INVENTION An object of the present invention is to provide an ultraviolet ray absorbing effect, physical strength, stain resistance, uniformity of a coating film, and a coating film which are easily hardened by ultraviolet rays and hardened at around 300 nm. A weather-resistant ultraviolet shielding multilayer coating film excellent in adhesion. Further, an object of the present invention is to provide a substrate comprising the ultraviolet shielding multilayer coating film on the surface thereof and a method for producing the same. The ultraviolet shielding coating film of the present invention is characterized by comprising: (1) an undercoat layer comprising a curable resin 丨〇〇 mass part, and a UV absorbing agent in an amount of 5 to 100 parts by mass, and a film thickness at the time of coating is 1 〇~2〇〇, and [1 (parts by mass) of the ultraviolet absorber per 100 parts by mass of the curable resin raw material monomer] [film thickness of the undercoat layer at the time of coating (^111)] In the range of 1 〇〇 to 1 ', the 'and (II) hardened layer' is formed on the surface of the undercoat layer, and is irradiated by high-energy rays to contain the following components (Α) to (D). Photocurable resin composition is photocured. _ (Α) Polyfunctional acrylate or polyfunctional methacrylate 1 〇〇 by mass, (Β) organo alkoxy decane having an aliphatic unsaturated bond ^^0 parts by mass, (C) colloidal cerium oxide 1 to 3 parts by mass, and (D) photopolymerization initiator 〇〇1 to 3 parts by mass. Furthermore, in the ultraviolet shielding coating film of the present invention, the curable resin can be preferably used as (a) an acrylic resin, and the curable resin raw material monomer is (al) an acrylic resin raw material monomer. Undercoat. That is, the ultraviolet shielding coating film of the present invention is preferably a purple 146540.doc 201038686 outer shielding layer coating film, characterized by comprising: (z) an acrylic primer layer characterized by containing (a) The acrylic resin 丨〇〇 mass part and the ultraviolet absorber 5~1 〇〇 parts by mass, the film thickness at the time of coating is 丨〇~2〇〇μιη, and [with respect to 1 〇〇 mass part per body (a (b) the content of the ultraviolet absorbing agent (parts by mass) of the acrylic resin raw material] x [the film thickness (μιη) of the undercoat layer at the time of coating] is in the range of 100 to 1000; and (II) the hardened layer The photocurable resin composition comprising the following components (Α) to (D) is photocured by high energy ray irradiation on the surface of the undercoat layer: (Α) polyfunctional C 1 part by mass of a dilute acid ester or a polyfunctional mercaptopropionate, 1 part by mass of an organoalkoxy decane having an aliphatic unsaturated bond, (C) 1 to 300 parts by mass of a colloidal cerium oxide; And (D) photopolymerization initiator 〇. 〇 1 to 30 parts by mass. The acrylic primer layer (I) is preferably one obtained by curing the undercoat layer coating composition containing the following components (a1) to (d): (al) acrylic resin raw material monomer 100 mass And (b) 5 to 100 parts by mass of the ultraviolet absorber, (c) 0 to 20 parts by mass of the hindered amine light stabilizer, and (d) 1 to 100 parts by mass of the organoalkoxydecane having an aliphatic unsaturated bond . Here, the component (al) acrylic resin raw material monomer is more specifically: an acrylate monomer, a mercapto acrylate monomer, or a monomer comprising the same and 146540.doc 201038686 can be copolymerized with the 忒4 monomer. A free radical copolymerizable mixture of monomers containing unsaturated bonds. The first feature of the ultraviolet shielding coating film of the present invention is that the amount of the ultraviolet absorber in the above-mentioned undercoat layer and the film thickness of the undercoat layer at the time of coating are within a specific range, and both satisfy [relative to (b) content (parts by mass) of the ultraviolet absorber per 100 parts by mass of the curable resin raw material monomer] x [film thickness (μηι) of the undercoat layer at the time of coating] in a specific relationship in the range of 100 to 1000 . In particular, [(b) the content of the ultraviolet absorber (parts by mass) per 100 parts by mass of the curable resin raw material monomer] x [the film thickness (pm) of the undercoat layer at the time of coating] is better. It is a range of 120 to 600, and particularly preferably a range of 16 to 4 inches. Further, a second feature of the ultraviolet shielding coating film of the present invention is that the undercoat layer has an organoalkane having a polyfunctional acrylate or a polyfunctional methacrylate and having an aliphatic unsaturated bond. An overcoat layer formed of a polyfluorene-based photocurable resin composition comprising oxydecane, colloidal cerium oxide, and a photopolymerization initiator. The substrate to which the ultraviolet shielding layer coating film of the present invention is applied is formed by coating the surface of the substrate with the ultraviolet shielding layer coating film, and the substrate is preferably transparent in a thickness range of 0.005 m to 0.1 m. Plate polycarbonate resin. Further, the substrate to which the ultraviolet shielding layer coating film is adhered can be obtained by coating a primer layer containing 10 parts by mass of the curable resin raw material monomer and 5 to 100 parts by mass of the ultraviolet absorber. The cloth composition has a film thickness of 10 to 200 μm when applied, and [(b) the content of the ultraviolet absorber (parts by mass) per 100 parts by mass of the curable resin raw material monomer] χ [primer coating The film thickness (μιη) at the time of coating is applied to the surface of the 146540.doc 201038686 substrate and hardened in an amount in the range of 100 to 1000, thereby coating the surface of the substrate with the undercoat layer, and then at the bottom. The substrate is coated with a photocurable resin composition containing the following components (component A), and light-hardened by a high-energy line, thereby sequentially coating the substrate: (A) polyfunctional acrylate Or polyfunctional methacrylate 1 〇〇 by mass, (B) organoalkoxy decane having an aliphatic unsaturated bond, (C) colloidal cerium oxide 1 to 300 parts by mass, and (D) light The polymerization initiator 〇.〇1 to 3〇 parts by mass. The outer line shielding product of the present invention The coating film comprises the following hardened layer as an outer coating layer, that is, the hardened layer contains an organoalkoxydecane containing a polyfunctional acrylate or a polyfunctional methacrylate, having an aliphatic unsaturated bond, and colloidal dioxide特定 and a specific photopolymerizable resin composition of a photopolymerization initiator, which can be easily cured by ultraviolet rays, and physical strength, stain resistance, and uniformity of the coating film after curing An excellent hardened film is used to coat the substrate. Further, the purple (iv) shielding layer coating film of the present invention (4) is provided with a UV absorber containing a specific amount, and the film thickness at the time of coating is hardened within a specific range. The undercoat layer of the resin, so that the overcoat layer is firmly adhered to the surface of the substrate through the undercoat layer and exhibits excellent ultraviolet shielding properties. Therefore, adhesion and weather resistance of the coating film can be provided. In particular, the wire is excellent, and especially when coated with a substrate containing a polycarbonate resin, it is not ultraviolet (four) due to the wavelength of 300, and the adhesion of the substrate is 146540. .doc 20 1038686 Ultraviolet-shielding laminated coating film which is maintained in time. [Embodiment] The first feature of the ultraviolet shielding multilayer coating film of the present invention is that it contains an undercoat layer, and the 6-coating layer is characterized in that it contains curability. 1 part by mass of the resin and 5 to 100 parts by mass of the ultraviolet absorber, the film thickness at the time of coating is 10 to 200 μηι, and [relative to the ultraviolet absorber of the curable resin raw material monomer per 1 part by mass) The content (parts by mass) χ [the film thickness 底 (μίη) of the undercoat layer at the time of coating] is in the range of 100 to 1000. Since the undercoat layer contains an ultraviolet absorber, the laminated film of the present invention can be imparted. Further, the undercoat layer is made of a curable resin as a main component, and the specific polyoxynene-based photocurable resin composition described below is firmly adhered to a substrate, thereby improving the present invention. The adhesion between the laminated coating film and the substrate. On the other hand, in the ultraviolet shielding coating film of the present invention, the undercoat layer containing the ultraviolet ray absorbing agent is formed by curing the poly fluorinated photocurable resin composition and coating the outer coating layer. When used for a long period of time, it can prevent the UV absorber from eluting and maintain excellent UV shielding properties. If a large amount of the ultraviolet absorber is blended in the polyoxygen-based photocurable resin composition without using the undercoat layer, there is a possibility that hardening of the high-energy line irradiation or adhesion of the coating film to the substrate may occur. . In the case where the undercoat layer containing the ultraviolet absorber is not used, the adhesion of the overcoat layer containing the photocurable resin composition of the polyfluorene-based resin is insufficient, and the obtained The ultraviolet shielding property of the laminated coating film is insufficient. The curable resin is a main component of the undercoat layer, and is a synthetic resin-based curable resin obtained by preliminarily polymerizing a curable resin 146540.doc 201038686. Such a curable resin can be used as a primer for improving the adhesion to a substrate. The curable resin is not particularly limited as long as it has excellent compatibility with the ultraviolet absorber, and may be heat-cured or high. Any of the light-hardening types of the energy ray irradiation. More specifically, the curable resin may, for example, be an acrylic resin, a urethane resin, a fluorine resin, an ester resin, a polyamine resin, a polyimide resin, or an epoxy resin. Or a polyolefin resin. In the above-mentioned curable resin raw material monomer, an acrylic resin raw material monomer may, for example, be an acrylate monomer, a methacrylate monomer, a polyfunctional acrylate or a polyfunctional methacrylate. In the same manner, as the raw material monomer of the urethane resin, an isocyanate monomer such as a diisocyanate or a polyol monomer such as ethylene glycol can be exemplified. As the fluorine-based resin raw material monomer, a fluorinated olefinic monomer can be exemplified. The polyvalent carboxylic acid such as terephthalic acid or a polyol-based monomer such as ethylene glycol can be exemplified as the raw material of the raw material of the vinegar-based resin. The polyamine-based resin raw material monomer may, for example, be a guanamine monomer such as ε-caprolactam, a diamine monomer such as hexamethylenediamine or a polyvalent carboxylic acid such as terephthalic acid. The polyimine-based resin raw material monomer is, for example, a tetracarboxylic dianhydride or a diamine-based material which is a raw material of poly-pyridyl acid (p〇lyamie acid) which is a prepolymer of a polyfluorene-based resin. monomer. The epoxy resin raw material monomer may, for example, be an aromatic monomer such as bisphenol or an epoxy functional compound such as a surface alcohol. The polyolefin-based resin raw material monomer may, for example, be an unsaturated hydrocarbon-based monomer such as ethylene or propylene. These curable resins can be obtained by polymerizing or copolymerizing the above-mentioned hard resin raw material monomers by a known polymerization method. In view of the fact that the curable resin can be heat-hardened or photohardened on the basis of the substrate 146540.doc -12- 201038686, the curable resin constituting the undercoat layer of the present invention is preferably an acrylic resin or an amine group. An acid ester resin, a polyester resin or a polyamide resin. In particular, in the ultraviolet shielding coating film of the present invention, a suitable hardening resin is (a) an acrylic resin, and as the curable resin raw material monomer, (al) an acrylic resin raw material monomer is suitable. This is because the use of the undercoat layer containing the (a) acrylic resin makes it easy to apply an ultraviolet absorber, which can be easily applied to a substrate and easily hardened by heating or high-energy irradiation. . That is, the ultraviolet shielding multilayer coating film of the present invention is preferably characterized by having the inner grain as the first feature comprising: (1) an acrylic primer layer comprising (a) an acrylic resin i 〇 〇 parts by mass, (b) 5 to 1 part by mass of the ultraviolet absorbing agent, the film thickness at the time of coating is 1 〇 2 〇〇 μm, and [100 parts by mass per part of the acrylic resin material per body) (b) Content of the ultraviolet absorber (parts by mass)]x [The film thickness (μιη) of the undercoat layer at the time of coating] is in the range of from 100 to 1,000. Since the undercoat layer contains an ultraviolet absorber, ultraviolet ray shielding properties can be imparted to the laminated coating film of the present invention. Further, since the undercoat layer contains an acrylic resin, the polysiloxane-based photocurable resin composition described below is firmly adhered to the substrate to improve the laminated coating film and the substrate of the present invention. Adhesiveness. (a) The component is an acrylic resin which is a main component of the undercoat layer, and the main component thereof is exemplified by a polyacrylic resin, a polymethacrylic resin, a polyfunctional product, a raw propylene, an under-g 曰 or a polyfunctionality. a polymer of methacrylate. As the acrylic resin, an acrylic resin containing a polyacrylic resin or a polymethyl propylene 146540.doc •13·201038686 acid resin as a main component is preferably used, and it is particularly preferable to use a polyacrylonitrile-based resin. A propylene oxime resin having a resin as a main component. The acrylic resin can form an undercoat layer excellent in ultraviolet shielding property by blending an ultraviolet absorber, and can remarkably improve the adhesion to the polysulfide-based photocurable resin composition which forms the coating layer other than the present invention. . The acrylic resin of the component (a) is a polymer having a (a) acrylic resin raw material monomer as a constituent unit, and in the present invention, a monomer comprising (al) acrylic resin raw material and a known polymerization can be obtained. The primer coating composition of the initiator is applied onto a substrate and heated or irradiated with light of a high energy line such as ultraviolet rays. (al) Acrylic resin raw material monomer means more specifically an acrylate type monomer, a mercapto acrylate type monomer, a monomer containing a polyfunctional acrylate or a polyg valence & methacrylate, A saccharide selected from the monomers or a mixture of two or more kinds thereof may be used. Similarly, the (ai) acrylic resin raw material monomer usable in the present invention includes a monomer mixture containing the monomers and a monomer having an unsaturated bond copolymerizable with the monomers, and can be used. The monomer mixture comprises: a mixture selected from the group consisting of an acrylate monomer, a methacrylic acid S monomer, a polyfunctional acrylic acid, and a polyfunctional methacrylate. The amount of the monomer or the two or more kinds of monomers is 7 〇 to 1% by mass, and the monomer having an unsaturated bond copolymerizable with a monomer such as hydrazine is 〇3 to 3% by mass. (al) The acrylic resin raw material monomer is preferably an acrylate monomer, a ruthenium methacrylate monomer, or a single monomer comprising the monomer and an unsaturated bond-containing monomer copolymerizable with the monomers Body mixture. More specifically, 146540.doc 14 201038686 may suitably be used: methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc. as the acrylate of the alkyl acrylate Monomer; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, etc. as methacrylate monomer of alkyl methacrylate . Further, examples of the unsaturated bond-containing monomer copolymerizable with the monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene. In the present invention, the acrylic resin of the component (a) is suitable for the ultraviolet shielding property obtained by the ultraviolet shielding coating film and the substrate, and the ultraviolet shielding property by blending the ultraviolet absorber. The main component is a polymethacrylic resin containing the above methacrylate monomer as a main component. It is particularly preferable to use a polymethyl methacrylate resin having decyl decyl acrylate as the (al) component as a main constituent element. Particularly preferably, 75 to 100% by mass of the (al) component is methyl methacrylate, and the polymethyl methacrylate resin obtained by polymerizing the component (a1). (b) The ultraviolet ray absorbing agent is a component that imparts ultraviolet shielding properties to the laminated coating film of the present invention, and the amount of the component (b) is preferably 100 parts by mass based on the curable resin, relative to the (a) acrylic resin. And for $~1〇〇 part by mass. Further, in the present invention, the undercoat layer coating agent composition for forming an undercoat layer contains a curable resin raw material monomer at a stage before curing, suitably 01) an acrylic resin raw material monomer, and (b) ) UV absorbers. Therefore, the blending amount of the component (b) is a blending amount with respect to 100 parts by mass of the (al) acrylic resin raw material monomer in the stage before the acrylic resin is cured to form the undercoat layer. 146540.doc -15· 201038686 (b) The amount of the ultraviolet absorber is preferably in the range of 5 to 1 part by mass based on 100 parts by mass of the (a) acrylic resin, with respect to the curable resin. It is 7 to 60 parts by mass, more preferably 75 to 4 parts by mass, and most preferably 8 to 20 parts by mass. When the amount of the ultraviolet absorbing agent (b) is less than the above lower limit, the ultraviolet shielding property of the laminated coating film of the present invention may be insufficient. In addition, when the amount of the ultraviolet absorber (b) exceeds the above upper limit, even when the undercoat layer is used, the cured film of the photocurable resin composition containing the polyfluorene-based resin is adhered to the substrate. The properties are also insufficient, and the adhesion of the laminated film of the present invention such as peeling off may occur. When the ultraviolet shielding coating film of the present invention is used as a substrate protective layer covering a substrate such as a polycarbonate resin which is easily decomposed by ultraviolet rays having a wavelength of around 300 nm, (b) the ultraviolet absorber is preferably used. The (b ′) ultraviolet absorbing agent having an absorption wavelength at 260 to 400 nm. Further, the composition is particularly preferably selected from the group consisting of a hydroxyphenyl tri-till compound, a benzophenone compound, and a cyanoacrylate compound. In the group, the ultraviolet absorber having an absorption wavelength of 22 〇 to 4 〇〇 nm may be used singly or in combination of two or more. More specifically, the component (b) is one selected from the following compounds. More than 1 external line absorbent: 2-[4-[(2- mercapto-3-dodecyloxypropyl)oxybu 4,6-bis(2,4-indenylphenyl)- 1,3,5-tripa well and 2-[4-[(2-trans)-3-trioxooxypropyl)oxy]_4,6-bis(2,4-dimethylphenyl) -1,3,5-three-thyl 1-nonoxy-2-propanol solution, 2_[4_[(2-hydroxyethyl)hexyl)oxybu 2-hydroxyphenyl]-4,6- Bis(2,4-dimethylphenyl)-1,3,5-triple, 2_(2-hydroxy-4-[l-octyl Carbonyl ethoxy]phenyl)_4,6_bis (4-phenylphenyl 146540.doc •16- 201038686 three-till hydroxyphenyl tri-tillate compound; 2,4-dihydroxybenzophenone, 2 a benzophenone compound such as -hydroxy-4-n-dodecyloxybenzophenone or 2-hydroxy-4-decyloxybenzophenone; 2-cyano-3,3'-diphenyl A cyanoacrylate compound such as 2-ethylhexyl acrylate or 2-cyano-3,3^diphenylacrylate. The most preferred one is a hydroxyphenyl tri-till compound. As a UV absorber which is commercially available as a hydroxyphenyl tri-tillage compound, the product number (registered trademark: TINUVIN) supplied by Ciba Specialty Chemicals Co., Ltd.: "TINUVIN 400" can be suitably used. "TINUVIN 405" and "TINUVIN 479", "TINUVIN 400" (registered trademark: TINUVIN) can be used particularly well. Hereinafter, the structural formula of a suitable ultraviolet absorbing agent for a hydroxyphenyl tri-farming compound will be exemplified. ]

OHOH

II

[化2] 146540.doc -17- 201038686[Chemical 2] 146540.doc -17- 201038686

[化3][Chemical 3]

構成本發明之紫外線吸收性積層塗膜之底塗層中 的是含有硬化性樹脂、適宜的是丙烯酸系樹脂1 〇〇質j 份及（b)紫外線吸收劑5〜1 〇〇質量份，且硬化後形成該底塗 層之底塗層塗佈組合物係含有硬化性樹脂原料單體、適造 的是（al)丙烯酸系樹脂原料單體1〇〇質量份以及（b)紫外錢 吸收劑5〜10 〇質量份者，更i商古^1 a、& ^ 文週且的是進而含有（c)受阻胺爲 光穩定劑。該成分（C)具有捕捉M iA 士， ?疋蜡由紫外線照射而產生之| 146540.doc 201038686 由基種的效果，故而藉由將其與上述紫外線吸收劑（成分 (b))併用，上述底塗層之紫外線防禦效果、耐候性之改善 可獲得優異之相乘效果。該受阻胺系光穩定劑可為低分子 • 里型，亦可為咼分子量型。又，構成本發明之紫外線吸收 性積層塗膜之底塗層中可混合調配2種以上之（c)受阻胺系 光穩疋劑。就本發明之紫外線吸收性積層塗膜與基材、尤 其是包含聚碳酸酯樹脂之基材之密著性的觀點而言，較好 的是低分子量型之受阻胺系光穩定劑。 作為低分子量型之受阻胺系光穩定劑，可例示：2,4_雙 [N-丁基-N_(1_環己氧基_2,2,6,6_四曱基哌啶_4_基）胺基]_6_ (2-羥基乙基胺）、癸二酸雙（2,2,6,6_四甲基·4_哌啶基）酯、 癸二酸雙（1-辛氧基_2,2,6,6_四曱基_4_哌啶基）酯、癸二酸 雙（1，2,2,6,6·五甲基-4_0辰唆基）酯、2_(3 5二第三丁基_4_ 經基节基）-2-正丁基丙二酸雙〇,2,2,6,6_五甲基_4_娘〇定基） 酉曰、四（1，2,2,6,6-五甲基_4_哌啶基丁烷四甲酸 〇 酯、l2,2’6,6-五甲基-4-0辰啶基/十三烷基-1，2,3,4-丁烷四曱 I s曰 〇,2,2,6,6-五甲基-4-哌啶基/β，β，β·,β，_ 四甲基 _3,9_ [2,4,8,1G四氧雜螺（5,5)十-烧]二乙基卜…,丁烧四甲 酸S旨。 作為冋刀子里型之受阻胺系光穩定劑，可例示：琥珀酸 一曱自曰1-(2-羥基乙基）_4_羥基_2,2,6,6_四甲基哌啶聚縮合 物N’n雙（3-胺基丙基）乙二胺_2,4_雙[N_ 丁基-N_ (1，2,2,6,6-五甲基_4_派咬基）胺基]·6_氣三畊縮合 物、聚[[6-[(1，1，3,3_四甲基丁基）胺基卜^^三味_2,4_二 146540.doc •19- 201038686 基][(2,2,6,6-四甲基-4-哌啶基）亞胺基]]、聚[{6·(1，1，3-三甲 基戊基）胺基-1，3,5-三唯-2,4-二基}{(Ν-曱基-2,2,6,6-四甲 基-哌啶基）亞胺基}八亞曱基饩Ν_甲基_2,2,6,6-四甲基-哌啶 基）亞胺基}]、聚[(6-畊啉基_均三畊_2,4_二）[1,2,2,6,6-五甲 基-4-哌啶基]亞胺基卜六亞曱基五曱基_4_哌啶 基）亞胺基]]、聚[{6-(l，l,3,3-四曱基丁基）胺基-l，3,5-三畊-2,4-二基}{(2,2,6,6-四甲基-哌啶基）亞胺基}六亞曱基 {(2,2,6,6-四曱基-哌啶基）亞胺基}]。 該等光穩定劑於市場上有售，可列舉：由汽巴精化股份 有限公司提供之產品編號（註冊商標：TINUVIN):The undercoat layer constituting the ultraviolet absorbing laminated coating film of the present invention contains a curable resin, preferably an acrylic resin 1 quinone j part, and (b) an ultraviolet absorbing agent 5 〜 1 〇〇 mass part, and The undercoat layer coating composition which forms the undercoat layer after hardening contains a curable resin raw material monomer, and is suitable for (al) acrylic resin raw material monomer 1 part by mass and (b) ultraviolet money absorbent 5 to 10 〇 by mass, more i 商古^1 a, & ^ The week further contains (c) a hindered amine as a light stabilizer. The component (C) has a capture M iA, and the wax is produced by ultraviolet irradiation | 146540.doc 201038686 The effect of the base species is combined with the above ultraviolet absorber (component (b)), The ultraviolet protection effect and weather resistance of the undercoat layer can be improved to obtain an excellent multiplication effect. The hindered amine light stabilizer may be of a low molecular weight type or a ruthenium molecular weight type. Further, two or more kinds of (c) hindered amine-based light stabilizers may be blended and mixed in the undercoat layer constituting the ultraviolet absorbing laminated coating film of the present invention. The low molecular weight hindered amine light stabilizer is preferred from the viewpoint of adhesion of the ultraviolet absorbing laminated film of the present invention to a substrate, particularly a substrate containing a polycarbonate resin. As the low molecular weight type hindered amine light stabilizer, 2,4_bis[N-butyl-N_(1_cyclohexyloxy-2,2,6,6-tetradecylpiperidine-4) can be exemplified. _yl)amino]_6_(2-hydroxyethylamine), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-octyloxy) sebacate Base 2,2,6,6-tetradecyl-4(piperidinyl) ester, bis(1,2,2,6,6·pentamethyl-4-0 chenyl) sebacate, 2_( 3 5 2 tert-butyl _4_ phenyl group)-2-n-butylmalonic acid biguanide, 2,2,6,6-pentamethyl_4_Nymidine base 酉曰, four (1 , 2,2,6,6-pentamethyl-4-piperidinylbutanetetracarboxylic acid decyl ester, l2,2'6,6-pentamethyl-4-0 henidinyl/tridecyl-1 , 2,3,4-butane tetraindole I s,2,2,6,6-pentamethyl-4-piperidinyl/β,β,β·,β,_tetramethyl-3, 9_ [2,4,8,1G tetraoxaspiro (5,5) deca-sinter]diethyl b..., butadiene tetracarboxylic acid S. As a hindered amine light stabilizer of the shovel type, it can be exemplified :Succinic acid monoterpene from 1-(2-hydroxyethyl)_4_hydroxy-2,2,6,6-tetramethylpiperidine polycondensate N'n bis(3-aminopropyl)ethylene Amine_2,4_bis[N-butyl-N_(1,2,2,6,6-pentamethyl_4_pyranyl)amine ]·6_ gas three ploughing condensate, poly[[6-[(1,1,3,3_tetramethylbutyl))amine) ^^三味_2,4_二146540.doc •19- 201038686 [[2,2,6,6-tetramethyl-4-piperidinyl)imido]], poly[{6·(1,1,3-trimethylpentyl)amino-1 ,3,5-Sanwei-2,4-diyl}{(Ν-fluorenyl-2,2,6,6-tetramethyl-piperidinyl)imide)} Base 2,2,6,6-tetramethyl-piperidinyl)imine}], poly[(6-cultivated base_all three tillage_2,4_2)[1,2,2, 6,6-pentamethyl-4-piperidinyl]iminopyridinium quinolate- 4-piperidinyl)imido]], poly[{6-(l,l,3, 3-tetradecylbutyl)amino-l,3,5-trinyl-2,4-diyl}{(2,2,6,6-tetramethyl-piperidinyl)imido} Amidino {(2,2,6,6-tetradecyl-piperidinyl)imido}]. These light stabilizers are available on the market, including the product number (registered trademark: TINUVIN) supplied by Ciba Specialty Chemicals Co., Ltd.:

「TINUVIN 111 FDL」、「TINUVIN 123」、「TINUVIN"TINUVIN 111 FDL", "TINUVIN 123", "TINUVIN

144」、「TINUVIN 152」、「TINUVIN 292」、「TINUVIN 5 1 00」等，該等光穩定劑之結構如下述式所示。 [化4]144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 5 1 00", etc., and the structure of these light stabilizers is as follows. [Chemical 4]

[化5][Chemical 5]

146540.doc •20· 201038686 [化6]146540.doc •20· 201038686 [Chem. 6]

HNHN

Ν ΗΝ Η

[化7][Chemistry 7]

CH3 [化8]CH3 [化8]

-OCH* [化9] 146540.doc -21 - 201038686 HN (CN^rN*<CH2}rN-iCM^rNH . 1 I 喔-OCH* [Chemical 9] 146540.doc -21 - 201038686 HN (CN^rN*<CH2}rN-iCM^rNH . 1 I 喔

我敦 R RI am R R

進行硬化而形成上述底塗層之底塗層塗佈組合物中成 分（C)之調配量相對於合成樹脂原料單體、適宜的是丙 烯酸系樹脂原料單體100質量份而為〇丨〜2〇質量份，適宜 的是0.5〜15質量份，較好的是卜1()質量份。若未達上述下 限，則存在作為與成分⑻之相乘效果而產生之底塗層之紫 外線遮蔽性、耐候性之改善變得不充分的情況；若成分⑷ 之調配量過多，則尤其是利用紫外線來硬化該底塗層時， 存在底塗層之硬化特性降低之情況。 ，订硬化而形成上述底塗層之底塗層塗佈組合物，較好 的疋進而3有⑷具有腊肪族不飽和鍵之有機炫氧基石夕炫。 /成:（）係與（al)丙;^酸系樹脂原料單體交聯而提昇底塗 層乂 H _a_藉由加熱或高能量線照射而對上述底塗層 塗佈，且口物職予硬化性的成分。成分⑷可含氟原子亦可不 含’通常不含款原子。 ’ ”〜崎八.RiaYSl(ORU斤表示之化 物。式中，R丨為不且右 卜’知肪族不飽和鍵的經取代或未經 代之-價煙基（例如碳原子數為卜2G)，可例示·甲基、: 146540.doc •22· 201038686 土丙基τ基'異丁基、辛基、癸基等烧基；苯基等芳 基；3,3,3-三氟甲基、全氟丁基乙基、全氟辛基乙基等含 氟烷基。該等中’較好的是甲基、乙基、丙基、丁基、異 . 丁基。R為烷基，較好的是碳原子數為1〜10之烷基，特別 #的疋甲基、乙基、丙基。γ為具有脂肪族不飽和鍵之— 價有機基(例如碳原子數為H〇)，可例示：甲基丙烯醯氧 基、丙烯醯氧基、3_(甲基丙烯醯氧基)丙基、3_(丙烯醯氧 〇 基:丙基等含丙烯醯基之有機基；乙烯基、己烯基、烯丙 基等烯基；苯乙烯基、乙稀醚基等。&為Mi。 作為成分（d)，具體可列舉：3_甲基丙烯醯氧基三甲氧基 石夕烧、3-(甲基丙埽醯氧基）丙基三甲氧基石夕烧、3_(甲基丙 稀酿氧基）丙基三乙氧基石夕烧、3(甲基丙婦酿氧基）丙基甲 基一甲氧基矽烷、3-(丙稀醯氧基）丙基三甲氧基矽烷、乙 稀基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基乙烯基二 曱氧基矽烷、烯丙基三乙氧基矽烷。 〇 進行硬化而形成上述底塗層之底塗層塗佈組合物中，成 分（d)之調配量相對於合成樹脂原料單體、適宜的是（^)丙 烯酸系樹脂原料單體100質量份而為卜丨⑼質量份，較好的 是5〜50質量份。 ' 含有上述成分（al)〜成分（句之底塗層塗佈組合物，可藉 由將其塗佈於基材上，利用任意方法進行加熱而於基材表: 面形成加熱硬化型之底塗層。另一方面，於藉由照射紫外 線等南能量線而形成光硬化型之底塗層之情形時，需要在 上述底塗層塗佈組合物中調配公知之光聚合起始劑。 146540.doc -23- 201038686 於構成本發明之紫外線遮蔽性積層塗膜的底塗層係使用 光硬化型之底塗層之情形時，上述光聚合起始劑較好的是 (e)於波長360〜450 nm具有吸收波長之光聚合起始劑。其原 因在於’由於本發明之底塗層含有（b)紫外線吸收劑，故而 當使用於波長小於300 nm之側具有吸收的光聚合起始劑 時，存在於紫外線等高能量線之照射下引起硬化阻礙的情 況。 進而’藉由使用（e)於波長360〜450 nm具有吸收波長之 光聚合起始劑，於進行紫外線硬化時，促使聚碳酸酯樹脂 等發生光分解、劣化的300 nm附近之紫外線被上述成分 (b)吸收，對聚碳酸酯樹脂等影響較小之波長即36〇〜45〇 nm之紫外線促進硬化，故而具有可抑制上述底塗層之紫外 線硬化所伴隨的聚碳酸酯樹脂等基材之光分解、劣化。 作為特別適宜之成分（e)，可例示：2,4,6_三甲基苯甲醯 基二苯基氧化膦、2_甲基小[4_(曱硫基）苯基]_2咪琳基丙 _、1-經基環己基苯基酮、2_节基_2_二甲基胺基^(心味 啉苯基）丁酮。該等光聚合起始劑於市場上有售，可適宜 地使用由π巴精化股份有限公司提供之產品編號（註冊商 標· Irgacure) :「Irgacure 9〇7」、「卜胖⑶代 」、 「Irgacure 369」等。 上述底塗層係含有硬化性樹脂、適宜的是上述成分⑷以 及成分⑻者，進而係任意地含有上述⑷〜⑷者。又，進行 硬化而形成上述底塗層之底塗層塗佈組合物係含有硬化性 樹月曰原料單體、適宜的是上述成分（al)以及成分⑻者，進 146540.doc .24- 201038686 而係任意地含有上述（C)〜(e)者。 於上述底塗層塗佈組合物中，進而可任意地使用（f)自由 基聚合起始劑來代替用於光硬化之光聚合起始劑，或與光 聚合起始劑一同地使用（f)自由基聚合起始劑。該自由基聚 合起始劑係促進底塗層之熱硬化之成分，通常使用自由基 聚合法所使用之先前公知之化合物。具體可例示：2,2，-偶 氮雙異丁腈、2,2’-偶氮雙（2-甲基丁腈）、2,2'-偶氮雙（2,4-二曱基戊腈）等偶氮雙系化合物；過氧化苯甲醯、過氧化 月桂醯、過氧化苯曱酸第三丁酯、過氧化2_乙基己酸第三 丁酯等有機過氧化物。 上述底塗層塗佈組合物中，可與上述自由基聚合起始劑 一同調配公知之矽烷醇縮合觸媒。又，可調配有機溶劑作 為上述各成分之稀釋劑。進而，只要在無損本發明之目的 之範圍内，則可於上述底塗層塗佈組合物中視需要添加調 配：抗氧化劑；增稠劑；調平劑、消泡劑、抗沈澱劑、分 散劑、抗靜電劑、防霧劑等界面活性劑；各種顏料、染料 專著色劑，紹粉聚（aluminium paste)、滑石、玻璃料、金 屬粉等填充劑；丁基化羥基甲苯（BHT)、酚噻_ (ρτζ)等丙 浠酸酯類之自聚抑制劑等。 對於構成本發明之紫外線遮蔽性積層塗膜之底塗層，其 塗佈時之膜厚必需在1〇〜2〇〇 之範圍内，較好的是膜厚 在12.5〜5〇0111之範圍内，特別好的是膜厚在15〜3〇4111之範 圍内。若底塗層之膜厚未達上述下限，則存在因發揮遮蔽 紫外線之作用之底塗層過薄，而導致積層塗膜之紫外線遮 146540.doc -25- 201038686 蔽性變得不充分的情形。另一方面，若底塗層之膜厚超過 上述上限，則用以提高與基材之密著性之底塗層過厚，結 果無法充分改善基材與形成本案發明之外塗層的聚矽氧系° 之光硬化性樹脂組合物的密著性，引起本發明之積層塗媒 自基材上剝落等密著不良。 、 構成本發明之紫外線遮蔽性積層塗膜之底塗層，首先係 遮蔽紫外線之保護層，其次係改善外塗層即包含聚石夕氧系 之光硬化性樹脂組合物之硬化物與基材的密著性之層。另 一方面，若紫外線吸收劑之調配量增加，則雖積層塗膜整 體之紫外線遮蔽性獲得改善，但經由底塗層的包含聚石夕氧 系之光硬化性樹脂組合物之硬化物與基材之密著性會降 低。又，若底塗層過薄，則密著性之改善效果不充分，並 且紫外線遮蔽性亦下降。但是，若底塗層過厚，則包含聚 矽氧系之光硬化性樹脂組合物之硬化物與基材之密著性的 改善效果不充分。 如上所述，底塗層中之紫外線吸收劑之調酉己量以及底塗 層之膜厚，分別與本發明之積層塗膜之紫外線遮蔽性以及 與基材之密著性密切相關，且對本發明之積層塗膜施以相 反之影響。因此，若不使兩者形成—定關係，則無法實現 本案發明之目的。 更具體而s ’構成本發明之紫外線遮蔽性積層塗膜之底 塗層⑴之特徵在於：[㈣於每⑽質量份硬化性樹脂原料 單體之紫外線吸收劑之含量（質量份）]與[底塗層於塗佈時 之膜厚（μπί)]相乘所得之值在1〇〇〜1〇〇〇之範圍内。即使上 146540.doc .26· 201038686 述紫外線吸收劑之含量處於上述上限值或下限值内，且底 塗層於塗佈時之膜厚處於上述上限值或下限值内，但該值 不滿足上述關係時，紫外線遮蔽性及與基材之密著性之任 一者亦會變得不充分。另一方面，即使底塗層中之紫外線 吸收劑之調配量與底塗層之膜厚相乘所得之值在上述範圍 内，但紫外線吸收劑之調配量或底塗層之膜厚不在上述範 圍内時，所得之積層塗膜之紫外線遮蔽性及與基材之密著 性之任一者亦會變得不充分，仍無法實現本發明之目的。 於本發明中，適宜之硬化性樹脂為丙烯酸系樹脂，[相 對於每體100質量份（al)丙烯酸系樹脂原料之（b)紫外線吸 收劑之含量（質量份）]與[底塗層於塗佈時之膜厚（μιη)]相乘 所得之值較好的是在120-600之範圍内，更好的是14〇〜5〇〇 之範圍内’特別好的是16〇〜400之範圍。最適宜的是在 170〜350之範圍内，如此，包含該丙烯酸系底塗層及聚矽 氧系之光硬化物之積層塗膜會成為紫外線遮蔽性及與基材 之密著性優異的基材保護層。 其次’對構成本發明之紫外線遮蔽性積層塗膜的硬化層 進行詳細說明’該硬化層係（Π)形成於上述底塗層表面， 且藉由咼能量線照射使包含下述成分（Α)〜成分⑺）之光硬 化性樹脂組合物光硬化而成者： (Α)多官能性丙稀酸酯或多官能性甲基丙稀酸酯1 〇〇質量份 (Β)具有脂肪族不飽和鍵之有機烧氧基石夕烧1〜1〇〇質量份 (C) 膠體二氧化矽1〜3 00質量份 (D) 光聚合起始劑0.01〜30質量份。 146540.doc -27- 201038686 使上述光硬化性樹脂組合物光硬化而成之硬化層，係硬 度、抗油脂污潰㈣性、油脂污潰拭除性、耐擦傷性、透 明性、斥水性、密著性、平滑性及均勾性優異的耐候性硬 化皮膜，其經由上述之底塗層而牢固地密著於基材上，作 為外塗層而發揮保護基材之作用。 上述光硬化性樹脂組合物本質上係由上述成分⑷〜成分 ⑼所構成，但較好的是進而任意含有下述成分•成分 (F): (E) 胺基改質有機聚矽氧烷〇 (F) 含有醇之有機溶劑1〇〜1〇0〇質量份 又’上述光硬化性樹脂組合物除上述成分⑷〜成分⑻以 外，亦可任意含有下述成分（G): (G) 水〇·5〜20質量份。 以下，對成分（Α)〜成分⑴進行詳細說明。 匕成分（Α)為多官能性丙烯酸®旨或多官能性甲基丙烯酸 醋’其係對組合物賦予紫外線硬化性之成分。該成分（A) ^好的是多官能性丙烯酸酿，可含有氟原子及/或石夕原 降不含較好的是不含氟原子及發原子。該多官能 梳於t酸醋為2官能性以上（例如2官能性〜2〇官能性）之丙 烯酸酯單體或2官能性以上（例如2官能 ^ Ug肊性〜20官能性）之丙 烯酸δ曰低聚物，就硬化性方 wy t , 平乂对的疋使用5官能性以 上（例如5官能性〜丨〇官能性） n金 歸酸日。作為該多官能性 丙Γ具體可列舉：1，6_己二醇二丙歸㈣、α丁 —醇二丙稀酸酿、乙二醇二丙烯酸醋、二乙二酵二丙浠酸 146540.doc -28- 201038686 酯、四乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、新戍二 醇二丙烯酸酯、1，4-丁二醇二甲基丙烯酸酯、聚（丁二醇） 二丙烯酸酯、四乙二醇二甲基丙烯酸酯、1，3_丁二醇二丙 稀酸自曰、二乙一醇《一丙稀酸醋、二異丙二醇二丙稀·酸醋、 聚乙二醇二丙烯酸酯、雙酚A二曱基丙烯酸酯等2官能性丙 缚酸酯單體；三經曱基丙烧三丙烯酸酯、三經甲基丙烧三 曱基丙烯酸酯、季戊四醇單羥基三丙烯酸酯、乙氧基化三 羥曱基丙炫三丙烯酸酯等3官能性丙浠酸酯單體；季戊四 醇四丙烯酸酯、二（三羥甲基丙烷）四丙烯酸酯等4官能性丙 烯酸酯單體；二季戊四醇六丙烯酸酯、二季戊四醇五丙婦 酸（單羥基）酯等5官能性以上之丙烯酸酯單體；雙紛a環氧 一丙稀酸醋、6官能性芳香族胺基曱酸醋丙稀酸醋[商標： Ebecryl 220]、脂肪族胺基甲酸酯二丙烯酸酯[商標：The amount of the component (C) in the undercoat layer coating composition which is cured to form the undercoat layer is 〇丨~2 with respect to the synthetic resin raw material monomer, preferably 100 parts by mass of the acrylic resin raw material monomer. The mass part is preferably 0.5 to 15 parts by mass, more preferably 1 part by mass. When the lower limit is not reached, the ultraviolet shielding property and the weather resistance of the undercoat layer which is produced by the synergistic effect with the component (8) may be insufficient, and if the amount of the component (4) is too large, the use thereof is particularly utilized. When the undercoat layer is hardened by ultraviolet rays, there is a case where the hardening property of the undercoat layer is lowered. The undercoat layer coating composition which is formed by hardening to form the above-mentioned undercoat layer, and preferably has a (4) organoxyloxy group having a waxy aliphatic unsaturated bond. /成: () is associated with (al) C; ^ acid resin raw material monomer cross-linking to enhance the undercoat layer 乂H _a_ by the heating or high-energy line irradiation to coat the above primer layer, and the mouth Serve the hardening ingredients. The component (4) may or may not contain a fluorine atom or a fluorine atom. ' ”~崎八.RiaYSl (ORU kg represents the compound. In the formula, R丨 is not and right '' knows the substituted or unsubstituted aldehyde group of the aliphatic unsaturated bond (for example, the number of carbon atoms is 2G), which can be exemplified by methyl group: 146540.doc • 22· 201038686 Tertyl-t-butyl-isobutyl, octyl, decyl and the like; an aryl group such as phenyl; 3,3,3-trifluoro A fluorine-containing alkyl group such as a methyl group, a perfluorobutylethyl group or a perfluorooctylethyl group. Preferred among these are a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group. R is an alkane. The group is preferably an alkyl group having 1 to 10 carbon atoms, particularly a methyl group, an ethyl group or a propyl group. γ is a valent organic group having an aliphatic unsaturated bond (for example, a carbon number H) 〇), which may be exemplified by a methacryloxy group, a propylene methoxy group, a 3-(methacryloxy) propyl group, an alkyl group containing an acryl fluorenyl group such as a propylene group; Alkenyl group such as hexyl group, hexenyl group or allyl group; styryl group, ethyl ether group, etc. & Mi. As component (d), specifically, 3-methacryloxymethoxymethoxyxyl Burned, 3-(methylpropoxy)propyl three Oxygen zephyr, 3_(methyl propylene oxide) propyl triethoxy zebra, 3 (methyl propyl oxy) propyl methyl monomethoxy decane, 3- (acrylic oxime) Oxy) propyl trimethoxy decane, ethylene trimethoxy decane, vinyl triethoxy decane, methyl vinyl dimethoxy decane, allyl triethoxy decane. In the undercoat layer coating composition of the undercoat layer, the blending amount of the component (d) is a mass of the synthetic resin raw material, preferably 100 parts by mass of the acrylic resin raw material monomer, and is a quality of the dip (9). It is preferably 5 to 50 parts by mass. 'The above-mentioned component (al) to the component (the undercoat layer coating composition of the sentence can be applied by heating to any of the substrates by any method) In the case of the substrate: the surface is formed with a heat-curable undercoat layer. On the other hand, when a light-curable undercoat layer is formed by irradiating a south energy ray such as ultraviolet rays, it is necessary to apply the primer layer to the above-mentioned primer layer. A well-known photopolymerization initiator is formulated in the medium. 146540.doc -23- 201038686 When the undercoat layer of the barrier coating film is a photocurable primer layer, the photopolymerization initiator is preferably (e) a photopolymerization initiator having an absorption wavelength at a wavelength of 360 to 450 nm. The reason for this is that since the undercoat layer of the present invention contains (b) an ultraviolet absorber, when it is used for a photopolymerization initiator having absorption at a wavelength of less than 300 nm, it is present under irradiation of a high-energy line such as ultraviolet rays. In the case of causing hardening and deterioration of the polycarbonate resin, the photopolymerization initiator having an absorption wavelength at a wavelength of 360 to 450 nm is used to cause photodegradation and deterioration of the polycarbonate resin and the like at 300 nm. The ultraviolet ray in the vicinity is absorbed by the above-mentioned component (b), and the ultraviolet ray of 36 〇 to 45 〇 nm which is a wavelength which is less affected by the polycarbonate resin or the like is promoted and hardened, so that it is possible to suppress the ultraviolet ray accompanied by the ultraviolet ray hardening of the undercoat layer. The base material such as an ester resin is decomposed and deteriorated. As a particularly suitable component (e), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-methylmethyl[4_(indolylthio)phenyl]_2imilinyl can be exemplified C-, 1-trans-cyclohexyl phenyl ketone, 2 - benzyl 2 - dimethylamino group (heart phenyl phenyl) butanone. These photopolymerization initiators are commercially available, and the product number (registered trademark Irgacure) supplied by π巴精化股份有限公司 can be suitably used: "Irgacure 9〇7", "Bu fat (3) generation", "Irgacure 369" and so on. The undercoat layer contains a curable resin, preferably the above component (4) and component (8), and further optionally contains the above (4) to (4). Further, the undercoat layer coating composition which is cured to form the undercoat layer contains a curable sapphire raw material monomer, preferably the above component (al) and component (8), and 146540.doc.24-201038686 The above (C) to (e) are arbitrarily contained. In the above primer coating composition, (f) a radical polymerization initiator may be optionally used instead of the photopolymerization initiator for photocuring or used together with a photopolymerization initiator (f a free radical polymerization initiator. The radical polymerization initiator is a component which promotes thermal hardening of the undercoat layer, and a conventionally known compound used in a radical polymerization method is usually used. Specific examples are: 2,2,-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-didecylpentene An azobis compound such as nitrile; an organic peroxide such as benzamidine peroxide, laurel peroxide, tert-butyl peroxybenzoate, and tert-butyl peroxy-2-ethylhexanoate. In the above primer coating composition, a known stanol condensation catalyst can be blended together with the above-mentioned radical polymerization initiator. Further, an organic solvent may be formulated as a diluent for each of the above components. Further, as long as it does not impair the purpose of the present invention, it may be optionally formulated in the above undercoat layer coating composition: an antioxidant; a thickener; a leveling agent, an antifoaming agent, an antiprecipitating agent, a dispersing agent. Surfactants such as antistatic agents and anti-fogging agents; various pigments, dye-specific pigments, fillers such as aluminum paste, talc, glass frit, metal powder; butylated hydroxytoluene (BHT), phenol A self-polymerization inhibitor such as a thiol ester such as thiophene (ρτζ). The undercoat layer constituting the ultraviolet shielding coating film of the present invention must have a film thickness of 1 〇 to 2 Å, preferably a film thickness of 12.5 to 5 〇 0111. It is particularly preferable that the film thickness is in the range of 15 to 3 〇 4111. If the film thickness of the undercoat layer is less than the above lower limit, there is a case where the undercoat layer which is effective for shielding ultraviolet rays is too thin, and the ultraviolet ray of the laminated coating film becomes insufficiently 146540.doc -25 - 201038686 . On the other hand, if the film thickness of the undercoat layer exceeds the above upper limit, the undercoat layer for improving the adhesion to the substrate is too thick, and as a result, the substrate and the polylayer forming the coating other than the present invention cannot be sufficiently improved. The adhesion of the photocurable resin composition of the oxygen system causes adhesion defects such as peeling of the build-up coating medium of the present invention from the substrate. The undercoat layer constituting the ultraviolet shielding coating film of the present invention firstly shields the protective layer of the ultraviolet ray, and secondarily improves the outer coating layer, that is, the cured product and the substrate containing the photocurable resin composition of the polyoxazine system. The layer of adhesion. On the other hand, when the amount of the ultraviolet absorbing agent is increased, the ultraviolet shielding property of the entire laminated coating film is improved, but the cured product and the base of the photocurable resin composition containing the polyoxazine based on the undercoat layer are improved. The tightness of the material will decrease. Further, when the undercoat layer is too thin, the effect of improving the adhesion is insufficient, and the ultraviolet shielding property is also lowered. However, when the undercoat layer is too thick, the effect of improving the adhesion between the cured product of the photocurable resin composition containing the polyoxymethylene-based resin and the substrate is insufficient. As described above, the amount of the ultraviolet absorbing agent in the undercoat layer and the film thickness of the undercoat layer are closely related to the ultraviolet shielding property of the laminated coating film of the present invention and the adhesion to the substrate, respectively. The inventive laminate film exerts the opposite effect. Therefore, the object of the present invention cannot be achieved without forming a relationship between the two. More specifically, the undercoat layer (1) constituting the ultraviolet shielding coating film of the present invention is characterized in that [(4) the content (parts by mass) of the ultraviolet absorber per (10) parts by mass of the curable resin raw material monomer] and [ The film thickness (μπί) of the undercoat layer at the time of coating is multiplied by a value of 1 〇〇 to 1 〇〇〇. Even if the content of the ultraviolet absorber is 146540.doc.26·201038686, the content of the ultraviolet absorber is within the above upper limit or lower limit, and the film thickness of the undercoat layer at the time of coating is within the above upper limit or lower limit, but When the value does not satisfy the above relationship, either of the ultraviolet shielding property and the adhesion to the substrate may be insufficient. On the other hand, even if the amount of the ultraviolet absorber in the undercoat layer multiplied by the film thickness of the undercoat layer is within the above range, the amount of the ultraviolet absorber or the film thickness of the undercoat layer is not in the above range. In the meantime, the ultraviolet shielding property of the obtained laminated coating film and the adhesion to the substrate may be insufficient, and the object of the present invention may not be achieved. In the present invention, a suitable curable resin is an acrylic resin, [(b) the content of the ultraviolet absorber (parts by mass) with respect to 100 parts by mass of the (al) acrylic resin raw material] and [the undercoat layer The value obtained by multiplying the film thickness (μιη) at the time of coating is preferably in the range of 120-600, more preferably in the range of 14〇~5〇〇, particularly preferably 16〇~400. range. It is most preferable that it is in the range of 170 to 350, and the laminated coating film containing the acrylic undercoat layer and the polyfluorinated photocured material is excellent in ultraviolet shielding properties and adhesion to the substrate. Protective layer. Next, the hardened layer constituting the ultraviolet shielding coating film of the present invention will be described in detail. The hardened layer is formed on the surface of the undercoat layer and is irradiated by krypton energy rays to contain the following components (Α). The photocurable resin composition of the component (7) is photocured by: (Α) polyfunctional acrylate or polyfunctional methyl acrylate: 1 part by mass (Β) having aliphatic unsaturation The organic alkoxylate of the bond is 1-2 parts by mass (C) colloidal cerium oxide 1 to 30,000 parts by mass (D) the photopolymerization initiator is 0.01 to 30 parts by mass. 146540.doc -27- 201038686 The hardened layer obtained by photohardening the photocurable resin composition is hardness, anti-grease staining, grease staining, scratch resistance, transparency, water repellency, The weather-resistant film which is excellent in adhesion, smoothness, and uniformity is firmly adhered to the substrate via the undercoat layer described above, and functions as a protective layer for the undercoat layer. The photocurable resin composition is basically composed of the above components (4) to (9), but preferably further contains the following components: (F): (E) Amine-modified organic polyoxaxane (F) The organic solvent containing an alcohol is 1 〇1 to 1 〇0 parts by mass. The above photocurable resin composition may optionally contain the following components (G) in addition to the above components (4) to (8): (G) Water 〇·5~20 parts by mass. Hereinafter, the component (Α) to the component (1) will be described in detail. The bismuth component (Α) is a polyfunctional acrylic acid- or polyfunctional methacrylic acid vinegar which is a component which imparts ultraviolet curability to the composition. The component (A) is preferably a polyfunctional acrylic acid, and may contain a fluorine atom and/or a fluorene atom. The fluorine atom and the atom are not contained. The polyfunctional comb is an acrylate monomer having a bifunctionality or more (for example, a bifunctional ～2 〇 functionality) or a bifunctional or higher (for example, a bifunctional urethane -20 functional) δ. For the oligomer, the sputum of the sputum is yt, and the yttrium of the yttrium is more than a 5-functional (for example, a 5-functional oxime-functional) n-gold-based acid day. Specific examples of the polyfunctional fluorene include 1,6-hexanediol dipropylene (IV), α-butanol dipropylene acid brewing, ethylene glycol diacrylate vinegar, and diethylene glycol dipropionate 146540. Doc -28- 201038686 Ester, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neodecanediol diacrylate, 1,4-butanediol dimethacrylate, poly(butylene glycol) diacrylate Ester, tetraethylene glycol dimethacrylate, 1,3-butanediol dipropylene acid self-purifying, diethylene glycol "acrylic acid vinegar, diisopropyl glycol dipropylene acid vinegar, polyethylene glycol Bifunctional acrylate monomer such as diacrylate or bisphenol A dimercapto acrylate; tri-propyl mercapto triacrylate, trimethyl propyl tridecyl acrylate, pentaerythritol monohydroxy triacrylate a trifunctional phthalate monomer such as an ester or an ethoxylated trishydroxypropyl propyl triacrylate; a tetrafunctional acrylate monomer such as pentaerythritol tetraacrylate or bis(trimethylolpropane) tetraacrylate Bifunctional pentaerythritol hexaacrylate, dipentaerythritol penta-butanoic acid (monohydroxy) ester, etc. Ethyl ester monomer; double a-epoxy-acrylic acid vinegar, 6-functional aromatic amine phthalic acid acetoacetate acrylic acid vine [trademark: Ebecryl 220], aliphatic urethane diacrylate [trademark :

Ebecryl 230]、4官能性聚酯丙烯酸醋[商標：Ebecryi 80]之 丙稀酸Sb低聚物。該等多g能性丙稀酸醋可單獨使用1 種’亦可將2種以上組合使用。其中，較好的是含有$官能 性以上之丙烯酸酯，其含量較好的是成分（A)之3〇重量。/〇以 上（例如30重量％〜100重量％)，更好的是5〇重量。/。以上，更 好的是80重量％以上。 成分（B)為具有脂肪族不飽和鍵之有機烧氧基石夕烧，可 例示與上述成分（d)相同之成分。於上述光硬化性樹脂組合 物中，成分（B)係對（C)膠體二氧化矽進行表面處理而提高 其與成分（A)之親和性’從而對該組合物賦予良好之保存 穩定性。又，就硬化時與成分（A)交聯而提昇硬化物之交 146540.doc -29- 201038686 聯度之方面而士，士 物賦予紫外線i化ΓΓΓ係對上述光硬化性樹脂組合 分㈧_質量份而為。成分(B)之調配量相對於成 份。 、置伤而為1〜丨〇〇質量份，較好的是5〜50質量 成刀(C)為膠體二氧化矽，其係將使上述光硬化性樹脂 ::ΓΓ化而成之皮臈的高硬度化而提昇耐擦傷性之成 ^分（C)之調配量相對於成分㈧⑽質量份而為卜綱 权好的疋5〜200質量份。只要無損本發明之目 亦可利用水解性石夕基切烧醇基對成分（C)膠體二 乳石之-氧化石夕表面進行修飾。又，由於 可獲得二氧化石夕表面之處理成刀（B) 飾之膠體二童“处理效果故而具有亦可使用未修 矽的優點。該未修飾之膠體二氧化矽可以 酉文性或驗性之公私躺> 態之膠體二氧態而獲得。於本發明中，任一形 句可使用，但使用鹼性膠體二氧化矽 畔’為了防止組合物夕，戌娜μ 分散系中沈殿，較二?:1並且防止二氧切自膠體 調節為酸性。 的…添加有機酸等方法將分散體 士成:(C)之分散介質並無特別限定，就乾燥性等方面而 3 ，交好的是滞點相對較低（例如，於1大氣壓下為 30〜扇。C ’尤其是4〇〜12〇。〇之溶劑，即通常 容 劑。作為該分散介質，具體可例示m乙醇: :醇、正丁醇、2-甲基丙醇、4_膝4_甲基·2_戊嗣、乙： -丙一醇早甲喊（PGM)、聚乙二醇單甲鍵（PG (例如碳原子數為丨…基赛路蘇、乙基赛路蘇、丁基 146540.doc •30- 201038686 賽路穌等賽路穌類（例如碳原 數為1〜10);二甲基乙醯 胺、曱本、二甲苯、乙酸曱萨 …曰、乙酸乙酯、乙酸丁酯、丙 酮等。特別好的是使用水、醇類 叫頸’特別好的是使用丙二醇 單甲醚（腦)作為分散介質1了，將膠t氧化#分 散其之分散介質的一體物稱為膠體二氧化梦分散液。對於 膠體二氧切之平均粒徑，就其分散性方面而言適當的是 200麵以下，較好的是平均粒經為1〜⑽⑽，特別好的是 Ο Ο 1〜50 nm。又，製成膠體二氧化石夕分散液使用之情形時， 膠體二氧切之含量、即濃度為任意，就操作之容易度方 面而言，較好的是1 〇~70重量〇/0。 成分（D)為光聚合起始劑，其係藉由紫外線等高能量線 之照射而促進本發明組合物之硬化的成分。本發明之紫外 線遮蔽性積層塗膜具有了述優，點：當藉由”卜線照射來使 上述光硬化性樹脂組合物硬化時，促使聚碳酸酯樹脂等發 生光分解、劣化的300 nm附近之紫外線會被位於該硬化層 之下的底塗層所吸收，從而可抑制包含聚碳酸酯樹脂等之 基材之光分解、劣化。 更具體而言’成分（D)之光聚合起始劑特別好的是選自 下述化合物之光聚合起始劑：2,4,6-三曱基苯曱醯基二苯 基氧化膦、2-甲基甲硫基）苯基]_2-味啉基丙酮、卜 羥基環己基苯基酮、2-苄基-2-二曱基胺基_ι_(4_味啉苯 基）-丁酮 '雙-2,6-二甲氧基苯曱醯基_2,4,4_三甲基戊基氧 化膦、二苯曱酮、9-氧硫p山哇、2-氣-9-氧硫p山p星' 2,4-二 乙基-9-氧硫p山π星、異丙基-9-氧硫tr山p星、1-氣_4_丙氧基_9_ 146540.doc -31 · 201038686 氧硫咄P星，該等除可單獨使用一種以外，亦可併用兩種以 上。 進而’為避免使用會促使聚碳酸酯樹脂等發生光分解、 劣化之300 nm附近之紫外線的高能量線硬化，可適宜使用 (D1)於300-450 nm具有吸收波長之光聚合起始劑來作為成 分（D)。最好的是使用（D2)於360〜450 nm具有吸收波長之 光聚合起始劑。作為該等光聚合起始劑，可例示與上述成 分（e)相同之成分。 成分（D)之調配量相對於成分（Α) ι〇〇質量份而為〇 〇1〜3〇 質量份，就硬化皮膜之耐候性之改善性及組合物整體之硬 化特性的觀點而言，較好的是5〜2〇質量份。其原因在於， 若未達上述下限’則存在組合物之紫外線硬化性不充分之 情況；若超過上述上限，則存在所得硬化皮膜之物理強度 下降之情況。 上述光硬化性樹脂組合物本質上包含上述成分（A)〜成分 (D)，但較好的是進而任意地含有（E)胺基改質有機聚石夕氧 烷。成分（E)係對構成外塗層之硬化皮膜賦予斥水性或潤 滑性之成分’可列舉在分子鏈末端或側鏈之一部分具有該 胺基官能性有機基的有機聚矽氧烷液體。 作為成分（E)之胺基官能性有機基，可例示：2_胺基乙 基、3-胺基丙基、3_(2_胺基乙基）胺基丙基、6胺基己基。 作為胺基官能性有機基以外之鍵結於石夕原子上之基團，可 列舉：曱基、乙基、丙基等烷基；苯基等芳基；甲氧基、 乙氧基、丙氧基等烷氧基；羥基。該等中，較好的是甲 146540.doc -32- 201038686 基。有機聚矽氧烷之分子結構較好的是直鏈狀或一部分具 有分枝之直鏈狀。X，其梦氧烧聚合度較好的是2〜1000之 範圍，更好的是2〜5〇〇之範圍’特別好的是2〜3〇〇之範圍。 作為此種成分（E)，可較好地例示如下述式之含有一級 胺基的有機聚矽氧烷。下述平均分子式中，Me為f基。 [化 10] NH2CsH6-Me9Si〇 (MegSi〇) 10S i M e2-C3H6N Hs 〇Ebecryl 230], a tetrafunctional polyester acrylate vinegar [trademark: Ebecryi 80], an acrylic Sb oligomer. These multi-g-energy acrylic vinegars may be used singly or in combination of two or more. Among them, an acrylate having a functionality of more than $ is preferred, and the content thereof is preferably a weight of the component (A) of 3 Å. Above / (for example, 30% by weight to 100% by weight), more preferably 5 〇 by weight. /. More preferably, it is 80% by weight or more. The component (B) is an organic alkoxylate having an aliphatic unsaturated bond, and the same components as the above component (d) can be exemplified. In the photocurable resin composition, the component (B) is surface-treated with (C) colloidal ceria to improve its affinity with the component (A), thereby imparting good storage stability to the composition. In addition, when it is hardened, it is crosslinked with the component (A) to enhance the crosslinking of the cured product. 146540.doc -29- 201038686. In terms of the degree of association, the material is given to the ultraviolet light i-chemical system to the above photocurable resin combination (eight)_ The quality is divided. The blending amount of the component (B) is relative to the component. And the wound is 1 to 丨〇〇 part by mass, preferably 5 to 50 mass of the knives (C) is a colloidal cerium oxide, which is obtained by smashing the above-mentioned photocurable resin: The amount of the high-hardness and the improvement of the scratch resistance is 5 to 200 parts by mass based on the component (8) (10) by mass. The component (C) colloidal titanate-oxidized stone surface may be modified by a hydrolyzable schizophylping alcohol base as long as the object of the present invention is not impaired. Moreover, since the treatment of the surface of the oxidized stone of the oxidized stone can be obtained, the colloidal two-child of the knives (B) can be used for the treatment effect, and the unmodified colloidal cerium oxide can be used for examination or examination. In the present invention, any form can be used, but an alkaline colloidal cerium oxide is used to prevent the composition of the eve, and the 戌Na μ dispersion system 2:1 and prevent the dioxate from being adjusted to be acidic. The method of adding an organic acid or the like to disperse the dispersion: (C) is not particularly limited in terms of drying medium, etc. 3 Preferably, the stagnation point is relatively low (for example, 30 to fan at 1 atm. C' is especially 4 〇 to 12 〇. The solvent of hydrazine, that is, a usual solvent. As the dispersion medium, specifically, m ethanol is exemplified: : alcohol, n-butanol, 2-methylpropanol, 4_ knee 4_methyl·2_pentanyl, B:-propanol early nail shouting (PGM), polyethylene glycol monomethyl bond (PG ( For example, the number of carbon atoms is 丨... 基赛路苏, ethyl 赛路苏, butyl 146540.doc • 30- 201038686 For example, the carbon number is 1 to 10); dimethylacetamide, transcript, xylene, acetic acid, cesium, ethyl acetate, butyl acetate, acetone, etc. Particularly preferred is the use of water, alcohol The neck is particularly good to use propylene glycol monomethyl ether (brain) as the dispersion medium, and the integral of the dispersion medium in which the glue t is oxidized and dispersed is called a colloidal dioxide oxidation dispersion. The average particle for colloidal dioxygen cutting The diameter is suitably 200 or less in terms of dispersibility, and it is preferred that the average particle diameter is 1 to 10 (10), particularly preferably Ο 1 to 50 nm. Further, it is made into a colloidal silica dispersion. In the case of use, the content of the colloidal dioxotomy, that is, the concentration is arbitrary, and in terms of ease of handling, it is preferably from 1 70 to 70% 〇 / 0. The component (D) is a photopolymerization initiator. It is a component which accelerates the hardening of the composition of the present invention by irradiation with a high-energy line such as ultraviolet rays. The ultraviolet shielding multilayer coating film of the present invention is excellent in that the light hardening is performed by "wire irradiation" When the resin composition is hardened, the polycarbonate resin or the like is caused to occur. The ultraviolet rays in the vicinity of 300 nm which are decomposed and deteriorated are absorbed by the undercoat layer located under the hardened layer, thereby suppressing photodecomposition and deterioration of the substrate containing the polycarbonate resin or the like. More specifically, the composition (D) The photopolymerization initiator is particularly preferably a photopolymerization initiator selected from the group consisting of 2,4,6-trimercaptophenylphosphonium diphenylphosphine oxide, 2-methylmethylthio group) Phenyl]_2-morpholinylacetone, hydroxycyclohexyl phenyl ketone, 2-benzyl-2-didecylamino group_ι_(4_morpholine phenyl)-butanone 'double-2,6- Dimethoxybenzoinyl 2,4,4-trimethylpentylphosphine oxide, diphenyl fluorenone, 9-oxo sulphur p, wow, 2-gas-9-oxysulfur p-p-p'2 , 4-diethyl-9-oxo-sulfur p-shan π-star, isopropyl-9-oxo-sulfur-tr-p-star, 1-qi___propoxy-9_ 146540.doc -31 · 201038686 P star, these may be used alone or in combination of two or more. Further, in order to avoid high-energy ray hardening of ultraviolet rays near 300 nm which causes photodecomposition and deterioration of a polycarbonate resin or the like, it is possible to suitably use (D1) a photopolymerization initiator having an absorption wavelength at 300 to 450 nm. As component (D). It is preferable to use (D2) a photopolymerization initiator having an absorption wavelength at 360 to 450 nm. As such a photopolymerization initiator, the same components as the above component (e) can be exemplified. The amount of the component (D) is 〇〇1 to 3 parts by mass based on the mass of the component (Α) ι, and the viewpoint of the improvement of the weather resistance of the cured film and the hardening property of the entire composition is It is preferably 5 to 2 parts by mass. The reason for this is that if the lower limit is not reached, the ultraviolet curability of the composition may be insufficient, and if it exceeds the above upper limit, the physical strength of the obtained cured film may be lowered. The photocurable resin composition essentially contains the above components (A) to (D), but preferably further contains (E) an amine-modified organic polyoxosiloxane. The component (E) is a component which imparts water repellency or lubricity to the hardened film constituting the overcoat layer. The organic polyoxyalkylene liquid having the amino group-functional organic group at one end of the molecular chain or in one side chain is exemplified. The amine functional organic group as the component (E) may, for example, be 2-aminoethyl, 3-aminopropyl, 3-(2-aminoethyl)aminopropyl or 6-aminohexyl. Examples of the group bonded to the austenite atom other than the amino group-functional organic group include an alkyl group such as a mercapto group, an ethyl group, and a propyl group; an aryl group such as a phenyl group; a methoxy group, an ethoxy group, and a propyl group. Alkoxy group such as oxy; hydroxy group. Among these, a preferred one is 146540.doc -32- 201038686. The molecular structure of the organic polyoxyalkylene is preferably linear or partially branched and linear. X, the degree of polymerization of the dream oxygen burning is preferably in the range of 2 to 1000, more preferably in the range of 2 to 5 Å, and particularly preferably in the range of 2 to 3 Å. As such a component (E), an organopolyoxane containing a primary amino group of the following formula can be preferably exemplified. In the average molecular formula described below, Me is an f group. NH2CsH6-Me9Si〇 (MegSi〇) 10S i M e2-C3H6N Hs 〇

Me Μ θ Μ eMe Μ θ Μ e

I I I NH2C2H4NHC3HrS iO (S i 〇) eS i-C3HeN H C2H4N H,I I I NH2C2H4NHC3HrS iO (S i 〇) eS i-C3HeN H C2H4N H,

IIIIII

Me Μ θ Μ e βMe Μ θ Μ e β

MesS i O (MegS ! 〇) ^ (MeS i O) eS i MMesS i O (MegS ! 〇) ^ (MeS i O) eS i M

Q MegS I O (MeaS i 〇) M (M e S i 〇) l0S i M C3H«NHC2HdNH， 於上述光硬化性樹脂組合物中，成分（E)之調配量相對 於成分（A) 100質量份而為〇2〜2〇質量份，較好的是卜1〇質 ΐ份。又，成分（E)之調配量更好的是下述量，即成分 中之合計胺基之莫耳量少於成分（A)中之丙烯酸酯官能基 或甲基丙烯酸酯官能基之莫耳量的調配量。進而，就可獲 得良好之性能方面而言’成分（幻之重量較好的是成分 146540.doc •33· 201038686 之重量之1/5以下。 :述光硬化性樹脂組合物中可進而調配溶劑，例如有楨 二 ’、疋醇來作為稀釋劑，特別好的是使用（F)含有 醇之有機溶劑。 成T(F)可單獨為醇，亦可為醇與其他溶劑之混合物。 又醇、其他溶劑均可併用2種以上。於上述光硬化性樹 脂組合物中，忐八β 4兀炅化！·生樹 而較好的”。〜J 配量相對於成分㈧1〇0質量份 疋 〇〇質量份之範圍，更好的是10〜500質量 份之範圍。 里 矿’、體而吕’成分(F)之醇可列舉：甲醇、乙醇、異丙 醇、丁醇、異丁醇、乙二醇、二乙二醇、三乙乙一 甲賦=—乙二醇翠甲謎、三乙二醇單甲鍵、丙二醇單 〜乙二料f _GME)等醇類。χ，作為醇以外 等=容劑’可列舉：丙嗣、甲基乙基嗣、甲基異丁基嗣 列如碳原子數為㈣）；曱苯、二甲苯等芳香族系煙 f子數為2〜叫；己烧、钱、钱等脂肪族系煙 (:::炭原子數為5〜20);氯仿、二氣甲烧、三氣乙稀、四 gt衩等有機氯系溶劑（例如碳原子數為1〜20);乙酸乙 龜、乙酸丁醋、乙酸異丁酷等_類（例如碳原子^ ^醇之含有率較好的是在全部溶劑合計量之1〇〜9〇重 /〇的範圍内’更好的是30〜70重量％。 進而，上述光硬化性樹脂組合物中可調配水作為成分 ^ 1成分（G)係用於成分（B)之水解的任意成分， 里較好的是相對於成分⑻⑽質量份而為卜㈣量份之範 14654〇,d〇c •34· 201038686 圍，更好的是5〜30質量份之範圍.再者，成分（G)通常與 成分（C)膠體二氧化石夕表面之石夕烧醇基反應，進而利用該 成分（G)而進行水解，因此該成分（G)之調配量亦可少於能 夠將成分（B)完全水解之量。 於本發明之紫外線遮蔽性積層塗膜中，包含上述光硬化 性樹脂組合物之光硬化層為外塗層，其硬度、抗油脂污潰 附著性、油脂污潰拭除性、耐擦傷性優異。另一方面，上 述底塗層具有改善紫外線遮蔽性及上述光硬化層之密著性 的功能。但是，上述光硬化性樹脂組合物中可進而調配 (H)紫外線吸收劑0.01〜20質量份以及（j)受阻胺系光穩定劑 0.1〜15質量份’藉此可進一步改善紫外線遮蔽性積層塗膜 之功能。尤其是亦可於外塗層中調配與上述底塗層中所調 配者種類不同之紫外線吸收劑或受阻胺系光穩定劑，藉此 可進一步改善紫外線遮蔽性。 可調配於上述光硬化性樹脂組合物中之（H)紫外線吸收 劑或（J)受阻胺系光穩定劑，可例示與上述成分（b)或成分 (c)相同之成分。 於使用包含含有上述成分（H)及成分（J)之光硬化性樹脂 組合物的光硬化型硬化皮膜之情形時，特別好的是併用 (H1)於220〜400 nm具有吸收波長之紫外線吸收劑0.01〜20 質量份以及（D1)於3 00〜450 nm具有吸收波長之光聚合起始 劑0_01~30質量份。其原因在於，與上述成分（H1)所吸收的 220〜400 nm之短波長之紫外線相比，波長稍長之300〜450 nm之紫外線更能促進本發明組合物之硬化，且該成分（D1) 146540.doc -35- 201038686 具有以下優點：幾乎不會受到由成分（H1)之紫外線吸收劑 所引起之硬化阻礙的影響，可藉由紫外線迅速且容易地使 硬化後會形成外塗層之光硬化性樹脂組合物硬化。 只要在無損本發明之目的之範圍内，則亦可於上述光硬 化性樹脂組合物中添加調配上述以外之成分。例如可列 舉：四甲氧基石夕燒、四乙氧基石夕燒、四異丙氧基石夕院等四 烧氧基钱；甲基三甲氧基㈣、甲基三乙氧基錢、甲 基三異丙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽 烷、乙基三異丙氧基矽烷等烷基烷氧基矽烷。 進而，可在無損本發明之目的之範圍内，視需要於上述 光硬化性樹脂組合物中添加調配如下成分：抗氧化劑；增 稠劑；調平劑、消泡劑、抗沈澱劑、分散齊卜抗靜電劑、 ，霧劑等界面活性劑；各種顏料、染料等著色劑；紹粉 漿、滑石、玻璃料、金屬粉等填充劑；丁基化羥基心 (BHT)、㈣啊ρτζ)等丙稀酸酯類之自聚抑制劑等。就該 組合物之保存敎性之觀點而言，特別好的是㈣於成^ (Α)卿量份，調配G._〜㈣丨質量份之㈣时叫 等丙烯酸酯類之自聚抑制劑。 上述光硬化性樹脂組合物由於各成分之相容性優異，故 而外觀均勾，塗佈於上述底塗層上之情形時，可妒成 =度優異之塗膜…上述光硬化性樹脂組‘物具有 優點：以公知之塗佈方法進行塗佈之情形時，可以所 分離^=進行塗佈’並且不會發生滴液或塗佈後各成分 146540.doc •36- 201038686 本發明之紫外線遮蔽性積層塗膜可藉由如下方式獲得： 藉由於⑴底塗層上塗佈（II)光硬化性樹脂組合物，利用高 能量線使之光硬化而獲得硬化層，利用該硬化層依序被覆 該基材。 • 由本發明之紫外線遮蔽性積層塗膜被覆之基材並無特別 限疋最好的疋包含容易藉由波長300 nm附近之紫外線而 發生光分解之聚碳酸酯樹脂等熱塑性樹脂的基材。基材之 0 材貝例如可列舉：聚乙烯、聚丙烯等聚烯烴系樹脂，聚對 苯二甲酸乙二酯、聚間苯二甲酸乙二酯、聚萘二曱酸乙二 酯、聚對苯二甲酸丁二酯或該等之共聚物等聚酯系樹脂， 聚甲搭等聚醯胺系樹脂’聚苯乙埽、聚（甲基）丙烯酸醋、 聚丙烯腈、聚乙酸乙烯酯、聚碳酸酯、賽璐凡、聚醯亞 胺聚趟醯亞胺、聚苯颯、聚硬、聚趟酮、離子聚合物樹 脂、氟碳樹脂等熱塑性樹脂，三聚氰胺樹脂、聚胺基甲酸 面曰樹知環氧樹脂、酚樹脂、不飽和聚酯樹脂、醇酸樹 〇 脂、脲樹脂、聚矽氧樹脂等熱硬化性樹脂等之各種塑膠； 玻璃，P旬瓷；鋁、辞、鐵、鎳、鈷、銅、錫、鈦、金、 . 銀、麵或包含該等之合金等金屬混凝土、木材、纖維 布纖維、不織布、皮革、紙及石材（包括大理石）。 - 本發明之紫外線遮蔽性積層塗膜係波長30〇 nmm近之紫 外線吸收效果、硬度、抗油脂污清附著性、油脂污潰拭除 性、耐擦傷性、透明性、斥水性、密著性、平滑性及= 性優異的耐候性塗膜。因此，本發明之紫外線遮蔽性積層 塗膜適。於破覆在如下基材之表面的用途：尤其是在室外 146540.doc -37· 201038686 等長時間曝露於太陽光下之環境中使用，且要求美觀及強 度之基材（更具體而言，代替汽車用窗玻璃之塑膠構件、 或代替建材用窗玻璃之塑膠構件等）。特別好的是被覆聚 碳酸醋樹脂製之汽車用外部裝飾構件、聚碳酸酯樹脂製之 建築用外部裝飾構件之表面。 作為由本發明之紫外線遮蔽性積層塗膜所被覆之基材的 材質，㈣的是熱塑性塑膠。特別適宜的是利用本發明之 紫外線遮蔽性積層塗膜來被覆聚碳酸醋樹脂，其原因在 於.透明性優異’且可顯著改善耐候性及物理強度。基材 之形狀並無特別限定，可列舉：板狀、膜狀、薄片狀、瓶 狀、固體狀。其中，較好的是熱塑性塑膠板或熱塑性塑膠 膜。基材之厚度並無特別限定，於為膜狀或薄片狀之情形 時，基材之厚度通常在5〜1〇〇 μηι之範圍内；於為具有一定 厚度之板狀之情形時，基材之厚度在〇 〇〇1 m〜〇1 m之範圍 内。 尤其是，可容易地獲得利用本發明之紫外線遮蔽性積層 塗膜被覆厚度在0.001 m〜0.1 m之範圍内的板狀聚碳酸酯樹 脂之兩面或單面而成之附著紫外線遮蔽性積層塗膜之聚碳 酸S旨樹脂基材。 又’本發明之紫外線遮蔽性積層塗膜實質上為透明，使 作為基材之板狀聚碳酸酯樹脂對波長420 nm以上之可見光 之光透射率為80%以上，且使所獲得之附著紫外線遮蔽性 積層塗膜之聚碳酸酯樹脂基材對波長420 nm以上之可見光 之光透射率為75%以上，從而可獲得附著紫外線遮蔽性積 146540.doc -38- 201038686 層塗膜之聚碳酸酯樹脂基材。該等聚碳酸酯樹脂基材可特 別適宜地用作建築材料或汽車用之車窗用材料。 本發明之紫外線遮蔽性積層塗膜可藉由如下方式來製 - 造：以塗佈時之膜厚為10〜200 μηι，且[相對於每1〇〇質量 份硬化性樹脂原料單體之（b)紫外線吸收劑之含量（質量 份）]x[底塗層於塗佈時之膜厚（μιη)]在1〇〇〜1〇〇〇之範圍内的 里’將上述底塗層塗佈組合物塗佈於基材表面並使之硬 化’藉此利用底塗層被覆基材表面，然後於該底塗層上塗 〇 佈上述光硬化性樹脂組合物且利用高能量線將其光硬化， 藉此依序對該基材進行被覆。 底塗層塗佈組合物之塗佈方法並無特別限定，例如可利 用流動塗佈、浸潰被覆、旋轉塗佈（spin coating)、吹附塗 佈、簾幕式塗佈、凹板印刷塗佈、繞線棒（Meyer bar)塗 佈、浸潰塗佈等公知之方法，於各種基材表面形成底塗 層又，亦可對塗佈前之基材表面預先進行利用石夕院偶合 Q 劑或其水解物等之底塗處理、以及電暈處理等表面活化處 理。其中，於製造本發明之紫外線遮蔽性積層塗膜時，必 需以下述量來塗佈底塗層塗佈組合物且使其硬化，即，底 塗層塗佈組合物之塗佈時之膜厚為1〇〜2〇〇 μιη，且[相對於 - 每100質量份硬化性樹脂原料單體之（b)紫外線吸收劑之含 量（質量份）]x[底塗層於塗佈時之膜厚（μπι)]在1〇〇〜1〇〇〇之 範圍内的量。 為了使塗佈於基材上之底塗層塗佈組合物硬化，可選擇 加熱或照射紫外線等高能量線之方法。若為上述熱硬化型 146540.doc -39- 201038686 之底塗層’則可選擇烘箱等公知之加熱裝置；若為光硬化 型之底塗層，則可藉由下述之高能量線照射而於極短時間 内實現硬化。 製造本發明之紫外線遮蔽性積層塗膜時，需要於基材上 預先將底㈣塗佈組合物光硬化或熱硬化，藉此以底塗層 被覆基材，、原因在於，若塗佈底塗層塗佈組合物後不 進行光硬化而於未硬化之底塗劑㈣層上塗佈上述光硬化 性樹脂組合物，則光硬化所必需之紫外線會被外塗層即將 光硬化性樹脂組合物硬化而成之硬化層所吸收，而存在底 塗層之硬化不充分的情況。 作為將上述光硬化性樹脂組合物塗佈於底塗層上之方 法，可例示與底塗層塗佈組合物之塗佈方法相同之方法。 對於該光硬化㈣触合物之㈣量，於要求耐擦傷性之 情形時，較好的是層之厚度為〇 5〜25㈣之量，更好的是 為1〜20 _之量。塗佈後將薄膜乾燥後，可藉由下述之高 能量線照射而於極短時間内實現硬化。 構成本發明之紫外線逆益a* •'深遴蔽性積層塗膜的硬化層係藉由下 述方式形成：預先以底塗層被覆基材後於該底塗層上塗 佈上述光硬化性樹脂組合物且加以乾燥，然後照射高能量 線，藉此依序被覆基材。作為高能量線，可例示紫外線、 電子束”射線。本發明組合物由於紫外線硬化特性極為 優異’故而最好的是利用紫外線進行硬化。其原因在於， 於使用紫外線之情形時，可於極短時間内形成硬化薄膜 層。紫外線照射量至少鼻2 m Τ / 2 V為2 mj/cm ’較好的是100〜3000 146540.doc -40· 201038686 於常溫下乾 nU/cm。再者，上述光硬化性樹脂組合物係 趣’欲使其更快乾燥之情形時，可進行加熱。 以下，揭示實施例及比較例來具體說明本發明，伸本發 :並不限定於下述之實施例。再者，下述之例中，份均為 質量份。黏度係於25。(：下測定之值。實施例及比較例之各 特性係依據以下之方法進行測定。Q MegS IO (MeaS i 〇) M (M e S i 〇) l0S i M C3H «NHC2HdNH, the amount of the component (E) in the photocurable resin composition is 100 parts by mass based on the component (A). It is preferably 2 to 2 parts by mass, and preferably 1 to 2 parts by mass. Further, the blending amount of the component (E) is more preferably an amount in which the total amount of the amine group in the component is less than the molar amount of the acrylate functional group or the methacrylate functional group in the component (A). The amount of the amount. Further, in terms of good performance, the component (the weight of the phantom is preferably 1/5 or less of the weight of the component 146540.doc • 33· 201038686. : The solvent can be further formulated in the photocurable resin composition. For example, there are bismuth bisphenol and decyl alcohol as a diluent, and it is particularly preferable to use (F) an organic solvent containing an alcohol. The T (F) may be an alcohol alone or a mixture of an alcohol and another solvent. Two or more kinds of other solvents may be used in combination. In the above-mentioned photocurable resin composition, it is preferable to use 生8β 4 ! · 生 生 生 生 生 〜 〜 〜 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配 配The range of the mass part is preferably in the range of 10 to 500 parts by mass. The alcohol of the minerals of the mine, the body and the body of the body (F) can be exemplified by methanol, ethanol, isopropanol, butanol and isobutanol. Alcohols such as ethylene glycol, diethylene glycol, triethylene ethyl ketone = ethylene glycol triad, triethylene glycol monomethyl bond, propylene glycol mono-ethylene glycol f _GME). Etc. = container ' can be enumerated: propionate, methyl ethyl hydrazine, methyl isobutyl fluorene column such as carbon number (four)); The number of aromatic smokes such as benzene and xylene is 2~called; aliphatic, smoke, money, money and other aliphatic smoke (::: carbon number is 5~20); chloroform, two gas, three gas An organic chlorine-based solvent such as ethylene or tetraglycol (for example, a carbon number of 1 to 20); an acetic acid tortoise, a butyl acetate, an isobutyl sulfate, etc. (for example, a carbon atom; It is more preferably 30 to 70% by weight in the range of 1 〇 to 9 〇 weight/〇 of all the total amount of the solvent. Further, the photocurable resin composition can be formulated with water as the component (1). It is preferably any component which is used for the hydrolysis of the component (B), and is preferably a component of (4) parts by weight of the component (4) (10), a sample of 14654〇, d〇c • 34· 201038686, more preferably 5~ The range of 30 parts by mass. Further, the component (G) is usually reacted with the component (C) colloidal silica dioxide on the surface of the cerium oxide, and further hydrolyzed by the component (G), so the component (G) The amount of the coating may be less than the amount capable of completely hydrolyzing the component (B). The ultraviolet shielding layer coating film of the present invention comprises the above photohardenable tree. The photohardenable layer of the composition is an outer coating layer, and is excellent in hardness, grease-resistant adhesion, grease stain-off property, and scratch resistance. On the other hand, the undercoat layer has improved ultraviolet shielding properties and the above-mentioned photohardening. Further, the photocurable resin composition may further contain (H) an ultraviolet absorber of 0.01 to 20 parts by mass and (j) a hindered amine light stabilizer of 0.1 to 15 parts by mass. The function of the ultraviolet shielding layer coating film can be further improved, and in particular, an ultraviolet absorber or a hindered amine light stabilizer different from the type of the primer in the above primer layer can be blended in the top coat layer, thereby further improving UV shielding. The (H) ultraviolet ray absorbing agent or the (J) hindered amine light stabilizer which can be blended in the above photocurable resin composition can be exemplified by the same components as the above component (b) or component (c). In the case of using a photocurable hardening film containing the photocurable resin composition containing the above component (H) and component (J), it is particularly preferable to use (H1) ultraviolet absorption having an absorption wavelength at 220 to 400 nm. 0.01 to 20 parts by mass of the agent and (D1) 0 to 01 to 30 parts by mass of the photopolymerization initiator having an absorption wavelength at 300 to 450 nm. The reason for this is that, compared with the short-wavelength ultraviolet light of 220 to 400 nm absorbed by the above component (H1), the ultraviolet light having a wavelength slightly longer of 300 to 450 nm can promote the hardening of the composition of the present invention, and the component (D1) 146540.doc -35- 201038686 has the following advantages: it is hardly affected by the hardening inhibition caused by the ultraviolet absorber of the component (H1), and the outer coating layer can be formed quickly and easily by ultraviolet rays. The photocurable resin composition is cured. The components other than the above may be added to the above-mentioned photohardenable resin composition as long as the object of the present invention is not impaired. For example, tetramethoxy oxime, tetraethoxy zeshi, tetraisopropoxy zexiyuan, etc., four alkoxy groups; methyltrimethoxy (tetra), methyl triethoxy money, methyl three An alkyl alkoxy decane such as isopropoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane or ethyl triisopropoxy decane. Further, it is possible to add the following components to the photocurable resin composition as needed within the scope of the object of the present invention: an antioxidant; a thickener; a leveling agent, an antifoaming agent, an antiprecipitant, and a dispersion. Bustatic antistatic agent, surfactants and other surfactants; various pigments, dyes and other colorants; Shaoshuang slurry, talc, glass frit, metal powder and other fillers; butylated hydroxyl core (BHT), (four) ah ρτζ) Self-polymerization inhibitors of acrylates, and the like. From the viewpoint of the preservation of the composition, it is particularly preferable that (4) the amount of G._~(4)丨(4) is formulated as a self-polymerization inhibitor of the acrylate type. . The photocurable resin composition is excellent in compatibility with each component, and therefore has a good appearance. When applied to the undercoat layer, it can be formed into a coating film excellent in the degree of the photocurable resin group. It has the advantage that in the case of coating by a known coating method, the coating can be separated and the components are not dripped or coated. 146540.doc • 36- 201038686 The ultraviolet shielding of the present invention The adhesive layer coating film can be obtained by: (1) coating the (II) photocurable resin composition on the undercoat layer, and hardening the light with a high energy ray to obtain a hardened layer, which is sequentially coated with the hardened layer. The substrate. The substrate coated with the ultraviolet shielding coating film of the present invention is not particularly limited to a substrate containing a thermoplastic resin such as a polycarbonate resin which is easily photodecomposed by ultraviolet rays having a wavelength of around 300 nm. Examples of the material of the base material include polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene. a polyester resin such as butyl phthalate or a copolymer of the above, a polyamido resin such as polymethyl phthalate, poly(meth)acrylic acid vinegar, polyacrylonitrile, polyvinyl acetate, Polycarbonate, celecoxib, polyimine, polyphenylene, polyphenylene, polyanthracene, ionic polymer resin, fluorocarbon resin, thermoplastic resin, melamine resin, polyaminoformate Knowing various plastics such as epoxy resin, phenol resin, unsaturated polyester resin, alkyd resin, urea resin, polyoxyxylene resin, etc.; glass, P-ceramic; aluminum, rhetoric, iron, Nickel, cobalt, copper, tin, titanium, gold, silver, surface or metal concrete containing such alloys, wood, fiber cloth, non-woven fabric, leather, paper and stone (including marble). - The ultraviolet shielding coating film of the present invention is an ultraviolet absorbing effect, hardness, anti-grease staining adhesion, grease repellency, scratch resistance, transparency, water repellency, and adhesion at a wavelength of 30 〇 nmm Weather resistant coating film with excellent smoothness and =. Therefore, the ultraviolet shielding layer coating film of the present invention is suitable. Use for breaking on the surface of the following substrates: especially in outdoor environments such as outdoor 146540.doc -37· 201038686 exposed to sunlight, and requiring aesthetics and strength of the substrate (more specifically, It replaces the plastic component of the window glass for automobiles, or the plastic component of the window glass for building materials, etc.). Particularly preferred is a surface of an exterior decorative member for automobiles coated with polycarbonate resin and a structural external decorative member made of polycarbonate resin. As a material of the base material coated with the ultraviolet shielding coating film of the present invention, (4) is a thermoplastic plastic. It is particularly preferable to coat the polycarbonate resin with the ultraviolet shielding layer coating film of the present invention because the transparency is excellent, and the weather resistance and physical strength can be remarkably improved. The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a bottle shape, and a solid shape. Among them, thermoplastic plastic sheets or thermoplastic plastic films are preferred. The thickness of the substrate is not particularly limited. When it is in the form of a film or a sheet, the thickness of the substrate is usually in the range of 5 to 1 〇〇μηι; in the case of a plate having a certain thickness, the substrate is used. The thickness is in the range of 〇〇〇1 m to 〇1 m. In particular, it is possible to easily obtain an ultraviolet shielding multilayer coating film which is coated on both sides or one side of a plate-like polycarbonate resin having a thickness of 0.001 m to 0.1 m by the ultraviolet shielding coating film of the present invention. The polycarbonate S is a resin substrate. In addition, the ultraviolet shielding coating film of the present invention is substantially transparent, and the light transmittance of the plate-like polycarbonate resin as the substrate to visible light having a wavelength of 420 nm or more is 80% or more, and the obtained ultraviolet rays are adhered. The polycarbonate resin substrate of the shielding layer coating film has a light transmittance of 75% or more for visible light having a wavelength of 420 nm or more, thereby obtaining a polycarbonate having a UV coating property of 146540.doc -38 - 201038686 layer coating film. Resin substrate. These polycarbonate resin substrates can be suitably used as materials for building materials or window materials for automobiles. The ultraviolet shielding coating film of the present invention can be produced by coating a film having a film thickness of 10 to 200 μm, and [relative to 1 part by mass of the curable resin raw material monomer ( b) the content of the ultraviolet absorber (parts by mass)]x [the film thickness (μιη) of the undercoat layer at the time of coating] in the range of 1 〇〇 to 1 ' 'coating the above undercoat layer Applying the composition to the surface of the substrate and hardening it, thereby coating the surface of the substrate with an undercoat layer, then coating the photocurable resin composition on the undercoat layer and photohardening it with a high energy line, Thereby, the substrate is coated in this order. The coating method of the undercoat layer coating composition is not particularly limited, and for example, flow coating, dipping coating, spin coating, blow coating, curtain coating, or gravure printing can be used. Known methods such as cloth, Meyer bar coating, dipping coating, etc., forming an undercoat layer on the surface of various substrates, and pre-coating the surface of the substrate before coating using Shi Xiyuan coupling Q A surface treatment such as a primer treatment or a hydrolyzate or the like, and a surface treatment such as corona treatment. In the production of the ultraviolet shielding multilayer coating film of the present invention, it is necessary to apply and harden the undercoat layer coating composition in the following amounts, that is, the film thickness at the time of coating the undercoat layer coating composition. 1〇~2〇〇μιη, and [relative to - (b) content of ultraviolet absorber (parts by mass) per 100 parts by mass of the curable resin raw material monomer] x [film thickness of the undercoat layer at the time of coating (μπι)] The amount in the range of 1〇〇~1〇〇〇. In order to harden the undercoat coating composition applied to the substrate, a method of heating or irradiating a high-energy line such as ultraviolet rays may be selected. If it is the undercoat layer of the above-mentioned thermosetting type 146540.doc -39-201038686, a known heating device such as an oven can be selected; if it is a photocurable undercoat layer, it can be irradiated by the following high-energy rays. Hardening is achieved in a very short time. When the ultraviolet shielding coating film of the present invention is produced, it is necessary to photo-harden or thermally cure the bottom (four) coating composition on the substrate to thereby coat the substrate with the undercoat layer because the primer is applied. After the layer coating composition is applied, the photocurable resin composition is applied onto the uncured primer (4) layer without photocuring, and the ultraviolet rays necessary for photocuring are coated with the photocurable resin composition. The hardened layer is absorbed, and the hardening of the undercoat layer is insufficient. As a method of applying the photocurable resin composition to the undercoat layer, the same method as the method of applying the undercoat layer coating composition can be exemplified. For the amount of the photohardenable (four) contact compound, in the case where the scratch resistance is required, it is preferred that the thickness of the layer is 〇 5 to 25 (d), more preferably 1 to 20 _. After the film is dried after coating, it can be hardened in a very short time by irradiation with the following high-energy rays. The hardened layer constituting the ultraviolet ray inverse a* • 'deep viscous laminated coating film of the present invention is formed by coating the substrate with an undercoat layer before applying the above photocurability to the undercoat layer. The resin composition is dried and then irradiated with a high energy ray to thereby sequentially coat the substrate. The high-energy line can be exemplified by ultraviolet rays or electron beam rays. The composition of the present invention is excellent in ultraviolet light-curing characteristics. Therefore, it is preferable to use ultraviolet rays for curing. The reason is that in the case of using ultraviolet rays, it can be extremely short. The hardened film layer is formed in a time. The amount of ultraviolet radiation is at least 2 m Τ / 2 V 2 mj/cm '. It is preferably 100 to 3000 146540.doc -40· 201038686 dried nU/cm at normal temperature. The photocurable resin composition may be heated when it is desired to be dried more quickly. Hereinafter, the present invention will be specifically described by way of examples and comparative examples, and the present invention is not limited to the following examples. Further, in the following examples, the parts are all parts by mass, and the viscosity is 25 (the value measured). The respective characteristics of the examples and the comparative examples were measured by the following methods.

[光硬化型塗佈劑之黏度] 使用浸潰於溫度調整為25°C之恆溫水槽内的烏式黏度計 進行測定。 [耐候性試驗] 使用岩崎電氣股份有限公司製造之EYE Super紫外線^ 驗機SUV-W151，依據下述表1所示之條件，以照射、黑 暗 '結露之順序為週期而實施耐候性試驗。於96小時、 1 92小時、288小時後取出樣品，確認物性。 [表1] 照射時 黑面板溫度 63〇C 濕度 70% RH 照度 90 mW/cm2 時間 4小時 黑暗時 黑面板溫度 70°C 濕度 90% RH 時間^ 4小時 結露時 黑面板溫度 30°C 濕度 98% RH 時間 4小時 146540.doc -41- 201038686 [色差] 使用BYK-Gardner公司製造之c〇l〇r_guide 45/〇，測定耐 候性試驗前後之亮度（L)、彩度（a、b)，計算出其差值△[、 △ a、Ab 〇 [鉛筆硬度] 硬化皮膜之鉛筆硬度係依據JIS K56〇〇所記載之方法進 行測定。用施加有750 g負載之鉛筆刮劃硬化薄膜，將不 留刮痕之鉛筆之硬度的最高值作為鉛筆硬度。 [耐擦傷性] 以Taber磨耗試驗前後硬化皮膜之濁度之差值進行 評價。Taber磨耗試驗係於下述條件下進行：磨耗輪：cs_ l〇F ’負載：500 g，轉速：500轉/分。 [光硬化型塗佈劑之製備例1] 於燒瓶中’投入甲基乙基酮（以下稱為MEK) 14.2 g、胺 基甲酸酯丙烯酸酯系樹脂[日本化藥（股）製造，商品名 KAYARAD UX-5000] 17.4 g、分子鏈兩末端由3·胺基丙基 封端之聚二曱基石夕氧烧（Dow Corning Toray (股）公司製造； BY16-853U) 〇_36 g，將該等於50°C下加熱攪拌1小時。暫 時冷卻，依序加入3 -曱基丙烯醯氧基三曱氧基矽燒578 g、膠體二氧化矽之PGM分散液（濃度為30 wt%，膠體二氧 化矽之平均粒徑為13 nm) 57.8 g、水0.58 g並攪拌後，加 熱至50°C且攪拌1小時。冷卻後’添加作為光聚合起始劑 之2-曱基-1-[4·(甲硫基）苯基]-2-咪啉基丙酮[汽巴精化（股） 公司製造，商品名lrgacure 907] 2.10 g、作為紫外線吸收 146540.doc • 42- 201038686 劑之2-[4-[(2-羥基-3-十二烷氧基丙基）氧基]-4,6-雙（2,4-二 甲基苯基）-1,3,5-三畊及2-[4-[(2-羥基-3-十三烷氧基丙基） 氧基]-4,6-雙（2,4-二甲基苯基）-1，3,5-三畊之1-曱氧基-2-丙 醇溶液[汽巴精化（股）公司製造，TINUVIN 400] 1.0 g、作 為光穩定劑之2,4-雙[N-丁基-N-(l-環己氧基-2,2,6,6-四甲 基哌啶-4-基）胺基]-6-(2-羥基乙基胺）[汽巴精化（股）公司製 造，TINUVIN 152] 0.8 g、及酚噻畊4.3 mg，製備「光硬 化型塗佈劑」。該光硬化型塗佈劑之黏度為6 mPa·s。 [底塗劑之製備例（實施例1、比較例1〜3)] 利用機械力將下表2所示之成分混合均勻，製備底塗劑 1〜底塗劑4。底塗劑1係作為本案發明之實施例的熱硬化性 底塗劑組合物，底塗劑2~4係作為比較例的含有自由基聚 合起始劑之光硬化性底塗層塗佈劑。表中，各成分之調配 量係以質量份表示。 [表2] 成分/(質量份） 實施例1 底塗劑1 比較例1 底塗劑2 比較例2 底塗劑3 比較例3 底塗劑4 甲基丙烯酸甲酯 26.47 多官能性丙烯酸酯 DPHA(*1) 40.00 50.00 60.00 3-甲基丙烯醯氧基三曱氧 基秒炫 11.35 4.00 5.00 6.00 <自由基聚合起始劑> 2,2'-偶氮雙(2-甲基丁腈） 0.46 <水解縮合觸媒> 二甲基二新癸基錫 0.05 <光聚合起始劑> Irgacure 184(*2) 0.50 0.60 0.70 146540.doc -43- 201038686 <光聚合起始劑> Irgacure 819(*3) 0.30 0.40 0.50 <紫外線吸收劑> TINUVIN 400(*4) 3.38 <紫外線吸收劑> TINUVIN 479(*5) 2.40 3.00 4.00 <光穩定劑> TINUVIN 152(*6) 2.72 1.90 2.40 2.90 二甲苯 46.76 環己酮 8.81 曱基異丁基酮 15.00 15.00 15.00 丙二醇單甲醚 35.90 23.60 11.30 (* 1) DPHA (日本化藥製造多官能性丙烯酸酯商品名 KAYARAD DPHA) 二季戊四醇六丙烯酸酯/二季戊四醇五丙烯酸酯 (*2) Irgacure 184(汽巴精化（股）公司製造商品名Irgacure 184) 1 -羥基環己基苯基酮 (*3) Irgacure 819(汽巴精化（股）公司製造商品名Irgacure 819) 雙（2,4,6-三曱基苯甲醢基）苯基氧化膦 (*4) TINUVIN 400(汽巴精化（股）公司製造TINUVIN 400) 2-[4-[(2-羥基-3-十二烷氧基丙基）氧基]-4,6-雙（2,4-二曱基 苯基）-1,3,5-三畊及2-[4-[(2-羥基-3-十三烷氧基丙基）氧基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三畊之1-甲氧基-2-丙醇溶液 (*5) TINUVIN 479(汽巴精化（股）公司製造 商品名 TINUVIN 479) 2-(2-羥基-4-[l-辛氧羰基乙氧基]苯基）-4,6-雙（4-苯基苯 基）-1,3,5-三畊 146540.doc -44- 201038686 (6) TINUVIN 152(汽巴精化（股）公司製造TINUVIN l52) 2,4_雙[N-丁基養（1_環己氧基-2,2,6,6,曱基旅咬_4•基）胺 基]-6-(2-羥基乙基胺） [實施例1] 使用旋轉塗佈機，將上述底塗劑1均勻地塗佈於3 _厚 之聚碳酸酯板上，於烘箱中於⑽下靜置2小時，藉此利 用熱使底塗劑1進行自由基聚合及水解縮合，於該聚礙酸 板表面形成包含底㈣1的均句之底塗層（底塗層之厚度 〇 約為 20 μπι)。 繼而，在形成於3 mm厚之聚礙酸醋板上之該底塗層 上，使用旋轉塗佈機均勻地塗佈上述光硬化型塗佈劑，於 12(TC下乾燥2分鐘。進而，使用usm〇電機製造之uvc_ 02512S1AA01(燈：金屬 _ 素燈 UVH_〇25lc_22〇〇)，照射 2000 mJ/cm2之紫外線而使上述光硬化型塗佈劑硬化，獲 得於約8 μπι厚之硬化塗佈皮膜與基材之間包含約2〇 ^^之 Q 底塗層的聚碳酸酯板。初期之利用Taber磨耗試驗機所測 出之濁度變化為6.0%。 將該基材之耐候性試驗之結果示於表3。又，將耐候性 試驗之色差變化及鉛筆硬度之變化示於表4。 • [比較例1〜3] 使用旋轉塗佈機，將上述底塗劑2〜4分別均句地塗佈於3 mm厚之聚碳酸酯板上，於烘箱中於12〇<t下乾燥5分鐘。 進而’使用USHIO電機製造之uvc_〇2512SlAA〇1(燈：金 屬鹵素燈UVH-0251C-2200)，照射2〇00 mj/cm2之紫外線 146540.doc -45· 201038686 而使上述底塗劑2〜4光硬化，於該聚碳酸酯板表面形成包 含底塗劑2〜4的均勻之底塗層。將底塗層之膜厚示於表3。 繼而，使用旋轉塗佈機，在形成於3 mm厚之聚碳酸酯 板上之該底塗層上均勻地塗佈上述光硬化型塗佈劑，於 120°C下乾燥2分鐘。進而，使用USHIO電機製造之11乂(：-02512S1AA01 (燈：金屬鹵素燈 UVH-0251C-2200)，照射 2000 mJ/cm2之紫外線而使上述光硬化型塗佈劑硬化，獲 得於硬化塗佈皮膜與基材之間包含底塗層之聚碳酸酯板。 將塗佈皮膜之膜厚以及該基材之耐候性試驗之結果示於表 3 ° [比較例4] 除不使用底塗劑以外，以與實施例1相同之方式獲得僅 具有厚度5 μιη之上述光硬化型塗佈劑之硬化皮膜的聚碳酸 酯板。將該基材之耐候性試驗之結果示於表3。 [表3] 實施例1 比較例1 比較例2 比較例3 比較例4 底塗劑 底塗劑1 底塗劑2 底塗劑3 底塗劑4 無 底塗劑之種類 熱聚合及 縮合 光硬化性 - (Α)紫外線吸收劑含量 (質量份） 12.77 6.00 6.00 6.67 - (Β)底塗層膜厚(μπι) 20.1 3.6 6.0 9.4 - (A)x(B) 256.7 21.6 36.0 62.7 - 塗佈膜厚(μιη) 8.2 4.8 5.2 5.2 5.3 <耐候性試驗> 96小時 無剝離、 黃變 剝離 剝離 剝離 膜消失、 黃變 192小時 無剝離、 黃變 膜消失、 黃變 膜消失、 黃變 膜消失、 黃變 - 288小時 無剝離、 黃變 膜消失、 黃變 膜消失、 黃變 膜消失、 黃變 - 146540.doc 46· 201038686 [表4][Viscosity of Photocurable Coating Agent] The measurement was carried out using a Ubum viscometer immersed in a constant temperature water bath adjusted to a temperature of 25 °C. [Weather resistance test] The weather resistance test was carried out in the order of irradiation and darkening in the order of the EYE Super Ultraviolet Tester SUV-W151 manufactured by Iwasaki Electric Co., Ltd. according to the conditions shown in Table 1 below. The samples were taken after 96 hours, 192 hours, and 288 hours to confirm the physical properties. [Table 1] Black panel temperature when irradiated 63〇C Humidity 70% RH Illuminance 90 mW/cm2 Time 4 hours Darkness Black panel temperature 70°C Humidity 90% RH Time ^ 4 hours Condensation black panel temperature 30°C Humidity 98 % RH Time 4 hours 146540.doc -41- 201038686 [Color difference] Using the c〇l〇r_guide 45/〇 manufactured by BYK-Gardner, the brightness (L) and saturation (a, b) before and after the weather resistance test were measured. The pencil hardness of the hardened film of the difference Δ[, Δ a, Ab 〇 [pencil hardness] was calculated according to the method described in JIS K56〇〇. The hardened film was scratched with a pencil applied with a load of 750 g, and the highest value of the hardness of the pencil which did not leave a scratch was taken as the pencil hardness. [Scratch resistance] The difference between the turbidity of the hardened film before and after the Taber abrasion test was evaluated. The Taber abrasion test was carried out under the following conditions: abrasion wheel: cs_l〇F ’ load: 500 g, rotation speed: 500 rpm. [Preparation Example 1 of Photocurable Coating Agent] Into a flask, 'injection of methyl ethyl ketone (hereinafter referred to as MEK), 14.2 g, urethane acrylate resin, manufactured by Nippon Kayaku Co., Ltd. KAYARAD UX-5000] 17.4 g, polydimethyl fluorene terminated by 3·aminopropyl at both ends of the molecular chain (Dow Corning Toray Co., Ltd.; BY16-853U) 〇 _36 g, This was heated and stirred at 50 ° C for 1 hour. Temporarily cooled, sequentially adding 578 g of 3-mercaptopropenyloxytrimethoxy oxime, a PGM dispersion of colloidal cerium oxide (concentration of 30 wt%, and an average particle diameter of colloidal cerium oxide of 13 nm) After 57.8 g of water and 0.58 g of water were stirred, the mixture was heated to 50 ° C and stirred for 1 hour. After cooling, 'addition of 2-mercapto-1-[4·(methylthio)phenyl]-2-imidoylpropanone as a photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name lrgacure 907] 2.10 g, as UV absorption 146540.doc • 42- 201038686 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-4,6-bis (2, 4-dimethylphenyl)-1,3,5-three tillage and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-4,6-bis (2 , 4-dimethylphenyl)-1,3,5-three-pound 1-methoxy-2-propanol solution [Ciba Specialty Chemicals Co., Ltd., TINUVIN 400] 1.0 g, as light stable 2,4-bis[N-butyl-N-(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2- Hydroxyethylamine) [manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 152] 0.8 g, and phenol sulphate 4.3 mg to prepare a "photocurable coating agent". The photocurable coating agent has a viscosity of 6 mPa·s. [Preparation Example of Primer (Example 1, Comparative Examples 1 to 3)] The components shown in the following Table 2 were uniformly mixed by mechanical force to prepare a primer 1 to a primer 4. The primer 1 is a thermosetting primer composition as an example of the present invention, and the primers 2 to 4 are photocurable primer coating agents containing a radical polymerization initiator as a comparative example. In the table, the amount of each component is expressed in parts by mass. [Table 2] Ingredients/(parts by mass) Example 1 Primer 1 Comparative Example 1 Primer 2 Comparative Example 2 Primer 3 Comparative Example 3 Primer 4 Methyl methacrylate 26.47 Polyfunctional acrylate DPHA (*1) 40.00 50.00 60.00 3-Methyl propylene decyloxy decyloxy sec. 11.35 4.00 5.00 6.00 <Free radical polymerization initiator> 2,2'-azobis(2-methylbutyronitrile 0.46 <hydrolyzed condensation catalyst> dimethyldixindecyltin 0.05 <photopolymerization initiator> Irgacure 184(*2) 0.50 0.60 0.70 146540.doc -43- 201038686 <photopolymerization initiation Agent> Irgacure 819(*3) 0.30 0.40 0.50 <UV absorber> TINUVIN 400(*4) 3.38 <UV absorber> TINUVIN 479(*5) 2.40 3.00 4.00 <Light stabilizer> TINUVIN 152 (*6) 2.72 1.90 2.40 2.90 xylene 46.76 cyclohexanone 8.81 decyl isobutyl ketone 15.00 15.00 15.00 propylene glycol monomethyl ether 35.90 23.60 11.30 (* 1) DPHA (Nippon Chemical Co., Ltd. manufactures polyfunctional acrylates under the trade name KAYARAD DPHA) dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (*2) Irgacure 184 (steam Refined (stock) company made the trade name Irgacure 184) 1 -hydroxycyclohexyl phenyl ketone (*3) Irgacure 819 (Ciba Specialty Chemicals Co., Ltd. trade name Irgacure 819) Double (2,4,6-three Benzyl benzhydryl) phenylphosphine oxide (*4) TINUVIN 400 (TINUVIN 400 manufactured by Ciba Specialty Chemicals Co., Ltd.) 2-[4-[(2-hydroxy-3-dodecyloxypropyl) )oxy]-4,6-bis(2,4-dimercaptophenyl)-1,3,5-three tillage and 2-[4-[(2-hydroxy-3-tridecyloxypropane) Alkyloxy]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trinol 1-methoxy-2-propanol solution (*5) TINUVIN 479 ( Ciba Specialty Chemicals Co., Ltd. Manufactured under the trade name TINUVIN 479) 2-(2-hydroxy-4-[l-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl) -1,3,5-three tillage 146540.doc -44- 201038686 (6) TINUVIN 152 (COPU Refined (stock) company made TINUVIN l52) 2,4_ double [N-butyl (1_cyclohexene) Oxyl-2,2,6,6, anthracenyl bromide-4-(2-hydroxyethylamine) [Example 1] The above primer was applied using a spin coater 1 uniformly applied to a 3 mm thick polycarbonate plate and allowed to stand in an oven at (10) for 2 hours. Primer 1 that the heat radical polymerization and hydrolysis condensate, poly obstacle to the acid forming the undercoat layer surface of the plate includes a bottom ㈣1 of each sentence (the square of the thickness of the undercoat layer is about 20 μπι). Then, the photocurable coating agent was uniformly applied onto the undercoat layer formed on a 3 mm thick barrier vinegar plate by a spin coater, and dried at 12 (TC for 2 minutes. Further, Using uvc_ 02512S1AA01 (lamp: metal _ lamp UVH_〇25lc_22〇〇) manufactured by usm〇 motor, the above-mentioned photo-curing coating agent is hardened by irradiating ultraviolet rays of 2000 mJ/cm2 to obtain a hard coating of about 8 μm thick. A polycarbonate sheet containing about 2 Å of Q undercoat between the film and the substrate. The initial change in turbidity measured by a Taber abrasion tester was 6.0%. The results are shown in Table 3. Further, the change in color difference and the change in pencil hardness of the weather resistance test are shown in Table 4. • [Comparative Examples 1 to 3] The primers 2 to 4 were each obtained by a spin coater. The sentence was applied to a 3 mm thick polycarbonate plate and dried in an oven at 12 ° < t for 5 minutes. Further 'Uvc1〇2512SlAA〇1 manufactured by USHIO motor (light: metal halide UVH- 0251C-2200), irradiating ultraviolet rays 146540.doc -45· 201038686 of 2〇00 mj/cm2 and making the above primer 2~4 light After hardening, a uniform undercoat layer containing primers 2 to 4 was formed on the surface of the polycarbonate sheet. The film thickness of the undercoat layer is shown in Table 3. Then, using a spin coater, it was formed at a thickness of 3 mm. The photocurable coating agent was uniformly coated on the undercoat layer on the polycarbonate plate, and dried at 120 ° C for 2 minutes. Further, 11 乂 (:-02512S1AA01 (light: metal) manufactured by USHIO motor The halogen lamp UVH-0251C-2200) is cured by irradiating ultraviolet rays of 2000 mJ/cm2 to cure the photocurable coating agent, and obtains a polycarbonate plate containing an undercoat layer between the cured coating film and the substrate. The film thickness of the film and the weather resistance test of the substrate are shown in Table 3 [Comparative Example 4] The above light having a thickness of only 5 μm was obtained in the same manner as in Example 1 except that the primer was not used. A polycarbonate sheet of a hardened coating of a hardening type coating agent. The results of the weather resistance test of the substrate are shown in Table 3. [Table 3] Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Primer Primer 1 Primer 2 Primer 3 Primer 4 No primer type Thermal polymerization and shrinkage Light hardening - (Α) UV absorber content (parts by mass) 12.77 6.00 6.00 6.67 - (Β) Undercoat film thickness (μπι) 20.1 3.6 6.0 9.4 - (A)x(B) 256.7 21.6 36.0 62.7 - Coated Film thickness (μιη) 8.2 4.8 5.2 5.2 5.3 < Weather resistance test> 96 hours without peeling, yellowing peeling peeling peeling film disappearing, yellowing 192 hours without peeling, yellowing film disappearing, yellowing film disappearing, yellowing Membrane disappears, yellowing - no peeling in 288 hours, disappearing of yellowing film, disappearing of yellowing film, disappearing of yellowing film, yellowing - 146540.doc 46· 201038686 [Table 4]

誠驗前 96小時後 192小時後 288小時後 L 73.38 73.03 71.87 72.76 a -1.00 卜-0.79 -0.50 -0.76 b 2.10 2.93 3.79 2.94 △L - -0.36 T52 -2.47 △a - 0.21 0.50 0.96 △b - 0.83 1.68 1.75 鉛筆硬度 2H 2H 2H 2H 0 如表3所示般，實施例1之具有底塗層之聚碳酸酯板即使 經過288小時之耐候性試驗後，硬化皮膜亦不剝離，且色 差之變化亦非常小，可防止於聚碳酸酯中成為問題之黃 變。相對於此，比較例1〜3中，於96小時之耐候性試驗後 硬化皮膜即產生剝離，於192小時後之後皮膜完全消失， 可見聚碳酸酯板明顯黃變。又，不具有底塗層之比較例4 之聚碳酸酯板於96小時後皮膜即已消失，顯示明顯之黃 變。比較例1〜4之聚碳酸酯板之耐候性遜於實施例i。 Q [產業上之可利用性] 本發明之紫外線遮蔽性積層塗膜係波長3〇〇 〇111附近之紫 . 外線吸收效果、硬度、抗油脂污潰附著性、油脂污潰拭除 性、耐擦傷性、透明性、斥水性、密著性、平滑性及均句 性優異的耐候性塗膜。因此，本發明之紫外線遮蔽性積層 塗膜極適合於被覆如下基材之表面的用途：尤其是在Μ 等長時間曝露於太陽光下之環境中使用，且要求美觀及強 度之基材(更具體而言，代替汽車用窗玻璃之塑膠構件、 或代替建材用窗玻璃之塑膠構件等）。 146540.doc •47-After 96 hours before 192 hours and 288 hours after the test, L 73.38 73.03 71.87 72.76 a -1.00 卜 -0.79 -0.50 -0.76 b 2.10 2.93 3.79 2.94 △L - -0.36 T52 -2.47 △a - 0.21 0.50 0.96 △b - 0.83 1.68 1.75 Pencil hardness 2H 2H 2H 2H 0 As shown in Table 3, the polycarbonate sheet with the undercoat layer of Example 1 did not peel off the cured film even after 288 hours of weather resistance test, and the change in color difference was also observed. It is very small and can prevent the yellowing of the problem in polycarbonate. On the other hand, in Comparative Examples 1 to 3, after the weather resistance test for 96 hours, the film was peeled off, and after 192 hours, the film completely disappeared, and the polycarbonate plate was markedly yellowed. Further, the polycarbonate sheet of Comparative Example 4 which did not have the undercoat layer disappeared after 96 hours, showing a marked yellowing. The weather resistance of the polycarbonate sheets of Comparative Examples 1 to 4 was inferior to that of Example i. Q [Industrial Applicability] The ultraviolet shielding coating film of the present invention is a violet having a wavelength of around 3〇〇〇111. The external absorption effect, the hardness, the anti-grease adhesion, the grease detergency, and the resistance A weather-resistant coating film excellent in abrasion resistance, transparency, water repellency, adhesion, smoothness, and uniformity. Therefore, the ultraviolet shielding multilayer coating film of the present invention is extremely suitable for use for coating the surface of a substrate such as a substrate which is used in an environment where it is exposed to sunlight for a long time, and which requires aesthetics and strength (more Specifically, it replaces a plastic member for a window glass for an automobile or a plastic member for a window glass for a building material. 146540.doc •47-

Claims (1)

201038686 七、申請專利範圍： 1. 一種紫外線遮蔽性積層塗膜，其特徵在於包含·· (I) 底塗層，其特徵在於含有硬化性樹脂ι〇〇質量 份、及紫外線吸收劑5〜100質量份，塗佈時之膜厚為 10〜200 μπι，且[相對於每1〇〇質量份硬化性樹脂原料單 體之紫外線吸收劑之含量（質量份）]χ[底塗層於塗佈時之 膜厚（μηι)]在1〇〇〜1〇〇〇之範圍内，·及 (II) 硬化層’其係形成於上述底塗層表面，藉由高能 D 量線照射使包含下述成分⑷〜成分（D)之光硬化性樹脂組 合物光硬化而成者： (A) 多官能性丙烯酸酯或多官能性曱基丙烯酸酯 100質量份、 (B) 具有脂肪族不飽和鍵之有機烷氧基矽烷丨〜1〇〇 質量份、 (C) 膠體二氧化矽1〜300質量份、及 (D) 光聚合起始劑〇.〇1〜3〇質量份。 2. 如請求項1之紫外線遮蔽性積層塗膜，其中上述硬化性 樹脂為（a)丙烯酸系樹脂，上述硬化性樹脂原料單體為 (al)丙烯酸系樹脂原料單體。 3. 如請求項1之紫外線遮蔽性積層塗膜，其中上述底塗層 係使包含下述成分（al)〜(d)之底塗層塗佈組合物硬化而 成之丙烯酸系樹脂底塗層： (al)丙烯酸系樹脂原料單體1〇〇質量份、 (b)紫外線吸收劑5〜1〇〇質量份、 146540.doc 201038686 (C)文阻胺系光穩定劑〇·丨〜2〇質量份、及 (d)具有脂肪族不飽和鍵之有機烷氧基矽烷卜1〇〇質 量份。 4. 如請求項1或3之紫外線遮蔽性積層塗膜其中上述紫外 線吸收劑為（bl)於260〜400 nm具有吸收波長之紫外線吸 收劑。 5. 如凊求項1之紫外線遮蔽性積層塗膜，其中上述成分（A) 之多官能性丙烯酸酯為含有5官能性以上之丙烯酸酯的 多B月&性丙稀酸醋。 6. 如請求項1之紫外線遮蔽性積層塗膜，其中上述光硬化 性樹脂組合物係包含下述成分〜成分者： (A 1) 5官能性以上之丙烯酸酯1 〇〇質量份、 (B) 具有脂肪族不飽和鍵之有機烷氧基矽烷〗〜；!〇〇質 量份、 (C) 膠體二氧化矽1〜300質量份、 (D1)於300〜450 nm具有吸收波長之光聚合起始劑 0·01〜30質量份、 (Ε) 胺基改質有機聚矽氧烷0.2〜20質量份、及 (F) 含有醇之有機溶劑10〜1000質量份。 7. 如請求項1之紫外線遮蔽性積層塗膜，其中上述底塗層 係使包含下述成分（al)〜(d)之底塗層塗佈組合物加熱硬 化而成的熱硬化型之丙烯酸系樹脂底塗層： (al)丙烯酸系樹脂原料單體1〇〇質量份、 (b)紫外線吸收劑5〜100質量份、 146540.doc 201038686 (c) 受阻胺系光穩定劑o.l〇〜20質量份、及 (d) 具有脂肪族不飽和鍵之有機烷氧基矽烷卜1〇〇質 量份。 "8·如請求項1之紫外線遮蔽性積層塗膜，其中上述底塗層 • 耗由高能量線照射使包含下述成分（al)〜⑷之底塗層塗 佈組合物光硬化而成的光硬化型之丙烯酸系樹脂底塗 層： 〇 (al)丙烯酸系樹脂原料單體1〇〇質量份、 (bl)於260〜400 nm具有吸收波長之紫外線吸收劑 5〜100質量份、 (c) 受阻胺系光穩定劑〇. 1 〇〜2〇質量份、 (d) 具有脂肪族不飽和鍵之有機烷氧基矽烷卜丨⑽質 量份、及 (e) 於360〜450 nm具有吸收波長之光聚合起始劑 0.01〜3〇質量份。 〇 9·:種附著紫外線遮蔽性積層塗膜之基材，其係使用如請 求項1至8中任一項之紫外線遮蔽性積層塗膜被覆基材表 面而成者。 10·如請求項9之附著紫外線遮蔽性積層塗膜之基材，其中 t、’〔基材係厚度在〇·_ m〜0a瓜之範圍内之板狀聚碳酸 画曰樹月曰，且基材之兩面或單面由如請求項1至8中任一項 之紫外線遮蔽性積層塗膜所被覆。 求項10之附著紫外線遮蔽性積層塗膜之基材，其中 作為基材之板狀聚碳酸酯樹脂對波長4 2 0 n m以上之可見 146540.doc 201038686 光之光透射率為80%以上，所獲得之附著積層型硬化塗 膜之聚碳酸酯樹脂基材對波長42〇 ηιη以上之可見光之光 透射率為75°/。以上。 12. 13. 一種建築材料或汽車用車窗用之材料，其包含如請求項 9至11中任一項之附著紫外線遮蔽性積層塗膜之基材。 一種附著紫外線遮蔽性積層塗膜之基材之製造方法，其 特徵在於： (I)將含有硬化性樹脂原料單體丨〇〇質量份、及紫外 線吸收劑5〜100質量份之底塗層塗佈組合物，以塗佈時 之膜厚為10〜200 μιη，且[相對於每1〇〇質量份硬化性樹 脂原料單體之紫外線吸收劑之含量（質量份）]χ[底塗層於 塗佈時之膜厚〇1«1)]在100〜1000之範圍内的量進行塗佈並 使其硬化，藉此於基材表面被覆底塗層，然後， (π)於該底塗層上塗佈含有下述成分（Α)〜成分⑴）之光 硬化性樹脂組合物，並利用高能量線使其光硬化，藉此 依序對該基材進行被覆： Β月匕性甲基丙烯酸酯 (Α)多官能性丙烯酸酯或多 100質量份、 (Β) 質量份、 具有脂肪族不飽和鍵之有 機烷氧基矽烷1〜100 (C) 膠體二氧化矽1〜300質量份、及 (D) 光聚合起始劑〇·〇1〜3〇質量份。 I46540.doc 201038686 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 146540.doc201038686 VII. Patent application scope: 1. An ultraviolet shielding coating film characterized by comprising (I) an undercoat layer characterized by containing a curable resin ι mass and a UV absorber 5 to 100. The film thickness at the time of coating is 10 to 200 μm, and [the content (parts by mass) of the ultraviolet absorber per 1 part by mass of the curable resin raw material monomer] χ [undercoat layer coating The film thickness (μηι) is in the range of 1 〇〇 to 1 ,, and (II) the hardened layer is formed on the surface of the undercoat layer by high-energy D-ray irradiation to include the following The photocurable resin composition of the component (4) to the component (D) is photocured: (A) 100 parts by mass of a polyfunctional acrylate or a polyfunctional methacrylate, and (B) having an aliphatic unsaturated bond The organoalkoxydecane 丨~1 〇〇 parts by mass, (C) colloidal cerium oxide 1 to 300 parts by mass, and (D) photopolymerization initiator 〇.〇1 to 3 〇 parts by mass. 2. The ultraviolet shielding coating film according to claim 1, wherein the curable resin is (a) an acrylic resin, and the curable resin raw material monomer is (al) an acrylic resin raw material monomer. 3. The ultraviolet shielding coating film of claim 1, wherein the undercoat layer is an acrylic resin primer layer obtained by hardening an undercoat layer coating composition comprising the following components (a1) to (d) : (al) Acrylic resin raw material monomer 1 part by mass, (b) UV absorber 5 to 1 part by mass, 146540.doc 201038686 (C) Resistance amine light stabilizer 〇·丨~2〇 Parts by mass, and (d) 1 part by mass of the organoalkoxydecane having an aliphatic unsaturated bond. 4. The ultraviolet shielding multilayer coating film according to claim 1 or 3, wherein the ultraviolet absorbing agent is (bl) an ultraviolet absorbing agent having an absorption wavelength at 260 to 400 nm. 5. The ultraviolet shielding multilayer coating film according to Item 1, wherein the polyfunctional acrylate of the component (A) is a multi-B month & acrylic acid acrylate containing a acrylate having a functional group of 5 or more. 6. The ultraviolet shielding coating film according to claim 1, wherein the photocurable resin composition contains the following components to components: (A 1) acrylate having 1 or more functionalities, 1 〇〇 by mass, (B) ) an alkoxy decane having an aliphatic unsaturated bond 〜 〜 〇〇 mass part, (C) colloidal cerium oxide 1 to 300 parts by mass, (D1) photopolymerization having an absorption wavelength at 300 to 450 nm 0 to 01 parts by mass of the starting agent, 0.2 to 20 parts by mass of the amine-modified organic polyoxane, and (F) 10 to 1000 parts by mass of the organic solvent containing an alcohol. 7. The ultraviolet shielding coating film according to claim 1, wherein the undercoat layer is a thermosetting acrylic resin obtained by heat-hardening an undercoat layer coating composition comprising the following components (al) to (d). Resin base coat: (al) acrylic resin raw material monomer 1 part by mass, (b) ultraviolet absorber 5 to 100 parts by mass, 146540.doc 201038686 (c) hindered amine light stabilizer ol〇~20 Parts by mass, and (d) 1 part by mass of an organoalkoxydecane having an aliphatic unsaturated bond. <8. The ultraviolet shielding coating film of claim 1, wherein the undercoat layer is light-cured by irradiation with a high energy ray to form an undercoat layer coating composition comprising the following components (al) to (4). Photocurable acrylic resin undercoat layer: al (al) acrylic resin raw material monomer 1 〇〇 by mass, (bl) 5 to 100 parts by mass of ultraviolet absorbing agent having absorption wavelength at 260 to 400 nm, ( c) a hindered amine light stabilizer 1. 1 〇~2〇 parts by mass, (d) an organoalkoxyquinone having an aliphatic unsaturated bond (10) parts by mass, and (e) having an absorption at 360 to 450 nm The photopolymerization initiator of the wavelength is 0.01 to 3 parts by mass. 〇 9: A substrate in which an ultraviolet shielding layer coating film is adhered, and the surface of the substrate is coated with the ultraviolet shielding multilayer coating film according to any one of claims 1 to 8. 10. The substrate to which the ultraviolet shielding layer coating film of claim 9 is attached, wherein t, 'the thickness of the substrate is in the range of 〇·_ m~0a, and the platy polycarbonate is drawn in the eucalyptus, and Both sides or one side of the substrate are covered with the ultraviolet shielding multilayer coating film according to any one of claims 1 to 8. The substrate of the ultraviolet shielding layer coated film of the item 10, wherein the plate-like polycarbonate resin as the substrate has a light transmittance of 806% or more with respect to a wavelength of 420,540.doc 201038686 The polycarbonate resin substrate obtained by adhering the laminated hardened coating film had a light transmittance of 75 °/ to visible light having a wavelength of 42 〇ηη or more. the above. 12. A material for a building material or a window for an automobile, comprising the substrate to which the ultraviolet shielding layer coating film is attached according to any one of claims 9 to 11. A method for producing a substrate to which an ultraviolet shielding coating film is adhered, characterized in that: (I) a primer layer containing a curable resin raw material monomer in an amount of 5 parts by mass and a UV absorber in an amount of 5 to 100 parts by mass The cloth composition has a film thickness of 10 to 200 μm when applied, and [the content (parts by mass) of the ultraviolet absorber per 1 part by mass of the curable resin raw material monomer] χ [undercoat layer The film thickness 涂布1 «1)] at the time of coating is applied and hardened in an amount in the range of 100 to 1000, whereby the undercoat layer is coated on the surface of the substrate, and then (π) is applied to the undercoat layer. The photocurable resin composition containing the following components (Α) to (1)) is applied to the substrate, and the substrate is coated with a high-energy line to form a photocurable resin: Ester (Α) polyfunctional acrylate or more than 100 parts by mass, (Β) parts by mass, organo alkoxy decane having an aliphatic unsaturated bond 1 to 100 (C) colloidal cerium oxide 1 to 300 parts by mass, and (D) Photopolymerization initiator 〇·〇1 to 3〇 parts by mass. I46540.doc 201038686 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 146540.doc
TW099105370A 2009-02-25 2010-02-24 Ultraviolet ray shielding layered coating, substrate with said layered coating, and production method therefor TW201038686A (en)

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WO2012105297A1 (en) * 2011-01-31 2012-08-09 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 Process for producing functional colloidal silica solution, ultraviolet-curable resin composition for hard coats using same, and cured product thereof
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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4353959A (en) * 1979-12-21 1982-10-12 General Electric Company Abrasion resistant silicone coated polycarbonate article having an acrylic primer layer containing a U.V. absorbing compound
JPS6038438A (en) * 1983-08-12 1985-02-28 Mitsubishi Gas Chem Co Inc Production of composite polycarbonate molding excellent in surface property
JPS6393378A (en) * 1986-10-09 1988-04-23 Mazda Motor Corp Resin product having weatherability and abrasion resistance and its preparation
JP4236226B2 (en) * 1999-08-11 2009-03-11 Ｓｄｃテクノロジーズ・アジア株式会社 Coated polycarbonate plate
JP4429515B2 (en) * 2000-03-09 2010-03-10 帝人株式会社 Polymer resin laminate, method for producing the same, and molded article comprising the laminate
JP4601850B2 (en) * 2001-04-11 2010-12-22 大日本印刷株式会社 Hard film coated article
JP4646497B2 (en) * 2003-03-06 2011-03-09 東レ・ダウコーニング株式会社 High energy ray curable acryloxy functional silicone composition

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