TW201016777A - Curable resin composition and reflective sheet - Google Patents

Curable resin composition and reflective sheet Download PDF

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Publication number
TW201016777A
TW201016777A TW098122651A TW98122651A TW201016777A TW 201016777 A TW201016777 A TW 201016777A TW 098122651 A TW098122651 A TW 098122651A TW 98122651 A TW98122651 A TW 98122651A TW 201016777 A TW201016777 A TW 201016777A
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Taiwan
Prior art keywords
resin composition
curable resin
cured product
photopolymerization initiator
titanium oxide
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TW098122651A
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Chinese (zh)
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TWI561569B (en
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Mami Nousaka
Takenori Kakutani
Shigeru Ushiki
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Taiyo Ink Mfg Co Ltd
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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Abstract

A curable resin composition is provided which attains excellent resolution even when titanium oxide is contained therein in a large amount, and which gives a high-resolution cured object having a high reflectance. Also provided is a reflective sheet obtained from the composition. The curable resin composition is characterized by comprising a resin containing an ethylenically unsaturated group and a carboxy group in the molecule, a bisacylphosphine oxide photopolymerization initiator, a monoacylphosphine oxide photopolymerization initiator, titanium oxides and an organic solvent.

Description

201016777 六、發明說明： 【發明所屬之技術領域】 本發明係關於硬化性樹脂組成物及反射薄片。 具體而言爲下列四項。 其一爲儘管在高反射率下亦可形成高精細圖型之硬化 性樹脂組成物，以及使用該樹脂組成物之反射薄片。 另一爲可獲得儘管在高反射率下亦可形成高精細圖型 〇 ，且對難接著性熱可塑性基材之密著性優異之硬化物之硬 化性樹脂組成物，以及使用該樹脂組成物於難接著性熱可 塑性基材之反射薄片。 又一爲可獲得儘管在高反射率下亦可形成高精細圖型 ，且耐熱性優異之硬化物之硬化性樹脂組成物，以及使用 該樹脂組成物之反射薄片。 再一爲可獲得儘管在高反射率下亦可形成高精細圖型 ，且可用於可撓性基材之耐熱性優異之硬化物之硬化性樹 • 脂組成物，以及使用該樹脂組成物於可撓性基材之反射薄 片。 【先前技術】 使用樹脂組成物於基板上形成圖型之方法有各種方法 ，舉例爲例如網版印刷法或光微影蝕刻法等。該等方法中 ，由於光微影蝕刻法相較於其他圖型形成方法具有下列之 優異性能、效果，因此被廣泛的用於印刷電路板或半導體 之圖型、或液晶彩色濾光片之形成等（參照專利文獻1、 -5- 201016777 2)。亦即，與其他圖型形成方法比較在獲得高精細之圖 型時，由於使用印刷版並不須決定圖型之位置，可以藉由 光罩圖型對準圖型位置，故可提高印刷位置之精準度，且 圖型形成中即使無熟練技術亦可以高良率獲得均勻精準度 之圖型，且不會發生於網版印刷易於產生之污染或擦傷。 該光微影蝕刻法係對樹脂組成物照射UV光等進行圖 案化。因此爲使UV光等穿透過樹脂組成物，故於使樹脂 組成物著色之情況通常使用儘可能少量之顏料或染料。 據此，例如爲了使發光二極體（LED )等光反射而含 有大量的白色顏料（氧化鈦等）之樹脂組成物中，由於氧 化鈦會吸收UV光等並反射，造成難以使用光微影蝕刻法 形成圖型。因此，要求有即使含有大量氧化鈦等白色顔料 亦可使用光微影蝕刻法形成圖型之樹脂組成物。 又，含有大量上述氧化鈦等之樹脂組成物可用於攜帶 式終端機、個人電腦、電視等液晶顯示器之可有效利用背 光板或照明器具之光源等，尤其是在低電力下發光之LED 等光之反射材中。因此爲作爲該反射材之一，有由該樹脂 組成物之硬化物構成之反射薄片。 因此，作爲於反射薄片中使用之基材，由聚乙烯等聚 烯烴系基材、尼龍等聚醯胺系基材、聚對苯二甲酸乙二酯 等聚酯基材等之熱可塑性樹脂構成之基材（以下稱爲「熱 可塑性基材」）在加工性、耐久性、價格方面受到注目。 然而，由於該等熱可塑性基材均爲化學安定，因此不 溶解於有機溶劑類或單體類中。另外由於該等基材幾乎不 -6- 201016777 具有與反射薄片中使用之樹脂組成物反應之官能基，因此 該樹脂組成物及該硬化物對該基材之密著性困難。又，本 說明書中，將該等樹脂組成物難以密著之熱可塑性基材稱 爲「難接著性熱可塑性基材」，舉例爲聚烯烴系基材、聚 醯胺系基材、聚酯系基材等。 又’由於難接著性熱可塑性基材具有熱可塑性，因此 該基材在未到達熔點之前亦因熱引起收縮或伸張而容易造 0 成變形。據此，難以藉熱硬化對難接著性熱可塑性基材進 行高精細之圖型形成。因此，要求有即使含有大量氧化鈦 等白色顏料亦可使用光微影蝕刻法形成高精細圖型，且對 難接著性熱可塑性基材具有高密著性之樹脂組成物。 又’作爲使難接著性熱可塑性基材之聚酯基材彼此接 著之接著劑，已提出有例如使用聚酯樹脂之特殊接著劑之 相關發明（參照專利文獻3 )。 又如上述，含有大量氧化鈦等之樹脂組成物有使用於 ® 利用LED等光之反射材中，作爲此反射材之一，有由該 樹脂組成物之硬化物構成之反射薄片。因此，作爲該反射 薄片中使用之基材，伴隨著攜帶式終端機等電子設備之小 型化，具有可撓性之基材正受到矚目。 其中，此等樹脂組成物之硬化物依據形成圖型之基材 之用途等而要求耐熱性。該等情況下，爲了對該硬化物賦 予耐熱性，而於該樹脂組成物中調配環氧化合物。 使用含有此環氧化合物之樹脂組成物獲得之硬化物之 耐熱性或耐藥品性等優異。然而由於該硬化物較脆故而無 201016777 法利用於可撓性之基材中，而成爲問題。因此，要求有即 使含有大量氧化鈦等白色顔料亦可使用光微影鈾刻法形成 高精細圖型、耐熱性優異且可用於可撓性基材中之樹脂組 成物。 更具體而言，要求即使含有環氧化合物，亦可使用輥 對輥製程加工之聚醯亞胺薄膜或銅箔、鋁箔等可撓性基材 中使用之硬化性樹脂組成物。 [專利文獻1]特公平1 -543 90號 [專利文獻2]特公平7- 1 773 7號 [專利文獻3]特開2007-321004號 【發明內容】 [發明欲解決之課題] 本發明目的之一爲提供一種即使含有大量氧化鈦，其 解像性亦優異、進而可在高反射率下形成高精細硬化物之 硬化性樹脂組成物，及使用該樹脂組成物之反射薄片。 本發明之另一目的爲提供一種即使含有大量氧化鈦， 其解像性亦優異、且在高反射率下獲得高精細之硬化物， 進而獲得對難接著性熱可塑性基材之密著性優異之硬化物 之硬化性樹脂組成物，及於難接著性熱可塑性基材中使用 該樹脂組成物之反射薄片。 另外，本發明之其他目的係提供一種即使含有大量氧 化鈦，其解像性亦優異、且獲得耐熱性優異之硬化物之硬 化性樹脂組成物，以及使用該樹脂組成物之反射薄片。 -8 - 201016777 再者，本發明之其他目的係提供一種即使含有大量氧 化鈦，其解像性亦優異、且可獲得高反射率、高精細及耐 熱性優異之硬化物，進而獲得可用於可撓性基材之硬化物 之硬化性樹脂組成物，以及於可撓性基材中使用該樹脂組 成物之反射薄片。 [解決課題之手段] 爲達成上述目的，於本發明，倂用雙醯基氧化膦系光 聚合起始劑及單醯基氧化膦系光聚合起始劑作爲光聚合起 始劑。據此，即使爲含有大量氧化鈦之硬化性樹脂組成物 ，亦可形成解像性優異之圖型。 又，於本發明，在上述硬化性樹脂組成物中調配胺基 甲酸酯丙烯酸酯。據此，即使含有大量氧化鈦，其解像性 亦優異，進而可形成對難接著性熱可塑性基材之密著性優 異之圖型。 •再者，於本發明，對硬化性樹脂組成物之硬化物要求 耐熱性時，可於上述硬化性樹脂組成物中調配環氧化合物 。更具體而言，係於上述硬化性樹脂組成物中調配環氧化 合物及胺基甲酸酯丙烯酸酯。據此，可形成解像性及耐熱 性優異，且可形成可用於可撓性基材中之圖型。 亦即，本發明之硬化性樹脂組成物及反射薄片具備有 下列構成。 首先，本發明之硬化性樹脂組成物之特徵爲含有一分 子內包含乙烯性不飽和基及羧基之樹脂、雙醯基氧化膦系 -9- 201016777 光聚合起始劑、單醯基氧化膦系光聚合起始劑、氧化鈦及 有機溶劑。 具體而言，其特徵爲本發明之硬化性樹脂組成物之氧 化鈦調配量，相對於100質量份之除有機溶劑以外之成分 ，爲40至80質量份。 - 又，氧化鈦以金紅石型氧化鈦較佳。 、 再者，一分子內包含乙烯性不飽和基及羧基之樹脂較 好爲由含有羧基之（甲基）丙烯酸系共聚合樹脂與一分子 @ 中具有環氧乙烷環及乙烯性不飽和基之化合物反應所得之 具有羧基之共聚合系樹脂。 再者，一分子中具有環氧乙烷環及乙烯性不飽和基之 化合物較好爲由脂肪族聚合性單體所生成之化合物》 又，本發明之硬化性樹脂組成物中可調配胺基甲酸酯 丙烯酸酯。 再者，對該硬化物要求耐熱性時，可於本發明之硬化 性樹脂組成物中調配環氧化合物。更具體而言，本發明之 @ 硬化性樹脂組成物中可調配環氧化合物、抗氧化劑及胺基 甲酸酯丙烯酸酯。 接著本發明之反射薄片之特徵爲由上述硬化性樹脂組 成物之硬化物所構成。 具體而言，本發明之反射薄片之特徵爲由難接著性熱 可塑性基材以及設於該基材上之含有胺基甲酸酯丙烯酸酯 之本發明之硬化性樹脂組成物之硬化物所構成。 再者，本發明之反射薄片之特徵爲由含有環氧化合物 -10- 201016777 與抗氧化劑之本發明硬化性樹脂組成物之硬化物所構成。 更具體而言，本發明之反射薄片之特徵爲由含有可撓性基 材、設於該基材上之含有環氧化合物與抗氧化劑及胺基甲 酸酯丙烯酸酯之本發明硬化性樹脂組成物之硬化物所構成 〇 又本發明之反射薄片爲由硬化性樹脂組成物之硬化物 構成之反射薄片，其中該硬化物之特徵爲含有一分子內包 • 含乙烯性不飽和基及羧基之樹脂、雙醯基氧化膦系光聚合 起始劑、單醯基氧化膦系光聚合起始劑及氧化鈦。 更具體而言，本發明之反射薄片之特徵爲相對於100 質量份之上述硬化物含有40至80質量份之氧化鈦。 [發明效果] 本發明之效果之一爲可提供一種即使含有大量氧化鈦 ，其解像性亦優異、進而可在高反射率下形成高精細硬化 • 物之硬化性樹脂組成物，及使用該樹脂組成物之反射薄片 〇 本發明之其他效果爲可提供一種即使含有大量氧化鈦 ’其解像性亦優異、且可獲得在高反射率下形成高精細硬 化物、進而對難接著性熱可塑性基材之密著性優異之硬化 性樹脂組成物’及將該樹脂組成物用於難接著性熱可塑性 基材中之反射薄片。 又本發明之其他效果爲在硬化性樹脂組成物之硬化物 要求耐熱性時’即使含有大量氧化鈦，其解像性亦優異、 201016777 進而可獲得高反射率、高精細及耐熱性優異之硬化物之硬 化性樹脂組成物，及使用該樹脂組成物所得之反射薄片。 更具體而言，可提供一種即使含有大量氧化鈦，其解 像性亦優異，且可獲得高反射率、高精細及耐熱性優異之 硬化物，進而可獲得可使用於可撓性基材之硬化物之硬化 性樹脂組成物，以及於可撓性基材中使用此樹脂組成物之 反射薄片。 【實施方式】 以下針對本發明加以詳細說明。 本發明之硬化性樹脂組成物含有一分子內包含乙烯性 不飽和基及羧基之樹脂、雙醯基氧化膦系光聚合起始劑、 單醯基氧化膦系光聚合起始劑、氧化鈦及有機溶劑。又本 發明之硬化性樹脂組成物，除該等以外，亦含有胺基甲酸 酯丙烯酸酯。又，本發明之硬化性樹脂組成物，除上述硬 化性樹脂組成物以外，亦含有環氧化合物及抗氧化物。更 具體而言，本發明之硬化性樹脂組成物包含環氧化合物及 抗氧化劑與胺基甲酸酯丙烯酸酯。 又，以下所謂本件塗膜意指使用本發明之硬化性樹脂 組成物形成之塗膜。另外所謂的硬化物意指使本發明之硬 化性樹脂組成物經光硬化或者經光硬化及熱硬化而硬化者 (組成物之各成分） 201016777 [一分子內包含乙烯性不飽和基及羧基之樹脂] 一分子內包含乙烯性不飽和基與羧基之樹脂（以下稱 爲「光硬化性樹脂」）只要爲一分子內具有光硬化性之乙 烯性不飽和基與可用以藉弱鹼性水溶液顯像之羧基之樹脂 即可。又，光硬化性樹脂可較好地使用以下列（1 )至（3 )所列舉之樹脂（可爲寡聚物或聚合物之任一種），但並 不限於特定者。 0 (1)對於含有羧基之（甲基）丙烯酸系共聚合樹脂 反應一分子中具有環氧乙烷環與乙烯性不飽和基之化合物 而獲得之含有感光性羧基之樹脂。 (2) 對於一分子中具有一個環氧基與一個不飽和雙 鍵之化合物與具有不飽和雙鍵之化合物之共聚物，反應不 飽和單羧酸，對藉由該反應生成之二級羥基反應飽和或不 飽和多元酸酐所獲得之含有感光性羧基之樹脂。 (3) 對於含有羥基之聚合物反應飽和或不飽和多元 ® 酸酐之後，對於藉由該反應生成之羧基反應一分子中具有 一個環氧基與一個不飽和雙鍵之化合物所獲得之含有感光 _ 性羥基及羧基之樹脂。 該等中，（1)之含有羧基之樹脂中，較好使用藉由 含有羧基之（甲基）丙烯酸系共聚合樹脂與一分子中具有 環氧乙烷環與乙烯性不飽和基之化合物反應獲得之具有羧 基之共聚合系樹脂作爲光硬化性樹脂。 含有羧基之（甲基）丙烯酸系共聚合樹脂爲使（甲基 )丙烯酸酯及一分子中具有一個不飽和基及一個以上羧基 -13- 201016777 之化合物共聚合而獲得。至於（甲基）丙烯酸酯舉例爲（ 甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯 酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（ 甲基）丙烯酸己酯等（甲基）丙烯酸烷酯類，（甲基）丙 烯酸2·羥基乙酯、（甲基）丙烯酸羥基丙酯、（甲基） 丙烯酸羥基丁酯、己內酯改質之（甲基）丙烯酸2-羥基 乙酯等含有羥基之（甲基）丙烯酸酯類，（甲基）丙烯酸 甲氧基二乙二醇酯、（甲基）丙烯酸乙氧基二乙二醇酯、 _ (甲基）丙烯酸異辛氧基二乙二醇酯、（甲基）丙烯酸甲 氧基三乙二醇酯、（甲基）丙烯酸甲氧基聚乙二醇酯等之 二醇改質之（甲基）丙烯酸酯類等。該等可單獨使用亦可 混合複數種使用。又，本說明書中，所謂的（甲基）丙烯 酸酯爲丙烯酸酯及甲基丙烯酸酯之總稱的用語，針對其他 類似之表現亦同。 又，一分子中具有一個不飽和基及一個以上羧基之化 合物舉例爲丙烯酸、甲基丙烯酸、不飽和基與羧酸之間經 β 鏈延長之改質不飽和單羧酸（（甲基）丙烯酸β-羧基乙 酯、琥珀酸2-丙烯醯氧基乙酯、六氫苯二甲酸2-丙烯醯 氧基乙酯、藉由內酯改質等之具有酯鍵之不飽和單羧酸、 具有醚鍵之改質不飽和單羧酸）、馬來酸等之分子中含有 複數個羧基者等。該等可單獨使用，亦可混合複數種使用 〇 一分子中具有環氧乙烷環及乙烯性不飽和基之化合物 較好使用由脂肪族單體生成之化合物。尤其，使用由脂肪 -14- 201016777 族聚合性單體生成之化合物時，由於可抑制起因於光硬化 性樹脂中所含芳香環之藉由光引起之硬化物劣化故而較佳 。由脂肪族單體生成之化合物舉例爲（甲基）丙烯酸縮水 甘油酯、（甲基）丙烯酸α-甲基縮水甘油酯、（甲基） 丙烯酸3,4-環氧基環己基甲酯、（甲基）丙烯酸3,4-環氧 基環己基乙酯、（甲基）丙烯酸3,4-環氧基環己基丁酯、 丙烯酸3,4-環氧基環己基甲基胺基酯、（甲基）丙烯酸 〇 3，4-環氧基環己基甲酯等。一分子中具有環氧乙烷環與乙 烯性不飽和基之化合物可單獨使用，亦可混合複數種使用 〇 光硬化性樹脂之酸價有必要在50〜200mgKOH/g之範 圍。光硬化性樹脂之酸價未達50mgKOH/g時，顯像時難 以以弱鹼性水溶液去除本件塗膜之未曝光部分。又，光硬 化性樹脂之酸價超過200mgKOH/g時，會產生硬化物之耐 水性、電特性劣化等之問題。 ® 又，光硬化性樹脂之重量平均分子量較好在5,000〜 1 00,000之範圍。光硬·化性樹脂之重量平均分子量未達 5,000時，本件塗膜之指觸乾燥性有顯著劣化之傾向。又 ，光硬化性樹脂之重量平均分子量超過100,000時，由於 本件塗膜之顯像性及本發明之硬化性樹脂組成物之儲存安 定性顯著的惡化故而不佳。 [雙醯基氧化膦系光聚合起始劑] 雙醯基氧化膦系光聚合起始劑（以下稱爲「BAPO」 -15- 201016777 )舉例爲雙-(2,6-二氯苯甲醯基）苯基氧化堪 2,6·二氯苯甲醯基）-2,5-二甲基苯基氧化鱗、雙 氯苯甲醯基）-4-丙基苯基氧化膦、雙-(2,6·二 基）-1-萘基氧化膦、雙-(2,6-二甲氧基苯甲醯 氧化鱗、雙- (2,6-二甲氧基苯甲醯基）-2,4，4-三 氧化膦、雙-(2,6-二甲氧基苯甲醯基）-2,5-二 氧化膦、雙-(2,4,6-三甲基苯甲醯基）苯基氧 2,5,6-三甲基苯甲醯基）-2,4,4-三甲基戊基氧化 等中雙·（ 2,4,6-三甲基苯甲醯基）苯基氧化鱗（ 本（股）製造，商品名；Irgacure819)容易取_ [單醯基氧化膦系光聚合起始劑] 單醯基氧化膦系光聚合起始劑（以下稱爲f )舉例爲2,4,6-三甲基苯甲醯基二苯基氧化膦、 氧基苯甲醯基二苯基氧化膦、2,6-二氯苯甲醯基 化膦、2,4,6-三甲基苯甲醯基苯基膦酸甲酯、2-醯基二苯基氧化膦、特戊醯基苯基膦酸異丙酯等 2，4,6-三甲基苯甲醯基二苯基氧化膦（汽巴•日 製造，商品名；DAROCUR TPO )容易取得。 本發明中，藉由倂用BAPO及MAPO，即使 大量氧化鈦之樹脂組成物形成高反射率之塗膜， 量光通過塗膜亦可使其硬化。據此，即使使用該 成物及其塗膜，亦可形成解像性優異之高精細圖 因此，藉由改變BAPO與MAPO之調配比率 !、雙 _ ( ( 2,6-二 氯苯甲醯 基）苯基 甲基戊基 甲基苯基 化膦、（ 膦等。該 汽巴•日 MAPO」 2,6-二甲 二苯基氧 甲基苯甲 。其中以 本（股） 使用含有 藉由使少 等樹脂組 型。 ，可微調 201016777 整本發明之硬化性樹脂組成物之感光性。亦即，基材上形 成之圖型之剖面形狀中，基材面側之深部硬化性不足而容 易出現側蝕（undercut)時，可增大BAPO之調配比率。 又，由於本件塗膜之表面硬化性不足，因此顯像後，圖型 之表面狀態變差時，則增大MAPO之調配比率。 BAPO與MAPO之調配比率以質量比計爲90比10至 1比99，較好爲80比20至2比98。在該調配比率之範 φ 圍外，因倂用BAPO與MAPO之效果少，無法獲得使本件 塗膜硬化所需之光感度，故無法形成高精細之圖型。 又，BAPO與MAPO之合計調配量，相對於1〇〇質量 份之光硬化性樹脂，較好爲1~30質量份，更好爲2〜25質 量份。當BAPO與MAPO之合計調配量相對於1〇〇質量份 之光硬化性樹脂未達1質量份時，本件塗膜之光硬化性下 降，難以在曝光、顯像後形成圖型故而不佳。又，當 BAPO與MAPO之合計調配量相對於1〇〇質量份之光硬化 ❹ 性樹脂超過30質量份時，源自光聚合起始劑之塗膜著色 變大，進而成爲成本高之原因故而不佳。 [氧化鈦] 氧化鈦可使用銳鈦礦型氧化鈦、金紅石型氧化鈦之任 一種，尤其以金紅石型氧化鈦較佳。銳鈦礦型氧化鈦相較 於金紅石型氧化鈦，由於在紫外線區域與可見光區域之交 界附近之反射率高，因此就白色度與反射率之觀點作爲白 色顏料較適宜。然而，由於銳鈦礦型氧化鈦具有光觸媒活 -17- 201016777 TIPAQUE R-680 TIPAQUE R-850 TIPAQUE CR-80 TIPAQUE CR-95 TIPAQUE CR-63 TIPAQUE CR-85 性，故有因其光活性引起硬化性樹脂組成物樹脂變色之情 況。相對地，金紅石型氧化鈦其白色度雖比銳鈦礦型氧化 鈦稍差，但由於幾乎不具有光活性，故可抑制本發明之硬 化性樹脂組成物之樹脂劣化，可獲得安定之硬化物。至於 金紅石型氧化鈦可使用TIPAQUE R-820、TIPAQUE R-830 、TIPAQUE R-930、TIPAQUE R-5 50 ' TIPAQUE R-63 0、 TIPAQUE R-68 0、TIPAQUE R-670 TIPAQUE R-780 TIPAQUE CR-57 TIPAQUE CR-93 TIPAQUE CR-60 TIPAQUE CR-58201016777 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a curable resin composition and a reflective sheet. Specifically, the following four items. One is a curable resin composition which can form a high-definition pattern even at a high reflectance, and a reflective sheet using the resin composition. The other is a curable resin composition which can obtain a cured product which is excellent in adhesion to a difficult-to-adhere thermoplastic substrate, and which can form a high-definition pattern 高 at a high reflectance, and which is used. A reflective sheet of a difficult thermoplastic substrate. Further, it is a curable resin composition which can obtain a cured product which is excellent in heat resistance even in the case of forming a high-definition pattern at a high reflectance, and a reflective sheet using the resin composition. Further, it is a curable resin composition which can obtain a high-definition pattern which can form a high-definition pattern at a high reflectance and which can be used for a heat-resistant property of a flexible substrate, and a resin composition using the resin composition A reflective sheet of a flexible substrate. [Prior Art] There are various methods for forming a pattern on a substrate using a resin composition, and examples thereof include, for example, a screen printing method or a photolithography method. Among these methods, since the photolithography method has the following excellent performance and effects as compared with other pattern forming methods, it is widely used for patterning of printed circuit boards or semiconductors, or formation of liquid crystal color filters, and the like. (Refer to Patent Document 1, -5-201016777 2). That is, compared with other pattern forming methods, when obtaining a high-definition pattern, since the printing plate does not need to determine the position of the pattern, the position of the pattern can be aligned by the mask pattern, so that the printing position can be improved. The accuracy and pattern formation can achieve a uniform image with high yield even without skill, and it will not occur in the pollution or scratch that is easy to be generated by screen printing. This photolithography method is a pattern in which a resin composition is irradiated with UV light or the like. Therefore, in order to allow UV light or the like to penetrate the resin composition, it is usual to use a pigment or a dye as small as possible in order to color the resin composition. According to this, for example, in order to reflect light such as a light-emitting diode (LED), a resin composition containing a large amount of white pigment (titanium oxide or the like) absorbs UV light or the like and reflects it, thereby making it difficult to use light lithography. The etching method forms a pattern. Therefore, a resin composition which forms a pattern by photolithography can be used even if it contains a large amount of white pigment such as titanium oxide. Further, a resin composition containing a large amount of the above-mentioned titanium oxide or the like can be used for a liquid crystal display such as a portable terminal, a personal computer, or a television, and can effectively use a light source such as a backlight or a lighting fixture, especially an LED that emits light under low power. In the reflective material. Therefore, as one of the reflecting materials, there is a reflective sheet composed of a cured product of the resin composition. Therefore, the base material used for the reflective sheet is made of a thermoplastic resin such as a polyolefin base material such as polyethylene, a polyamide base material such as nylon, or a polyester base material such as polyethylene terephthalate. The substrate (hereinafter referred to as "thermoplastic substrate") has attracted attention in terms of workability, durability, and price. However, since these thermoplastic substrates are chemically stable, they are not dissolved in organic solvents or monomers. Further, since these substrates hardly have a functional group reactive with the resin composition used in the reflective sheet, the resin composition and the cured product are difficult to adhere to the substrate. In the present specification, the thermoplastic substrate to which the resin composition is hard to adhere is referred to as a "difficult adhesive thermoplastic substrate", and examples thereof include a polyolefin-based substrate, a polyamide-based substrate, and a polyester-based system. Substrate, etc. Further, since the difficult-to-adhesive thermoplastic substrate has thermoplasticity, the substrate is easily deformed by shrinkage or stretching due to heat before reaching the melting point. Accordingly, it is difficult to form a high-definition pattern on the difficult-to-adhere thermoplastic substrate by thermal hardening. Therefore, it is required to form a high-definition pattern by photolithography using a large amount of a white pigment such as titanium oxide, and to have a high-adhesive resin composition for a difficult-to-adhere thermoplastic substrate. Further, as an adhesive agent for bonding the polyester base materials of the hard-adhesive thermoplastic substrate to each other, for example, a related invention using a special adhesive for a polyester resin has been proposed (see Patent Document 3). Further, as described above, a resin composition containing a large amount of titanium oxide or the like is used for a light reflecting material such as an LED, and as one of the reflecting materials, there is a reflective sheet composed of a cured product of the resin composition. Therefore, as a substrate to be used for the reflective sheet, a flexible substrate has been attracting attention as electronic devices such as portable terminals have been miniaturized. Among them, the cured product of the resin composition requires heat resistance depending on the use of the substrate on which the pattern is formed or the like. In these cases, an epoxy compound is blended in the resin composition in order to impart heat resistance to the cured product. The cured product obtained by using the resin composition containing the epoxy compound is excellent in heat resistance, chemical resistance, and the like. However, since the cured product is brittle, the 201016777 method is not used in a flexible substrate, which is a problem. Therefore, it is required to form a resin composition which can form a high-definition pattern by using a photolithography uranium engraving method, and which is excellent in heat resistance and can be used in a flexible substrate even if a white pigment such as a large amount of titanium oxide is contained. More specifically, it is required to use a curable resin composition which is used in a roll-to-roll process, a polyimide film, a flexible substrate such as a copper foil or an aluminum foil, even if an epoxy compound is contained. [Patent Document 1] Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-321004 [Patent Document 3] JP-A-2007-321004 [Summary of the Invention] One of them is to provide a curable resin composition which is excellent in resolvability even when a large amount of titanium oxide is contained, and which can form a high-hardness cured product at a high reflectance, and a reflective sheet using the resin composition. Another object of the present invention is to provide a cured product which is excellent in resolution even when a large amount of titanium oxide is contained and which is high in high reflectance, and which is excellent in adhesion to a difficult-to-adhere thermoplastic substrate. The curable resin composition of the cured product and the reflective sheet of the resin composition are used for the difficult-to-adhere thermoplastic substrate. In addition, another object of the present invention is to provide a hard resin composition which is excellent in resolution and which is excellent in heat resistance even when a large amount of titanium oxide is contained, and a reflective sheet using the resin composition. -8 - 201016777 Further, another object of the present invention is to provide a cured product which is excellent in resolvability even when a large amount of titanium oxide is contained, and which is excellent in high reflectance, high definition, and heat resistance, and is available for use. A curable resin composition of a cured product of a flexible substrate, and a reflective sheet of the resin composition used in the flexible substrate. [Means for Solving the Problem] In order to achieve the above object, in the present invention, a bis-indenylphosphine oxide-based photopolymerization initiator and a monofluorenylphosphine oxide-based photopolymerization initiator are used as a photopolymerization initiator. According to this, even if it is a curable resin composition containing a large amount of titanium oxide, a pattern excellent in resolution can be formed. Further, in the invention, the urethane acrylate is blended in the curable resin composition. According to this, even if a large amount of titanium oxide is contained, the resolution is excellent, and further, the pattern of excellent adhesion to the difficult-to-adhere thermoplastic substrate can be formed. Further, in the present invention, when heat resistance is required for the cured product of the curable resin composition, the epoxy compound can be formulated in the curable resin composition. More specifically, an epoxide and a urethane acrylate are formulated in the above curable resin composition. According to this, it is excellent in resolution and heat resistance, and can form a pattern usable in a flexible substrate. In other words, the curable resin composition and the reflective sheet of the present invention have the following constitutions. First, the curable resin composition of the present invention is characterized by containing a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule, a bis-indenylphosphine oxide-based-9-201016777 photopolymerization initiator, and a monofluorenylphosphine oxide system. Photopolymerization initiator, titanium oxide and organic solvent. Specifically, the titanium oxide compounding amount of the curable resin composition of the present invention is 40 to 80 parts by mass based on 100 parts by mass of the components other than the organic solvent. Further, titanium oxide is preferably rutile-type titanium oxide. Further, the resin containing an ethylenically unsaturated group and a carboxyl group in one molecule is preferably a (meth)acrylic copolymer resin containing a carboxyl group and an oxirane ring and an ethylenically unsaturated group in one molecule of @ The copolymerized resin having a carboxyl group obtained by the reaction of the compound. Further, a compound having an oxirane ring and an ethylenically unsaturated group in one molecule is preferably a compound formed from an aliphatic polymerizable monomer. Further, an amine group can be formulated in the curable resin composition of the present invention. Formate acrylate. Further, when heat resistance is required for the cured product, an epoxy compound can be formulated in the curable resin composition of the present invention. More specifically, the @curable resin composition of the present invention may be formulated with an epoxy compound, an antioxidant, and an urethane acrylate. Next, the reflective sheet of the present invention is characterized by being composed of a cured product of the above curable resin composition. Specifically, the reflective sheet of the present invention is characterized by comprising a hard-to-adhere thermoplastic substrate and a cured product of the curable resin composition of the present invention containing urethane acrylate provided on the substrate. . Further, the reflective sheet of the present invention is characterized by being composed of a cured product of the curable resin composition of the present invention containing an epoxy compound -10-201016777 and an antioxidant. More specifically, the reflective sheet of the present invention is characterized by comprising a flexible substrate, an epoxy compound containing an epoxy compound and an antioxidant, and a urethane acrylate provided on the substrate. The cured sheet of the present invention is a reflective sheet composed of a cured product of a curable resin composition, wherein the cured product is characterized by containing a molecular inclusion of an ethylenically unsaturated group and a carboxyl group. A resin, a bis-indenylphosphine oxide-based photopolymerization initiator, a monofluorenylphosphine oxide-based photopolymerization initiator, and titanium oxide. More specifically, the reflective sheet of the present invention is characterized by containing 40 to 80 parts by mass of titanium oxide with respect to 100 parts by mass of the above cured product. [Effect of the Invention] One of the effects of the present invention is to provide a curable resin composition which is excellent in resolution even when a large amount of titanium oxide is contained, and which can form a high-hardening material at a high reflectance, and Reflective sheet of the resin composition. The other effect of the present invention is to provide an excellent resolution even when a large amount of titanium oxide is contained, and it is possible to form a high-hardness cured product at a high reflectance and further to form a hard-to-adhesive thermoplasticity. A curable resin composition excellent in adhesion of a base material' and a resin sheet used for a reflective sheet in a difficult-to-adhere thermoplastic substrate. In addition, when the cured product of the curable resin composition is required to have heat resistance, it is excellent in resolution even when a large amount of titanium oxide is contained, and 201016777 can obtain hardening with high reflectance, high definition, and excellent heat resistance. A curable resin composition of the material, and a reflective sheet obtained by using the resin composition. More specifically, it is possible to provide a cured product which is excellent in resolvability even when a large amount of titanium oxide is contained, and which is excellent in high reflectance, high definition, and heat resistance, and can be obtained for use in a flexible substrate. A curable resin composition of a cured product, and a reflective sheet of the resin composition used in the flexible substrate. [Embodiment] Hereinafter, the present invention will be described in detail. The curable resin composition of the present invention contains a resin containing an ethylenically unsaturated group and a carboxyl group in a molecule, a bis-indenylphosphine oxide-based photopolymerization initiator, a monofluorenylphosphine oxide-based photopolymerization initiator, titanium oxide, and Organic solvents. Further, the curable resin composition of the present invention contains urethane acrylate in addition to these. Further, the curable resin composition of the present invention contains an epoxy compound and an antioxidant in addition to the above-mentioned hard resin composition. More specifically, the curable resin composition of the present invention contains an epoxy compound and an antioxidant and a urethane acrylate. Further, the following coating film means a coating film formed using the curable resin composition of the present invention. Further, the term "hardened material" means that the curable resin composition of the present invention is cured by photohardening or photohardening and thermosetting (components of the composition) 201016777 [Resin containing an ethylenically unsaturated group and a carboxyl group in one molecule A resin containing an ethylenically unsaturated group and a carboxyl group in one molecule (hereinafter referred to as "photocurable resin") is a photo-curable ethylenically unsaturated group in one molecule and can be used to image a weakly alkaline aqueous solution. The carboxyl resin can be used. Further, as the photocurable resin, the resins (which may be either an oligomer or a polymer) exemplified in the following (1) to (3) are preferably used, but are not limited thereto. (1) A resin containing a photosensitive carboxyl group obtained by reacting a compound having an oxirane ring and an ethylenically unsaturated group in one molecule with a carboxyl group-containing (meth)acrylic copolymer resin. (2) For a copolymer of a compound having one epoxy group and one unsaturated double bond in one molecule and a compound having an unsaturated double bond, reacting an unsaturated monocarboxylic acid to react with a secondary hydroxyl group formed by the reaction A resin containing a photosensitive carboxyl group obtained by a saturated or unsaturated polybasic acid anhydride. (3) After reacting a saturated or unsaturated polybasic anhydride with a hydroxyl group-containing polymer, the photosensitive material obtained by reacting a carboxyl group formed by the reaction with a compound having an epoxy group and an unsaturated double bond in one molecule A resin of a hydroxyl group and a carboxyl group. Among these, in the carboxyl group-containing resin of (1), it is preferred to use a (meth)acrylic copolymer resin containing a carboxyl group and a compound having an oxirane ring and an ethylenically unsaturated group in one molecule. The obtained copolymerization resin which has a carboxyl group is used as a photocurable resin. The (meth)acrylic copolymer resin containing a carboxyl group is obtained by copolymerizing a (meth) acrylate and a compound having one unsaturated group and one or more carboxyl groups -13 to 201016777 in one molecule. As the (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, ( (Meth)acrylic acid alkyl esters such as methyl hexyl acrylate, 2, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone modified a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate or ethoxydiethylene glycol (meth)acrylate , diol modification of _(meth)acrylic acid isooctyloxydiethylene glycol ester, (meth)acrylic acid methoxytriethylene glycol ester, (meth)acrylic acid methoxypolyethylene glycol ester (meth) acrylates and the like. These may be used alone or in combination. Further, in the present specification, the term "(meth) acrylate" is a generic term for acrylate and methacrylate, and the same applies to other similar expressions. Further, a compound having one unsaturated group and one or more carboxyl groups in one molecule is exemplified by a modified unsaturated monocarboxylic acid ((meth)acrylic acid) which is extended by a β chain between acrylic acid, methacrylic acid, an unsaturated group and a carboxylic acid. Β-carboxyethyl ester, 2-propenyloxyethyl succinate, 2-propenyloxyethyl hexahydrophthalate, an unsaturated monocarboxylic acid having an ester bond modified by a lactone, or the like A compound having a plurality of carboxyl groups in a molecule such as a modified unsaturated monocarboxylic acid of an ether bond or a maleic acid. These may be used singly or in combination of a plurality of compounds. A compound having an oxirane ring and an ethylenically unsaturated group in one molecule is preferably a compound formed from an aliphatic monomer. In particular, when a compound produced from a polymerizable monomer of the aliphatic group -14 - 201016777 is used, it is preferable to suppress deterioration of the cured product due to light caused by the aromatic ring contained in the photocurable resin. Examples of the compound formed from the aliphatic monomer are glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethylaminoacrylate, ( Methyl methacrylate acrylate 3,4-epoxycyclohexyl methyl ester or the like. The compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be used singly or in combination of plural kinds. The acid value of the photocurable resin is preferably in the range of 50 to 200 mgKOH/g. When the acid value of the photocurable resin is less than 50 mgKOH/g, it is difficult to remove the unexposed portion of the coating film with a weakly alkaline aqueous solution during development. When the acid value of the photohardenable resin exceeds 200 mgKOH/g, problems such as water resistance of the cured product and deterioration of electrical properties may occur. ® Further, the photocurable resin preferably has a weight average molecular weight of from 5,000 to 10,000,000. When the weight average molecular weight of the photohardenable resin is less than 5,000, the dryness of the touch coating of the present coating film tends to be remarkably deteriorated. When the weight average molecular weight of the photocurable resin exceeds 100,000, the development of the coating film of the present invention and the storage stability of the curable resin composition of the present invention are remarkably deteriorated. [Doubly-based phosphine oxide-based photopolymerization initiator] The bis-indenylphosphine oxide-based photopolymerization initiator (hereinafter referred to as "BAPO" -15-201016777) is exemplified by bis-(2,6-dichlorobenzamide). Phenyl oxide can be 2,6·dichlorobenzhydryl)-2,5-dimethylphenyl oxidized scale, bischlorobenzino)-4-propylphenylphosphine oxide, bis-( 2,6·diyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzamide oxidized scale, bis-(2,6-dimethoxybenzylidene)-2 , 4,4-triphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,5-phosphine oxide, bis-(2,4,6-trimethylbenzylidene Benzyloxy 2,5,6-trimethylbenzhydryl)-2,4,4-trimethylpentyl oxidization and the like bis(2,4,6-trimethylbenzylidene) Phenyl oxidized scale (manufactured by this product, trade name; Irgacure 819) is easy to take _ [monodecyl phosphine oxide photopolymerization initiator] monothiol phosphine oxide photopolymerization initiator (hereinafter referred to as f) Is 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, oxybenzylidene diphenylphosphine oxide, 2,6-dichlorobenzylated phosphine, 2,4,6 - Methyltrimethylbenzhydrylphenylphosphonate, 2-mercaptoyl Diphenyl phosphine oxide, phosphine oxide, pivaloyl acyl phenylphosphonic acid isopropyl group 2,4,6-trimethyl benzoyl (manufactured by Ciba • day, trade name; DAROCUR TPO) easily available. In the present invention, by using BAPO and MAPO, even if a large amount of the titanium oxide resin composition forms a coating film having a high reflectance, the amount of light can be hardened by the coating film. According to this, even if the product and the coating film thereof are used, a high-definition pattern excellent in resolution can be formed. Therefore, by changing the blending ratio of BAPO and MAPO!, bis((2,6-dichlorobenzidine) Phenylmethylpentylmethylphenylphosphine, (phosphine, etc.. Ciba·Day MAPO) 2,6-dimethyldiphenyloxymethylbenzene, which is used in this (share) The photosensitive resin composition of the present invention can be finely adjusted by the use of a resin composition having a small amount of the same, that is, in the cross-sectional shape of the pattern formed on the substrate, the deep side hardenability of the surface side of the substrate is insufficient. When the undercut is prone to occur, the blending ratio of BAPO can be increased. Moreover, since the surface hardenability of the coating film is insufficient, the surface ratio of the pattern is deteriorated after development, and the ratio of MAPO is increased. The ratio of BAPO to MAPO is 90 to 10 to 1 to 99 by mass ratio, preferably 80 to 20 to 2 to 98. Outside the range of the ratio, the effect of using BAPO and MAPO is less. The light sensitivity required to harden the coating film of this film cannot be obtained, so that a high-definition pattern cannot be formed. The total amount of BAPO and MAPO is preferably from 1 to 30 parts by mass, more preferably from 2 to 25 parts by mass, per part by mass of the photocurable resin. When the total amount of BAPO and MAPO is relative to When the amount of the photocurable resin is less than 1 part by mass, the photocurability of the coating film of the present film is lowered, and it is difficult to form a pattern after exposure and development. Further, when the total amount of BAPO and MAPO is adjusted, When the amount of the photocurable oxime resin is more than 30 parts by mass based on 1 part by mass, the coloring of the coating film derived from the photopolymerization initiator becomes large, which is disadvantageous because of high cost. [Titanium oxide] Any one of anatase type titanium oxide and rutile type titanium oxide is used, and particularly rutile type titanium oxide is preferred. Anatase type titanium oxide is compared with rutile type titanium oxide in the ultraviolet region and the visible light region. The reflectance near the junction is high, so the whiteness and reflectivity are preferred as white pigments. However, since anatase titanium oxide has photocatalyst activity -17- 201016777 TIPAQUE R-680 TIPAQUE R-850 TIPAQUE CR-80 TIPAQUE CR-95 TIP AQUE CR-63 TIPAQUE CR-85 is a property of the resin of the curable resin composition due to its photoactivity. In contrast, rutile-type titanium oxide is slightly inferior in whiteness to anatase-type titanium oxide. Since it is hardly photoactive, deterioration of the resin of the curable resin composition of the present invention can be suppressed, and a stable cured product can be obtained. As for the rutile type titanium oxide, TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R- can be used. 930, TIPAQUE R-5 50 ' TIPAQUE R-63 0, TIPAQUE R-68 0, TIPAQUE R-670 TIPAQUE R-780 TIPAQUE CR-57 TIPAQUE CR-93 TIPAQUE CR-60 TIPAQUE CR-58

TIPAQUE R-670 TIPAQUE CR-50 TIPAQUE CR-90 TIPAQUE CR-97 TIPAQUE CR-67 TIPAQUE UT771 (石原產業（股）製造），TI-PURE R-100、TI-PURE R-101、TI-PURE R-102、TI-PURE R-103TIPAQUE R-670 TIPAQUE CR-50 TIPAQUE CR-90 TIPAQUE CR-97 TIPAQUE CR-67 TIPAQUE UT771 (made by Ishihara Sangyo Co., Ltd.), TI-PURE R-100, TI-PURE R-101, TI-PURE R- 102, TI-PURE R-103

、TI-PURE R-104、TI-PURE R-105、TI-PURE R-108、TI· PURE R-900、TI-PURE R-902、TI-PURE R-960、TI-PURE R-706、TI-PURE R-93 1 (杜邦（股）製造）、TITONR-25 ' ΤΙΤΟΝ R-21 ' ΤΙΤΟΝ R-32 ' ΤΙΤΟΝ R-7E ' ΤΙΤΟΝ R-5Ν、ΤΙΤΟΝ R-61N、ΤΙΤΟΝ R-62N、ΤΙΤΟΝ R-42、ΤΙΤΟΝ R-45M、ΤΙΤΟΝ R-44、ΤΙΤΟΝ R-49S、ΤΙΤΟΝ GTR-100、 ΤΙΤΟΝ GTR-3 00、ΤΙΤΟΝ D-918、ΤΙΤΟΝ TCR-29、ΤΙΤΟΝ TCR-52、TITONFTR-7 00(堪化學工業（股）製造）等。 又，銳鈦礦型氧化鈦舉例爲 ΤΑ-100、ΤΑ-200、ΤΑ-300、ΤΑ-400、ΤΑ-500 (富士 鈦工業（股）製造）， -18- 201016777 TIPAQUE A-100、TIPAQUE A-22 0、TIP AQUE W-10 (石 原產業（股）製造），TITANIX JA-1、TITANIX JA-3、 TITANIX JA-4、TITANIX JA-5 ( TAYCA (股）製造）， KRONOS KA-10、KRONOS KA-15、KRONOS KA-20、 KRONOS KA-30(鈦工業（股）製造），A-100、A-100、 A-100、SA-1、SA-1L (堺化學工業（股）製造）。 氧化鈦之調配量相對於100質量份之本發明之硬化性 # 組成物除有機溶劑以外之成分（包含氧化鈦）爲40~80質 量份，該樹脂組成物中調配超過上述調配量之範圍之氧化 鈦時，亦無法大幅的提昇該樹脂組成物、本件塗膜及硬化 物之反射率，再者於此情況，該樹脂組成物之光硬化性下 降，硬化深度下降故而不佳。另一方面，氧化鈦之調配量 相對於本發明之硬化性組成物除有機溶劑以外之成分未達 40質量份時，由於該樹脂組成物之遮蔽力變小，難以獲 得高反射率之硬化物而不佳。 ❹ [有機溶劑] 有機溶劑爲使本發明之硬化性樹脂組成物成爲容易塗 佈於基材等之狀態，以及爲了將含有有機溶劑之該樹脂組 成物塗佈於基材等之上，經乾燥形成塗膜而使用。有機溶 劑舉例爲甲基乙基酮、環己酮等酮類；甲苯、二甲苯、四 甲基苯等芳香族烴類；甲基溶纖素、乙基溶纖素、丁基溶 纖素、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二乙 二醇單乙基醚、二丙二醇單乙基醚、三乙二醇單乙基醚等 -19- 201016777 二醇醚類；乙酸乙酯、乙酸丁酯、溶纖素乙酸酯、二乙二 醇單乙基醚乙酸酯及上述二醇醚類之酯化物等之酯類；乙 醇、丙醇、乙二醇、丙二醇等醇類；辛烷、癸烷等脂肪族 烴類；石油醚、石油腦、氫化石油腦、溶劑油（Solvent naphtha)等石油系溶劑等。 有機溶劑可單獨或以複數種之混合物使用。有機溶劑 之調配量相對於1〇〇質量份之光硬化性樹脂較好爲 2 0〜3 0 0質量份。 [胺基甲酸酯丙烯酸酯] 本發明之硬化性樹脂組成物可調配胺基甲酸酯丙烯酸 酯。胺基甲酸酯丙烯酸酯主要係由於下列目的而調配。其 一爲可將本發明之硬化性樹脂組成物利用於難接著性熱可 塑性基材中，以提高硬化物對該基材之密著性。接著另一 爲賦予硬化物耐熱性之目的而於本發明之硬化性樹脂組成 物中調配環氧化合物及抗氧化劑時，可於將該樹脂組成物 @ 利用於可撓性基材中以提高硬化物之可撓性，且可使硬化 物對於基材曲度具有追隨性。 至於該胺基甲酸酯丙烯酸酯可使用CN929、CN940、 CN944B85 、 CN959 、 CN961H81 、 CN962 、 CN963A80 、 CN963B80、CN963E75、CN963E80、CN963J75、CN964、 CN964A85、CN964E75 ' CN965、CN965A80、CN966A80 、CN966B85 、 CN966H90 、 CN966J75 、 CN966R60 、 CN968 、 CN980 、 CN981 、 CN981A75 、 CN981B88 、 -20- 201016777 CN982A75 、 CN982B88 、 CN982E75 、 CN982P90 、 CN983 、CN985B88 、 CN989 ' CN991 、 CN996 、 CN9001 、 CN9002 、 CN9004 、 CN9005 、 CN9006 、 CN9007 、 CN9008 、CN9009 、 CN9010、 CN9011 、 CN9014 、 CN9178、 CN9788 ' CN9893 ( Sartomer 公司製造）、M-1100、M-1200、M-1210、M- 1 600 (東亞合成（股）製造）、U-2PPA、U-4HA、U-6HA、UA-100H、U-6LPA、U-15HA、 參 UA-32P、U-324A、UA-NDP、U-4H、U-6H、U-108A、U-200AX、UA-511、U-412A、UA-4100、UA-4200、UA-4400、HU-340P ' UA-2235PE、UA-345 8P、UA-160TM、 UA-6100、UA-6200U-108、U A-4 0 0 0、U A -1 2 2 P、U A - 5 20 1 、UA-5 12、UA-63 73 P (新中村化学工業（股）製造）等 〇 胺基甲酸酯丙烯酸酯之調配量相對於100質量份之光 硬化性樹脂較好爲10〜100質量份，更好爲20~80質量份 • 。胺基甲酸酯丙烯酸酯之調配量相對於100質量份之光硬 化性樹脂超過100質量份時，硬化物之物性下降故而不佳 。另一方面，胺基甲酸酯丙烯酸酯之調配量相對於100質 量份之光硬化性樹脂未達10質量份時，關於硬化物無法 獲得充分之密著性或可撓性故而不佳。 [環氧化合物] 硬化物要求耐熱性時，爲賦予硬化物耐熱性之目的， 可於本發明之硬化性樹脂組成物中調配環氧化合物。至於 -21 - 201016777 環氧化合物舉例爲雙酚S型環氧樹脂、苯二甲酸二縮水甘 油酯樹脂、三縮水甘油異尿氰酸酯（日產化學工業（股） 製造之TEPIC-H (具有對於S-三嗪環骨架面之3個環氧 基以同一方向鍵結之構造之/5體），或TEPIC (泠體與具 有對於S -三嗪環骨架面之一個環氧基與其他兩個環氧基 ’ 以不同方向鍵結之構造之α體之混合物）等）等之雜環式 環氧樹脂、雙二甲酚型環氧樹脂、聯苯型環氧樹脂、四縮 水甘油基二甲酚基乙烷樹脂等之於稀釋劑中難溶性之環氧 _ 樹脂，或雙酚Α型樹脂、氫化雙酚Α型樹脂、雙酚F型 樹脂、溴化雙酚A型環氧樹脂、酚類酚醛清漆型或甲酚 酚醛清漆型環氧樹脂、脂環式環氧樹脂、雙酚A之酚醛 清漆型環氧樹脂、螯合型環氧樹脂、乙二醛型環氧樹脂、, TI-PURE R-104, TI-PURE R-105, TI-PURE R-108, TI·PURE R-900, TI-PURE R-902, TI-PURE R-960, TI-PURE R-706, TI-PURE R-93 1 (manufactured by DuPont), TITONR-25 'ΤΙΤΟΝ R-21 ' ΤΙΤΟΝ R-32 ' ΤΙΤΟΝ R-7E ' ΤΙΤΟΝ R-5Ν, ΤΙΤΟΝ R-61N, ΤΙΤΟΝ R-62N, ΤΙΤΟΝ R-42, R-45M, R-44, R-49S, GTR-100, GTR-3 00, D-918, TCR-29, TCR-52, TITONFTR-7 00 ( Chemical industry (stock) manufacturing) and so on. Further, anatase type titanium oxides are exemplified by ΤΑ-100, ΤΑ-200, ΤΑ-300, ΤΑ-400, ΤΑ-500 (manufactured by Fuji Titanium Industries, Ltd.), -18-201016777 TIPAQUE A-100, TIPAQUE A -22 0, TIP AQUE W-10 (made by Ishihara Industry Co., Ltd.), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5 (made by TAYCA), KRONOS KA-10, KRONOS KA-15, KRONOS KA-20, KRONOS KA-30 (manufactured by Titanium Industry Co., Ltd.), A-100, A-100, A-100, SA-1, SA-1L (Manufactured by 堺Chemical Industry Co., Ltd.) ). The amount of the titanium oxide is 40 to 80 parts by mass based on 100 parts by mass of the curable composition of the present invention excluding the organic solvent (including titanium oxide), and the resin composition is blended in a range exceeding the above-mentioned blending amount. In the case of titanium oxide, the reflectance of the resin composition, the coating film of the article, and the cured product cannot be greatly improved. Further, in this case, the photocurability of the resin composition is lowered, and the hardening depth is lowered, which is not preferable. On the other hand, when the amount of the titanium oxide is less than 40 parts by mass of the component other than the organic solvent of the curable composition of the present invention, it is difficult to obtain a cured product having high reflectance because the shielding force of the resin composition is small. Not good.有机 [Organic solvent] The organic solvent is a state in which the curable resin composition of the present invention is easily applied to a substrate or the like, and the resin composition containing the organic solvent is applied to a substrate or the like, and dried. A coating film is formed and used. Examples of the organic solvent are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl group. Carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. -19-201016777 glycol ethers; Esters of ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate, and esters of the above glycol ethers; ethanol, propanol, ethylene glycol, propylene glycol Such as alcohols; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent oil (Solvent naphtha). The organic solvent may be used singly or in a mixture of plural kinds. The amount of the organic solvent to be added is preferably from 20 to 300 parts by mass based on 1 part by mass of the photocurable resin. [urethane acrylate] The curable resin composition of the present invention can be formulated with a urethane acrylate. The urethane acrylate is mainly formulated for the following purposes. One of them is that the curable resin composition of the present invention can be used in a difficult-to-adhesive thermoplastic substrate to improve the adhesion of the cured product to the substrate. When the epoxy compound and the antioxidant are blended in the curable resin composition of the present invention for the purpose of imparting heat resistance to the cured product, the resin composition @ can be used in a flexible substrate to improve hardening. The flexibility of the object and the ability of the cured product to follow the curvature of the substrate. As the urethane acrylate, CN929, CN940, CN944B85, CN959, CN961H81, CN962, CN963A80, CN963B80, CN963E75, CN963E80, CN963J75, CN964, CN964A85, CN964E75 'CN965, CN965A80, CN966A80, CN966B85, CN966H90, CN966J75 can be used. CN966R60, CN968, CN980, CN981, CN981A75, CN981B88, -20- 201016777 CN982A75, CN982B88, CN982E75, CN982P90, CN983, CN985B88, CN989 'CN991, CN996, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009 , CN9010, CN9011, CN9014, CN9178, CN9788 'CN9893 (manufactured by Sartomer Co., Ltd.), M-1100, M-1200, M-1210, M-1600 (manufactured by East Asia Synthetic Co., Ltd.), U-2PPA, U-4HA , U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A, UA-NDP, U-4H, U-6H, U-108A, U-200AX, UA-511, U-412A, UA-4100, UA-4200, UA-4400, HU-340P 'UA-2235PE, UA-345 8P, UA-160TM, UA-6100, UA-6200U-108, U A-4 0 0 0 , UA -1 2 2 P, UA - 5 20 1 , UA-5 12, UA-63 73 P ( The amount of the urethane acrylate to be used is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass per 100 parts by mass of the photocurable resin. When the amount of the urethane acrylate is more than 100 parts by mass based on 100 parts by mass of the photohardenable resin, the physical properties of the cured product are deteriorated, which is not preferable. On the other hand, when the amount of the urethane acrylate is less than 10 parts by mass based on 100 parts by mass of the photocurable resin, it is not preferable that the cured product cannot obtain sufficient adhesion or flexibility. [Epoxy compound] When the cured product is required to have heat resistance, the epoxy compound can be formulated in the curable resin composition of the present invention for the purpose of imparting heat resistance to the cured product. As for the -21 - 201016777 epoxy compound, bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate (TEPIC-H manufactured by Nissan Chemical Industries Co., Ltd.) a structure in which the three epoxy groups of the S-triazine ring skeleton are bonded in the same direction, or TEPIC (the steroid has an epoxy group with respect to the S - triazine ring skeleton surface and the other two a heterocyclic epoxy resin, a bisxylenol type epoxy resin, a biphenyl type epoxy resin, a tetraglycidyl dimethyl group, etc., which is a mixture of epoxy groups which are bonded in different directions, etc.) A phenolic ethane resin such as a poorly soluble epoxy resin in a diluent, or a bisphenol oxime resin, a hydrogenated bisphenol oxime resin, a bisphenol F resin, a brominated bisphenol A epoxy resin, or a phenol Novolac type or cresol novolac type epoxy resin, alicyclic epoxy resin, bisphenol A novolak type epoxy resin, chelating epoxy resin, glyoxal type epoxy resin,

含有胺基之環氧樹脂、橡膠改質之環氧樹脂、二環戊二烯 酚型環氧樹脂、矽氧改質之環氧樹脂、ε-己內酯改質之 環氧樹脂等之於稀釋劑中可溶性之環氧樹脂等。該等環氧 樹脂可單獨使用或組合複數種使用。 G 本發明之硬化性樹脂組成物中調配環氧化合物時，其 調配量相對於100質量份之光硬化性樹脂較好爲5~70質 量份，更好爲5-60質量份。環氧化合物之調配量相對於 1 〇〇質量份之光硬化性樹脂超過質量份時，本件塗膜 於顯像液中之未曝光部份之溶解性下降，容易產生顯像殘 留而難以形成圖型。另一方面，環氧化合物之調配量相對 於100質量份之光硬化性樹脂未達5質量份時，由於光硬 化性樹脂之羧基以未反應狀態殘存於硬化物中’難以充分 -22- 201016777 獲得硬化物之電特性、焊錫耐熱性、耐藥品性。 又，當本發明之硬化性樹脂組成物中調配環氧化合物 時，光硬化性樹脂之羧基與環氧化合物之環氧基係藉由開 環聚合而反應。該情況下，若亦於該樹脂組成物中添加對 於有機溶劑或該樹脂組成物之其他物質易溶性之環氧樹脂 ，則藉由形成本件塗膜之際之乾燥熱，易使上述羧基與環 氧基進行交聯。據此，當欲抑制該交聯反應而加長乾燥時 〇 間時，可單獨調配對有機溶劑或該樹脂組成物之其他物質 難溶性之環氧樹脂，或較好與易溶性環氧樹脂一起調配。 [抗氧化劑] 於本發明之硬化性樹脂組成物中調配環氧化合物時， 爲了減少硬化物因熱劣化而變色之目的可於該樹脂組成物 中調配抗氧化劑。至於抗氧化劑較好爲受阻酚系化合物， 但並不限於此。受阻酚系化合物舉例爲NOCRAC 200、 ❹ NOCRAC M-17、NOCRAC SP、NOCRAC SP-N、NOCRAC NS-5、NOCRAC NS-6、NOCRAC NS-30、NOCRAC 300、 NOCRAC NS-7、NOCRAC DAH (以上均爲大內新興化學 工業（股）製造）；MARK AO-30、MARK AO-40、MARK AO-50、MARK AO-60、MARK AO-616、MARK AO-635、 MARK AO-658、MARK AO-15、MARK AO-18 ' MARK 328 、MARK AO-37 (以上均爲ADEKA化學（股）製造）； IRGONAX 245 、 IRGONAX 259 、 IRGONAX 565 、 IRGONAX 1010 、 IRGONAX 1 035 、 IRGONAX 1 076 、 -23- 201016777 IRGONAX 1081、IRGONAX 1098、IRGONAX 1222、 IRGONAX 1 330、IRGONAX 1 4 2 5 W L (以上均爲汽巴·曰 本（股）製造）等。 於本發明之硬化性樹脂組成物中調配抗氧化劑時，其 調配量相對於100質量份之光硬化性樹脂較好爲0.4〜25 質量份，更好爲0.8〜15質量份。抗氧化劑之調配量相對 於100質量份之光硬化性樹脂未達0.4質量份時，硬化物 因熱劣化而變色之防止效果減少。又抗氧化劑之調配量相 對於100質量份之光硬化性樹脂超過25質量份時，本件 塗膜之顯像性下降，使圖型化有缺陷。 又，爲了改善氧化鈦之分散性、沉降性，可於本發明 之硬化性樹脂組成物中調配分散劑。至於分散劑舉例爲 ANTI-TERRA-U、ANTI-TERRA-U100、ANTI-TERRA-2 04 ' ANTI-TERRA-205 ' DI S P ERB YK -1 0 1、DI S P ERB Y K -1 0 2 、DISPERBYK-1 03、DISPERB YK-1 06、DI SPERB YK-1 0 8 、DISPERBYK-1 09 ' DISPERB YK-1 1 0、DISPERBYK-1 1 1 、DISPERBYK-1 12 ' DISPERBYK-1 1 6 ' DI SPERB YK-1 3 0 、DISPERBYK-140、DISPERB YK-1 42、DI SPERB YK-1 45 、DISPERBYK-1 6 1、DISPERB YK-1 62、DISPERB YK-1 63 、DISPERB YK-1 64 ' DISPERB YK-1 66、DISPERBYK-167 、DISPERBYK-168、DISPERB YK-1 70、DISPERB YK-1 7 1 、DISPERBYK-1 74 ' DISPERB YK-1 80、DISPERBYK-182 、DISPERBYK-183、DI S P ERB YK-1 8 5、DISPERB YK-1 84 、DISPERBYK-2000 、 DISPERB YK-200 1 、 DISPERB YK- -24- 201016777 2009 、 DISPERB YK-2020 、 DI S P E RB YK - 2 0 2 5 、 DISPERB YK-20 50 ' DISPERB YK-2070、DISPERB YK-2096 、DISPERB YK-2150、 BYK-P104、 BYK-P104S、BYK-P105、BYK-9076、BYK-9077、BYK-220S ( BYK 日本( 股）製）、DYSPRON 2150、 DYSPRON 1210、 DYSPRON KS-860 、 DYSPRON KS-873N 、 DYSPRON 7004 、 DYSPRON 1 83 0、DYSPRON 1 860、DYSPRON 1 85 0、 φ DYSPRON DA-400N、DYSPRON PW-36、DYSPRON DA- 703 -50 (楠本化成（股）製）、FLOWLEN G-450、 FLOWLEN G-600、FLOWLEN G-820、FLOWLEN G-700 > FLOWLEN DOPA-44、FLOWLEN D Ο P A -1 7 (共榮社化學 (股）製）等。 爲達成上述目的，分散劑調配量相對於100質量份之 氧化鈦爲0.1〜10質量份，較好爲0.5~5質量份。 再者，本發明之硬化性樹脂組成物可調配受阻胺系光 © 安定劑以減少光劣化。 該等受阻胺系光安定劑舉例爲 TINUVIN 622LD、 TINUVIN 144 ； CHIMASSORB 944LD 、 CHIMASSORB 119FL (以上均爲汽巴•日本（股）製造）；MARK LA- 57 ' LA-62、LA-67、LA-63、LA-68 (以上均爲 ADEKA 氣體化學（股）製造）：THANOR LS-770、LS-765、LS-292 、 LS-2626 、 LS-1114 、 LS-744 (以上均爲三共Amine-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenol epoxy resin, oxime-modified epoxy resin, ε-caprolactone modified epoxy resin, etc. Soluble epoxy resin in the diluent. These epoxy resins may be used singly or in combination of plural kinds. When the epoxy compound is blended in the curable resin composition of the present invention, the amount thereof is preferably 5 to 70 parts by mass, more preferably 5 to 60 parts by mass, per 100 parts by mass of the photocurable resin. When the amount of the epoxy compound is more than 1 part by mass based on 1 part by mass of the photocurable resin, the solubility of the uncoated portion of the coating film in the developing solution is lowered, and development of the image is liable to occur, making it difficult to form a pattern. type. On the other hand, when the amount of the epoxy compound is less than 5 parts by mass based on 100 parts by mass of the photocurable resin, the carboxyl group of the photocurable resin remains in the hardened state in an unreacted state. Obtain the electrical properties of the cured product, solder heat resistance, and chemical resistance. Further, when the epoxy compound is blended in the curable resin composition of the present invention, the carboxyl group of the photocurable resin and the epoxy group of the epoxy compound are reacted by ring-opening polymerization. In this case, if an epoxy resin which is easily soluble in an organic solvent or other substance of the resin composition is added to the resin composition, the carboxyl group and the ring are easily formed by the drying heat at the time of forming the coating film of the present invention. The oxy group is crosslinked. Accordingly, when it is desired to suppress the crosslinking reaction and lengthen the drying time during the drying, the epoxy resin which is insoluble with the organic solvent or other substances of the resin composition may be separately adjusted, or preferably blended with the easily soluble epoxy resin. . [Antioxidant] When an epoxy compound is blended in the curable resin composition of the present invention, an antioxidant may be formulated in the resin composition for the purpose of reducing discoloration of the cured product due to thermal deterioration. The antioxidant is preferably a hindered phenol compound, but is not limited thereto. Examples of hindered phenolic compounds are NOCRAC 200, ❹ NOCRAC M-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC 300, NOCRAC NS-7, NOCRAC DAH (above) All are manufactured by Ou Nei Xin Chemical Industry Co., Ltd.); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO -15, MARK AO-18 ' MARK 328 , MARK AO-37 (all manufactured by ADEKA Chemical Co., Ltd.); IRGONAX 245 , IRGONAX 259 , IRGONAX 565 , IRGONAX 1010 , IRGONAX 1 035 , IRGONAX 1 076 , -23- 201016777 IRGONAX 1081, IRGONAX 1098, IRGONAX 1222, IRGONAX 1 330, IRGONAX 1 4 2 5 WL (all of which are manufactured by Ciba and Sakamoto). When the antioxidant is formulated in the curable resin composition of the present invention, the amount thereof is preferably 0.4 to 25 parts by mass, more preferably 0.8 to 15 parts by mass, per 100 parts by mass of the photocurable resin. When the amount of the antioxidant is less than 0.4 part by mass based on 100 parts by mass of the photocurable resin, the effect of preventing discoloration of the cured product due to thermal deterioration is reduced. When the amount of the antioxidant is more than 25 parts by mass based on 100 parts by mass of the photocurable resin, the developability of the coating film of the present material is lowered to cause patterning defects. Further, in order to improve the dispersibility and sedimentation property of titanium oxide, a dispersant may be formulated in the curable resin composition of the present invention. As the dispersing agent, for example, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-2 04 'ANTI-TERRA-205 'DI SP ERB YK -1 0 1, DI SP ERB YK -1 0 2 , DISPERBYK- 1 03, DISPERB YK-1 06, DI SPERB YK-1 0 8 , DISPERBYK-1 09 ' DISPERB YK-1 1 0, DISPERBYK-1 1 1 , DISPERBYK-1 12 ' DISPERBYK-1 1 6 ' DI SPERB YK- 1 3 0 , DISPERBYK-140, DISPERB YK-1 42, DI SPERB YK-1 45, DISPERBYK-1 6 1, DISPERB YK-1 62, DISPERB YK-1 63, DISPERB YK-1 64 ' DISPERB YK-1 66 DISPERBYK-167, DISPERBYK-168, DISPERB YK-1 70, DISPERB YK-1 7 1 , DISPERBYK-1 74 ' DISPERB YK-1 80, DISPERBYK-182, DISPERBYK-183, DI SP ERB YK-1 8 5. DISPERB YK-1 84 , DISPERBYK-2000 , DISPERB YK-200 1 , DISPERB YK- -24- 201016777 2009 , DISPERB YK-2020 , DI SPE RB YK - 2 0 2 5 , DISPERB YK-20 50 ' DISPERB YK-2070 DISPERB YK-2096, DISPERB YK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (BYK Japan), DYSPRON 2150, DYSPRON 1210, DYSPRON KS-860, DYSPRON KS-873N, D YSPRON 7004, DYSPRON 1 83 0, DYSPRON 1 860, DYSPRON 1 85 0, φ DYSPRON DA-400N, DYSPRON PW-36, DYSPRON DA- 703 -50 (made by Nanben Chemical Co., Ltd.), FLOWLEN G-450, FLOWLEN G -600, FLOWLEN G-820, FLOWLEN G-700 > FLOWLEN DOPA-44, FLOWLEN D Ο PA -1 7 (Kyoeisha Chemical Co., Ltd.). In order to achieve the above object, the amount of the dispersant is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the titanium oxide. Further, the curable resin composition of the present invention can be formulated with a hindered amine light source to stabilize light to reduce photodegradation. Examples of such hindered amine light stabilizers are TINUVIN 622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba and Japan); MARK LA-57 'LA-62, LA-67, LA- 63, LA-68 (all of which are manufactured by ADEKA Gas Chemical Co., Ltd.): THANOR LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are three

Lifetech (股）製造）等。 受阻胺系光安定劑之調配量相對於100質量份之光硬 -25- 201016777 化性樹脂以〇 · 1 ~ 1 〇質量份較佳。 本發明之硬化性樹脂組成物可額外調配噻噸酮系光聚 合起始劑作爲光聚合起始劑。據此’可對本發明之硬化性 樹脂組成物提高對曝光時之光之感度。噻噸酮系光聚合起 始劑舉例爲噻噸酮、2 -乙基噻噸酮、2 -異丙基噻噸酮'2-氯噻噸酮、2,4 -二甲基噻噸酮、2,4 -二乙基噻噸酮、2，4-二異丙基噻噸酮等。 又，本發明之硬化性樹脂組成物中可調配噻噸酮系等 0 之光聚合增感劑、聚合抑制劑、增黏劑、消泡劑、勻流劑 、偶合劑、難燃助劑等。 (組成物之使用） 以下對使用該樹脂組成物製造之反射薄片作爲本發明 之硬化性樹脂組成物之使用例加以說明。 (使用例1 ) . 本發明硬化性樹脂組成物中，含有一分子內包含乙烯 性不飽和基與羧基之樹脂、雙醯基氧化膦系光聚合起始劑 、單醯基氧化膦系光聚合起始劑、氧化鈦、有機溶劑及胺 基甲酸酯丙烯酸酯之硬化性樹脂組成物（以下稱爲「組成 物1」）調整成適合於塗佈方法之黏度。 接著’以網版印刷法、簾塗法、噴塗法或輥塗法等方 法將經黏度調整之組成物1塗佈於聚酯基材等難接著性熱 可塑性基材上。隨後，在70〜9(TC之溫度下使塗佈於基材 -26- 201016777 上之組成物1中所含有機溶劑揮發乾燥，形成塗膜（以下 稱爲「塗膜1」）。 隨後，通過光罩以選擇之活性能量線對塗膜1進行曝 光。接著，可使用鹼性水溶液使曝光後之塗膜1之未曝光 部份顯像，形成電路圖型，以製造本發明之反射薄片。 該情況下，難接著性熱可塑性基材舉例爲烯烴系基材 、聚醯胺系基材、聚酯系基材等。烯烴系基材舉例爲高密 φ 度聚乙烯（HDPE)、中密度聚乙烯（MDPE)、低密度聚 乙基（LDPE )、聚丙烯（PP)、環烯烴聚合物等。聚醯 胺系基材舉例爲尼龍6、尼龍1、尼龍12、尼龍66、尼龍 612、尼龍6T、尼龍610等。聚酯系基材舉例爲聚對苯二 甲酸乙二酯（PET)、聚萘酸乙二酯（PEN)、聚對苯二 甲酸甲三酯（PTT)、聚對苯二甲酸丁二酯（PBT)、聚 萘酸丁二酯（PBN )等。其他基材舉例爲聚氯化亞乙烯、 聚四氟乙烯（PTFE)、聚乙縮醛（POM)、聚苯醚（PPE β )、聚苯硫醚（PPS)等。 (使用例2) 將本發明硬化性樹脂組成物中，含有一分子內包含乙 嫌性不飽和基與羧基之樹脂、雙醯基氧化膦系光聚合起始 劑、單醯基氧化膦系光聚合起始劑、氧化鈦、有機溶劑、 胺基甲酸酯丙烯酸酯、環氧化合物及抗氧化劑之硬化性樹 脂組成物（以下稱爲「組成物2」）調整成適合於塗佈方 法之黏度。 -27- 201016777 接著，以網版印刷法、簾塗法、噴塗法、或輥塗法等 方法將經黏度調整之組成物2塗佈於可撓性基材上。隨後 ，在70~90°C之溫度下使塗佈於基材上之組成物2中所含 有機溶劑揮發乾燥，形成塗膜（以下稱爲「塗膜2」）。 隨後，通過光罩以選擇之活性能量線對塗膜2進行曝 光。接著，使用鹼性水溶液使曝光後之塗膜2之未曝光部 份顯像，形成圖型，接著，藉由在l〇〇°C~200°C之溫度使 該形成之圖型熱硬化，可製造本發明之反射薄片。。 @ 此時，作爲可撓性基材可舉例爲 APICAL AH、 APICAL NPI ( KANAKA (股）製造），ΚΑΡΤΟΝ Η、 ΚΑΡΤΟΝ V ' ΚΑΡΤΟΝ ΕΝ (東麗•杜邦（股）製造）， UBELEX 25S、UBELEX 75S (宇部興產（股）製造）等之 聚醯亞胺薄膜、銅箔、鋁箔、不鏽鋼箔、鈦箔、鎳箔等金 屬箔等。 又，作爲用以使塗膜1及塗膜2曝光之照射光源可使 用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈 Θ 、氙氣燈或金屬鹵素燈等。其他，亦可利用雷射光等做爲 活性光源。 又，作爲塗膜1及塗膜2之顯像中使用之顯像液之鹼 性水溶液通常爲〇.5~5質量％之碳酸鈉水溶液，但亦可使 用其他鹼性水溶液。其他鹼性水溶液舉例爲氫氧化鉀、氫 氧化鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等鹼性水溶 液0 -28- 201016777 實施例 以下實施例及比較例具體說明本發明，但本發明並不 受下列實施例之限制。 樹脂溶液1之合成·’ 於具備攪拌機、溫度計、回流冷卻器、滴加漏斗及氮 氣導入管之2升分離燒瓶中添加900克溶劑（二乙二醇二 Ο 甲基醚）及21.4克聚合起始劑（第三丁基過氧基2-乙基 己酸酯，日本油脂（股）製造，商品名：PERBUTYL Ο ) ，且加熱至90 °C。加熱後，於3小時內將309.9克甲基丙 烯酸、116.4克甲基丙烯酸甲酯、109.8克內酯改質之甲 基丙烯酸2-羥基乙酯（DICEL化學工業（股）製造，商 品名：BLOCKCELL FM1 )及21 ·4克聚合起始劑（雙（4-第三丁基環己基）過氧基二碳酸酯，日本油脂（股）製造 ，商品名：PEROYL TCP )滴加於上述燒瓶中。接著藉由 β 使該混合物熟成6小時，獲得含有羧基之共聚合樹脂。又 ’該等反應係在氮氣氛圍下進行。 . 接著，於該含羧基之共聚合樹脂中添加3 63.9克丙烯 酸3,4-環氧基環己基甲酯（DICEL化學（股）製造，商品 名：CYCLOMERA2 00) 、3.6克開環觸媒（二甲基苄基胺 )、1.80克聚合抑制劑（氫醌單甲基醚），且使該等加熱 至100 °C並攪拌，進行環氧基之開環加成反應。自攪拌結 束1 6小時後，自該攪拌物獲得含有53.8質量％ (不揮發 份）之固體成分之酸價爲l〇8.9mg KOH/g、重量平均分子 -29- 201016777 量25,000之不具有芳香環之含羧基樹脂之溶液。以下稱 該反應溶液爲樹脂溶液1。 [實施例（1)] 各硬化性樹脂組成物（實施例1〜3，比較例1〜6 )之 製作= 攪拌依據表1中所述調配各成分而成者，接著以3軸 輥使之分散，製備硬化性樹脂組成物（實施例1〜3，比較 例1〜6)。又，比較例1顯示氧化鈦之調配量比本發明之 規定調配量少之組成物，比較例2顯示氧化鈦之調配量比 本發明之規定調配量多之組成物，比較例3顯示僅調酉己 BAPO作爲光聚合起始劑而成之組成物，比較例4顯示僅 調配MAPO作爲光聚合起始劑而成之組成物，比較例5顯 示調配BAPO及MAP Ο以外之光聚合起始劑作爲光聚合起 始劑而成之組成物，比較例6顯示調配光聚合性單體取# 胺基甲酸酯丙烯酸酯而成之組成物。另外，表1中之數字 係表示質量份。 -30- 201016777Lifetech (manufacturing) and so on. The compounding amount of the hindered amine light stabilizer is preferably 〇1 to 1 〇 by mass based on 100 parts by mass of the optical hardener. The thioxanthone-based photopolymerization initiator may be additionally formulated as a photopolymerization initiator in the curable resin composition of the present invention. According to this, the curable resin composition of the present invention can improve the sensitivity to light at the time of exposure. Examples of the thioxanthone photopolymerization initiator are thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone '2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. Further, the curable resin composition of the present invention may be formulated with a photopolymerization sensitizer such as a thioxanthone or the like, a polymerization inhibitor, a tackifier, an antifoaming agent, a flow agent, a coupling agent, a flame retardant aid, etc. . (Use of the composition) A reflective sheet produced using the resin composition will be described below as an example of use of the curable resin composition of the present invention. (Use Example 1) The curable resin composition of the present invention contains a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule, a bis-indenylphosphine oxide-based photopolymerization initiator, and a monofluorenylphosphine oxide-based photopolymerization. The curable resin composition (hereinafter referred to as "composition 1") of the initiator, titanium oxide, organic solvent, and urethane acrylate is adjusted to a viscosity suitable for the coating method. Next, the viscosity-adjusted composition 1 is applied to a difficult-to-adhesive thermoplastic substrate such as a polyester substrate by a screen printing method, a curtain coating method, a spray coating method or a roll coating method. Subsequently, the organic solvent contained in the composition 1 coated on the substrate -26-201016777 is volatilized and dried at 70 to 9 (the temperature of TC) to form a coating film (hereinafter referred to as "coating film 1"). The coating film 1 is exposed through a mask with a selected active energy ray. Next, an unexposed portion of the exposed coating film 1 can be developed using an alkaline aqueous solution to form a circuit pattern to produce the reflective sheet of the present invention. In this case, the difficult-to-adhesive thermoplastic substrate is exemplified by an olefin-based substrate, a polyamide-based substrate, a polyester-based substrate, etc. The olefin-based substrate is exemplified by high-density φ polyethylene (HDPE) and medium-density poly Ethylene (MDPE), low density polyethyl (LDPE), polypropylene (PP), cycloolefin polymer, etc. Polyamide substrate is exemplified by nylon 6, nylon 1, nylon 12, nylon 66, nylon 612, nylon. 6T, nylon 610, etc. Polyester substrates are exemplified by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polyparaphenylene. Butylene dicarboxylate (PBT), polybutylene naphthalate (PBN), etc. Other substrates are exemplified by poly(ethylene chloride) , polytetrafluoroethylene (PTFE), polyacetal (POM), polyphenylene ether (PPE β ), polyphenylene sulfide (PPS), etc. (Use Example 2) The curable resin composition of the present invention contains a resin containing a bivalent unsaturated group and a carboxyl group in one molecule, a bis-decylphosphine oxide photopolymerization initiator, a monofluorenylphosphine oxide photopolymerization initiator, titanium oxide, an organic solvent, a urethane The curable resin composition of acrylate, epoxy compound, and antioxidant (hereinafter referred to as "composition 2") is adjusted to a viscosity suitable for the coating method. -27- 201016777 Next, screen printing method, curtain coating method The viscosity-adjusted composition 2 is applied to the flexible substrate by a method such as a spray coating method or a roll coating method, and then the composition coated on the substrate is applied at a temperature of 70 to 90 ° C. The organic solvent contained in the solvent is evaporated and dried to form a coating film (hereinafter referred to as "coating film 2"). Subsequently, the coating film 2 is exposed through a mask with a selected active energy ray. Then, an alkaline aqueous solution is used to expose the film. The unexposed portion of the coating film 2 is imaged to form a pattern, and then, by l〇 The formed pattern can be thermally cured by a temperature of from ° C to 200 ° C to produce the reflective sheet of the present invention. @ In this case, as a flexible substrate, APICAL AH, APICAL NPI (KANAKA) can be exemplified. ), ' Η, ΚΑΡΤΟΝ V ' ΚΑΡΤΟΝ ΕΝ (made by Toray DuPont (share)), UBELEX 25S, UBEELE 75S (made by Ube Industries Co., Ltd.), polyimide film, copper foil, aluminum foil, stainless steel foil Metal foil such as titanium foil or nickel foil, etc. Further, as the irradiation light source for exposing the coating film 1 and the coating film 2, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halogen can be used. Lights, etc. Others can also use laser light or the like as an active light source. Further, the aqueous alkali solution used as the developing solution for the development of the coating film 1 and the coating film 2 is usually a sodium carbonate aqueous solution of 5% to 5% by mass, but other alkaline aqueous solution may be used. Other alkaline aqueous solutions are exemplified by alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium citrate, ammonia, amines, etc. Examples 28 to 201016777 Examples The following examples and comparative examples specifically illustrate the present invention. However, the invention is not limited by the following examples. Synthesis of Resin Solution 1· Add 900 g of solvent (diethylene glycol dimethyl ether) and 21.4 g of polymerization in a 2-liter separation flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. Starting agent (t-butylperoxy 2-ethylhexanoate, manufactured by Nippon Oil & Fats Co., Ltd., trade name: PERBUTYL®), and heated to 90 °C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone modified 2-hydroxyethyl methacrylate (made by DISEC Chemical Industry Co., Ltd., trade name: BLOCKCELL) within 3 hours FM1) and 21 g of a polymerization initiator (bis(4-t-butylcyclohexyl)peroxydicarbonate, manufactured by Nippon Oil & Fats Co., Ltd., trade name: PEROYL TCP) were added dropwise to the above flask. Then, the mixture was aged for 6 hours by β to obtain a carboxyl group-containing copolymer resin. Further, these reactions were carried out under a nitrogen atmosphere. Next, 36.99% of 3,4-epoxycyclohexyl acrylate (manufactured by DIDIC Chemical Co., Ltd., trade name: CYCLOMERA2 00) and 3.6 g of ring-opening catalyst were added to the carboxyl group-containing copolymer resin. Dimethylbenzylamine), 1.80 g of a polymerization inhibitor (hydroquinone monomethyl ether), and the mixture was heated to 100 ° C and stirred to carry out a ring-opening addition reaction of an epoxy group. After the completion of the stirring for 16 hours, the solid content of the solid content containing 53.8 mass% (nonvolatile matter) was l〇8.9 mg KOH/g, and the weight average molecule -29-201016777 amount 25,000 was not aromatic. A solution of a carboxyl-containing resin of the ring. Hereinafter, the reaction solution is referred to as a resin solution 1. [Example (1)] Preparation of each curable resin composition (Examples 1 to 3, Comparative Examples 1 to 6) = stirring was carried out according to the conditions described in Table 1, and then a 3-axis roll was used. The composition of the curable resin (Examples 1 to 3, Comparative Examples 1 to 6) was prepared by dispersion. Further, Comparative Example 1 shows a composition in which the amount of titanium oxide is less than the amount specified in the present invention, and Comparative Example 2 shows a composition in which the amount of titanium oxide is more than the amount specified in the present invention, and Comparative Example 3 shows only adjustment. A composition obtained by using BAPO as a photopolymerization initiator, Comparative Example 4 shows a composition in which only MAPO is used as a photopolymerization initiator, and Comparative Example 5 shows a photopolymerization initiator other than BAPO and MAP. As a composition obtained as a photopolymerization initiator, Comparative Example 6 shows a composition obtained by blending a photopolymerizable monomer with urethane acrylate. In addition, the numbers in Table 1 indicate parts by mass. -30- 201016777

[表1] 表 1 實施 例1 實施 例2 實施 例3 比較 例1 比較 例2 比較 例3 比較 例4 比較 例5 比較 例6 樹脂溶液 186 186 186 186 186 186 186 186 186 光聚合起始劑1 13 13 13 13 13 20 13 光聚合起始劑2 7 7 7 7 7 20 7 光聚合起始劑3 20 胺基甲酸酯丙烯酵酯 84 84 84 84 84 84 84 84 光聚合性單體 84 氧化鈦 150 340 880 110 1320 340 340 340 340 分散劑 1 3 7 1 10 3 3 3 3 消泡劑 8 8 8 8 8 8 8 8 8 有機溶劑 10 20 50 5 80 20 20 20 20 光聚合起始劑1 ( BAPO ):雙-(2,4,6-三甲基苯甲 醯基）苯基氧化膦IRGACURE 819(汽巴•日本（股）製 造） 光聚合起始劑2(MAPO) :2,4,6-三甲基苯甲醯基二 苯基氧化膦DIROCURE TPO (汽巴.日本（股）製造） 光聚合起始劑3: IRGACURE 907(汽巴.日本（股 )製造） 胺基甲酸酯丙烯酸酯：CN9178 (SATOMER公司製造 ) 光聚合性單體：二季戊四醇六丙烯酸酯 氧化鈦（金紅石型）：CR-Super 70 (石原產業（股 )製造） 增感劑：2,4-二乙基噻噸酮 KYACURE DETX-S (日 -31 - 201016777 本化藥（股）製造） 有機溶劑：卡必醇乙酸酯 消泡劑：矽氧油KS-66 (信越化學工業（股）製造） 以下列條件進行試驗以調査使用各硬化性樹脂組成物 形成之硬化物之諸性質，且進行評價。 (1 ) 解像性 使用100網目之聚酯（BIAS製造）之網版，以網版 印刷法以使塗膜膜厚成爲60 m之方式將各硬化性樹脂 組成物全面印刷於 PET (大小：100mmxl50mm，厚度： lOOym)上。接著以熱風循環式乾燥爐使該PET乾燥（ 溫度：80 °C，時間：20分鐘）形成上述各樹脂組成物之 塗膜。接著，利用曝光機HMW-680GW ( OAK製作所（股 )製造），使用描繪之線與50"m之脫除型線之 光罩圖型，以700mJ/cm2之累積光量使上述各塗膜經紫外 線曝光。隨後，對該曝光之各塗膜，以1質量％之碳酸鈉 水溶液（溫度：30 °C )作爲顯像液，使用顯像機顯像60 秒，製備各試驗片。 確認該試驗片，且使用下列評價方法進行解像性之評 價。結果列於表2。 〇光罩圖型殘存80 μιη之直線，或50/zm之脫除型 直線脫落 X因顯像導致直線消失，或因影像模糊（halation) 201016777 (2) 密著性 使用100網目之聚酯（BIAS製造）之網版，以網版 印刷法以使塗膜膜厚成爲60//in之方式將各硬化性樹脂 組成物全面印刷於PET (大小：1 OOmrax 1 5 0mm ’厚度： 100/zm)上。接著以熱風循環式乾燥爐使該PET乾燥（ 溫度：80 °C，時間：20分鐘）形成上述各樹脂組成物之 〇 塗膜。接著，利用曝光機HMW-680GW ( OAK製作所（ 股）製造），以殘留80mm邊長之負的負圖型之方式，以 700mJ/em2之累積光量使上述各塗膜經紫外線曝光。隨後 ，對該曝光之各塗膜，以1質量％之碳酸鈉水溶液（溫度 :30 °C )作爲顯像液’使用顯像機顯像60秒，製備各試 驗片。 使該等試驗片捲成直徑lcm長度20cm之圓筒，且再 度恢復成平面狀。觀察此時各試驗片之硬化塗膜（關於實 ® 施例（1)’以下稱爲「塗膜」）之狀態，使用下列評價 方法評價密著性。結果列於表2。 〇塗膜狀態無變化 △塗膜一部份脫落 X整面塗膜脫落，幾乎沒有殘存 (3 ) 反射率 以與（2)相同之方法製作試驗片，且使用色彩色差 計CR-400 ( Konica min〇lta (股）製造），測定各試驗 -33- 201016777 片之XYZ表色系之Y値，求得反射率。又，本實施例中 ，假設使作爲反射板之LED等之亮度提高之情況，以Υ 値75以上設爲合格。 結果列於表2。如表2中所示，除比較例1以外，均 獲得Y値爲75以上之高反射率塗膜。 [表2] 表 2 實施 例1 實施 例2 實施 例3 比較 例1 比較 例2 比較 例3 比較 例4 比較 例5 比較 例6 ⑴解像性 線殘存 〇 〇 〇 〇 X X X X 〇 脫落型 〇 〇 〇 〇 〇 X 〇 X 〇 ⑵密著性 塗臟態 〇 〇 〇 〇 〇 〇 〇 〇 (3)反射率 Y値 86.1 89.7 91.4 69.1 90.8 89.3 89.8 89.0 89.9[Table 1] Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Resin solution 186 186 186 186 186 186 186 186 186 Photopolymerization initiator 1 13 13 13 13 13 20 13 Photopolymerization initiator 2 7 7 7 7 7 20 7 Photopolymerization initiator 3 20 Amino acrylate ester 84 84 84 84 84 84 84 84 Photopolymerizable monomer 84 Oxidation Titanium 150 340 880 110 1320 340 340 340 340 Dispersant 1 3 7 1 10 3 3 3 3 Defoamer 8 8 8 8 8 8 8 8 8 Organic solvent 10 20 50 5 80 20 20 20 20 Photopolymerization initiator 1 (BAPO): bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide IRGACURE 819 (manufactured by Ciba (Japan)) Photopolymerization initiator 2 (MAPO): 2,4 ,6-trimethylbenzimidyldiphenylphosphine oxide DIROCURE TPO (manufactured by Ciba. Japan) Photopolymerization initiator 3: IRGACURE 907 (manufactured by Ciba. Japan) Aminocarboxylic acid Ester acrylate: CN9178 (manufactured by SATOMER) Photopolymerizable monomer: dipentaerythritol hexaacrylate titanium oxide (rutile type): CR-Super 70 (Ishihara Industry ( )Manufacturing) Sensitizer: 2,4-Diethylthioxanthone KYACURE DETX-S (Day-31 - 201016777 Manufactured by Chemicals) Organic Solvent: Carbitol Acetate Defoamer: Oxygen Oil KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.) The properties of the cured product formed using each of the curable resin compositions were investigated and evaluated under the following conditions. (1) Reproducibility Using a screen of 100 mesh polyester (manufactured by BIAS), each curable resin composition was printed on PET in a screen printing method so that the film thickness of the coating film was 60 m (size: 100mmxl50mm, thickness: lOOym). Then, the PET was dried in a hot air circulating drying oven (temperature: 80 ° C, time: 20 minutes) to form a coating film of each of the above resin compositions. Then, using the exposure machine HMW-680GW (manufactured by OAK Co., Ltd.), the above-mentioned respective coating films were subjected to ultraviolet rays at a cumulative light amount of 700 mJ/cm 2 using a pattern of the line of the drawing and the removal pattern of the 50" exposure. Subsequently, each of the exposed coating films was developed by using a 1% by mass aqueous solution of sodium carbonate (temperature: 30 ° C) as a developing solution, and developed for 60 seconds using a developing machine to prepare test pieces. The test piece was confirmed, and the evaluation of the resolution was carried out using the following evaluation methods. The results are shown in Table 2. 〇 〇 图 图 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 2010 80 80 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 In the screen printing method manufactured by BIAS, each curable resin composition is printed on PET in a screen printing method so that the film thickness of the coating film becomes 60//in (size: 100 Åramx 150 mm) thickness: 100/zm )on. Then, the PET was dried in a hot air circulating drying oven (temperature: 80 ° C, time: 20 minutes) to form a ruthenium coating film of each of the above resin compositions. Then, each of the above coating films was exposed to ultraviolet light at a cumulative light amount of 700 mJ/cm 2 by a negative negative pattern of 80 mm side length by using an exposure machine HMW-680GW (manufactured by OAK Co., Ltd.). Subsequently, each of the exposed coating films was developed by using a 1% by mass aqueous sodium carbonate solution (temperature: 30 ° C) as a developing solution for 60 seconds using a developing machine to prepare each test piece. The test pieces were wound into a cylinder having a diameter of 1 cm and a length of 20 cm, and returned to a flat shape again. The state of the cured coating film (hereinafter referred to as "coating film") of each test piece at this time was observed, and the adhesion was evaluated by the following evaluation method. The results are shown in Table 2. There is no change in the state of the 〇 coating film. △ The coating film is partially peeled off. The entire surface of the coating film is peeled off, and there is almost no residue. (3) Reflectance A test piece is produced in the same manner as (2), and a color difference meter CR-400 (Konica) is used. 〇 〇 a a a a 〇 〇 〇 〇 〇 〇 〇 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Further, in the present embodiment, it is assumed that the brightness of the LED or the like as the reflecting plate is increased by Υ75 or more. The results are shown in Table 2. As shown in Table 2, a high-reflectance coating film having a Y値 of 75 or more was obtained except for Comparative Example 1. [Table 2] Table 2 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (1) Resolving line residual 〇〇〇〇XXXX 〇 shedding type 〇〇〇 〇〇X 〇X 〇(2)Adhesive coating dirty state(3) Reflectance Y値86.1 89.7 91.4 69.1 90.8 89.3 89.8 89.0 89.9

(4) 耐光性 對實施例1至3,以與（3)相同之方法製作試驗片 ，且使用色彩色差計CR-400 (Konica minolta (股）製造 〇 )，測定各試驗片之XYZ表色系之Y値及L*a*b*表色系 之各値作爲初期値。隨後，使用輸送帶型UV照射機 QRM-20 8 2-E-01 ( OAK製作所（股）製造），以金屬鹵化 物燈、冷反射鏡、80\^/〇111><3燈、輸送帶速度6.5111/分鐘 (累積光量lOOOmJ/cm2)之條件，以UV重複照射上述各 試驗片1 〇〇次。接著，接著以與初期値相同之條件測定上 述各試驗片之色差，且評價各試驗片之劣化狀態。另外， 以目視評價該各試驗片。 -34- 201016777 表 3中，Y表示XYZ表色系之反射率，L*表示 L*a*b*表色系之亮度。AE + ab爲L*a*b*之各値中，取劣 化試驗後之測定値與初期値之差之平方，獲得其總和之平 方根者。a*表示紅色方向，-a*表不綠色方向，b*表示黃 色方向，-b*表示藍色方向，零附近表示沒有彩度。△ E * ab表示色彩變化。該値愈小表示色彩之變化愈小。 又，目視評價項目如下° 〇 〇未感覺到變色 △ 有稍許變色 X 有明顯變色 如表3中所述，可了解實施例1至3之硬化物因UV 而變色非常少。 [表3] ❹ 表 (4 )耐光性 初 期 値 Y L氺 a氺 b氺 Y L氺 U V 照 射 後 氺 b氺 A E 氺 ab 目視評價 5施例1 實施例2 實施例3 86.1 89.7 9 1.4 94.3 95.9 96.6 -0.29 -0.3 1 -0.33 0.21 0.20 -0.24 83.7 87.1 90.0 93.3 94.8 96.0 -0.13 -0.15 -0.16 0.44 0.42 0.4 1 1.04 1.13 0.90 〇 〇 〇 -35- 201016777 由上述，可知依據本實施例，可獲得對聚酯等難接著 性熱可塑性基材足夠之密著性、且可獲得形成即使對光亦 具有良好耐劣化性之高反射率硬化物之硬化性樹脂組成物 。又可了解，該樹脂組成物可藉由曝光形成高精細之圖型 ，且具有良好之解像性。 [實施例（2)] 各硬化性樹脂組成物（實施例4~6，比較例7〜1 3 )之 製作： 攪拌依據表4中所述調配各成分而成者，接著以3軸 輥使之分散，製備硬化性樹脂組成物（實施例4~6，比較 例7~ 1 3 )。又，比較例7顯示未調配抗氧化劑之組成物 ，比較例8顯示調配光聚合性單體代替胺基甲酸酯丙烯酸 酯之組成物，比較例9顯示氧化鈦之調配量比本發明之規 定調配量少之組成物，比較例10顯示氧化鈦之調配量比 本發明之規定調配量多之組成物，比較例11顯示僅調配 BAPO作爲光聚合起始劑而成之組成物，比較例12顯示 僅調配MAPO作爲光聚合起始劑而成之組成物，比較例 13顯示調配BAPO及MAPO以外之光聚合起始劑作爲光 聚合起始劑而成之組成物。另外，表4中之數字表示質量 份。 -36- 201016777 Ο [表4] 表 4 實施 例4 實施 例5 實施 例6 比較 例7 比較 例8 比較 例9 比較 例10 比較 例11 比較 例12 比較 例13 樹脂溶液 186 186 186 186 186 186 186 186 186 186 光聚雜始劑1 3 3 3 3 3 3 3 6 光聚合起始劑2 3 3 3 3 3 3 3 6 光聚雜讀3 6 胺基甲酸酯 丙烯_ 50 50 50 50 50 50 50 50 50 光聚潍單體 50 氧化鈦 130 300 800 130 130 110 1100 130 130 130 環氧化合物 40 40 40 40 40 40 40 40 40 40 抗氧化劑 1 1 1 1 1 1 1 1 1 消泡劑 1 1 1 1 1 1 1 1 1 1 有機溶劑 20 50 130 20 20 20 20 20 20 20 光聚合起始劑1 ( ΒΑΡΟ ):雙·（ 2,4,6-三甲基苯甲 醯基）苯基氧化膦 IRGACURE 819(汽巴.日本（股）製 • 造） 光聚合起始劑2 ( ΜΑΡΟ ) : 2,4,6-三甲基苯甲醯基二 苯基氧化膦 DIROCURE ΤΡΟ (汽巴•日本（股）製造） 光聚合起始劑3 : IRGACURE 907 (汽巴.日本（股 )製造） 胺基甲酸酯丙烯酸酯：CN9178 ( SATOMER公司製造 ) 光聚合性單體：二季戊四醇六丙烯酸酯 氧化鈦（金紅石型）：CR-Super 70 (石原產業（股 -37- 201016777 )製造） 環氧化合物（聯苯型）：ΥΧ-4000 (日本環氧樹脂（ 股）製造） 抗氧化劑：IRGANOX 1010 (汽巴•日本（股）製造 ) 消泡劑：矽氧油 KS-66 (信越化學工業（股）製造 ) 有機溶劑：卡必醇乙酸酯 以下列條件進行試驗以調査使用各硬化性樹脂組成物 形成之硬化物之諸性質，且進行評價。 (1 ) 解像性 使用100網目之聚酯（BIAS製造）之網版，以網版 印刷法以使塗膜膜厚成爲60/im之方式將各硬化性樹脂 組成物全面印刷於銘箱（大小：100mmxl50mm，厚度： 150gm)上。接著以熱風循環式乾燥爐使該鋁箔乾燥（ @ 溫度：80 °C ’時間：20分鐘）形成上述各樹脂組成物之 塗膜。接著，利用曝光機HMW-680GW ( OAK製作所（股 )製造），使用描繪有80//m之線之光罩圖型，以 700mJ/cm2之累積光量使上述各塗膜經紫外線曝光。隨後 ’對該曝光之各塗膜，以1質量％之碳酸鈉水溶液（溫度 :30°C )作爲顯像液’使用顯像機顯像60。接著，使顯 像後之各塗膜使用熱風循環式乾燥爐（溫度：150 °C，時 間：60分鐘）進行熱硬化，製備各試驗片。 -38- 201016777 確認該試驗片中殘存之線寬，使用下列評價方法進行 評價。結果列於表5。 〇線殘留 X線未殘留 (2) 可撓性 使用100網目之聚酯（BIAS製造）之網版，以網版 • 印刷法以使塗膜膜厚成爲60 μιη之方式將各硬化性樹脂 組成物全面印刷於銘箱（大小：100mmxl50mm，厚度： 150/zm)上。接著以熱風循環式乾燥爐使該鋁箔乾燥（ 溫度：80°C，時間：20分鐘）形成上述各樹脂組成物之 塗膜。接著，利用曝光機HMW-680GW ( OAK製作所（股 )製造），以殘留80mm邊長之負的負圖型之方式，以 700mJ/cm2之累積光量使上述各塗膜經紫外線曝光。隨後 ，對該曝光之各塗膜，以1質量％之碳酸鈉水溶液（溫度 © :30°C)作爲顯像液，使用顯像機顯像60秒。接著，使 用熱風循環式乾燥爐（溫度：150 °C，時間：60分鐘）使 顯像後之各塗膜熱硬化，製備各試驗片。 使該等試驗片捲成直徑2cm長度20cm之圓筒，觀察 此時之硬化塗膜（實施例（2)中，以下稱爲「塗膜」） 之狀態，且使用下列評價方法評價可撓性。結果列於表5 中。 〇塗膜上完全沒有割痕，狀態沒有變化 △塗膜上有少許割痕 -39- 201016777 X塗膜有明顯割痕 (3 ).反射率 以與（2)相同之方法製作試驗片，且使用色彩色差 計CR-400 ( Konica minolta (股）製造），測定各試驗片 之XYZ表色系之Y値，求得反射率。又，本實施例中， 假設使作爲反射板之LED等之亮度提高之情況，以Y値 75以上設爲合格。 結果列於表5。如表5所示，除比較例9外，均獲得 Y値爲75以上之高反射率塗膜。 [表5] 表5 實施 例4 實施 例5 實施 例6 比較 例7 比較 例8 比較 例9 比較 例10 比較 例11 比較 例12 比較 例13 ⑴解像性 〇 〇 〇 〇 〇 〇 X X X X (2)密著性 〇 〇 〇 〇 X 〇 〇 〇 〇 〇 (3)娜率 82.9 84.5 85.1 82.2 83.3 73.8 84.9 82.4 83.1 81.7 (4) 耐光耐熱性 對實施例4至6及比較例7，以與（3 )相同之方法 製作試驗片，使用色彩色差計CR-400 ( Konica minolta ( 股）製造），測定各試驗片之XYZ表色系之γ値及 L* a* b*表色系之各値作爲初期値。隨後，使用輸送帶型 UV照射機QRM-2082-E-01 (〇AK製作所（股）製造） ，以金屬鹵化物燈、冷反射鏡、80W/cmx3燈、輸送帶速 -40- 201016777 度6.5m/分鐘（累積光量l〇〇〇mJ/cm2)之條件，以UV重 複照射上述各試驗片20次。接著使用輸送帶式加熱爐重 覆加熱該各試驗片2次。隨後，以與初期値相同之條件測 定上述各試驗片之色差，且評價各試驗片之劣化狀態。另 外，以目視評價該各試驗片。結果列於表6。又，圖1顯 示加熱爐之加熱溫度。 表 6中，Y表示 XYZ表色系之反射率，L*表示 φ 表色系之亮度。△ E*ab爲對L*a*b*之各値，取劣 化試驗後之測定値與初期値之差之平方，獲得其總和之平 方根者。a*表示紅色方向，-a*表示綠色方向，b*表示黃 色方向，-b*表示藍色方向，零附近表示沒有彩度。△ E*ab表示色彩變化。該値愈小表示色彩之變化愈小。 又，目視評價項目如下。 〇幾乎沒有變色 △ 稍有變色 . X明顯變色 如表6所示，實施例4至6以目視幾乎看不見劣化， 且維持反射率之Y値在75以上之高反射率。另一方面， 不含抗氧化劑之比較例7不僅明顯變黃，且反射率亦顯著 降低。 -41 - 201016777 [表6] 表6(4) Light resistance To the examples 1 to 3, test pieces were produced in the same manner as in (3), and the XYZ color of each test piece was measured using a color difference meter CR-400 (manufactured by Konica Minolta Co., Ltd.). The Y値 and L*a*b* color systems of the system are used as initial parameters. Subsequently, a conveyor belt type UV irradiator QRM-20 8 2-E-01 (manufactured by OAK Manufacturing Co., Ltd.) was used, and a metal halide lamp, a cold mirror, an 80\^/〇111><3 lamp, and a conveyor were used. Each of the above test pieces was irradiated with UV for 1 time with UV under the conditions of a speed of 6.5111 / min (accumulated light amount of 1000 mJ/cm2). Next, the color difference of each of the test pieces was measured under the same conditions as in the initial stage, and the deterioration state of each test piece was evaluated. Further, each test piece was visually evaluated. -34- 201016777 In Table 3, Y represents the reflectance of the XYZ color system, and L* represents the brightness of the L*a*b* color system. AE + ab is the square of the difference between the measured enthalpy after the deterioration test and the initial enthalpy of each of L*a*b*, and the square root of the sum is obtained. a* indicates the red direction, -a* indicates no green direction, b* indicates yellow direction, -b* indicates blue direction, and zero indicates no chroma. △ E * ab represents a color change. The smaller the sag, the smaller the change in color. Further, the visual evaluation items were as follows: 〇 〇 〇 did not feel discoloration △ slight discoloration X marked discoloration As described in Table 3, it was found that the cured products of Examples 1 to 3 discolored very little due to UV. [Table 3] ❹ Table (4) Initial light resistance 値 氺 氺 氺 氺 氺 氺 UV 照射 氺 氺 氺 氺 visual evaluation 5 Example 1 Example 2 Example 3 86.1 89.7 9 1.4 94.3 95.9 96.6 - 0.29 -0.3 1 -0.33 0.21 0.20 -0.24 83.7 87.1 90.0 93.3 94.8 96.0 -0.13 -0.15 -0.16 0.44 0.42 0.4 1 1.04 1.13 0.90 〇〇〇-35- 201016777 From the above, it can be seen that according to the present embodiment, the polyester can be obtained. The difficult-to-adhesive thermoplastic substrate is sufficiently sturdy, and a curable resin composition which forms a high-reflectance cured product which has good deterioration resistance even to light can be obtained. It is also known that the resin composition can form a high-definition pattern by exposure and has good resolution. [Example (2)] Preparation of each curable resin composition (Examples 4 to 6, Comparative Examples 7 to 13): Stirring was carried out according to the conditions described in Table 4, and then a 3-axis roll was used. The composition was dispersed to prepare a curable resin composition (Examples 4 to 6, Comparative Examples 7 to 13). Further, Comparative Example 7 shows a composition in which an antioxidant is not formulated, Comparative Example 8 shows a composition in which a photopolymerizable monomer is blended instead of a urethane acrylate, and Comparative Example 9 shows a blending amount of titanium oxide as compared with the specification of the present invention. The composition having a small amount of blending, Comparative Example 10 shows a composition in which the amount of titanium oxide is more than the amount specified in the present invention, and Comparative Example 11 shows a composition in which only BAPO is blended as a photopolymerization initiator, Comparative Example 12 A composition in which only MAPO was used as a photopolymerization initiator was shown, and Comparative Example 13 showed a composition in which a photopolymerization initiator other than BAPO and MAPO was added as a photopolymerization initiator. In addition, the numbers in Table 4 indicate the parts by mass. -36-201016777 Ο [Table 4] Table 4 Example 4 Example 5 Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Resin solution 186 186 186 186 186 186 186 186 186 186 photopolymerization initiator 1 3 3 3 3 3 3 3 6 photopolymerization initiator 2 3 3 3 3 3 3 3 3 photopoly read 3 6 urethane propylene _ 50 50 50 50 50 50 50 50 50 Photopolymerization monomer 50 Titanium oxide 130 300 800 130 130 110 1100 130 130 130 Epoxy compound 40 40 40 40 40 40 40 40 40 40 Antioxidant 1 1 1 1 1 1 1 1 1 Defoamer 1 1 1 1 1 1 1 1 1 1 Organic solvent 20 50 130 20 20 20 20 20 20 20 Photopolymerization initiator 1 ( ΒΑΡΟ ): bis(2,4,6-trimethylbenzylidene)phenyl oxide Phosphine IRGACURE 819 (made by Ciba. Japan) Made of photopolymerization initiator 2 ( ΜΑΡΟ ) : 2,4,6-trimethylbenzimidyl diphenylphosphine oxide DIROCURE ΤΡΟ (Ciba • Japan (manufactured by the company) Photopolymerization initiator 3 : IRGACURE 907 (manufactured by Ciba. Japan) Amino acrylate: CN9178 (manufactured by SATOMER) Photopolymerizable monomer: dipentaerythritol hexaacrylate titanium oxide (rutile type): CR-Super 70 (manufactured by Ishihara Industry Co., Ltd. (JP-37-201016777)) Epoxy compound (biphenyl type): ΥΧ-4000 (Japanese ring) Oxygen resin (manufactured by Oxygen Resin) Antioxidant: IRGANOX 1010 (manufactured by Ciba (Japan) Defoamer: Oxygenated oil KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.) Organic solvent: carbitol acetate The test was conducted under the following conditions to investigate the properties of the cured product formed using each of the curable resin compositions, and evaluation was performed. (1) Reproducibility Using a screen of 100 mesh polyester (manufactured by BIAS), each curable resin composition was printed in the name box in a screen printing method so that the film thickness of the coating film became 60/im. Size: 100mmxl50mm, thickness: 150gm). Then, the aluminum foil was dried in a hot air circulating drying oven (@temperature: 80 °C' time: 20 minutes) to form a coating film of each of the above resin compositions. Then, using the exposure machine HMW-680GW (manufactured by OAK Co., Ltd.), the respective coating films were exposed to ultraviolet light at a cumulative light amount of 700 mJ/cm 2 using a mask pattern of a line drawn with 80/m. Subsequently, each of the exposed coating films was developed using a developing machine with a 1% by mass aqueous sodium carbonate solution (temperature: 30 ° C) as a developing solution. Then, each of the coating films after the development was thermally cured by using a hot air circulating drying oven (temperature: 150 ° C, time: 60 minutes) to prepare test pieces. -38- 201016777 The line width remaining in the test piece was confirmed and evaluated by the following evaluation methods. The results are shown in Table 5. Residual X-rays of the twisted wire are not left. (2) Flexibility A 100-mesh polyester (manufactured by BIAS) screen is used to form each curable resin in a screen printing method so that the film thickness becomes 60 μm. The material is printed on the box (size: 100mmxl50mm, thickness: 150/zm). Then, the aluminum foil was dried in a hot air circulating drying oven (temperature: 80 ° C, time: 20 minutes) to form a coating film of each of the above resin compositions. Then, each of the above coating films was exposed to ultraviolet light at a cumulative light amount of 700 mJ/cm 2 by using a exposure machine HMW-680GW (manufactured by OAK Co., Ltd.) in a negative pattern having a side length of 80 mm. Subsequently, each of the exposed coating films was developed with a 1% by mass aqueous sodium carbonate solution (temperature: :30 ° C) as a developing solution for 60 seconds using a developing machine. Then, each of the coating films after development was thermally cured by using a hot air circulating drying oven (temperature: 150 ° C, time: 60 minutes) to prepare test pieces. These test pieces were wound into a cylinder having a diameter of 2 cm and a length of 20 cm, and the state of the cured coating film (hereinafter referred to as "coating film" in Example (2)) was observed, and the flexibility was evaluated by the following evaluation method. . The results are shown in Table 5. There is no cut on the coating film, and there is no change in the state. There is a slight cut on the coating film. -39- 201016777 The X coating film has obvious cut marks (3). The reflectance is made in the same way as (2), and The Y 値 of the XYZ color system of each test piece was measured using a color difference meter CR-400 (manufactured by Konica Minolta Co., Ltd.) to obtain a reflectance. Further, in the present embodiment, it is assumed that the brightness of the LED or the like as the reflecting plate is increased, and Y 値 75 or more is regarded as acceptable. The results are shown in Table 5. As shown in Table 5, except for Comparative Example 9, a high reflectance coating film having a Y値 of 75 or more was obtained. [Table 5] Table 5 Example 4 Example 5 Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 (1) Resolution 〇〇〇〇〇〇XXXX (2) Adhesion 〇〇〇〇X 〇〇〇〇〇(3) Na rate 82.9 84.5 85.1 82.2 83.3 73.8 84.9 82.4 83.1 81.7 (4) Light resistance heat resistance to Examples 4 to 6 and Comparative Example 7, with (3) In the same manner, a test piece was prepared, and a color difference meter CR-400 (manufactured by Konica Minolta Co., Ltd.) was used to measure the γ 値 and L* a* b* color 之 of each XYZ color system of each test piece as an initial stage. value. Subsequently, a conveyor belt type UV irradiator QRM-2082-E-01 (manufactured by AK AK Manufacturing Co., Ltd.) was used, with metal halide lamps, cold mirrors, 80 W/cm x 3 lamps, and conveyor belt speed -40 - 201016777 degrees 6.5 Under the conditions of m/min (accumulated light amount l〇〇〇mJ/cm2), each of the above test pieces was repeatedly irradiated with UV for 20 times. Then, each test piece was repeatedly heated twice using a conveyor belt type furnace. Subsequently, the chromatic aberration of each of the above test pieces was measured under the same conditions as the initial enthalpy, and the deterioration state of each test piece was evaluated. Further, each test piece was visually evaluated. The results are shown in Table 6. Further, Fig. 1 shows the heating temperature of the heating furnace. In Table 6, Y represents the reflectance of the XYZ color system, and L* represents the brightness of the φ color system. △ E*ab is the square of the difference between the measured 値 and the initial 后 after the deterioration test, and the square root of the sum is obtained. a* indicates the red direction, -a* indicates the green direction, b* indicates the yellow direction, -b* indicates the blue direction, and zero indicates no chroma. △ E*ab indicates the color change. The smaller the sag, the smaller the change in color. Also, the visual evaluation items are as follows. 〇 almost no discoloration △ slight discoloration. X marked discoloration As shown in Table 6, Examples 4 to 6 showed almost no deterioration by visual observation, and maintained a high reflectance of Y 値 of 75 or more. On the other hand, Comparative Example 7 containing no antioxidant not only markedly yellowed, but also the reflectance was remarkably lowered. -41 - 201016777 [Table 6] Table 6

(4)耐光性 實施例4 實施例5 實施例6 比較例7 初 期 値 Y 82.9 84.5 85.1 82.2 L氺 93.0 93.7 93.9 92.7 a氺 -0.34 -0.36 -0.37 -0.33 b氺 0.16 0.21 0.23 0.37 U V 照 射 後 Y 77.6 79.4 80.5 70.8 L氺 90.6 91.4 91.9 87.4 a本 •0.21 -0.23 -0.20 -0.25 b氺 2.42 2.38 2.39 5.70 △ E 氺 ab 3.31 3.16 2.95 7.52 g視評價 〇 〇 〇 X(4) Light resistance Example 4 Example 5 Example 6 Comparative Example 7 Initial 値Y 82.9 84.5 85.1 82.2 L氺93.0 93.7 93.9 92.7 a氺-0.34 -0.36 -0.37 -0.33 b氺0.16 0.21 0.23 0.37 UV After irradiation Y 77.6 79.4 80.5 70.8 L氺90.6 91.4 91.9 87.4 a •0.21 -0.23 -0.20 -0.25 b氺2.42 2.38 2.39 5.70 △ E 氺ab 3.31 3.16 2.95 7.52 g depending on evaluation 〇〇〇 X

(5 ) 焊錫耐熱性 對實施例4至6，於以與（2)相同之方法製作之各 試驗片上塗佈松脂系助焊劑，且在260°C之焊錫槽中通過 10秒。隨後，以丙二醇單甲基醚乙酸酯洗淨該各試驗片 ，並經乾燥。隨後，以賽璐吩黏著膠帶對乾燥之各試驗片 進行剝離試驗，且使用下列評價方法評價塗膜之剝離。結 果列於表7。 〇塗膜未剝離 X 塗膜有剝離 (6 ) 耐溶劑性 將對實施例4至6中以與（2)相同之方法製作之各 試驗片浸漬於丙二醇單甲基醚乙酸酯中30分鐘，並經乾 -42- 201016777 燥。隨後，以賽璐吩黏著膠帶對乾燥之各試驗片進行剝離 試驗。使用以下評價方法評價塗膜之剝離及變色。結果列 於表7。 〇塗膜沒有剝離或變色 X 塗膜有剝離或變色 (7) 絕緣電阻試驗 # 對實施例4至6，以FR-4取代鋁箔，且使用IPC B- 25試驗圖型之梳型電極B試樣（coupon)，除此之外餘 與（2)相同之條件及方法製作試驗片。於該各試驗片上 施加DC 5 00V之偏壓，測定絕緣電阻値。結果列於表7。 [表7] 表7 實施例4 實施例5 實施例6 (5)焊錫耐熱性 〇 〇 〇 (6)耐溶劑性 〇 〇 〇 ⑺絕緣抵抗試驗（Ω) 1 xlO13以上 lxlO13以上 1 Χίο13以上 由上表可知，依據本實施例可獲得於可撓性基材上形 成XYZ表色系之Y値在75以上之高反射率硬化物之硬化 性樹脂組成物。又，可知該樹脂組成物可藉由曝光形成高 精細之圖型，且具有良好之解像性。再者，使用上述樹脂 組成物形成之硬化物亦爲隨著光或熱之劣化變少且具有焊 錫耐熱性者。 -43- 201016777 【圖式簡單說明】 圖1爲顯示實施例（2)中耐光耐熱性試驗中使用之 加熱爐之加熱條件之圖。(5) Solder heat resistance For each of the test pieces prepared in the same manner as in (2), the rosin-based flux was applied to Examples 4 to 6, and passed through a solder bath at 260 ° C for 10 seconds. Subsequently, the test pieces were washed with propylene glycol monomethyl ether acetate and dried. Subsequently, each of the dried test pieces was subjected to a peeling test with an adhesive tape, and the peeling of the coated film was evaluated using the following evaluation method. The results are shown in Table 7. The ruthenium coating film was not peeled off. The X coating film was peeled off (6) Solvent resistance. Each of the test pieces prepared in the same manner as in (2) in Examples 4 to 6 was immersed in propylene glycol monomethyl ether acetate for 30 minutes. And dried -42- 201016777 dry. Subsequently, each of the dried test pieces was subjected to a peeling test with an adhesive tape. The peeling and discoloration of the coating film were evaluated using the following evaluation methods. The results are shown in Table 7. The enamel coating film is not peeled off or discolored. X The coating film is peeled off or discolored (7) Insulation resistance test # For Examples 4 to 6, the aluminum foil is replaced by FR-4, and the comb electrode B test using the IPC B-25 test pattern is tested. In the same manner as in (2), a test piece was prepared. A bias voltage of DC 5 00 V was applied to each of the test pieces, and the insulation resistance 値 was measured. The results are shown in Table 7. [Table 7] Table 7 Example 4 Example 5 Example 6 (5) Solder heat resistance 〇〇〇 (6) Solvent resistance 〇〇〇 (7) Insulation resistance test (Ω) 1 x lO13 or more lxlO13 or more 1 Χ ίο13 or more As can be seen from the table, a curable resin composition having a high reflectance cured product having a Y値 of 75 or more in the YZ color system on the flexible substrate can be obtained. Further, it is understood that the resin composition can form a high-definition pattern by exposure and has good resolution. Further, the cured product formed by using the above resin composition is also one which has little deterioration in light or heat and has solder heat resistance. -43- 201016777 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing heating conditions of a heating furnace used in a light resistance heat resistance test in Example (2).

-44--44-

Claims (1)

201016777 七、申請專利範圍： 1.—種硬化性樹脂組成物，其特徵爲含有： —分子內包含乙烯性不飽和基及羧基之樹脂； 雙醯基氧化膦系光聚合起始劑； 單醯基氧化膦系光聚合起始劑； 氧化鈦；及 有機溶劑。 φ 2. 一種硬化性樹脂組成物，其特徵爲含有： 一分子內包含乙烯性不飽和基及羧基之樹脂； 雙醯基氧化膦系光聚合起始劑； 單醯基氧化膦系光聚合起始劑； 有機溶劑；及 相對於100質量份之除有機溶劑以外之成分，含有40 至80質量份之氧化鈦。 3. 如申請專利範圍第1或2項之硬化性樹脂組成物， 〇 其中氧化鈦爲金紅石型氧化鈦。 4. 如申請專利範圍第1或2項之硬化性樹脂組成物， 其中一分子內包含乙烯性不飽和基及羧基之樹脂係由含有 羧基之（甲基）丙烯酸系共聚合樹脂與一分子中具有環氧 乙烷環及乙烯性不飽和基之化合物反應所得之具有羧基之 共聚合系樹脂。 5. 如申請專利範圍第4項之硬化性樹脂組成物，其中 一分子中具有環氧乙烷環及乙烯性不飽和基之化合物係由 脂肪族聚合性單體所生成之化合物》 -45- 201016777 6. 如申請專利範圍第1或2項之硬化性樹脂組成物， 其中包含胺基甲酸酯丙烯酸酯。 7. 如申請專利範圍第1或2項之硬化性樹脂組成物， 其中含有環氧化合物及抗氧化劑。 8. 如申請專利範圍第1或2項之硬化性樹脂組成物， 其中含有環氧化合物、抗氧化劑及胺基甲酸酯丙烯酸酯。 9. 一種反射薄片，其特徵係由申請專利範圍第1或2 項之硬化性樹脂組成物之硬化物所構成。 10. —種反射薄片，其特徵係由難接著性熱可塑性基 材以及設於該基材上之申請專利範圍第6項之硬化性樹脂 組成物之硬化物所構成。 11. 一種反射薄片，其特徵係由申請專利範圍第7項 之硬化性樹脂組成物之硬化物所構成。 12. —種反射薄片，其特徵係由具有可撓性之基材以 及設於該基材上之申請專利範圍第8項之硬化性樹脂組成 物之硬化物所構成。 13. —種反射薄片，其特徵係由基材以及設於該基材 上之硬化性樹脂組成物之硬化物所構成，其中該硬化物含 有： 具有乙烯性不飽和基之化合物； 雙醯基氧化膦系光聚合起始劑； 單醯基氧化膦系光聚合起始劑；及 氧化鈦。 -46-201016777 VII. Patent application scope: 1. A curable resin composition characterized by: - a resin containing an ethylenically unsaturated group and a carboxyl group in the molecule; a bisphosphonium phosphine oxide photopolymerization initiator; Base phosphine oxide photopolymerization initiator; titanium oxide; and organic solvent. Φ 2. A curable resin composition comprising: a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule; a bis-indenylphosphine oxide-based photopolymerization initiator; a mono-fluorenylphosphine oxide-based photopolymerization The starting agent; the organic solvent; and 40 to 80 parts by mass of titanium oxide based on 100 parts by mass of the components other than the organic solvent. 3. The curable resin composition according to claim 1 or 2, wherein the titanium oxide is rutile-type titanium oxide. 4. The curable resin composition according to claim 1 or 2, wherein the resin containing an ethylenically unsaturated group and a carboxyl group in one molecule is a (meth)acrylic copolymer resin containing a carboxyl group and a molecule A copolymerized resin having a carboxyl group obtained by reacting a compound having an oxirane ring and an ethylenically unsaturated group. 5. The curable resin composition of claim 4, wherein the compound having an oxirane ring and an ethylenically unsaturated group in one molecule is a compound formed from an aliphatic polymerizable monomer. 201016777 6. The curable resin composition according to claim 1 or 2, which comprises a urethane acrylate. 7. The curable resin composition according to claim 1 or 2, which comprises an epoxy compound and an antioxidant. 8. The curable resin composition according to claim 1 or 2, which comprises an epoxy compound, an antioxidant, and a urethane acrylate. A reflective sheet comprising the cured product of the curable resin composition of claim 1 or 2. A reflective sheet comprising a hardenable thermoplastic substrate and a cured product of the curable resin composition of claim 6 set on the substrate. A reflective sheet comprising the cured product of the curable resin composition of claim 7 of the patent application. A reflective sheet characterized by comprising a flexible substrate and a cured product of the curable resin composition of claim 8 which is provided on the substrate. 13. A reflective sheet characterized by comprising a substrate and a cured product of a curable resin composition provided on the substrate, wherein the cured product comprises: a compound having an ethylenically unsaturated group; a phosphine oxide-based photopolymerization initiator; a monodecylphosphine oxide-based photopolymerization initiator; and titanium oxide. -46-
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