TW201127891A

TW201127891A - Composite resin composition

Info

Publication number: TW201127891A
Application number: TW099133780A
Authority: TW
Inventors: Yoshiyuki Morita; Nobuaki Aoki; Shingo Kanaya; Tetsuya Hosomi
Original assignee: Nagase Chemtex Corp
Priority date: 2009-10-28
Filing date: 2010-10-05
Publication date: 2011-08-16
Also published as: JP2011116943A; JP5505726B2; KR20110046346A; KR101769149B1; TWI499623B

Abstract

The objective of this invention is to provide a composite resin composition capable of forming a cured product having excellent stability, uniformity, high refractivity, transparency, heat resistance and light resistance. The composite resin composition according to this invention is composed of inorganic particles, in which the average particle size is 1 to 100nm, synthesized by a vapor phase method, and a polycarboxylic acid resin having at least one condense ring structure selected from the groups consisting of indene, tetrahydronaphthalene, fluorine, xanthene, anthracene, and benzoanthracene.

Description

201127891 六、發明說明：【發明所屬之技術領域】本發明係關於-種由無機微粒子與具有縮環結構之驗 1=':所構成之驗可溶性複合樹脂組成物、將該組成物硬化而成之薄膜、成形體及使半導體元件。心膜、顯不元件、【先前技術】究有為了實現有機系材料之高功能化，正盛行研九有機材料與無機材料之丁研無機材粗夕、隹人有挺出猎由有機材料與 e / °化而一併具有有機材料之柔軟性或成形性良好、無機材料之耐熱性 …f生率等）的材料。上述複1料右 d學特性（高折射元素導入s'才科，有以共價鍵將矽或鈦等金屬、有機系樹脂骨架中之有鱼 θ 有機樹脂中均勾分1 h i …、機此成树月曰、或於等。 S有π米級無機微粒子之分散系材料光性上=材料可用於近年來要求高水準之透明性、耐元件等用途。尤之各種光學膜或顯示元件、半導體計自由度更5且二、上返用途中，正進行研究可製造設散有夺平… 準特性之薄膜、成形體之均勾分月疋男不米級無機微粒料中分散無機微粒:散糸材料。通常，欲於有機材而採取於摻八斧由马了構築均勻且穩定之分散系，而，此種；劑:::了散劑或界面活性劑等方法。然之均句性或穩定性提/然大大有助於製造分散系 π且透明性良好之成形體，但有時由 201127891 ;刀政劑或界面活性劑本身之耐光性或耐熱性之問題合導致所得成形體耐光性或耐熱性降低。進而，當分散劑或界面活性劑與其他摻合成分之相容性較差時，有時會產生所得之成形體白濁等問題。進而，於此種用途t’大多需進灯圖案化，於分散有對用於圖案化之驗性顯影液等溶解性較低之無機微粒子的樹脂組成物中，’亦要求表現良好圖案性之材料〇、例如，於專利文獻丨中，揭示—種塗佈組成物可形成 ^明性優異，高折射率且高硬度之塗佈膜，該塗佈組成物含有：有機無舰成樹脂之i種即倍半石夕氧烧樹脂、與微 :子狀金屬氧化物。於專利文獻2中，揭示-種樹脂組成可形成具有較高透明性、折射率之成形體，該樹脂組成勿由具有第骨架之基礎樹脂、與至少包含平均粒徑為％· 以下之氧化結成分之無機微粒子成分構成。於專利文獻3 中，揭示一種可進行鹼顯影之感光性樹脂組成物，該樹脂組成物含有將環氧樹脂改質而成之含有（甲基）丙稀醯基及幾基之親水性樹脂、體積平均粒徑為^〜㈣之無機微 2子1及光自由基聚合起始劑。此處’藉由使用具有適田HBL值或Sp值之上述親水性樹脂，可獲得顯影性提高，圖案性良好之樹脂組成物。 #於上述狀況’要求-種分散之穩定性、均勾性優異，透明陡、耐熱性、耐光性較高，可提供較高之光學特性(高折射率）的樹脂組成物。專利文獻1 .日本特開2007-9079號公報 201127891 專利文獻2 .曰本特開2〇〇8_ 133379號公報專利文獻3 :曰本特開2〇〇9133961號公報【發明内容】然而’於專利文獻1中，耗可形成透明性良好且高折射率之薄膜、成形體，但為了提高分散性而添加有分散劑，因此於耐光性或耐熱性方面存在問題。於專利文獻2 中’記載有藉由使用具有第骨架之樹脂可使分散變得良好’但為了均勻地分散奈米級微粒子，僅導入第骨架仍不充刀，尤其是存在越提高粒子之摻合量，分散之穩定性、均勾性越降低之傾向，難以獲得高透明性之均質塗膜。又， :專利文獻3巾’無機微粒子之填充量於樹脂組成物中未 :重量％ ’於超出5〇重量％之高度填充之組成中，難以 :持穩定且均勾之分散系。因此，於高度填充有無機微粒千之組成中，難以獲得良好之顯影性。本發明之目的在於提供一種可形成穩定性、均勾性優複〜高折射率且透明性、耐熱性、耐光性優異之硬化物的 ==組成物。進而’本發明之目的在於提供一種高折用复=性、耐熱性、耐光性優異之薄膜、成形體及使紙、半導體㈣。 ^慮先片、觸控面板 '電子徑^明人等發現，藉由選擇利用氣相法合成之平均粒 ⑽㈣之無機微粒子作為無機微粒子由郎、四氫萘、第、。山。星、贫、及η “ 有選自少，w 及本开蒽所構成之群中至夕1種縮環結構的多元铋醅谢t 户疋竣酸树脂，而所得之複合樹脂組成 201127891 物之力散穩定性、均勻性古薄膜、成形體的透明性'耐:/複5組成物硬化而成之 ^ 4^- A+ ^ ^熱性、耐光性較高，進而容易 6周整折射率’從而完成本發明。即，本發明係關於— 組成構成：、ϋ脂組成物’其係由以下子：用亂相法合成之平均粒徑為1〜1〇〇 nm之無機微粒千、及 /、有選自由節、四翁技構成之群中至…二，星、葱、及苯編夕縮環結構的多元羧酸樹脂。上述無機微粒子較佳為金屬氧化物。上述金屬氧化物較佳為選自由氧化鈦' 氧化錯 '及氧化铌所構成之群中至少1種。上述金屬氧化物較佳為選自由推雜有紐之氧化鈦、及摻雜有銳之氧化鈦所構成之群中至少i種。上述具有縮環結構之多讀酸樹脂較佳為具有口山口星、及第之任一鈿環結構者，且為含有不飽和基者。上述具有縮環結構之多元叛酸樹脂較佳為含有放射線聚合性官能基者。進而’較佳為含有光聚合起始劑。進而，本發明劍於一種i述複合樹脂組成物硬化而獲得之薄膜。 ‘進而，本發明係關於一種上述複合樹脂組成物硬化而獲得之成形體。進而，本發明係關於一種光學膜，其特徵在於：具有 6 201127891 上述複合樹脂組成物硬化而獲得之薄膜。進而，本發明係關於一種顯示元件，其特徵在於：具有上述複合樹脂組成物硬化而獲得之薄膜。進而，本發明係關於一種半導體元件，其特徵在於：具有使上述複合樹脂組成物硬化而獲得之成形體。根據本發明，可製造一種無機微粒子之分散穩定性、均句性優異之複合樹脂組成物。進而，將該複合樹脂植成物硬化而獲得之薄膜、成形體的透明性較高，耐熱性、耐 2性優異。進而，可於較廣範圍内調整無機微粒子之填充量，故可根據用途自由調整折射率、膜硬度等。因此，、本發明之複合樹脂組成物適合於光學用膜、顯示元件、彩色 f光片、觸控面板、電子紙、太陽電池'半導體、成零件用途。再【實施方式】 …本發明之複合樹脂組成物係由利用氣相法合成之 =1〜1〇“m之無機微粒子，及具有選自由節、四氫萘、、❸星、蒽、及苯并蒽所構成之群中至少的多元羧酸樹脂。禋細衣，·、。構 (無機微粒子）用氣复合樹脂組成物中所使用之無機微粒子係利合成之平均粒徑1—的奈米級無機微粒子。通吊，無機微粒子之傲 > 古、、土 , t 法、液相…“ 致分類已知有固相 ^ ^ M fir ^ / 藉由機械性粉碎固體拉子之方法，但微粒子化達奈米級則有其極限。 201127891 因此、，獲得奈米級微粒子之方法，通常使用液相法或氣相 Ί相法可列舉：於溶液中發生化學反應，使結晶成長而獲付微粒子之溶膠凝膠法；或以水等液體作為介質，於液體介質中機械性粉碎結晶之機械粉碎法。氣相法舉 :射熱分解法、燃燒法、電聚蒸化攀；；vapor 子:方'ί成法等’稱為於氣相’發生反應而合成無機微粒於液相法之情形時，用於製造之介質，其大多數為水，故為了用作為複合樹脂系，於妷人+ 』镠。之樹月曰亦必需為水 €;Φ介“ φ存在較大限制。因此，較理想為於有機溶劑中亦穩定分散之舛軲工书微'合面多數情況是含=二Γ液相法合成之微粒子之表使疏水性ρ 極性較高之官能基，故為了由大量表2之有機溶劑中的分散系保持穩定，而必需藉量分散劑或界面二 =1 行處理，或者添加大公報丨生…例如曰本專利特開2008-266⑹號201127891 VI. Description of the Invention: [Technical Field] The present invention relates to a composition of a soluble composite resin composed of inorganic fine particles and a test having a condensed ring structure, which is formed by curing the composition. The film, the molded body, and the semiconductor element. The pericardium, the display element, and the [previous technique] In order to realize the high functionalization of the organic material, the research and development of the organic materials and the inorganic materials of the Dingyan inorganic materials are rare, and the monks have been hunted by organic materials and e A material having a good flexibility or formability of an organic material, heat resistance of an inorganic material, etc.). The right d-characteristics of the above-mentioned composite materials (high-refraction elements are introduced into the s' genus, and the metals such as ruthenium or titanium and the fish θ organic resin in the organic resin skeleton are all coherently separated by 1 k ... This is a tree-shaped sputum, or the like. S has a π-meter-class inorganic fine particle dispersion material. The material can be used for high-level transparency, resistance to components, etc. in recent years, especially various optical films or display elements. The degree of freedom of the semiconductor meter is 5 and 2. In the use of the upper return, the research is being carried out to make the dispersion and the flatness... The film of the quasi-characteristics and the formed body are all divided into the inorganic fine particles in the men's non-meter-grade inorganic microparticles. : Dilated materials. Usually, it is intended to be used in organic materials to build a uniform and stable dispersion system. In addition, the agent::: powder or surfactant. Sexuality or stability greatly contributes to the production of a molded body having a dispersion system of π and good transparency, but sometimes the resulting molded body is caused by the problem of light resistance or heat resistance of the coating agent or the surfactant itself. Light resistance or heat resistance is reduced. When the dispersant or the surfactant is inferior in compatibility with other blending components, the resulting molded body may be turbid or the like. Further, in such use t', most of the lamps need to be patterned, and dispersed. In the resin composition for the inorganic fine particles having low solubility such as a patterned developer, 'a material which exhibits good pattern properties is also required. For example, in the patent document, a coating composition can be disclosed. A coating film having excellent visibility, high refractive index, and high hardness is formed, and the coating composition contains an organic spheroidal resin, i.e., a sesquivalent oxy-oxygen resin, and a micro:substrate metal oxide. Patent Document 2 discloses that a resin composition can form a molded body having high transparency and a refractive index, and the resin composition is not formed of a base resin having a first skeleton and an oxidation containing at least an average particle diameter of %·· or less. In the case of the patent document 3, a photosensitive resin composition capable of alkali development is disclosed, and the resin composition contains (meth) propylene which is modified by modifying an epoxy resin. a hydrophilic resin having a base and a plurality of groups, an inorganic micro-particle 1 having a volume average particle diameter of (4), and a photoradical polymerization initiator. Here, by using the above hydrophilicity having an HBL value or a Sp value Resin, a resin composition having improved developability and good pattern properties can be obtained. # In the above-mentioned condition, it is required to have excellent stability and uniformity in dispersion, and has high transparency, high heat resistance and light resistance, and can provide a higher quality. The resin composition of the optical property (high refractive index). Patent Document 1. Japanese Patent Laid-Open Publication No. 2007-9079 No. 201127891 Patent Document 2 曰本特开开〇〇2〇〇8_133379号 Patent Document 3: 曰本特开2〇〇〇 396 396 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 There are problems in the aspect. Patent Document 2 describes that the dispersion can be made good by using a resin having a first skeleton. However, in order to uniformly disperse the nano-sized fine particles, only the introduction of the first skeleton is still not filled, and in particular, the presence of the particles is increased. The combination of the amount of dispersion, the stability of dispersion, and the lowering of the hooking property make it difficult to obtain a uniform coating film having high transparency. Further, in the composition in which the amount of the inorganic fine particles filled in the resin composition is not more than 5% by weight in the resin composition, it is difficult to maintain a stable and uniform dispersion. Therefore, in the composition in which the inorganic fine particles are highly filled, it is difficult to obtain good developability. An object of the present invention is to provide a == composition which can form a cured product which is excellent in stability, uniformity, high refractive index, and excellent in transparency, heat resistance and light resistance. Further, the object of the present invention is to provide a film, a molded article, a paper sheet, and a semiconductor (4) which are excellent in high-complexity, heat resistance and light resistance. ^Effects on the first film and the touch panel 'Electronic path ^Ming Man et al. found that by using the inorganic particles of the average particle (10) (4) synthesized by the vapor phase method as inorganic fine particles, lang, tetrahydronaphthalene, and the first. mountain. Star, lean, and η "There are a variety of oxime resin selected from the group consisting of less, w, and this open scorpion, and the resulting composite resin is composed of 201127891. Force dispersion stability, uniformity, transparency of the ancient film and the molded body 'Resistance: / The composition of the complex 5 is hardened ^ 4^- A+ ^ ^The heat and light resistance are high, and the 6-week refractive index is easy The present invention has been completed. That is, the present invention relates to a composition of: a rouge composition which is composed of the following: an inorganic particle having an average particle diameter of 1 to 1 〇〇 nm synthesized by a chaotic phase method, and/or There is a polyvalent carboxylic acid resin selected from the group consisting of a section, a four-dimensional technique, a star, an onion, and a benzene condensed ring structure. The inorganic fine particles are preferably a metal oxide. At least one selected from the group consisting of titanium oxide 'oxidation error' and cerium oxide is selected. The metal oxide is preferably selected from the group consisting of titanium oxide which is doped with neodymium and titanium oxide doped with sharp titanium oxide. At least i. The above multi-reading acid resin having a condensed ring structure preferably has a mouth The Yamaguchi star and any of the anthracene ring structures are those having an unsaturated group. The above-mentioned multi-repulsive resin having a condensed ring structure preferably contains a radiation-polymerizable functional group. Further, it is preferably a photopolymerization. Further, the present invention relates to a film obtained by curing a composite resin composition. Further, the present invention relates to a molded body obtained by curing the above composite resin composition. Further, the present invention relates to a film. Further, the present invention relates to a film obtained by curing the composite resin composition of the above-mentioned composite resin composition. The present invention relates to a display device comprising a film obtained by curing the composite resin composition. According to the present invention, there is provided a molded article obtained by curing the composite resin composition. According to the present invention, a composite resin composition having excellent dispersion stability and uniformity of inorganic fine particles can be produced. The film obtained by hardening the composite resin plant and the transparency of the molded body are more transparent Further, the heat resistance and the secondary resistance are excellent. Further, since the filling amount of the inorganic fine particles can be adjusted in a wide range, the refractive index, the film hardness, and the like can be freely adjusted depending on the application. Therefore, the composite resin composition of the present invention is suitable for optical use. Film, display element, color f-light sheet, touch panel, electronic paper, solar cell 'semiconductor, component use. [Embodiment] The composite resin composition of the present invention is synthesized by a gas phase method = The inorganic fine particles of "m" and a polyvalent carboxylic acid resin having at least a group selected from the group consisting of a node, tetralin, a comet, an anthracene, and a benzopyrene.禋 fine clothes, ·,. Structure (Inorganic Fine Particles) Nano-sized inorganic fine particles having an average particle diameter of 1 - synthesized by the inorganic fine particles used in the gas composite resin composition. Through the hanging, the pride of inorganic particles > ancient, soil, t method, liquid phase... "The classification is known to have a solid phase ^ ^ M fir ^ / by mechanically pulverizing the solid pull, but the micronized Dana The rice grade has its limit. 201127891 Therefore, the method of obtaining nano-sized microparticles is usually a liquid phase method or a gas phase enthalpy phase method, which can be exemplified by a chemical reaction occurring in a solution to grow crystals and obtain a sol-gel of the microparticles. a mechanical pulverization method for mechanically pulverizing and crystallization in a liquid medium using a liquid such as water as a medium. A gas phase method: a pyrolysis method, a combustion method, an electropolymerization vaporization method; a vapor sub: square ' When a method such as "forming in the gas phase" is used to synthesize inorganic fine particles in the liquid phase method, most of the medium used for the production is water, so in order to use it as a composite resin system, it is used in the 妷人+ 镠The tree must also be water for the month; Φ "there is a large limit on φ. Therefore, it is preferred that the micro-combination of the micro-composite surface which is stably dispersed in an organic solvent is a functional group containing a microparticle synthesized by the liquid phase method, such that the hydrophobicity ρ has a higher polarity, so A large number of dispersions in the organic solvent of Table 2 are stable, and it is necessary to disperse the dispersant or interface 2 = 1 row, or add Ta Kung Pao... For example, the patent application No. 2008-266(6)

^ ^添加劑有可能frf紐# V*L _L 響，進而，由於性或耐光性造成不良影機微粒子所1有之量增加’故難以引出無丁吓兵有之較高特性。易分=Γ，Γ氣相法獲得之無機微粒子具有不僅容 (例如曰本專利特:且二容易分散於各種有機溶劑㈣氣相法合成之無_ 4 327432戒公報）。因此，含有利用取I無機微粒子之分散處理或分散劑、界面活性劑，添加極少量之表面 4者疋全不添加該等，亦可 8 201127891 保持相對穩定之分散狀態，故可減少不需要之有機成分，由包含該等成分之複合樹脂组成物所獲得之薄膜、成形體的耐光性或㈣性優異。進而，可提高摻合中之無機微粒子本身之含量，並容易引出無機微粒子原本之特性，而適合作為本發明之複合樹脂組成物中之無機微粒子。本發明之利用氣相法合成之無機微粒子的製造方法，較佳為產量較高且適合量產《雷射法或瞬間氣相生成法。無機微粒子之粒徑，較佳為l〜1〇〇nm，更佳為卜5〇函。於大於100nm之情形時，因薄膜或成形體中之粒子所致之光散射變得激烈，而無法維持較高之透明性。又，若小於i麵，則微粒子之比表面積變大，内聚能（cohesive ⑽rgy)變高，而難以保持分散穩定性。粒徑可利用動態光散射法、雷射繞射法、超離心沈澱法等之裝置進行測定。上述無機微粒子，例如可列舉：氧化锆（Zr02)、氧化鈦 (以02)、氧化矽（Si02)、氧化鋁（Al2〇3)、氧化鐵（Fe2〇3、Fe〇、 k3〇4)、氧化銅（Cu0、Cu2〇)、氧化鋅（Zn〇)、氧化釔（Y2〇3)、氧化鈮（Nb2〇5)、氧化鉬（Μο〇3)、氧化銦（1以〇3、〗〜〇)、氧化錫（Sn〇2)、氧化钽（Ta2〇5)、氧化鎢（w〇3、W2〇5)、氧化鉛 (Pb〇、Pb〇2)、氧化鉍（Bi2〇3)、氧化鈽（Ce〇2、Ce2〇3)、氧= 録（sb2〇3、Sb2〇5)、氧化鍺（Ge〇2、Ge〇)等金屬氧化物微粒子1切、氮化蝴等氮化物等。又，亦可使用鈦酸鎖等鈦酸鹽、鈦/石夕複合氧化物、釔穩定氧化錯等由2種以上金屬元素所構成之複合氧化物等。該等之中，就獲得之容易程度、容易調整折射率等光學特性之方面而言，較佳為氧 201127891 化鈦微粒子或氧化鍅微粒子咬粒子可單獨使用，亦可混合使用1^粒子。上述無機微队卬z種以上。又，亦可使用於金屬氧化物令合物。上述化合物’可列舉摻雜“之=種 ::r 等，—用，二:= 上述複合氧化物不僅包括由多合物或固溶體’而且還包括具：：全：構成之化覆之核殼結構者，以及：有:：物微粒子之周圍加以被 # 八有如於1個金屬氧化物微粒子中 :二有複數個其他金屬氧化物微粒子之多成分分散型之結押“：發月中’上述無機微粒子可為經表面處理者。所 :ί! ’係指結合偶合劑等可與微粒子表面存在之羥石八# 上述表面處理可藉由將無機微粒而:容劑中’於酸性條件下混合偶合劑，並使其作用 =仃。可用於上述表面處理之偶合劑，可列舉石夕炫偶合劑^太偶合劑’例如可列舉：3_(甲基）丙稀酿氧基丙基三甲 =夕烧3(甲基）丙烯醯氧基丙基甲基二甲氧基石夕院等（甲基）丙稀醯氧基錢類，」·環氧丙氧基丙基三f氧基錢、 3-%乳丙氧基丙基三乙氧基残' 3_環氧丙氧基丙基曱基二乙氧基石夕烧' 2.(3,4·環氧環己基）乙基三f氧基石夕烧等石夕院類；乙稀基三甲氧基石夕烧、乙稀基三乙氧基石夕烧、乙烯基甲氧基乙氧基）⑯烧、二甲基乙烯基甲氧基石夕 201127891 烷、乙烯基三氣矽烷、二曱基乙烯基氣矽烷等乙烯基矽烧類；N-2-(胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三曱氧基矽烷、N-2-(胺基乙基）-3-胺基丙基曱基二曱氧基石夕烷等胺基矽烷類；N·(乙烯基节基）-2-胺基乙基-3-胺基丙基三曱氧基矽烷之鹽酸鹽等四級銨鹽類；對笨乙稀基三曱氧基矽烷；苯基三曱氧基矽烷；異丙基二曱基丙烯基異硬脂醢基鈥酸酯、異丙基二丙稀基異硬脂醯基欽酸酯等鈦酸酷類等。該等可僅使用1種’亦可使用2種以上。較佳為具有反應性官能基，與本發明之樹脂組成物之樹脂一起硬化，於硬化膜、成形體中容易固定無機微粒子之環氧矽烷類或（甲基）丙烯醯氧基石夕烧類。上述金屬氧化物微粒子之摻八吾★ 。里相對於上述具有縮環結構之多元羧酸樹脂1 〇〇重量份而盏里忉而為0.1〜5000重量份。若未達0 · 1重量份，則無法充分發揸赞禪i攻粒子之特性，若超出 5000重量份’則製膜性降低。較平乂佳為1〜2000重量份，更佳為5〜1000重量份。又，於， ...θ '本申化案發明之複合樹脂組成物中可摻合大I無機微粒子。 π an舌旦八女. 例如’相對於多元羧酸樹月曰1 00重1伤，亦可摻合通常吊難U摻合之200重詈份以上，進而500重量份以上。更S <刀以上於摻合上述金屬氧化物微粒各種溶劑中者。上述溶劑，可列兴.寺’：使用預先分散於丁醇等醇類；乙酸乙酯、乙酸丁+ _甲醇、乙醇、2_丙醇、甲醚乙酸酿、卜丁内酿等§旨類；：、孔酸乙醋、丙二醇單苴耷功妓、 —乙峻、乙二醇覃甲醚（甲土赛珞蘇）、乙一醇單乙_(乙美裳功— 土赛珞蘇）、乙二醇單丁醚（丁 201127891 基賽路蘇）、二乙二醇單甲醚、二乙二醇單***等醚類；丙酮、甲基乙基酮'甲基異丁基酮、乙醢丙酮（acetylacet〇ne)、環己酮等酮類；苯'甲苯、二甲笨、乙基苯等芳香族烴；一甲基甲醯胺、N，N_二甲基乙醯基乙醯胺 (l^’N-dimethylacetoacetamide)、N-甲基吡咯烷酮等醯胺類等。此時’溶劑與金屬氧化物微粒子之摻合比例較佳為3 〇 ·· 70〜90 : 1〇〇進而，視需要亦可添加不會對本發明之效果造成影響之種類的分散劑或不會對本發明之效果造成影響之量的分散劑於添加分散劑之情形時，例如可使用聚丙烯酸系分散劑、聚羧酸系分散劑、磷酸系分散劑、矽系分散劑等。分散劑之添加量，相對於無機微粒子丨〇〇重量份，較佳為5 重量份以下’更佳為2重量份以下。若多⑨5重量份，則存在所得硬化物之耐熱性或财光性降低之虞。& 了使益機 :粒子分散於樹脂中’依據樹脂或無機微粒子需要添加大量分散劑’但若為本發明中所使用之多元绩酸樹脂與無機填充劑’料不使用分散劑，即便使用亦為5重量份以下之極少量，便可大量均勻地分散無機微粒子。 (多元羧酸樹脂）上述具有選自由茚、四氫萘'筢不弗口山口星、蒽、及苯并編成之群中至少Μ縮環結構的多元繞酸樹脂⑼，係環氧醋樹脂(C)與多元叛酸或其酐反應所得之樹脂，而該環氧酯樹脂（C)是下述通式（1)所表示之衣孔樹脂（Α)與一元羧西欠之反應物、或者是下述通式（1〇)所矣一所表不之醇化合物（Β)與 12 201127891 鈿水甘油酯化合物之万施^ 應物。尤其是就分散性或耐熱異之方面而言，上述呈.… …改優有°山°星、及第之任-縮環結構者。具^ ^Additives may have frf New #V*L _L ringing, and further, due to the sexual or light resistance caused by the increase in the amount of defective lens particles, it is difficult to lead to higher characteristics. Easy to divide = Γ, the inorganic fine particles obtained by the gas phase method have not only capacity (for example, 曰专利专利 : : 且且且。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 Therefore, the dispersion treatment or dispersant containing the inorganic fine particles of I, and the surfactant are added, and a very small amount of the surface 4 is added, and the dispersion is maintained at a relatively stable state, so that the unnecessary state can be reduced. The organic component is excellent in light resistance or (tetra) property of a film or a molded article obtained from a composite resin composition containing the components. Further, the content of the inorganic fine particles in the blending itself can be increased, and the original characteristics of the inorganic fine particles can be easily extracted, and the inorganic fine particles in the composite resin composition of the present invention can be suitably used. The method for producing inorganic fine particles synthesized by the vapor phase method of the present invention preferably has a high yield and is suitable for mass production "laser method or transient gas phase generation method. The particle diameter of the inorganic fine particles is preferably from 1 to 1 〇〇 nm, more preferably a 〇 5 函 letter. When it is larger than 100 nm, light scattering due to particles in a film or a formed body becomes intense, and high transparency cannot be maintained. Further, when it is smaller than the i-plane, the specific surface area of the fine particles becomes large, and the cohesive energy (cohesive (10) rgy) becomes high, and it is difficult to maintain dispersion stability. The particle size can be measured by a device such as a dynamic light scattering method, a laser diffraction method, or an ultracentrifugation method. Examples of the inorganic fine particles include zirconium oxide (ZrO 2 ), titanium oxide (as 02), cerium oxide (SiO 2 ), alumina (Al 2 〇 3 ), iron oxide (Fe 2 〇 3 , Fe 〇 , k 3 〇 4 ), Copper oxide (Cu0, Cu2〇), zinc oxide (Zn〇), yttrium oxide (Y2〇3), yttrium oxide (Nb2〇5), molybdenum oxide (Μο〇3), indium oxide (1 to 〇3, 〖~ 〇), tin oxide (Sn〇2), yttrium oxide (Ta2〇5), tungsten oxide (w〇3, W2〇5), lead oxide (Pb〇, Pb〇2), bismuth oxide (Bi2〇3), Metal oxide fine particles such as cerium oxide (Ce〇2, Ce2〇3), oxygen=recorded (sb2〇3, Sb2〇5), yttrium oxide (Ge〇2, Ge〇), nitrides such as nitride, etc. . Further, a composite oxide composed of two or more kinds of metal elements such as titanate, titanium/inverted composite oxide, and yttrium-stabilized oxidative error may be used. Among these, in terms of the ease of obtaining and the optical characteristics such as the refractive index, it is preferable that the oxygen 201127891 titanium nitride fine particles or the cerium oxide fine particle biting particles may be used singly or in combination. The above inorganic micro-teams are more than z kinds. Further, it can also be used for a metal oxide compound. The above compound 'is exemplified by doping "the type::r, etc., -, and the second: = the above composite oxide includes not only the complex or the solid solution" but also includes: The core-shell structure, as well as: There are:: Around the particles of the particles, it is like a metal oxide microparticle: two of the other metal oxide microparticles are dispersed in a multi-component dispersion type: The above inorganic fine particles may be surface treated. : ί! ' means a combination of a coupling agent and the like which can be present on the surface of the microparticles. The above surface treatment can be carried out by mixing the coupling agent under acidic conditions with inorganic particles: . Examples of the coupling agent which can be used for the above surface treatment include, for example, Shi Xi Xuan coupling agent, too coupling agent, for example, 3 - (meth) acrylonitrile oxypropyl trimethyl sulphide = kiln 3 (methyl) propylene oxime (Methyl) propylene oxime oxime, etc., propylmethyldimethoxy zeshi et al., · glycidoxypropyl tri-foxy money, 3-% lactopropyl propyl triethoxy Base residue '3_glycidoxypropyl fluorenyl diethoxy sulphur smelting' 2. (3,4·epoxycyclohexyl)ethyltrifoxide, sulphur, etc.; Trimethoxy zephyr, ethylene triethoxy zeoxime, vinyl methoxy ethoxy) 16 calcined, dimethyl vinyl methoxy oxime 201127891 alkane, vinyl trioxane, dimercapto ethylene Vinyl oxime such as valerane; N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxy decane, N-2-(amine Amino decanes such as ethyl ethyl)-3-aminopropyl decyl decyloxy oxalate; N. (vinyl benzyl)-2-aminoethyl-3-aminopropyl trioxane a quaternary ammonium salt such as a hydrochloride of decane; a triethyl decyl decane ; phenyl trimethoxy decane; isopropyl dimercaptopropenyl isostearyl decyl phthalate, isopropyl dipropylene isostearyl phthalate, and the like. These may be used alone or in combination of two or more. It is preferably an epoxy decane or a (meth) propylene oxirane which is hardened by a resin having a reactive functional group and which is hardened with the resin of the resin composition of the present invention in the cured film or the molded body. The above metal oxide microparticles are mixed with ahwu ★. It is 0.1 to 5000 parts by weight based on 1 part by weight of the polyvalent carboxylic acid resin having a condensed ring structure. If it is less than 0.1 part by weight, the characteristics of the particles are not sufficiently tempered, and if it exceeds 5000 parts by weight, the film formability is lowered. It is preferably from 1 to 2000 parts by weight, more preferably from 5 to 1000 parts by weight. Further, in the composite resin composition of the invention of the present invention, large I inorganic fine particles can be blended. π an tongue and eight females. For example, 'with respect to the polycarboxylic acid tree, the monthly weight of 1 00 is 1 injury, and it is also possible to blend 200 parts by weight or more, and more preferably 500 parts by weight or more, which is usually blended with U. Further, the S < knife is added to the various solvents of the above metal oxide fine particles. The above solvent can be used in Lexing. Temple: using alcohols pre-dispersed in butanol; ethyl acetate, butyl acetate + methanol, ethanol, 2-propanol, methyl ether acetate, brewing, etc. ;:, hole acid ethyl vinegar, propylene glycol monoterpene, 乙、, ethylene glycol 覃 methyl ether (甲土赛珞苏), ethyl alcohol monoethyl _ (B Mei Sang Gong - Tusai Susu), B Alcohol monobutyl ether (丁201127891 基赛路苏), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and other ethers; acetone, methyl ethyl ketone 'methyl isobutyl ketone, acetamidine acetone ( Acetylacetoxime, ketones such as cyclohexanone; aromatic hydrocarbons such as benzene'toluene, dimethyl benzene, ethylbenzene; monomethylformamide, N,N-dimethylglycidylamine ^'N-dimethylacetoacetamide), guanamine such as N-methylpyrrolidone. In this case, the blending ratio of the solvent to the metal oxide fine particles is preferably 3 〇·· 70 to 90: 1 〇〇 Further, if necessary, a dispersing agent which does not affect the effects of the present invention may be added or may not be added. When a dispersing agent is added to the amount of the dispersing agent which affects the effect of the present invention, for example, a polyacrylic dispersing agent, a polycarboxylic acid dispersing agent, a phosphoric acid dispersing agent, an anthraquinone dispersing agent or the like can be used. The amount of the dispersant added is preferably 5 parts by weight or less or more preferably 2 parts by weight or less based on the parts by mass of the inorganic fine particles. When the amount is 95 parts by weight, the heat resistance or the tarnishability of the obtained cured product may be lowered. & The machine: the particles are dispersed in the resin. 'There is a large amount of dispersant to be added according to the resin or the inorganic fine particles. 'But if the multi-component acid resin and the inorganic filler used in the present invention do not use a dispersant, even if it is used Also, in an extremely small amount of 5 parts by weight or less, a large amount of inorganic fine particles can be uniformly dispersed. (Polycarboxylic acid resin) The above-mentioned polybasic acid resin (9) having at least a shrink ring structure selected from the group consisting of ruthenium, tetrahydronaphthalene, 筢Bufukoushankou, 蒽, and benzo, is an epoxy vinegar resin ( C) a resin obtained by reacting a multi-reactive acid or an anhydride thereof, and the epoxy ester resin (C) is a reaction product of a pene resin (Α) represented by the following formula (1) and a monocarboxylic acid ketone, or It is an alcohol compound (Β) which is represented by the following formula (1), and a pharmaceutically acceptable compound of 12 201127891 glycidyl ester compound. In particular, in terms of dispersibility or heat resistance, the above-mentioned improvement is improved by the angle of the mountain, and the structure of the first and the condensed ring. With

江具有、％環結構之多元羧酸樹脂較之二式⑺或下述通式⑴A polycarboxylic acid resin having a % ring structure and a second ring structure (7) or the following formula (1)

(2) 此處’ Ys〜6為分別獨立谐ό 苟立選自通式（2)或下述通式（3)之(2) where Y s ~ 6 are independent enthalpy, respectively, selected from the general formula (2) or the following general formula (3)

Psi分別獨立為〇至4之整數。 ⑶ r147 m8 四氫笑Γ下打·/ ⑴、（2)之2係包含由節（下述式⑷） (下述g(下述式（6))、〇山〇星（下述式⑺）、》工））、本并蒽（下述式⑼)構成之縮環結構的二價基 13 201127891 RI〜6分別獨立為碳數1至1 〇之直鏈狀、支鏈狀或環狀之烷基或烯基、碳* !至5之烷氧基、可具有取代基之苯基、或齒素原子，qh分別獨立為。通式⑴、⑺，之R…分^^之1^ ^而，上述 S,〜2分別獨立為0至U)之楚數為氫原子或甲基1卜8、不對稱。X，複數個、/結構式可左右對稱，亦可 1〜6可相同，亦可不同。 U)Psi is independently an integer from 〇 to 4. (3) r147 m8 Tetrahydrogen Γ 打 · / / / / / / / / / / / / / / / / / / / / / / / / / / / / / ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ), "Working"), the divalent group of the condensed ring structure composed of the present formula (9): 201127891 RI~6 are each independently a linear, branched or cyclic carbon number of 1 to 1 〇. An alkyl group or an alkenyl group, a carbon*! to alkoxy group of 5, a phenyl group which may have a substituent, or a dentate atom, and qh are each independently. The general formulae (1), (7), and R are divided into 1^^, and the above S, 〜2 are independently 0 to U), and the number is a hydrogen atom or a methyl group. X, plural, / structural type can be symmetrical, or 1~6 can be the same or different. U)

u)u)

(8) 14 (9)201127891(8) 14 (9) 201127891

(10) 此處，Z斑卜、+.上之直鍵狀、支鍵=同一分別獨立為碳數…。氧基、可具有取代，狀之烧基或稀基、碳數1至5之院〇至4之整數，/之本基、“素原子，fl〜2分別獨立為別獨立為。至a:?立為氫原子或¥“一之1數，並且Γι〜2分別獨立為1至5之整，、、’。構式可左右對稱，亦可不對稱…複數可相同，亦可不同。 5 18 本申請案之多元羧酸樹脂（D)可溶於鹼。用於製備上述環氧酯樹脂（C)之一元羧酸，可列舉具有 1個羧基之如下化合物，但並不限定於該等：（甲基）丙烯酸、環丙烷曱酸、2,2,3,3_四曱基_丨_環丙烷甲酸、環戊烷曱酸、 2-環戊烯基甲酸、2-呋喃曱酸、2 -四氫呋喃曱酸、環己烧甲酸、4-丙基環己烷曱酸、4-丁基環己烷甲酸、4_戊基環己院甲酸、4·己基環己烷甲酸、4-庚基環己烷甲酸、4_氰基環己燒-1·曱酸、4-羥基環己烷甲酸、1，3,4,5-四羥基環己烧_丨-甲 15 201127891 酸'2-(1,2-二羥基-4-曱基環己基）丙酸、莽草酸、3-羥基-3,3-二苯基丙酸、3-(2 -氧基環己基）丙酸、3 -環己烯-1-曱酸、4-環己烯-1，2-二曱酸氫烷基酯、環庚烷曱酸、降冰片烯曱酸、四環十二烯甲酸、金剛烷甲酸、（4-三環[5_2.1.02.6]癸-4-基）乙酸、對曱基苯曱酸' 對乙基苯曱酸、對辛基苯曱酸、對癸基苯甲酸、對十二烷基苯甲酸、對甲氧基苯甲酸、對乙氧基苯甲酸、對丙氧基苯甲酸、對丁氧基苯甲酸、對戊氧基苯甲酸、對己氧基苯甲酸、對氟苯甲酸、對氣苯曱酸、對氣甲基苯甲酸、五氟苯曱酸、五氣苯曱酸、4-乙醢氧基苯甲酸、2,6-二羥基苯曱酸、3,5·二-第三丁基-4-羥基苯曱酸、鄰苯甲醯基苯甲酸、鄰石肖基苯曱酸、鄰（乙醯氧基苯甲醢氧基）苯曱酸（o-(acetoxybenzoyloxy)benzoic acid)、對苯二曱酸單甲酯、間苯二甲酸單曱酯、間笨二曱酸單環己酯、苯氧基乙酸、氣苯氧基乙酸、苯硫基乙酸、苯基乙酸、2·氧基_3· 笨基丙酸、鄰溴笨基乙酸、鄰碘苯基乙酸、甲氧基笨基乙酸、6-苯基己酸、聯苯甲酸、α _萘甲酸、冷-萘甲酸、蒽曱酸、菲曱酸、蒽醌-2-曱酸、茚滿曱酸、丨，4-二氧基-丨，4-二氫萘-2-曱酸' 3，3 -二苯基丙酸、煙鹼酸、異煙鹼酸、肉桂酸、 3 -曱氧基肉桂酸、4 -曱氧基肉桂酸、啥琳甲酸等，該等可單獨使用，亦可組合使用2種以上。尤其是作為適合之一元叛Sx ’較佳為含有可導入放射線聚合性官能基之不飽和基者，例如較佳為（曱基）丙烯酸。此處，所謂放射線聚合性官忐基，係指具有藉由各種放射線而產生聚合反應之性質的 S能基。所謂「放射線」，包含可見光線、紫外線、遠紫 201127891 卜線/射線、電子束、分子束、，射線、同步加速器放射線、質子束射線等。用於製備上述％氧酉旨樹脂（c)之縮水甘油醋化合物，可列舉如下化合物’但並不限定於該等：（甲基）丙稀酸縮水甘油3曰乙Hjc甘油s旨、丁酸縮水甘油自旨、苯甲酸縮水甘油醋、對乙基苯甲酸縮水甘油雖、(對)苯二甲酸縮水甘油酿等，該等可單獨使用，亦可組合使用2種以上…元緩酸 =X甘尤佳，#中較佳為含有可導人放射線聚合性官此基之不飽和基者，例如較佳為（甲基）丙婦酸縮水甘油酿。上述環氧樹脂(A)與一元羧酸之反應、及醇化合物⑻ 與縮水甘油酿化合物之反應均視需要使用適當之溶劑，於 50〜I2(rcu度範圍内進行5〜3G小時。上述可使用之溶劑例如有.曱基賽路蘇乙酸酿、丙二醇單甲驗乙酸酿、乙二醇單甲醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單乙驗乙酸S旨、二乙-隨留丁 G —醇早丁醚乙酸酯、3·甲氧基丁基-丨_乙酸酯等伸烷基單烷基醚乙酸酯(alkyiene _〇a⑽】ether 似_)類；二乙二醇單曱喊、二乙二醇單乙喊、二乙二醇二丁酿等伸烧基單燒基喊（alkylene m。麵㈣類；甲基乙基酮、曱基戊基酮等酮類；&珀酸二曱酯、琥珀酸二乙酉曰、己一 @文—乙酯、丙二酸二乙酯、草酸二丁酯等酯類等。忒等之中’較佳為丙二醇單曱醚乙酸酯及曱氧基丁基-丨-乙酸S日。進而，相骨-Γ 視而要可使用觸媒及聚合抑制劑。所使用之觸g W如可列舉鱗鹽類、四級敍鹽類、膦化合物類、三級胺化合物類、咪嗤化合物類等，通常較佳為於反 17 201127891 應物鳌體t 0·01〜10重量％之範圍使用。又，所使用之聚合抑制劑’例如可列舉對苯二酚、甲基對苯二酚、對苯二盼單甲驗、4-甲I Al I, T暴喹啉、啡噻畊、2,6-二異丁基苯酚、2,6· 一第一丁基_4_曱基苯酚等，通常可於反應物整體之$重量 %之以下之範圍内進行添加。用於製備具有縮環結構之多元羧酸樹脂（D)之上述多元羧鲅為一羧§义、四羧酸等具有複數‘羧基之羧酸，此種多元羧酸或其酐，可列舉如下化合物：順丁烯二酸、琥拍酸、衣康酸、鄰苯二曱酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、曱基八氫鄰苯一甲g复、甲基内亞甲基四氫鄰苯二甲酸、氣橋酸(chlorendic acid)、甲基四氫鄰苯二曱冑、戊二酸等二敌酉夂及其等之酐，#苯三甲酸或其;均苯四甲酸 '二苯甲酮四曱酸（benzophenonetetracarb〇xyUc acid)、聯苯四曱酸 (blphenyltetracarboxylic acid)、聯苯醚四甲酸 ether tetracarboxylic acid)等四羧酸及其等之酸二酐等。上述具有縮環結構之多元鲮酸樹脂（1))之i例，例如可列舉下述通式（11)或通式（12)所表示之樹脂。(10) Here, the Z spot, the direct bond on the +., and the bond = the same are independent carbon numbers. An oxy group, which may have a substitution, a pyridyl group or a dilute group, a carbon number of 1 to 5, an integer of 4, a base of /, a "prime atom, and fl~2 are independently independent. To a: ? Established as a hydrogen atom or ¥ "one number, and Γι ~ 2 are independent of 1 to 5, respectively, '. The configuration can be symmetrical or asymmetrical... The plural can be the same or different. 5 18 The polycarboxylic acid resin (D) of the present application is soluble in a base. The monocarboxylic acid used for the preparation of the above epoxy ester resin (C) may, for example, be a compound having one carboxyl group, but is not limited thereto: (meth)acrylic acid, cyclopropanedecanoic acid, 2, 2, 3 , 3_tetradecyl _ 丨 _ cyclopropanecarboxylic acid, cyclopentane decanoic acid, 2-cyclopentenylcarboxylic acid, 2-furoic acid, 2-tetrahydrofuran decanoic acid, cyclohexane burning formic acid, 4-propylcyclohexane Alkanoic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexancarboxylic acid, 4·hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid, 4-cyanocyclohexene-1·曱Acid, 4-hydroxycyclohexanecarboxylic acid, 1,3,4,5-tetrahydroxycyclohexane?_丨-甲 15 201127891 Acid '2-(1,2-dihydroxy-4-indolylcyclohexyl)propionic acid , shikimic acid, 3-hydroxy-3,3-diphenylpropionic acid, 3-(2-oxocyclohexyl)propionic acid, 3-cyclohexene-1-decanoic acid, 4-cyclohexene-1, Hydrogen 2-alkyl dihydrogenate, cycloheptane decanoic acid, norbornene decanoic acid, tetracyclododecenoic acid, adamantanecarboxylic acid, (4-tricyclo[5_2.1.02.6]癸-4-yl Acetic acid, p-nonyl benzoic acid 'p-ethyl benzoic acid, p-octyl benzoic acid, p-nonyl benzoic acid, p-dodecyl benzoic acid, p-methoxy benzene Acid, p-ethoxybenzoic acid, p-propoxybenzoic acid, p-butoxybenzoic acid, p-pentyloxybenzoic acid, p-hexyloxybenzoic acid, p-fluorobenzoic acid, p-benzoic acid, gas Methylbenzoic acid, pentafluorobenzoic acid, pentaphenone, 4-ethyloxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5·di-t-butyl-4-hydroxyl Benzoic acid, o-benzhydrylbenzoic acid, o-stone succinyl benzoic acid, o-(acetoxybenzoyloxy)benzoic acid, terephthalic acid monomethyl Ester, monodecyl isophthalate, m-cyclohexylic acid monocyclohexyl ester, phenoxyacetic acid, gas phenoxyacetic acid, phenylthioacetic acid, phenylacetic acid, 2 oxy _3 · stupid propyl Acid, o-bromopictinoacetic acid, o-iodophenylacetic acid, methoxyphenyl acetic acid, 6-phenylhexanoic acid, dibenzoic acid, α-naphthoic acid, cold-naphthoic acid, citric acid, phenanthrenic acid,蒽醌-2-decanoic acid, indanic acid, hydrazine, 4-dioxy-indole, 4-dihydronaphthalene-2-decanoic acid 3,3-diphenylpropionic acid, nicotinic acid, isoniazid Alkali acid, cinnamic acid, 3-methoxy cinnamic acid, 4-methoxy cinnamic acid, 啥琳Formic acid or the like may be used singly or in combination of two or more. In particular, as a suitable element, the repellent Sx' is preferably an unsaturated group containing a radiation-polymerizable functional group, and is preferably, for example, (fluorenyl)acrylic acid. Here, the term "radiopolymerizable sulfhydryl group" means an S-energy group having a property of generating a polymerization reaction by various kinds of radiation. The so-called "radiation" includes visible light, ultraviolet light, far purple, 201127891, line/ray, electron beam, molecular beam, ray, synchrotron radiation, proton beam, and the like. The glycidol vinegar compound used for the preparation of the above-mentioned % oxo-resin resin (c) includes the following compounds, but is not limited thereto: (meth)acrylic acid glycidol 3 曰 ethyl Hjc glycerol s, butyric acid Glycidol, benzoic acid glycidol, p-ethyl benzoic acid glycidol, (p-) phthalic acid glycidol, etc., these may be used alone or in combination of two or more... Ganyoujia, # is preferably an unsaturated base containing a radiation-polymerizable group, and is preferably, for example, (meth)propionic acid glycidol. The reaction of the above epoxy resin (A) with a monocarboxylic acid, and the reaction of the alcohol compound (8) with the glycidol brewing compound are carried out by using a suitable solvent in an amount of 5 to 3 G in an amount of 5 to 3 G. Solvents used are, for example, thioglycolic acid, propylene glycol monoacetic acid, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoacetic acid acetic acid S Alkyl monoalkyl ether acetate (alkyiene _〇a(10)]ether like G-alcoholic early butyl ether acetate, 3·methoxybutyl-hydrazine-acetate _) class; diethylene glycol monoterpene shunt, diethylene glycol single-ethyl shout, diethylene glycol dibutyl brewing, etc., extrusion base single-burning base shouting (alkylene m. surface (four); methyl ethyl ketone, hydrazine Ketones such as pentyl ketone; &didecyl succinate, diethyl succinate, hexyl-ethyl ester, diethyl malonate, dibutyl oxalate, etc. 'It is preferably propylene glycol monoterpene ether acetate and decyloxybutyl-indole-acetic acid S. Further, it is possible to use a catalyst and a polymerization inhibitor for the phase-bone. List Salts, quaternary salts, phosphine compounds, tertiary amine compounds, imipenem compounds, etc., are generally preferably used in the range of 0.001 to 10% by weight of the compound 17 201127891. The polymerization inhibitor to be used is, for example, hydroquinone, methyl hydroquinone, p-benzoic acid, 4-methyl I Al I, T quinolin, thiophene, 2, 6 -diisobutylphenol, 2,6.-first butyl-4-indolylphenol, etc., may be usually added in the range of less than or less than 5% by weight of the entire reactant. The polyvalent carboxylic acid of the polycarboxylic acid resin (D) is a carboxylic acid having a complex 'carboxy group, such as a carboxyl group or a tetracarboxylic acid, and the polyvalent carboxylic acid or an anhydride thereof may, for example, be the following compound: maleic acid, Acacia acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, decyl octahydrophthalic acid, methyl endomethylene tetrahydroortylene Formic acid, chlorendic acid, methyltetrahydrophthalic acid, glutaric acid, etc., and its anhydride, #benzenetricarboxylic acid or its pyromellitic acid a tetracarboxylic acid such as benzophenonetetracarb xy Uc acid, blphenyltetracarboxylic acid or ether tetracarboxylic acid, or the like, and the like. The i-type of the polyvalent tannin resin (1)) is, for example, a resin represented by the following formula (11) or (12).

18 (12) (12)20112789118 (12) (12) 201127891

此處，Z為包含茚、四氫萘、荞、0山D星、蒽、笨并蒽之任縮環結構之二價基’ A!、A〕為四叛酸二酐之殘基， 2八4為二缓酸酐之殘基。又’此處，U、U2平均為〇至 130 〇 :上述通式（11)、（12)中，較佳為Z為含有包含aJja星或第骨架之縮環結構之二價基。日於z為含有包含卩山卩星或苐骨架之縮環結構之二價基 2 ’此種多元羧酸樹脂（D)之折射率較高，於可減小與無，粒子之折射率差之方面較為有利。結構環結構之多讀酸樹脂（D)可藉由上述含有缩環 ^，衣^樹脂（C)與多元羧酸或其酐反應而獲得。又亦 $ 了提向所得樹脂之耐熱性或耐熱黃變性 ^使夕几醇類共存而進行反應。广述多元醇類’可列舉：乙二醇、私、1，3-丙-辟叶丙二 Λ 1 〜、二丙二醇、1，3-丁二醇、1 4-丁-酿戍二醇、2-甲美】7工砰i，4 丁一知、新醇、1，6-壬二：醇、3·甲基个5-戊二醇、…己二曱醇、三環：二壬Ϊ醇等脂肪族二醇；M_環己境二之環氧乙烷、^ I化雙酚Α等脂環式二醇；雙酚八甲基丙烧、C成物等芳香族二醇…、三經山梨糖醇、：：甲基乙燒、二-三經甲基丙烧、季戊四醇、〜季戊四醇等三元以上之醇等。％ 19 201127891 於該反應中，環氧酯樹脂（c)、多元醇類、以及多元緩酸或其軒之添加順序並無限制。例如有同時混合該等進行反應之方法；以及將環氧酯樹脂多元醇加以混合，繼而添加多元緩酸或其酐’進行混合而反應等方法。又，亦可進而於該等反應產物中添加多元羧酸進行反應。藉由適當選擇多元羧酸或其酐之種類，可製造具有縮環結構骨架且結構不同之各種多元羧酸樹脂（D_a)、進而與多元醇反應而成之多元叛酸樹脂（D-b)。具體而言，例如可製備以下之（D-a-i)〜（D-a-iii)、（D-b-i)〜（D-b-iii)所示之第 1 〜第6之多元羧酸樹脂（D)，該等為例示。 (D-a-i)第1之多元羧酸樹脂：將環氧酯樹脂（c)、與1 種多元羧酸或其酐加以混合、反應所獲得之樹脂； (D-a-n)第2之多元羧酸樹脂：將環氧酯樹脂（c)、與2 種或2種以上之多元羧酸或其酐之混合物（例如二羧酸酐及四緩酸一酐之混合物）加以混合、反應所獲得之樹脂；以及 (D - a - i i i)第3之多元叛酸樹脂：環氧g旨樹脂（c)與四緩酸或其二酐反應’所得之反應產物再與二叛酸或其酐進行反應而獲得之樹脂》 (D-b-i)第4之多元羧酸樹脂：將環氧酯樹脂（c)、多元醇、及1種多元羧酸或其酐加以混合、反應所獲得之樹脂； (D-b-u)第5之多元羧酸樹脂：將環氧酯樹脂（c)、多元醇、及2種或2種以上之多元羧酸或其酐之混合物（例如二幾酸酐及四羧酸二酐之混合物）加以混合、反應而獲得之樹脂；及 20 201127891 弟多元緩酸樹脂：環氧酿樹脂（c)、多醇、及四㈣或其項進行反應，所得之反應產物再與羧酸或其酐反應而獲得之樹脂。以上述方式獲得之結構不同之夕_ , 之夕70綾酸樹脂（D-a)或 (D - b)分別根據目標用途進行利用。再者，所謂「多元敌酸或其軒」，係羧酸及與其對應之酐中之至少一夕」’例如若多元雜s拿為鄰苯二曱⑯，則係指鄰苯二曱酸及 … 邱本—Ψ酸肝中之至少一者。又，所謂「2種或2種以上之多元物」，係指至少2種多元羧酸，、酐 ..，m ,.Λ 飞其肝同時存在。因此，於上述（D-a-u)及⑺氺-丨丨）々方法中，至參與反應。少2種夕元羧酸或其酐於上述任一方法中，多元_樹脂造：使環氧顆樹脂(c)、多元醇、及…曰由以下方式製例示之方法(順序)，溶解(懸二：：其針以上述丁基赛路蘇乙酸醋等賽路蘇系溶基賽路穌乙酸醋、 B曱氧基丁基乙酸醋等院二醇單：：：單甲… 溶劑，甲基乙基酮、甲A显丁 I 類與乙酸之醋系中，進行加熱使其反鹿二環己綱等_系溶劑等用之觸媒，例如T、y _而，視需要可添加觸媒。所使列如可列舉鎮鹽龆三級胺化合物_ + & 、，及銨鹽類、膦化合物類、。物頬、咪唑化合物體之〇.〇1〜1〇曾曰通吊較佳為於反應物整重1%之範圍内使用。於上述多元羧酸樹脂之製化中，於使用多元醇之情形 21 201127891 時，較佳為調整環氧酯樹脂（c)與多元醇，使得環氧酯樹脂 (c)之羥基與多元醇之羥基之莫耳比（環氧酯樹脂之羥基/ 多元醇之羥基）成為99/1〜50/50,更佳為95/5〜6〇/4〇。若多元醇之羥基之莫耳比超出50%，則存在所得樹脂之分子量急劇增大’產生凝膠化之虞…若未達1%，則存在難以提高耐熱性或耐熱變色性之傾向。多元羧酸或其酐相對於環氧酯樹脂（c)之羥基（於使用多元醇之情形時為與多元醇之羥基之合計）丨當量（莫耳），以酸酐基換算計較佳為以〇」〜！當量，更佳為以㈣叫當量之比例供於反應。若多元羧酸或其酐以酸酐基換算計未達〇. 1當量，則存在所得多元羧酸樹脂之分子量不會充分變高之情形。因&，於使用包含此種驗可溶性樹脂之感放射線性樹脂組成物進行曝光及顯影時，存在所得被膜之耐熱性不充分，或者被膜殘存於基板上之情形。於上述多元羧酸或其酐以酸酐基換算計超出丨當量時，存在殘存未反應之酸或酸針，戶斤得多元羧酸樹脂之分子量變低，&含該樹脂之感放射線性樹脂組成物之顯影性較差之情形。再者，所謂酸針基換算，係指將使用之多元叛酸或其酐中所含之羧基及酸酐基全部換算成酸酐時之量。於製造上述第2、第3及第5、第6之多元羧酸樹脂(D) 時，使用2種以上之多元羧酸或其酐。通常使用二羧酸酐與四羧酸二if。：緩酸針與四敌酸二肝之比例（二叛酸肝/ 四羧酸二酐）以莫耳比計較佳為1/99〜9〇/1〇，更佳為〜80/20 0右一羧酸酐之比例未達總酸酐之1莫耳％ ’則存 22 201127891 在樹脂黏度變高，作業性降低之虞。進而，所得樹脂之分子量變得過大’故於使用包含該樹脂之感放射線性樹脂組成物’於基板上形成薄膜並進行曝光時，存在該曝光部難以溶解於顯影液，從而難以獲得目標圖案之傾向。若二緩酸酐之比例超出總酸酐之90莫耳。/G，則所得樹脂之分子量變得過小’故於使用包含該樹脂之組成物於基板上形成塗膜時，容易產生於預烘烤後之塗膜上殘留黏性等問題。於上述任一情形下當環氧酯樹脂（c)與多元羧酸或其酐、以及視需要之多兀醇反應時，反應溫度較佳為5〇〜】3〇 °C，更佳為70〜120°C。若反應溫度超出13〇<t，則會局部產生羧基與羥基之縮合，分子量急劇增大。另一方面若未達飢，則反應不會順利進行，而殘存未反應之多元竣酸或其酐。 (複合樹脂組成物）於本發明之複合樹脂組成物中，多元羧酸樹脂（D)較佳為含有放射線聚合性官能基’具體而言，較佳為含有(甲基) 丙烯醢基等不飽和基。於客&鉍^ 丞於多70竣酸樹脂（D)為含有放射線聚 5性s能基之樹脂時，本福人接w τ 不硬0树脂組成物具有光硬化性，故可用作為感光性複合樹脂組成物（Ε)。此處，所謂感光性，係扣丄Λ 係扣藉由各種放射線產生化學反應之性質，上述放射綾，可έ、、士 e + = 、、自’皮長較長者起依序列舉如可見光線、紫外線、電子类、γ ▲ 釆Χ射線、α射線、/5射線、及τ 射線。該等之中，就經濟性，从手性之方面而言’貫際應用中紫外線為最佳之放射峻。砂& 又耵綠紫外線，可較佳地使用自低 23 201127891 壓水銀燈、高壓水銀燈、超高壓水銀燈、電弧燈、氙氣燈等燈發出之紫外光。波長短於紫外線之放射線其化學反應 ! 生車乂而’理論上優於紫外線，但就經濟性之觀點而言紫外線較為實用。於本發明之複合樹脂組成物為感光性複合樹脂組成物 (E)之情形時，較佳為添加光聚合起始劑（F卜進而，為了調整硬化性’或者調整硬化後之硬度等膜特性，可於不損及本發明之效果之範圍内，於感光性複合樹脂組成物（E)中添加含有不飽和基之多元羧酸樹脂（D)以外之各種光硬化性單體或光硬化性樹脂（G)。所謂上述光聚合起始劑（F )，係指具有光聚合起始作月之化合物及/或具有增感效果之化合物。上述化合物，例女可列舉如下化合物：苯乙酮、2,2_二乙氧基苯乙啊、對二，基苯乙酮、對二曱基胺基苯丙酮、二氣苯乙酮、三氯苯乙酮、對第三丁基苯乙酮等苯乙酮類；二苯 …雙二甲基胺基二苯甲嗣等二苯曱嗣(be^ 類，本偶醯；安息香（benz〇in);安息香甲醚、安息香異丙醚安息香異丁…息香峻類；苯偶酿二甲基縮酮 (benzUdimethylketal);硫口山卩星、2·氣硫口山σ星、2心二乙其护口山咕、2-甲基硫㈣、2-異丙基硫〇山〇星等硫化合物；^ 基葱職、人甲基葱酿、！，2•苯并_、2,3_二苯基蒽酿等贫酿類；偶氮雙異丁腈1氧化苯甲醯、過氧化異丙苯等有，化物；…基苯并味。坐、2，基笨并時唾'2·疏基苯并噻唑等硫醇化合物。 24 201127891 上这先聚合起始劑（F)之摻合化人物丨1 篁相對於含有不飽和基之化。物100重量份，較佳為〜5.0重量份。 1〇.〇重量份’更佳為0.1 上述「含有不飽和基之化合樹脂組成物(E)中所含」、曰上述感光性複合化^，Λ 含有放射線硬化性不飽和基之 ° 匕括為本發明之多元鲮酸招+ t 仆，Μ：去、R I 兀蠼敲树脂（D)且具有放射線硬 #明之多元羧酸樹脂⑼以外之光硬化性單體或光硬化性樹脂（G)等。該等光聚合起始劑(F)可單獨使用丨種，亦可組合使用種以上。進而’亦可添加如其本身不起光聚合起始劑之作用仁藉由與上述化合物組合使用可增加光聚合起始劑之月&力的化合物。土卜插彳卜人从此種化合物，例如可列舉.若與二苯甲酮組合使用’則發揮效果之三乙醇胺等三級胺。人於多元鲮酸樹脂（D)不含不飽和基這樣的放射線聚吕月b基時，藉由含有各種光硬化性單體或光硬化性樹月曰（G)或醌一疊氮化合物（叫in〇nediazide)(⑴作為必須成刀而可發揮出作為感光性複合樹脂組成物（E)之功能。於添加上述醌二疊氮化合物（H)之情形時，本發明之感光性複合樹脂組成物（E)成為正型感光性複合樹脂組成物。於正型樹脂組成物之情形，進行感光時，組成物本身不硬化。於正型之情形時’為了於圖案化後獲得硬化膜，例如於感光性複合樹脂組成物（£)添加環氧化合物⑴等熱硬化性樹脂，於照射放射線 '顯影後使其熱硬化，藉此可形成硬化膜。該熱硬化主要係利用多元羧酸樹脂（D)之羧酸基與環 25 201127891 氧化合物（i)之環氧基藉由熱之交聯反應而進行。 i述光硬化性單體或光硬化性樹脂（G)為可利用放射線進ί丁聚合之單體或寡聚物，可根據符合組成物之使用目的之物性而含有。此種可利用放射線聚合之單體或寡聚物，可列舉以下之單體或寡聚物：（曱基）丙烯酸2-羥基乙酯 '(曱基）丙稀酸2·羥基丙酯、（曱基）丙烯酸3-羥基丙酯等具有羥基之（曱基）丙烯酸酯類；二（曱基）丙烯酸乙二醇酯、二（甲基）丙稀酸二乙二醇酯、二（甲基）丙烯酸三乙二醇酯、二（甲基）丙烯酸四乙二醇酯、二（曱基）丙烯酸丁二醇酯、三羥曱基丙烷三（曱基）丙烯酸酯、三羥曱基乙烷三（曱基）丙烯酸酯、二 (甲基）丙烯酸季戊四醇酯、三（甲基）丙烯酸季戊四醇酯、四 (甲基）丙烯酸季戊四醇酯 '四（甲基）丙烯酸二季戊四醇酯、六（甲基）丙烯酸二季戊四醇酯、（甲基）丙烯酸甘油酯等（曱基）丙烯酸酯類。該等單體或寡聚物可單獨使用丨種，亦可組合使用2種以上。該等單體或寡聚物係作為黏度調整劑或光交聯劑而發揮作用，可於不損及本發明之樹脂組成物之性質的範圍内含有。通常，上述單體及募聚物之至少丨種相對於多元羧酸樹脂_0()重量份，以5G重量份以下之範圍含於組成物中。若該單體或寡聚物之含量超出5〇重量份，則有可能於無機微粒子之分散性或均勻性方面產生問題。上述酿二疊氮化合物⑻，較佳為經！，2_酿二叠氮績酸所酿化之化合物’可列舉：三羥基二笨"同與u-萘醌二叠氮磺酸之醋化物、四羥基二苯甲_與1>2_萘醌二疊氮磺酸之 26 201127891 酉曰化物五&基一苯甲鲖與1，2-蔡酿二疊氮石黃酸之醋化物、 ”羥基一苯甲酮與丨，2-萘醌二疊氮磺酸之酯化物、雙（2，y_ 二羥基苯基)f烷與丨，2_萘醌二疊氮磺酸之酯化物、雙(對羥基苯基）f烧與1，2-奈藏二疊氮磺酸之酯化物、三（對羥基苯 f .)甲烧與1，2-奈蛾二疊氮磺酸之酯化物、1,丨，1 ·三（對羥基苯基）乙院與1，2-錢二疊氮績酸之酿化物、雙（2,3,4_三羥基苯基^與丨，2相二疊氮《之醋化物、2,2_雙（2,3,4-:經基本基）丙院與1>?.萘親二疊氮續酸之醋化物m #(’5甲基羥基苯基）-3-苯基丙烷與丨，2_萘醌二疊氮續酸之酯化物、4,4，-[l_「4 n「4 ρ a — « _[里基笨基]-丨_甲基乙基]苯基] 土，、1，2-奈醌二疊氮磺酸之酯化物、雙（2,5·二曱基-4-羥基苯基）·2_羥|| ’ 一基本基甲烷與i，2·萘醌二疊氮磺酸之 =化物、3,⑻|·四甲基]，i，刻切，5,，6,，7,·己醇與& 不醌一疊虱磺酸之酯化物、及 -二、 ^ ^ ，— T 基·7,2，4、三羥基 :萘醌二疊氮磺酸之酯化物等。進而述以外之醌二疊氮化合物。利用上上述環氧化合物⑴係指具有至或單體。具有至少〗個環氧广乳基之聚合物清漆型環ί m… 基之1合物’例如有笨酚酚醛 :&乳树月曰、甲齡㈣清漆型環氧樹脂、雙㈣脂、雙盼F型環氧樹脂、雙 “ 環氧樹脂、脂環式環氧樹脂等環氧樹脂以^、聯苯型具有至少丨個環氧基之單體，可列舉· 喊、對丁基苯盼縮水甘油驗、異三聚氛酸水甘油異二聚氰酸二縮水甘油酯、稀、、，甘油酯、烯丙基縮水甘油鱗、甲基丙稀 27 201127891 酸縮水甘油酉旨等。該等化合物獨種以上。苟便用，亦可組合使用2 该等環氧化合物⑴可於不損 ,,^ ^ 々货月之樹脂組成物之性夤的範圍内含有。通常，相對壬旦八 }對於夕兀羧酸樹脂（D)每100 重置伤，環氧化合物（I)係以5〇重量里里伤以下之比例含有。於超出5 0重量份之情形時，包含 B , 3 °玄成分之組成物硬化時，容易引起斷裂’密合性亦容易降低。進而，視需要可於本發明之複饭0樹月曰組成物中添加各種添加劑⑴。上述添加劑⑴’有熱聚合抑制劑、密合助劑、 %氧基硬化促進劑、界面活性劑、消泡劑等，料可以不損及本發明之目的之範圍的量含於組成物中。上述熱聚合抑制劑，可列舉對苯二紛、對苯二盼單甲醚、五倍子酚(Pyr〇gallol)、第三丁基鄰苯二酚、啡噻口井 (phenothiazine)等〇上述密合助劑係為了提高所得組成物之接著性而含有。密合助劑’較佳為具有縣、甲基丙稀酿基、異氣酸基、環氧基等反應性取代基之錢化合物（官能性錢偶合劑）。該官能性矽烷偶合劑之具體例，可列舉：三甲氧基矽烷基苯甲酸、甲基丙烯氧基丙基三甲氧基矽烷" -methacryl〇xypropyltrimethoxysilane)、乙烯基三乙醞氧基矽烷、乙烯基三甲氧基矽烷、r_異氰酸基丙基三乙氧基矽烷、r-垓氧丙氧基丙基三曱氧基矽烷、石_(3,4_環氧環己基）乙基三曱氧基矽烷等。 ^ 上述環氧基硬化促進劑，可列舉胺化合物類、咪唑化 28 201127891 合物類、羧酸類、酚類、四級銨鹽類或含羥甲基之化合物類等。藉由含有少量環氧基硬化促進劑，可使藉由加熱所付之硬化膜之耐熱性、对溶劑性、耐酸性、财鑛敷性、密合性、電氣特性、硬度等各特性提高。上述界面活性劑例如係為了容易將液狀組成物塗佈於基板上而含有，藉此所得膜之平坦度亦提高。界面活性劑，例如可列舉· BM-l〇〇〇(BM Chemie公司製造）、Megafac F142D、Megafac F172、Megafac F173 及 Megafac F183(大曰本油墨化學工業股份有限公司製造）、Fiu〇rad FC-135、Here, Z is a residue of a tetravalent base 'A!, A' which is a tetracyclic acid dianhydride containing a fluorene ring structure of anthracene, tetrahydronaphthalene, anthracene, fluorene, fluorene, and fluorene, 2 Oct. 4 is the residue of the bis-acid anhydride. Further, U and U2 have an average of from 〇 to 130 〇 : in the above formulae (11) and (12), Z is preferably a divalent group containing a condensed ring structure containing an aja or a skeleton. The z is a divalent group containing a condensed ring structure of the comet or the ruthenium skeleton. 2' The polycarboxylic acid resin (D) has a higher refractive index, and can reduce the refractive index difference between the particles and the particles. The aspect is more favorable. The multi-read acid resin (D) having a structural ring structure can be obtained by reacting the above-mentioned condensed ring-containing resin (C) with a polyvalent carboxylic acid or an anhydride thereof. Further, the heat resistance of the obtained resin or the heat-resistant yellowing property of the obtained resin is coexisted to carry out the reaction. A wide range of polyols can be exemplified by ethylene glycol, private, 1,3-propane-propionate, propylene glycol, 1,3-butanediol, and 1,4-butanediol. 2-甲美]7工砰i,4 丁一知,新醇,1,6-壬二: alcohol, 3·methyl 5-pentanediol, ... hexanediol, tricyclic: diterpenoid An aliphatic diol such as an alcohol; an alicyclic diol such as ethylene oxide of M_cyclohexane; alicyclic hydrazine; and an aromatic diol such as bisphenol octamethylpropane or C; A ternary or higher alcohol such as sorbitol, dimethyl ethoxide, di-trimethyl propyl ketone, pentaerythritol, and pentaerythritol. % 19 201127891 In this reaction, the order of addition of the epoxy ester resin (c), the polyol, and the polybasic acid or the oxime thereof is not limited. For example, there are a method in which the reaction is carried out at the same time; and a method in which an epoxy ester resin polyol is mixed, followed by addition of a polybasic acid or an anhydride thereof, followed by mixing and reaction. Further, a polyvalent carboxylic acid may be further added to the reaction products to carry out the reaction. By appropriately selecting the type of the polyvalent carboxylic acid or its anhydride, it is possible to produce a plurality of polybasic carboxylic acid resins (D-a) having a structure of a condensed ring structure and having different structures, and further reacting with a polyhydric alcohol to form a multi-repulsive resin (D-b). Specifically, for example, the first to sixth polycarboxylic acid resins (D) represented by the following (D-a-i) to (D-a-iii) and (D-b-i) to (D-b-iii) can be prepared, and these are exemplified. (Dai) The first polycarboxylic acid resin: a resin obtained by mixing and reacting an epoxy ester resin (c) with one polyvalent carboxylic acid or an anhydride thereof; (Dan) a second polycarboxylic acid resin: a resin obtained by mixing and reacting an epoxy ester resin (c), a mixture of two or more kinds of polycarboxylic acids or anhydrides thereof (for example, a mixture of a dicarboxylic anhydride and a tetrabasic acid anhydride); and (D) - a - iii) 3rd multi-repulsive resin: epoxy resin is a resin obtained by reacting a resin (c) with a tetra-hypo-acid or a dianhydride thereof to obtain a reaction product obtained by reacting two ortho-acids or an anhydride thereof. (Dbi) a fourth polycarboxylic acid resin: a resin obtained by mixing and reacting an epoxy ester resin (c), a polyhydric alcohol, and a polyvalent carboxylic acid or an anhydride thereof; (Dbu) a fifth polycarboxylic acid Resin: a mixture of an epoxy ester resin (c), a polyhydric alcohol, and a mixture of two or more polycarboxylic acids or anhydrides thereof (for example, a mixture of a dibasic acid anhydride and a tetracarboxylic dianhydride) is obtained by mixing and reacting Resin; and 20 201127891 Diversified acid retardant resin: epoxy resin (c), polyol, and four (four) or its Line reaction, the resulting reaction product then reacted with a carboxylic acid or anhydride to obtain the resin. The structure obtained in the above manner is different, and the 70 decanoic acid resin (D-a) or (D - b) is utilized according to the intended use. Furthermore, the term "multiple enantioic acid or its sulphate" is at least one of the carboxylic acid and its corresponding anhydride", for example, if the polydisperse s is phthalic acid 16, it means phthalic acid and ... Qiu Ben - at least one of the livers. Further, "two or more kinds of plural substances" means at least two kinds of polycarboxylic acids, and anhydrides.., m,. Therefore, in the above (D-a-u) and (7) 氺-丨丨) methods, the reaction is involved. In the above method, the two kinds of the ternary carboxylic acid or the anhydride thereof are obtained by dissolving the epoxy resin (c), the polyol, and the oxime by the method (sequence) exemplified in the following manner, and dissolving ( Suspension 2:: The needle is made of the above-mentioned butyl 赛路苏苏 acetate vinegar, etc. Sai Susu is a solution of acetaminophen, B-oxybutyl acetoacetate, etc.: diol: In the vinegar system of ketone ketone, ketone A, and acetic acid, a catalyst such as T and y _ can be added to the catalyst such as T, y _, which is heated, such as T, y _ The media can be listed as samarium sulphate tertiary amine compounds _ + &,, and ammonium salts, phosphine compounds, bismuth, imidazole compounds 〇. 〇1~1〇 Preferably, it is used in the range of 1% by weight of the reactant. In the preparation of the above polycarboxylic acid resin, in the case of using the polyol 21 201127891, it is preferred to adjust the epoxy ester resin (c) and the polyol. The molar ratio of the hydroxyl group of the epoxy ester resin (c) to the hydroxyl group of the polyol (the hydroxyl group of the epoxy ester resin / the hydroxyl group of the polyol) is 99/1 to 50/50. More preferably, it is 95/5~6〇/4〇. If the molar ratio of the hydroxyl group of the polyol exceeds 50%, the molecular weight of the obtained resin sharply increases, and the gelation occurs. If it is less than 1%, There is a tendency that it is difficult to improve heat resistance or heat discoloration resistance. The polyvalent carboxylic acid or its anhydride is equivalent to the hydroxyl group of the epoxy ester resin (c) (in the case of using a polyol, the total of the hydroxyl groups of the polyol) The molar amount is preferably from 〇" to ! equivalents, more preferably in the ratio of (iv) equivalents, in the case of an acid anhydride group. If the polycarboxylic acid or its anhydride is not converted in an acid anhydride group, it is less than 1 equivalent. The molecular weight of the obtained polyvalent carboxylic acid resin may not be sufficiently increased. When exposure and development are carried out using a radiation sensitive resin composition containing such a soluble resin, the heat resistance of the obtained film may be insufficient. When the polycarboxylic acid or its anhydride exceeds the oxime equivalent in terms of an acid anhydride group, the unreacted acid or acid needle remains, and the molecular weight of the polycarboxylic acid resin becomes low. & contains the resin In the case where the developability of the radiation-sensitive resin composition is inferior, the acid needle-based conversion means an amount in which all of the carboxyl group and the acid anhydride group contained in the polybasic acid or the anhydride thereof are converted into an acid anhydride. When the second, third, fifth, and sixth polycarboxylic acid resins (D) are produced, two or more kinds of polycarboxylic acids or anhydrides thereof are used. Usually, a dicarboxylic acid anhydride and a tetracarboxylic acid are used. The ratio of the needle to the four-acid di-hepatic liver (two resorcinating liver/tetracarboxylic dianhydride) is preferably 1/99 to 9 〇/1 Torr in terms of molar ratio, more preferably 〜80/20 0 右-carboxylic anhydride The ratio is less than 1 mol% of the total acid anhydride. 'There is a decrease in the viscosity of the resin and the workability is lowered. Further, the molecular weight of the obtained resin becomes too large. Therefore, the composition is composed of a radiation-sensitive resin containing the resin. When a film is formed on a substrate and exposed, the exposed portion is less likely to be dissolved in the developer, and it is difficult to obtain a target pattern. If the ratio of the di-anhydride is more than 90 moles of the total anhydride. In the case of /G, the molecular weight of the obtained resin becomes too small. Therefore, when a coating film is formed on a substrate by using a composition containing the resin, problems such as stickiness remaining on the coating film after prebaking tend to occur. In any of the above cases, when the epoxy ester resin (c) is reacted with a polycarboxylic acid or an anhydride thereof, and optionally a polyterpene alcohol, the reaction temperature is preferably 5 〇 to 3 〇 ° C, more preferably 70 ~120 °C. When the reaction temperature exceeds 13 Å < t, condensation of a carboxyl group and a hydroxyl group occurs locally, and the molecular weight sharply increases. On the other hand, if the hunger is not reached, the reaction will not proceed smoothly, and the unreacted polybasic acid or its anhydride remains. (Composite Resin Composition) In the composite resin composition of the present invention, the polyvalent carboxylic acid resin (D) preferably contains a radiation polymerizable functional group. Specifically, it preferably contains a (meth) acrylonitrile group or the like. Saturated base. When Yuke & 铋^ 丞多 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 Composite resin composition (Ε). Here, the photosensitive property is a property of chemical reaction generated by various kinds of radiation, and the above-mentioned radiation enthalpy, e, , e + = , and from the longer length of the skin, such as visible light , ultraviolet light, electrons, γ ▲ X-ray, α-ray, /5-ray, and τ-ray. Among these, in terms of economy, from the aspect of chirality, the ultraviolet rays in the continuous application are the best radiation. Sand & also green ultraviolet light, can be preferably used from low light 23 201127891 pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, arc lamp, xenon lamp and other lights emitted by ultraviolet light. The wavelength is shorter than the ultraviolet radiation and its chemical reaction! The car is 乂 and 'theoretically superior to the ultraviolet ray, but the ultraviolet ray is more practical from the economic point of view. In the case where the composite resin composition of the present invention is a photosensitive composite resin composition (E), it is preferred to add a photopolymerization initiator (F, further, in order to adjust the hardenability) or to adjust the film properties such as hardness after hardening. Addition of various photocurable monomers or photocurable materials other than the unsaturated group-containing polyvalent carboxylic acid resin (D) to the photosensitive composite resin composition (E) without impairing the effects of the present invention Resin (G) The photopolymerization initiator (F) is a compound having a photopolymerization initiation month and/or a sensitizing effect. The above compounds, for example, may be exemplified by the following compounds: acetophenone , 2,2-diethoxyphene, p-diacetophenone, p-didecylaminopropiophenone, diacetophenone, trichloroacetophenone, p-tert-butylacetophenone And other acetophenones; diphenyl bis-dimethylaminobenzhydrazide and other diphenyl hydrazines (be^, this oxime; benzoin (benz〇in); benzoin methyl ether, benzoin isopropyl ether benzoin Ding... Xiangxiangjun; benzoin dimethyl ketal (benzUdimethylketal); sulphur mountain comet, 2 Sulfur compounds such as Qiqikoushan σxing, 2xindiyi, its mouth, hawthorn, 2-methylsulfuric acid (tetra), 2-isopropylsulfonate, hawthorn, etc. , 2 • benzo- _, 2, 3 _ diphenyl phenolic brewing and other poor; azobisisobutyronitrile 1, benzophenone oxime, cumene peroxide, etc.; 2, a thiol compound such as a benzoyl benzothiazole. 24 201127891 The blending character 丨1 篁 of the first polymerization initiator (F) is relative to the unsaturated group. 100 parts by weight, preferably ～5.0 parts by weight. 1 〇. 〇 by weight, more preferably 0.1, as described above in the "unsaturated group-containing compound composition (E)", 曰 the above-mentioned photosensitive composite ^ , 含有 Containing a radiation-curable unsaturated group, including the polybasic acid of the present invention, Μ: 、, RI 兀蠼树脂 resin (D) and having a radioactive hardened polycarboxylic acid resin (9) Photocurable monomer or photocurable resin (G). The photopolymerization initiator (F) may be used singly or in combination of two or more kinds. Further, it may be added as it is. The function of the photopolymerization initiator is to use a compound which can increase the Moon & force of the photopolymerization initiator in combination with the above compound. From the compound, for example, if it is combined with diphenyl When a ketone is used in combination, a tertiary amine such as triethanolamine which exerts an effect is used. When a polybasic decanoic acid resin (D) does not contain an ultraviolet polycondensate b group such as an unsaturated group, it contains various photocurable monomers or A photocurable tree sap (G) or a quinone azide compound (called in〇nediazide) ((1) functions as a photosensitive composite resin composition (E) as a necessity to form a knives. In the case of the nitrogen compound (H), the photosensitive composite resin composition (E) of the present invention is a positive photosensitive composite resin composition. In the case of a positive resin composition, the composition itself is not hardened when photosensitive. In the case of a positive type, in order to obtain a cured film after patterning, for example, a thermosetting resin such as an epoxy compound (1) is added to the photosensitive composite resin composition (£), and the film is thermally cured after being irradiated with radiation. This can form a cured film. This thermosetting is mainly carried out by a crosslinking reaction of a carboxylic acid group of a polyvalent carboxylic acid resin (D) with an epoxy group of a ring compound (i) by heat. The photocurable monomer or the photocurable resin (G) is a monomer or oligomer which can be polymerized by radiation, and can be contained according to the physical properties of the composition for the purpose of use. Examples of such a monomer or oligomer which can be used for radiation polymerization include the following monomers or oligomers: (hydroxy) 2-hydroxyethyl acrylate (mercapto) acrylate 2 hydroxypropyl ester, ( (Hydroxy) hydroxy-based (hydrazino) acrylates such as 3-hydroxypropyl acrylate; ethylene glycol di(decyl) acrylate, diethylene glycol di(meth) acrylate, di(methyl) Triethylene glycol acrylate, tetraethylene glycol di(meth) acrylate, butylene glycol bis(decyl) acrylate, tris(hydroxy) propane tris(decyl) acrylate, trishydroxy ethane ethane Tris(indenyl)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, dipentaerythritol tetra(meth)acrylate, hexa(methyl) (N-decyl) acrylate such as dipentaerythritol acrylate or glyceryl (meth) acrylate. These monomers or oligomers may be used singly or in combination of two or more. These monomers or oligomers function as a viscosity adjusting agent or a photocrosslinking agent, and can be contained in a range that does not impair the properties of the resin composition of the present invention. Usually, at least the above monomers and the polymer are contained in the composition in an amount of 5 parts by weight or less based on the weight of the polycarboxylic acid resin _0 (). If the content of the monomer or oligomer exceeds 5 parts by weight, there is a possibility that problems occur in the dispersibility or uniformity of the inorganic fine particles. The above-mentioned brewed diazide compound (8) is preferably a warp! , 2_ brewed diazide acid compounded by the compound 'may be listed: trihydroxy di-bile " with u-naphthoquinone diazide sulfonic acid acetate, tetrahydroxy benzophenone _ and 1 > 2 _ Naphthoquinonediazidesulfonic acid 26 201127891 Telluride five & benzylidene oxime and 1,2-caffeine diazide acid acetate, "hydroxy benzophenone and hydrazine, 2-naphthalene An ester of quinonediazidesulfonic acid, an ester of bis(2,y-dihydroxyphenyl)fane with hydrazine, 2-naphthoquinonediazidesulfonic acid, bis(p-hydroxyphenyl)f and 1, Esterified product of 2-nazene diazidosulfonic acid, ester of tris(p-hydroxybenzene f.) and 1,2-nathromidine diazidosulfonic acid, 1, hydrazine, 1 · tris (p-hydroxybenzene) Base) B, and 1,2-money diazonitic acid brewing, bis (2,3,4_trihydroxyphenyl) and hydrazine, 2-phase diazide "acetate, 2,2_ double (2,3,4-: basic base) propyl institute and 1>?. naphthalene diazide acid acetate m #('5 methylhydroxyphenyl)-3-phenylpropane and hydrazine, 2 _Naphthoquinone diazide acid-esterified ester, 4,4,-[l_"4 n"4 ρ a — « _[里基笨基]-丨_methylethyl]phenyl] soil, 1 , 2-nine stack An ester of sulfonic acid, bis(2,5·didecyl-4-hydroxyphenyl)·2_hydroxy|| '-a basic methane and i,2·naphthoquinonediazidesulfonic acid =, 3,(8)|·Tetramethyl],i,cut,5,6,7,·hexanol and & an unantibiotic mixture of sulfonic acid, and -2, ^^, - T - 7,2,4, trihydroxyl: an esterified product of naphthoquinonediazidesulfonic acid, etc. Further a quinonediazide compound other than the above. The above epoxy compound (1) means having a toomer or a monomer. Epoxy broad-milk polymer varnish-type ring ί m... base compound 'for example, phenolic phenolic aldehyde: & milk tree sap, age-old (four) varnish-type epoxy resin, double (tetra) grease, double-hop F Type epoxy resin, epoxy resin such as double epoxy resin or alicyclic epoxy resin, and monomer having at least one epoxy group in biphenyl type, for example, shouting, p-butylbenzene, glycidol Test, isotrimole octahydrate diglycidyl diglycidyl diester, dilute, glycerol ester, allyl glycidol scale, methyl propylene oxide 27 201127891 acid glycidol hydrazine, etc. More than one species. It can be used in combination or in combination. 2 These epoxy compounds (1) can be contained in the range of the properties of the resin composition of the product, which is not damaged, usually. The epoxy resin (I) is contained in a ratio of less than 5 parts per 100 parts by weight of the resin (D), and is hardened by a composition containing B, 3 ° and more than 50 parts by weight. In addition, it is easy to cause breakage, and the adhesion is also easily lowered. Further, various additives (1) can be added to the composition of the rice cake of the present invention as needed. The additive (1)' may be a thermal polymerization inhibitor, an adhesion aid, a % oxygen hardening accelerator, a surfactant, an antifoaming agent, etc., and may be contained in the composition in an amount that does not impair the object of the present invention. The above thermal polymerization inhibitor may, for example, be benzodiazepine, p-benzoic acid monomethyl ether, pyrophenol (Pyr〇gallol), tert-butyl catechol, phenothiazine or the like. The auxiliary agent is contained in order to improve the adhesion of the obtained composition. The adhesion aid ' is preferably a money compound (functional money coupling agent) having a reactive substituent such as a county, a methyl propylene group, an isogas acid group or an epoxy group. Specific examples of the functional decane coupling agent include: trimethoxynonyl benzoic acid, methacryloxypropyl trimethoxy decane "-methacryl xypropyltrimethoxysilane, vinyl triethoxy decyl hydride, ethylene Trimethoxy decane, r-isocyanatopropyltriethoxy decane, r-methoxypropoxypropyltrimethoxy decane, stone _(3,4-epoxycyclohexyl)ethyl three曱oxydecane, and the like. ^ The above epoxy group hardening accelerator may, for example, be an amine compound, an imidazole 28 201127891 compound, a carboxylic acid, a phenol, a quaternary ammonium salt or a methylol group-containing compound. By containing a small amount of the epoxy group hardening accelerator, the heat resistance of the cured film to be heated and the properties such as solvent property, acid resistance, mineral filler property, adhesion, electrical properties, and hardness can be improved. The surfactant is contained, for example, in order to easily apply the liquid composition to the substrate, whereby the flatness of the resulting film is also improved. Examples of the surfactants include BM-l (manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.), and Fiu〇rad FC- 135,

Fluorad FC-170C、Fluorad FC-430 及 Fluorad FC-431(住友 3M 月又份有限公司製造）' Surfl〇n S-1 12、Surfi〇n s-l 13、 Surflcm S_131、Surfl〇n S141 及 Surn〇n s i45(旭硝子股份有限么司製造）、SH-28PA、SH-190、SH-193、SZ-6032、 SF 8428、DC-5 7 及 DC-190(T〇ray Silic〇ne 股份有限公司製造）等。 ★上述消泡劑，例如可列舉聚矽氧系、氟系、丙烯酸系等之化合物。本發明之複合樹脂組成物中可含之溶劑’只要為不與节成物中之各成分反應，且可溶解或分散該等之有機溶 ^ i則並無特別限制。例如可列舉如下化合物：曱醇、乙醇等醇類；四氫咬喃等喊類；乙二醇單曱醚、乙二醇二曱峻、乙 * 芮古田讨 —鮮甲基***、乙二醇單***等乙二醇醚類；曱基珞蘇乙酸酯、乙基賽珞蘇乙酸酯等乙二醇烷基醚乙酸類；_ 7 ^ 一醇二***、二乙二醇二曱醚、二乙二醇二丁醚、 29 201127891 二乙二醇乙基曱醚等二乙二醇二烷基醚類；二乙二醇單曱醚、二乙二醇單***、二乙二醇單丁醚等二乙二醇單烧基醚類；丙二醇單曱醚乙酸酯、丙二醇單***乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單*** 乙酸酯、二乙二醇單丁醚乙酸酯、3 ·.甲氧基丁基· 1 _乙酸醋荨烧二醇早烧基鍵乙酸醋類，曱本、·一甲本荨芳香族烴類；甲基乙基酮、曱基戊基酮、％己酮、4 -羧基-4 -甲基_2-戊酮等酮類；以及2-羥基丙酸乙酯、2-羥基-2-曱基丙酸甲醋、 2 -經基-2-曱基丙酸乙醋、乙氧基乙酸乙S旨、經基乙酸乙酿、 2-羥基-2-曱基丁酸曱酯、3-甲氧基丙酸甲酯、3-曱氧基丙酸乙醋、3·乙氧基丙酸曱g旨、3 -乙氧基丙酸乙g旨、乙酸乙自旨、乙酸丁酯 '乳酸甲酯、乳酸乙酯、琥珀酸二曱酿、號抬酸 —乙醋、己二酸二乙醋、丙二酸二乙S旨、草酸二丁酷等酷類。該等之中’較佳為乙二醇醚類、烷二醇單烷基醚乙酸略類、二乙二醇二烷基醚類、酮類及酯類，尤佳為3•乙氧基丙酸乙酯、乳酸乙酯、丙二醇單甲驗乙酸酿、_乙-醇單***乙酸酯及曱基戊基酮。該等溶劑可單獨使用1種，亦可混合使用2種以上。於添加上述溶劑之情形時，其摻合量較佳為組成物整體之5〜90重量％。 (薄膜及成形體）本發明中所使用之多元羧酸樹脂' 折射率大致為1 Μ 〜1.65(對於波長633 nm之光）’但對於高功能材料所要求 30 201127891 之：射率而&並不充分。又，本發明中所使用之利用氣相法合成之無機微粒子之折射率依無機微粒子之種類而大不相同，因此不能一概而論，例如於氧化鈦之情形時，雖亦取決於其結晶結構，但通常為UO〜21〇，高於多元羧酸樹脂。根據本發明，可於多元羧酸樹脂中摻合大量折射率更向之無機微粒子’故可由本發明之複合樹脂組成物獲得折射率極高之透明薄膜等’例如可使折射率& 175以上，較佳為1.8 0以上。將本發明之複合樹脂組成物硬化而獲得之硬化膜、成形體的折射率較高且透明性、耐熱性、耐光性等優異。因此本發明之組成物較佳地用作為例如以下者：顯示裝置、電子零件之保護膜用材料（例如用於彩色濾光片等液晶顯示元件、積體電路元件、固體攝影元件等之保護膜之形成材料）；層間絕緣膜及/或平坦化膜之形成材料；彩色光阻劑用黏合劑；印刷配線板製造中所使用之阻焊劑；以及於代替液晶顯示元件中珠粒間隔件之柱狀間隔件之形成中適用之鹼可溶型感光性組成物等。進而，本發明之組成物可較佳地用作各種光學零件（透鏡、LED、塑膠臈、基板、光碟等）之材料；該光學零件之保護膜形成用塗佈劑；光學零件用接著劑（光纖用接著劑等）；偏光板製造用塗佈劑；全像記錄用感光性樹脂組成物等。本發明之複合樹脂組成物硬化而得之薄膜及成形體亦為本發明之一。 31 201127891 [實施例] 以下’藉由實施例更具體說明本發明，但本發明並不限定於該等實施例。製造例1 (氣相法氧化鈦分散體之製備）將昭和電工股份有限公司製造之Super Titania F_2(氣相氧化法）100 g、及3_曱基丙烯醯基丙基三曱氧基矽烷（信越化學工業股份有限公司製造：KBM-503)50 g與丙二醇單曱醚乙酸酯（PGMEA)2000 g加以混合，以氧化鍅珠為媒介，利用塗料振盪器（Red Devil公司製造）分散5小時，獲得氧化鈦分散體。進而，將本分散體於6〇〜7(rc下加熱3小時，藉此進行表面處理，其後，利用減壓濃縮去除部分溶劑，獲侍固體成分為20重量％、平均粒徑為33 nm之氧化鈦分散體。製造例2(氣相法摻雜有銳之氧化鈦分散體之製備）將藉由瞬間氣相±成法合成之摻雜有銳之氧化鈦1 〇 g、及3-甲基丙稀醯基丙基三甲氧基石夕烧（信越化學工業股份有限公司製造·· KBM_5〇3)4 g與丙二醇單甲鱗乙酸酿 (PGMEA)2GG g加以混合，以氧化錯珠作為媒介，利用塗料振盪器_ —丨公司製造)分散5小時，獲得摻雜有铌之氧化鈦分散體。進而’將本分散體於6()〜耽下加執時，藉此進行表面處理，其後，利用減壓濃縮去除部分容劑，獲得固體成分為2〇重量％、平均粒徑為41·之穆雜有銀之氧化鈦分散體。藉由χ射線繞射分析確認該播雜有鈮之氧化鈦分散體為Nb固溶於⑽結晶中之固溶體。 32 201127891 製造例3(多元羧酸樹脂（i)之合成）於300 mi四口燒瓶中添加雙酚荞二縮水甘油醚 (bisphenol fluorene diglycidyl ether)(Osaka Gas Chemical 股份有限公司製造：0gsol PG)115 g(環氧當量27〇 g/eq)、作為觸媒之三乙基苄基氣化銨600 mg、作為聚合抑制劑之2,6-二異丁基苯酚30 mg、及丙烯酸36 g，一面以10 mL/分鐘之速度於其中吹入空氣，一面於90〜l〇〇t進行加熱溶解。繼而，將其緩緩升溫至12CTC。溶液成透明黏稠，於該狀態下繼續攪拌。於該期間，測定酸值，在酸值未達i .〇 mgK〇H/ g之前持續加熱攪拌，獲得淡黃色透明且固體狀之含縮環結構之環氧酯樹脂。酸值達到目標為止需要丨5小時。於該環氧酯樹脂中添加丙二醇單甲醚乙酸酯（PGMEA)65 g，：容解後’混合均苯四甲酸酐（PMDA)15 g、四氫鄰苯二曱酸酐 (THPA)7.6 g及溴化四乙基銨〇.1 g，使其緩緩升溫，於〜115°C下反應14小時。如此般，獲得多元羧酸樹脂（〇之 PGMEA溶液。酸酐之消失係藉由ir光譜確認。又，該多元緩酸樹脂⑴相當於上述多元羧酸樹脂 (D-a-ii) ° 製造例4(多元狻酸樹脂（2)之合成）以與製造例3同樣的方式獲得之含縮環結構之劈氧酿樹脂中添加丙二醇單曱醚乙酸酯（PGMEA)65 & β令 ’ S久多元醇之二-三羥曱基丙烷1.5 g，溶解後，混合均笑 J本四甲酸酐 (PMDA) 1 5 g及溴化四乙基銨〇_ 1 g，使其緩線斗。、、丌 '地，於1 1 0 〜1 1 5 °C下反應14小時。進而，添加四氫鄰！ _ I二曱酸針 33 201127891 (THPA)7.6 g，反應 10 小時Fluorad FC-170C, Fluorad FC-430 and Fluorad FC-431 (manufactured by Sumitomo 3M Ltd.) ' Surfl〇n S-1 12, Surfi〇n sl 13, Surflcm S_131, Surfl〇n S141 and Surn〇ns I45 (made by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF 8428, DC-5 7 and DC-190 (manufactured by T〇ray Silic〇ne Co., Ltd.) . The above antifoaming agent may, for example, be a compound such as polyfluorene, fluorine or acrylic. The solvent 'which may be contained in the composite resin composition of the present invention' is not particularly limited as long as it does not react with each component in the article and dissolves or disperses the organic solvent. For example, the following compounds may be mentioned: alcohols such as decyl alcohol and ethanol; tetrahydroanthracene and the like; ethylene glycol monoterpene ether, ethylene glycol ruthenium, ethylene* 芮 Gutian, fresh methyl ether, ethylene glycol Glycol ethers such as monoethyl ether; ethylene glycol alkyl ether acetates such as mercaptosulfuric acid ester and ethyl cyproterone acetate; _ 7 ^ monool diethyl ether, diethylene glycol dioxime ether , diethylene glycol dibutyl ether, 29 201127891 diethylene glycol dialkyl ether such as diethylene glycol ethyl oxime ether; diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol single Diethylene glycol monoalkyl ether such as butyl ether; propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethyl Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3 · methoxy butyl · 1 - acetic acid vinegar glycerol early burnt base bond acetic acid vinegar, 曱本,·一甲Benzo aromatic hydrocarbons; ketones such as methyl ethyl ketone, decyl amyl ketone, % hexanone, 4-carboxy-4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, 2 -hydroxy-2-mercaptopropionic acid methyl vinegar, 2-way -2-mercaptopropionic acid ethyl vinegar, ethoxyacetic acid ethyl s, transbasic acetic acid, 2-hydroxy-2-mercaptobutyrate, methyl 3-methoxypropionate, 3-hydrazine Ethyl oxypropionate, bismuth ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, diacetyl succinate Brewing, No. picking acid - Ethyl vinegar, adipic acid diacetic acid, malonic acid Diethyl S, oxalic acid Dibutyl cool and other cool categories. Among these, 'preferably, glycol ethers, alkanediol monoalkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters, and more preferably 3•ethoxypropane Ethyl acetate, ethyl lactate, propylene glycol monoacetic acid, _ ethyl-alcohol monoethyl acetate and decyl amyl ketone. These solvents may be used alone or in combination of two or more. In the case where the above solvent is added, the blending amount thereof is preferably from 5 to 90% by weight based on the whole of the composition. (Film and Shaped Body) The polycarboxylic acid resin used in the present invention has a refractive index of approximately 1 Μ to 1.65 (for a light having a wavelength of 633 nm) 'but is required for a highly functional material 30 201127891: Emissivity and & Not enough. Further, since the refractive index of the inorganic fine particles synthesized by the vapor phase method used in the present invention differs greatly depending on the type of the inorganic fine particles, it cannot be generalized. For example, in the case of titanium oxide, it depends on the crystal structure, but Usually UO~21〇, higher than the polycarboxylic acid resin. According to the present invention, a large amount of refractive index can be blended into the polyvalent carboxylic acid resin, so that a transparent film having a very high refractive index can be obtained from the composite resin composition of the present invention, for example, a refractive index & 175 or more can be obtained. Preferably, it is 1.80 or more. The cured film obtained by curing the composite resin composition of the present invention and the molded article have a high refractive index and are excellent in transparency, heat resistance, light resistance and the like. Therefore, the composition of the present invention is preferably used as, for example, a display device or a material for a protective film for an electronic component (for example, a protective film for a liquid crystal display element such as a color filter, an integrated circuit element, or a solid-state imaging element). Forming material); forming material of interlayer insulating film and/or planarizing film; adhesive for color photoresist; solder resist used in manufacturing of printed wiring board; and column for replacing bead spacer in liquid crystal display element An alkali-soluble photosensitive composition or the like which is suitable for formation of a spacer. Further, the composition of the present invention can be preferably used as a material for various optical parts (lenses, LEDs, plastic iridium, substrates, optical disks, etc.); a coating agent for forming a protective film of the optical parts; and an adhesive for optical parts ( An adhesive for optical fibers, etc.; a coating agent for producing a polarizing plate; a photosensitive resin composition for hologram recording, and the like. The film and the molded body obtained by curing the composite resin composition of the present invention are also one of the inventions. [Embodiment] Hereinafter, the present invention will be described more specifically by way of examples, but the invention is not limited to the examples. Production Example 1 (Preparation of a vapor phase titanium oxide dispersion) Super Titania F_2 (gas phase oxidation method) 100 g manufactured by Showa Denko Co., Ltd., and 3_mercaptopropenylpropyltrimethoxy decane ( Manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) 50 g mixed with propylene glycol monoterpene ether acetate (PGMEA) 2000 g, dispersed in a oxidized ruthenium beads using a paint shaker (manufactured by Red Devil) for 5 hours A titanium oxide dispersion was obtained. Further, the dispersion was heated at 6 Torr to 7 (rc) for 3 hours to carry out surface treatment, and then a part of the solvent was removed by concentration under reduced pressure to obtain a solid content of 20% by weight and an average particle diameter of 33 nm. Titanium oxide dispersion. Production Example 2 (Preparation of a vapor phase doped with a sharp titanium oxide dispersion) Doped with a sharp titanium oxide 1 〇g, and 3- Methyl propyl decyl propyl trimethoxy zebao (manufactured by Shin-Etsu Chemical Co., Ltd., KBM_5 〇 3) 4 g mixed with propylene glycol monomethylglycolic acid (PGMEA) 2GG g, using oxidized beads as a medium The dispersion was doped for 5 hours using a paint shaker (manufactured by Nippon Co., Ltd.) to obtain a titanium oxide doped dispersion. Further, when the dispersion was added to 6 () to the underarm, the surface treatment was carried out, and then a part of the solvent was removed by concentration under reduced pressure to obtain a solid content of 2% by weight and an average particle diameter of 41. It is a mixture of silver titanium oxide. It was confirmed by ray diffraction analysis that the cerium-doped titanium oxide dispersion was a solid solution in which Nb was dissolved in (10) crystals. 32 201127891 Production Example 3 (Synthesis of Polycarboxylic Acid Resin (i)) Bisphenol fluorene diglycidyl ether (Osaka Gas Chemical Co., Ltd.: 0 gsol PG) 115 was added to a 300-mil four-necked flask. g (epoxy equivalent: 27〇g/eq), triethylbenzylammonium vaporate 600 mg as a catalyst, 2,6-diisobutylphenol 30 mg as a polymerization inhibitor, and 36 g of acrylic acid Air was blown therein at a rate of 10 mL/min, and heated and dissolved at 90 to 1 Torr. Then, it slowly warmed up to 12 CTC. The solution became transparent and viscous, and stirring was continued in this state. During this period, the acid value was measured, and heating and stirring were continued until the acid value was less than 〇 mgK 〇 H / g to obtain a light yellow transparent and solid condensed ring structure-containing epoxy ester resin. It takes about 5 hours for the acid value to reach the target. Add propylene glycol monomethyl ether acetate (PGMEA) 65 g to the epoxy ester resin, after mixing, 'mixed pyromellitic anhydride (PMDA) 15 g, tetrahydrophthalic anhydride (THPA) 7.6 g And 1 g of tetraethylammonium bromide was added, and the temperature was gradually raised, and the reaction was carried out at -115 ° C for 14 hours. In this manner, a polycarboxylic acid resin (PGMEA solution of hydrazine was obtained. The disappearance of the acid anhydride was confirmed by ir spectroscopy. Further, the polybasic acid-reducing resin (1) corresponds to the above polycarboxylic acid resin (Da-ii). Production Example 4 (Multiple Synthesis of citric acid resin (2)) In the same manner as in Production Example 3, propylene glycol monoterpene ether acetate (PGMEA) 65 & Di-trihydroxypyranyl propane 1.5 g, after dissolving, mix J. tetramethyl anhydride (PMDA) 15 g and tetraethylammonium bromide 〇 1 g to make it slower. Ground, react at 14 ° C to 1 1 5 ° C for 14 hours. Further, add tetrahydroortho! _ I di citric acid needle 33 201127891 (THPA) 7.6 g, reaction for 10 hours

溶液。酸酐之消失係藉由丨尺光譜而姑ΜSolution. The disappearance of anhydride is based on the ruler spectrum

(D-b-iii)。製造例5 (多元叛酸樹脂（3)之合成）(D-b-iii). Production Example 5 (Synthesis of Multi-Resin Resin (3))

下反應14小時，獲得多元羧酸樹脂（3)之ρ(}ΜΕΑ 溶液。酸酐之消失係藉由IR光譜而確認。又，該多元羧酸樹脂（3)相當於上述多元羧酸樹脂 (D-a-i)。再者，下述式所示之環氧酯樹脂可利用曰本專利特開2009-1 85270號公報中揭示之方法而合成。The reaction was carried out for 14 hours to obtain a ρ(} 溶液 solution of the polyvalent carboxylic acid resin (3). The disappearance of the acid anhydride was confirmed by IR spectroscopy. Further, the polycarboxylic acid resin (3) corresponds to the above polycarboxylic acid resin (Dai) Further, the epoxy ester resin represented by the following formula can be synthesized by the method disclosed in Japanese Laid-Open Patent Publication No. 2009-1 85270.

比較製造例1 (多元羧酸樹脂（4)之合成）於3 0 〇 πι 1四口燒瓶中添加曱酴紛酸清漆型環氧樹脂 (〇1〇版份有限公司製造，丑卩1〇1〇11]^-680)115笆（環氧當量210 g/eq)作為觸媒之三乙基苄基氣化敍mg、作為聚合抑制劑之2,6-二異丁基笨紛3〇 mg、及丙稀酸36 g，一面以 10 mL/分鐘之速度於其中吹入空氣，一面於90〜i00°c下進 34 201127891 行加熱〉谷解。繼而，將其緩緩升溫至1 20°C。溶液成透明黏稠’於該狀態下繼續攪拌。於該期間測定酸值，在酸值未達1 ·〇 mgK〇H/ g之前持續加熱攪拌，獲得淡黃色透明且固體狀之環氧酯樹脂。酸值達到目標為止需要1 5小時。於該 %氧醋樹脂中添加丙二醇單曱醚乙酸酯（PGMEA)65 g，溶解後，混合四氫鄰苯二曱酸酐（THPA)7 6g及溴化四乙基銨〇」 g ,使其緩緩升溫，於丨1〇〜丨irc下反應14小時。如此般，獲得多元竣醆樹脂（4)之PGMEA溶液。酸酐之消失係藉由 IR光譜而確認。比較製造例2(利用液相法製備Ti〇2分散體）將作為利用液相法（水解）合成之氧化鈦的石原產業股份有限公司製造之氧化鈦TTO-5 1(A)(—次粒徑為3〇 nm)100 g、及作為分散劑之Βγκ Chemie Japan股份有限公司製造之DISPERBYK-112(固體成分為60重量％)16 7 g、 3-甲基丙烯醯基丙基三曱氧基矽烷（信越化學工業股份有限公司製造：KBM_5〇3)50 g與丙二醇單曱醚乙酸酯 (PGMEA)2000 g加以混合，以氧化锆珠作為媒介利用塗料振盪器（Red Devil公司製造）分散5小時，獲得氧化鈦分散體。進而，將本分散體於60〜7(rc下加熱3小時，藉此進行表面處理，其後，利用減壓濃縮去除部分溶劑，^得固體成分為21重量％、平均粒徑為35nm之氧化鈦分散體。實施例1〜5、比較例1〜2 根據表1之摻合而分別混合各成分，獲得複合樹脂組成物。此處，表丨所示之各成分之摻合比率係針對固^成 35 201127891 分（不包括溶劑）進行記載，分別添加.pgmea，以固體成分濃度成為20重量％之方式進行製備。對於所得之複合樹脂組成物，評價粒度分佈與穩定性。進而叫吏用旋轉器 (咖請），將該溶液塗佈於玻璃基板、切基板上，然後於 9〇°C之加熱板上預烘烤12()秒，形成厚度約i 口之塗膜。於氮氣環境下，使用25〇 w之高壓水銀燈，以4〇5nm之波長，以能量成為關她^之方式對具有該塗膜之玻璃基板及矽基板之塗膜表面照射光強度為9 5邊爪2之紫外、.良繼而使用〇.1重量％之碳酸鈉水溶液，於2 3。〇下進行 120秒之顯影處理，去除塗膜之未曝光部。其後，利用超純水進行清洗處理。將具有所得之薄膜之基板放人則之供箱中，進行30分鐘之後烘烤處理，使薄膜加熱硬化（以下，將以該方式硬化之膜稱作加熱硬化膜）。 < 1 >粒度分佈使用Malvern公司製造之Zetasizer Nan〇 zs，利用動態光散射法進行測定，根據散射強度分佈算出複合樹脂組成物之Z -平均粒徑。 < 2 >穩定性將實施例1〜5、比較例卜2中所得之複合樹脂組成物於密閉容器中以40t保存2週，以與上述〈i〉相同之方法測定保存後之粒度分佈。進而，求出z平均粒徑之變化率 [丨(於40C下保存2週後之Z-平均粒徑)_ (剛分散後之z平均粒徑）|/(剛分散後之Z_平均粒徑）]χ1〇〇。於該評價中值越小分散穩定性越良好。 36 201127891 m < 3 >總光線穿透率使用Suga Test Instruments股份有限公司製造之測霾古十 (hazemeter)HZ-2，對上述於玻璃基板上進行製膜所得之加熱硬化膜進行測定。 < 4>霧值使用Suga Test Instruments股份有限公司製造之測霾計 Η Z 2，對上述於玻璃基板上進行製膜所得之加熱硬化膜進行測定。 < 5 >折射率利用光干涉式膜質測定機，對上述所得之加熱硬化膜測定於6 3 2.8 n m之折射率。 <6>分光穿透率利用日立製造之分光光度計U-2000，對上述所得之加熱硬化膜測定可見光區域之分光穿透率，記錄400 nm之穿透率。 < 7 >顯影性不對上述具有預烘烤後之塗膜之玻璃基板進行曝光處理，而將其於〇. 1重量％之碳酸鈉水溶液中浸潰1 20秒，進行顯影。顯影後，利用流水將基板清洗3〇秒，以目視觀察送風乾燥後之基板狀態’確認有無殘留物，根據下述評價基準進行顯影性之評價。 ◎:於基板上無殘留物〇：於基板上見到少量殘留物 X .於基板上見到大量樹脂或無機微粒子之殘留物 37 201127891 < 8 >解析度於上述所得之具有預烘烤後之塗膜的玻璃基板上放置具有有10〜1 〇〇 V m線寬之線與間隙型圖案的遮罩，於上述條件下照射紫外線後，進行顯影處理。對於所得之基板，利用光學顯微鏡進行觀察，將殘留於基板上之線寬最小之圖案之線寬記錄為解析度。 < 9 >耐光性利用曰光式耐候測試機（Sunshine wether me ter)對上述所得之加熱硬化膜照射丨〇〇〇小時。求出照射前後分光穿透率之變化[(照射前之波長4〇〇 nm之穿透率）_ (照射後之波長400 nm之穿透率）]。於該評價中，值越小财光性越好。 < 1 0 >耐熱性將上述所得之加熱硬化膜於25〇t之烘箱中放置3小時，進行加熱。求出加熱前後分光穿透率之變化[(加熱前之波長400 nm之穿透率）_(加熱後之波長4〇〇 nm之穿透率）]。於該評價中，值越小对熱性越好。將以上結果示於表1中。 38 201127891 【1 <〕比較例編號 (N 1 1 1 ί 〇〇 1 1.56 1 85.9 0.88 1.85 89.2 〇 (N ro 1 1 1 1 5(註 4) Cs fO 0.10 87.0 0.54 1.73 90.8 ◎ 〇 (N CN 12.4 實施例編號 1 1 1 〇 1 1 〇 1 Os ro 0.01 87.4 0.32 in v〇 90.9 ◎ 〇〇 Ο (Ν 寸 1 1 〇 1 1 1 〇 1 0.02 88.1 0.55 CN 00 ◎ 〇 (N iTi Ο m • 1 1 i 〇 1 in 〇 1 ^T) 0.01 88.1 0.33 | 1.67 91.0 ◎ 〇 ^Τ) r·^ iTi CN (N 〇 1 ί 1 1 1 IT) 〇 m 0.01 87.2 0.42 1.81 89.9 ◎ CN 1 1 〇 1 1 1 〇 1 0.03 86.2 0.61 1.86 90.1 ◎ α\ ο (Ν 製造例1(氣相法）製造例2(氣相法）比較製造例2(液相法）製造例3 製造例4 製造例5 比較製造例1 IC907C註 1) 分散劑(註2) 光硬化性單體(註3) 平均粒徑穩定性總可見光穿透率(％) 霧值(％) 折射率(633 nm) 分光穿透率(400 nm) 顯影性解析度耐光性财熱性無機微粒子多元羧酸樹脂 _^1 聚合起始劑添加劑摻合物物性硬化膜之特性 201127891 (s主1 )Ciba Japan股份有限公司製造irgacure 907 (註 2)BYK Chemie Japan股份有限公司製造 DISPERBYK-1 12 (註3)曰本化藥股份有限公司製造Kayarad DPHA(二六丙烯酸季戊四醇酯） (註4)表示製備比較製造例2之Ti〇2分散體時所摻合之分散劑之量根據表1可知，本發明之複合樹脂組成物於無機微粒子之摻合量較高之情形下亦可形成穩定性較高，且各種光學特性、耐光性、耐熱性優異之硬化膜。 [產業上之可利用性] 本發明之複合樹脂組成物適合於光學用膜、顯示元件、彩色濾光片、觸控面板、電子紙、太陽電池、半導：元件等之構成零件用途β Α 【圖式簡單說明】無【主要元件符號說明】無 40Comparative Production Example 1 (Synthesis of Polycarboxylic Acid Resin (4)) A phthalic acid varnish type epoxy resin was added to a 30 〇πι 1 four-necked flask (manufactured by 〇1〇 Edition Co., Ltd., ugly 1〇1) 〇11]^-680) 115笆 (epoxy equivalent 210 g/eq) as a catalyst for triethyl benzyl gasification, 2,6-diisobutyl as a polymerization inhibitor, 3 〇mg And 36 g of acrylic acid, and air was blown into it at a rate of 10 mL/min on one side, and heated at a temperature of 90 to i00 °c. Then, slowly warm it to 1200 °C. The solution became transparent and viscous, and stirring was continued in this state. The acid value was measured during this period, and heating and stirring were continued until the acid value was less than 1 · 〇 mgK 〇 H / g to obtain a pale yellow transparent and solid epoxy ester resin. It takes 15 hours for the acid value to reach the target. 65 g of propylene glycol monoterpene ether acetate (PGMEA) was added to the % oxyacetate resin, and after dissolving, tetrahydrophthalic anhydride (THPA) 76 g and tetraethylammonium bromide were added to make Slowly warm up and react for 14 hours under 丨1〇~丨irc. In this manner, a PGMEA solution of a multi-component resin (4) was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy. Comparative Production Example 2 (Preparation of Ti〇2 dispersion by liquid phase method) Titanium oxide TTO-5 1 (A) manufactured by Ishihara Sangyo Co., Ltd., which is a titanium oxide synthesized by a liquid phase method (hydrolysis) 〇γκ Chemie Japan Co., Ltd. DISPERBYK-112 (solid content: 60% by weight) 16 7 g, 3-methylpropenyl propyl tridecyloxy group as a dispersing agent 50 g of decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM_5〇3) was mixed with 2000 g of propylene glycol monoterpene ether acetate (PGMEA), and dispersed by a paint shaker (manufactured by Red Devil Co., Ltd.) using zirconia beads as a medium. After hours, a dispersion of titanium oxide was obtained. Further, the dispersion was heated at 60 to 7 (rc for 3 hours to carry out surface treatment, and then a part of the solvent was removed by concentration under reduced pressure to obtain an oxide having a solid content of 21% by weight and an average particle diameter of 35 nm. Titanium dispersions Examples 1 to 5 and Comparative Examples 1 to 2 According to the blending of Table 1, the respective components were mixed to obtain a composite resin composition. Here, the blending ratio of each component shown in Table 系 is for solids. ^成35 201127891 (excluding solvent) was described, and .pgmea was added, and the solid content concentration was 20% by weight. The obtained composite resin composition was evaluated for particle size distribution and stability. Rotator (coffee), the solution was applied to a glass substrate, cut into a substrate, and then pre-baked on a hot plate at 9 ° C for 12 () seconds to form a coating film having a thickness of about i. Next, using a high-pressure mercury lamp of 25 〇w, the surface of the coating film of the glass substrate and the ruthenium substrate having the coating film is irradiated with light intensity of 9 边 5 nm at a wavelength of 4 〇 5 nm. UV, good, and then use 〇.1 heavy The amount of sodium carbonate aqueous solution was subjected to a development treatment for 120 seconds under a crucible for 120 seconds to remove the unexposed portion of the coating film. Thereafter, the cleaning treatment was performed by using ultrapure water, and the substrate having the obtained film was released. In the case, the film is baked for 30 minutes, and the film is heat-hardened (hereinafter, the film hardened in this manner is referred to as a heat-cured film). <1 > The particle size distribution is Zetasizer Nan〇zs manufactured by Malvern. The measurement was carried out by a dynamic light scattering method, and the Z-average particle diameter of the composite resin composition was calculated from the scattering intensity distribution. < 2 > Stability The composite resin compositions obtained in Examples 1 to 5 and Comparative Example 2 were subjected to The sealed container was stored at 40 t for 2 weeks, and the particle size distribution after storage was measured in the same manner as in the above <i>. Further, the rate of change of the z average particle diameter was determined [丨 (Z-average after 2 weeks of storage at 40 C) Particle size)_(z average particle diameter immediately after dispersion)|/(Z_average particle diameter immediately after dispersion)]χ1〇〇. The smaller the value in the evaluation, the better the dispersion stability. 36 201127891 m < 3 > Total light penetration using Suga Test In The hazemeter HZ-2 manufactured by struments Co., Ltd. was used to measure the heat-cured film obtained by forming the film on the glass substrate. <4> The fog value was measured by Suga Test Instruments Co., Ltd. The heat-cured film obtained by forming the film on the glass substrate was measured by Z 2 , and the refractive index of the obtained heat-cured film was measured at 6 3 2.8 by an optical interference film quality measuring machine. The refractive index of nm. <6> Spectroscopic transmittance The spectral transmittance of the visible light region was measured for the heat-cured film obtained above by using a spectrophotometer U-2000 manufactured by Hitachi, and the transmittance at 400 nm was recorded. <7 > developability The glass substrate having the above-mentioned pre-baked coating film was not subjected to exposure treatment, and it was immersed in a 1% by weight aqueous sodium carbonate solution for 1 to 20 seconds to carry out development. After the development, the substrate was washed with running water for 3 seconds, and the state of the substrate after the air-dried drying was visually observed to confirm the presence or absence of the residue, and the developability was evaluated in accordance with the following evaluation criteria. ◎: no residue on the substrate: a small amount of residue X was observed on the substrate. A large amount of resin or inorganic fine particles remained on the substrate. 37 201127891 < 8 > Resolution The pre-baking obtained in the above A mask having a line width of 10 to 1 〇〇V m line width and a gap pattern was placed on the glass substrate of the subsequent coating film, and after being irradiated with ultraviolet rays under the above conditions, development treatment was performed. The obtained substrate was observed by an optical microscope, and the line width of the pattern having the smallest line width remaining on the substrate was recorded as the resolution. <9 > Light resistance The heat-cured film obtained above was irradiated for a few hours by a glow-type weathering tester (Sunshine wether me ter). The change in the spectral transmittance before and after the irradiation [(the transmittance of the wavelength before irradiation of 4 〇〇 nm) _ (the transmittance of the wavelength after irradiation of 400 nm)] was determined. In this evaluation, the smaller the value, the better the fiscal property. <1 0 > Heat resistance The heat-cured film obtained above was allowed to stand in an oven of 25 Torr for 3 hours, and heated. The change in the spectral transmittance before and after heating [(the transmittance at a wavelength of 400 nm before heating) _ (the transmittance at a wavelength of 4 〇〇 nm after heating)] was determined. In this evaluation, the smaller the value, the better the heat. The above results are shown in Table 1. 38 201127891 [1 <] Comparative example number (N 1 1 1 ί 〇〇1 1.56 1 85.9 0.88 1.85 89.2 〇 (N ro 1 1 1 1 5 (Note 4) Cs fO 0.10 87.0 0.54 1.73 90.8 ◎ 〇 (N CN 12.4 Example No. 1 1 1 〇1 1 〇1 Os ro 0.01 87.4 0.32 in v〇90.9 ◎ 〇〇Ο (Ν inch 1 1 〇1 1 1 〇1 0.02 88.1 0.55 CN 00 ◎ 〇 (N iTi Ο m • 1 1 i 〇1 in 〇1 ^T) 0.01 88.1 0.33 | 1.67 91.0 ◎ 〇^Τ) r·^ iTi CN (N 〇1 ί 1 1 1 IT) 〇m 0.01 87.2 0.42 1.81 89.9 ◎ CN 1 1 〇1 1 1 〇1 0.03 86.2 0.61 1.86 90.1 ◎ α\ ο (Ν Production Example 1 (Gas-Finding Method) Production Example 2 (Gas-Fraction Method) Comparative Production Example 2 (Liquid Phase Method) Production Example 3 Production Example 4 Production Example 5 Comparative Manufacturing Example 1 IC907C Note 1) Dispersant (Note 2) Photocurable monomer (Note 3) Average particle size stability Total visible light transmittance (%) Fog value (%) Refractive index (633 nm) Spectral transmittance ( 400 nm) developability resolution light resistance, heat, inorganic fine particles, polycarboxylic acid resin, _1, polymerization initiator additive, property, physical properties, hardening film, characteristics, 201127891 (s 1) Ciba Japan Co., Ltd. manufactures irgacure 907 (Note 2) BYPER ChemK Japan Co., Ltd. manufactures DISPERBYK-1 12 (Note 3) Kayarad DPHA (pentaerythritol dihexaacrylate) manufactured by Sakamoto Chemical Co., Ltd. (Note 4) The amount of the dispersant blended in the preparation of the Ti 2 dispersion of Comparative Example 2 is shown in Table 1. It can be seen that the composite resin composition of the present invention can form stability even in the case where the amount of the inorganic fine particles is high. A cured film which is excellent in various optical properties, light resistance, and heat resistance. [Industrial Applicability] The composite resin composition of the present invention is suitable for an optical film, a display element, a color filter, and a touch panel. , electronic paper, solar cell, semi-conductor: components, components, etc. Use of parts Α [Simple description of the diagram] No [Main component symbol description] No 40

Claims

201127891 七、申請專利範圍： 1 ·種複合樹脂組成物，其係由利用氣相法合成之平岣粒徑為1〜1〇〇 nm之無機微粒子、及二具有選自由茚、四氫萘、苐、0山D星、蒽、及笨并蒽所構成之群中至少1種縮環結構的多元羧酸樹脂所構成。 2. 如申請專利範圍第丨項之複合樹脂組成物，其中該| 機微粒子為金屬氧化物。 3. 如申請專利範圍第2項之複合樹脂組成物，其中該金屬氧化物為選自由氧化鈦、氧化錯、及氧化銳所構成之群中至少1種。；士申明專利範圍第2項之複合樹脂組成物，其中該金屬氧化物為選自由摻雜有组之氧化鈦、及摻雜有铌之氧化鈦所構成之群中至少1種。 5 .如申明專利範圍第1項至第4項中任一項之複合树月曰，.且成物，其中邊具有縮環結構之多元羧酸樹脂係具有D山α星及苐之任一縮環結構者，且係含有不飽和基者。 6 ·如申請專利範圍第丨項至第4項中任一項之複合樹脂組成物，其中該具有縮環結構之多元羧酸樹脂係含有放射線聚合性官能基者。 7. 如申請專利範圍第6項之複合樹脂組成物’其進而含有光聚合起始劑。 8. 一種薄膜’其係使申請專利範圍第1項至第7項中任一項之複合樹脂組成物硬化而獲得。 9· 一種成形體’其係使巾請專利範圍第1項至第7項中 41 201127891 任一項之複合樹脂組成物硬化而獲得。 ίο.—種光學膜，其特徵在於：具有使申請專利範圍第1項至第7項樹脂組成物硬化而獲得之薄膜。11. 一種顯示元件，其特徵在於：具有使申請專利範圍第丨項至第7項樹脂組成物硬化而獲得之薄膜。 12. —種半導體元件，其特徵在於：具有使申請專利範圍第1項至第7項樹脂組成物硬化而獲得之成形體。任一項之複合任一項之複合任一項之複合八、圖式：無 42201127891 VII. Patent application scope: 1 . A composite resin composition which is composed of inorganic fine particles having a particle size of 1 to 1 〇〇 nm synthesized by a vapor phase method, and two selected from the group consisting of ruthenium and tetrahydronaphthalene. A polyvalent carboxylic acid resin having at least one condensed ring structure of a group consisting of 苐, 0, D, 蒽, and 笨蒽. 2. The composite resin composition of claim 3, wherein the machine microparticles are metal oxides. 3. The composite resin composition according to claim 2, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, oxidized oxidization, and oxidized sharp. The composite resin composition of the second aspect of the invention, wherein the metal oxide is at least one selected from the group consisting of titanium oxide doped with a group and titanium oxide doped with antimony. 5. A composite tree of the compound of any one of claims 1 to 4, wherein the polycarboxylic acid resin having a condensed ring structure has any one of D mountain alpha star and strontium. A condensed ring structure, and those containing an unsaturated base. The composite resin composition according to any one of claims 4 to 4, wherein the polyvalent carboxylic acid resin having a condensed ring structure contains a radiation polymerizable functional group. 7. The composite resin composition as claimed in claim 6 which further contains a photopolymerization initiator. A film which is obtained by hardening a composite resin composition according to any one of claims 1 to 7. 9. A molded body which is obtained by hardening a composite resin composition according to any one of claims 2011 to 1 of claim 41. An optical film comprising: a film obtained by curing a resin composition of the first to seventh aspects of the patent application. A display element comprising: a film obtained by hardening a resin composition of the third to seventh aspects of the patent application. A semiconductor device comprising a molded article obtained by curing a resin composition of the first to seventh aspects of the patent application. Any combination of any one of the composites of any one. 8. Pattern: None 42