TW201624115A - Colored curable composition, color filter, pattern forming method, method for producing color filter, solid-state imaging element and image display device - Google Patents
Colored curable composition, color filter, pattern forming method, method for producing color filter, solid-state imaging element and image display device Download PDFInfo
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Abstract
Description
本發明係有關一種著色硬化性組成物、彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件及圖像顯示裝置。The present invention relates to a color hardening composition, a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and an image display device.
近年來,由於數位相機、帶相機行動電話等的普及,電荷耦合器件(CCD)圖像感測器等固體攝像元件的需求大幅增加。作為該種顯示器、光學元件的主要裝置而使用彩色濾光片,進一步高感度化、小型化的要求提高。該種彩色濾光片通常具備紅(R)、緑(G)及藍(B)這3原色的著色圖案,發揮著將透射光分解為3原色之功能。In recent years, demand for solid-state imaging elements such as charge coupled device (CCD) image sensors has increased significantly due to the spread of digital cameras, camera-equipped mobile phones, and the like. As a main device of such a display or an optical element, a color filter is used, and the demand for further high sensitivity and miniaturization is improved. Such a color filter usually has red (R), green (G), and blue (B). The color patterns of the three primary colors function to decompose the transmitted light into three primary colors.
例如,在專利文献1~3中記載有使用含有呫噸色素之有機溶劑系著色硬化性組成物而製造彩色濾光片。For example, Patent Literatures 1 to 3 describe the production of a color filter using an organic solvent-based colored curable composition containing a xanthene dye.
【先前技術文獻】[Previous Technical Literature]
【專利文獻】[Patent Literature]
【專利文獻1】日本特開2013-235257號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-235257
【專利文獻2】日本特開2012-207158號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-207158
【專利文獻3】日本特開2013-61619號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-61619
在使用於彩色濾光片等之有機溶劑系著色硬化性組成物中,要求能夠形成顯影前後之分光變動較小,且耐光性優異之硬化膜。In the organic solvent-based coloring curable composition used for a color filter or the like, it is required to form a cured film having a small spectral variation before and after development and excellent light resistance.
例如,作為彩色濾光片的特性,耐光性為重要的課題,不僅著色劑相對於光之穩定性較低時,而且其他原材料相對於光之穩定性較低時,亦能夠使彩色濾光片的分光變動。本發明人等經過對呫噸色素進行各種研究之結果,被N-烷基化之呫噸具有耐光性較低的傾向,例如在使用了含有胺之分散劑之情況下,可知因由分散劑的分解產生之著色而具有產生損失藍色的分光之分光變動之傾向。For example, as a characteristic of a color filter, light resistance is an important subject, and a color filter can be made not only when the stability of the coloring agent with respect to light is low, but also when the stability of other materials with respect to light is low. The spectroscopic change. As a result of various studies on xanthene pigments, the present inventors have a tendency to have low light resistance by N-alkylated xanthene. For example, in the case of using an amine-containing dispersant, it is known that the dispersant is used. The color generated by the decomposition tends to cause a change in the spectral light that causes the loss of the blue splitting.
並且,在專利文献1~3中揭示有呫噸色素分散於有機溶劑中之著色硬化性組成物,但是依據本發明者的研究,在專利文献1~3中揭示之著色硬化性組成物中呫噸色素的分散性差,其結果,可知呫噸色素溶解於顯影液中,在顯影之後容易產生褪色,顯影前後的分光變動較大。進一步可知耐光性亦差。Further, in Patent Literatures 1 to 3, a color-curable composition in which a xanthene pigment is dispersed in an organic solvent is disclosed. However, in the color hardening composition disclosed in Patent Documents 1 to 3, according to the study of the present inventors, The dispersibility of the ton dye was poor, and as a result, it was found that xanthene pigment was dissolved in the developer, and fading was likely to occur after development, and the spectral shift before and after development was large. Further, it is known that light resistance is also poor.
本發明係鑑於該種情況而完成者,其目的在於提供能夠形成顯影前後的分光變動較小,且耐光性優異之膜之著色硬化性組成物。並且,其目的在於提供彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件及圖像顯示裝置。The present invention has been made in view of such circumstances, and an object of the invention is to provide a color-curable composition capable of forming a film having a small spectral variation before and after development and having excellent light resistance. Further, an object of the invention is to provide a color filter, a pattern forming method, a method of manufacturing a color filter, a solid-state image sensor, and an image display device.
本發明人等經過詳細的研究之結果,發現藉由使用著色硬化性組成物而能夠實現上述目的,並完成了本發明,該著色硬化性組成物含有後述之式(1)中表示之結構的呫噸化合物,亦即著色劑A、硬化性化合物及有機溶劑,並且著色劑A分散於有機溶劑中。本發明提供以下內容。As a result of a detailed study, the present inventors have found that the above object can be attained by using a colored curable composition containing a structure represented by the formula (1) described later. The xanthene compound, that is, the colorant A, the curable compound, and the organic solvent, and the colorant A is dispersed in an organic solvent. The present invention provides the following.
<1>一種著色硬化性組成物,含有具有下式(1)所表示之結構之著色劑A、硬化性化合物及有機溶劑,且著色劑A分散於有機溶劑中;<1> A colored curable composition comprising a coloring agent A having a structure represented by the following formula (1), a curable compound, and an organic solvent, and the coloring agent A is dispersed in an organic solvent;
【化學式1】 [Chemical Formula 1]
式中,R1 ~R10 分別獨立地表示氫原子、鹵素原子、烷基、芳基、-ORX1 、-SRX1 、-CORX1 、-COORX1 、-OCORX1 、-NRX1 RX2 、-NHCORX1 、-CONRX1 RX2 、-NHCONRX1 RX2 、-NHCOORX1 、-SO2 RX1 、-SO2 ORX1 或-NHSO2 RX1 ,In the formula, R 1 to R 10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR X1 , -SR X1 , -COR X1 , -COOR X1 , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 or -NHSO 2 R X1 ,
RX1 及RX2 分別獨立地表示氫原子、烷基或芳基,R X1 and R X2 each independently represent a hydrogen atom, an alkyl group or an aryl group.
R11 表示磺酸基或雙(磺醯基)醯亞胺基。R 11 represents a sulfonic acid group or a bis(sulfonyl) fluorenylene group.
<2>如<1>所記載之著色硬化性組成物,其中,在著色劑A中,式(1)的R1 、R5 、R6 及R10 分別獨立地為烷基。<2> The colored curable composition according to <1>, wherein, in the colorant A, R 1 , R 5 , R 6 and R 10 in the formula (1) are each independently an alkyl group.
<3>如<1>所記載之著色硬化性組成物,其中,在著色劑A中,式(1)的R1 、R5 、R6 及R10 分別獨立地為甲基、乙基或異丙基。<3> The colored curable composition according to <1>, wherein, in the colorant A, R 1 , R 5 , R 6 and R 10 of the formula (1) are each independently a methyl group, an ethyl group or Isopropyl.
<4>如<1>~<3>中任一項所記載之著色硬化性組成物,其中,在著色劑A中,式(1)的R11 為磺酸基,R2 、R3 、R4 、R7 、R8 及R9 為氫原子。In the coloring agent A, R 11 of the formula (1) is a sulfonic acid group, and R 2 and R 3 are , in the coloring agent A, the colored curing composition according to any one of the above-mentioned items. R 4 , R 7 , R 8 and R 9 are a hydrogen atom.
<5>如<1>~<4>中任一項所記載之著色硬化性組成物,其中,有機溶劑為選自由酯溶劑、醚溶劑、酮溶劑及醇溶劑之至少1種。The colored curable composition according to any one of <1> to <4>, wherein the organic solvent is at least one selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, and an alcohol solvent.
<6>如<1>~<5>中任一項所記載之著色硬化性組成物,其中,進一步含有光聚合起始劑,硬化性化合物為自由基聚合性化合物。The colored curing composition according to any one of the above aspects, further comprising a photopolymerization initiator, wherein the curable compound is a radical polymerizable compound.
<7>如<1>~<6>中任一項所記載之著色硬化性組成物,其中,進一步含有酸值為30mgKOH/g以上的酸性分散劑。The colored curable composition as described in any one of <1> to <6> further containing an acidic dispersing agent having an acid value of 30 mgKOH/g or more.
<8>如<7>中所記載之著色硬化性組成物,其中,含有2種以上酸性分散劑。<8> The colored curable composition as described in <7>, which contains two or more types of acidic dispersing agents.
<9>如<1>~<8>中任一項所記載之著色硬化性組成物,其中,進一步含有具有酞菁骨架之顔料。The colored hardening composition as described in any one of <1> to <8> which further contains the pigment which has a phthalocyanine skeleton.
<10>如<1>~<9>中任一項所記載之著色硬化性組成物,其中,進一步含有染料而作為著色劑A以外的著色劑。The colored curable composition as described in any one of <1> to <9> which further contains a dye as a coloring agent other than the coloring agent A.
<11>如<10>中所記載之著色硬化性組成物,其中,染料為具有選自酞菁、三芳基甲烷及吡咯亞甲基(Pyrromethene)之骨架之染料。<11> The colored curable composition according to <10>, wherein the dye is a dye having a skeleton selected from the group consisting of phthalocyanine, triarylmethane, and pyrromethene.
<12>如<1>~<11>中任一項所記載之著色硬化性組成物,其用於彩色濾光片。<12> The colored curable composition according to any one of <1> to <11> which is used for a color filter.
<13>一種彩色濾光片,其使用<1>~<12>中任一項所記載之著色硬化性組成物而形成。<13> A color filter which is formed using the colored curable composition according to any one of <1> to <12>.
<14>一種圖案形成方法,其包括以下步驟:使用<1>~<12>中任一項所記載之著色硬化性組成物,在支撐體上形成著色硬化性組成物層;將著色硬化性組成物層呈圖案狀進行曝光;及顯影去除未曝光部而形成著色圖案。<14> A pattern forming method comprising the step of forming a colored curable composition layer on a support by using the colored curable composition according to any one of <1> to <12>; The composition layer is exposed in a pattern; and the unexposed portion is removed by development to form a colored pattern.
<15>一種彩色濾光片的製造方法,其包括<14>所記載之圖案形成方法。<15> A method of producing a color filter, comprising the pattern forming method described in <14>.
<16>一種固體攝像元件,其具有<13>所記載之彩色濾光片,或者藉由<15>所記載之彩色濾光片的製造方法而得到之彩色濾光片。<16> A solid-state image sensor having the color filter described in <13> or a color filter obtained by the method for producing a color filter according to <15>.
<17>一種圖像顯示裝置,其具有<13>所記載的彩色濾光片,或者藉由<15>所記載的彩色濾光片的製造方法而得到之彩色濾光片。<17> An image display device comprising the color filter described in <13> or a color filter obtained by the method for producing a color filter according to <15>.
依本發明,可以提供能夠形成顯影前後之分光變動較小且耐光性優異之膜之著色硬化性組成物、彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件及圖像顯示裝置。According to the present invention, it is possible to provide a color-curable composition, a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and a pattern capable of forming a film having a small spectral variation before and after development and having excellent light resistance. Like a display device.
以下,對本發明的內容進行詳細的說明。Hereinafter, the contents of the present invention will be described in detail.
本說明書中之基團(原子團)的標記中,未標註取代及無取代之標記係包含不具有取代基者和具有取代基者。例如“烷基”係不僅包含不具有取代基之烷基(無取代烷基),而且亦包含具有取代基之烷基(取代烷基)者。In the label of the group (atomic group) in the present specification, the label which is not labeled and unsubstituted includes those having no substituent and having a substituent. For example, "alkyl" means not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
在本說明書中,光是指活性光線或放射線。並且,“活性光線”或“放射線”是指例如水銀灯的明線光譜、準分子雷射所代表之遠紫外線、極紫外線(EUV光)、X射線、電子束等。In the present specification, light means active light or radiation. Further, "active light" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like.
在本說明書中的“曝光”,只要沒有特別的說明,則不僅是指水銀灯的明線光譜、準分子雷射所代表之遠紫外線、X射線、EUV光等之曝光,電子束、離子束等粒子束之描畫亦包含於曝光中。The "exposure" in the present specification means not only the bright line spectrum of a mercury lamp, but also the exposure of far ultraviolet rays, X-rays, EUV light, etc. represented by excimer lasers, electron beams, ion beams, etc., unless otherwise specified. The painting of the particle beam is also included in the exposure.
在本說明書中,用“~”表示之數值範圍是指將“~”的前後所記載之數值作為下限值及上限值而包括在內之範圍。In the present specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.
在本說明書中,總固體成分是指從著色硬化性組成物的總體組成去除溶劑之後的成分的總質量。In the present specification, the total solid content refers to the total mass of the components after the solvent is removed from the overall composition of the colored curable composition.
在本說明書中,“(甲基)丙烯酸酯”表示丙烯酸酯及丙烯酸甲酯兩者或任一者,“(甲基)丙烯酸”表示丙烯酸及甲基丙烯酸兩者或任一者,“(甲基)烯丙基”表示烯丙基及甲基烯丙基兩者或任一者,“(甲基)丙烯醯基”表示丙烯醯基及甲基丙烯醯基兩者或任一者。In the present specification, "(meth) acrylate" means either or both of acrylate and methyl acrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A) The "allyl" group means either or both of an allyl group and a methallyl group, and "(meth)acryloyl group" means either or both of an acryloyl group and a methacryl group.
在本說明書中,聚合性化合物是指具有聚合性官能基之化合物,可以為單體,亦可為聚合物。聚合性官能基是指參與聚合反應之基團。In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in the polymerization reaction.
在本說明書中,“步驟的用語不僅包括獨立步驟,而且即使在無法與其他步驟明確地區別之情況下,只要能夠發揮其步驟的所期待的作用,則亦包括於該用語中。In the present specification, "the terminology of the step includes not only the independent steps but also the term as long as it can clearly exhibit the desired effect of the steps, even if it cannot be clearly distinguished from the other steps.
在本說明書中,結構式中之Me表示甲基,Et表示乙基,iPr表示異丙基。In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, and iPr represents an isopropyl group.
在本說明書中,重量平均分子量及數量平均分子量被定義為基於凝膠滲透色譜法(GPC)測定之聚苯乙烯換算值。In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by gel permeation chromatography (GPC).
在本說明書中,顔料是指不易溶解於溶劑之不溶性色素化合物。典型的是顔料以分散於有機溶劑中之狀態存在。在此,溶劑可以舉出任意的溶劑,例如可以舉出後述之溶劑一欄中例示之溶劑。在本發明中使用之顔料例如相對於23℃的丙二醇單甲醚乙酸酯100g之溶解量、及相對於23℃的水100g之溶解量均為0.1g以下為較佳。In the present specification, a pigment means an insoluble pigment compound which is not easily dissolved in a solvent. It is typical that the pigment exists in a state of being dispersed in an organic solvent. Here, the solvent may be any solvent, and examples thereof include a solvent exemplified in the solvent column described later. The pigment used in the present invention is preferably, for example, a dissolved amount of 100 g of propylene glycol monomethyl ether acetate at 23 ° C and a dissolved amount of 100 g with respect to water at 23 ° C of 0.1 g or less.
在本說明書中,染料是指容易溶解於溶劑的色素化合物。典型的是染料以在組成物中溶解有色素化合物之狀態存在。在此,溶劑可以舉出任意的溶劑,例如可以舉出在後述之溶劑一欄中例示之溶劑。在本發明中使用之染料例如相對於23℃的丙二醇單甲醚乙酸酯100g之溶解量超過2.0g為較佳。In the present specification, a dye means a dye compound which is easily dissolved in a solvent. It is typical that the dye exists in a state in which the pigment compound is dissolved in the composition. Here, the solvent may be any solvent, and examples thereof include a solvent exemplified in a solvent column to be described later. The dye used in the present invention is preferably dissolved in an amount of more than 2.0 g per 100 g of propylene glycol monomethyl ether acetate at 23 ° C.
在本說明書中只要沒有特別的說明,則具有重複單元之化合物中之重複單元比表示莫耳比。In the present specification, the repeating unit ratio in the compound having a repeating unit means a molar ratio unless otherwise specified.
<著色硬化性組成物><Coloring hardenable composition>
本發明的著色硬化性組成物含有具有在後述之式(1)中表示之結構之著色劑A、硬化性化合物及有機溶劑,著色劑A分散於有機溶劑中。The colored curable composition of the present invention contains a coloring agent A having a structure represented by the formula (1) to be described later, a curable compound, and an organic solvent, and the coloring agent A is dispersed in an organic solvent.
該著色劑A為固體,另外,相對於有機溶劑之溶解性較低,因此能夠抑制顯影後的褪色,並能夠製造在顯影前後之分光變動較小的彩色濾光片。並且,藉由使用本發明的著色硬化性組成物而能夠形成耐光性優異之彩色濾光片。Since the coloring agent A is a solid and has low solubility with respect to an organic solvent, it is possible to suppress fading after development, and it is possible to manufacture a color filter having a small variation in spectral light before and after development. Further, by using the colored curable composition of the present invention, a color filter excellent in light resistance can be formed.
另外,在本發明的著色硬化性組成物中,由於著色劑A分散於有機溶劑中而存在,因此能夠抑制著色劑的沉澱、凝聚等,且分散穩定性優異。並且,由於著色劑A難以熱拡散,因此能夠形成耐熱性優異之彩色濾光片。In addition, since the coloring agent A is dispersed in the organic solvent, the coloring agent A of the present invention can suppress precipitation, aggregation, and the like of the coloring agent, and is excellent in dispersion stability. Further, since the colorant A is hard to be thermally dispersed, it is possible to form a color filter excellent in heat resistance.
另外,在本發明中,“著色劑A分散於有機溶劑中”是指在有機溶劑中,著色劑A的粒子以漂浮或懸浮之狀態存在。著色劑A分散於有機溶劑中,例如能夠藉由使用動態光散射法之粒徑分佈測定來確認。Further, in the present invention, the "dispersion of the colorant A in the organic solvent" means that the particles of the colorant A exist in a state of floating or suspended in the organic solvent. The colorant A is dispersed in an organic solvent, and can be confirmed, for example, by particle size distribution measurement using a dynamic light scattering method.
以下,對本發明進行詳細的說明。Hereinafter, the present invention will be described in detail.
<<著色劑A>><<Coloring agent A>>
本發明的著色硬化性組成物含有具有在下式(1)中表示之結構之著色劑A。The color hardening composition of the present invention contains the coloring agent A having a structure represented by the following formula (1).
【化學式2】 [Chemical Formula 2]
R1 ~R10 分別獨立地表示氫原子、鹵素原子、烷基、芳基、-ORX1 、-SRX1 、-CORX1 、-COORX1 、-OCORX1 、-NRX1 RX2 、-NHCORX1 、-CONRX1 RX2 、-NHCONRX1 RX2 、-NHCOORX1 、-SO2 RX1 、-SO2 ORX1 或-NHSO2 RX1 ,R 1 to R 10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR X1 , -SR X1 , -COR X1 , -COOR X1 , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 or -NHSO 2 R X1 ,
RX1 及RX2 分別獨立地表示氫原子、烷基或芳基。R X1 and R X2 each independently represent a hydrogen atom, an alkyl group or an aryl group.
作為鹵素原子可以舉出氟原子、氯原子、溴原子、碘原子。Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
烷基的碳原子數為1~10為較佳,1~5為更佳,1~3為尤佳。烷基可以為直鏈、支鏈、環狀中的任意者,直鏈或支鏈為較佳。烷基為甲基、乙基、丙基或異丙基為較佳,甲基、乙基或異丙基為更佳。The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain, and a straight chain or a branched chain is preferred. The alkyl group is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and more preferably a methyl group, an ethyl group or an isopropyl group.
芳基可以是單環,亦可以是多環。芳基的碳原子數為6~25為較佳,6~15為進一步較佳,6~12為更佳。芳基亦可以含有雜原子。雜原子為氮原子、氧原子或硫原子為較佳。The aryl group may be a single ring or a polycyclic ring. The aryl group has preferably 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 12 carbon atoms. The aryl group may also contain a hetero atom. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
在式(1)中,R1 和R6 、R2 和R7 、R3 和R8 、R4 和R9 、R5 和R10 為相同的基團為較佳。In the formula (1), R 1 and R 6 , R 2 and R 7 , R 3 and R 8 , R 4 and R 9 , R 5 and R 10 are preferably the same group.
R1 、R5 、R6 及R10 為烷基為較佳。R1 、R5 、R6 及R10 分別獨立地為甲基、乙基或異丙基進一步較佳。依據該態樣,可以得到降低溶劑溶解性之效果。R 1 , R 5 , R 6 and R 10 are preferably an alkyl group. R 1 , R 5 , R 6 and R 10 are each independently preferably a methyl group, an ethyl group or an isopropyl group. According to this aspect, the effect of reducing the solubility of the solvent can be obtained.
R2 及R7 為氫原子為較佳。It is preferred that R 2 and R 7 are a hydrogen atom.
R3 及R8 分別獨立地為氫原子或烷基為較佳,氫原子為更佳。R 3 and R 8 are each independently a hydrogen atom or an alkyl group, and a hydrogen atom is more preferable.
R4 及R9 分別獨立地為氫原子、鹵素原子、烷基、芳基、-ORX1 、-SRX1 、-CORX1 、-COORX1 、-OCORX1 、-NRX1 RX2 、-NHCORX1 、-CONRX1 RX2 、-NHCONRX1 RX2 、-NHCOORX1 、-SO2 RX1 、-SO2 ORX1 或-NHSO2 RX1 為較佳,氫原子為更佳。R 4 and R 9 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR X1 , -SR X1 , -COR X1 , -COOR X1 , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 or -NHSO 2 R X1 are preferred, and a hydrogen atom is more preferred.
在本發明中,R2 、R3 、R4 、R7 、R8 及R9 為氫原子為尤佳。依據該態樣,可以得到提高每單元質量的吸光度之效果。In the present invention, R 2 , R 3 , R 4 , R 7 , R 8 and R 9 are preferably a hydrogen atom. According to this aspect, the effect of improving the absorbance per unit mass can be obtained.
R11 表示磺酸基或雙(磺醯基)醯亞胺基。從降低溶劑溶解性之觀點來看,磺酸基為較佳。R 11 represents a sulfonic acid group or a bis(sulfonyl) fluorenylene group. A sulfonic acid group is preferred from the viewpoint of reducing solvent solubility.
作為雙(磺醯基)醯亞胺基,可以舉出在下式(AN-1)中表示之基團。The bis(sulfonyl) fluorenylene imino group is a group represented by the following formula (AN-1).
【化學式3】 [Chemical Formula 3]
式中,R100 表示鹵素原子、烷基或芳基。In the formula, R 100 represents a halogen atom, an alkyl group or an aryl group.
鹵素原子為氟原子為較佳。It is preferred that the halogen atom is a fluorine atom.
烷基的碳原子數為1~10為較佳,1~5為更佳,1~3進一步較佳。烷基為直鏈或支鏈為較佳,直鏈為更佳。烷基中一部分氫原子被氟原子取代為較佳,所有氫原子被氟原子取代為更佳。R100 表示之烷基為所有氫原子被氟原子取代且碳原子數為1~10的烷基(全氟烷基)為較佳,碳原子數為1~4的全氟烷基進一步較佳,三氟甲基為尤佳。The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkyl group is preferably a straight chain or a branched chain, and a straight chain is more preferred. It is preferred that a part of hydrogen atoms in the alkyl group are substituted by a fluorine atom, and it is more preferable that all hydrogen atoms are replaced by a fluorine atom. The alkyl group represented by R 100 is preferably an alkyl group (perfluoroalkyl group) in which all hydrogen atoms are substituted by a fluorine atom and has 1 to 10 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms is further preferably used. Trifluoromethyl is especially preferred.
芳基的碳原子數為6~20為更佳,6~14為更佳,6~10進一步較佳。芳基可以具有取代基。作為取代基,可以舉出鹵素原子、烷基、烷氧基、羰基、羰氧基、胺基甲醯基、磺基、磺醯胺基、硝基等,鹵素原子或烷基為較佳、氟原子或烷基為更佳。The aryl group has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aryl group may have a substituent. The substituent may, for example, be a halogen atom, an alkyl group, an alkoxy group, a carbonyl group, a carbonyloxy group, an aminomethylcarbonyl group, a sulfo group, a sulfonylamino group or a nitro group, and a halogen atom or an alkyl group is preferred. A fluorine atom or an alkyl group is more preferable.
另外,在式(1)中表示之化合物中,陽離子如下非定域化而存在,下述結構係相同含義,且均係包含於本發明者。Further, in the compound represented by the formula (1), the cation is present as follows without delocalization, and the following structures have the same meanings and are included in the inventors.
【化學式4】 [Chemical Formula 4]
在本發明中,著色劑A為在下式(1a)中表示之結構為較佳,在下式(1b)中表示在結構為更佳。In the present invention, the colorant A is preferably a structure represented by the following formula (1a), and is more preferably represented by the following formula (1b).
【化學式5】 [Chemical Formula 5]
在上述式中,R1 ~R11 係與式(1)中說明之範圍相同含義,較佳的範圍亦相同。In the above formula, R 1 to R 11 have the same meanings as those described in the formula (1), and the preferred ranges are also the same.
著色劑A的分子量為500~900為較佳,550~800為更佳。著色劑A的分子量為由結構式求出之理論值。The colorant A preferably has a molecular weight of from 500 to 900, more preferably from 550 to 800. The molecular weight of the colorant A is a theoretical value obtained from the structural formula.
作為著色劑A的具體例,可以舉出以下者。Specific examples of the colorant A include the following.
【化學式6】 [Chemical Formula 6]
在本發明中,著色劑A相對於有機溶劑之溶解性較小為較佳。具體而言,著色劑A相對於23℃的丙二醇單甲醚乙酸酯100g之溶解量、著色劑A相對於23℃的環己酮100g之溶解量、及著色劑A相對於23℃的環戊酮100g之溶解量中的任一者為1g以下為較佳,前述著色劑A相對於各有機溶劑之的溶解量分別為1g以下為更佳。In the present invention, the solubility of the colorant A with respect to the organic solvent is preferably small. Specifically, the amount of the colorant A dissolved in 100 g of propylene glycol monomethyl ether acetate at 23 ° C, the amount of the colorant A dissolved in 100 g of cyclohexanone at 23 ° C, and the ring of the coloring agent A with respect to 23 ° C Any one of the amounts of the pentanone 100 g dissolved is preferably 1 g or less, and the amount of the colorant A dissolved in each organic solvent is preferably 1 g or less.
在本發明中,著色劑A係微細且被整粒化者為較佳。作為著色劑A的微細化方法,例如可以舉出將著色劑A、有機溶劑及水溶性無機鹽類一同製備高黏度的液體狀組成物,並使用濕式粉碎裝置等施加應力而進行磨碎之方法等。In the present invention, it is preferred that the coloring agent A is fine and granulated. As a method of refining the coloring agent A, for example, a liquid composition having a high viscosity is prepared by using a coloring agent A, an organic solvent, and a water-soluble inorganic salt, and is ground by applying a stress using a wet pulverizing apparatus or the like. Method, etc.
作為有機溶劑,可以舉出後述之有機溶劑。微細化步驟中之有機溶劑的使用量,相對於100質量份的著色劑A為50~300質量份為較佳,100~200質量份為更佳。The organic solvent mentioned later can be mentioned as an organic solvent. The amount of the organic solvent used in the refining step is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of the coloring agent A.
作為水溶性無機鹽類,可以舉出氯化鈉、氯化鉀、氯化鈣、氯化鋇、硫酸鈉等。微細化步驟中之水溶性無機鹽類的使用量為相對於1質量份的著色劑A為1~50質量份為較佳,1~10質量份為更佳。並且,使用水份為1%以下的水溶性無機鹽類為較佳。Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate. The amount of the water-soluble inorganic salt to be used in the refining step is preferably 1 to 50 parts by mass, more preferably 1 to 10 parts by mass, per part by mass of the coloring agent A. Further, a water-soluble inorganic salt having a water content of 1% or less is preferably used.
關於著色劑A的微細化步驟中之濕式粉碎裝置的運轉條件並無特別的限制,為了有效地進行由粉碎介質進行之磨碎,當裝置係捏合機時的運轉條件為,裝置內的葉片的轉速為10~200rpm為較佳,並且二軸的旋轉比相對較大者磨碎效果較大而較佳。運轉時間聯同乾式粉碎時間為1~8小時為較佳,裝置的內部溫度為50~150℃為較佳。並且作為粉碎介質之水溶性無機鹽的粉碎粒度為5~50μm、粒徑的分佈窄、且球形為較佳。The operating conditions of the wet pulverizing apparatus in the miniaturization step of the coloring agent A are not particularly limited, and in order to efficiently perform the grinding by the pulverizing medium, the operating conditions when the apparatus is a kneading machine are the blades in the apparatus. The rotation speed is preferably from 10 to 200 rpm, and the two-axis rotation ratio is relatively large, and the grinding effect is large and preferable. The running time in combination with the dry pulverization time is preferably from 1 to 8 hours, and the internal temperature of the apparatus is preferably from 50 to 150 °C. Further, the water-soluble inorganic salt as the pulverization medium has a pulverized particle size of 5 to 50 μm, a narrow particle diameter distribution, and a spherical shape.
本發明的著色硬化性組成物中,著色劑A在組成物中作為粒子而存在為較佳。尤其,著色劑A的平均粒徑(r)滿足20nm≤r≤300nm,滿足25nm≤r≤250nm為較佳,滿足30nm≤r≤200nm為尤佳。若著色劑A的平均粒徑(r)在上述範圍內,則能夠得到高對比度且高光透射率的彩色濾光片。在此所謂之“平均粒徑”是指關於著色劑A的一次粒子(單微晶)聚集之二次粒子的平均粒徑。能夠用掃描型電子顕微鏡(SEM)或透射型電子顕微鏡(TEM)進行観察,在粒子未凝集之部分計測100個粒子的尺寸並計算出平均值,從而求出平均粒徑。In the color hardening composition of the present invention, the coloring agent A is preferably present as particles in the composition. In particular, the average particle diameter (r) of the colorant A satisfies 20 nm ≤ r ≤ 300 nm, preferably 25 nm ≤ r ≤ 250 nm, and more preferably 30 nm ≤ r ≤ 200 nm. When the average particle diameter (r) of the colorant A is within the above range, a color filter having high contrast and high light transmittance can be obtained. The "average particle diameter" as used herein means the average particle diameter of secondary particles in which primary particles (single crystallites) of the colorant A are aggregated. The average particle diameter can be determined by scanning with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring the size of 100 particles in a portion where the particles are not aggregated, and calculating an average value.
並且,期望在本發明中可以使用之著色劑A的二次粒子的粒徑分佈(以下簡稱為“粒徑分佈”)中,在(平均粒徑±100)nm內的二次粒子為整體的70質量%以上,80質量%以上為較佳。另外,在本發明中,粒徑分佈利用散射強度分佈來測定。Further, in the particle size distribution of the secondary particles of the coloring agent A (hereinafter simply referred to as "particle size distribution") which can be used in the present invention, it is desirable that the secondary particles in the (average particle diameter ± 100) nm are integral. 70% by mass or more and 80% by mass or more are preferable. Further, in the present invention, the particle size distribution is measured by the scattering intensity distribution.
在本發明的著色硬化性組成物中,上述著色劑A相對於著色硬化性組成物的總固體成分之含量為10~80質量%為較佳。下限為20質量%以上為更佳,30質量%以上進一步較佳。上限為70質量%以下為更佳,60質量%以下進一步較佳。In the colored curable composition of the present invention, the content of the coloring agent A relative to the total solid content of the colored curable composition is preferably from 10 to 80% by mass. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.
並且,著色劑總量中之上述著色劑A的含量為30~100質量%為較佳。下限為40質量%以上為更佳,50質量%以上進一步較佳。上限為90質量%以下為更佳,80質量%以下進一步較佳。Further, the content of the coloring agent A in the total amount of the colorant is preferably from 30 to 100% by mass. The lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
著色劑A可以係1種。並且,上述通式(1)的R1 ~R11 亦可以係含有2種以上不同之組合的化合物者。在含有2種以上之情況下,總量在上述範圍內為較佳。The coloring agent A can be one type. Further, R 1 to R 11 in the above formula (1) may be a compound containing two or more different combinations. When two or more types are contained, the total amount is preferably in the above range.
<<其他著色劑>><<Other coloring agents>>
本發明的著色硬化性組成物亦可以含有除上述著色劑A以外的其他著色劑,含有其他著色劑者為較佳。其他著色劑可以係染料及顔料中的任一者,亦可以併用兩者。其他著色劑可以為1種,亦可以為2種以上。The colored curable composition of the present invention may contain a coloring agent other than the above-mentioned coloring agent A, and it is preferable to contain other coloring agents. Other colorants may be any of a dye and a pigment, or both may be used in combination. The other coloring agents may be used alone or in combination of two or more.
作為顔料,可以舉出以往公知的各種無機顔料或有機顔料。並且,無論是無機顔料,還是有機顔料,在考慮係高透射率者為較佳時,盡可能使用平均粒徑較小的顔料為較佳,亦考慮處理性時,上述顔料的平均粒徑為0.01~0.1μm為較佳,0.01~0.05μm為更佳。Examples of the pigment include various conventional inorganic pigments or organic pigments. Further, in the case of an inorganic pigment or an organic pigment, in consideration of a high transmittance, it is preferred to use a pigment having a small average particle diameter as much as possible, and in consideration of handleability, the average particle diameter of the pigment is It is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.
作為無機顔料,可以舉出由金屬氧化物、金屬錯鹽等表示之金屬化合物,具體而言,可以舉出碳黑、鈦黑等黑色顔料、鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等金屬氧化物及上述金屬的複合氧化物。Examples of the inorganic pigment include a metal compound represented by a metal oxide, a metal salt or the like, and specific examples thereof include black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, and titanium. a metal oxide such as magnesium, chromium, zinc or bismuth and a composite oxide of the above metals.
本發明中作為能夠優選使用之有機顔料,可以舉出以下者。但是本發明係不限定於該等者。In the present invention, the following organic pigments can be preferably used. However, the present invention is not limited to these.
色指數(Color Index)(C.I.)顏料黃1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214等,Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34 , 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86 , 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128 , 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174 , 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.
C.I.顏料橙2、5、13、16、17:1、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、71、73等,CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 Wait,
C.I.顏料紅1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48:1、48:2、48:3、48:4、49、49:1、49:2、52:1、52:2、53:1、57:1、60:1、63:1、66、67、81:1、81:2、81:3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、270、272、279CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279
C.I.顏料綠7、10、36、37、58C.I. Pigment Green 7, 10, 36, 37, 58
C.I.顏料紫1、19、23、27、32、37、42C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C.I.顏料藍1、2、15、15:1、15:2、15:3、15:4、15:6、16、22、60、64、66、79、80C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80
C.I.顏料黑1C.I. Pigment Black 1
該些有機顔料能夠單獨使用,或者為了提高色彩純度而能夠組合各種顏料而使用。These organic pigments can be used singly or in combination with various pigments in order to improve color purity.
其中,具有酞菁骨架之顔料(亦稱作酞菁顔料)為較佳,C.I.顏料藍15:6為更佳。Among them, a pigment having a phthalocyanine skeleton (also referred to as a phthalocyanine pigment) is preferred, and C.I. Pigment Blue 15:6 is more preferred.
作為染料能夠使用例如揭示於日本特開昭64-90403號公報、日本特開昭64-91102號公報、日本特開平1-94301號公報、日本特開平6-11614號公報、日本特登2592207號、美國專利4808501號說明書、美國專利5667920號說明書、美國專利505950號說明書、美國專利5667920號說明書、日本特開平5-333207號公報、日本特開平6-35183號公報、日本特開平6-51115號公報、日本特開平6-194828號公報等中之色素。若作為化學結構而區分,能夠使用吡唑偶氮化合物、吡咯亞甲基化合物、苯胺基偶氮化合物、三苯基甲烷化合物、蒽醌化合物、亞芐基化合物、氧雜菁化合物、吡唑并***偶氮化合物、吡啶酮偶氮化合物、花青化合物、啡噻嗪化合物、吡咯并吡唑偶氮次甲基(pyrrolo pyrazole azomethine)化合物等。並且,作為染料亦可以使用色素多聚物。作為色素多聚物,可以舉出在日本特開2011-213925號公報、日本特開2013-041097號公報中記載之化合物。For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, and JP-A No. 2592207 can be used. , U.S. Patent No. 4,808, 051, U.S. Patent No. 5, 568, 920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 595, 950, U.S. Patent No. 5,567, 920, Japanese Patent Application Laid-Open No. Hei No. Hei No. 5-333207, Japanese Patent Laid-Open No. Hei 6-35183, No. 6-51115 A pigment in the publication of Japanese Laid-Open Patent Publication No. Hei 6-194928. If it is distinguished as a chemical structure, a pyrazole azo compound, a pyrrolemethylene compound, an anilino azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxophthalocyanine compound, or a pyrazole can be used. A triazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, or the like. Further, a dye polymer can also be used as the dye. The compound described in JP-A-2011-213925, and JP-A-2013-041097 can be mentioned as a pigment.
在本發明中,染料為具有選自酞菁、三芳基甲烷及吡咯亞甲基之骨架之染料為較佳,具有酞菁骨架或三芳基甲烷骨架之染料為更佳,具有酞菁骨架之染料進一步較佳。藉由含有該些染料,能夠在組成物中提高上述著色劑A的分散性。另外,提高耐熱性及耐光性。In the present invention, the dye is preferably a dye having a skeleton selected from the group consisting of phthalocyanine, triarylmethane and pyrromethylene, and a dye having a phthalocyanine skeleton or a triarylmethane skeleton is more preferable, and a dye having a phthalocyanine skeleton. Further preferred. By containing these dyes, the dispersibility of the above-mentioned coloring agent A can be improved in the composition. In addition, heat resistance and light resistance are improved.
具有酞菁骨架之染料(亦稱作酞菁染料)例如可以舉出下式(F)中表示之化合物。The dye having a phthalocyanine skeleton (also referred to as a phthalocyanine dye) may, for example, be a compound represented by the following formula (F).
式(F)Formula (F)
【化學式7】 [Chemical Formula 7]
在式(F)中,M1 表示金屬原子或金屬化合物。作為金屬原子或金屬化合物,可以舉出2價的金屬原子、2價的金屬氧化物、2價的金屬氫氧化物或2價的金屬氯化物。例如可以舉出Zn、Mg、Si、Sn、Rh、Pt、Pd、Mo、Mn、Pb、Cu、Ni、Co及Fe等金屬原子、AlCl、InCl、FeCl、TiCl2 、SnCl2 、SiCl2 、GeCl2 等金屬氯化物、TiO、VO等金屬氧化物、Si(OH)2 等金屬氫氧化物。尤其Cu為較佳。In the formula (F), M 1 represents a metal atom or a metal compound. Examples of the metal atom or the metal compound include a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. For example, metal atoms such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, AlCl, InCl, FeCl, TiCl 2 , SnCl 2 , SiCl 2 , Metal chloride such as GeCl 2 , metal oxide such as TiO or VO, or metal hydroxide such as Si(OH) 2 . In particular, Cu is preferred.
Rp1 ~Rp16 分別獨立地表示氫原子、鹵素原子、烷基、芳基、-ORX1 、-SRX1 、-CORX1 、-COORX1 、-OCORX1 、-NRX1 RX2 、-NHCORX1 、-CONRX1 RX2 、-NHCONRX1 RX2 、-NHCOORX1 、-SO3 M2 、-SO2 RX1 、-SO2 ORX1 、-NHSO2 RX1 或-SO2 NRX1 RX2 ,RX1 及RX2 分別獨立地表示氫原子、烷基或芳基,M2 可以舉出四級銨陽離子、1價的金屬原子例如鈉、鋰、鉀等,2價的金屬原子例如Mg、Ca、Zn、Mg、Si、Sn、Rh、Pt、Pd、Mo、Mn、Pb、Cu、Ni、Co等。在分光優異之觀點上,在下式(F-1)中表示之化合物為尤佳。Rp 1 to Rp 16 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR X1 , -SR X1 , -COR X1 , -COOR X1 , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 3 M 2 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 or -SO 2 NR X1 R X2 ,R X1 and R X2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and M 2 may be a quaternary ammonium cation, a monovalent metal atom such as sodium, lithium or potassium, or a divalent metal atom such as Mg or Ca. Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and the like. From the viewpoint of excellent spectroscopicity, a compound represented by the following formula (F-1) is particularly preferable.
式(F-1)Formula (F-1)
【化學式8】 [Chemical Formula 8]
在式(F-1)中,M1 表示金屬原子或金屬化合物。式(F-1)的M1 與式(F)的M1 係相同含義,較佳的範圍亦相同。In the formula (F-1), M 1 represents a metal atom or a metal compound. The same meaning as M 1 M Department of formula (F-1) 1 and the formula (F), the preferred range is also the same.
在式(F-1)中,Ra 及Rb 分別獨立地表示氫原子、烷基、或芳基。In the formula (F-1), R a and R b each independently represent a hydrogen atom, an alkyl group, or an aryl group.
Ra 及Rb 表示之烷基的碳原子數為1~10為較佳。烷基為直鏈或支鏈為較佳。烷基可以無取代,亦可以具有取代基。作為取代基,可以舉出芳基、烷氧基、烯丙氧基、芳氧基、鹵素原子等。The alkyl group represented by R a and R b preferably has 1 to 10 carbon atoms. It is preferred that the alkyl group be a straight chain or a branched chain. The alkyl group may be unsubstituted or may have a substituent. The substituent may, for example, be an aryl group, an alkoxy group, an allyloxy group, an aryloxy group or a halogen atom.
Ra 及Rb 表示之芳基可以為單環,亦可以為多環。碳原子數為6~25為較佳,6~15進一步較佳,6~12為更佳。芳基可以含有雜原子。雜原子為氮原子、氧原子或硫原子為較佳。芳基可以無取代,亦可以具有取代基。作為取代基,可以舉出烷基、烷氧基、烯丙氧基、鹵素原子等。The aryl group represented by R a and R b may be a single ring or a polycyclic ring. The number of carbon atoms is preferably 6 to 25, more preferably 6 to 15, and even more preferably 6 to 12. The aryl group may contain a hetero atom. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The aryl group may be unsubstituted or may have a substituent. The substituent may, for example, be an alkyl group, an alkoxy group, an allyloxy group or a halogen atom.
在式(F-1)中,X可以舉出羧基、磺基等酸基及其鹽。作為構成鹽之原子或原子團,可以舉出鋰、鈉、鉀等金屬原子、四丁基銨等四級銨。In the formula (F-1), X may be an acid group such as a carboxyl group or a sulfo group or a salt thereof. Examples of the atom or atomic group constituting the salt include a metal atom such as lithium, sodium or potassium, and a quaternary ammonium salt such as tetrabutylammonium.
n表示1~10的整數,1~5為較佳。n represents an integer of 1 to 10, and 1 to 5 is preferred.
a、b、c分別獨立地表示0~8,a及b中的至少一者為1以上,a、b、c的合計為1~8。a, b, and c each independently represent 0 to 8, and at least one of a and b is 1 or more, and the total of a, b, and c is 1 to 8.
作為酞菁染料的具體例,例如可以舉出以下化合物、或国際公開WO2009/119364號小冊子的段落號0044~0059中記載的化合物。Specific examples of the phthalocyanine dye include the following compounds, and the compounds described in paragraphs 0044 to 0059 of WO2009/119364 pamphlet.
【化學式9】 [Chemical Formula 9]
具有三芳基甲烷骨架之染料(亦稱作三芳基甲烷染料)例如可以舉出下式(TP)中表示之化合物。The dye having a triarylmethane skeleton (also referred to as a triarylmethane dye) may, for example, be a compound represented by the following formula (TP).
式(TP)Formula (TP)
【化學式10】 [Chemical Formula 10]
在式(TP)中,Rtp1 ~Rtp4 分別獨立地表示氫原子、烷基或芳基。Rtp5 表示氫原子、烷基、芳基或NRtp9 Rtp10 (Rtp9 及Rtp10 表示氫原子、烷基或芳基)。Rtp6 、Rtp7 及Rtp8 表示取代基。a、b及c表示0~4的整數。在a、b及c為2以上的情況下,Rtp6 、Rtp7 及Rtp8 亦可以分別連接而形成環。X- 表示陰離子結構。In the formula (TP), Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp 5 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 9 Rtp 10 (Rtp 9 and Rtp 10 represent a hydrogen atom, an alkyl group or an aryl group). Rtp 6 , Rtp 7 and Rtp 8 represent a substituent. a, b, and c represent integers from 0 to 4. When a, b, and c are 2 or more, Rtp 6 , Rtp 7 , and Rtp 8 may be bonded to each other to form a ring. X - represents an anionic structure.
在式(TP)中,作為X- 表示之陰離子結構,選自磺酸陰離子、羧酸陰離子、磺醯亞胺陰離子、雙(烷基磺醯基)醯亞胺陰離子、三(烷基磺醯基)甲基化物陰離子、羧酸陰離子、四芳基硼酸陰離子、-CON- CO-、-CON- SO2 -、BF4 - 、PF6 - 、SbF6 - 、B- (CN)3 OCH3 之至少一種為較佳。選自磺酸陰離子、磺醯亞胺陰離子、雙(烷基磺醯基)醯亞胺陰離子、三(烷基磺醯基)甲基化物陰離子、羧酸陰離子、四芳基硼酸陰離子、BF4 - 、PF6 - 及SbF6 - 之至少一種為更佳。In the formula (TP), the anion structure represented by X - is selected from the group consisting of a sulfonic acid anion, a carboxylic acid anion, a sulfonimide anion, a bis(alkylsulfonyl) quinone imine anion, and a tris(alkylsulfonate). yl) methide anion, carboxylate anion, tetraarylborate anion, -CON - CO -, - CON - SO 2 -, BF 4 -, PF 6 -, SbF 6 -, B - (CN) 3 OCH 3 At least one of them is preferred. Selected from a sulfonate anion, a sulfonium imide anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl)methide anion, a carboxylate anion, a tetraarylborate anion, BF 4 - at least one of PF 6 - and SbF 6 - is more preferred.
在式(TP)中,Rtp1 ~Rtp6 為氫原子、碳原子數1~5的直鏈或支鏈的烷基及苯基為較佳。Rtp5 為氫原子或NRtp9 Rtp10 為較佳、NRtp9 Rtp10 為尤佳。In the formula (TP), Rtp 1 to Rtp 6 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp 5 is preferably a hydrogen atom or NRtp 9 Rtp 10 , and NRtp 9 Rtp 10 is particularly preferred.
在式(TP)中,Rtp9 及Rtp10 為氫原子、碳原子數1~5的直鏈或支鏈的烷基或苯基為較佳。In the formula (TP), Rtp 9 and Rtp 10 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or a phenyl group.
在式(TP)中,Rtp6 、Rtp7 及Rtp8 為碳原子數1~5的直鏈或支鏈的烷基、碳原子數為1~5的烯基、碳原子數為6~15的芳基、羧基或磺基為較佳,碳原子數為1~5的直鏈或支鏈的烷基、碳原子數為1~5的烯基、苯基或羧基進一步較佳。Rtp6 、Rtp8 為碳原子數1~5的烷基為較佳,Rtp7 為烯基(尤其,相鄰之2個烯基所連接之苯基為較佳)、苯基或羧基為較佳。In the formula (TP), Rtp 6 , Rtp 7 and Rtp 8 are a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and 6 to 15 carbon atoms. The aryl group, the carboxyl group or the sulfo group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a phenyl group or a carboxyl group. Rtp 6 and Rtp 8 are preferably an alkyl group having 1 to 5 carbon atoms, Rtp 7 is an alkenyl group (in particular, a phenyl group in which two adjacent alkenyl groups are bonded is preferred), and a phenyl group or a carboxyl group is preferred. good.
在式(TP)中,a、b或c分別獨立地表示0~4的整數。a及b分別為0或1為較佳,c為0~2的整數為較佳。In the formula (TP), a, b or c each independently represents an integer of 0 to 4. Preferably, a and b are 0 or 1 respectively, and c is an integer of 0 to 2, preferably.
作為三芳基甲烷染料的具體例,例如可以舉出在以下化合物、或日本特開2014-186342號公報的段落號0176~0177中記載的化合物。Specific examples of the triarylmethane dye include the following compounds, and the compounds described in paragraphs 0176 to 0177 of JP-A-2014-186342.
【化學式11】 [Chemical Formula 11]
具有吡咯亞甲基骨架之染料(亦稱作吡咯亞甲基染料)例如可以舉出下式(PM)中表示之化合物。The dye having a pyrrolethymethylene skeleton (also referred to as a pyrromethene dye) may, for example, be a compound represented by the following formula (PM).
式(PM)Formula (PM)
【化學式12】 [Chemical Formula 12]
R11 及R16 分別獨立地表示烷基、烯基、芳基、烷氧基、芳氧基、烷胺基或芳胺基。R11 及R16 為烷基、烯基、芳基為較佳,烷基、烯基、芳基進一步較佳,烷基為尤佳。R 11 and R 16 each independently represent an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group or an arylamine group. R 11 and R 16 are preferably an alkyl group, an alkenyl group or an aryl group, and an alkyl group, an alkenyl group or an aryl group is further preferred, and an alkyl group is particularly preferred.
R12 ~R15 分別獨立地表示氫原子或取代基。R 12 to R 15 each independently represent a hydrogen atom or a substituent.
在R12 ~R15 中,R12 及R15 為烷氧羰基、芳氧基羰基、胺基甲醯基、烷基磺醯基、芳基磺醯基、腈基、亞胺基或胺甲醯基磺醯基為較佳,烷氧羰基、芳氧基羰基、胺基甲醯基、烷基磺醯基、腈基、亞胺基、胺甲醯基磺醯基為更佳,烷氧羰基、芳氧基羰基、胺基甲醯基、腈基、亞胺基、胺甲醯基磺醯基進一步較佳。In R 12 to R 15 , R 12 and R 15 are alkoxycarbonyl, aryloxycarbonyl, aminomethylindenyl, alkylsulfonyl, arylsulfonyl, nitrile, imine or amine Further, a mercaptosulfonyl group is preferred, and an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethylcarbonyl group, an alkylsulfonyl group, a nitrile group, an imido group, an amine formylsulfonyl group is more preferred, and an alkoxy group is preferred. A carbonyl group, an aryloxycarbonyl group, an aminomethylguanidinyl group, a nitrile group, an imido group, an amine formylsulfonyl group is further preferred.
在R12 ~R15 中,、R13 及R14 為烷基或芳基為較佳。Among R 12 to R 15 , R 13 and R 14 are preferably an alkyl group or an aryl group.
R17 表示氫原子、鹵素原子、烷基或芳基。R17 為氫原子為較佳。R 17 represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. It is preferred that R 17 is a hydrogen atom.
Ma表示金屬原子或金屬化合物。作為金屬原子或金屬化合物,可以舉出式(F)中進行說明者,Zn、Cu、Co或V=O為較佳,Zn為更佳。Ma represents a metal atom or a metal compound. The metal atom or the metal compound is exemplified in the formula (F), and Zn, Cu, Co or V=O is preferable, and Zn is more preferable.
X2 及X3 分別獨立地表示NRx (Rx 表示氫原子、烷基、烯基、芳基、醯基、烷基磺醯基或芳基磺醯基)、氮原子、氧原子或硫原子。X2 及X3 為氧原子為較佳。X 2 and X 3 each independently represent NR x (R x represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom, an oxygen atom or sulfur atom. It is preferred that X 2 and X 3 are oxygen atoms.
Y1 及Y2 分別獨立地表示NRy (Ry 表示氫原子、烷基、烯基、芳基、醯基、烷基磺醯基或芳基磺醯基)、氮原子或碳原子。R11 和Y1 可以彼此鍵結而形成5員、6員、或7員的環,R16 和Y2 亦可以彼此鍵結而形成5員、6員、或7員的環。Y1 為NH,Y2 為氮原子為較佳。Y 1 and Y 2 each independently represent NR y (R y represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom or a carbon atom. R 11 and Y 1 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 16 and Y 2 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members. Y 1 is NH, and Y 2 is preferably a nitrogen atom.
X1 表示可以與Ma鍵結的基團。X1 只要是可以與Ma鍵結的基團則可以是任意者,具體而言,可以舉出水、醇類(例如甲醇、乙醇、丙醇)等,此外,在“金屬螯合物”([1]坂口武一、上野景平著(1995年 南江堂);[2](1996年);[3](1997年)等)中記載的化合物。其中,從製造的觀點來看,水、羧酸化合物、醇類為較佳,水、羧酸化合物為更佳。X 1 represents a group which can be bonded to Ma. X 1 may be any one as long as it can bond to Ma, and specific examples thereof include water, an alcohol (for example, methanol, ethanol, or propanol), and the like, and a "metal chelate compound" ( [1] Compounds described in Shoukou Wuyi, Ueno Jingping (1995 Nanjiangtang); [2] (1996); [3] (1997), etc.). Among them, water, a carboxylic acid compound, and an alcohol are preferable from the viewpoint of production, and water or a carboxylic acid compound is more preferable.
a表示0~2的整數,0或1為較佳。a represents an integer of 0 to 2, and 0 or 1 is preferred.
作為吡咯亞甲基染料,例如可以舉出以下化合物、或日本特開2014-186342號公報的段落號0100~0102中記載的化合物。Examples of the pyrrolethymethylene dye include the following compounds, and the compounds described in paragraphs 0100 to 0102 of JP-A-2014-186342.
【化學式13】 [Chemical Formula 13]
在本發明的著色硬化性組成物中含有其他著色劑之情況下,其他著色劑的含量,相對於100質量份的著色劑A為0.1~20質量份為較佳,0.1~15質量份為更佳,0.1~10質量份進一步較佳。When the coloring-curable composition of the present invention contains another coloring agent, the content of the other coloring agent is preferably 0.1 to 20 parts by mass, and 0.1 to 15 parts by mass, per 100 parts by mass of the coloring agent A. Preferably, 0.1 to 10 parts by mass is further preferred.
並且,酞菁顔料的含量,相對於100質量份的著色劑A為80~300質量份為較佳,90~250質量份為更佳,100~200質量份進一步較佳。若為上述範圍則可以得到分光優異之效果。另外,酞菁顔料可以僅使用1種,亦可以併用2種以上。在併用2種以上之情況下,合計為上述範圍為較佳。Further, the content of the phthalocyanine pigment is preferably from 80 to 300 parts by mass, more preferably from 90 to 250 parts by mass, even more preferably from 100 to 200 parts by mass, per 100 parts by mass of the color former A. If it is the above range, the effect of excellent spectroscopicity can be obtained. In addition, the phthalocyanine pigment may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to add up to the above range.
並且,染料的含量,相對於100質量份的著色劑A為1~30質量份為較佳,1~25質量份為更佳,1~20質量份進一步較佳。若染料的含量為上述範圍,則著色劑A的分散性提高,著色硬化性組成物的分散穩定性更優異。另外,染料可以僅使用1種,亦可以併用2種以上。在併用2種以上之情況下,合計為上述範圍為較佳。Further, the content of the dye is preferably 1 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 1 to 20 parts by mass, per 100 parts by mass of the coloring agent A. When the content of the dye is in the above range, the dispersibility of the colorant A is improved, and the dispersion stability of the colored curable composition is further improved. Further, the dye may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to add up to the above range.
本發明的著色硬化性組成物中,著色劑相對於著色硬化性組成物中的總固體成分之含量為10~90質量%為較佳。下限為20質量%以上為更佳,30質量%以上進一步較佳。上限為80質量%以下為更佳,70質量%以下更佳。In the colored curable composition of the present invention, the content of the colorant with respect to the total solid content in the colored curable composition is preferably from 10 to 90% by mass. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
<<硬化性化合物>><<Cure compound>>
本發明的著色硬化性組成物含有硬化性化合物。作為硬化性化合物,可以使用能夠藉由自由基、酸或熱而交聯之公知的化合物。例如可以舉出含具有乙烯性不飽和鍵之基團、環狀醚(環氧、氧雜環丁烷)基、羥甲基等之化合物。作為具有乙烯性不飽和鍵之基團,可以舉出乙烯基、(甲基)烯丙基、(甲基)丙烯醯基等。The colored curable composition of the present invention contains a curable compound. As the curable compound, a known compound which can be crosslinked by a radical, an acid or heat can be used. For example, a compound containing a group having an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane) group, or a methylol group can be given. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group.
在本發明中,硬化性化合物為自由基聚合性化合物為較佳。In the present invention, the curable compound is preferably a radically polymerizable compound.
在本發明中,自由基聚合性化合物(以下亦稱作聚合性化合物)例如可以是單體、預聚物,亦即可以是二聚物、三聚物及寡聚物,或者該等之混合物,以及該等之多聚物等化學形態中的任一者。In the present invention, the radically polymerizable compound (hereinafter also referred to as a polymerizable compound) may be, for example, a monomer or a prepolymer, that is, may be a dimer, a trimer, and an oligomer, or a mixture thereof. And any of the chemical forms such as the multimers.
聚合性化合物為3~15官能的(甲基)丙烯酸酯化合物為較佳,3~6官能的(甲基)丙烯酸酯化合物為更佳。The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.
作為單體、預聚物的例子,可以舉出不飽和羧酸(例如丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、馬來酸等)或其酯類、醯胺類以及該等之多聚物,較佳為不飽和羧酸和脂肪族多元醇化合物之酯、不飽和羧酸和脂肪族多元胺化合物之醯胺類、以及該等之多聚物。並且,亦可適當地使用具有羥基、胺基、巰基等親核性取代基之不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類之加成反應物,及與單官能或多官能的羧酸之脱水縮合反應物等。並且,亦可適當地使用具有異氰酸酯基、環氧基等親電子性取代基之不飽和羧酸酯或醯胺類與單官能或多官能的醇類、胺類、硫醇類之反應物,及具有鹵素基、甲苯磺醯氧基等脱離性取代基之不飽和羧酸酯或醯胺類與單官能或多官能的醇類、胺類、硫醇類之反應物。並且,亦可使用將上述不飽和羧酸取代為不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯基醚、烯丙基醚等之化合物群。Examples of the monomer and the prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines, and the like. Such polymers are preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and such polymers. Further, an addition reaction product of an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group with a monofunctional or polyfunctional isocyanate or an epoxy group may be suitably used, and A dehydration condensation reaction of a monofunctional or polyfunctional carboxylic acid or the like. Further, a reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol may be suitably used. And a reaction product of an unsaturated carboxylic acid ester or a guanamine having a detachable substituent such as a halogen group or a tosyloxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, a group of compounds in which the above unsaturated carboxylic acid is substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether or an allyl ether can also be used.
作為該些具體的化合物,亦可將在日本特開2009-288705號公報的段落號〔0095〕~〔0108〕中記載之化合物適當地使用於本發明中。As the specific compound, the compound described in Paragraph Nos. [0095] to [0108] of JP-A-2009-288705 can be suitably used in the present invention.
在本發明中,作為聚合性化合物,含有1個以上具有乙烯性不飽和鍵之基團、且在常壓下具有100℃以上的沸點之化合物亦為較佳。作為其例子,例如可以參照在日本特開2013-29760號公報的段落0227、日本特開2008-292970號公報的段落號0254~0257中記載的化合物,並將該內容併入到本申請案說明書中。In the present invention, a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C or higher at normal pressure is also preferable as the polymerizable compound. As an example, for example, a compound described in paragraph 0227 of JP-A-2013-29760, and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents are incorporated in the specification of the present application. in.
聚合性化合物較佳為二季戊四醇三丙烯酸酯(市售品為KAYARAD D-330;NIPPON KAYAKU CO.,LTD.製造)、二季戊四醇四丙烯酸酯(市售品為KAYARAD D-320;NIPPON KAYAKU CO.,LTD.製造)二季戊四醇五(甲基)丙烯酸酯(市售品為KAYARAD D-310;NIPPON KAYAKU CO.,LTD.製造)、二季戊四醇六(甲基)丙烯酸酯(市售品為KAYARAD DPHA;NIPPON KAYAKU CO.,LTD.製造、A-DPH-12E;SHIN-NAKAMURA CHEMICAL CO.,LTD.製造)、及該等之(甲基)丙烯醯基經由乙二醇、丙二醇残基之結構(例如由SARTOMER Company,Inc.市售之SR454、SR499)。亦可以使用該等的寡聚物類型。並且亦可使用KAYARAD RP-1040(NIPPON KAYAKU CO.,LTD.製造)。The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., LTD.) or dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; NIPPON KAYAKU CO.). , manufactured by LTD.) dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA) ; manufactured by NIPPON KAYAKU CO., LTD., manufactured by A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., and the structure of the (meth)acryloyl group via ethylene glycol and propylene glycol residues ( For example, SR454, SR499, marketed by SARTOMER Company, Inc.). These types of oligomers can also be used. Further, KAYARAD RP-1040 (manufactured by NIPPON KAYAKU CO., LTD.) can also be used.
以下表示較佳的聚合性化合物的形態。The form of a preferred polymerizable compound is shown below.
聚合性化合物可以具有羧基、磺酸基、磷酸基等酸基。作為具有酸基之聚合性化合物,脂肪族多羥基化合物與不飽和羧酸的酯為較佳,使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基反應而具有酸基之聚合性化合物為更佳,該酯中脂肪族多羥基化合物為季戊四醇及/或二季戊四醇者為尤佳。作為市售品,例如可以舉出TOAGOSEI CO.,LTD.製造的作為多元酸改質丙烯酸系寡聚物的M-510、M-520等。The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group polymerizability. More preferably, the compound is preferably an aliphatic polyhydroxy compound of the ester which is pentaerythritol and/or dipentaerythritol. For example, M-510, M-520, etc. which are polybasic acid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD. can be mentioned as a commercial item.
作為具有酸基之聚合性化合物的酸值,0.1~40mgKOH/g為較佳,5~30mgKOH/g為尤佳。若聚合性化合物的酸值為0.1mgKOH/g以上,則顯影溶解特性良好,若為40mgKOH/g以下,則在製造和處理上有利。進而,光聚合性能良好且硬化性優異。The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH/g, more preferably from 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Further, the photopolymerization performance is good and the curability is excellent.
聚合性化合物中具有己內酯結構之化合物亦為較佳態様。A compound having a caprolactone structure in the polymerizable compound is also a preferred state.
作為具有己內酯結構之化合物,只要在分子內具有己內酯結構則無特別的限定,例如可舉出ε-己內酯改質多官能(甲基)丙烯酸酯,該ε-己內酯改質多官能(甲基)丙烯酸酯可以藉由將三羥甲基乙烷、二-三羥甲基乙烷、三羥甲基丙烷、二-三羥甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇、甘油、二甘油、三羥甲基三聚氰胺等多元醇與(甲基)丙烯酸及ε-己內酯加以酯化而得到。其中,具有下述通式(Z-1)中表示之己內酯結構之化合物為較佳。The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate, which is ε-caprolactone. The modified polyfunctional (meth) acrylate can be obtained by using trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, three Polyols such as pentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferred.
【化學式14】 [Chemical Formula 14]
在通式(Z-1)中,6個R全部為下述通式(Z-2)中表示之基團,或者6個R中的1~5個為下述通式(Z-2)中表示之基團,其餘為下述通式(Z-3)中表示之基團。In the general formula (Z-1), all of the six R groups are groups represented by the following formula (Z-2), or one to five of the six R groups are represented by the following formula (Z-2). The group represented by the above is the group represented by the following formula (Z-3).
【化學式15】 [Chemical Formula 15]
在通式(Z-2)中,R1 表示氫原子或甲基,m表示1或2的數,“*”表示結合鍵。In the formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.
【化學式16】 [Chemical Formula 16]
在通式(Z-3)中,R1 表示氫原子或甲基,“*”表示結合鍵。In the formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bond.
具有己內酯結構之聚合性化合物例如由NIPPON KAYAKU CO., LTD.CO.,LTD.作為KAYARAD DPCA系列而市售,可以舉出DPCA-20(上述式(Z-1)~(Z-3)中m=1、式(Z-2)中表示之基團的個數=2、R1 全部為氫原子之化合物)、DPCA-30(上述式(Z-1)~(Z-3)中m=1、式(Z-2)中表示之基團的個數=3、R1 全部為氫原子之化合物)、DPCA-60(上述式(Z-1)~(Z-3)中m=1、式(Z-2)中表示之基的個數=6、R1 全部為氫原子之化合物)、DPCA-120(上述式(Z-1)~(Z-3)中,m=2、式(Z-2)中表示之基團的個數=6、R1 全部為氫原子之化合物)等。A polymerizable compound having a caprolactone structure is commercially available, for example, from NIPPON KAYAKU CO., LTD. CO., LTD. as KAYARAD DPCA series, and DPCA-20 (the above formula (Z-1) to (Z-3) can be mentioned. Wherein m = 1, the number of groups represented by the formula (Z-2) = 2, the compound in which all R 1 are a hydrogen atom), DPCA-30 (the above formula (Z-1) to (Z-3) m = 1, the number of groups represented by the formula (Z-2) = 3, a compound in which all R 1 are a hydrogen atom), and DPCA-60 (in the above formula (Z-1) to (Z-3)) m = 1, the number of the groups represented by the formula (Z-2) = 6, the compound in which all of R 1 is a hydrogen atom), DPCA-120 (in the above formula (Z-1) to (Z-3), m = 2, the number of groups represented by the formula (Z-2) = 6, the compound in which all of R 1 is a hydrogen atom), and the like.
聚合性化合物可以使用下述通式(Z-4)或(Z-5)中表示之化合物。As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can be used.
【化學式17】 [Chemical Formula 17]
在通式(Z-4)及(Z-5)中,E分別獨立地表示-((CH2 )y CH2 O)-或-((CH2 )y CH(CH3 )O)-,y分別獨立地表示0~10的整數,X分別獨立地表示(甲基)丙烯醯基、氫原子或羧基。In the general formulae (Z-4) and (Z-5), E independently represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom or a carboxyl group.
在通式(Z-4)中,(甲基)丙烯醯基的合計為3個或4個,m分別獨立地表示0~10的整數,各m的合計為0~40的整數。In the general formula (Z-4), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40.
在通式(Z-5)中,(甲基)丙烯醯基的合計為5個或6個,n分別獨立地表示0~10的整數,各n的合計為0~60的整數。In the general formula (Z-5), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
在通式(Z-4)中,m為0~6的整數為較佳,0~4的整數為更佳。In the general formula (Z-4), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferably.
並且,各m的合計為2~40的整數為較佳,2~16的整數為更佳,4~8的整數為尤佳。Further, the total of each m is preferably an integer of from 2 to 40, more preferably from 2 to 16, more preferably an integer of from 4 to 8.
在通式(Z-5)中,n為0~6的整數為較佳,0~4的整數為更佳。In the general formula (Z-5), n is an integer of 0 to 6 and preferably an integer of 0 to 4 is more preferable.
並且,各n的合計為3~60的數為較佳,3~24的整數為更佳,6~12的整數為尤佳。Further, the total of n is preferably 3 to 60, the integer of 3 to 24 is more preferably, and the integer of 6 to 12 is more preferably.
並且,在通式(Z-4)或通式(Z-5)中的-((CH2 )y CH2 O)-或-((CH2 )y CH(CH3 )O)-較佳為氧原子側的末端與X鍵結之形態。Further, -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- in the formula (Z-4) or the formula (Z-5) is preferably It is a form in which the end of the oxygen atom side is bonded to X.
通式(Z-4)或通式(Z-5)中表示之化合物可以單獨使用1種,亦可以併用2種以上。尤其,在通式(Z-5)中,6個X全部為丙烯醯基之形態為較佳。The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), it is preferred that all of the six X atoms are acrylonitrile groups.
並且,作為通式(Z-4)或通式(Z-5)中表示之化合物的聚合性化合物中之總含量,20質量%以上為較佳、50質量%以上為更佳。In addition, the total content of the polymerizable compound of the compound represented by the formula (Z-4) or the formula (Z-5) is preferably 20% by mass or more, more preferably 50% by mass or more.
通式(Z-4)或通式(Z-5)中表示之化合物能夠藉由以下以往公知的步驟而合成:藉由開環加成反應使環氧乙烷或環氧丙烷的開環骨架鍵結於季戊四醇或二季戊四醇之步驟;及例如使(甲基)丙烯醯氯與開環骨架的末端羥基反應而導入(甲基)丙烯醯基之步驟。各步驟為被廣為人知之步驟,本領域技術人員能夠容易地合成通式(Z-4)或(Z-5)中表示之化合物。The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by a conventionally known procedure: a ring-opening skeleton of ethylene oxide or propylene oxide by a ring-opening addition reaction a step of bonding to pentaerythritol or dipentaerythritol; and, for example, a step of introducing (meth)acrylonium chloride to a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group. Each step is a well-known step, and those skilled in the art can easily synthesize the compound represented by the formula (Z-4) or (Z-5).
通式(Z-4)或通式(Z-5)中表示之化合物中,季戊四醇衍生物及/或二季戊四醇衍生物亦為更佳。Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative are also more preferable.
具體而言,可以舉出下述式(a)~(f)中表示之化合物(以下亦稱作“例示化合物(a)~(f)”),其中,例示化合物(a)、(b)、(e)、(f)為較佳。Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)"), wherein the compounds (a) and (b) are exemplified. , (e), (f) are preferred.
【化學式18】 [Chemical Formula 18]
【化學式19】 [Chemical Formula 19]
作為通式(Z-4)、(Z-5)所表示之聚合性化合物的市售品,例如可以舉出SARTOMER Company,Inc.製造之具有4個乙烯氧基(ethyleneoxy)鏈之4官能丙烯酸酯之SR-494,NIPPON KAYAKU CO.,LTD.製造之具有6個戊烯氧基(pentyleneoxy)鏈之6官能丙烯酸酯之DPCA-60、具有3個異丁烯氧基鏈之3官能丙烯酸酯之TPA-330等。As a commercial item of the polymerizable compound represented by the general formula (Z-4) or (Z-5), for example, a 4-functional acrylic acid having four ethyleneoxy chains manufactured by SARTOMER Company, Inc. Ester-SR-494, DPCA-60 of 6-functional acrylate having 6 pentyleneoxy chains manufactured by NIPPON KAYAKU CO., LTD., TPA of trifunctional acrylate having 3 isobutyleneoxy chains -330 and so on.
作為聚合性化合物,如日本特公昭48-41708號公報、日本特開昭51-37193號公報、日本特公平2-32293號公報、日本特公平2-16765號公報中記載之胺基甲酸酯丙烯酸酯類,日本特公昭58-49860號公報、日本特公昭56-17654號公報、日本特公昭62-39417號公報、日本特公昭62-39418號公報中記載的具有環氧乙烷系骨架之胺基甲酸酯化合物類亦較佳。並且,藉由使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平1-105238號公報中記載之、在分子內具有胺基結構和硫化物結構之加成聚合性化合物類,能夠得到感光速度非常優異之著色硬化性組成物。The urethane described in Japanese Patent Publication No. Hei 2-16765, and Japanese Patent Publication No. Hei 2-26765 The acrylate-based structure having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Amino acid compound is also preferred. In addition, it has an amine-based structure and a sulfide structure in the molecule, as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. A polymerizable compound can be obtained as a color-curable composition having an excellent photospeed.
作為市售品,可以舉出胺基甲酸酯寡聚物UAS-10、UAB-140(SANYO-KOKUSAKU PULP CO.,LTD.製造)、UA-7200(SHIN-NAKAMURA CHEMICAL CO.,LTD.製造)、DPHA-40H(NIPPON KAYAKU CO.,LTD.製造)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(KYOEISHA CO.,LTD.製造)等。Commercially available products include urethane oligomer UAS-10, UAB-140 (made by SANYO-KOKUSAKU PULP CO., LTD.), and UA-7200 (SHIN-NAKAMURA CHEMICAL CO., LTD. ), DPHA-40H (manufactured by NIPPON KAYAKU CO., LTD.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CO., LTD.).
<<<具有環氧基之化合物>>><<<Compound with epoxy group>>>
本發明中作為硬化性化合物能夠使用具有環氧基之化合物。In the present invention, a compound having an epoxy group can be used as the curable compound.
在由乾式蝕刻法形成圖案之情況下,可較佳地具有環氧基之化合物用作硬化性化合物。In the case of patterning by dry etching, a compound having an epoxy group is preferably used as the curable compound.
作為具有環氧基之化合物,在1個分子內具有2個以上環氧基者為較佳。藉由使用在1個分子內具有2個以上環氧基之化合物,能夠更有效地發揮本發明的效果。環氧基在1分子內具有2~10個為較佳,2~5個為更佳,3個為尤佳。As the compound having an epoxy group, it is preferred to have two or more epoxy groups in one molecule. By using a compound having two or more epoxy groups in one molecule, the effects of the present invention can be exhibited more effectively. The epoxy group is preferably 2 to 10 in one molecule, more preferably 2 to 5, and particularly preferably 3.
在本發明中具有環氧基之化合物可較佳地使用具有2個苯環由烴基連接之結構者。烴基為碳原子數為1~6的伸烷基為較佳。The compound having an epoxy group in the present invention can preferably be used as a structure having two benzene rings bonded by a hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.
並且,環氧基經由連接基團而連接為較佳。作為連接基團,可以舉出包含選自伸烷基、亞芳基、-O-、由-NR’-(R’表示氫原子、可具有取代基之烷基或可具有取代基之芳基,氫原子為較佳)表示之結構、-SO2 -、-CO-、-O-及-S-之至少一者之基團。Further, it is preferred that the epoxy group is connected via a linking group. The linking group may, for example, be an aryl group selected from an alkyl group, an arylene group, -O-, an alkyl group which may have a substituent, or an alkyl group which may have a substituent, represented by -NR'- (R' represents a hydrogen atom. A hydrogen atom is preferably a structure represented by at least one of -SO 2 -, -CO-, -O-, and -S-.
具有環氧基之化合物中環氧當量(=具有環氧基之化合物的分子量/環氧基之數量)為500g/eq以下為較佳,100~400g/eq為更佳,100~300g/eq進一步較佳。The epoxy equivalent of the compound having an epoxy group (=the molecular weight of the compound having an epoxy group/the number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 to 400 g/eq, and 100 to 300 g/eq. Further preferred.
具有環氧基之化合物可以為低分子化合物(例如分子量小於2000,進而,分子量小於1000),亦可以為高分子化合物(macromolecule)的任一個(例如分子量為1000以上,在聚合物之情況下,重量平均分子量為1000以上)。具有環氧基之化合物的重量平均分子量為200~100000為較佳,500~50000為更佳。The compound having an epoxy group may be a low molecular compound (for example, having a molecular weight of less than 2,000, and further, a molecular weight of less than 1,000), or may be any one of a macromolecular compound (for example, a molecular weight of 1,000 or more, in the case of a polymer, The weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000.
具有環氧基之化合物,能夠使用日本特開2013-011869號公報的段落號0034~0036、日本特開2014-043556號公報的段落號0147~0156、日本特開2014-089408號公報的段落號0085~0092中記載之化合物。將該些內容併入到本說明書中。For the compound having an epoxy group, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraph numbers of JP-A-2014-089408 can be used. The compound described in 0085 to 0092. This is incorporated into the present specification.
作為市售品,例如可以舉出“EHPE3150、DAICEL CHEMICAL INDUSTRIES,CO.,LTD.製造”、“EPICLON N660(DIC Corporation製造)”等。As a commercial item, "EHPE3150, DAICEL CHEMICAL INDUSTRIES, CO., LTD.", "EPICLON N660 (made by DIC Corporation)", etc. are mentioned, for example.
在本發明的著色硬化性組成物中,硬化性化合物的含量相對於著色硬化性組成物的總固體成分為0.1~40質量%為較佳。下限例如為0.5質量%以上為更佳,1質量%以上進一步較佳。上限例如為30質量%以下為更佳,20質量%以下進一步較佳。硬化性化合物可以單獨使用1種,亦可以併用2種以上。在併用2種以上之情況下,總量成為上述範圍為較佳。In the colored curable composition of the present invention, the content of the curable compound is preferably from 0.1 to 40% by mass based on the total solid content of the colored curable composition. The lower limit is, for example, 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, 30% by mass or less, more preferably 20% by mass or less. One type of the curable compound may be used alone or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably in the above range.
<<多官能硫醇化合物>><<Multifunctional thiol compound>>
本發明的著色硬化性組成物以促進聚合性化合物的反應等為目的,可以含有在分子內具有2個以上的巰基之多官能硫醇化合物。多官能硫醇化合物為二級烷烴硫醇類為較佳,尤其,係具有下述通式(T1)中表示之結構之化合物為較佳。The colored curable composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly, a compound having a structure represented by the following formula (T1) is preferred.
通式(T1)General formula (T1)
【化學式20】 [Chemical Formula 20]
(在式(T1)中,n表示2~4的整數,L表示2~4價的連接基團。)(In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valence.)
在上述通式(T1)中,連接基團L係碳原子數為2~12的脂肪族基團為較佳,n為2,L係碳原子數為2~12的伸烷基為尤佳。多官能硫醇化合物的具體的例子可以舉出下述結構式(T2)~(T4)中表示之化合物,式(T2)中表示之化合物為尤佳。該些多官能硫醇可以使用1種或組合複數種而使用。In the above formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and an L-alkyl group having 2 to 12 carbon atoms is particularly preferred. . Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulae (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used singly or in combination of plural kinds.
【化學式21】 [Chemical Formula 21]
在本發明的著色硬化性組成物含有多官能硫醇之情況下,多官能硫醇的含量相對於著色硬化性組成物的總固體成分為0.3~8.9質量%為較佳,0.8~6.4質量%為更佳。並且,多官能硫醇亦可以以改善穩定性、臭味、解析度、顯影性、密合性等為目的而添加。In the case where the colored curable composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol is preferably 0.3 to 8.9% by mass, and preferably 0.8 to 6.4% by mass based on the total solid content of the colored curable composition. For better. Further, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.
<<有機溶劑>><<Organic solvent>>
本發明的著色硬化性組成物含有有機溶劑。The colored curable composition of the present invention contains an organic solvent.
有機溶劑只要滿足各成分的溶解性、著色硬化性組成物的塗佈性,則基本上沒有特別的限制,但是考慮著色劑、樹脂、硬化性化合物等各自的溶解性、塗佈性及安全性而進行選擇為較佳。其中,從上述著色劑A的分散性的觀點來看,有機溶劑為選自酯系溶劑、醚系溶劑、酮系溶劑及醇系溶劑之至少1種為較佳。有機溶劑可以使用1種,亦可以混合2種以上來使用。另外,在本發明中,“醚系溶劑”是指含有醚鍵之溶劑,“酯系溶劑”是指含有酯鍵之溶劑,“酮系溶劑”是指含有酮鍵之溶劑。亦即,例如含有醚鍵之醇系溶劑既是醚系溶劑”,亦是“醇系溶劑”。並且,具有醚鍵和酯鍵之溶劑既是“醚系溶劑”,亦是“酯系溶劑”。The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the coating property of the coloring-curable composition. However, solubility, coating property, and safety of each of a coloring agent, a resin, and a curable compound are considered. It is better to make a choice. In particular, the organic solvent is preferably at least one selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, and an alcohol solvent, from the viewpoint of the dispersibility of the coloring agent A. The organic solvent may be used singly or in combination of two or more. In the present invention, the "ether solvent" means a solvent containing an ether bond, the "ester solvent" means a solvent containing an ester bond, and the "ketone solvent" means a solvent containing a ketone bond. In other words, the alcohol-based solvent containing an ether bond is an ether solvent or an alcohol solvent, and the solvent having an ether bond and an ester bond is an "ether solvent" or an "ester solvent".
作為酯系溶劑,可以舉出乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯、γ-丁內酯、丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、二丙二醇單甲醚乙酸酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯等。Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, Cyclohexanol acetate, γ-butyrolactone, propylene glycol diacetate, 1,3-butylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether Acid ester, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, 2-ethoxypropane Methyl ester, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl Alkyl acetate, 3-methyl-3-methoxybutyl acetate, and the like.
作為醚系溶劑,可以舉出在上述酯系溶劑中具有醚鍵之溶劑、乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚等乙二醇單烷基醚類;二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚等二乙二醇單烷基醚類;丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚等丙二醇單烷基醚類;四氫呋喃、四氫吡喃、1,4-二噁烷等環狀醚類;二乙二醇二甲醚、二乙二醇二***、二乙二醇乙基甲基醚、二乙二醇二丙醚、二乙二醇二丁醚等二乙二醇二烷基醚類;二丙二醇二甲醚等二丙二醇二烷基醚類;苯甲醚,苯***,甲基苯甲醚等酚醚類;3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇等。Examples of the ether solvent include a solvent having an ether bond in the above ester solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Monoalkyl ethers; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single Propylene glycol monoalkyl ethers such as propyl ether and propylene glycol monobutyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; Alkyl ether, phenethyl ether, methyl aniether and other phenol ethers; 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, and the like.
作為酮系溶劑,可以舉出在上述溶劑中具有酮鍵之溶劑、4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮、異佛爾酮等。Examples of the ketone solvent include a solvent having a ketone bond in the above solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, and 4 - heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
作為醇系溶劑,可以舉出上述溶劑中之醇者、甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、甘油等。Examples of the alcohol-based solvent include alcohols in the above solvents, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
在本發明中,有機溶劑中過氧化物的含有率為0.8mmmpl/L以下為較佳,實質上不含有過氧化物為更佳。In the present invention, the content of the peroxide in the organic solvent is preferably 0.8 mm mpl/L or less, and more preferably no peroxide is contained.
在本發明中,有機溶劑的SP(Solubility Parameter)值為15~25(MPa)1/2 為較佳,19~23(MPa)1/2 為更佳。另外,SP值在本發明中使用基於Hoy法之值。Hoy法的文献,可以適當地舉出H.L.Hoy:J.Paint Tech.,42(540),76-118(1970)和SP值基礎、應用及計算方法(山本、諮詢機構、2005)。In the present invention, the SP (Solubility Parameter) value of the organic solvent is preferably 15 to 25 (MPa) 1/2, more preferably 19 to 23 (MPa) 1/2 . In addition, the SP value is used in the present invention based on the value of the Hoy method. The literature of the Hoy method can be appropriately cited by HL Hoy: J. Paint Tech., 42 (540), 76-118 (1970) and SP value basis, application and calculation method (Yamamoto, consulting organization, 2005).
就有機溶劑的含量而言,從塗佈性的觀點來看,著色硬化性組成物的總固體成分濃度為5~80質量%之量為較佳。下限例如為5質量%以上為更佳,10質量%以上進一步較佳。上限例如為60質量%以下為更佳,50質量%以下進一步較佳。The content of the organic solvent is preferably from 5 to 80% by mass in terms of the total solid content concentration of the colored curable composition from the viewpoint of coatability. The lower limit is, for example, 5% by mass or more, more preferably 10% by mass or more. The upper limit is, for example, 60% by mass or less, more preferably 50% by mass or less.
本發明的著色硬化性組成物可以僅含有1種有機溶劑,亦可以含有2種以上有機溶劑。在含有2種以上之情況下,其總量成為上述範圍為較佳。The colored curable composition of the present invention may contain only one organic solvent, or may contain two or more organic solvents. When two or more types are contained, it is preferable that the total amount becomes the above range.
<<樹脂>><<Resin>>
本發明的著色硬化性組成物含有樹脂為較佳。樹脂例如以使著色劑分散於組成物中之用途、黏合劑的用途而配合。另外,將主要為了使顔料等著色劑分散而使用之樹脂亦稱作分散劑。但是,樹脂的該種用途為一個例子,亦可以將該種用途以外作為目的而使用。The colored curable composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing the colorant in the composition or the use of the binder. Further, a resin mainly used for dispersing a colorant such as a pigment is also referred to as a dispersant. However, such use of the resin is an example, and it may be used for the purpose other than the use.
在本發明的著色硬化性組成物中,樹脂的含量相對於著色硬化性組成物的總固體成分為5~90質量%為較佳,10~80質量%為更佳。若樹脂的含量為上述範圍,則著色劑的分散性良好。In the colored curable composition of the present invention, the content of the resin is preferably from 5 to 90% by mass, more preferably from 10 to 80% by mass, based on the total solid content of the colored curable composition. When the content of the resin is in the above range, the dispersibility of the colorant is good.
在本發明的著色硬化性組成物中,酸性樹脂的含量相對於著色硬化性組成物的總固體成分為5~90質量%為較佳,10~80質量%為更佳。若酸性樹脂的含量為上述範圍,則顯影性良好。In the colored curable composition of the present invention, the content of the acidic resin is preferably from 5 to 90% by mass, more preferably from 10 to 80% by mass, based on the total solid content of the colored curable composition. When the content of the acidic resin is in the above range, the developability is good.
在本發明的著色硬化性組成物中,樹脂總質量中之酸性樹脂的比例為50~100質量%為較佳,60~100質量%為更佳,70~100質量%進一步較佳。In the colored curable composition of the present invention, the ratio of the acidic resin in the total mass of the resin is preferably from 50 to 100% by mass, more preferably from 60 to 100% by mass, still more preferably from 70 to 100% by mass.
<<<分散劑>>><<<Dispersant>>>
在本發明中,著色硬化性組成物含有分散劑為較佳。分散劑可以舉出酸性分散劑(酸性樹脂)、鹼性分散劑(鹼性樹脂)。In the present invention, it is preferred that the colored curable composition contains a dispersing agent. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (basic resin).
分散劑至少含有酸性分散劑為較佳,僅為酸性分散劑為更佳。藉由至少含有酸性分散劑,分散劑能夠有效地抑制針狀異物的產生。並且,著色劑的分散性提高,且不易產生亮度不均。進而,由於可以得到優異之顯影性,因此能夠由光刻法(photolithography)適當地進行圖案形成。另外,分散劑僅為酸性分散劑是指,例如在分散劑的總質量中之酸性分散劑的含量為99質量%以上為較佳,亦可以設為99.9質量%以上。The dispersant preferably contains at least an acidic dispersant, and more preferably an acidic dispersant. The dispersant can effectively suppress the generation of acicular foreign matter by containing at least an acidic dispersant. Further, the dispersibility of the colorant is improved, and unevenness in brightness is less likely to occur. Further, since excellent developability can be obtained, pattern formation can be appropriately performed by photolithography. In addition, the content of the acidic dispersant in the total mass of the dispersant is preferably 99% by mass or more, and may be 99.9% by mass or more.
在此,酸性分散劑(酸性樹脂)表示酸基的量比鹼性基的量多的樹脂。將酸基的量和鹼性基的量之總量設為100莫耳%時,酸性分散劑(酸性樹脂)為酸基的量佔70莫耳%以上之樹脂為較佳,實質上僅由酸基構成之樹脂為更佳。酸性分散劑(酸性樹脂)所具有之酸基為羧基為較佳。Here, the acidic dispersant (acid resin) represents a resin having a larger amount of acid groups than the amount of the basic group. When the total amount of the acid group and the amount of the basic group is set to 100 mol%, the acidic dispersant (acid resin) is preferably a resin having an acid group content of 70 mol% or more, substantially only A resin composed of an acid group is more preferable. The acid group of the acidic dispersant (acid resin) is preferably a carboxyl group.
並且,鹼性分散劑(鹼性樹脂)表示鹼性基的量比酸基的量多的樹脂。將酸基的量和鹼性基的量之總量設為100莫耳%時,鹼性分散劑(鹼性樹脂)為鹼性基的量佔50莫耳%以上之樹脂為較佳。鹼性分散劑所具有之鹼性基為胺基為較佳。Further, the alkaline dispersant (basic resin) means a resin having a larger amount of a basic group than the acid group. When the total amount of the acid group and the amount of the basic group is set to 100 mol%, it is preferred that the basic dispersant (basic resin) is a resin having a basic group content of 50 mol% or more. It is preferred that the basic group of the basic dispersant is an amine group.
酸性分散劑(酸性樹脂)的酸值為30mgKOH/g以上為較佳,40~105mgKOH/g為更佳,50~105mgKOH/g進一步較佳,60~105mgKOH/g為尤佳。另外,在本發明中,所謂酸值係表示將每1g固體成分中的酸性成分進行中和所需要之氫氧化鉀的mg數者。The acid dispersant (acid resin) preferably has an acid value of 30 mgKOH/g or more, more preferably 40 to 105 mgKOH/g, more preferably 50 to 105 mgKOH/g, and particularly preferably 60 to 105 mgKOH/g. In the present invention, the acid value means the number of mg of potassium hydroxide required to neutralize the acidic component per 1 g of the solid component.
在本發明中,分散劑的含量相對於上述著色劑A的100質量份為100~500質量份為較佳,150~400質量份為更佳。In the present invention, the content of the dispersant is preferably from 100 to 500 parts by mass, more preferably from 150 to 400 parts by mass, per 100 parts by mass of the colorant A.
在本發明中,分散劑可以單獨使用1種,亦可以併用2種以上。在併用2種以上之情況下,併用2種以上的酸性分散劑為較佳。依據該態様,能夠提高組成物的分散穩定性。In the present invention, the dispersing agent may be used singly or in combination of two or more. When two or more types are used in combination, it is preferred to use two or more kinds of acidic dispersants in combination. According to this state, the dispersion stability of the composition can be improved.
作為分散劑,例如可以舉出高分子分散劑〔例如聚醯胺-胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、改質聚胺基甲酸酯、改質聚酯、改質聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物、萘磺酸福馬林縮合物〕、聚氧乙烯烷基磷酸酯、聚氧乙烯烷基胺、烷醇胺等。The dispersing agent may, for example, be a polymer dispersing agent (for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester) And modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, and the like.
高分子分散劑可根據其結構進一步分類為直鏈狀高分子、末端改質型高分子、接枝型高分子、嵌段型高分子。高分子分散劑吸著於顔料的表面,以防止再凝聚的方式發揮作用。因此作為較佳的結構,可舉出具有向顔料表面的錨定(Anchor)部位之末端改質型高分子、接枝型高分子、嵌段型高分子。The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure. The polymer dispersant adsorbs on the surface of the pigment to prevent re-agglomeration. Therefore, as a preferable structure, the terminal modified type polymer, the graft type polymer, and the block type polymer which have an anchor part to the surface of a pigment are mentioned.
作為末端改質型高分子,例如可以舉出日本特開平3-112992號公報、日本專利公表2003-533455號公報等中記載的在末端具有磷酸基之高分子,日本特開2002-273191號公報等中記載的在末端具有磺酸基之高分子,日本特開平9-77994號公報等中記載的具有有機色素的部分骨架或雜環之高分子等。並且,日本特開2007-277514號公報中記載的在高分子末端導入2個以上的對顔料表面的錨定部位(酸基、鹼性基、有機色素的部分骨架或雜環等)之高分子的分散穩定性亦優異,故較佳。For example, JP-A-2002-273191 discloses a polymer having a phosphate group at a terminal, which is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2003-533455. The polymer having a sulfonic acid group at the terminal, and a polymer having a partial skeleton or a heterocyclic ring of an organic dye described in JP-A-9-77994, and the like. Further, in the polymer terminal, two or more polymers which are anchored to the surface of the pigment (acid group, basic group, partial skeleton of organic dye or heterocyclic ring) are introduced into the polymer terminal, as described in JP-A-2007-277514. The dispersion stability is also excellent, so it is preferred.
作為接枝型高分子,例如可以舉出聚酯系分散劑等。具體而言,可以舉出日本特開昭54-37082號公報、日本專利公表平8-507960號公報、日本特開2009-258668號公報等中記載的聚(低級伸烷基亞胺)與聚酯的反應產物;日本特開平9-169821號公報等中記載的聚烯丙基胺與聚酯的反應產物;日本特開平10-339949號公報、日本特開2004-37986號公報、国際揭示小冊子WO2010/110491等中記載的巨單體與氮原子單體的共聚物;日本特開2003-238837號公報、日本特開2008-9426號公報、日本特開2008-81732號公報等中記載的具有有機色素的部分骨架或雜環之接枝型高分子;日本特開2010-106268號公報等中記載的巨單體與含酸基單體的共聚物;日本特開2009-203462號公報中記載的具有鹼性基和酸基之両性樹脂等。The graft type polymer may, for example, be a polyester-based dispersant or the like. Specifically, poly(lower alkylene imine) and poly group described in JP-A-H05-370820, JP-A-H08-507960, JP-A-2009-258668, and the like. The reaction product of the polyallylamine and the polyester described in Japanese Laid-Open Patent Publication No. Hei 9-169821, and the like, and the publication of the International Publication No. 2004-37986 A copolymer of a macromonomer and a nitrogen atom monomer described in WO2010/110491, etc., as described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like. A graft-type polymer having a partial skeleton or a heterocyclic ring of an organic dye; a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268, and the like; An inert resin having a basic group and an acid group.
作為藉由自由基聚合來製造接枝型高分子時使用之巨單體,可以使用公知的巨單體,可以舉出TOAGOSEI CO.,LTD.製造的巨單體AA-6(末端基為甲基丙烯醯基之聚甲基丙烯酸甲酯)、AS-6(末端基為甲基丙烯醯基之聚苯乙烯)、AN-6S(末端基為甲基丙烯醯基之苯乙烯和丙烯腈的共聚物)、AB-6(末端基為甲基丙烯醯基之聚丙烯酸丁酯)、DAICEL CHEMICAL INDUSTRIES CO.,LTD.製造的PLACCEL FM5(甲基丙烯酸2-羥基乙酯的ε-己內酯5莫耳當量加成品)、FA10L(丙烯酸2-羥基乙酯ε-己內酯10莫耳當量加成品)、及日本特開平2-272009號公報中記載的聚酯系巨單體等。As the macromonomer used in the production of the graft polymer by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 (end group A) manufactured by TOAGOSEI CO., LTD. can be used. Acryl fluorenyl polymethyl methacrylate), AS-6 (polystyrene based terminal group is methacryl fluorenyl), AN-6S (styrene and acrylonitrile whose terminal group is methacryl fluorenyl) Copolymer), AB-6 (polybutyl acrylate of methacryl fluorenyl group), PLACEL FM5 manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD. (ε-caprolactone of 2-hydroxyethyl methacrylate) 5 molar equivalents of the finished product), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10 mil equivalents of the finished product), and the polyester-based macromonomer described in JP-A No. 2-272009.
作為嵌段型高分子,日本特開2003-49110號公報、日本特開2009-52010號公報等中記載的嵌段型高分子為較佳。As the block type polymer, a block type polymer described in, for example, JP-A-2003-49110, and JP-A-2009-52010 is preferable.
用作分散劑之樹脂含有具有酸基之重複單元為較佳。藉由樹脂含有具有酸基之重複單元,從而在藉由光刻法而形成著色圖案時,能夠進一步減少產生於著色畫素的基底之殘渣。The resin used as the dispersing agent preferably contains a repeating unit having an acid group. When the resin contains a repeating unit having an acid group, when a colored pattern is formed by photolithography, the residue generated on the base of the colored pixel can be further reduced.
具有酸基之重複單元可使用具有酸基之單體而構成。作為來源於酸基之單體,可以舉出具有羧基之乙烯基單體、具有磺酸基之乙烯基單體、具有磷酸基之乙烯基單體等。The repeating unit having an acid group can be constituted using a monomer having an acid group. Examples of the acid group-derived monomer include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.
作為具有羧基之乙烯基單體,可以舉出(甲基)丙烯酸、乙烯基苯甲酸、馬來酸、馬來酸單烷基酯、富馬酸、衣康酸、巴豆酸、桂皮酸、丙烯酸二聚物等。並且,亦可利用2-羥乙基(甲基)丙烯酸酯等具有羥基之單聚體與如馬來酸酐、鄰苯二甲酸酐、琥珀酸酐、環己烷二羧酸酐那樣的環酐的加成反應物,ω-羧基-聚己內酯單(甲基)丙烯酸酯等。並且,作為羧基的前驅物,可以使用馬來酸酐、衣康酸酐、檸康酸酐等含酐單體。其中,從未曝光部的顯影去除性的觀點來看,2-羥乙基(甲基)丙烯酸酯等具有羥基之單聚體與如馬來酸酐、鄰苯二甲酸酐、琥珀酸酐、環己烷二羧酸酐那樣的環酐的加成反應物為較佳。Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid. Dimer and the like. Further, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride or cyclohexane dicarboxylic anhydride may be used. The reactant is ω-carboxy-polycaprolactone mono(meth)acrylate or the like. Further, as the precursor of the carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride can be used. Among them, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a monomer such as maleic anhydride, phthalic anhydride, succinic anhydride, or cyclohexane, from the viewpoint of development removability of the unexposed portion. An addition reactant of a cyclic anhydride such as an alkanedicarboxylic acid anhydride is preferred.
作為具有磺酸基之乙烯基單體,可以舉出2-丙烯醯胺基-2-甲基丙烷磺酸等。Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid and the like.
作為具有磷酸基之乙烯基單體,可以舉出磷酸單(2-丙烯醯氧基乙基酯)、磷酸單(1-甲基-2-丙烯醯氧基乙基酯)等。Examples of the vinyl monomer having a phosphoric acid group include mono(2-propenyloxyethyl ester) phosphate and mono(1-methyl-2-propenyloxyethyl phosphate).
並且,作為具有酸基之重複單元,可以參照日本特開2008-165059號公報的段落號0067~0069的記載,該內容包括在本說明書中。Further, as a repeating unit having an acid group, the description of paragraphs 0067 to 0069 of JP-A-2008-165059 can be referred to, and the content is included in the present specification.
並且,在本發明中,作為分散劑,可使用包含通式(A1)及通式(A2)中的任一者表示之重複單元和具有酸基之重複單元之接枝共聚物。該接枝共聚物可用作酸性分散劑。Further, in the present invention, as the dispersing agent, a graft copolymer comprising a repeating unit represented by any one of the formula (A1) and the formula (A2) and a repeating unit having an acid group can be used. The graft copolymer can be used as an acidic dispersant.
【化學式22】 [Chemical Formula 22]
通式(A1)及(A2)中,R1 ~R6 分別獨立地表示氫原子或1價的有機基,X1 及X2 分別獨立地表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-或亞苯基,L1 及L2 分別獨立地表示單鍵或2價的有機連接基團,A1 及A2 分別獨立地表示1價的有機基,m及n分別獨立地表示2~8的整數,p及q分別獨立地表示1~100的整數。In the general formulae (A1) and (A2), R 1 to R 6 each independently represent a hydrogen atom or a monovalent organic group, and X 1 and X 2 each independently represent -CO-, -C(=O)O-. , -CONH-, -OC(=O)- or phenylene, and L 1 and L 2 each independently represent a single bond or a divalent organic linking group, and A 1 and A 2 each independently represent a monovalent organic group. The bases, m and n each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.
R1 ~R6 分別獨立地表示氫原子或1價的有機基。作為1價的有機基,經取代或無取代的烷基為較佳。作為烷基,碳原子數為1~12的烷基為較佳,碳原子數為1~8的烷基為更佳,碳原子數為1~4的烷基為尤佳。R 1 to R 6 each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferred. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.
作為R1 、R2 、R4 及R5 ,氫原子為較佳,作為R3 及R6 ,從對顔料表面的吸著效率的觀點來看,氫原子或甲基亦為最佳。As R 1 , R 2 , R 4 and R 5 , a hydrogen atom is preferred, and as R 3 and R 6 , a hydrogen atom or a methyl group is also preferable from the viewpoint of the adsorption efficiency on the surface of the pigment.
X1 及X2 分別獨立地表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-或亞苯基。其中,從對顔料的吸著性的觀點來看,-C(=O)O-、-CONH-、亞苯基為較佳,-C(=O)O-為最佳。X 1 and X 2 each independently represent -CO-, -C(=O)O-, -CONH-, -OC(=O)- or a phenylene group. Among them, from the viewpoint of the sorption property to the pigment, -C(=O)O-, -CONH-, and phenylene are preferred, and -C(=O)O- is preferred.
L1 及L2 分別獨立地表示單鍵或2價的有機連接基團。作為2價的有機連接基團,取代或無取代的伸烷基、由伸烷基和雜原子或伸烷基和含有雜原子之部分結構構成之2價的有機連接基團為較佳。L 1 and L 2 each independently represent a single bond or a divalent organic linking group. As the divalent organic linking group, a substituted or unsubstituted alkylene group, a divalent organic linking group composed of an alkylene group and a hetero atom or an alkylene group and a partial structure containing a hetero atom are preferred.
作為伸烷基,碳原子數為1~12的伸烷基為較佳,碳原子數為1~8的伸烷基為更佳,碳原子數為1~4的伸烷基為尤佳。The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.
作為含有雜原子之部分結構中之雜原子,例如可以舉出氧原子、氮原子、硫原子,其中,氧原子、氮原子為較佳。Examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Among them, an oxygen atom or a nitrogen atom is preferred.
作為2價的有機連接基團,從對顔料的吸著性的觀點來看,較佳的是在上述伸烷基的末端具有選自-C(=O)-、-OC(=O)-、-NHC(=O)-之雜原子或含有雜原子之部分結構,經由雜原子或含有雜原子之部分結構而與相鄰之氧原子連接者。在此,相鄰之氧原子是指對於通式(A1)中之L1 、及通式(A2)中之L2 ,在側鏈末端側鍵結之氧原子。As the divalent organic linking group, from the viewpoint of the sorption property to the pigment, it is preferred to have a terminal group selected from -C(=O)-, -OC(=O)- at the terminal of the above alkylene group. a hetero atom of -NHC(=O)- or a partial structure containing a hetero atom, which is bonded to an adjacent oxygen atom via a hetero atom or a partial structure containing a hetero atom. Here, the adjacent oxygen atom means the general formula (A1) in the L 1, and the formula (A2), the L 2, an oxygen atom of the side chain end side key junction.
A1 及A2 分別獨立地表示1價的有機基。作為1價的有機基,取代或無取代的烷基或取代或無取代的芳基為較佳。作為取代基,可以舉出在日本特開2009-256572號公報的段落號0028中記載之取代基,將該些內容併入到本說明書中。A 1 and A 2 each independently represent a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferred. The substituents described in Paragraph No. 0027 of JP-A-2009-256572 are incorporated herein by reference.
作為A1 及A2 ,從分散穩定性、顯影性的觀點來看,碳原子數為1~20的直鏈烷基、碳原子數為3~20的支鏈烷基、碳原子數為5~20的環狀烷基為較佳,碳原子數為4~15的直鏈烷基、碳原子數為4~15的支鏈烷基、碳原子數為6~10的環狀烷基為更佳,碳原子數為6~10的直鏈烷基、碳原子數為6~12的支鏈烷基進一步較佳。A 1 and A 2 are a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and 5 carbon atoms from the viewpoint of dispersion stability and developability. The cyclic alkyl group of -20 is preferable, the linear alkyl group having 4 to 15 carbon atoms, the branched alkyl group having 4 to 15 carbon atoms, and the cyclic alkyl group having 6 to 10 carbon atoms are More preferably, a linear alkyl group having 6 to 10 carbon atoms or a branched alkyl group having 6 to 12 carbon atoms is further more preferable.
m及n分別獨立地表示2~8的整數。從分散穩定性、顯影性的觀點來看,4~6為較佳,5為最佳。m and n each independently represent an integer of 2-8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferred, and 5 is most preferred.
p及q分別獨立地表示1~100的整數。亦可以混合2種以上p的不同者及q的不同者。從分散穩定性、顯影性的觀點來看,p及q為5~60為較佳、5~40為更佳,5~20進一步較佳。p and q each independently represent an integer of 1 to 100. It is also possible to mix two or more different types of p and different ones of q. From the viewpoint of dispersion stability and developability, p and q are preferably from 5 to 60, more preferably from 5 to 40, still more preferably from 5 to 20.
對於通式(A1)中表示之重複單元、通式(A2)中表示之重複單元的詳細內容,可以參照日本特開2012-173356號公報的段落號0060~0084的記載內容,將該些內容併入到本說明書中。For the details of the repeating unit represented by the formula (A1) and the repeating unit represented by the formula (A2), the contents of the paragraphs 0060 to 0084 of JP-A-2012-173356 can be referred to. Incorporated into this specification.
作為具有酸基之重複單元,可以舉出上述者。Examples of the repeating unit having an acid group include the above.
上述接枝共聚物的詳細內容,可以參照日本特開2012-173356號公報的段落號0060~0109的記載內容,將該些內容併入到本說明書中。作為上述接枝共聚物的具體例,例如可以舉出以下者。The details of the graft copolymer described above can be referred to in the specification of the paragraphs 0060 to 0109 of JP-A-2012-173356. Specific examples of the graft copolymer include the following.
【化學式23】 [Chemical Formula 23]
並且,在本發明中,作為分散劑可使用在主鏈及側鏈的至少一者含有氮原子之寡聚亞胺(Oligoimine)系樹脂。作為寡聚亞胺系樹脂,較佳為具有重複單元和側鏈,且在主鏈及側鏈的至少一方具有鹼性氮原子之樹脂,其中,該重複單元具備具有pKa 14以下的官能基之部分結構X,該側鏈含有原子數為40~10,000的寡聚物鏈或聚合物鏈Y。Further, in the present invention, an oligomeric imine (Oligoimine) resin containing a nitrogen atom in at least one of a main chain and a side chain can be used as the dispersant. The oligomeric imide resin is preferably a resin having a repeating unit and a side chain and having a basic nitrogen atom in at least one of a main chain and a side chain, wherein the repeating unit has a functional group having a pKa 14 or less Part of the structure X, the side chain contains an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000.
在此,鹼性氮原子只要為呈鹼性之氮原子則無特別的限制。寡聚亞胺系樹脂含有具有鹽強度pKb 14以下的氮原子之結構為較佳,含有具有pKb 10以下的氮原子之結構為更佳。Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The oligomeric imide resin preferably has a structure having a nitrogen atom having a salt strength of pK b 14 or less, and more preferably has a structure having a nitrogen atom of pK b 10 or less.
在本發明中,鹽強度pKb 是指水溫25℃下的pKb ,係用於定量地表示鹽強度之指標之一,係與鹼度常數相同含義。鹽強度pKb 和後述的酸強度pKa 具有pKb =14-pKa 的關係。In the present invention, the salt refers to the strength pK b pK b at temperature 25 ℃, based index for quantitatively showing one salt intensity, the basicity constant based same meaning. The salt strength pK b and the acid strength pK a described later have a relationship of pK b =14-pK a .
寡聚亞胺系樹脂為具有重複單元(i)和側鏈(ii)為尤佳,其中,該重複單元(i)係選自聚(低級伸烷基亞胺)系重複單元、聚烯丙基胺系重複單元、聚二烯丙基胺系重複單元、間二甲苯二胺-表氯醇縮聚物系重複單元、及聚乙烯胺系重複單元之至少1種的具有鹼性氮原子之重複單元,並且具有與鹼性氮原子鍵結且包含pKa 14以下的官能基之部分結構X,該側鏈(ii)含有原子數40~10,000的寡聚物鏈或聚合物鏈Y。The oligomeric imine resin is preferably a repeating unit (i) and a side chain (ii), wherein the repeating unit (i) is selected from the group consisting of poly(lower alkylene imine) repeating units, polyallyl Repeating of at least one of a basic amine repeating unit, a polydiallylamine repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and a polyvinylamine repeating unit having a basic nitrogen atom And a partial structure X having a functional group bonded to a basic nitrogen atom and containing pK a 14 or less, the side chain (ii) having an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000.
聚(低級伸烷基亞胺)可以為鏈狀,亦可以為網目狀。在此,在本發明中,低級伸烷基亞胺是指含有碳原子數為1~5的伸烷基鏈之伸烷基亞胺。The poly(lower alkylene imide) may be in the form of a chain or a mesh. Here, in the present invention, the lower alkyleneimine means an alkyleneimine having an alkylene chain having 1 to 5 carbon atoms.
上述重複單元(i)形成寡聚亞胺系樹脂中之主鏈部為較佳。主鏈部的數量平均分子量,亦即,從寡聚亞胺系樹脂中去除上述側鏈(ii)部分的數量平均分子量為100~10,000為較佳,200~5,000進一步較佳,300~2,000為最佳。能夠由藉由核磁共振分光法測定之末端基與主鏈部的氫原子積分值的比率求出主鏈部的數量平均分子量,或藉由測定含有作為原材料之胺基之寡聚物或聚合物的分子量求出主鏈部的數量平均分子量。It is preferred that the repeating unit (i) forms a main chain portion in the oligomeric imide resin. The number average molecular weight of the main chain portion, that is, the number average molecular weight of the side chain (ii) portion removed from the oligomeric imide resin is preferably from 100 to 10,000, more preferably from 200 to 5,000, and further preferably from 300 to 2,000. optimal. The number average molecular weight of the main chain portion can be determined from the ratio of the hydrogen atom integrated value of the terminal group and the main chain portion measured by the nuclear magnetic resonance spectroscopy, or the oligomer or polymer containing the amine group as a raw material can be determined. The molecular weight of the main chain portion was determined by the molecular weight.
寡聚亞胺系樹脂的最佳態様的一種,可以舉出包含下述通式(I-1)中表示之重複單元、及通式(I-2)中表示之重複單元之態様。One of the most preferable examples of the oligo-imine-based resin is a state in which a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2) are contained.
【化學式24】 [Chemical Formula 24]
在通式(I-1)及(I-2)中,R1 及R2 分別獨立地表示氫原子、鹵素原子或烷基,a分別獨立地表示1~5的整數,*表示重複單元之間的連接部,X表示具有pKa 14以下的官能基之基團,Y表示原子數為40~10,000的寡聚物鏈或聚合物鏈。In the general formulae (I-1) and (I-2), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and a each independently represents an integer of 1 to 5, and * represents a repeating unit. In the connection portion, X represents a group having a functional group of pK a 14 or less, and Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.
寡聚亞胺系樹脂進一步含有通式(I-3)中表示之重複單元為較佳。依據該態様,著色劑等的分散性會進一步提高。The oligomeric imide resin further preferably contains a repeating unit represented by the formula (I-3). According to this state, the dispersibility of the coloring agent or the like is further improved.
【化學式25】 [Chemical Formula 25]
在通式(I-3)中,R1 、R2 及a與通式(I-1)中之R1 、R2 及a具有相同含義。Y’表示具有陰離子基團之原子數為40~10,000的寡聚物鏈或聚合物鏈。可藉由在主鏈部具有一級或二級胺基之樹脂中添加具有與胺反應而形成鹽之基團之寡聚物或聚合物而使其進行反應,從而形成通式(I-3)中表示之重複單元。In the formula (I-3), R 1 , R 2 and a have the same meanings as R 1 , R 2 and a in the formula (I-1). Y' represents an oligomer chain or a polymer chain having an anion group having an atomic number of 40 to 10,000. The compound (I-3) can be formed by adding an oligomer or a polymer having a group which forms a salt by reacting with an amine in a resin having a primary or secondary amine group in the main chain portion. The repeating unit indicated in .
在通式(I-1)、通式(I-2)及通式(I-3)中,R1 及R2 為氫原子為較佳。從原材料獲取性的觀點來看,a為2為較佳。In the general formula (I-1), the general formula (I-2) and the general formula (I-3), R 1 and R 2 are preferably a hydrogen atom. From the viewpoint of raw material availability, a is preferably 2.
寡聚亞胺系樹脂除了含有通式(I-1)、通式(I-2)及通式(I-3)中表示之重複單元以外,亦可以含有具有一級或三級胺基之低級伸烷基亞胺作為重複單元。另外,低級伸烷基亞胺重複單元中之氮原子亦可以進一步鍵結有由X、Y或Y’表示之基團。The oligomeric imide resin may contain a lower group having a primary or tertiary amine group in addition to the repeating unit represented by the formula (I-1), the formula (I-2) and the formula (I-3). The alkylimine is used as a repeating unit. Further, the nitrogen atom in the lower alkylene imine repeating unit may be further bonded to a group represented by X, Y or Y'.
通式(I-1)中表示之重複單元在包含於寡聚亞胺系樹脂之總重複單元中含有1~80莫耳%為較佳,含有3~50莫耳%為最佳。The repeating unit represented by the formula (I-1) is preferably contained in an amount of from 1 to 80 mol%, more preferably from 3 to 50 mol%, based on the total repeating unit contained in the oligomeric imide resin.
通式(I-2)中表示之重複單元在包含於寡聚亞胺系樹脂中之總重複單元含有10~90莫耳%為較佳,含有30~70莫耳%為最佳。The repeating unit represented by the formula (I-2) is preferably 10 to 90 mol%, and preferably 30 to 70 mol%, based on the total repeating unit contained in the oligomeric imide resin.
從分散穩定性及親疏水性平衡的觀點來看,重複單元(I-1)及重複單元(I-2)的含有比率〔(I-1):(I-2)〕以莫耳比計為10:1~1:100的範圍為較佳,1:1~1:10的範圍為更佳。From the viewpoint of dispersion stability and hydrophilic-hydrophobic balance, the content ratio of the repeating unit (I-1) and the repeating unit (I-2) [(I-1): (I-2)] is expressed in terms of molar ratio. The range of 10:1 to 1:100 is preferable, and the range of 1:1 to 1:10 is more preferable.
另外,依據需要而併用之通式(I-3)中表示之重複單元係,含有原子數為40~10,000的寡聚物鏈或聚合物鏈Y’之部分結構與主鏈的氮原子離子鍵結者,在包含於寡聚亞胺系樹脂之總重複單元中,從效果的觀點來看,含有0.5~20莫耳%為較佳,含有1~10莫耳%為最佳。另外,能夠藉由紅外分光法、鹽滴定法來確認離子鍵結有聚合物鏈Y’。Further, the repeating unit represented by the formula (I-3) used in combination as needed contains an oligomer chain having an atomic number of 40 to 10,000 or a partial structure of the polymer chain Y' and a nitrogen atom ionic bond of the main chain. In the total repeating unit contained in the oligoenimine resin, it is preferably from 0.5 to 20 mol%, and preferably from 1 to 10 mol%, from the viewpoint of the effect. Further, it was confirmed by ion spectrometry or salt titration that the polymer chain Y' was ion-bonded.
寡聚亞胺系樹脂亦可使用日本特開2009-258668號公報的段落號0016~0018、日本特開2009-203462號公報的段落號0021~0080中記載之化合物。將該些內容併入到本說明書中。The oligo-imine-based resin may be a compound described in paragraphs 0021 to 0018 of JP-A-2009-258668 and paragraphs 0021 to 0080 of JP-A-2009-203462. This is incorporated into the present specification.
並且,在本發明中,作為酸性分散劑,可使用日本特開2008-165059號公報的段落號0020~0075中記載之具有酸基和不飽和雙鍵之樹脂。Further, in the present invention, as the acidic dispersing agent, a resin having an acid group and an unsaturated double bond described in paragraphs 0020 to 0075 of JP-A-2008-165059 can be used.
亦可作為市售品而獲取分散劑,作為該種具體例,可以舉出KUSUMOTO Chemicals,LTD.製造的“DA-7301”;BYK-Chemie GmbH製造的“DISPERBYK-101(聚醯胺-胺磷酸鹽)、107(羧酸酯)、110(含有酸基之共聚物)、111(磷酸系分散劑)、130(聚醯胺)、161、162、163、164、165、166、170、171、174、176、180、182、2000、2001、2050、2150、P104、P105、LPN21116”;BYK-Chemie GmbH製造的“BYK-6919”、EFKA公司製造的“EFKA4047、4050~4010~4165(聚胺基甲酸酯系)、EFKA4330~4340(嵌段共聚物)、4400~4402(改質聚丙烯酸酯)、5010(聚酯醯胺)、5765(高分子量聚羧酸鹽)、6220(脂肪酸聚酯)、6745(酞菁衍生物)、6750(偶氮顔料衍生物)”;AJINOMOTO FINE-TECHNO Co.,Inc製造的“AJISPER PB821、PB822、PB880、PB881”;KYOEISHA Chemical Co.,Ltd製造的“FLOWLEN TG-710(聚胺基甲酸酯寡聚物)”、“POLYFLOW No.50E、No.300(丙烯酸系共聚物)”;KUSUMOTO Chemicals,Ltd製造的“DISPARLON KS-860、873SN、874、#2150(脂肪族多價羧酸)、#7004(聚醚酯)、DA-703-50、DA-705、DA-725”;KAO Corporation製造的“DEMOL RN、N(萘磺酸福馬林縮聚物)、MS、C、SN-B(芳香族磺酸福馬林縮聚物)”、“HOMOGENOL L-18(高分子聚羧酸)”、“EMULGEN920、930、935、985(聚氧乙烯壬基苯基醚)”、“ACETAMIN86(硬脂基胺乙酸鹽)”;LUBRIZOL JAPAN ,LTD.製造的“SOLSPERSE5000(酞菁衍生物)、22000(偶氮顔料衍生物)、13240(聚酯胺)、3000、12000、17000、20000、27000(在末端部具有功能部之高分子)、24000、28000、32000、38500(接枝型高分子)”;Nikko Chemicals Co., Ltd.製造的“NIKKOR T106(聚氧乙烯山梨糖醇單油酸酯)、MYS-IEX(聚氧乙烯單硬脂酸酯)”;KAWAKEN FINE CHEMICALS CO.,LTD.製造的HINOACT T-8000E等;SHIN-ETSU CHEMICAL CO.,LTD.製造的有機矽氧烷聚合物KP341;YUSHO CO.,LTD.製造的“W001:陽離子系界面活性劑”、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油烯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖醇脂肪酸酯等非離子界面活性劑、“W004、W005、W017”等陰離子系界面活性劑,MORISHITA&CO.,LTD.製造的“EFKA-46、EFKA-47、EFKA-47EA、EFKA聚合物100、EFKA聚合物400、EFKA聚合物401、EFKA聚合物450”、SUN NOPCO LIMITED製造的“DISPERSE AID 6、DISPERSE AID 8、DISPERSE AID 15、DISPERSE AID 9100”等高分子分散劑,ADEKA CORPORATION製造的“ADEKA PLURONIC L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、P84、F87、P94、L101、P103、F108、L121、P-123”、及SANYO CHEMICAL INDUSTRIES,LTD.製造的“IONET(商品名稱)S-20”等。並且,亦可使用ACRYBASE FFS-6752、ACRYBASE FFS-187、ACRYCURE-RD-F8、CYCLOMER P。A dispersant can be obtained as a commercial product. As a specific example, "DA-7301" manufactured by KUSUMOTO Chemicals, LTD.; "DISPERBYK-101 (polyamide-amine phosphoric acid) manufactured by BYK-Chemie GmbH Salt), 107 (carboxylate), 110 (copolymer containing acid group), 111 (phosphate dispersant), 130 (polyamine), 161, 162, 163, 164, 165, 166, 170, 171 , 174, 176, 180, 182, 2000, 2001, 2050, 2150, P104, P105, LPN21116"; "BYK-6919" manufactured by BYK-Chemie GmbH, "EFKA 4047, 4050-4010 ~ 4165" manufactured by EFKA Corporation Amino acid ester), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid) Polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative); "AJISPER PB821, PB822, PB880, PB881" manufactured by AJINOMOTO FINE-TECHNO Co., Inc.; manufactured by KYOEISHA Chemical Co., Ltd. "FLOWLEN TG-710 (polyurethane oligomer)", "POLYFLOW No. 50E, No. 300 (propylene Acid Copolymer)"; DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA- manufactured by KUSUMOTO Chemicals, Ltd. 705, DA-725"; "DEMOL RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (aromatic sulfonate fumarate polycondensate)", "HOMOGENOL L-18" manufactured by KAO Corporation (Polymer polycarboxylic acid)", "EMULGEN920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN86 (stearylamine acetate)"; "SOLSPERSE5000" manufactured by LUBRIZOL JAPAN, LTD. (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional portion at the terminal portion), 24000, 28000, 32000, 38500 (graft type polymer)"; "NIKKOR T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikko Chemicals Co., Ltd.; HINOACT T-8000E manufactured by KAWAKEN FINE CHEMICALS CO., LTD.; organic 矽 manufactured by SHIN-ETSU CHEMICAL CO., LTD. Alkyl polymer KP341; "W001: cationic surfactant" manufactured by YUSHO CO., LTD., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octane Nonionic surfactants such as phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, "W004, Anionic surfactant such as W005, W017", "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 manufactured by MORISHITA & CO., LTD. Polymer dispersant such as "DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100" manufactured by SUN NOPCO LIMITED, "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68 manufactured by ADEKA CORPORATION" ", L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and "IONET (trade name) S-20" manufactured by SANYO CHEMICAL INDUSTRIES, LTD. Also, ACRYBASE FFS-6752, ACRYBASE FFS-187, ACRYCURE-RD-F8, and CYCLOMER P can be used.
另外,利用上述分散劑進行說明之樹脂,亦可以以分散劑以外的用途進行使用。例如亦能夠用作黏合劑。Further, the resin described by the above dispersant may be used in applications other than the dispersant. For example, it can also be used as a binder.
<<<鹼可溶性樹脂>>><<<Alkali Soluble Resin>>
本發明的著色硬化性組成物能夠含有鹼可溶性樹脂而作為樹脂。藉由含有鹼可溶性樹脂,顯影性及圖案形成性提高。另外,鹼可溶性樹脂亦可用作分散劑和黏合劑。The colored curable composition of the present invention can contain an alkali-soluble resin as a resin. The developability and pattern formability are improved by containing an alkali-soluble resin. In addition, alkali-soluble resins can also be used as a dispersant and a binder.
作為鹼可溶性樹脂的分子量並無特別的限定,重量平均分子量(Mw)為5000~100,000為較佳。並且數量平均分子量(Mn)為1000~20,000為較佳。The molecular weight of the alkali-soluble resin is not particularly limited, and the weight average molecular weight (Mw) is preferably from 5,000 to 100,000. Further, a number average molecular weight (Mn) of from 1,000 to 20,000 is preferred.
作為鹼可溶性樹脂,可以係線性有機高分子聚合物,亦可以從在分子(以丙烯酸系共聚物、苯乙烯系共聚物為主鏈之分子為較佳)中至少具有1個促進鹼可溶性之基團之鹼可溶性樹脂中適當地進行選擇。The alkali-soluble resin may be a linear organic high molecular polymer, or may have at least one base which promotes alkali solubility in a molecule (a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The alkaloid-soluble resin is appropriately selected.
作為鹼可溶性樹脂,從耐熱性的觀點來看,多羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂為較佳,從控制顯影性之觀點來看,丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂為較佳。The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of controlling developability, an acrylic resin, an acrylamide resin, and an acrylic/acrylamide copolymer resin are preferable.
作為促進鹼可溶性之基團(以下,亦稱作酸基),例如可以舉出羧基、磷酸基、磺酸基、酚性羥基等,可溶於有機溶劑中,且可利用弱鹼水溶液進行顯影者為較佳,作為尤佳者可舉出(甲基)丙烯酸。該些酸基可以僅為1種,亦可以為2種以上。Examples of the group which promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are soluble in an organic solvent, and can be developed by using a weak alkali aqueous solution. It is preferred, and (meth)acrylic acid is preferred as a preferred one. These acid groups may be used alone or in combination of two or more.
在製造鹼可溶性樹脂時,例如能夠適用公知的利用自由基聚合法之方法。用自由基聚合法製造鹼可溶性樹脂時的溫度、壓力、自由基起始劑的種類及其量、溶劑的種類等聚合條件可由本領域技術人員容易地設定,亦可以實驗性地設定條件。In the case of producing an alkali-soluble resin, for example, a known method using a radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be experimentally set.
作為鹼可溶性樹脂,在側鏈具有羧酸之聚合物為較佳,可以舉出甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、馬來酸共聚物、部分酯化馬來酸共聚物、酚醛型樹脂(novolak type resin)等鹼可溶性酚樹脂(phenol resin)等;以及在側鏈具有羧基之酸性纖維素衍生物、在具有羥基之聚合物上加成酸酐而成者。尤其,(甲基)丙烯酸和可與其共聚合之其他單體的共聚物適合作為鹼可溶性樹脂。作為可與(甲基)丙烯酸共聚合的其他單體,可以舉出(甲基)丙烯酸烷基酯、(甲基)丙烯酸芳基酯、乙烯基化合物等。作為(甲基)丙烯酸烷基酯及(甲基)丙烯酸芳基酯,可以舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸甲苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸環己基酯等,作為乙烯基化合物,可以舉出苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲基丙烯酸縮水甘油酯、丙烯腈、乙酸乙烯酯、N-乙烯基吡咯啶酮、甲基丙烯四氫糠酯、聚苯乙烯巨單體、聚甲基丙烯酸甲酯巨單體等,在日本特開平10-300922號公報中記載的作為N位取代馬來醯亞胺單體,能舉出N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等。另外,可與該些(甲基)丙烯酸共聚合之其他單體可以僅為1種,亦可以為2種以上。As the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial ester. An alkali-soluble phenol resin such as a maleic acid copolymer or a novolak type resin; and an acid cellulose derivative having a carboxyl group in a side chain; and an acid anhydride added to a polymer having a hydroxyl group; Adult. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc., and examples of the vinyl compound include styrene, α-methylstyrene, and vinyltoluene. , glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, methacrylic tetrahydrofurfuryl ester, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. Examples of the N-substituted maleimide monomer described in Japanese Laid-Open Patent Publication No. Hei 10-300922 include N-phenylmaleimide and N-cyclohexylmaleimide. Further, the other monomers copolymerizable with the (meth)acrylic acid may be used alone or in combination of two or more.
並且,為了提高本發明中之著色硬化性組成物的交聯效率,可以使用具有聚合性基團之鹼可溶性樹脂。作為聚合性基團,可以舉出(甲基)烯丙基、(甲基)丙烯醯基等。具有聚合性基團之鹼可溶性樹脂,在側鏈含有聚合性基團之鹼可溶性樹脂等是有用的。Further, in order to improve the crosslinking efficiency of the color hardening composition in the present invention, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include a (meth)allyl group and a (meth)acryl fluorenyl group. An alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin containing a polymerizable group in a side chain.
含有聚合性基團之鹼可溶性樹脂,如下樹脂等為較佳:預先使異氰酸酯基與羥基反應而殘留1個未反應的異氰酸酯基,且含有(甲基)丙烯醯基等聚合性基團之化合物、與含有羧基之丙烯酸系樹脂進行反應而得到;且經胺基甲酸酯改質之鹼可溶性樹脂;藉由含有羧基之丙烯酸樹脂與在分子內具有環氧基及聚合性雙鍵之化合物的反應而得到之鹼可溶性樹脂;酸側基(Acid pendant)型環氧丙烯酸酯樹脂;使含有羥基之丙烯酸樹脂與具有聚合性雙鍵之二元酸酐反應而得到之鹼可溶性樹脂;使含有羥基之丙烯酸樹脂與具有異氰酸酯及聚合性基團之化合物進行反應而得到之鹼可溶性樹脂;日本特開2002-229207號公報及日本特開2003-335814號公報中記載之藉由對以下樹脂進行鹼性處理而得到之鹼可溶性樹脂,前述樹脂在側鏈上具有在α位或β位具有鹵素原子或磺酸基等脱離基之酯基。The alkali-soluble resin containing a polymerizable group is preferably a resin or the like which is obtained by reacting an isocyanate group with a hydroxyl group to leave an unreacted isocyanate group, and a polymerizable group such as a (meth)acryl fluorenyl group. An alkali-soluble resin obtained by reacting with a carboxyl group-containing acrylic resin; and modified by a urethane; a resin having a carboxyl group and a compound having an epoxy group and a polymerizable double bond in the molecule; An alkali-soluble resin obtained by the reaction; an acid pendant acrylic acrylate resin; an alkali-soluble resin obtained by reacting a hydroxyl group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond; An alkali-soluble resin obtained by reacting an acrylic resin with a compound having an isocyanate and a polymerizable group; and the following resin is subjected to alkaline treatment as described in JP-A-2002-229207 and JP-A-2003-335814 The alkali-soluble resin obtained has a halogen atom or a sulfonic acid group at the α-position or the β-position in the side chain. Group of the ester group.
作為含有聚合性基團之鹼可溶性樹脂,可以舉出DIANAL NR系列(MITSUBISHI RAYON SHARES CO.,LTD.製造)、Photomer6173(含COOH的polyurethane acrylic oligomer,Diamond Shamrock Co., Ltd.製造)、VISCOAT R-264、KS RESIST 106(均為OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製造)、CYCLOMER P系列(例如ACA230AA)、PLACCEL CF200系列(均為DAICEL CHEMICAL INDUSTRIES CO.,LTD.製造)、Ebecryl 3800(DAICEL UCB CO.,LTD.製造)、Akurikyua-RD-F8(NIPPON SHOKUBAI CO.,LTD.製造)等。Examples of the alkali-soluble resin containing a polymerizable group include DIANAL NR series (manufactured by MITSUBISHI RAYON SHARES CO., LTD.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), and VISCOAT R. -264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.), and Ebecryl 3800 (DAICEL UCB CO.) , manufactured by LTD., Akurikyua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), and the like.
鹼可溶性樹脂可較佳地使用(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸苄酯/(甲基)丙烯酸/(甲基)丙烯酸-2-羥基乙酯共聚物、包含(甲基)丙烯酸苄酯/(甲基)丙烯酸/其他單體之多元共聚物。並且,亦可以較佳使用將2-羥乙基(甲基)丙烯酸酯共聚合而成者,日本特開平7-140654號公報中記載的(甲基)丙烯酸-2-羥基丙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物,丙烯酸-2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物,甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物,甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。As the alkali-soluble resin, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl copolymer may be preferably used. And a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. Further, it is also possible to use 2-hydroxyethyl (meth) acrylate copolymerized, and 2-hydroxypropyl (meth)acrylate/polyphenyl group described in JP-A-7-140654 Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/A Benzyl acrylate / methacrylic acid copolymer and the like.
鹼可溶性樹脂包含聚合物(a)亦較佳,該聚合物(a)藉由將含有下述通式(ED1)中表示之化合物及/或下述通式(ED2)中表示之化合物(以下,有時亦將該些化合物稱作“醚二聚物”)之單體成分聚合而構成。It is also preferred that the alkali-soluble resin comprises a polymer (a) which will contain a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (below) Further, the monomer components of these compounds are sometimes referred to as "ether dimers".
【化學式26】 [Chemical Formula 26]
通式(ED1)中,R1 及R2 分別獨立地表示氫原子或可以具有取代基之碳原子數為1~25的烴基。In the formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
【化學式27】 [Chemical Formula 27]
通式(ED2)中,R表示氫原子或碳原子數為1~30的有機基團。作為通式(ED2)的具體例,可以參照日本特開2010-168539號公報的記載。In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP-A-2010-168539 can be referred to.
通式(ED1)中,作為由R1 及R2 表示之可以具有取代基之碳原子數為1~25的烴基並無特別的限制,例如可以舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、叔丁基、叔戊基、硬脂基、月桂基、2-乙基己基等直鏈狀或支鏈狀的烷基;苯基等芳基;環己基、叔丁基環己基、二環戊二烯基、三環癸烷基、異冰片基、金剛烷基、2-甲基-2-金剛烷基等脂環式基團;1-甲氧基乙基、1-乙氧基乙基等經烷氧基取代之烷基;苄基等經芳基取代之烷基等。其中,尤其,從耐熱性的觀點來看,如甲基、乙基、環己基、苄等那樣的不易因酸或熱而脫離之一級或二級碳的取代基為較佳。In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. a linear or branched alkyl group such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; an aryl group such as phenyl; An alicyclic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl or 2-methyl-2-adamantyl; An alkyl group substituted with an alkoxy group such as an oxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among them, in particular, from the viewpoint of heat resistance, a substituent such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group which is not easily desorbed from a primary or secondary carbon by acid or heat is preferred.
作為醚二聚物的具體例,例如可舉出二甲基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二乙基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(正丙基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(異丙基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(正丁基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(異丁基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(叔丁基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(叔戊基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(硬脂基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(月桂基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(2-乙基己基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(1-甲氧基乙基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(1-乙氧基乙基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二芐基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二苯基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二環己基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(叔丁基環己基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(二環戊二烯基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(三環癸烷基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(異冰片基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二金剛烷基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二(2-甲基-2-金剛烷基)-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯等。其中,二甲基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二乙基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二環己基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯、二芐基-2,2’-[氧基雙(亞甲基)]雙-2-丙烯酸酯為尤佳。該些醚二聚物可以僅為1種,亦可以為2種以上。來源於通式(ED)所表示之化合物的結構體亦可以使其他單體共聚合。Specific examples of the ether dimer include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate and diethyl-2,2'-[oxygen Bis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl) -2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butyl)-2,2'-[oxy double (methylene Base]] bis-2-acrylate, bis(tert-amyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(stearyl)-2,2' -[oxybis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2- Ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxybis (methylene Bis-2-]acrylate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butylcyclohexyl)-2,2'-[oxybis(methylene) )] bis-2-acrylate, bis(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tricyclodecyl)- 2,2'-[oxybis(methylene)]bis-2-acrylate, bis(isobornyl)-2,2'-[oxybis(methylene)]bis-2-acrylate , diamantyl-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxy Bis(methylene)] bis-2-acrylate. Wherein, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis-2 - acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxybis(methylene)] double -2-Acrylate is especially preferred. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the general formula (ED) may also copolymerize other monomers.
鹼可溶性樹脂亦可以含有來源於下述式(X)中表示之化合物之結構單元。The alkali-soluble resin may also contain a structural unit derived from a compound represented by the following formula (X).
【化學式28】 [Chemical Formula 28]
在式(X)中,R1 表示氫原子或甲基,R2 表示碳原子數為2~10的伸烷基,R3 表示氫原子或可以含有苯環的碳原子數為1~20的烷基。n表示1~15的整數。In the formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or may have a benzene ring having 1 to 20 carbon atoms. alkyl. n represents an integer of 1 to 15.
在上述式(X)中,R2 的伸烷基的碳原子數為2~3為較佳。並且,R3 的烷基的碳原子數為1~20,1~10為更佳,R3 的烷基亦可以含有苯環。作為由R3 表示之含有苯環之烷基,可以舉出苄基、2-苯基(異)丙基等。In the above formula (X), the alkylene group of R 2 has preferably 2 to 3 carbon atoms. Further, the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R 3 may contain a benzene ring. The alkyl group containing a benzene ring represented by R 3 may, for example, be a benzyl group or a 2-phenyl(iso)propyl group.
鹼可溶性樹脂可以參照日本特開2012-208494號公報段落0558~0571(對應之美國專利申請揭示第2012/0235099號說明書的[0685]~[0700])之後的記載,將該些內容併入到本申請案說明書中。The alkali-soluble resin can be incorporated into the description after the following paragraphs 0558 to 0571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to [0685] to [0700] of the specification of the Japanese Patent Application Publication No. 2012/0235099) In the specification of the present application.
另外,亦可使用日本特開2012-32767號公報中記載的段落號0029~0063中記載的共聚物(B)及實施例中使用之鹼可溶性樹脂、日本特開2012-208474號公報的段落號0088~0098中記載的黏合劑樹脂及實施例中使用之黏合劑樹脂、日本特開2012-137531號公報的段落號0022~0032中記載的黏合劑樹脂及在實施例中使用之黏合劑樹脂、日本特開2013-024934號公報的段落號0132~0143中記載的黏合劑樹脂及在實施例中使用之黏合劑樹脂、日本特開2011-242752號公報的段落號0092~0098及實施例中使用之黏合劑樹脂、日本特開2012-032770號公報的段落號0030~0072中記載的黏合劑樹脂。將該些內容併入到本申請案說明書中。In addition, the copolymer (B) described in paragraphs 0029 to 0063 described in JP-A-2012-32767, the alkali-soluble resin used in the examples, and the paragraph number of JP-A-2012-208474 can be used. The adhesive resin described in 0088 to 0098 and the adhesive resin used in the examples, the adhesive resin described in paragraphs 0022 to 0032 of JP-A-2012-137531, and the adhesive resin used in the examples, The adhesive resin described in paragraphs 0132 to 0143 of JP-A-2013-024934, and the adhesive resin used in the examples, paragraphs 0092 to 0098 of JP-A-2011-242752, and the examples are used. The adhesive resin described in paragraphs 0030 to 0072 of JP-A-2012-032770. This is incorporated into the specification of the present application.
鹼可溶性樹脂的酸值為30~500mgKOH/g為較佳。下限為50mgKOH/g以上為更佳,70mgKOH/g以上為進一步較佳。上限為400mgKOH/g以下為更佳,200mgKOH/g以下為進一步較佳,150mgKOH/g以下為尤佳,120mgKOH/g以下為進一步較佳。The acid value of the alkali-soluble resin is preferably from 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and still more preferably 120 mgKOH/g or less.
在著色硬化性組成物含有鹼可溶性樹脂之情況下,鹼可溶性樹脂的含量相對於著色硬化性組成物的總固體成分為1~15質量%為較佳,2~12質量%為更佳,3~10質量%為進一步較佳。本發明的著色硬化性組成物可以僅含有1種鹼可溶性樹脂,亦可以含有2種以上。在含有2種以上鹼可溶性樹脂之情況下,其總量成為上述範圍為較佳。When the coloring curable composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably from 1 to 15% by mass based on the total solid content of the colored curable composition, and more preferably from 2 to 12% by mass. ~10% by mass is further preferred. The colored curable composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. In the case where two or more kinds of alkali-soluble resins are contained, the total amount thereof is preferably in the above range.
<<顔料衍生物>><<Pigment Derivative>>
本發明的著色硬化性組成物含有顔料衍生物為較佳。顔料衍生物為具有由酸性基、鹼性基或鄰苯二甲醯基取代有機顔料的一部分之結構之化合物為較佳。作為顔料衍生物,從著色劑A的分散性及分散穩定性的觀點來看,具有酸性基或鹼性基之顔料衍生物為較佳。具有鹼性基之顔料衍生物為尤佳。並且,就上述樹脂(分散劑)與顏料衍生物的組合而言,分散劑為酸性分散劑且顔料衍生物具有鹼性基之組合為較佳。The colored curable composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted by an acidic group, a basic group or a phthalyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferred from the viewpoint of dispersibility and dispersion stability of the colorant A. A pigment derivative having a basic group is particularly preferred. Further, in the combination of the above resin (dispersant) and the pigment derivative, it is preferred that the dispersant is an acidic dispersant and the pigment derivative has a combination of basic groups.
作為用於構成顔料衍生物的有機顔料,可以舉出二酮吡咯并吡咯系顔料、偶氮系顏料、酞菁系顏料、蒽醌系顏料、喹吖啶酮系顏料、二噁嗪系顏料、紫環酮系顏料、苝系顏料、硫靛系顏料、異吲哚啉系顏料、異吲哚啉酮系顏料、喹酞酮系顏料、士林系顏料、金屬錯合物系顏料等。Examples of the organic pigment constituting the pigment derivative include a diketopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a dioxazine pigment. A purple ring ketone pigment, an anthraquinone pigment, a thioindole pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinophthalone pigment, a Shilin pigment, a metal complex pigment, and the like.
並且,作為顔料衍生物所具有之酸性基,磺酸基、羧酸基及其鹽為較佳,羧酸基及磺酸基進一步較佳,磺酸基為尤佳。作為顔料衍生物所具有之鹼性基,胺基為較佳,三級胺基為尤佳。Further, as the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferred, a carboxylic acid group and a sulfonic acid group are further preferred, and a sulfonic acid group is particularly preferred. As the basic group of the pigment derivative, an amine group is preferred, and a tertiary amine group is particularly preferred.
在本發明的著色硬化性組成物含有顔料衍生物之情況下,顔料衍生物的含量相對於著色劑A的質量為1~30質量%為較佳,3~20質量%為進一步較佳。顔料衍生物可以僅使用1種,亦可以併用2種以上。In the case where the colored curable composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 30% by mass based on the mass of the colorant A, and more preferably from 3 to 20% by mass. The pigment derivative may be used alone or in combination of two or more.
<<光聚合起始劑>><<Photopolymerization initiator>>
本發明的著色硬化性組成物可以進一步含有光聚合起始劑。The color hardening composition of the present invention may further contain a photopolymerization initiator.
作為光聚合起始劑,只要具有引發聚合性化合物的聚合的能力,則無特別的限制,可以從公知的光聚合起始劑中適當地進行選擇。例如對紫外線區域至可見光線具有感光性者為較佳。並且,可以是與被光激發之增感劑產生某些作用而生成活性自由基之活性劑,亦可以是根據單體的種類而引發陽離子聚合之起始劑。The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-stimulated sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.
並且,光聚合起始劑至少含有1種在約300nm~800nm(330nm~500nm為更佳)的範圍內至少具有約50莫耳吸光係數之化合物為較佳。Further, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of from about 300 nm to 800 nm (more preferably from 330 nm to 500 nm).
作為光聚合起始劑,例如可以舉出鹵化烴衍生物(例如具有三嗪骨架者、具有噁二唑骨架者等)、醯基膦氧化物等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫代化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮等。Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaarylbisimidazole or an anthracene. An anthracene compound such as a derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone.
並且,從曝光感度的觀點來看,選自由三鹵甲基三嗪化合物、芐基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三烯丙基咪唑二聚物、鎓化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵錯合物及其鹽、鹵甲基噁二唑化合物、經3-芳基取代的香豆素化合物構成之群之化合物為較佳。Further, from the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, and a phosphine oxide compound. , metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron mismatch A compound of the group consisting of a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound is preferred.
三鹵甲基三嗪化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、肟化合物、三烯丙基咪唑二聚物、鎓化合物、二苯甲酮化合物、苯乙酮化合物為進一步較佳,選自由三鹵甲基三嗪化合物、α-胺基酮化合物、肟化合物、三烯丙基咪唑二聚物、二苯甲酮化合物構成之群之至少一種化合物為尤佳。a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound, and an acetophenone compound are Further preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound is particularly preferred.
尤其,在製造固體攝像元件的彩色濾光片時使用本發明的著色硬化性組成物之情況下,由於需要以尖細形狀形成微細圖案,因此硬化性和對未曝光部無殘渣的方式進行顯影比較重要。從該種觀點來看,作為光聚合起始劑而使用肟化合物為尤佳。尤其,在固體攝像元件中形成微細之圖案之情況下,硬化用曝光中使用步進機曝光,但是該曝光機有時會因鹵素而損傷,還需要將光聚合起始劑的添加量抑制得較低,因此考慮到該點,如固體攝像元件那樣在形成微細圖案時,作為光聚合起始劑而使用肟化合物為尤佳。並且,藉由使用肟化合物而能夠更優化移染性。In particular, when the colored curable composition of the present invention is used in the production of a color filter of a solid-state image sensor, it is necessary to form a fine pattern in a tapered shape, so that curing is performed and development is performed without residue on the unexposed portion. More important. From such a viewpoint, it is especially preferable to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, exposure by a stepper is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator. In view of this point, it is preferable to use a ruthenium compound as a photopolymerization initiator when forming a fine pattern like a solid-state image sensor. Moreover, the transferability can be more optimized by using a ruthenium compound.
作為光聚合起始劑的具體例,例如可以參照日本特開2013-29760號公報的段落0265~0268,將該內容併入到本申請案說明書中。Specific examples of the photopolymerization initiator can be referred to the specification of the present application by referring to paragraphs 0265 to 0268 of JP-A-2013-29760, for example.
作為光聚合起始劑,能夠適當地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言,例如亦可以使用日本特開平10-291969號公報中記載的胺基苯乙酮系起始劑、專利第4225898號公報中記載的醯基膦系起始劑。As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and a mercaptophosphine-based initiator described in Patent No. 4,258,899 can be used.
作為羥基苯乙酮系起始劑,可以使用IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959,IRGACURE-127(商品名稱:均為BASF SE製造)。As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF SE) can be used.
作為胺基苯乙酮系起始劑,可以使用作為市售品之IRGACURE-907、IRGACURE-369及IRGACURE-379(商品名稱:均為BASF SE製造)。胺基苯乙酮系起始劑亦可使用吸收波長與365nm或405nm等長波光源匹配之日本特開2009-191179公報中記載的化合物。As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF SE) which are commercially available can be used. The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched with a long-wavelength light source such as 365 nm or 405 nm.
作為醯基膦系起始劑,可以使用市售品之IRGACURE-819、DAROCUR-TPO(商品名稱:均為BASF SE製造)。As the mercaptophosphine-based initiator, commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: all manufactured by BASF SE) can be used.
作為光聚合起始劑,更佳可以舉出肟化合物。As the photopolymerization initiator, a ruthenium compound is more preferable.
作為肟化合物的具體例,可以使用日本特開2001-233842號公報記載的化合物、日本特開2000-80068號公報記載的化合物、日本特開2006-342166號公報記載的化合物。As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used.
作為能夠適合使用於本發明之肟化合物,例如可以舉出3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-(4-甲苯磺醯氧基)亞胺基丁烷-2酮及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。Examples of the ruthenium compound which can be suitably used in the present invention include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3- Propyl methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2one and 2-ethoxycarbonyloxy Amino-1-phenylpropan-1-one and the like.
並且,亦可以舉出J.C.S.Perkin II(1979年)pp.1653-1660、J.C.S.Perkin II(1979年)pp.156-162、Journal of Photopolymer Science and Technology(1995年)pp.202-232、日本特開2000-66385號公報記載的化合物、日本特開2000-80068號公報、日本專利公表2004-534797號公報、日本特開2006-342166號公報等各公報中記載的化合物等。Further, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, and Japanese specials are also mentioned. The compound described in each of the publications such as JP-A-2000-80068, JP-A-2000-80068, and JP-A-2006-342166, and the like.
市售品中亦可適當地使用IRGACURE-OXE01(BASF SE製造)、IRGACURE-OXE02(BASF SE製造)。並且,亦可使用TR-PBG-304(CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.,LTD.製造)、ADEKA ARKLS NCI-831及ADEKA ARKLS NCI-930(ADEKA Corporation製造)。IRGACURE-OXE01 (manufactured by BASF SE) and IRGACURE-OXE02 (manufactured by BASF SE) can also be suitably used in the commercial product. Further, TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) can also be used.
並且,作為上述記載以外的肟化合物,亦可使用肟連接於咔唑N位之日本專利公表2009-519904號公報中記載的化合物、在二苯甲酮部位導入有雜取代基之美國專利第7626957號公報中記載的化合物、在色素部位導入有硝基之日本特開2010-15025號公報及美國特開2009-292039號中記載的化合物、国際揭示專利2009-131189號公報中記載的酮肟化合物、在同一分子內含有三嗪骨架和肟骨架之在美國專利7556910號公報中記載的化合物、具有405nm的最大吸收,且對g線光源具有良好的感度之日本特開2009-221114號公報記載的化合物等。In addition, as the ruthenium compound other than the above-mentioned, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is attached to the N-position of the carbazole, and a U.S. Patent No. 7,626,957 in which a hetero substituent is introduced at the benzophenone site can be used. The compound described in the Japanese Patent Laid-Open Publication No. 2010-15025, and the ketone oxime compound described in Japanese Laid-Open Patent Publication No. 2009-131189. The compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption of 405 nm, and has a good sensitivity to a g-line light source, as described in JP-A-2009-221114. Compounds, etc.
較佳為例如可以參照日本特開2013-29760號公報的段落0274~0275,將該內容併入到本申請案說明書中。For example, it is preferable to refer to paragraphs 0274 to 0275 of JP-A-2013-29760, which is incorporated herein by reference.
具體而言,作為肟化合物,下述式(OX-1)中表示之化合物為較佳。另外,肟的N-O鍵可以為(E)體的肟化合物,亦可以為(Z)體的肟化合物,亦可以為(E)體與(Z)體的混合物。Specifically, as the hydrazine compound, a compound represented by the following formula (OX-1) is preferred. Further, the N-O bond of ruthenium may be an oxime compound of the (E) form, a ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form.
【化學式29】 [Chemical Formula 29]
在通式(OX-1)中,R及B分別獨立地表示一價取代基,A表示二價有機基,Ar表示芳基。In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
在通式(OX-1)中,作為由R表示之一價取代基,一價非金屬原子團為較佳。In the general formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferred.
作為一價的非金屬原子團,可以舉出烷基、芳基、醯基、烷氧羰基、芳氧基羰基、雜環基、烷硫基羰基、芳硫基羰基等。並且,該些基團亦可具有1以上的取代基。並且,前述取代基亦可以進一步被其他取代基取代。The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above substituent may be further substituted with another substituent.
作為取代基,可以舉出鹵素原子、芳氧基、烷氧基羰基或芳氧基羰基、醯氧基、醯基、烷基、芳基等。The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group.
在通式(OX-1)中,作為由B表示之一價取代基,芳基、雜環基、芳基羰基或雜環羰基為較佳。該些基團亦可以具有1個以上的取代基。作為取代基,可例示前述取代基。In the formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.
在通式(OX-1)中,作為由A表示之二價有機基,碳原子數為1~12的伸烷基、環伸烷基、亞炔基為較佳。該些基團亦可以具有1個以上的取代基。作為取代基,能夠例示前述取代基。In the general formula (OX-1), as the divalent organic group represented by A, an alkylene group having a carbon number of 1 to 12, a cycloalkylene group or an alkynylene group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.
通式(OX-1)中表示之化合物的具體例如下表示,但是本發明並非係限定於該等者。Specific examples of the compound represented by the formula (OX-1) are shown below, but the present invention is not limited to these.
【化學式30】 [Chemical Formula 30]
肟化合物為在350nm~500nm的波長區域具有極大吸收波長者為較佳,在360nm~480nm的波長區域具有吸收波長者為更佳,365nm及455nm的吸光度較高者為尤佳。The ruthenium compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and preferably having a higher absorbance at 365 nm and 455 nm.
肟化合物中,從感度的觀點來看,365nm或405nm中之莫耳吸光係數為1,000~300,000為較佳,2,000~300,000為更佳,5,000~200,000為尤佳。Among the ruthenium compounds, from the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, still more preferably from 5,000 to 200,000.
化合物的莫耳吸光係數可使用公知的方法,例如由紫外可見分光光度計(Varian公司製造的Cary-5 spectrophotometer),並使用乙酸乙酯溶劑,以0.01g/L的濃度進行測定為較佳。The molar absorption coefficient of the compound can be preferably measured by a known method, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L.
使用於本發明之光聚合起始劑,亦可根據需要而組合2種以上進行使用。The photopolymerization initiator to be used in the present invention may be used in combination of two or more kinds as needed.
在本發明的著色硬化性組成物含有光聚合起始劑之情況下,光聚合起始劑的含量相對於著色硬化性組成物的總固體成分為0.1~50質量%為較佳,0.5~30質量%為更加,1~20質量%進一步較佳。在該範圍下,可以得到更加良好的感度和圖案形成性。In the case where the colored curing composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, based on the total solid content of the colored curable composition, and is from 0.5 to 30% by weight. The mass % is more preferably 1 to 20% by mass. Within this range, more excellent sensitivity and pattern formation can be obtained.
本發明的組成物可以僅含有1種光聚合起始劑,亦可以含有2種以上。在含有2種以上光聚合起始劑之情況下,其總量成為上述範圍為較佳。The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. In the case where two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.
<<聚合抑制劑>><<Polymerization inhibitor>>
在本發明的著色硬化性組成物中,為了在著色硬化性組成物的製造中或保存中阻止聚合性化合物的不需要的熱聚合,理想的是添加少量的聚合抑制劑。In the color hardening composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the colored curable composition, it is preferred to add a small amount of a polymerization inhibitor.
作為聚合抑制劑,可以舉出對苯二酚、對甲氧基苯酚、二-叔丁基對甲酚、鄰苯三酚、叔丁基鄰苯二酚、苯醌、4,4’-硫代雙(3-甲基-6-叔丁基苯酚)、2,2’-亞甲基雙(4-甲基-6-叔丁基苯酚)、N-亞硝基苯基羥胺第一鈰鹽等。Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-sulfur. Di-bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first Salt and so on.
在本發明的著色硬化性組成物含有聚合抑制劑之情況下,聚合抑制劑的含量相對於著色硬化性組成物的質量為約0.01~5質量%為較佳。In the case where the colored curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably from about 0.01 to 5% by mass based on the mass of the colored curable composition.
本發明的著色硬化性組成物可以僅含有1種聚合抑制劑,亦可以含有2種以上。在含有2種以上聚合抑制劑之情況下,其總量成為上述範圍為較佳。The colored curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types of polymerization inhibitors are contained, the total amount thereof is preferably in the above range.
<<界面活性劑>><<Interfacial active agent>>
從進一步提高塗佈性之觀點來看,亦可以向本發明的著色硬化性組成物中添加各種界面活性劑。作為界面活性劑,可以使用氟系界面活性劑、非離子界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑、矽酮系界面活性劑等各種界面活性劑。From the viewpoint of further improving the coatability, various surfactants may be added to the colored curable composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.
例如,藉由含有氟系界面活性劑,製備成塗佈液時的液體特性(尤其流動性)進一步提高。亦即,在使用含有氟系界面活性劑之著色硬化性組成物而形成膜之情況下,藉由使被塗佈面與塗佈液之間的界面張力減小,對被塗佈面的潤濕性得到改善,對被塗佈面的塗佈性提高。因此,即使在以少量的液體量形成數μm程度的薄膜時,亦可以進一步適當地進行厚度不均較小且均一厚度的膜形成就該點而言是有效的。For example, when a coating liquid is prepared by containing a fluorine-based surfactant, liquid characteristics (especially fluidity) at the time of preparation of a coating liquid are further improved. In other words, when a film is formed using a color-curable composition containing a fluorine-based surfactant, the interface tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is moistened. The wettability is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to further appropriately form a film having a small thickness unevenness and a uniform thickness.
氟系界面活性劑中的氟含有率為3~40質量%為較佳,5~30質量%為更佳,7~25質量%為尤佳。氟含有率為該範圍內之氟系界面活性劑在塗佈膜的厚度均一性、省液性方面是有效的,且著色硬化性組成物中之溶解性亦良好。The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, still more preferably from 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in thickness uniformity and liquid-saving property of the coating film, and the solubility in the colored curable composition is also good.
作為氟系界面活性劑,例如可以舉出:MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F176、MEGAFAC F177、MEGAFAC F141、MEGAFAC F142、MEGAFAC F143、MEGAFAC F144、MEGAFAC R30、MEGAFAC F437、MEGAFAC F475、MEGAFAC F479、MEGAFAC F482、MEGAFAC F554、MEGAFAC F780、MEGAFAC F781(以上,DIC Corporation製造);FLUORAD FC430、FLUORAD FC431、FLUORAD FC171(以上,SUMITOMO 3M Limited製造);SURFLON S-382、SURFLON SC-101、SURFLON SC-103、SURFLON SC-104、SURFLON SC-105、SURFLON SC1068、SURFLON SC-381、SURFLON SC-383、SURFLON S393、SURFLON KH-40(以上,ASAHI GLASS CO.,LTD.製造);PF636、PF656、PF6320、PF6520、PF7002(OMNOVA Solutions Inc.製造)等。Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, and MEGAFAC F479. , MEGAFAC F482, MEGAFAC F554, MEGAFAC F780, MEGAFAC F781 (above, manufactured by DIC Corporation); FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (above, manufactured by SUMITOMO 3M Limited); SURFLON S-382, SURFLON SC-101, SURFLON SC- 103, SURFLON SC-104, SURFLON SC-105, SURFLON SC1068, SURFLON SC-381, SURFLON SC-383, SURFLON S393, SURFLON KH-40 (above, manufactured by ASAHI GLASS CO., LTD.); PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like.
作為氟系界面活性劑亦可以使用嵌段聚合物,作為具體例,例如可以舉出在日本特開2011-89090號公報中記載之化合物。As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090.
作為非離子界面活性劑,具體可以舉出甘油、三羥甲基丙烷、三羥甲基乙烷及該等之乙氧基化物及丙氧基化物(例如丙氧基化甘油、乙氧基化甘油等)、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油烯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖醇脂肪酸酯(BASF SE製造的PLURONIC L10、L31、L61、L62、10R5、17R2、25R2、TETRONIC 304、701、704、901、904、150R1)、SOLSPERSE 20000(LUBRIZOL JAPAN ,LTD.)等。並且,亦可使用TAKEMOTO OIL&FAT CO.,LTD.製造的PIONIN D-6112-W。Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like, and ethoxylates and propoxylates (for example, propoxylated glycerol, ethoxylated). Glycerin, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Laurate, polyethylene glycol distearate, sorbitan fatty acid ester (PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, manufactured by BASF SE, 904, 150R1), SOLSPERSE 20000 (LUBRIZOL JAPAN, LTD.), and the like. Further, PIONIN D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD. can also be used.
作為陽離子系界面活性劑,具體而言,可以舉出酞菁衍生物(商品名稱:EFKA-745、MORISHITA & CO.,LTD.製造)、有機矽氧烷聚合物KP341(SHIN-ETSU CHEMICAL CO.,LTD.製造)、(甲基)丙烯酸系(共)聚合物POLYFLOW No.75、No.90、No.95(KYOEISHA CHEMICAL CO.,LTD.製造)、W001(YUSHOCO.,LTD.製造)等。Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), and an organic siloxane polymer KP341 (SHIN-ETSU CHEMICAL CO.). (manufactured by LTD.), (meth)acrylic (co)polymers POLYFLOW No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), W001 (manufactured by YUSHOCO., LTD.), etc. .
作為陰離子系界面活性劑,具體可以舉出W004、W005、W017(YUSHOCO.,LTD.製造)等。Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by YUSHOCO., LTD.).
作為矽酮系界面活性劑,例如可以舉出:DOW CORNING TORAY CO.,LTD.製造的“TORAY SILICONE DC3PA”、“TORAY SILICONE SH7PA”、“TORAY SILICONE DC11PA”、“TORAY SILICONE SH21PA”、“TORAY SILICONE SH28PA”、“TORAY SILICONE SH29PA”、“TORAY SILICONE SH30PA”、“TORAY SILICONE SH8400”;MOMENTIVE PERFORMANCE MATERIALS Inc.製造的“TSF-4440”、“TSF-4300”、“TSF-4445”、“TSF-4460”、“TSF-4452”;SHIN-ETSU CHEMICAL CO.,LTD.製造的“KP341”、“KF6001”、“KF6002”;BYK Chemie CO.,LTD.製造的“BYK307”、“BYK323”、“BYK330”等。Examples of the anthrone-based surfactants include "TORAY SILICONE DC3PA", "TORAY SILICONE SH7PA", "TORAY SILICONE DC11PA", "TORAY SILICONE SH21PA", and "TORAY SILICONE" manufactured by DOW CORNING TORAY CO., LTD. SH28PA", "TORAY SILICONE SH29PA", "TORAY SILICONE SH30PA", "TORAY SILICONE SH8400"; "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" manufactured by MOMENTIVE PERFORMANCE MATERIALS Inc. ""TSF-4452"; "KP341", "KF6001", "KF6002" manufactured by SHIN-ETSU CHEMICAL CO., LTD.; "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie CO., LTD. "Wait.
在本發明的著色硬化性組成物含有界面活性劑之情況下,界面活性劑的含量相對於著色硬化性組成物的總質量為0.001~2.0質量%為較佳,0.005~1.0質量%為更佳。In the case where the colored curable composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass based on the total mass of the colored curable composition, and more preferably 0.005 to 1.0% by mass. .
本發明的著色硬化性組成物可以僅含有1種界面活性劑,亦可以含有2種以上。在含有2種以上界面活性劑之情況下,其總量成為上述範圍為較佳。The colored curable composition of the present invention may contain only one type of surfactant, or may contain two or more types. In the case where two or more kinds of surfactants are contained, the total amount thereof is preferably in the above range.
<<矽烷偶合劑>><<decane coupling agent>>
本發明的著色硬化性組成物可以含有矽烷偶合劑。The color hardening composition of the present invention may contain a decane coupling agent.
作為矽烷偶合劑,在一個分子中具有至少2種反應性不同之官能基之矽烷化合物亦為較佳,作為官能基而具有胺基和烷氧基者為尤佳。作為該種矽烷偶合劑,例如有N-β-胺基乙基-γ-胺基丙基-甲基二甲氧基矽烷(Shin-Etsu Chemical Co., Ltd. 製造,商品名稱 KBM-602)、N-β-胺基乙基-γ-胺基丙基 - 三甲氧基矽烷(Shin-Etsu Chemical Co., Ltd. 製造,商品名稱 KBM-603,Shin-Etsu Chemical Co., Ltd. 製)、N-β-胺基乙基-γ-胺基丙基 - 三乙氧基矽烷(Shin-Etsu Chemical Co., Ltd. 製造,商品名稱 KBE-602)、γ-胺基丙基 - 三甲氧基矽烷(Shin-Etsu Chemical Co., Ltd. 製造,商品名稱 KBM-903)、γ-胺基丙基 - 三乙氧基矽烷(Shin-Etsu Chemical Co., Ltd. 製造,商品名稱,KBE-903)、3-甲基丙烯醯氧基丙基三甲氧基矽烷(Shin-Etsu Chemical Co., Ltd. 製造,商品名稱,KBM-503)等。關於矽烷偶合劑的詳細內容,可以參照日本特開2013-254047號公報的段落號0155~0158的記載,將該內容併入到本說明書中。As the decane coupling agent, a decane compound having at least two functional groups having different reactivity in one molecule is also preferable, and those having an amine group and an alkoxy group as a functional group are particularly preferable. As such a decane coupling agent, for example, N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602) is available. N-β-Aminoethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) , N-β-aminoethyl-γ-aminopropyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyl-trimethoxy Base decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyl-triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBE- 903), 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBM-503), and the like. The details of the decane coupling agent can be referred to in the present specification by referring to the descriptions of paragraphs 0155 to 0158 of JP-A-2013-254047.
在本發明的著色硬化性組成物含有矽烷偶合劑之情況下,矽烷偶合劑的含量相對於著色硬化性組成物的總固體成分為0.001~20質量%為較佳,0.01~10質量%為更佳,0.1質量%~5質量%為尤佳。In the case where the colored curable composition of the present invention contains a decane coupling agent, the content of the decane coupling agent is preferably 0.001 to 20% by mass based on the total solid content of the colored curable composition, and more preferably 0.01 to 10% by mass. Preferably, 0.1% by mass to 5% by mass is particularly preferred.
本發明的著色硬化性組成物可以僅含有1種矽烷偶合劑,亦可以含有2種以上。在含有2種以上矽烷偶合劑之情況下,其總量成為上述範圍為較佳。The colored curable composition of the present invention may contain only one type of decane coupling agent, or may contain two or more types. In the case where two or more kinds of decane coupling agents are contained, the total amount thereof is preferably in the above range.
<<其他添加劑>><<Other additives>>
在本發明的著色硬化性組成物中,可以根據需要而能夠配合各種添加物,例如填充劑、抗氧化劑、紫外線吸收劑、凝集抑制劑等。作為該些添加物,可以舉出日本特開2004-295116號公報的段落0155~0156中記載者,將該些內容併入到本申請案說明書中。In the color hardening composition of the present invention, various additives such as a filler, an antioxidant, an ultraviolet absorber, a coagulation inhibitor, and the like can be blended as needed. The above-mentioned additives are described in paragraphs 0155 to 0156 of JP-A-2004-295116, and the contents are incorporated in the specification of the present application.
在本發明的著色硬化性組成物中,能夠含有在日本特開2004-295116號公報的段落0078中記載的增感劑和光穩定劑、在前述公報的段落0081中記載的熱聚合抑制劑。In the coloring-curable composition of the present invention, the sensitizer and the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the above-mentioned publication can be contained.
<著色硬化性組成物的製備方法><Method for Preparing Colored Curable Composition>
本發明的著色硬化性組成物藉由混合前述成分而製備。The color hardening composition of the present invention is prepared by mixing the above components.
在製備著色硬化性組成物時,可以統一配合構成著色硬化性組成物之各成分,亦可以在將各成分溶解和分散於溶劑中之後逐次進行配合。並且,配合時的放入順序、作業條件不受特別制約。例如可以將所有成分同時溶解、分散於溶劑中而製備著色硬化性組成物,根據需要,亦可以將各成分適當地製成2種以上的溶液、分散液中,並在使用時(塗佈時)將該些進行混合而製備組成物。In the preparation of the colored curable composition, the components constituting the colored curable composition may be uniformly blended, or may be blended one by one after the components are dissolved and dispersed in a solvent. Moreover, the order of placement and the working conditions at the time of fitting are not particularly restricted. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a colored curable composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and when used (at the time of coating) These were mixed to prepare a composition.
以去除異物和減少缺陷等目的,本發明的著色硬化性組成物用過濾器進行過濾為較佳。作為過濾器,只要是先前用於過濾用途等者,則可以無特別的限定地使用。例如可以舉出由聚四氟乙烯(PTFE)等氟樹脂、尼龍-6、尼龍-6,6等聚醯胺系樹脂、聚乙烯、聚丙烯(PP)等聚烯烴樹脂(包含高密度、超高分子量)等構成之過濾器。該些原材料中聚丙烯(包含高密度聚丙烯)為較佳。The colored hardenable composition of the present invention is preferably filtered by a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without particular limitation as long as it is used for filtration purposes or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6, 6, a polyolefin resin such as polyethylene or polypropylene (PP) (including high density and super) may be mentioned. A filter composed of a high molecular weight or the like. Among these raw materials, polypropylene (including high density polypropylene) is preferred.
過濾器的孔徑為0.01~7.0μm程度比較合適,0.01~3.0μm程度為較佳,0.05~0.5μm程度為進一步較佳。藉由設為該範圍,在後續步驟中能夠可靠地去除阻礙均一且順利地製備著色硬化性組成物之微細的異物。The filter has a pore diameter of about 0.01 to 7.0 μm, preferably 0.01 to 3.0 μm, and more preferably 0.05 to 0.5 μm. By setting this range, it is possible to reliably remove fine foreign matter which hinders uniform and smooth preparation of the colored curable composition in the subsequent step.
在使用過濾器時,亦可以組合不同的過濾器來使用。此時,利用第1過濾器可以僅進行1次過濾,亦可以進行2次以上。When using a filter, it is also possible to combine different filters for use. In this case, the first filter may be used for filtration only once or twice or more.
並且,亦可以在上述範圍內組合不同孔徑的第1過濾器。此處的孔徑可參照過濾器製造商的標稱值。作為市售的過濾器,例如能夠從NIHON PALL LTD.、ADVANTECH TOYO KAISHA,LTD.、NIHON ENTEGRIS K.K.(Mykrolis Corporation)或KITZ MICROFILTER CORPORATION 等提供之各種過濾器中選擇。Further, the first filter having different pore diameters may be combined within the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., ADVANTECH TOYO KAISHA, LTD., NIHON ENTEGRIS K.K. (Mykrolis Corporation), or KITZ MICROFILTER CORPORATION.
第2過濾器可使用由與上述第1過濾器相同材料等形成者。The second filter can be formed of the same material or the like as the first filter described above.
例如利用第1過濾器的過濾僅由分散液進行,亦可以在混合其他成分之後,進行第2過濾。For example, the filtration by the first filter may be performed only by the dispersion, or the second filtration may be performed after mixing the other components.
由於本發明的著色硬化性組成物能夠形成耐光性、移染性、平坦性良好的硬化膜,因此可適合用於形成彩色濾光片的著色層。並且,本發明的著色硬化性組成物可適合用於形成電荷耦合器件(CCD)、互補式金屬氧化物半導體(CMOS)等固體攝像元件、及液晶顯示裝置等圖像顯示裝置中使用之彩色濾光片等的著色圖案之用途。另外,亦可適合用於製作印刷油墨、噴墨油墨及塗料等用途。其中,可適合用於CCD及CMOS等固體攝像元件用的彩色濾光片的製造。Since the colored curable composition of the present invention can form a cured film excellent in light resistance, transfer property, and flatness, it can be suitably used for forming a coloring layer of a color filter. Further, the colored curable composition of the present invention can be suitably used for forming a solid-state imaging device such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), and a color filter used in an image display device such as a liquid crystal display device. The use of colored patterns such as light sheets. In addition, it is also suitable for use in printing inks, inkjet inks, and coatings. Among them, it is suitable for use in the manufacture of color filters for solid-state imaging devices such as CCDs and CMOSs.
<彩色濾光片、圖案形成方法、彩色濾光片的製造方法><Color filter, pattern forming method, and method of manufacturing color filter>
接著,關於圖案形成方法,藉由其製造方法而進行詳述。關於彩色濾光片,藉由其製造方法而進行詳述。並且對使用了本發明的圖案形成方法之彩色濾光片的製造方法亦進行說明。Next, the pattern forming method will be described in detail by the manufacturing method. The color filter is described in detail by its manufacturing method. Further, a method of manufacturing a color filter using the pattern forming method of the present invention will be described.
本發明的彩色濾光片係使用本發明的著色硬化性組成物而成者。The color filter of the present invention is obtained by using the colored curable composition of the present invention.
本發明的圖案形成方法中,使用本發明的著色硬化性組成物在支撐體上形成著色硬化性組成物層,並去除不需要部分而形成著色圖案。In the pattern forming method of the present invention, the colored curable composition layer of the present invention is used to form a colored curable composition layer on a support, and an unnecessary portion is removed to form a colored pattern.
本發明的圖案形成方法能夠適合應用於形成彩色濾光片的著色圖案。The pattern forming method of the present invention can be suitably applied to a colored pattern forming a color filter.
本發明的圖案形成方法可以藉由所謂光刻法進行圖案形成,亦可以藉由乾式蝕刻法進行圖案形成。The pattern forming method of the present invention may be patterned by a so-called photolithography method or may be patterned by a dry etching method.
亦即,本發明的彩色濾光片的製造方法的第一態様包括:用本發明的著色硬化性組成物,在支撐體上形成著色硬化性組成物層之步驟;將著色硬化性組成物層曝光成圖案狀之步驟;及對未曝光部進行顯影去除而形成著色圖案之步驟。根據需要,亦可以設定將著色硬化性組成物層進行烘烤之步驟(預烘烤步驟)、及將顯影之著色圖案進行烘烤之步驟(後烘烤步驟)。That is, the first aspect of the method for producing a color filter of the present invention includes the step of forming a colored curable composition layer on a support by using the colored curable composition of the present invention; and the colored curable composition layer a step of exposing to a pattern; and a step of developing and removing the unexposed portion to form a colored pattern. If necessary, a step of baking the colored curable composition layer (prebaking step) and a step of baking the developed colored pattern (post-baking step) may be also provided.
並且,本發明的彩色濾光片的製造方法的第二態様包括:使用本發明的著色硬化性組成物,在支撐體上形成著色硬化性組成物層,並進行硬化而形成著色層之步驟;在著色層上形成光阻層之步驟;藉由曝光及顯影,將光阻層圖案化而獲得抗蝕圖案之步驟;及將抗蝕圖案作為蝕刻遮罩,對著色層進行乾式蝕刻,從而形成著色圖案之步驟。Further, the second aspect of the method for producing a color filter of the present invention includes the step of forming a colored curable composition layer on a support by using the colored curable composition of the present invention, and curing to form a colored layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask to dry-etch the colored layer to form The step of coloring the pattern.
本發明的彩色濾光片能夠藉由上述製造方法而適當地得到。以下,對該等進行詳述。The color filter of the present invention can be suitably obtained by the above production method. Hereinafter, the details will be described.
<<形成著色硬化性組成物層之步驟>><<Steps of forming a color hardening composition layer>>
在形成著色硬化性組成物層之步驟中,使用本發明的著色硬化性組成物在支撐體上形成著色硬化性組成物層。In the step of forming the colored curable composition layer, the colored curable composition layer is formed on the support using the colored curable composition of the present invention.
作為支撐體,例如能夠使用在基板(例如矽基板)上設置有CCD、CMOS等固體攝像元件(受光元件)之固體攝像元件用基板。As the support, for example, a substrate for a solid-state imaging device in which a solid-state imaging device (light-receiving element) such as a CCD or a CMOS is provided on a substrate (for example, a germanium substrate) can be used.
作為本發明中之著色圖案,可以形成於固體攝像元件用基板的固體攝像元件形成面側(表面),亦可以形成於固體攝像元件非形成面側(背面)。The colored pattern in the present invention may be formed on the solid-state imaging device forming surface side (surface) of the solid-state imaging device substrate, or may be formed on the solid-state imaging device non-forming surface side (back surface).
根據需要,為了改善與上部層的密合、防止物質的拡散或實現基板表面的平坦化,亦可以在支撐體上設置下塗層。If necessary, in order to improve the adhesion to the upper layer, prevent the scattering of the substance, or achieve flattening of the surface of the substrate, an undercoat layer may be provided on the support.
作為在支撐體上適用本發明的著色硬化性組成物的方法,可使用狹縫塗佈、噴墨法、旋轉塗佈、流延塗佈、輥塗佈、絲網印刷法等各種方法。As a method of applying the color hardening composition of the present invention to a support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.
適用於支撐體上之著色硬化性組成物層的乾燥(預烘烤),可以用加熱板、烘箱等在50~140℃的溫度下進行10~300秒。The drying (prebaking) of the colored hardening composition layer applied to the support can be carried out at a temperature of 50 to 140 ° C for 10 to 300 seconds using a hot plate, an oven or the like.
<<曝光步驟>><<Exposure step>>
接著,將形成於支撐體上之著色硬化性組成物層呈圖案狀進行曝光(曝光步驟)。例如對形成於支撐體上之著色硬化性組成物層,使用步進機等曝光裝置,經由具有規定的遮罩圖案之遮罩進行曝光,藉此能夠進行圖案曝光。藉此能夠使曝光部分硬化。Next, the colored curable composition layer formed on the support is exposed in a pattern (exposure step). For example, the coloring-curable composition layer formed on the support can be exposed by exposure using a mask having a predetermined mask pattern by using an exposure apparatus such as a stepper. Thereby, the exposed portion can be hardened.
作為可以在曝光時使用之放射線(光),使用g線、i線等紫外線為較佳(i線為尤佳)。照射量(曝光量)例如為30~1500mJ/cm2 為較佳,50~1000mJ/cm2 為更佳,80~500mJ/cm2 為最佳。As the radiation (light) which can be used for exposure, it is preferable to use ultraviolet rays such as g-line or i-line (i-line is preferable). The irradiation amount (exposure amount) is preferably, for example, 30 to 1,500 mJ/cm 2 , more preferably 50 to 1000 mJ/cm 2 , and most preferably 80 to 500 mJ/cm 2 .
硬化膜的膜厚為1.0μm以下為較佳,0.1~0.9μm為更佳,0.2~0.8μm為進一步較佳。藉由將膜厚設為1.0μm以下,容易獲得高解析度、高密合性。The film thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and still more preferably 0.2 to 0.8 μm. By setting the film thickness to 1.0 μm or less, it is easy to obtain high resolution and high adhesion.
<<圖案形成步驟>><<Pattern forming step>>
接著,將未曝光部顯影去除而形成著色圖案(圖案形成步驟)。未曝光部的顯影去除可以使用顯影液而進行。藉此,曝光步驟中之未曝光部的著色硬化性組成物層溶出於顯影液,僅殘留光硬化之部分。Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming step). The development removal of the unexposed portion can be performed using a developer. Thereby, the colored curable composition layer of the unexposed portion in the exposure step is dissolved in the developer, and only the portion where the light is hardened remains.
顯影液不會對基底的固體攝像元件和電路等造成損傷之有機鹼性顯影液為較佳。An organic alkaline developing solution in which the developer does not damage the solid image sensor, the circuit, or the like of the substrate is preferable.
顯影液的溫度例如為20~30℃為較佳。顯影時間為20~180秒為較佳。並且,為了提高殘渣去除性,亦可以每隔60秒將顯影液進行振蕩,進一步重複進行幾次重新供給顯影液之步驟。The temperature of the developer is preferably, for example, 20 to 30 °C. The development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the developer may be oscillated every 60 seconds, and the step of re-supplying the developer may be repeated several times.
作為使用於顯影液之鹼劑,例如可以舉出氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化芐基三甲基銨、膽鹼、吡咯、哌啶、1,8-二氮雜雙環[5.4.0]-7-十一烯等有機鹼性化合物。以濃度成為0.001~10質量%(0.01~1質量%為較佳)的方式,用純水稀釋該些鹼劑而得到之鹼性水溶液作為顯影液而被較佳使用。Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and hydroxide. An organic basic compound such as tetrabutylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo[5.4.0]-7-undecene. The alkaline aqueous solution obtained by diluting the alkali chemicals with pure water as a developing solution is preferably used in an amount of 0.001 to 10% by mass (preferably 0.01 to 1% by mass).
並且,亦可在顯影液中使用無機鹼。作為無機鹼,例如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉等為較佳。Further, an inorganic base can also be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate or the like is preferable.
另外,在使用由該種鹼性水溶液構成之顯影液之情況下,通常在顯影後使用純水來進行清洗(沖洗)。Further, in the case of using a developer composed of such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.
在顯影之後,在實施乾燥後進行加熱處理(後烘烤)為較佳。若形成多色的著色圖案,則能夠對每一個顏色依次重複進行步驟而製造硬化膜。藉此可以得到彩色濾光片。After the development, it is preferred to carry out heat treatment (post-baking) after drying. When a multicolor coloring pattern is formed, it is possible to repeat the steps for each color to produce a cured film. Thereby, a color filter can be obtained.
後烘烤係用於使硬化設為安全者的顯影後的加熱處理,加熱溫度例如100~240℃為較佳、200~240℃為更佳。The post-baking is used for heat treatment after development in which the curing is made safe, and the heating temperature is preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
可以使用加熱板、對流式烘箱(熱風循環式乾燥機)、高頻加熱機等加熱機構,以成為上述條件之方式,以連續式或分批式對顯影後的膜進行後烘烤處理。The film after development can be post-baked in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high frequency heater.
本發明的彩色濾光片可適合應用於CCD、CMOS等固體攝像元件中,尤其適合於超過100万畫素之高解析度的CCD、CMOS等中。The color filter of the present invention can be suitably applied to a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for use in a high-resolution CCD, CMOS, or the like of more than one million pixels.
本發明的彩色濾光片例如可用作在構成CCD或CMOS之各畫素的受光部與用於聚光的微透鏡之間配置之彩色濾光片。The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of a CCD or CMOS and a microlens for collecting light.
本發明的彩色濾光片中之著色圖案(著色畫素)的膜厚為2.0μm以下為較佳,1.0μm以下為更佳,0.7μm以下為進一步較佳。下限例如能夠設為0.1μm以上,亦可以設為0.2μm以上。The coloring pattern (colored pixel) of the color filter of the present invention has a film thickness of preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.
並且,作為著色圖案(著色畫素)的尺寸(圖案寬度),2.5μm以下為較佳,2.0μm以下為更佳,1.7μm以下為尤佳。下限例如可以設為0.1μm以上,亦可以設為0.2μm以上。Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.
在藉由乾式蝕刻而形成圖案之情況下,可參照日本特開2013-64993號公報的記載,將該些內容併入到本申請案說明書中。In the case of forming a pattern by dry etching, the contents of this application can be incorporated by reference to the contents of the Japanese Patent Application Publication No. 2013-64993.
<固體攝像元件><Solid image sensor>
本發明的固體攝像元件具備上述本發明的彩色濾光片。作為本發明的固體攝像元件的構成,只要是具備本發明的彩色濾光片且作為固體攝像元件而發揮功能之構成,則無特別的限定,例如可以舉出如以下的構成。The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
固體攝像元件在支撐體上具有固體攝像元件(CCD圖像感測器、CMOS圖像感測器等)的受光區域之複數個光電二極體、及由聚矽氧等構成之轉移電極,在光電二極體及轉移電極上具有僅使光電二極體的受光部開口之由鎢等構成之遮光膜,在遮光膜上具有以覆蓋遮光膜整個面及光電二極體受光部的方式形成之由氮化矽等構成之裝置保護膜,在裝置保護膜上具有本發明的固體攝像元件用彩色濾光片。The solid-state imaging device has a plurality of photodiodes in a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) on a support, and a transfer electrode composed of polyfluorene or the like. The photodiode and the transfer electrode have a light-shielding film made of tungsten or the like that opens only the light-receiving portion of the photodiode, and the light-shielding film is formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. A device protective film made of tantalum nitride or the like has a color filter for a solid-state imaging device of the present invention on a device protective film.
另外,亦可以為在裝置保護層上且彩色濾光片的下側(接近支撐體的一側)具有聚光機構(例如微透鏡等。以下相同)之構成、或在彩色濾光片上具有聚光機構之構成等。Further, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the protective layer of the device and on the lower side of the color filter (the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.
<圖像顯示裝置><Image display device>
本發明的彩色濾光片能夠使用於液晶顯示裝置、有機電致發光顯示裝置等圖像顯示裝置。尤其適合於液晶顯示裝置的用途。具備本發明的彩色濾光片之液晶顯示裝置能夠顯示顯示圖像的色調良好且顯示特性優異之高畫質圖像。The color filter of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. It is especially suitable for the use of liquid crystal display devices. The liquid crystal display device including the color filter of the present invention can display a high-quality image in which the hue of the displayed image is good and the display characteristics are excellent.
關於顯示裝置的定義、各顯示裝置的詳細內容,記載於例如“電子顯示器裝置(佐々木 昭夫 著 Kogyo Chosakai Publishing Co.,Ltd.,1990年發行)”、“顯示器裝置(伊吹 順章著、Sangyo Tosho Co.,Ltd.,平成元年發行)”等。並且,關於液晶顯示裝置,例如記載於“下一代液晶顯示器技術(內田 龍男編輯、Kogyo Chosakai Publishing Co.,Ltd.,1994年發行)”。本發明能夠適用之液晶顯示裝置並無特別的限制,例如能夠適用於記載於上述“下一代液晶顯示器技術”中之各種方式的液晶顯示裝置。The definition of the display device and the details of each display device are described, for example, in "Electronic display device (Kogyo Chosakai Publishing Co., Ltd., issued in 1990)", "Display device (Ibuki Shun, "Sangyo Tosho" Co., Ltd., issued in the first year of Heisei)" and so on. Further, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Edited by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".
本發明的彩色濾光片亦可使用於彩色TFT(Thin Film Transistor)方式的液晶顯示裝置。關於彩色TFT方式的液晶顯示裝置,例如記載於“彩色TFT液晶顯示器(KYORITSU SHUPPAN CO.,LTD.,1996年發行)”。另外,本發明亦可以適用於IPS(In Plane Switching)等橫向電場駆動方式、MVA(Multi-domain Vertical Alignment)等畫素分割方式等的視角被擴大之液晶顯示裝置、或STN(Super-Twist Nematic)、TN(Twisted Nematic)、VA(Vertical Alignment)、OCS(on-chip spacer)、FFS(fringe field switching)、及R-OCB(Reflective Optically Compensated Bend)等中。The color filter of the present invention can also be used in a liquid crystal display device of a color TFT (Thin Film Transistor) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD., issued in 1996)". In addition, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field pulsation method such as IPS (In Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment) is expanded, or STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend).
並且,本發明之彩色濾光片亦可以提供於明亮且高清晰之COA(Color-filter On Array)方式。在COA方式的液晶顯示裝置中,對彩色濾光片層之要求特性除了如前述之通常的要求特性以外,有時還需要對層間絶縁膜之要求特性,亦即低介電常數及剥離液耐性。本發明的彩色濾光片由於耐光性等優異,因此能夠提供解析度高、長期耐久性優異之COA方式的液晶顯示裝置。另外,為了滿足低介電常數的要求特性,亦可以在彩色濾光片層之上設置樹脂被膜。Moreover, the color filter of the present invention can also be provided in a bright and high-resolution COA (Color-filter On Array) method. In the liquid crystal display device of the COA type, in addition to the usual required characteristics as described above, in addition to the usual required characteristics, the required characteristics of the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance may be required. . Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
關於該些圖像顯示方式,例如記載於“EL、PDP、LCD顯示器-技術和市場的最新動向-(Toray Research Center,Inc.)調査研究部門,2001年發行)”的43頁等。These image display methods are described, for example, in "EL, PDP, LCD Display - Technology and Market Trends - (Toray Research Center, Inc. Research and Research Department, issued in 2001)", page 43 and the like.
本發明之具備彩色濾光片之液晶顯示裝置中,除了本發明之彩色濾光片以外,還藉由電極基板、偏光膜、相位差膜、背光裝置、間隔件(Spacer)、視角保障膜等各種構件所構成。本發明的彩色濾光片能夠適用於由該些公知的構件構成之液晶顯示裝置。關於該些構件,例如記載於“’94液晶顯示器周邊材料及化學產品的市場(島 健太郎 CMC CO.,LTD.1994年發行)”、“2003液晶關連市場的現狀及未來展望(下卷)(表良吉 FUJI CHIMERA RESEARCH INSTITUTE, INC.,2003年發行)”。In the liquid crystal display device including the color filter of the present invention, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle assurance film, and the like are used. It is composed of various components. The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. These components are described, for example, in "The Market of Materials and Chemical Products for Liquid Crystal Display (Island Kent Co., Ltd., CMC Co., Ltd., 1994)", "The Status and Future of the 2003 Liquid Crystal Related Markets (Vol. 2)" "FUJI CHIMERA RESEARCH INSTITUTE, INC., issued in 2003)".
關於背光,記載於SID meeting Digest 1380(2005)(A.Konno et.al)、月刊顯示器2005年12月號的18~24頁(島 康裕)、月刊顯示器25~30頁(八木隆明)等。The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et. al), monthly publication December 2005, pages 18 to 24 (Island Kangyu), monthly publication 25 to 30 pages (Yamamu Takamori), and the like.
若將本發明之彩色濾光片使用於液晶顯示裝置,則與先前公知的冷陰極管的三波長管組合時能夠實現較高的對比度,另外,藉由將紅、緑、藍的発光二極體(LED)光源作為背光,能夠提供亮度較高且色彩純度較高的色彩再現性良好的液晶顯示裝置。When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and by using red, green, and blue light-emitting diodes As a backlight, a body (LED) light source can provide a liquid crystal display device having high brightness and high color reproducibility.
[實施例][Examples]
以下,例舉實施例對本發明進行更具體的說明。以下實施例中表示之材料、使用量、比例、處理內容、處理順序等,只要不脱離本發明的主旨,則能夠適當地進行變更。從而,本發明的範圍係並非限定於以下所示之具體例者。另外,只要沒有特別的說明,則“份”、“%”為質量基準。Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are mass standards.
<重量平均分子量及數量平均分子量的測定><Measurement of Weight Average Molecular Weight and Number Average Molecular Weight>
重量平均分子量及數量平均分子量由以下方法測定。 色譜柱的種類:將TSKgelSuperAW4000、TSKgelSuperAW3000、TSKgelSuperAW2500及TSKgelSuperAW2500進行連接 展開溶劑:N-甲基吡咯烷酮(10mmol/L 含有LiBr) 色譜柱溫度:50℃ 流量(樣品註入量):20μL 流速:0.25ml/min 裝置名稱:TOSOH Corporation製造HLC-8220 GPC校準曲線基礎樹脂:聚苯乙烯The weight average molecular weight and the number average molecular weight were determined by the following methods. Column type: TSKgelSuperAW4000, TSKgelSuperAW3000, TSKgelSuperAW2500 and TSKgelSuperAW2500 were connected to develop solvent: N-methylpyrrolidone (10mmol/L containing LiBr) Column temperature: 50°C Flow rate (sample injection amount): 20μL Flow rate: 0.25ml/ Min Device name: HLS-8220 GPC calibration curve manufactured by TOSOH Corporation Base resin: Polystyrene
<酸值的測定方法><Method for measuring acid value>
將測定樣品溶解於四氫呋喃/水=9/1(質量比)混合溶劑中,並使用電位差滴定裝置(商品名稱:AT-510、KYOTO ELECTRONICS MANUFACTURING CO.,LTD.製造),將所得到之溶液在25℃下在0.1mol/L氫氧化鈉水溶液中進行了中和滴定。將滴定pH曲線的拐點作為滴定終點,由下式算出酸值。The measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and the obtained solution was obtained by using a potentiometric titration apparatus (trade name: AT-510, KYOTO ELECTRONICS MANUFACTURING CO., LTD.). Neutralization titration was carried out in a 0.1 mol/L aqueous sodium hydroxide solution at 25 °C. The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated from the following formula.
A=56.11×Vs×0.1×f/w A:酸值(mgKOH/g) Vs:滴定所需要之0.1mol/L氫氧化鈉水溶液的使用量(mL) f:0.1mol/L氫氧化鈉水溶液的滴定量(Titer) w:測定樣品的質量(g)(固體成分換算)A=56.11×Vs×0.1×f/w A: Acid value (mgKOH/g) Vs: The amount of 0.1 mol/L sodium hydroxide aqueous solution required for titration (mL) f: 0.1 mol/L sodium hydroxide aqueous solution Titration (Titer) w: Determination of sample mass (g) (solid content conversion)
<胺值的測定方法><Method for measuring amine value>
將測定樣品溶解於乙酸,並使用電位差滴定裝置(商品名稱:AT-510、KYOTO ELECTRONICS MANUFACTURING CO.,LTD.製造),將所得到之溶液在0.1mol/L過氯酸/乙酸溶液中進行中和滴定。將滴定pH曲線的拐點作為滴定終點並由下式算出胺值。The measurement sample was dissolved in acetic acid, and the obtained solution was subjected to a 0.1 mol/L perchloric acid/acetic acid solution using a potentiometric titration apparatus (trade name: AT-510, KYOTO ELECTRONICS MANUFACTURING CO., LTD.). And titration. The inflection point of the titration pH curve was taken as the end point of the titration and the amine value was calculated from the following formula.
B=56.11×Vs×0.1×f/w B:胺值(mgKOH/g) Vs:滴定所需要之0.1mol/L過氯酸/乙酸溶液的使用量(mL) f:0.1mol/L過氯酸/乙酸溶液的滴定量 w:測定樣品的質量(g)(固體成分換算)B = 56.11 × Vs × 0.1 × f / w B: Amine value (mgKOH / g) Vs: 0.1 mol / L perchloric acid / acetic acid solution required for titration (mL) f: 0.1 mol / L perchlorine The titer of the acid/acetic acid solution w: the mass (g) of the measured sample (solid content conversion)
(合成例)(synthesis example)
【化學式31】 [Chemical Formula 31]
<著色劑A-1的合成例><Synthesis Example of Colorant A-1>
將DCSF(Chugai kasei Company,Limited製造)50份、2,6-二甲基苯胺74.76份、氯化鋅27.58份、環丁碸200份放入到燒瓶中,在外部溫度200度下攪拌4小時。然後,將所得到之反應溶液放冷至室溫,並滴入於2mol/L鹽酸500份,將析出之結晶進行過濾。將結晶用40度的乙腈300份進行分散清洗、過濾收集,吹風乾燥10小時,得到46.5份(收率:65.6%)的著色劑A-1。50 parts of DCSF (manufactured by Chugai Kasei Company, Limited), 74.76 parts of 2,6-dimethylaniline, 27.58 parts of zinc chloride, and 200 parts of cyclobutyl hydrazine were placed in a flask, and stirred at an external temperature of 200 ° C for 4 hours. . Then, the obtained reaction solution was allowed to cool to room temperature, and dropped into 500 parts of 2 mol/L hydrochloric acid, and the precipitated crystals were filtered. The crystals were dispersed and washed with 300 parts of 40-degree acetonitrile, collected by filtration, and dried by air drying for 10 hours to obtain 46.5 parts (yield: 65.6%) of the coloring agent A-1.
<中間體1的合成><Synthesis of Intermediate 1>
將20份著色劑A-1及106份三氯氧磷放入到燒瓶中,在60℃下攪拌2小時。將所得到之反應溶液放冷至室溫,並將反應溶液滴入冰水1500份中攪拌30分鐘。將所得到之結晶進行過濾,並用水200份進行清洗,吹風乾燥10小時,得到18.5份(收率:89.4%)中間體1。20 parts of the colorant A-1 and 106 parts of phosphorus oxychloride were placed in a flask, and stirred at 60 ° C for 2 hours. The obtained reaction solution was allowed to cool to room temperature, and the reaction solution was dropped into 1500 parts of ice water and stirred for 30 minutes. The obtained crystal was filtered, washed with 200 parts of water, and dried by air drying for 10 hours to obtain 18.5 parts (yield: 89.4%) of Intermediate 1.
<著色劑A-4的合成><Synthesis of Colorant A-4>
將7份中間體1、2.05份苯磺醯胺溶解於氯仿40份中,並滴入二氮雜雙環(1,8-二吖雙環[5.4.0]十一-7-烯)(1,8-diazabicyclo[5.4.0]undec-7-ene)2.32份,在室溫下攪拌了1小時。然後,將水100份放入到所得到之反應溶液中進行水洗,接著分取有機層。用硫酸鈉乾燥有機層,並藉由管柱層析法精製,進行減壓濃縮而得到3份(收率:34%)著色劑A-4。7 parts of intermediate 1, 2.05 parts of benzenesulfonamide were dissolved in 40 parts of chloroform, and diazabicyclo (1,8-dioxabicyclo[5.4.0]undec-7-ene) was added dropwise (1, 8-diazabicyclo [5.4.0]undec-7-ene) 2.32 parts, stirred at room temperature for 1 hour. Then, 100 parts of water was placed in the obtained reaction solution for washing with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, and purified by column chromatography, and concentrated under reduced pressure to give 3 (yield: 34%) of coloring agent A-4.
<著色劑A-2的合成例><Synthesis Example of Colorant A-2>
將於著色劑A-1的合成中使用之2,6-二甲基苯胺變更為2,6-二乙基苯胺,從而合成著色劑A-2。The coloring agent A-2 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2,6-diethylaniline.
<著色劑A-3的合成例><Synthesis Example of Colorant A-3>
將於著色劑A-1的合成中使用之2,6-二甲基苯胺變更為2,6-二異丙基苯胺,從而合成著色劑A-3。The coloring agent A-3 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2,6-diisopropylaniline.
<著色劑A-5的合成例><Synthesis Example of Colorant A-5>
將於著色劑A-4的合成中使用之苯磺醯胺變更為三氟甲基磺醯胺,從而合成著色劑A-5。The coloring agent A-5 was synthesized by changing the benzenesulfonamide used in the synthesis of the colorant A-4 to trifluoromethylsulfonamide.
<著色劑A-6的合成例><Synthesis Example of Colorant A-6>
將於著色劑A-4的合成中使用之苯磺醯胺變更為甲苯磺醯胺,從而合成著色劑A-6。The coloring agent A-6 was synthesized by changing the benzenesulfonamide used in the synthesis of the colorant A-4 to toluenesulfonamide.
<著色劑A-7的合成例><Synthesis Example of Colorant A-7>
將於著色劑A-1的合成中使用之2,6-二甲基苯胺變更為2,4,6-三甲基苯胺,從而合成著色劑A-7。The coloring agent A-7 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2,4,6-trimethylaniline.
<著色劑A-8的合成例><Synthesis Example of Colorant A-8>
【化學式32】 [Chemical Formula 32]
將DCSF(CHUGAI KASEI CO.,LTD.製造)50份、2,6-二異丙基苯胺52.5份、環丁碸200份放入燒瓶中,在外部溫度80度下攪拌4小時。然後,將所得到之反應溶液放冷至室溫,並滴入於2mol/L鹽酸500份中,將所析出之結晶進行過濾。在用40度的乙腈300份對結晶進行分散清洗之後,過濾收集,並吹風乾燥10小時,得到28份(收率:45%)中間體2。50 parts of DCSF (manufactured by CHUGAI KASEI CO., LTD.), 52.5 parts of 2,6-diisopropylaniline, and 200 parts of cyclobutyl hydrazine were placed in a flask, and stirred at an external temperature of 80 °C for 4 hours. Then, the obtained reaction solution was allowed to cool to room temperature, and dropped into 500 parts of 2 mol/L hydrochloric acid, and the precipitated crystals were filtered. After the crystals were subjected to dispersion washing with 300 parts of acetonitrile of 40 degrees, the mixture was collected by filtration and dried by air drying for 10 hours to obtain 28 parts (yield: 45%) of Intermediate 2.
添加25份中間體2、14.4份2,6-二甲基苯胺、11.1份氯化鋅、100份環丁碸,並在外部溫度200度下攪拌4小時。然後,將所得到之反應溶液放冷至室溫,並滴入到2mol/L鹽酸200份中,將所析出之結晶進行了過濾。在用40度的乙腈120份對結晶進行分散清洗之後,過濾收集,並吹風乾燥10小時,得到25.1份(收率:86%)的著色劑A-8。25 parts of the intermediate 2, 14.4 parts of 2,6-dimethylaniline, 11.1 parts of zinc chloride, 100 parts of cyclobutyl hydrazine were added, and stirred at an external temperature of 200 °C for 4 hours. Then, the obtained reaction solution was allowed to cool to room temperature, and dropped into 200 parts of 2 mol/L hydrochloric acid, and the precipitated crystals were filtered. After dispersing and washing the crystals with 120 parts of acetonitrile at 40 degrees, the mixture was collected by filtration and dried by air drying for 10 hours to obtain 25.1 parts (yield: 86%) of the coloring agent A-8.
<著色劑A-9的合成例><Synthesis Example of Colorant A-9>
將於著色劑A-1的合成中使用之2,6-二甲基苯胺變更為N-(3-胺基-2,4,6-三甲基苯基)乙醯胺,從而合成著色劑A-9。The 2,6-dimethylaniline used in the synthesis of the colorant A-1 was changed to N-(3-amino-2,4,6-trimethylphenyl)acetamide to synthesize a color former. A-9.
<著色劑A-10的合成例><Synthesis Example of Colorant A-10>
將於著色劑A-1的合成中使用之2,6-二甲基苯胺變更為2-甲基苯胺,從而合成著色劑A-10。The coloring agent A-10 was synthesized by changing 2,6-dimethylaniline used in the synthesis of the colorant A-1 to 2-methylaniline.
【化學式33】 [Chemical Formula 33]
<著色劑的溶劑溶解性評價><Evaluation of Solvent Solubility of Colorant>
向樣品管瓶中投入著色劑0.1g,接著,用全吸管(Whole Pipette)投入下述表1所示之有機溶劑10ml,在塞嚴之後用超音波進行了3分鐘的處理。將所得到之溶液在23℃的水浴中静置保管了60分鐘。用孔徑為5μm的PTFE製造的膜濾器過濾該上清液5ml,進而,用孔徑為0.25μm的PTFE製造膜濾器進行過濾而去除不溶物。To the sample vial, 0.1 g of the coloring agent was placed, and then 10 ml of the organic solvent shown in the following Table 1 was placed in a Whole Pipette, and the mixture was treated with ultrasonic waves for 3 minutes after the stopper. The obtained solution was allowed to stand in a water bath at 23 ° C for 60 minutes. 5 ml of this supernatant was filtered with a membrane filter made of PTFE having a pore size of 5 μm, and further, a membrane filter made of PTFE having a pore diameter of 0.25 μm was used for filtration to remove insoluble matter.
利用紫外可見分光光度計(AGILENT Corporation製造 CARY5000),並使用1cm的單元(cell)測定濾液的吸光分光。求出各著色劑的最大吸收波長之吸光度。此時,若極大吸收波長之吸光度小於2,則能夠評價為著色劑實質上不溶解於有機溶劑,並可評價為著色劑的溶解度為1(g/100g有機溶劑)以下。另外,由本測定方法測量之吸光度的測定極限為0.005。將結果示於表1中。表中的PGMEA為丙二醇單甲醚乙酸酯的縮寫。The absorbance spectroscopy of the filtrate was measured using an ultraviolet-visible spectrophotometer (CARY 5000 manufactured by AGILENT Corporation) and using a cell of 1 cm. The absorbance at the maximum absorption wavelength of each colorant was determined. At this time, when the absorbance at the maximum absorption wavelength is less than 2, it can be evaluated that the colorant is substantially not dissolved in the organic solvent, and the solubility of the colorant can be evaluated to be 1 (g/100 g of the organic solvent) or less. Further, the measurement limit of the absorbance measured by the present measurement method was 0.005. The results are shown in Table 1. PGMEA in the table is an abbreviation for propylene glycol monomethyl ether acetate.
[表1]
如上述表所示,A-1~A-10的著色劑實質上不溶解於PGMEA、環己酮及環戊酮,對該些有機溶劑之溶解度為1(g/100g有機溶劑)以下。As shown in the above table, the color formers of A-1 to A-10 are substantially insoluble in PGMEA, cyclohexanone, and cyclopentanone, and the solubility in these organic solvents is 1 (g/100 g of organic solvent) or less.
<使用(A)著色劑之分散液的製備><Preparation of dispersion using (A) colorant>
將(A)著色劑、(B)分散劑、(C)顔料衍生物、(H)染料以及溶劑,分別以下述表2所示之比例進行混合,在攪拌混合均勻之後,使用直徑為0.5mm的鋯珠,藉由珠磨機分散5小時而製備出分散液。The (A) colorant, (B) dispersant, (C) pigment derivative, (H) dye, and solvent were mixed at a ratio shown in the following Table 2, and after stirring and mixing uniformly, a diameter of 0.5 mm was used. The zirconium beads were dispersed by a bead mill for 5 hours to prepare a dispersion.
[表2]
表中記載的化合物如下。The compounds described in the table are as follows.
(A)著色劑 A-1~A-10:上述結構的著色劑A-1~A-10 R-1~R-5:比較化合物(下述結構)(A) Colorant A-1 to A-10: Color former A-1 to A-10 R-1 to R-5 of the above structure: comparative compound (structure described below)
【化學式34】 [Chemical Formula 34]
(B)分散劑(B) Dispersant
[表3]
【化學式35】 [Chemical Formula 35]
(C)顔料衍生物 C-1:下述結構(C) Pigment Derivative C-1: The following structure
【化學式36】 [Chemical Formula 36]
(H)染料 H-1~H-3:下述結構(H) Dye H-1 to H-3: the following structure
【化學式37】 [Chemical Formula 37]
1.著色硬化性組成物的製備1. Preparation of colored curable composition
1-1.顔料分散液的製備1-1. Preparation of pigment dispersion
<藍色顔料分散液P1的製備><Preparation of Blue Pigment Dispersion P1>
如下製備藍色顔料分散液P1。The blue pigment dispersion P1 was prepared as follows.
將混合13.0份C.I.Pigment Blue15:6(藍色顔料;以下亦稱作“PB15:6”)(藍色顔料、平均粒徑55nm)、5.0份作為分散劑之Disperbyk111、82.0份PGMEA而成之混合液,藉由珠磨機(鋯珠0.3mm直徑)混合、分散3小時。然後,進一步使用帶有減壓機構的高壓分散機NANO-3000-10(NIHON B.E.E. CO.,LTD.製造),在2000kg/cm3 的壓力下,以500g/min的流量對前述混合液進行分散處理。重複10次該分散處理,得到在實施例或比較例的著色硬化性組成物中使用之藍色顔料分散液P1(C.I.Pigment Blue15:6分散液、顔料濃度13%)。A mixture of 13.0 parts of CIPigment Blue 15:6 (blue pigment; hereinafter also referred to as "PB15:6") (blue pigment, average particle diameter 55 nm), 5.0 parts of Disperbyk 111 as a dispersing agent, and 82.0 parts of PGMEA was mixed. It was mixed and dispersed by a bead mill (zirconium beads 0.3 mm diameter) for 3 hours. Then, a high-pressure disperser NANO-3000-10 (manufactured by NIHON BEE CO., LTD.) equipped with a pressure-reducing mechanism was further used, and the mixture was dispersed at a flow rate of 500 g/min under a pressure of 2000 kg/cm 3 . deal with. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion liquid P1 (CIPigment Blue 15:6 dispersion liquid, pigment concentration 13%) used in the color hardening composition of the examples or the comparative examples.
當藉由動態光散射法(Microtrac Nanotrac UPA-EX150(日機裝公司(Nikkiso Co.,Ltd.)製造))測定顔料的平均粒徑時,所得到之藍色顔料分散液P1為24nm。When the average particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), the obtained blue pigment dispersion liquid P1 was 24 nm.
<藍色顔料分散液P2的製備><Preparation of Blue Pigment Dispersion P2>
將19.4質量份PB15:6(平均粒徑55nm)、2.95質量份作為分散劑之BYK-161(BYK-Chemie GmbH製造)、以固體成分換算為2.95質量份(溶液9.93質量份)的鹼可溶性樹脂1(甲基丙烯酸苄酯/甲基丙烯酸的共聚物、30%PGMEA溶液)、165.3質量份PGMEA進行混合而成之混合液,藉由珠磨機(鋯珠0.3mm直徑)混合、分散3小時。然後,進一步使用帶有減壓機構高壓分散機NANO-3000-10(NIHON B.E.E.CO.,LTD.製造),在2000kg/cm3 的壓力下,以500g/min的流量對前述混合液進行分散處理。重複10次該分散處理,得到藍色顔料分散液P2。在藉由動態光散射法(Microtrac Nanotrac UPA-EX150(日機裝公司(Nikkiso Co., Ltd.)製))而測定顔料的平均粒徑時,所得到之藍色顔料分散液P2為24nm。19.4 parts by mass of PB15:6 (average particle diameter: 55 nm), 2.95 parts by mass of BYK-161 (manufactured by BYK-Chemie GmbH), and a solid content of 2.95 parts by mass (solution: 9.93 parts by mass) of an alkali-soluble resin 1 (mixture of benzyl methacrylate/methacrylic acid copolymer, 30% PGMEA solution) and 165.3 parts by mass of PGMEA, mixed and dispersed by a bead mill (zirconium beads 0.3 mm diameter) for 3 hours . Then, the mixture liquid was further subjected to dispersion treatment at a flow rate of 500 g/min under a pressure of 2000 kg/cm 3 using a high pressure dispersing machine NANO-3000-10 (manufactured by NIHON BEECO., LTD.) equipped with a pressure reducing mechanism. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion liquid P2. When the average particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), the obtained blue pigment dispersion liquid P2 was 24 nm.
<藍色顔料分散液P3的製備><Preparation of Blue Pigment Dispersion P3>
在上述藍色顔料分散液P2的製備中,作為分散劑使用下述分散劑D1來代替BYK-161,除此之外,以相同的方法製備藍色顔料分散液P3。In the preparation of the above-described blue pigment dispersion liquid P2, a blue pigment dispersion liquid P3 was prepared in the same manner except that the following dispersant D1 was used as a dispersant instead of BYK-161.
【化學式38】 [Chemical Formula 38]
分散劑D1的酸值為100mgKOH/g。並且,分散劑D1的重量平均分子量為20000。並且,在分散劑D1的結構中,x和y的質量比為50:50,n為20。The acid value of the dispersant D1 was 100 mgKOH/g. Further, the weight average molecular weight of the dispersant D1 was 20,000. Further, in the structure of the dispersant D1, the mass ratio of x and y was 50:50, and n was 20.
<藍色顔料分散液P4的製備><Preparation of Blue Pigment Dispersion P4>
在上述藍色顔料分散液P2的製備中,作為分散劑使用下述分散劑D2,除此之外,以相同的方法製備顔料分散液P4。In the preparation of the blue pigment dispersion liquid P2 described above, the pigment dispersion liquid P4 was prepared in the same manner except that the following dispersant D2 was used as a dispersant.
【化學式39】 [Chemical Formula 39]
分散劑D2的酸值為100mgKOH/g。並且,分散劑D2的重量平均分子量為20000。並且,在分散劑D2的結構中,x和y的質量比為15:85,n為20。The acid value of the dispersant D2 was 100 mgKOH/g. Further, the weight average molecular weight of the dispersant D2 was 20,000. Further, in the structure of the dispersant D2, the mass ratio of x and y was 15:85, and n was 20.
1-2.著色硬化性組成物的製備1-2. Preparation of colored curable composition
混合下述各成分並進行分散、溶解,得到各實施例及比較例的著色硬化性組成物。 ・使用著色劑(A)之分散液(上述分散液PA1~PA46):0.31份 ・溶劑(PGMEA、環己酮或環戊酮):0.863份 ・鹼可溶性樹脂(下述J1或J2的化合物):0.03份 ・分散劑(SOLSPERSE20000:(1%環己烷溶液、LUBRIZOL JAPAN ,LTD.製造):0.125份 ・光聚合起始劑(下述C-5或C-9的化合物):0.012 份 ・藍色顔料分散液(上述藍色顔料分散液P1~P4)(顔料濃度13%):0.615份 ・硬化性化合物:0.07份 ・界面活性劑(甘油丙醇鹽:(1%環己烷溶液)0.048份Each of the following components was mixed, dispersed, and dissolved to obtain a colored curable composition of each of Examples and Comparative Examples.・Dispersion of coloring agent (A) (the above-mentioned dispersions PA1 to PA46): 0.31 parts, solvent (PGMEA, cyclohexanone or cyclopentanone): 0.863 parts • Alkali-soluble resin (compounds of J1 or J2 described below) : 0.03 parts, dispersing agent (SOLSPERSE 20000: (1% cyclohexane solution, manufactured by LUBRIZOL JAPAN, LTD.): 0.125 parts ・ Photopolymerization initiator (compounds of C-5 or C-9 described below): 0.012 parts Blue pigment dispersion (the above-mentioned blue pigment dispersions P1 to P4) (pigment concentration: 13%): 0.615 parts, curable compound: 0.07 parts, surfactant (glycerol propanolate: (1% cyclohexane solution) 0.048 parts
另外,實施例15及23使用下述J1和J2的混合物(J1:J2=1:1(質量比))作為鹼可溶性樹脂。Further, in Examples 15 and 23, a mixture of J1 and J2 (J1: J2 = 1:1 (mass ratio)) was used as the alkali-soluble resin.
並且,實施例36~45使用下述C-5和C-9的混合物(C-5:C-9=1:1(質量比))作為光聚合起始劑。Further, Examples 36 to 45 used a mixture of C-5 and C-9 (C-5: C-9 = 1:1 (mass ratio)) as a photopolymerization initiator.
<評價><evaluation>
<<顯影前後的分光評價>><<Spectral evaluation before and after development>>
在玻璃晶圓上,以乾燥膜厚成為0.1μm的方式塗佈CT-4000L溶液(FUJIFILM ELECTRONIC MATERIALS CO.,LTD.製造;透明底塗劑)並使其乾燥,在形成透明膜之後,在220℃下加熱處理5分鐘。A CT-4000L solution (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.; a transparent primer) was applied to a glass wafer so as to have a dry film thickness of 0.1 μm, and dried, and after forming a transparent film, at 220 Heat treatment at ° C for 5 minutes.
在形成有透明膜之玻璃晶圓上,以乾燥膜厚成為0.6μm的方式用旋轉塗佈機塗佈上述著色硬化性組成物,並使用100℃的加熱板進行120秒的加熱處理(預烘烤)。接著,使用i線步進機曝光裝置FPA-3000i5+(CANON Inc.製造),以365nm的波長、500mJ/cm2 的曝光量進行了曝光。藉此得到彩色濾光片。On the glass wafer on which the transparent film was formed, the colored curable composition was applied by a spin coater so that the dry film thickness was 0.6 μm, and heat treatment was performed for 120 seconds using a hot plate at 100 ° C (prebaking) grilled). Next, exposure was performed using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by CANON Inc.) at a wavelength of 365 nm and an exposure amount of 500 mJ/cm 2 . Thereby, a color filter is obtained.
將這樣得到之彩色濾光片,用紫外可鍵近紅外分光光度計UV3600(SHIMADZU Corporation製造)的分光光度計(參照:玻璃基板)在300nm~800nm的波長域測定透射率。The color filter thus obtained was measured for transmittance in a wavelength range of 300 nm to 800 nm by a spectrophotometer (see: glass substrate) of an ultraviolet bondable near-infrared spectrophotometer UV3600 (manufactured by SHIMADZU Corporation).
將測定透射率後的彩色濾光片載置於旋轉噴淋顯影機(DW-30型,CHEMITRONICS CO.,LTD.製造)的水平旋轉台上,並使用CD-2000(FUJIFILM ELECTRONIC MATERIALS CO.,LTD.製造),在23℃下進行60秒的攪拌式(paddle)顯影。接著,藉由旋轉裝置使上述彩色濾光片以50r.p.m.的轉速進行旋轉,同時從其旋轉中心的上方將純水自噴出噴嘴呈噴淋狀供給而進行沖洗處理,然後進行噴霧乾燥。在將彩色濾光片乾燥之後,再次測定透射率。由以下基準評價顯影前後的透射率變動(將顯影前的上述透射率設為T0、將顯影後的上述透射率設為T1之情況下,由式|T0-T1|表示之值)。 A:良好 在300nm~800nm的整個區域,顯影前後的透射率的最大變動值小於2% B:稍微良好 在300nm~800nm的整個區域,顯影前後的透射率的最大變動值為2%以上且小於5% C:充分 在300nm~800nm的整個區域,顯影前後的透射率的最大變動值為5%以上且小於10% D:不充分,在300nm~800nm的整個區域,顯影前後的透射率的最大變動值為10%以上The color filter after measuring the transmittance was placed on a horizontal rotary table of a rotary spray developing machine (Model DW-30, manufactured by CHEMITRONICS CO., LTD.), and CD-2000 (FUJIFILM ELECTRONIC MATERIALS CO., (manufactured by LTD.), paddle development was carried out at 23 ° C for 60 seconds. Next, the color filter was rotated at a number of revolutions of 50 r.p.m. by a rotating device, and pure water was supplied from a discharge nozzle in a shower form from above the center of rotation to perform a rinsing treatment, followed by spray drying. After the color filter was dried, the transmittance was measured again. The transmittance variation before and after development (the transmittance before development is T0 and the transmittance after development is T1, and the value represented by the formula |T0-T1|) is evaluated by the following criteria. A: The maximum variation of the transmittance before and after development is preferably less than 2% in the entire region of 300 nm to 800 nm. B: slightly better in the entire region of 300 nm to 800 nm, the maximum variation of the transmittance before and after development is 2% or more and less than 5% C: Fully in the entire region of 300 nm to 800 nm, the maximum variation of transmittance before and after development is 5% or more and less than 10%. D: Insufficient, the maximum transmittance before and after development in the entire region of 300 nm to 800 nm. The change value is 10% or more
<<耐熱性評價>><<Heat resistance evaluation>>
關於由上述得到之彩色濾光片,用色度計MCPD-1000(OTSUKA ELECTRONICS CO.,LTD.製造)測定加熱前後的色差(ΔE*ab值),並按照下述判定基準評價了耐熱性。彩色濾光片以與晶圓表面接觸的方式載置於200℃的加熱板上加熱1個小時。ΔE*ab值中值較小者表示耐熱性良好。另外,ΔE*ab值為由基於CIE1976(L*,a*,b*)空間表色系之以下色差公式而求出之值(日本色彩學会編 新編色彩科學手冊(昭和60年)p.266)。以ΔE*ab={(ΔL*)2+(Δa*)2+(Δb*)2}1/2以下的基準進行評價。 A:ΔE*ab的值為0以上、小於1.0 B:ΔE*ab的值為1.0以上、小於2.0 C:ΔE*ab的值為2.0以上、小於3.0 D:ΔE*ab的值為3.0以上With respect to the color filter obtained above, the color difference (ΔE*ab value) before and after heating was measured with a colorimeter MCPD-1000 (manufactured by OTSUKA ELECTRONICS CO., LTD.), and the heat resistance was evaluated according to the following criteria. The color filter was placed on a hot plate at 200 ° C for 1 hour in contact with the surface of the wafer. A smaller median value of ΔE*ab indicates good heat resistance. In addition, the ΔE*ab value is a value obtained by the following color difference formula based on the CIE1976 (L*, a*, b*) spatial color system (Japanese Color Society, New Color Science Handbook (Showa 60) p. 266). The evaluation was performed on the basis of ΔE*ab={(ΔL*)2+(Δa*)2+(Δb*)2}1/2 or less. A: The value of ΔE*ab is 0 or more and less than 1.0 B: The value of ΔE*ab is 1.0 or more and less than 2.0 C: The value of ΔE*ab is 2.0 or more and less than 3.0 D: the value of ΔE*ab is 3.0 or more
<<耐光性評價>><<Light resistance evaluation>>
關於由上述所得到之彩色濾光片,用耐光試験裝置(SUGA TEST INSTRUMENTS CO.,LTD.製造SX-75),在黑面板溫度63℃、石英內部濾光片、275nm截止外部濾光片、照度75mw/m2 (300~400nm)、濕度50%的條件下,實施了10小時耐光性試験。The color filter obtained as described above was subjected to a light-resistant test apparatus (SX-75 manufactured by SUGA TEST INSTRUMENTS CO., LTD.) at a black panel temperature of 63 ° C, a quartz internal filter, and a 275 nm cut-off external filter. The light resistance test was carried out for 10 hours under the conditions of an illuminance of 75 mW/m 2 (300 to 400 nm) and a humidity of 50%.
用分光光度計MCPD-3000(OTSUKA ELECTRONICS CO.,LTD.製造)測定耐光性試験前後的色差(ΔE*ab)。依據所測定之色差(ΔE*ab),按照下述評價基準對耐光性進行評價。可以說該數值越小,則耐光性越良好。 A:ΔE*ab的值為0以上、小於1.0 B:ΔE*ab的值為1.0以上、小於2.0 C:ΔE*ab的值為2.0以上、小於3.0 D:ΔE*ab的值為3.0以上The color difference (ΔE*ab) before and after the light resistance test was measured with a spectrophotometer MCPD-3000 (manufactured by OTSUKA ELECTRONICS CO., LTD.). Based on the measured color difference (ΔE*ab), the light resistance was evaluated in accordance with the following evaluation criteria. It can be said that the smaller the value, the better the light resistance. A: The value of ΔE*ab is 0 or more and less than 1.0 B: The value of ΔE*ab is 1.0 or more and less than 2.0 C: The value of ΔE*ab is 2.0 or more and less than 3.0 D: the value of ΔE*ab is 3.0 or more
<<分散穩定性評價>><<Dispersion stability evaluation>>
關於著色硬化性組成物,用E型黏度計(TOKI SANGYO CO.,LTD.製造、RE-85L),在室溫下測定剛分散後的黏度η1(單元mPa・s)、及分散後在45℃下放置3天後的黏度η2(單元mPa・s),並算出黏度增加率=(η2-η1)/η1×100。依據所算出之黏度增加率,按照下述評價基準對分散穩定性進行了評價。For the coloring-curable composition, the viscosity η1 (unit mPa·s) immediately after dispersion and the dispersion were measured at room temperature by an E-type viscosity meter (manufactured by TOKI SANGYO CO., LTD., RE-85L). The viscosity η2 (unit mPa·s) after leaving for 3 days at ° C, and the viscosity increase rate = (η2-η1) / η1 × 100 was calculated. Based on the calculated viscosity increase rate, the dispersion stability was evaluated in accordance with the following evaluation criteria.
黏度增加率越小,表示分散穩定性越良好。The smaller the viscosity increase rate, the better the dispersion stability.
按以下基準進行評價。 A:黏度增加率為10%以下 B:黏度增加率大於10%且20%以下 C:黏度增加率大於20%Evaluation was performed on the basis of the following criteria. A: The viscosity increase rate is 10% or less B: The viscosity increase rate is more than 10% and less than 20% C: The viscosity increase rate is more than 20%
[表4]
[表5]
如上述表4及5所示,在實施例中,顯影前後的分光變動較小,能夠形成耐光性優異之膜。另外,耐熱性亦優異。並且,實施例的著色硬化性組成物的分散穩定性優異。As shown in the above Tables 4 and 5, in the examples, the spectral variation before and after development was small, and a film excellent in light resistance can be formed. In addition, heat resistance is also excellent. Further, the colored curable composition of the examples was excellent in dispersion stability.
另一方面,在比較例中,無法同時實現顯影前後的分光變動和耐光性。On the other hand, in the comparative example, the spectral fluctuation and the light resistance before and after the development cannot be simultaneously achieved.
表4、5所示之化合物如下。The compounds shown in Tables 4 and 5 are as follows.
鹼可溶性樹脂:下述結構Alkali-soluble resin: the following structure
【化學式40】 [Chemical Formula 40]
光聚合起始劑:下述結構Photopolymerization initiator: the following structure
【化學式41】 [Chemical Formula 41]
硬化性化合物 KAYARAD DPHA(二季戊四醇六丙烯酸酯、SHIN-NAKAMURA CHEMICAL CO.,LTD.製造) NK酯A-DPH-12E(SHIN-NAKAMURA CHEMICAL CO.,LTD.製造) KAYARAD RP-1040(NIPPON KAYAKU CO.,LTD.製造) 多官能硫醇化合物(鏈轉移劑(Chain-Transfer agent)):下述結構The sclerosing compound KAYARAD DPHA (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) NK ester A-DPH-12E (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) KAYARAD RP-1040 (NIPPON KAYAKU CO) , manufactured by LTD.) Multifunctional thiol compound (Chain-Transfer agent): the following structure
【化學式42】 [Chemical Formula 42]
環氧化合物 E-1:EHPE3150、DAICEL CHEMICAL INDUSTRIES CO.,LTD.製造Epoxy compound E-1: EHPE3150, manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.
E-3:EPICLON N660(DIC CO.,LTD.製造)E-3: EPICLON N660 (manufactured by DIC CO., LTD.)
無no
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