TWI444439B - Modified pigment, and pigment dispersion composition, colored photosensitive composition, color filter, liquid crystal element, and solid-state imaging element using the same - Google Patents

Modified pigment, and pigment dispersion composition, colored photosensitive composition, color filter, liquid crystal element, and solid-state imaging element using the same Download PDF

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TWI444439B
TWI444439B TW097138638A TW97138638A TWI444439B TW I444439 B TWI444439 B TW I444439B TW 097138638 A TW097138638 A TW 097138638A TW 97138638 A TW97138638 A TW 97138638A TW I444439 B TWI444439 B TW I444439B
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pigment
meth
acid
acrylate
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TW200925215A (en
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Wataru Kikuchi
Kazuhiro Fujimaki
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Materials For Photolithography (AREA)

Description

加工顏料與使用它之顏料分散組成物、著色感光性組成物、彩色濾光片、液晶顯示元件及固體攝像元件Process pigment, pigment dispersion composition using the same, coloring photosensitive composition, color filter, liquid crystal display element, and solid-state imaging element

本發明係有關於一種能夠使用於塗料、印刷油墨(ink)、彩色顯示板等廣闊範圍之加工顏料，含有該加工顏料之顏料分散組成物，含有該顏料分散組成物之著色感光性組成物及使用該著色感光性組成物所製造的彩色濾光片(color filter)。又，本發明係有關於一種具備該彩色濾光片之液晶顯示元件及固體攝像元件。The present invention relates to a wide range of processing pigments which can be used in paints, printing inks, color display panels, and the like, a pigment dispersion composition containing the processed pigment, and a colored photosensitive composition containing the pigment dispersion composition and A color filter made of the colored photosensitive composition was used. Moreover, the present invention relates to a liquid crystal display element and a solid-state imaging element including the color filter.

彩色濾光片能夠藉由混合顏料分散組成物(使有機顏料及/或無機顏料分散而成)、多官能單體、光聚合引發劑、鹼可溶性樹脂及其他成分而成為著色感光性組成物，並使用其且藉由光微影法等形成著色圖案來製造。The color filter can be a coloring photosensitive composition by mixing a pigment dispersion composition (dispersing an organic pigment and/or an inorganic pigment), a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components. It is produced by using a photolithographic method or the like to form a colored pattern.

近年來，彩色濾光片在液晶顯示元件(LCD：Liquid Crystal Display)用途，不只是監視器而且在電視(TV：television)的用途亦有擴大的傾向。隨著該用途擴大的傾向，彩色濾光片之色度及對比等被要求具有高度的色特性。又，在影像傳感器(image sensor)(固體攝像元件(solid-state imaging elecment))用途的彩色濾光片，亦同樣地被要求具有高的色特性。In recent years, color filters have been used for liquid crystal display devices (LCDs), and are not only monitors but also have a tendency to expand in televisions (TVs). As the use expands, color chromaticity and contrast of color filters are required to have high color characteristics. Further, a color filter used for an image sensor (solid-state imaging elecment) is similarly required to have high color characteristics.

對於上述要求，含有著色感光性組成物之顏料被要求分散成為微細的粒子(良好的分散性)且以安定的狀態分散(良好的分散性)。顏料的分散性不充分時，會有在所形成的著色光阻膜產生繸狀邊緣(fringe)(邊緣部的鋸齒狀)或產生表面凹凸，所製造的彩色濾光片之色度或尺寸精確度降低，或對比(contrast)明顯劣化之間題。In response to the above-described requirements, the pigment containing the coloring photosensitive composition is required to be dispersed into fine particles (good dispersibility) and dispersed in a stable state (good dispersibility). When the dispersibility of the pigment is insufficient, a fringe (a zigzag shape of the edge portion) or surface unevenness is generated in the formed colored photoresist film, and the color filter or the size of the manufactured color filter is accurate. The degree is reduced, or the contrast is significantly degraded.

又，顏料的分散安定性不充分時，在彩色濾光片的製程、特別是在著色感光性組成物的塗布製程會有容易產生膜厚度的均勻性低落、或是在曝光製程之感光敏感度低落、或是在顯像製程之鹼溶解性低落之問題。而且，顏料的分散性差時，隨著時間的經過，著色感光性組成物的構成成分產生凝集，亦會有適用期(pot life)極短之間題。但是將顏料粒徑微細化時，因為顏料粒子的表面積變大，會有顏料粒子間的凝集力變強，欲兼具高度水準的分散性及分散安定性多半是困難的。Further, when the dispersion stability of the pigment is insufficient, the process of the color filter, particularly in the coating process of the coloring photosensitive composition, tends to cause a decrease in the uniformity of the film thickness or the sensitivity of the exposure process. Low, or the problem of low solubility of alkali in the development process. Further, when the dispersibility of the pigment is poor, the constituent components of the colored photosensitive composition are agglomerated with the passage of time, and there is also a problem that the pot life is extremely short. However, when the particle diameter of the pigment is made fine, the surface area of the pigment particles becomes large, and the cohesive force between the pigment particles becomes strong, and it is difficult to achieve a high level of dispersibility and dispersion stability.

又，就顯示鮮明的色調或高著色力而言，實用上重要的顏料多半係由微細粒子所構成。通常，顏料一次粒子的粒徑之微細化已熟知之方法(鹽磨(salt milling)法)，係將顏料、水溶性的無機鹽及實質上不會溶解該無機鹽之水溶性有機溶劑藉由揑合器(kneader)等機械性混煉之方法。接著，將所得到的微細顏料一次粒子的混合物投入水中，並使用攪拌器(mixer)等攪拌而成為漿體(slurry)狀。接著，將該漿體過濾及水洗後乾燥，能夠以顏料一次粒子凝集體的二次凝集體之方式來得到微細顏料。藉由砂磨機(sand mill)、球磨機(ball mill)等通常的分散機之分散製程係將顏料一次粒子凝集體的二次凝集體解開來得近一次粒子的狀態之分散體之製程。Further, in terms of vivid color tone or high coloring power, most practically important pigments are composed of fine particles. In general, a method known in the art for miniaturizing the particle diameter of a pigment primary particle (salt milling method) is a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent which does not substantially dissolve the inorganic salt. A method of mechanical kneading such as a kneader. Next, the obtained mixture of the fine pigment primary particles is put into water, and stirred by a mixer or the like to have a slurry shape. Next, the slurry is filtered, washed with water, and dried, whereby a fine pigment can be obtained as a secondary aggregate of pigment primary particle aggregates. The process of dispersing the state of the primary particles is obtained by dissolving the secondary aggregate of the pigment primary particle agglomerates by a dispersion process of a usual disperser such as a sand mill or a ball mill.

但是通常將顏料一次粒子的粒徑越微細化時，越容易凝集且越容易生成漿體，或是在乾燥時越容易生成凝集體(2次凝集體)。又，隨著將顏料一次粒子的粒徑微細化，越容易產生堅強的二次凝集體。因此，欲再分散至一次粒子係非常困難的。使用存在有許多二次凝集體之分散體所形成的彩色濾光片，其對比顯著地降低。因此，顏料分散組成物被希望含有未凝集且安定地分散至一次粒子而成之微細粒子且容易處理。However, in general, when the particle diameter of the primary pigment particles is made finer, the aggregate is more likely to aggregate and the slurry is more likely to be formed, or the aggregate is more likely to be formed during drying (secondary aggregate). Further, as the particle diameter of the primary pigment particles is made finer, a stronger secondary aggregate is more likely to be generated. Therefore, it is very difficult to redistribute to the primary particle system. The color filter formed by the dispersion in which many secondary aggregates are present is significantly reduced in contrast. Therefore, the pigment dispersion composition is desirably containing fine particles which are not aggregated and stably dispersed to primary particles and are easy to handle.

為了抑制該微細顏料之堅強的二次凝集之目的，特許第3130217號公報或特開2004-233727號公報揭示在各自鹽磨製程時，添加松香(rosin)或松香衍生物、或非水溶性單體或低聚物來處理顏料，且使用該顏料的分散體能夠得到高對比的彩色濾光片。但是該等方法時，對比、分散性及分散安定性係不充分的。In order to suppress the strong secondary agglomeration of the fine pigment, Japanese Patent Publication No. 3130217 or JP-A-2004-233727 discloses the addition of rosin or a rosin derivative or a water-insoluble single in the respective salt milling process. The body or oligomer is used to treat the pigment, and the dispersion using the pigment enables a high contrast color filter to be obtained. However, in these methods, contrast, dispersibility, and dispersion stability are insufficient.

因此，本發明的目的係提供一種分散性經提升的加工顏料，其即便具有經微細化粒徑的顏料亦能夠抑制二次凝集體的形成，能夠以一次粒子的狀態使其分散，而且是一種能夠安定地維持經分散後的1次粒子之分散安定性優良的加工顏料。Accordingly, an object of the present invention is to provide a process pigment having improved dispersibility, which can suppress the formation of secondary aggregates even if it has a fine particle diameter, and can be dispersed in a state of primary particles, and is a kind of It is possible to stably maintain the processed pigment excellent in dispersion stability of the dispersed primary particles.

本發明的另外目的係提供一種使用此種加工顏料而成之顏料分散性及分散安定性優良之顏料分散組成物，而且，提供一種含有此種顏料分散組成物而構成之硬化性優良的著色感光性組成物。Another object of the present invention is to provide a pigment dispersion composition which is excellent in pigment dispersibility and dispersion stability by using such a processed pigment, and further provides a coloring photosensitive property which is excellent in hardenability and which is composed of such a pigment dispersion composition. Sexual composition.

又，本發明的另外目的係提供一種使用此種著色感光性組成物而成之高對比的彩色濾光片。Further, another object of the present invention is to provide a high contrast color filter using such a colored photosensitive composition.

而且，本發明的另外目的係提供一種具備此種彩色濾光片之液晶顯示元件及固體攝像元件。Further, another object of the present invention is to provide a liquid crystal display element and a solid-state imaging element including such a color filter.

發現上述課題能夠藉由以下的方法來達成，而完成本發明。The above problems have been found to be achieved by the following methods, and the present invention has been completed.

<1>一種加工顏料，其係含有顏料及高分子化合物，該高分子化合物係用以被覆該顏料，且該高分子化合物在側鏈具有選自由羥基、醯胺基、胺基甲醯基及脲基所組成群組之至少一種，而且重量平均分子量為1,000～100,000。<1> A processed pigment comprising a pigment and a polymer compound, wherein the polymer compound is used to coat the pigment, and the polymer compound has a hydroxyl group, a mercaptoamine group, an aminomethylcarbenyl group and a side chain. At least one of the groups consisting of urea groups, and having a weight average molecular weight of 1,000 to 100,000.

<2>如<1>之加工顏料，其中前述顏料係選自由偶氮顏料及多環顏料所組成群組之至少1種。<2> The processed pigment according to <1>, wherein the pigment is at least one selected from the group consisting of an azo pigment and a polycyclic pigment.

<3>如<1>之加工顏料，其中前述顏料係選自由不溶性偶氮系、二系顏料、酞菁系顏料、二酮吡咯并吡咯系顏料、蒽醌系顏料、喹吖酮系顏料及苝系顏料所組成群組之至少1種。<3> The processed pigment according to <1>, wherein the pigment is selected from the group consisting of insoluble azo and At least one of a group consisting of a pigment, a phthalocyanine pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, a quinophthalone pigment, and an anthraquinone pigment.

<4>如<1>至<3>項中任一項之加工顏料，其中前述高分子化合物具有來自下述通式(1)所示單體，The processed pigment according to any one of <1> to <3>, wherein the polymer compound has a monomer derived from the following formula (1),

通式(1)中，R1 係表示氫原子、或是取代或未取代的烷基；R2 係表示單鍵、或2價的連結基；Y係表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-或伸苯基；Z係表示-O-、-CONH-、-CONHO-、或-NHCONH-；Z係表示-O-時，R3 為表示氫原子、Z係表示-O-以外時，R3 為表示取代或未取代的烷基或芳基。In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group; R 2 represents a single bond or a divalent linking group; and Y represents —CO—, —C(=O). O-, -CONH-, -OC(=O)- or phenyl group; Z system represents -O-, -CONH-, -CONHO-, or -NHCONH-; Z system represents -O-, R 3 When R is a hydrogen atom and Z is a group other than -O-, R 3 is a substituted or unsubstituted alkyl or aryl group.

<5>如<1>至<4>項中任一項之加工顏料，其中前述高分子化合物含有50～200mgKOH/g的範圍之羧基。<6>如<1>至<5>項中任一項之加工顏料，其中平均1次粒徑為5～25奈米。The process pigment according to any one of <1> to <4> wherein the polymer compound contains a carboxyl group in the range of 50 to 200 mgKOH/g. <6> The processed pigment according to any one of <1> to <5> wherein the average primary particle diameter is 5 to 25 nm.

<7>如<1>至<3>項中任一項之加工顏料，其中使用1-甲氧基-2-丙醇洗淨前述加工顏料後時，前述高分子化合物的游離基為30質量%以下。<7> The processed pigment according to any one of <1> to <3>, wherein, after washing the aforementioned processed pigment with 1-methoxy-2-propanol, the radical of the polymer compound is 30 mass %the following.

<8>如<1>至<7>項中任一項之加工顏料，其係在前述顏料的微細化製程添加前述高分子化合物來製造。<8> The processed pigment according to any one of <1> to <7>, which is produced by adding the polymer compound to the above-described pigment miniaturization process.

<9>一種顏料分散組成物，其係含有如<1至<8>項中任一項之加工顏料及用以分散前述加工顏料之有機溶劑。<9> A pigment dispersion composition containing the processed pigment according to any one of <1 to <8> and an organic solvent for dispersing the above-mentioned processed pigment.

<10>如<9>之顏料分散組成物，其中更含有顏料分散劑。<10> A pigment dispersion composition according to <9>, which further contains a pigment dispersant.

<11>如<9>或<10>之顏料分散組成物，其係使用於形成彩色濾光片之著色區域。<11> A pigment dispersion composition such as <9> or <10>, which is used for forming a colored region of a color filter.

<12>一種著色感光性組成物，其係含有如<9>至<11>項中任一項之顏料分散組成物、光聚合性化合物及光聚合引發劑。<12> A coloring photosensitive composition containing the pigment dispersion composition, the photopolymerizable compound, and the photopolymerization initiator according to any one of <9> to <11>.

<13>一種彩色濾光片，其係含有基板及在前述基板上使用如<12>之著色感光性組成物所形成的著色區域。<13> A color filter comprising a substrate and a colored region formed by using the colored photosensitive composition of <12> on the substrate.

<14>一種液晶顯示元件，其係具備如<13>之彩色濾光片。<14> A liquid crystal display element comprising a color filter such as <13>.

<15>一種固體攝像元件，其係具備如<13>之彩色濾光片。<15> A solid-state imaging device comprising a color filter such as <13>.

本發明係有關於一種加工顏料及其應用，該加工顏料係使用在側鏈具有選自由羥基、醯胺基、胺基甲醯基及脲基所組成群組之至少一種且重量平均分子量為1,000～100,000之高分子化合物(以下，會有稱為特定高分子化合物之情況)，被覆處理顏料而成。該加工顏料的分散性優良，藉由使用此種加工顏料，能夠得到顏料比先前良好地分散而成之顏料分散組成物，及具有良好的分散狀態之著色感光性組成物。而且，藉由使用該著色感光性組成物，能夠提供一種高對比的彩色濾光片，及一種具備其之液晶顯示元件及固體攝像元件。The present invention relates to a processed pigment which has at least one selected from the group consisting of a hydroxyl group, a mercaptoamine group, an aminomethylmercapto group and a urea group and has a weight average molecular weight of 1,000 in a side chain. A polymer compound of -100,000 (hereinafter referred to as a specific polymer compound) is coated with a pigment. The processed pigment has excellent dispersibility, and by using such a processed pigment, it is possible to obtain a pigment-dispersed composition in which the pigment is well dispersed, and a colored photosensitive composition having a good dispersed state. Further, by using the colored photosensitive composition, it is possible to provide a high contrast color filter, a liquid crystal display element including the same, and a solid-state imaging element.

亦即，認為將特定高分子化合物使用於顏料處理時，能夠有效地抑制顏料生成一次粒子凝集體亦即二次凝集體，或是有效地減弱二次凝集體的凝集力。因此，在分散製程，能夠得到接近一次粒子狀態之分散體。That is, it is considered that when a specific polymer compound is used for the pigment treatment, it is possible to effectively suppress the pigment from forming a primary aggregate, that is, a secondary aggregate, or to effectively attenuate the cohesive force of the secondary aggregate. Therefore, in the dispersion process, a dispersion close to the primary particle state can be obtained.

該作用雖然未明確，將在側鏈具有選自由羥基、醯胺基、胺基甲醯基及脲基所組成群組之至少一種且重量平均分子量為1,000～100,000之高分子化合物使用於顏料處理時，能夠有效地抑制顏料生成一次粒子凝集體亦即二次凝集體，或是有效地減弱二次凝集體的凝集力。認為因此在分散製程，能夠得到接近一次粒子狀態的分散體。Although this effect is not clear, a polymer compound having at least one selected from the group consisting of a hydroxyl group, a mercaptoamine group, an aminomethylmercapto group, and a urea group and having a weight average molecular weight of 1,000 to 100,000 in a side chain is used for pigment treatment. In this case, it is possible to effectively suppress the pigment from forming a primary aggregate, that is, a secondary aggregate, or to effectively attenuate the cohesive force of the secondary aggregate. It is considered that a dispersion close to the primary particle state can be obtained in the dispersion process.

這是特定高分子化合物在側鏈具有選自由羥基、醯胺基、胺基甲醯基及脲基所組成群組之至少一種結構，認為藉由該構造與顏料具有適當的靜電性相互作用，及藉由特定高分子化合物之堅強的分子間力，該特定高分子化合物堅強地吸附於顏料一次粒子，且在漿體、過濾及水洗時亦不會脫離之緣故，能夠有效地抑制顏料一次粒子之間的凝集。又，金屬錯合物的顏料時，認為特定高分子化合物在側鏈所具有的氮原子或氧原子亦對該金屬錯合物產生配位鍵之相互作用，而強力地吸附於顏料一次粒子。因此，成為分散性優良的加工顏料。This is a structure in which a specific polymer compound has at least one structure selected from the group consisting of a hydroxyl group, a mercaptoamine group, an aminomethylmercapto group, and a urea group in the side chain, and it is considered that the structure has an appropriate electrostatic interaction with the pigment. And by the strong intermolecular force of the specific polymer compound, the specific polymer compound is strongly adsorbed to the pigment primary particles, and is not detached during the slurry, filtration, and water washing, and can effectively suppress the pigment primary particles. Aggregation between. Further, in the case of a pigment of a metal complex, it is considered that a nitrogen atom or an oxygen atom of a specific polymer compound in a side chain also has a coordination bond with the metal complex, and is strongly adsorbed to the pigment primary particles. Therefore, it becomes a process pigment excellent in dispersibility.

又，藉由使用本發明的加工顏料，能夠解決在高溫、高濕度下彩色濾光片混濁且亦能夠解決製造彩色濾光片時產生混濁之問題。該等問題被認為是彩色濾光片中的微細顏料粒子凝集並結晶成長所引起的現象，且顏料一次粒子越微細時越容易產生。本發明的加工顏料因與先前同樣的理由，認為特定高分子化合物係堅強地吸附在微細顏料之緣故，即便在彩色濾光片中亦能夠有效地抑制顏料粒間的凝集。Further, by using the processed pigment of the present invention, it is possible to solve the problem that the color filter is turbid at high temperature and high humidity, and it is also possible to solve the problem of turbidity when the color filter is manufactured. These problems are considered to be a phenomenon caused by aggregation and growth of fine pigment particles in a color filter, and the finer the pigment primary particles, the more likely they are. In the processed pigment of the present invention, it is considered that the specific polymer compound is strongly adsorbed to the fine pigment for the same reason as described above, and the aggregation between the pigment particles can be effectively suppressed even in the color filter.

又，藉由使用本發明的加工顏料，彩色濾光片之電壓保持率優良。當彩色濾光片中的金屬離子濃度高時，容易產生電壓保持率低落。特別是使用鹽磨法製造微細顏料時，會有容易產生的問題。這是因為吸附於顏料粒子而成之鹽磨所使用的無機鹽(離子)從顏料粒子溶出之緣故。顏料一次粒子越微細，越容易包含離子性化合物，且難以藉由水洗及過濾來除去。因此，本發明的加工顏料能夠得到優良的電壓保持率係與先前同樣的理由，認為特定高分子化合物係堅強地吸附在微細顏料之緣故，能夠有效地抑制在分散製程或彩色濾光片中之離子的溶出。Further, by using the processed pigment of the present invention, the color filter has excellent voltage holding ratio. When the concentration of metal ions in the color filter is high, the voltage holding ratio is liable to be lowered. In particular, when a fine pigment is produced by a salt milling method, there is a problem that is likely to occur. This is because the inorganic salt (ion) used in the salt milling by the pigment particles is eluted from the pigment particles. The finer the primary particles of the pigment, the easier it is to contain the ionic compound, and it is difficult to remove it by washing with water and filtration. Therefore, the processed pigment of the present invention can obtain an excellent voltage holding ratio for the same reason as before, and it is considered that the specific polymer compound is strongly adsorbed to the fine pigment, and can be effectively suppressed in the dispersion process or the color filter. Dissolution of ions.

而且，藉由使用本發明的加工顏料，在彩色濾光片製程時，具有在顯像液中不容易產生析出物之優點。析出物多半係顏料粒子的凝集體。析出可以認為係藉由分散劑而分散的顏料分散體因鹼性顯像液致使分散劑脫離，微細顏料粒子凝集並結晶成長而析出之現象。因此，本發明的加工顏料係與先前同樣的理由，認為特定高分子化合物係堅強地吸附在微細顏料之緣故，即便鹼性顯像液，高分子化合物亦不會脫離，即便在鹼性顯像液中亦能夠安定地分散之緣故，所以在顯像液中不容易產生析出物。Further, by using the processed pigment of the present invention, there is an advantage that precipitates are less likely to be generated in the developing liquid during the color filter process. Most of the precipitates are aggregates of pigment particles. Precipitation is considered to be a phenomenon in which the pigment dispersion dispersed by the dispersant is desorbed by the alkaline developing solution, and the fine pigment particles are aggregated and crystallized and precipitated. Therefore, the processed pigment of the present invention is considered to be strongly adsorbed to the fine pigment by the same reason as in the prior art, and even if the alkaline developing solution is used, the polymer compound does not escape, even in the alkaline imaging. Since the liquid can be stably dispersed, the precipitate is less likely to be generated in the developing solution.

依照本發明，能夠提供一種分散性經提升的加工顏料，其即便具有經微細化的顏料亦能夠抑制二次凝集體的形成，能夠以一次粒子的狀態使其分散，而且係一種分散安定性優良的加工顏料，其能夠安定地維持經分散的一次粒子。According to the present invention, it is possible to provide a processed pigment having improved dispersibility, which can suppress the formation of secondary aggregates even if it has a fine pigment, can be dispersed in a state of primary particles, and is excellent in dispersion stability. A processed pigment that is capable of stably maintaining dispersed primary particles.

依照本發明，能夠提供一種顏料分散性及分散安定性優良之顏料分散組成物，其係使用此種加工顏料而成，而且，能夠提供一種硬化性優良的著色感光性組成物，其係含有此種顏料分散組成物而構成。According to the present invention, it is possible to provide a pigment dispersion composition excellent in pigment dispersibility and dispersion stability, which is obtained by using such a processing pigment, and further provides a coloring photosensitive composition excellent in curability, and the like The pigment is composed of a dispersion composition.

又，依照本發明，能夠提供一種高對比的彩色濾光片，其係使用此種著色感光性組成物而成。Further, according to the present invention, it is possible to provide a high contrast color filter which is obtained by using such a colored photosensitive composition.

而且，依照本發明，能夠提供一種液晶顯示元件及固體攝像元件，其係具備此種彩色濾光片。Moreover, according to the present invention, it is possible to provide a liquid crystal display element and a solid-state image sensor which are provided with such a color filter.

以下，詳細地說明本發明。Hereinafter, the present invention will be described in detail.

加工顏料Processing pigment

本發明的加工顏料，其特徵係使用在側鏈具有選自由羥基、醯胺基、胺基甲醯基及脲基所組成群組之至少一種，而且重量平均分子量為1,000～100,000之高分子化合物(特定高分子化合物)被覆處理顏料而成。The processed pigment of the present invention is characterized by using a polymer compound having at least one selected from the group consisting of a hydroxyl group, a mercaptoamine group, an aminomethylmercapto group and a urea group in a side chain, and having a weight average molecular weight of 1,000 to 100,000. (Specific polymer compound) is coated with a pigment.

此種微細加工顏料能夠經由以下製程來製造，包含：將i)顏料、ii)水溶性的無機鹽、iii)實質上不會溶解ii)之少量的水溶性有機溶劑及iv)特定高分子化合物混合，並藉由揑合器(kneader)等機械性混煉之製程(將該顏料的微細化製程稱為鹽磨)；將該混合物投入水中，並使用高速攪拌器(high-speed mixer)等攪拌而成為漿體狀之製程；及將該漿體過濾及水洗，且按照必要進行乾燥之製程。藉由此種製造方法，能夠得到微細且乾燥時顏料的凝集少之本發明的加工顏料。Such finely processed pigments can be produced by the following processes: i) pigments, ii) water-soluble inorganic salts, iii) substantially insoluble ii) small amounts of water-soluble organic solvents, and iv) specific polymer compounds Mixing, and by a mechanical kneading process such as a kneader (the micronization process of the pigment is referred to as salt milling); the mixture is poured into water and stirred using a high-speed mixer or the like. And into a slurry-like process; and the slurry is filtered and washed, and dried as necessary. According to such a production method, the processed pigment of the present invention which is fine and has a small amount of aggregation of the pigment upon drying can be obtained.

對上述之鹽磨更具體地說明。首先，在i)顏料與ii)水溶性的無機鹽的混合物，添加作為潤濕劑之少量的iii)水溶性有機溶劑，並藉由揑合器強烈地混煉後，將該混合物投入水中，並使用高速攪拌器等攪拌而成為漿體狀。接著，將該漿體過濾及水洗，且按照必要進行乾燥，能夠得到微細化的顏料。又，分散於油性的清漆(varnish)而使用時，亦能夠將乾燥前的處理顏料(稱為濾餅(cake))藉由通常稱為沖洗(flushing)之方法，邊除去水邊分散於油性的清漆。又，分散於水系的清漆時，處理顏料不必乾燥，能夠將濾餅直接分子量分散於清漆中。The salt grinding described above is more specifically described. First, in a mixture of i) a pigment and ii) a water-soluble inorganic salt, a small amount of iii) a water-soluble organic solvent as a wetting agent is added, and after kneading strongly by a kneader, the mixture is poured into water, and Stirring with a high-speed stirrer or the like to form a slurry. Next, the slurry is filtered and washed with water, and dried as necessary to obtain a fine pigment. Further, when it is dispersed in an oil-based varnish, it is also possible to disperse the oil before disposal by removing the water by a method generally called a flushing by a process pigment (referred to as a cake) before drying. Varnish. Further, when it is dispersed in a water-based varnish, the treated pigment does not have to be dried, and the filter cake can be directly dispersed in the varnish.

在本發明，鹽磨時藉由並用上述iii)有機溶劑及iv)至少一部分可溶的樹脂(亦即，特定高分子化合物)，能夠得到一種乾燥時顏料的凝集少之加工顏料，其更微細且表面係由iv)至少一部分可溶的樹脂被覆而成。In the present invention, by using the above iii) organic solvent and iv) at least a part of the soluble resin (that is, a specific polymer compound) in the salt milling, it is possible to obtain a processed pigment having less aggregation of the pigment during drying, which is finer. And the surface is made of iv) at least a portion of the soluble resin.

防止因乾燥引起凝集之方法，藉由在上述的漿體中添加溶解於鹼性水溶液而成的鹼可溶性樹脂，並充分攪拌後使用鹽酸或硫酸等的酸性水溶液中和來使樹脂沈附於顏料，或是藉由添加氯化鈣或氯化鋇等水溶性多價金屬鹽的水溶液，使樹脂析出並沈附於顏料，能夠防止乾燥凝集。In the method of preventing aggregation due to drying, an alkali-soluble resin obtained by dissolving in an alkaline aqueous solution is added to the above-mentioned slurry, and after sufficiently stirring, the resin is adhered to the pigment by neutralizing with an acidic aqueous solution such as hydrochloric acid or sulfuric acid. Alternatively, by adding an aqueous solution of a water-soluble polyvalent metal salt such as calcium chloride or cesium chloride, the resin is precipitated and adhered to the pigment, thereby preventing dry aggregation.

又，iv)特定高分子化合物可以在鹽磨初期全部添加，亦可以分割而添加。Further, iv) the specific polymer compound may be added all at the beginning of the salt milling, or may be added separately.

i)顏料i) pigment

在本發明所使用的顏料，可適當地選擇使用先前眾所周知的各種無機顏料或有機顏料。考慮本發明的顏料分散組成物係以適合使用彩色濾光片係以高透射率為佳等時，以有機顏料為佳，又，顏料的粒子尺寸係以盡可能使用粒子尺寸小的顏料為佳。考慮顏料分散組成物及含有其之光硬化性組成物的處理性時，顏料的平均一次粒徑以100奈米以下為佳，以30奈米以下為更佳，以5～25奈米為最佳。該粒徑在前述範圍內時，透射率高且色特性良好，同時對於形成高對比的彩色濾光片係有效的。平均一次粒徑係使用SEM或TEM觀察，並計測100個粒子未凝集位置的粒子尺寸，且算出平均值來求得。As the pigment used in the present invention, various inorganic pigments or organic pigments which have been previously known can be appropriately selected and used. It is preferable that the pigment dispersion composition of the present invention is preferably an organic pigment when it is suitable to use a color filter system with high transmittance, and the particle size of the pigment is preferably a pigment having a small particle size as much as possible. . In consideration of the handleability of the pigment dispersion composition and the photocurable composition containing the same, the average primary particle diameter of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 to 25 nm. good. When the particle diameter is within the above range, the transmittance is high and the color characteristics are good, and it is effective for forming a high contrast color filter system. The average primary particle diameter was determined by SEM or TEM, and the particle size of the non-agglutination position of 100 particles was measured, and the average value was calculated.

前述無機顏料的例子可舉出金屬氧化物及金屬錯鹽等的金屬化合物等，具體例可舉出鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅及銻等的金屬氧化物及前述金屬的複合氧化物。Examples of the inorganic pigment include a metal compound such as a metal oxide or a metal salt, and specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. A composite oxide of an oxide and the foregoing metal.

前述有機顏料的例子可舉出Examples of the aforementioned organic pigments can be exemplified

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、279、CI 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、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,

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、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 ,

C.I.顏料綠7、10、36、37、C.I. Pigment Green 7, 10, 36, 37,

C.I.顏料藍1、2、15、15：1、15：2、15：3、15：4、15：6、16、22、60、64、66、79、將79的C1取代基變更為OH而成者、80、CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, changing the C1 substituent of 79 to OH Founder, 80,

C.I.顏料紫1、19、23、27、32、37、42、C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,

C.I.顏料棕25、28、及C.I. Pigment Brown 25, 28, and

C.I.顏料黑1、7等。C.I. Pigment Black 1, 7, etc.

該等之中，可適合使用的顏料之例子可舉出以下者，但是本發明出未限定於該等。Among the above, examples of the pigment which can be suitably used include the following, but the present invention is not limited to these.

C.I.顏料黃11、24、108、109、110、138、139、150、151、154、167、180、185、C.I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C.I.顏料橙36、71、C.I. Pigment Orange 36, 71,

C.I.顏料紅122、150、171、175、177、209、224、242、254、255、264、C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I.顏料紫19、23、32、C.I. Pigment Violet 19, 23, 32,

C.I.顏料藍15：1、15：3、15：6、16、22、60、66、C.I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66,

C.I.顏料綠7、36、37、C.I. Pigment Green 7, 36, 37,

C.I.顏料黑1、7。C.I. Pigment Black 1, 7.

該等有機顏料可單獨使用，或是為了提高色純度亦可使用各種組合。上述的組合之具體例係如以下所示。例如，紅色顏料能夠單獨使用意醌系顏料、苝系顏料、二酮吡咯并吡咯(diketopyrrolopyrrole)系顏料，或使用該等之至少1種與二重氮(disazo)系黃色顏料、異吲哚滿系黃色顏料、喹啉黃系黃色顏料或苝系紅色顏料、蒽醌系紅色顏料、二酮吡咯并吡咯系紅色顏料之混合等。例如蒽醌系顏料可舉出C.I.顏料紅177，苝系顏料可舉出C.I.顏料紅155、C.I.顏料紅224，二酮吡咯并吡咯系顏料可舉出C.I.顏料紅254，就色再現性而言，以該等之至少1種與C.I.顏料黃83、C.I.顏料黃139或C.I.顏料紅177的混合為佳。又，紅色顏料與其他顏料之質量比以100：5～100：80為佳，100：4以下時因為難以抑制400奈米至500奈米的光透射率，會有無法提升色純度之情況。又，100：81以上時，會有發色力降低之情況。特別是上述質量比以在100：10～100：65之範圍為最佳。又，紅色顏料之間的組合時，能夠配合色度而調整。These organic pigments may be used singly or in various combinations in order to improve color purity. Specific examples of the above combinations are as follows. For example, the red pigment can be used alone as an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment, or at least one of these and a disazo yellow pigment, isoindole It is a mixture of a yellow pigment, a quinoline yellow-based yellow pigment or an anthraquinone-based red pigment, an anthraquinone-based red pigment, and a diketopyrrolopyrrole-based red pigment. For example, CI pigment red 177 is exemplified, CI pigment red 155 and CI pigment red 224 are exemplified, and CI pigment red 254 is mentioned as divalent pyrrolopy pyrrole pigment. It is preferred to mix at least one of these with CI Pigment Yellow 83, CI Pigment Yellow 139 or CI Pigment Red 177. Further, the mass ratio of the red pigment to the other pigment is preferably 100:5 to 100:80, and when it is 100:4 or less, since it is difficult to suppress the light transmittance of 400 nm to 500 nm, the color purity may not be improved. Moreover, when it is 100:81 or more, the coloring power may fall. In particular, the above mass ratio is preferably in the range of 100:10 to 100:65. Further, when the red pigments are combined, they can be adjusted in accordance with the chromaticity.

又，綠色顏料可單獨使用1種鹵化酞菁系顏料，或是使用其與二重氮系黃色顏料、喹啉黃(quinophthalone)系黃色顏料、甲亞胺(azomethine)系黃色顏料或異吲哚滿(isoindoline)系黃色顏料的混合。例如，此種例子以C.I.顏料綠7、36、37與C.I.顏料黃83、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃180或C.I.顏料黃185的混合為佳。綠色顏料與黃色顏料的質量比以100：5～100：200為佳。上述質量比小於100：5時，因為難以抑制400奈米至450奈米的光透射率，會有無法提升色純度之情況。又，100：200以上時，會有主波長係偏向長波長而從NTSC(美國國家電視系統委員會；National Television Standards Committee)目標色相偏移變大之情形。上述質量比係以100：20～100：150的範圍為特佳。Further, the green pigment may be used alone or in combination with a diazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindole. Iso (doindoline) is a mixture of yellow pigments. For example, such an example is preferably a mixture of C.I. Pigment Green 7, 36, 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Pigment Yellow 185. The mass ratio of the green pigment to the yellow pigment is preferably from 100:5 to 100:200. When the mass ratio is less than 100:5, since it is difficult to suppress the light transmittance of 400 nm to 450 nm, the color purity may not be improved. Further, when the ratio is 100:200 or more, the main wavelength is shifted to a long wavelength, and the target hue shift from the NTSC (National Television Standards Committee) becomes large. The above mass ratio is particularly preferably in the range of 100:20 to 100:150.

藍色顏料能夠單獨使用1種酞菁系顏料或混合使用其與二 系紫色顏料的混合。特佳例子可舉出C.I.顏料藍15：6與C.I.顏料紫23的混合。Blue pigment can be used alone or in combination with two phthalocyanine pigments A blend of purple pigments. A particularly preferred example is the mixing of CI Pigment Blue 15:6 with CI Pigment Violet 23.

藍色顏料與紫色顏料的質量比以100：0～100：100為佳，以100：70以下為更佳。The mass ratio of the blue pigment to the violet pigment is preferably from 100:0 to 100:100, more preferably from 100:70 or less.

又，適合於黑色基質用途之適合的顏料，能夠單獨使用碳黑、石墨、鈦黑、氧化鐵、氧化鈦或是該等的混合，以碳黑與鈦黑的組合為佳。又，碳黑與鈦黑之質量比以100：0～100：60的範圍為佳。100：61以上時，會有分散安定性低落之情形。Further, a suitable pigment suitable for the use of a black matrix can be a carbon black, graphite, titanium black, iron oxide, titanium oxide or a mixture thereof, and a combination of carbon black and titanium black is preferred. Further, the mass ratio of carbon black to titanium black is preferably in the range of 100:0 to 100:60. When the ratio is 100:61 or more, there is a case where the dispersion stability is low.

上述舉出的顏料之中，以偶氮顏料及多環顏料為佳，以不溶性偶氮系、二 系顏料、酞菁系顏料、二酮吡咯并吡咯系顏料、蒽醌系顏料、喹酮系顏料及苝系顏料為更佳。就該等能夠藉由凡德瓦力、偶極相互作用及氫鍵中任一者結合來使分子之間堅強地結合而言，乃是有利的。又，酞菁顏料(例如PG36、PB15：6等)或甲亞胺顏料(例如PY150)等的金屬錯合物的顏料，認為因為特定高分子化合物的側鏈具有之氮原子或氧原子亦對該金屬錯合物產生配位鍵之相互作用，而強力地吸附於顏料一次粒子，乃是較佳。Among the above-mentioned pigments, azo pigments and polycyclic pigments are preferred, and insoluble azo systems and Pigment, phthalocyanine pigment, diketopyrrolopyrrole pigment, anthraquinone pigment, quin Ketone pigments and lanthanoid pigments are more preferred. It would be advantageous to be able to bond strongly between molecules by virtue of any combination of van der Waals force, dipole interaction and hydrogen bonding. Further, a pigment of a metal complex such as a phthalocyanine pigment (for example, PG36 or PB15:6) or a methylimine pigment (for example, PY150) is considered to have a nitrogen atom or an oxygen atom in a side chain of a specific polymer compound. It is preferred that the metal complex produces a coordination bond interaction and strongly adsorbs to the pigment primary particles.

ii)水溶性的無機鹽Ii) water-soluble inorganic salts

本發明所使用的水溶性無機鹽若是能夠溶解於水中者沒有特別限定。可舉出例如氯化鈉、氯化鋇、氯化鉀及硫酸鈉等，從價格而言，以使用氯化鈉或硫酸鈉為佳。The water-soluble inorganic salt used in the present invention is not particularly limited as long as it can be dissolved in water. For example, sodium chloride, cesium chloride, potassium chloride, sodium sulfate, etc. may be mentioned, and it is preferable to use sodium chloride or sodium sulfate from a price.

鹽磨時所使用的無機鹽的量，從處理效率及生產效率兩方面而言，為有機顏料的1～30質量倍，以5～25質量倍為特佳。相對於有機顏料之無機鹽的量比越大時微細化效率越高，但是1次的顏料處理量會變少。The amount of the inorganic salt used in the salt milling is preferably from 1 to 30 times by mass of the organic pigment from the viewpoint of the treatment efficiency and the production efficiency, and is particularly preferably from 5 to 25 times by mass. When the amount ratio of the inorganic salt to the organic pigment is larger, the micronization efficiency is higher, but the amount of the pigment treatment once is less.

iii)實質上不會溶解ii)之少量的水溶性有機溶劑Iii) a small amount of water-soluble organic solvent that does not substantially dissolve ii)

水溶性有機溶劑具有將有機顏料及無機鹽潤濕之作用，若是溶解(混合)於水且實質上不會溶解所使用的無機鹽時沒有特別限定。但是因為鹽磨時係呈溫度上升且溶劑容易蒸發之狀態，從安定性而言，以沸點為120℃以上之高沸點溶劑為佳。水溶性有機溶劑可舉出例如2-甲氧基乙醇、2-丁氧基乙醇、2-(異戊氧基)乙醇、2-(己氧基)乙醇、乙二醇、二甘醇、二甘醇一乙基醚、二甘醇一乙基醚乙酸酯、二甘醇一丁基醚、三甘醇、三甘醇一甲基醚、液狀的聚乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、二伸丙甘醇、二伸丙甘醇一甲基醚、二伸丙甘醇一乙基醚及液狀的聚丙二醇等。The water-soluble organic solvent has a function of wetting the organic pigment and the inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and does not substantially dissolve the inorganic salt used. However, in the case of salt milling, the temperature rises and the solvent is easily evaporated. From the viewpoint of stability, a high boiling point solvent having a boiling point of 120 ° C or higher is preferred. The water-soluble organic solvent may, for example, be 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, ethylene glycol, diethylene glycol or the like. Glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy Base-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, and liquid polypropylene glycol .

水溶性有機溶劑的添加量係相對於無機鹽以5質量%～50質量%為佳，相對於無機鹽以10質量%～40質量%為更佳，相對於無機鹽以15質量%～35質量%為最佳。添加量小於5質量%時，難以均勻的混煉，粒子尺寸的分布變大，乃是不佳。添加量大於50質量%時，因為混煉組成物容易變為太軟而難以對混煉組成物施加剪切，無法得到充分的微細化效果。The amount of the water-soluble organic solvent to be added is preferably from 5% by mass to 50% by mass based on the inorganic salt, more preferably from 10% by mass to 40% by mass based on the inorganic salt, and from 15% by mass to 35% by mass based on the inorganic salt. % is the best. When the amount added is less than 5% by mass, it is difficult to knead uniformly, and the distribution of particle size becomes large, which is not preferable. When the amount of addition is more than 50% by mass, the kneaded composition tends to be too soft, and it is difficult to apply shear to the kneaded composition, and a sufficient miniaturization effect cannot be obtained.

iii)水溶性有機溶劑可以在鹽磨初期全部添加，亦可以分割而添加。水溶性有機溶劑可單獨使用，亦可以並用2種以上。Iii) The water-soluble organic solvent may be added all at the beginning of the salt milling, or may be added separately. The water-soluble organic solvent may be used singly or in combination of two or more.

iv)特定高分子化合物Iv) specific polymer compounds

特定高分子化合物係在側鏈具有選自由羥基、醯胺基、胺基甲醯基及脲基所組成群組之至少一種，而且重量平均分子量為1,000～100,000之高分子化合物。特定高分子化合物若是此種物時沒有特別限制，具有選自由羥基、醯胺基、胺基甲醯基及脲基所組成群組之官能基(以下，會有稱為特定官能基之情形)之側鏈，以連結於芳基為佳，以連結芳香族烴基為最佳。這是除了藉由本發明之在側鏈的羥基、醯胺基、胺基甲醯基及脲基之氫鍵以外，因為從亦能夠期待藉由芳基的π-π堆疊(stacking)之相互作用而言，乃是有利的。The specific polymer compound has a polymer compound having at least one selected from the group consisting of a hydroxyl group, a mercaptoamine group, an aminomethylmercapto group, and a urea group in the side chain, and having a weight average molecular weight of 1,000 to 100,000. The specific polymer compound is not particularly limited as long as it is such a substance, and has a functional group selected from the group consisting of a hydroxyl group, a mercaptoamine group, an aminomethylmercapto group, and a urea group (hereinafter, there may be a case where a specific functional group is called). The side chain is preferably bonded to an aryl group, and is preferably bonded to an aromatic hydrocarbon group. This is in addition to the hydrogen bonding of the hydroxyl group, the mercaptoamine group, the aminomethylamyl group and the urea group in the side chain by the present invention, since the interaction of π-π stacking by the aryl group can also be expected. In terms of it, it is beneficial.

特定高分子化合物以具有來自下述通式(1)所示單體之重複單位為佳。The specific polymer compound is preferably a repeating unit having a monomer derived from the following formula (1).

(通式(1)中，R1 係表示氫原子、或是取代或未取代的烷基。R2 係表示單鍵或2價的連結基。Y係表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-或伸苯基。Z係表示-O-、-CONH-、-CONHO-、或-NHCONH-，Z係表示-O-時，R3 為表示氫原子、Z係表示-O-以外時，R3 為表示取代或未取代的烷基或芳基)(In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. R 2 represents a single bond or a divalent linking group. Y represents a -CO-, -C(=O) O-, -CONH-, -OC(=O)- or phenyl group. Z system represents -O-, -CONH-, -CONHO-, or -NHCONH-, and Z system represents -O-, R 3 In the case of a hydrogen atom or a Z system other than -O-, R 3 is a substituted or unsubstituted alkyl or aryl group)

通式(1)中，R1 係表示氫原子、或是取代或未取代的烷基。該烷基的例子以碳1～12的烷基為佳，以碳數1～8的烷基為更佳，以碳數1～4的烷基為特佳。In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms.

R1 所示之烷基係具有取代基時，該取代基的例子可舉出羥基、烷氧基(較佳是碳數1～5，更佳是碳數1～3的烷氧基)、甲氧基、乙氧基及環己氧基等。When the alkyl group represented by R 1 has a substituent, examples of the substituent include a hydroxyl group and an alkoxy group (preferably, a carbon number of 1 to 5, more preferably an alkoxy group having 1 to 3 carbon atoms). Methoxy, ethoxy, cyclohexyloxy and the like.

R1 所示之較佳烷基的具體例可舉出甲基、乙基、丙基、正丁基、異丁基、第三丁基、正己基、環己基、2-羥乙基、3-羥丙基、2-羥丙基及2-甲氧基乙基等。Specific examples of the preferred alkyl group represented by R 1 include a methyl group, an ethyl group, a propyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-hexyl group, a cyclohexyl group, a 2-hydroxyethyl group, and 3 - Hydroxypropyl, 2-hydroxypropyl and 2-methoxyethyl, and the like.

R1 以氫原子或甲基為佳。R 1 is preferably a hydrogen atom or a methyl group.

通式(1)中，R2 係表示單鍵或2價的連結基。該2價的連結基之例子，可舉出伸烷基、伸苯基，以取代或未取代的伸烷基為佳。該伸烷基的例子以碳數1～12的伸烷基為佳，以碳數1～10的伸烷基為較佳，以碳數1～8的伸烷基為更佳，以碳數1～4的伸烷基為特佳。In the formula (1), R 2 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkyl group and a phenyl group, and a substituted or unsubstituted alkyl group is preferred. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. The alkylene group of 1 to 4 is particularly preferred.

R2 所示之伸烷基亦可以是透過雜原子(例如氧原子、氮原子或硫原子)連結2個以上而成者。The alkylene group represented by R 2 may be a mixture of two or more of a hetero atom (for example, an oxygen atom, a nitrogen atom or a sulfur atom).

R2 所示之較佳伸烷基的具體例，可舉出亞甲基、伸乙基、伸丙基、三亞甲基及四亞甲基。Specific examples of the preferred alkylene group represented by R 2 include a methylene group, an exoethyl group, a propyl group, a trimethylene group and a tetramethylene group.

R2 所示之較佳伸烷基係具有取代基時，該取代基可舉出例如羥基等。When the preferred alkylene group represented by R 2 has a substituent, the substituent may, for example, be a hydroxyl group or the like.

在通式(1)，R2 所示2價的連結基之例子，亦可以是在上述的伸烷基之末端具有選自-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-及-NHCO-之雜原子或含有雜原子之部分結構，且透過該雜原子或含有雜原子之部分結構與Z連結者。In the example of the divalent linking group represented by the formula (1) and R 2 , it may be selected from the group consisting of -O-, -S-, -C(=O)O- at the terminal of the above alkyl group. -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)O-, -NHC(=O)S-, -OC(=O)-, -OCONH-, and -NHCO- a hetero atom or a partial structure containing a hetero atom, and a structure in which the hetero atom or a hetero atom-containing portion is bonded to Z.

通式(1)中，R3 所示之烷基可舉出碳原子數1至20之直鏈狀、分枝狀或環狀的烷基。該烷基的具體例可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十六基、十八基、二十基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、1-甲基丁基、異己基、2-乙基己基、2-甲基己基、環己基、環戊基、2-降基。該等之中，以碳原子數1至12的直鏈狀烷基、碳原子數3～12之分枝狀的烷基及碳原子數5至10之環狀烷基為更佳。In the formula (1), the alkyl group represented by R 3 may, for example, be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group, and a thirteen group. Hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2- Ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-lower base. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

通式(1)，R3 所示之芳基可舉出1個至3個苯環形成稠環者，苯環與5員不飽和環形成稠環者及取代芳基。該芳基之具體例可舉出苯基、萘基、蒽基、菲基、茚基、苊基及第基。該等之中，以苯基、萘基為更佳。取代芳基係取代基鍵結於芳基而成者，在前述芳基的環形成碳原子上之取代基，能夠使用除了氫以外之一價的非金屬原子團。較佳之取代基的例子可舉出前述的烷基、取代烷基、及前面在取代烷基作為取代基所舉出者。該等取代芳基的較佳具體例可舉出聯苯基、甲苯基、二甲苯基、基(mesityl)、異丙苯基(cumenyl)、氯苯基、溴苯基、氟苯基、氯甲基苯基、三氟甲基苯基、羥苯基、甲氧基苯基、甲氧基乙氧基苯基、烯丙氧基苯基、苯氧基苯基、甲硫基苯基、甲苯硫基苯基、苯硫基苯基、乙胺基苯基、二乙胺基苯基、嗎啉苯基、乙醯氧基苯基、苯甲醯氧基苯基、N-環己基胺基甲醯氧基苯基、N-苯胺基甲醯氧基苯基、乙醯基胺基苯基、N-甲基苯甲醯基胺基苯基、羧苯基、甲氧基羰基苯基、芳氧基羰基苯基、氯苯氧基羰基苯基、胺基甲醯基苯基、N-甲基胺基甲醯基苯基、N,N-二丙基胺基甲醯基苯基、N-(甲氧基苯基)胺基甲醯基苯基、N-甲基-N-(磺酸基苯基)胺基甲醯基苯基、磺酸基苯基、膦酸根基苯基、胺磺醯基苯基、N-乙基胺磺醯基苯基、N-N-二丙基胺磺醯基苯基、N-甲苯基胺磺醯基苯基、N-甲基-N-(膦酸基苯基)胺磺醯基苯基、膦酸基苯基、膦酸根基苯基、二乙基膦酸基苯基、二苯基膦酸基苯基、甲基膦酸基苯基、甲基膦酸根基苯基、甲苯基膦酸基苯基、甲苯膦酸根基苯基、烯丙基、1-丙烯基甲基、2-丁烯基、2-甲基烯丙基苯基、2-甲基丙烯基苯基、2-丙烯基苯基、2-丁炔基苯基及3-丁炔基苯基等。The aryl group represented by the formula (1) and R 3 may be one in which one to three benzene rings form a fused ring, and the benzene ring forms a fused ring and a substituted aryl group with a 5-membered unsaturated ring. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, an anthracenyl group, and a first group. Among these, a phenyl group and a naphthyl group are more preferable. When a substituted aryl substituent is bonded to an aryl group, a substituent which is a carbon atom other than hydrogen can be used as a substituent on the ring of the aryl group. Examples of preferred substituents include the above-mentioned alkyl group, substituted alkyl group, and the above-mentioned substituted alkyl group as a substituent. Preferred examples of the substituted aryl group include a biphenyl group, a tolyl group, and a xylyl group. Mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxy Ethyl ethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, phenylthiophenyl, ethylaminophenyl, diethylaminophenyl , morpholinylphenyl, ethoxylated phenyl, benzhydryloxyphenyl, N-cyclohexylaminomethyloxyphenyl, N-anilinylmethyloxyphenyl, ethylamino Phenyl, N-methylbenzhydrylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, aryloxycarbonylphenyl, chlorophenoxycarbonylphenyl, aminomethylphenylphenyl, N-methylaminoformamidophenyl, N,N-dipropylaminocarbamidophenyl, N-(methoxyphenyl)aminoformamidophenyl, N-methyl-N -(sulfophenyl)aminomercaptophenyl, sulfonylphenyl, phosphonate phenyl, amidoximinophenyl, N-ethylaminesulfonylphenyl, NN-dipropyl Amine sulfonylphenyl, N-methylphenylsulfonyl phenyl, N-methyl-N-(phosphonophenyl)amine sulfonylphenyl, phosphophenyl phenyl, phosphonate Phenylphenyl, diethylphosphonic phenyl, diphenylphosphonic phenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolylphosphonic acid Phenyl, allyl, 1-propenylmethyl, 2-butenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propenylphenyl, 2-butyne Phenyl and 3-butynylphenyl groups.

以下，可舉出通式(1)所示單體之較佳具體例，但是本發明未限定於該等。Hereinafter, preferred specific examples of the monomer represented by the formula (1) are exemplified, but the present invention is not limited thereto.

特定高分子化合物可只有含有1種來自通式(1)所示單體之共聚合單位，亦可含有2種以上。The specific polymer compound may contain only one type of copolymerization unit derived from the monomer represented by the formula (1), and may contain two or more types.

在特定高分子化合物，來自通式(1)所示單體之共聚合單位的含量沒有特別限制，將在特定高分子化合物所含有的全部結構單位作為100質量%，通式(1)所示單體之共聚合單位的含量以含有5質量%以上為佳，以含有10～50質量%為更佳。In the specific polymer compound, the content of the copolymerization unit derived from the monomer represented by the formula (1) is not particularly limited, and all the structural units contained in the specific polymer compound are 100% by mass, as shown by the formula (1). The content of the copolymerization unit of the monomer is preferably 5% by mass or more, more preferably 10 to 50% by mass.

亦即，為了有效地抑制顏料一次粒子的凝集體亦即二次凝集體的生成，或是為了有效地減弱二次凝集體的凝集力，來自通式(1)所示單體之共聚合單位的含量以5質量%以上為佳。又，從使用含有顏料分散組成物之光硬化性組成物來製造彩色濾光片之顯像性的觀點，來自通式(1)所示單體之共聚合單位的含量以50質量%以下為佳。That is, in order to effectively suppress the aggregation of the primary particles of the pigment, that is, the formation of the secondary aggregate, or to effectively weaken the cohesive force of the secondary aggregate, the copolymerized unit derived from the monomer represented by the general formula (1) The content is preferably 5% by mass or more. In addition, the content of the copolymerization unit derived from the monomer represented by the general formula (1) is 50% by mass or less from the viewpoint of producing the color filter of the color-curable composition containing the pigment-dispersed composition. good.

特定高分子化合物以更含有來自具有酸基的單體之共聚合單位為佳。特定高分子化合物藉由更含有來自具有酸基的單體之共聚合單位，在將顏料分散組成物應用在光硬化性組成物，未曝光部的顯像除法性優良。The specific polymer compound preferably contains a copolymerization unit derived from a monomer having an acid group. When the specific polymer compound further contains a copolymerization unit derived from a monomer having an acid group, the pigment dispersion composition is applied to the photocurable composition, and the image-removing property of the unexposed portion is excellent.

具有酸基的單體之例子，可舉出丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、桂皮酸等的不飽和一羧酸類；順丁烯二酸、順丁烯二酸酐、反丁烯二酸、伊康酸、伊康酸酐、檸康酸(citraconic acid)、檸康酸酐、中康酸(mesaconic acid)等的不飽和二羧酸或其酐類；3價以上的不飽和多元羧酸或其酐類；琥珀酸一(2-丙烯醯氧基乙基)、琥珀酸一(2-甲基丙烯醯氧基乙基)、酞酸一(2-丙烯醯氧基乙基)、酞酸一(2-甲基丙烯醯基乙基)等的二價以上的多元羧酸的一[(甲基)丙烯醯氧基烷基]酯類；ω-羧基-聚己內酯一丙烯酸酯、ω-羧基-聚己內酯一甲基丙烯酸酯等的兩末端羧基聚合物的一(甲基)丙烯酸酯類等。Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and reversed Unsaturated dicarboxylic acid or its anhydrides such as enedic acid, itaconic acid, itaconic acid anhydride, citraconic acid, citraconic anhydride, mesaconic acid, etc.; Carboxylic acid or its anhydride; succinic acid mono(2-propenyloxyethyl), succinic acid mono(2-methylpropenyloxyethyl), decanoic acid mono(2-propenyloxyethyl) a [(meth)propenyloxyalkyl]ester of a divalent or higher polyvalent carboxylic acid such as decanoic acid (2-methylpropenylethyl); ω-carboxy-polycaprolactone A (meth) acrylate such as an acrylate or an ω-carboxy-polycaprolactone monomethacrylate or the like.

特定高分子化合物可以只有含有1種具有酸基的單體之共聚合單位，亦可含有2種以上。The specific polymer compound may be a copolymerized unit containing only one type of monomer having an acid group, or may be contained in two or more types.

特定高分子化合物在不損害其效果之範圍，亦可更含有來自能夠共聚合的乙烯系單體之共聚合單位。The specific polymer compound may further contain a copolymerization unit derived from a copolymerizable vinyl monomer, within a range not impairing the effect.

在此能夠使用的乙烯系單體沒有特別限制，其例子以(甲基)丙烯酸酯類、巴豆酸酯類(crotonic acid esters)、乙烯酯類、順丁烯二酸二酯類、反丁烯二酸二酯類、伊康酸二酯類、(甲基)丙烯醯胺類、乙烯醚類、乙烯醇的酯類、苯乙烯類、(甲基)丙烯醯基甲苯基等為佳。此種乙烯系單體的具體例可舉出例如以下的化合物。又，在本說明書，表示「丙烯酸及甲基丙烯酸」的任一者或雙方時會有記載為「(甲基)丙烯酸」之情形。The vinyl monomer which can be used herein is not particularly limited, and examples thereof include (meth) acrylates, crotonic acid esters, vinyl esters, maleic acid diesters, and antibutene. Desic acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) propylene fluorenyltolyl groups, and the like are preferred. Specific examples of such a vinyl monomer include the following compounds. In addition, in the present specification, any of "acrylic acid and methacrylic acid" or both of them may be described as "(meth)acrylic acid".

(甲基)丙烯酸酯可舉出例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸第三辛酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸乙醯氧基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙酯、(甲基)丙烯酸3-苯氧基-2-羥基丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二甘醇一甲基醚、(甲基)丙烯酸二甘醇一乙基醚、(甲基)丙烯酸三甘醇一甲基醚、(甲基)丙烯酸三甘醇一乙基醚、(甲基)丙烯酸聚乙二醇一甲基醚、(甲基)丙烯酸聚乙二醇一乙基醚、(甲基)丙烯酸β-苯氧基乙氧基乙酯、(甲基)丙烯酸壬基苯氧基聚乙二醇、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸三溴苯酯及(甲基)丙烯酸三溴苯氧基乙酯等。Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclo(meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, (meth)acrylic acid Ethoxyethyl ester, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate , 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, (methyl) Diethylene glycol monomethyl acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, (A) Poly(ethylene glycol) monomethyl ether, (meth)acrylic acid polyethylene glycol Ether, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Dicyclopentenyloxyethyl ester, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate, dicyclopentyl (meth)acrylate Ester, tribromophenyl (meth)acrylate, and tribromophenoxyethyl (meth)acrylate.

巴豆酸酯類可舉出例如巴豆酸丁酯及巴豆酸己酯等。Examples of the crotonate include butyl crotonate and hexyl crotonate.

乙烯酯類可舉出例如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、甲氧基乙酸乙烯酯及苯甲酸乙烯酯等。Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, methoxyvinyl acetate, and vinyl benzoate.

順丁烯二酸二酯類可舉出例如順丁烯二酸二甲酯、順丁烯二酸二乙酯及順丁烯二酸二丁酯等。Examples of the maleic acid diester include dimethyl maleate, diethyl maleate, and dibutyl maleate.

反丁烯二酸二酯類可舉出例如反丁烯二酸二甲酯、反丁烯二酸二乙酯及反丁烯二酸二丁酯等。Examples of the fumaric acid diester include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

伊康酸二酯類可舉出例如伊康酸二甲酯、伊康酸二乙酯及伊康酸二丁酯等。Examples of the itonic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(甲基)丙烯醯胺類可舉出例如(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-環己基(甲基)丙烯醯胺、N-(2-甲氧基乙基)(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-苄基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉及二丙酮丙烯醯胺等。Examples of the (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (A). Base acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (Meth) acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl ( Methyl) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene hydrazino, diacetone acrylamide, and the like.

乙烯醚類可舉出例如甲基乙烯醚、丁基乙烯醚、己基乙烯醚及甲氧基乙基乙烯醚等。Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

苯乙烯類可舉出例如苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、羥基苯乙烯、甲氧基苯乙烯、丁氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、氯甲基苯乙烯、被能夠使用酸性物質來脫保護的基(例如t-Boc等)保護之羥基苯乙烯、乙烯基苯甲酸甲酯及α-甲基苯乙烯等。Examples of the styrene include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy group. Styrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, a group that can be deprotected using an acidic substance (eg t-Boc Etc.) Protected hydroxystyrene, methyl benzoate, and α-methylstyrene.

特定聚合物的分子量係以重量平均分子量(Mw)為1000～100000的範圍，且數量平均分子量(Mn)為400～50000的範圍為佳。以重量平均分子量(Mw)為5000～50000的範圍，且數量平均分子量(Mn)為2000～30000的範圍為更佳。The molecular weight of the specific polymer is preferably in the range of from 1,000 to 100,000 by weight average molecular weight (Mw), and preferably in the range of from 400 to 50,000 in the number average molecular weight (Mn). The weight average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is preferably in the range of 2,000 to 30,000.

特別是以重量平均分子量(Mw)在8000～30000的範圍、數量平均分子量(Mn)在4000～12000的範圍為最佳。In particular, the weight average molecular weight (Mw) is preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is preferably in the range of 4,000 to 12,000.

亦即，從有效地抑制顏料生成一次粒子凝集體亦即二次凝集體，或是有效地減弱二次凝集體的凝集力的觀點，特定聚合物的重量平均分子量(Mw)以1000以上為佳。又，從使用含有顏料分散組成物之光硬化性組成物來製造彩色濾光片之顯像性的觀點，特定聚合物的重量平均分子量(Mw)以30000以下為佳。That is, from the viewpoint of effectively suppressing the generation of the primary particle aggregate, that is, the secondary aggregate, or effectively reducing the cohesive force of the secondary aggregate, the weight average molecular weight (Mw) of the specific polymer is preferably 1,000 or more. . Moreover, from the viewpoint of producing a color filter using a photocurable composition containing a pigment dispersion composition, the weight average molecular weight (Mw) of the specific polymer is preferably 30,000 or less.

特定高分子化合物例如能夠藉由使用通式(1)所示之單體、聚合性低聚物(大分子單體)及作為共聚合成分之其他的自由基聚合性化合物，依照通常的自由基聚合法來製造。通常係使用懸浮聚合法或溶液聚合法等。合成此種特定高分子化合物時所使用的溶劑可舉出例如二氯乙烷、環己酮、甲基乙基酮、丙酮、甲醇、乙醇、丙醇、丁醇、乙二醇一甲基醚、乙二醇一乙基醚、2-甲氧基乙基乙酸酯、1-甲氧基-2-丙醇、1-甲氧基-2-丙基乙酸酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸、甲苯、乙酸乙酯、乳酸甲酯及乳酸乙酯等。該等的溶劑可以單獨或混合2種以上。The specific polymer compound can be used, for example, by using a monomer represented by the formula (1), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymer component, in accordance with a usual radical. Manufactured by polymerization. Usually, a suspension polymerization method, a solution polymerization method, or the like is used. The solvent used in the synthesis of such a specific polymer compound may, for example, be dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol or ethylene glycol monomethyl ether. , ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-di Methylformamide, N,N-dimethylacetamide, dimethyl hydrazine, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These solvents may be used alone or in combination of two or more.

自由基聚合時，能夠使用自由基聚合引發劑，又，能夠進而使用鏈轉移劑(例如，2-氫硫基乙醇或十二烷基硫醇(docecyl mercaptan)。In the case of radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (for example, 2-hydroxythioethanol or docecyl mercaptan) can be further used.

特定高分子化合物的含量係質量比以顏料：特定聚合物=1：0.1～1：2為佳，以1：0.2～1：1為較佳，以1：0.4～1：0.7為更佳。The content of the specific polymer compound is preferably a pigment: specific polymer = 1:0.1 to 1:2, more preferably 1:0.2 to 1:1, still more preferably 1:0.4 to 1:0.7.

特定高分子化合物係在該化合物中使羧基具有50毫克KOH/克以上為佳，以50～200毫克KOH/克的範圍為特佳。亦即，就抑制在顯像液中析出物的生成而言，羧基的含量係以50毫克KOH/克以上為佳。為了有效地抑制生成顏料生成一次粒子凝集體亦即二次凝集體，或是有效地減弱二次凝集體的凝集力，羧基的含量以50～200毫克KOH/克為佳。該羧基係例如作為具有上述酸基之單體中的酸基而含有在特定高分子化合物中。The specific polymer compound preferably has a carboxyl group of 50 mgKOH/g or more in the compound, and particularly preferably a range of 50 to 200 mgKOH/g. That is, in order to suppress the formation of precipitates in the developing solution, the content of the carboxyl group is preferably 50 mgKOH/g or more. In order to effectively suppress the formation of a pigment to form a primary aggregate, that is, a secondary aggregate, or to effectively attenuate the cohesive force of the secondary aggregate, the content of the carboxyl group is preferably from 50 to 200 mgKOH/g. The carboxyl group is contained in a specific polymer compound, for example, as an acid group in a monomer having the above acid group.

在此，本發明的加工顏料其特徵係使用iv)特定高分子化合物被覆有機顏料等的i)顏料粒子，且藉由該特定高分子化合物係堅固地被覆在顏料粒子表面的一部分或全部，來達成本發明的效果，與通常的高分子分散劑係吸附在顏料而構成者不同。該被覆狀態能夠藉由使用以下所示有機溶劑洗淨並測定特定高分子化合物的游離量(游離率)來確認。亦即，只是吸附在顏料粒子之特定高分子化合物使用有機溶劑洗淨時，其幾乎、具體上係65%為游離或被除去。另一方面，如本發明之表面被覆而成的加工顏料時，特定高分子化合物的游離率極小，為30%以下。Here, the processed pigment of the present invention is characterized in that i) pigment particles such as an organic pigment are coated with a specific polymer compound, and the specific polymer compound is strongly coated on a part or all of the surface of the pigment particle. The effect of the present invention is achieved, and it is different from a conventional polymer dispersant which is adsorbed to a pigment. This covered state can be confirmed by washing with the organic solvent shown below and measuring the free amount (free rate) of the specific polymer compound. That is, only when a specific polymer compound adsorbed on the pigment particles is washed with an organic solvent, it is almost, specifically, 65% free or removed. On the other hand, when the surface of the present invention is coated with a processed pigment, the liberation ratio of the specific polymer compound is extremely small, and is 30% or less.

使用1-甲氧基-2-丙醇洗淨本發明的加工顏料，並算出特定高分子化合物的游離量。首先，將10克加工顏料投入100毫升1-甲氧基-2-丙醇中，並使用振盪機在室溫使其振盪3小時。隨後使用離心分離機以80,000rpm、8小時使顏料沈降，並藉由乾燥法來求得上部澄清液部分的固體成分。求取從顏料游離之特定高分子化合物的質量，並從與初期處理所使用的特定高分子化合物的質量之比，來算出游離率(%)。The processed pigment of the present invention was washed with 1-methoxy-2-propanol, and the free amount of the specific polymer compound was calculated. First, 10 g of the processed pigment was placed in 100 ml of 1-methoxy-2-propanol, and shaken at room temperature for 3 hours using a shaker. Subsequently, the pigment was sedimented at 80,000 rpm for 8 hours using a centrifugal separator, and the solid content of the upper clear liquid portion was determined by a drying method. The liberation ratio (%) was calculated from the ratio of the mass of the specific polymer compound released from the pigment to the mass of the specific polymer compound used in the initial treatment.

市售品等的加工顏料之游離率能夠藉由以下的方法測定。亦即，使用溶解顏料的溶劑(例如二甲基亞碸、二甲基甲醯胺、甲酸、硫酸等)，將加工顏料全體溶解後，利用特定高分子化合物與顏料之溶解性的差異使用有機溶劑分離，以作為「初期處理所使用的特定高分子化合物的質量」的方式算出。另外，使用1-甲氧基-2-丙醇洗淨加工顏料，將所得到的游離量除以「初期處理所使用的特定高分子化合物的質量」來求取游離率(%)。The liberation ratio of the processed pigments, such as a commercial item, can be measured by the following methods. That is, using a solvent that dissolves the pigment (for example, dimethyl hydrazine, dimethylformamide, formic acid, sulfuric acid, etc.), the entire processed pigment is dissolved, and the difference between the solubility of the specific polymer compound and the pigment is used. Solvent separation was calculated as "the mass of the specific polymer compound used in the initial treatment". Further, the processed pigment was washed with 1-methoxy-2-propanol, and the obtained free amount was divided by "the mass of the specific polymer compound used in the initial treatment" to obtain the liberation ratio (%).

游離率越小對顏料的被覆率越高，分散性及分散安定性越良好。游離率之較佳範圍為30%以下，以20%以下為更佳，以15%以下為最佳，理想為0%。The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. The preferred range of the liberation ratio is 30% or less, more preferably 20% or less, and most preferably 15% or less, and desirably 0%.

又，亦可按照必要，除了上述特定高分子化合物以外，亦同時使用其他的化合物。其他的化合物較佳是在室溫為固體，水不溶性且必須是對在鹽磨時的潤濕劑所使用的水溶性有機溶劑為至少一部分可溶，例如可使用天然樹脂、改性天然樹脂、合成樹脂、以天然樹脂改性而成的合成樹脂等。Further, other compounds may be used in addition to the above specific polymer compound as necessary. Other compounds are preferably solid at room temperature, water insoluble and must be at least partially soluble in the water-soluble organic solvent used in the wetting agent during salt milling, for example, natural resins, modified natural resins, A synthetic resin or a synthetic resin modified with a natural resin.

使用乾燥後的處理顏料時，所使用的化合物以在室溫為固體為佳。天然樹脂的例子係以松香為代表，改性天然樹脂可舉出例如松香衍生物、纖維素衍生物、橡膠衍生物、蛋白衍生物及該等的低聚物。合成樹脂可舉出例如環氧樹脂、丙烯酸樹脂、順丁烯二酸樹脂、丁縮醛樹脂、聚酯樹脂、三聚氰胺樹脂、酚樹脂及聚胺基甲酸酯樹脂等。以天然樹脂改性而成的合成樹脂之例子可舉出松香改性順丁烯二酸樹脂及松香改性酚樹脂等。When the treated pigment after drying is used, the compound to be used is preferably a solid at room temperature. Examples of the natural resin are rosin, and examples of the modified natural resin include rosin derivatives, cellulose derivatives, rubber derivatives, protein derivatives, and the like. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of the synthetic resin modified with a natural resin include a rosin-modified maleic acid resin and a rosin-modified phenol resin.

合成樹脂可舉出例如聚醯胺胺(polyamideamine)及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、聚胺基甲酸酯、聚酯、聚(甲基)丙烯酸酯、(甲基)丙烯酸酯系共聚物及萘磺酸福馬林縮合物。The synthetic resin may, for example, be a polyamide amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a polyurethane, a polyester, a poly(meth)acrylate, Methyl) acrylate copolymer and naphthalenesulfonic acid formalin condensate.

如此進行所得到之本發明的加工顏料，其顏料表面係被特定高分子化合物堅固地被覆，且成為分散性優良的加工顏料，其應用範圍廣闊，特別是調製顏料分散組成物係有用的。The processed pigment of the present invention obtained in this manner is strongly coated with a specific polymer compound and is a processed pigment excellent in dispersibility, and has a wide range of applications, and is particularly useful for preparing a pigment dispersion composition.

顏料分散組成物Pigment dispersion composition

接著，說明使用前述本發明的加工顏料而成之本發明的顏料分散組成物。Next, a pigment dispersion composition of the present invention obtained by using the above-described processed pigment of the present invention will be described.

本發明的顏料分散組成物係將上述可舉出的加工顏料分散於有機溶劑中而構成。The pigment dispersion composition of the present invention is obtained by dispersing the above-mentioned processed pigment in an organic solvent.

又，將本發明的加工顏料分散在有機溶劑中時，按照必要適當地使用(A)顏料衍生物或(B)顏料分散劑亦是較佳態樣。Further, when the processed pigment of the present invention is dispersed in an organic solvent, it is also preferred to use (A) a pigment derivative or (B) a pigment dispersant as appropriate.

有機溶劑Organic solvents

在本發明的顏料分散組成物之溶劑，有機溶劑沒有特別限制，能夠從眾所周知者適當地選擇使用。可舉出例如乙酸1-甲氧基-2-丙酯、1-甲氧基-2-丙醇、乙二醇一甲基醚、乙二醇一乙基醚、丙二醇一甲基醚、丙二醇一乙基醚、二甘醇一甲基醚、乙二醇一乙基醚等的(聚)伸烷基二醇一烷基醚及該等的乙酸酯類；乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯等的乙酸酯類；苯、甲苯、二甲苯等的芳香族烴類；甲基乙基酮、丙酮、甲基異丁基酮、環己酮等的酮類；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、二甘醇、甘油等的醇類等。該等可單獨使用1種，亦可並用2種以上。該等之中，以伸烷基二醇一烷基醚類及其乙酸酯類、乙酸酯類、甲基乙基酮等為佳。In the solvent of the pigment dispersion composition of the present invention, the organic solvent is not particularly limited, and can be appropriately selected from those skilled in the art. For example, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol can be mentioned. (poly)alkylene glycol monoalkyl ethers such as monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like; ethyl acetate, n-propyl acetate Acetate such as isopropyl acetate, n-butyl acetate or isobutyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl ethyl ketone, acetone, methyl isobutyl ketone and ring A ketone such as ketone or the like; an alcohol such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol or glycerin. These may be used alone or in combination of two or more. Among these, alkylene glycol monoalkyl ethers and acetates thereof, acetates, methyl ethyl ketone and the like are preferred.

在顏料分散組成物之溶劑的含量係按照顏料分散組成物用途等而適當地選擇。顏料分散組成物係使用於後述之光硬化性組成物的調製時，從處理性的觀點，包含顏料及顏料分散劑之固體成分濃度可含有5～50質量%。The content of the solvent in the pigment dispersion composition is appropriately selected depending on the use of the pigment dispersion composition or the like. When the pigment dispersion composition is used in the preparation of a photocurable composition to be described later, the solid content concentration of the pigment and the pigment dispersant may be 5 to 50% by mass from the viewpoint of handleability.

(4)顏料衍生物(4) Pigment derivatives

在本發明的顏料分散組成物，能夠按照必要添加顏料衍生物。藉由使導入與分散劑具有親和性的部分或極性基而成之顏料衍生物吸附於加工顏料表面，並將其利用作為分散劑的吸附點，能夠使顏料以作為微細的粒子的方式而分散在光硬化性組成物中，且能夠防止其再凝集，而且對於構成對比高、透明性優良的彩色濾光片係有效的。In the pigment dispersion composition of the present invention, a pigment derivative can be added as necessary. By adsorbing a pigment derivative obtained by introducing a moiety having a affinity with a dispersant or a polar group to a surface of a process pigment, and using it as a site of adsorption of a dispersant, the pigment can be dispersed as fine particles. In the photocurable composition, it is possible to prevent re-aggregation, and it is effective for a color filter system which is excellent in contrast and excellent in transparency.

顏料衍生物係具體上以有機顏料作為母體骨架，且以酸性基、鹼性基或芳香族基作為取代基而導入至側鏈而成的化合物。有機顏料的具體例可舉出喹吖酮系顏料、酞菁系顏料、偶氮系顏料、喹啉黃系顏料、異吲哚滿系顏料、異吲哚滿酮系顏料、喹啉顏料、二酮吡咯并吡咯顏料及苯并咪唑酮顏料等。亦包含通常稱為色素之萘系、蒽醌系、三系、喹啉系等的淡黃色芳香族多環化合物。色素衍生物可使用在特開平11-49974號公報、特開平11-189732號公報、特開平10-245501號公報、特開2006-265528號公報、特開平8-295810號公報、特開平11-199796號公報、特開2005-234478號公報、特開2003-240938號公報、特開2001-356210號公報所記載者。The pigment derivative is a compound obtained by specifically introducing an organic pigment as a matrix skeleton and introducing an acid group, a basic group or an aromatic group as a substituent to a side chain. Specific examples of the organic pigment include a quinophthalone pigment, a phthalocyanine pigment, an azo pigment, a quinoline yellow pigment, an isoindane pigment, an isoindolinone pigment, a quinoline pigment, and Ketopyrrolopyrrole pigments and benzimidazolone pigments. Also contains naphthalene, lanthanide, and tris, commonly known as pigments. A pale yellow aromatic polycyclic compound such as a quinoline system. The pigment derivative can be used in JP-A-H11-49974, JP-A-H11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A No. 8-295810, and JP-A-11- The ones which are described in the publications of the Japanese Patent Publication No. Hei. No. 2001-356210.

在本發明之顏料衍生物的顏料分散組成物之含量，係相對於加工顏料的質量以1～30質量%為佳，以3～20質量%為更佳。該含量係在前述範圍內時，能夠邊降低黏度邊使分散良好地進行，同時能夠提升分散後的分散安定性，能夠得到高透明性且優良的色特性。The content of the pigment dispersion composition of the pigment derivative of the present invention is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, based on the mass of the processed pigment. When the content is within the above range, the dispersion can be favorably performed while reducing the viscosity, and the dispersion stability after dispersion can be improved, and high transparency and excellent color characteristics can be obtained.

分散能夠藉由例如將預先將顏料及分散劑混合且使用均化器等預先分散而成者，採用使用鋯珠等之珠粒分散機(例如GETZMANN公司製的DISPERMAT)等其微分散來進行。分散時間以3～6小時左右為佳。The dispersion can be carried out by, for example, preliminarily dispersing a pigment and a dispersant in advance, and using a homogenizer or the like, and using a microdispersion such as a bead disperser (for example, DISPERMAT manufactured by GETZMANN Co., Ltd.) using zirconium beads or the like. The dispersion time is preferably about 3 to 6 hours.

(B)顏料分散劑(B) Pigment Dispersant

為了更提升顏料的分散性之目的，亦可添加先前眾所周知的顏料分散劑或界面活性劑等分散劑或其他成分。In order to further enhance the dispersibility of the pigment, a previously known dispersant or other component such as a pigment dispersant or a surfactant may be added.

眾所周知的分散劑(顏料分散劑)可舉出例如高分子分散劑[例如聚醯胺胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、改性聚胺基甲酸酯、改性聚酯、改性聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物、萘磺酸福馬林縮合物]、及聚氧乙烯烷基磷酸酯、聚氧乙烯烷基胺及烷醇胺、顏料衍生物等。As a known dispersant (pigment dispersant), for example, a polymer dispersant [for example, polyamidoamine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, Modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine and alkane Alcohol amines, pigment derivatives, and the like.

高分子分散劑能夠從其結構而分類為直鏈狀高分子、末端改性型高分子、椄枝(graft)型高分子及嵌段(block)型高分子。The polymer dispersant can be classified into a linear polymer, a terminal modified polymer, a graft type polymer, and a block type polymer from the structure thereof.

高分子分散劑之作用係吸附在顏料表面，來防止再凝集。因此，可舉出的較佳結構有對顏料表面具有錨(anchor)部位之末端改性型高分子、接枝型高分子、或是嵌段型高分子。另一方面，藉由顏料衍生物將顏料表面改性，具有促進高分子分散劑的吸附之效果。The action of the polymeric dispersant is adsorbed on the surface of the pigment to prevent re-aggregation. Therefore, a preferred structure may be a terminal-modified polymer having an anchor portion on the surface of the pigment, a graft polymer, or a block polymer. On the other hand, the surface of the pigment is modified by the pigment derivative to have an effect of promoting adsorption of the polymer dispersant.

嵌段型高分子Block polymer

嵌段型高分子的例子沒有特別限定，可舉出由吸附顏料嵌段及未吸附顏料嵌段所構成之嵌段型高分子。The example of the block type polymer is not particularly limited, and examples thereof include a block type polymer composed of an adsorbed pigment block and an unadsorbed pigment block.

構成吸附顏料嵌段之單體的例子沒有特別限制，可舉出例如具有能夠吸附顏料的官能基之單體。具體例可舉出具有有機色素結構或雜環結構之單體、具有酸性基之單體及具有鹼性基之單體等。The example of the monomer constituting the adsorbed pigment block is not particularly limited, and examples thereof include a monomer having a functional group capable of adsorbing a pigment. Specific examples thereof include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic group.

具有有機色素結構或雜環結構之單體可舉出例如酞菁系、不溶性偶氮系、可溶性偶氮(azolake)系、蒽醌系、喹吖酮系、二(dioxazine)系、二酮吡咯并吡咯系、氮染蒽(anthrapyridine)系、蒽嵌蒽醌(anthanthron)系、標準還原藍(indanethrone)系、黃蒽酮(flavanthrone)、紫環酮(perinone)、苝(perylene)系、硫靛藍(thioindigo)系的色素結構，或例如噻吩(thiophene)、呋喃、呫噸(xanthene)、吡咯、吡咯啉(pyrroline)、吡咯啶(pyrrolidine)、二氧雜戊環(dioxolan)、吡唑(pyrazole)、吡唑啉、吡唑啶、咪唑、唑、噻唑、二唑、***、噻二唑、吡喃(pyrane)、吡啶、哌啶(piperidine)、二烷、嗎啉(morpholine)、嗒、嘧啶、哌、三、三聚甲硫醛(trithiane)、異吲哚滿、異吲哚滿酮、苯并咪唑、苯并噻唑、琥珀醯亞胺(succinimide)、酞醯亞胺、萘醯亞胺、海因(hydantoin)、吲哚、喹啉、咔唑、吖啶、吖啶酮及蒽醌等具有雜環結構之單體。更具體地，沒有特別限制，可舉出以下結構之單體。Examples of the monomer having an organic dye structure or a heterocyclic structure include a phthalocyanine system, an insoluble azo system, a soluble azolake system, an anthraquinone system, and a quinacridone system. (dioxazine), diketopyrrolopyrrole, anthrapyridine, anthanthron, standard indanethrone, flavanthrone, perinone , perylene, thioindigo-based pigment structure, or, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxane Ring (dioxolan), pyrazole, pyrazoline, pyrazole, imidazole, Oxazole, thiazole, Diazole, triazole, thiadiazole, pyran, pyridine, piperididine, two Alkane, morpholine, 嗒 Pyrimidine, piperazine ,three , trithiane, isoindane, isoindanone, benzimidazole, benzothiazole, succinimide, quinone imine, naphthyl imine, hydanto A monomer having a heterocyclic structure such as hydantoin), hydrazine, quinoline, carbazole, acridine, acridone, and anthracene. More specifically, it is not particularly limited, and a monomer having the following structure can be mentioned.

具有酸性基之單體可舉出例如具有羧基之乙烯系單體、具有磺酸基之乙烯系單體、具有磷酸基之乙烯系單體、具有鹼性氮原子之單體及其他單體。Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, a vinyl monomer having a phosphoric acid group, a monomer having a basic nitrogen atom, and another monomer.

具有羧基之乙烯系單體可舉出例如(甲基)丙烯酸、乙烯基苯甲酸、順丁烯二酸、順丁烯二酸一烷酯、反丁烯二酸、伊康酸(itacon acid)、巴豆酸(crotonic acid)、桂皮酸(cinnamic acid)及丙烯酸二聚物等。又，亦可利用(甲基)丙烯酸2-羥基乙酯等具有羥基的單體與如順丁烯二酸酐、酞酸酐、或環己烷二羧酸酐的環狀酐之加成反應物、或ω-羧基一聚己內酯一(甲基)丙烯酸酯等。又，亦可使用順丁烯二酸酐、伊康酸酐、檸康酸酐等含酐單體作為羧基的先質。又，該等之中，從共聚合性或成本的觀點，以(甲基)丙烯酸為特佳。Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, and itaconic acid. , Crotonic acid, cinnamic acid and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, decanoic anhydride or cyclohexanedicarboxylic anhydride may be used, or Ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of a carboxyl group. Further, among these, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability and cost.

又，具有磺酸基之乙烯系單體可舉出例如2-丙烯醯胺-2-甲基丙烷磺酸等。具有磷酸基之乙烯系單體可舉出例如磷酸一(2-丙烯醯氧基乙酯)及磷酸一(1-甲基-2-丙烯醯氧基乙酯)等。Further, examples of the vinyl monomer having a sulfonic acid group include 2-propenylamine-2-methylpropanesulfonic acid. Examples of the vinyl monomer having a phosphoric acid group include mono(2-propenyloxyethyl) phosphate and mono(1-methyl-2-propenyloxyethyl phosphate).

具有鹼性氮原子之單體的例子，具有雜環的單體可舉出乙烯基吡啶(vinyl pyridine)、乙烯基咪唑、乙烯基***等；(甲基)丙烯酸酯可舉出(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯、(甲基)丙烯酸1-(N,N-二甲胺基)-1,1-一甲基甲酯、(甲基)丙烯酸N,N-二甲胺基己酯、(甲基)丙烯酸N,N-二乙胺基乙酯、(甲基)丙烯酸N,N-二異丙基胺基乙酯、(甲基)丙烯酸N,N-二正丁基胺基乙酯、(甲基)丙烯酸N,N-二異丁基胺基乙酯、(甲基)丙烯酸嗎啉乙酯、(甲基)丙烯酸哌啶基乙酯、(甲基)丙烯酸1-吡咯啶基乙酯、(甲基)丙烯酸N,N-甲基-2-吡咯啶基胺基乙酯及(甲基)丙烯酸N,N-甲基苯胺基乙基等；(甲基)丙烯醯胺類可舉出N-(N’,N’-二甲胺基乙基)丙烯醯胺、N-(N’,N’-二甲胺基乙基)甲基丙烯醯胺、N-(N’,N’-二乙胺基乙基)丙烯醯胺、N-(N’,N’-二乙胺基乙基)甲基丙烯醯胺、N-(N’,N’-二甲胺基丙基)丙烯醯胺、N-(N’,N’-二甲胺基丙基)甲基丙烯醯胺、N-(N’,N’-二乙胺基丙基)丙烯醯胺、N-(N’,N’-二乙胺基丙基)甲基丙烯醯胺、2-(N,N-二甲胺基)乙基(甲基)丙烯醯胺、2-(N,N-二乙胺基)乙基(甲基)丙烯醯胺、3-(N,N-二乙胺基)丙基(甲基)丙烯醯胺、3-(N,N-二甲胺基)丙基(甲基)丙烯醯胺、1-(N，N-二甲胺基)-1,1-二甲基甲基(甲基)丙烯醯胺、6-(N,N-二乙胺基)己基(甲基)丙烯醯胺、嗎啉(甲基)丙烯醯胺、哌啶基(甲基)丙烯醯胺、N-甲基-2-吡咯啶基(甲基)丙烯醯胺等；苯乙烯類可舉出N,N-二甲胺基苯乙烯、N,N-二甲胺基甲基苯乙烯等。Examples of the monomer having a basic nitrogen atom, and a monomer having a hetero ring may, for example, be vinyl pyridine, vinyl imidazole or vinyltriazole; and a (meth) acrylate may be exemplified (methyl) N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl (meth)acrylate, 1-(N,N-dimethylamino)-1,1 (meth)acrylate -monomethylmethyl ester, N,N-dimethylaminohexyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-di(meth)acrylate Propylaminoethyl ester, N,N-di-n-butylaminoethyl (meth)acrylate, N,N-diisobutylaminoethyl (meth)acrylate, morpholine (meth)acrylate Ethyl ester, piperidinyl (meth) acrylate, 1-pyrrolidinyl (meth) acrylate, N, N-methyl-2-pyrrolidinoethyl (meth) acrylate and N,N-methylanilinoethyl, etc.; (meth) acrylamide: N-(N',N'-dimethylaminoethyl) acrylamide, N-( N',N'-dimethylaminoethyl)methacrylamide, N-(N',N'-diethylaminoethyl) decylamine, N-(N',N'-diethyl Aminoethyl)methacrylamide, N-(N',N -dimethylaminopropyl)acrylamide, N-(N',N'-dimethylaminopropyl)methacrylamide, N-(N',N'-diethylaminopropyl) Acrylamide, N-(N',N'-diethylaminopropyl)methacrylamide, 2-(N,N-dimethylamino)ethyl(meth)acrylamide, 2- (N,N-diethylamino)ethyl(meth)acrylamide, 3-(N,N-diethylamino)propyl(meth)acrylamide, 3-(N,N-di Methylamino)propyl (meth) acrylamide, 1-(N,N-dimethylamino)-1,1-dimethylmethyl(meth) acrylamide, 6-(N,N -diethylamino)hexyl (meth) acrylamide, morpholine (meth) acrylamide, piperidinyl (meth) acrylamide, N-methyl-2-pyrrolidinyl (methyl) Examples of the styrenes include N,N-dimethylaminostyrene and N,N-dimethylaminomethylstyrene.

又，亦可使用具有脲基、胺基甲酸酯基、具有配位性氧原子且碳數為4以上之烴基、烷氧基矽烷基、環氧基、異氰酸酯基或羥基之單體。具體例可舉出以下結構的單體。Further, a monomer having a ureido group, a urethane group, a hydrocarbon group having a coordinating oxygen atom and having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group or a hydroxyl group can also be used. Specific examples include monomers having the following structures.

而且，能夠利用含有離子性官能基之單體。離子性乙烯系單體(亦即，陰離子性乙烯系單體及陽離子性乙烯系單體)的例子，陰離子性乙烯系單體可舉出具有前述酸性基之乙烯系單體的鹼金屬鹽及該乙烯系單體與有機胺(例如，三乙胺、二甲胺基乙醇等的3級胺)之鹽等，陽離子性乙烯系單體可舉出將前述含氮之乙烯單位藉由烷基鹵化物(烷基：C1～18、鹵素原子：氯原子、溴原子或碘原子)、苄基氯或是苄基溴等的苄基鹵化物、甲磺酸等的烷基磺酸酯(烷基：C1～18)、苯磺酸或甲苯磺酸等的芳基磺酸烷酯(烷基：C1～18)、或硫酸二烷酯(烷基：C1～4)等使其4級化而成者，及二烷基二烯丙銨鹽等。Further, a monomer having an ionic functional group can be utilized. Examples of the ionic vinyl monomer (that is, an anionic vinyl monomer and a cationic vinyl monomer), and the anionic vinyl monomer may, for example, be an alkali metal salt of a vinyl monomer having the above acidic group. a salt of the vinyl monomer and an organic amine (for example, a tertiary amine such as triethylamine or dimethylaminoethanol), and the cationic vinyl monomer may be an alkyl group having the nitrogen-containing ethylene unit. a halide (alkyl: C1 to 18, a halogen atom: a chlorine atom, a bromine atom or an iodine atom), a benzyl halide such as benzyl chloride or benzyl bromide, or an alkylsulfonate of methanesulfonic acid or the like (alkane) Base: C1 to 18), an alkyl sulfonate such as benzenesulfonic acid or toluenesulfonic acid (alkyl: C1 to 18), or a dialkyl sulfate (alkyl: C1 to 4), etc. The original, and the dialkyl diallylammonium salt and the like.

具有能夠吸附於顏料的官能基之單體，能夠按照分散顏料的種類而適當地選擇，該等可單獨使用，亦可並用2種以上。The monomer having a functional group capable of being adsorbed to the pigment can be appropriately selected depending on the type of the dispersed pigment, and these may be used alone or in combination of two or more.

構成未吸附於顏料的嵌段之單體的例子沒有特別限制，可舉出例如(甲基)丙烯酸酯類、巴豆酸酯類、乙烯酯類、順丁烯二酸二酯類、反丁烯二酸二酯類、伊康酸二酯類、(甲基)丙烯醯胺類、苯乙烯類、乙烯醚類、乙烯基甲酮類、烯烴類、順丁烯二醯亞胺類及(甲基)丙烯腈類等。該等單體可單獨使用，亦可並用2種以上。應用在必須鹼顯像處理的顏料分散組成物(著色感光性組成物)時，亦可並用構成上述未吸附於顏料的嵌段之單體及具有酸性基之乙烯系單體。Examples of the monomer constituting the block which is not adsorbed to the pigment are not particularly limited, and examples thereof include (meth) acrylates, crotonates, vinyl esters, maleic acid diesters, and antibutene. Diacid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimide and (a) Base) acrylonitrile and the like. These monomers may be used singly or in combination of two or more. When a pigment dispersion composition (coloring photosensitive composition) which requires alkali imaging treatment is used, a monomer constituting the above-mentioned block which is not adsorbed to the pigment and a vinyl monomer having an acidic group may be used in combination.

(甲基)丙烯酸酯類的例子可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸第三辛酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸乙醯氧基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙酯、(甲基)丙烯酸2-氯乙酯、(甲基)丙烯酸乙烯酯、(甲基)丙烯酸2-苯基乙烯酯、(甲基)丙烯酸1-丙烯酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-烯丙氧基乙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二甘醇一甲基醚、(甲基)丙烯酸二甘醇一乙基醚、(甲基)丙烯酸三甘醇一甲基醚、(甲基)丙烯酸三甘醇一乙基醚、(甲基)丙烯酸聚乙二醇一甲基醚、(甲基)丙烯酸聚乙二醇一乙基醚、(甲基)丙烯酸β-苯氧基乙氧基乙酯、(甲基)丙烯酸壬基苯氧基聚乙二醇酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸三溴苯氧基乙酯及(甲基)丙烯酸γ-丁內酯等。Examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, Tert-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylic acid Octacol ester, ethoxylated ethyl (meth) acrylate, phenyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (A) 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, vinyl (meth)acrylate, 2-Phenylvinyl (meth)acrylate, 1-propenyl (meth)acrylate, allyl (meth)acrylate, 2-allyloxyethyl (meth)acrylate, (meth)acrylic acid Propargyl propyl ester, benzyl (meth) acrylate, diethylene glycol (meth) acrylate Ether, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, poly(ethylene) (meth)acrylate Alcohol monomethyl ether, polyethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate Ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, (methyl) ) perfluorooctyl ethyl acrylate, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate and γ-butyl (meth)acrylate Lactones, etc.

巴豆酸酯類可舉出例如巴豆酸丁酯及巴豆酸己酯等。乙烯酯類可舉出例如乙酸乙烯酯、氯乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、甲氧基乙酸乙烯酯及苯甲酸乙烯酯等。Examples of the crotonate include butyl crotonate and hexyl crotonate. Examples of the vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.

順丁烯二酸二酯類可舉出例如順丁烯二酸二甲酯、順丁烯二酸二乙酯及順丁烯二酸二丁酯等。Examples of the maleic acid diester include dimethyl maleate, diethyl maleate, and dibutyl maleate.

反丁烯二酸二酯類可舉出例如反丁烯二酸二甲酯、反丁烯二酸二乙酯及反丁烯二酸二丁酯等。Examples of the fumaric acid diester include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

伊康酸二酯類可舉出例如伊康酸二甲酯、伊康酸二乙酯及伊康酸二丁酯等。Examples of the itonic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(甲基)丙烯醯胺類可舉出例如(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-環己基(甲基)丙烯醯胺、N-(2-甲氧基乙基)(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-硝基苯基丙烯醯胺、N-乙基-N-苯基丙烯醯胺、N-苄基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、二丙酮丙烯醯胺、N-羥甲基丙烯醯胺、N-羥乙基丙烯醯胺、乙烯基(甲基)丙烯醯胺、N,N-二烯丙基(甲基)丙烯醯胺及N-烯丙基(甲基)丙烯醯胺等。Examples of the (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (A). Base acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (Meth) acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl ( Methyl) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (methyl) Acrylamide, (meth) propylene decylmorpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N-diallyl (meth) acrylamide and N-allyl (meth) acrylamide.

苯乙烯類可舉出例如苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、羥基苯乙烯、甲氧基苯乙烯、丁氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、氯甲基苯乙烯、被能夠使用酸性物質來脫保護的基(例如t-Boc等)保護之羥基苯乙烯、乙烯基苯甲酸甲酯及α-甲基苯乙烯等。Examples of the styrene include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy group. Styrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, a group that can be deprotected using an acidic substance (eg t-Boc Etc.) Protected hydroxystyrene, methyl benzoate, and α-methylstyrene.

乙烯醚類的例子可舉出例如甲基乙烯醚、乙基乙烯醚、2-氯乙基乙烯醚、羥乙基乙烯醚、丙基乙烯醚、丁基乙烯醚、己基乙烯醚、辛基乙烯醚、甲氧基乙基乙烯醚及苯基乙烯醚等。Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and octyl ethylene. Ether, methoxyethyl vinyl ether and phenyl vinyl ether.

乙烯基甲酮類可舉出例如甲基乙烯基甲酮、乙基乙烯基甲酮、丙基乙烯基甲酮及苯基乙烯基甲酮等。Examples of the vinyl ketone include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

烯烴類可舉出例如乙烯、丙烯、異丁烯、丁二烯及異戊二烯(isoprene)等。Examples of the olefins include ethylene, propylene, isobutylene, butadiene, and isoprene.

順丁烯二醯亞胺類可舉出例如順丁烯二醯亞胺、丁基順丁烯二醯亞胺、環己基順丁烯二醯亞胺及苯基順丁烯二醯亞胺等。Examples of the maleimide group include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

(甲基)丙烯腈的例子可舉出甲基丙烯腈及丙烯腈等。具有前述酸性基之乙烯系單體可舉出例如具有羧基之乙烯系單體、具有磺酸基之乙烯系單體及具有磷酸基之乙烯系單體等。Examples of (meth)acrylonitrile include methacrylonitrile and acrylonitrile. The vinyl monomer having the acidic group may, for example, be a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphoric acid group.

具有羧基之乙烯系單體可舉出例如(甲基)丙烯酸、乙烯基苯甲酸、順丁烯二酸、順丁烯二酸一烷酯、反丁烯二酸、伊康酸、巴豆酸、桂皮酸及丙烯酸二聚物等。又，亦可利用(甲基)丙烯酸2-羥基乙酯等具有羥基的單體與如順丁烯二酸酐、酞酸酐、或環己烷二羧酸酐的環狀酐之加成反應物、或ω-羧基一聚己內酯一(甲基)丙烯酸酯等。又，亦可使用順丁烯二酸酐、伊康酸酐、檸康酸酐等含酐單體作為羧基的先質。又，該等之中，從共聚合性或成本的觀點，以(甲基)丙烯酸為特佳。Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, and crotonic acid. Cinnamic acid and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, decanoic anhydride or cyclohexanedicarboxylic anhydride may be used, or Ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of a carboxyl group. Further, among these, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability and cost.

又，具有磺酸基之乙烯系單體可舉出例如2-丙烯醯胺-2-甲基丙烷磺酸等，具有磷酸基之乙烯系單體可舉出例如磷酸一(2-丙烯醯氧基乙酯)及磷酸一(1-甲基-2-丙烯醯氧基乙酯)等。Further, examples of the vinyl-based monomer having a sulfonic acid group include 2-propenylamine-2-methylpropanesulfonic acid, and the vinyl-based monomer having a phosphoric acid group is, for example, phosphoric acid mono(2-propene oxide). Ethyl ethyl ester) and mono(1-methyl-2-propenyloxyethyl) phosphate.

而且，具有酸性基之乙烯系單體可舉出例如含有酚性羥基之乙烯系單體或含有磺醯胺基之乙烯系單體等。In addition, examples of the vinyl monomer having an acidic group include a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group.

得到本發明之嵌段型高分子之方法能夠利用先前眾所周知的方法。可舉出例如活性聚合(living polymerization)、引發轉移終止劑(iniferter)法等。而且，其他方法亦可舉出在將具有顏料吸附基的單體或未具有顏料吸附基的單體進行自由基聚合時，使硫醇羧酸或2-乙醯基乙硫醚、10-乙醯基硫代癸烷硫醇等在分子內含有硫酯及硫醇基之化合物共存而進行聚合來得到聚合物，將該得到的聚合物使用氫氧化鈉或氨等的鹼進行處理而成為在一末端具有硫醇基之聚合物，並在所得到之一末端具有硫醇基之聚合物的存在下，使另一方的嵌段的單體成分進行自由基聚合之方法。此等之中，以活性聚合為佳。The method of obtaining the block type polymer of the present invention can utilize a previously known method. For example, living polymerization, an intermerator method, and the like can be mentioned. Further, in other methods, when a monomer having a pigment adsorption group or a monomer having no pigment adsorption group is subjected to radical polymerization, a thiol carboxylic acid or 2-ethyl thioethyl sulfide, 10-B is used. A compound containing a thioester and a thiol group in a molecule is coexisted and polymerized to obtain a polymer, and the obtained polymer is treated with a base such as sodium hydroxide or ammonia to be A method in which a polymer having a thiol group at one end and a monomer component having the other block are subjected to radical polymerization in the presence of a polymer having a thiol group at one end. Among these, living polymerization is preferred.

嵌段型高分子的重量平均分子量沒有特別限制，以3,000～100,000的範圍為佳，以5,000～50,000的範圍為更佳。重量平均分子量為3,000以上時，能夠更有效地得到安定化效果，又，重量平均分子量100,000以下時，能夠更有效地吸附而發揮良好的分散性。The weight average molecular weight of the block type polymer is not particularly limited, and is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, the stabilization effect can be more effectively obtained, and when the weight average molecular weight is 100,000 or less, it can be more effectively adsorbed and exhibits good dispersibility.

嵌段型高分子亦可利用市售品。其具體例可舉出Disperbyk-2000、同-2001(以上BYK-Chemie公司製)、EFKA4330、同4340(以上EFKA公司製)等。Commercially available products can also be used as the block type polymer. Specific examples thereof include Disperbyk-2000, Tong-2001 (manufactured by BYK-Chemie Co., Ltd.), EFKA 4330, and 4340 (manufactured by EFKA Co., Ltd.).

接枝型高分子Grafted polymer

接枝型高分子沒有特別限制，可適合舉出特開昭54-37082號公報、特開昭61-174939號公報等所記載之使聚伸烷基亞胺與聚酯化合物反應而成之化合物、特開平9-169821號公報所記載之使用聚酯將聚烯丙胺的側鏈胺基改性而成之化合物，特開昭60-166318號公報所記載之聚酯型多元醇加成聚胺基甲酸酯等，而且可適合舉出特開平9-171253號公報或大分子單體的化學與工業(Chemistry and Industry of Macromonomer)(IPC出版部(Industrial Publishing & Consulting,Inc.)1989年)等所記載之將聚合性低聚物(以下稱為大分子單體)作為共聚合成分之接枝型高分子。The graft-type polymer is not particularly limited, and a compound obtained by reacting a polyalkyleneimine with a polyester compound described in JP-A-54-37092, JP-A-61-174939, and the like can be used. A compound obtained by modifying a side chain amine group of polyallylamine using a polyester described in JP-A-H09-166821, and a polyester polyol addition polyamine described in JP-A-60-166318 A carboxylic acid ester or the like, and is exemplified by the Japanese Patent Laid-Open No. Hei 9-171253 or the Chemistry and Industry of Macromonomer (Industrial Publishing & Consulting, Inc., 1989). A graft type polymer in which a polymerizable oligomer (hereinafter referred to as a macromonomer) is used as a copolymerization component as described above.

接枝型高分子的枝部之例子可適合舉出聚苯乙烯、聚環氧乙烷、聚環氧丙烷、聚(甲基)丙烯酸酯及聚己內酯等，以在枝部至少具有下述通式(2)所示之構成單位之接枝型高分子為更佳。Examples of the branch of the graft type polymer may, for example, be polystyrene, polyethylene oxide, polypropylene oxide, poly(meth)acrylate, polycaprolactone or the like to have at least a branch. The graft type polymer of the constituent unit represented by the above formula (2) is more preferable.

通式(2)中，R74 係表示氫原子或碳原子數1～8的烷基，Q係表示氰基、碳原子數6～30的芳基、或-COOR75 (在此，R75 係表示氫原子、碳原子數1～22的烷基、或碳原子數6～30的芳基。In the formula (2), R 74 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Q represents a cyano group, an aryl group having 6 to 30 carbon atoms, or -COOR 75 (here, R 75) It is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

通式(2)中，R74 所表示的烷基亦可具有取代基，以碳原子數1～6的烷基為佳，以甲基為特佳。烷基的取代基之例子可舉出鹵素原子、羧基、烷氧基羰基、烷氧基等。此種烷基的具體例可舉出甲基、乙基、己基、辛基、三氟甲基、羧甲基及甲氧基羰基甲基等。此種R74 之中，以氫原子、甲基為佳。In the formula (2), the alkyl group represented by R 74 may have a substituent, and is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group. Examples of the substituent of the alkyl group include a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group and the like. Specific examples of such an alkyl group include a methyl group, an ethyl group, a hexyl group, an octyl group, a trifluoromethyl group, a carboxymethyl group, and a methoxycarbonylmethyl group. Among such R 74 , a hydrogen atom or a methyl group is preferred.

通式(2)中，Q所表示的芳基亦可具有取代基，以碳原子數6～20的芳基為佳，以碳原子數6～12的芳基為特佳。芳基的取代基之例子可舉出鹵素原子、烷基、烷氧基、烷氧基羰基等。此種芳基的具體例可舉出苯基、萘基、甲苯基、二甲苯基、丙基苯基、丁基苯基、辛基苯基、十二烷基苯基、甲氧基苯基、乙氧基苯基、丁氧基苯基、十二烷氧基苯基、氯苯基、二氯苯基、溴苯基、甲氧基羰基苯基、乙氧基羰基苯基及丁氧基羰基苯基等。此種芳基之中，以未取代芳基或被鹵素原子、烷基、或烷氧基取代而成的芳基為佳，以未取代芳基或被烷基取代而成的芳基為特佳。In the general formula (2), the aryl group represented by Q may have a substituent, and an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is particularly preferred. Examples of the substituent of the aryl group include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and the like. Specific examples of such an aryl group include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a propylphenyl group, a butylphenyl group, an octylphenyl group, a dodecylphenyl group, and a methoxyphenyl group. , ethoxyphenyl, butoxyphenyl, dodecyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl and butoxy Alkylcarbonylphenyl and the like. Among such aryl groups, an aryl group which is unsubstituted aryl or substituted by a halogen atom, an alkyl group or an alkoxy group is preferred, and an aryl group which is unsubstituted aryl or substituted by an alkyl group is particularly good.

通式(2)的Q所示之-COOR75 中的R75 所示之烷基亦可具有取代基，以碳原子數1～12的烷基為佳，以碳原子數1～8的烷基為特佳。烷基的取代基之例子可舉出鹵素原子、烯基、芳基、羥基、烷氧基、烷氧基羰基、胺基、醯胺基及胺基甲醯基等。此種烷基的具體例可舉出甲基、乙基、丙基、丁基、庚基、己基、辛基、癸基、十二基、十三基、十四基、十六基、十八基、2-氯乙基、2-溴乙基、2-甲氧基羰基乙基、2-甲氧基乙基、2-溴丙基、2-丁烯基、2-戊烯基、3-甲基-2-戊烯基、2-己烯基、4-甲基-2-己烯基、苄基、苯乙(phenethyl)基、3-苯基丙基、萘甲基、2-萘乙基、氯苄基、溴苄基、甲苄基、乙苄基、甲氧基苄基、二甲基苄基、二甲氧基苄基、環己基、2-環己基乙基、2-環戊基乙基、雙環[3.2.1]辛-2-基、1-金剛烷(1-admantyl)基、二甲胺基丙基、乙醯胺基乙基及N,N-二丁胺基胺基甲醯基甲基等。此種烷基之中，以未取代烷基、或鹵素原子、芳基、或是亦可被羥基取代之烷基為佳，以未取代基為特佳。The alkyl group represented by R 75 in -COOR 75 represented by Q in the general formula (2) may have a substituent, preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. The base is especially good. Examples of the substituent of the alkyl group include a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amine group, a decylamino group, and an aminomethyl fluorenyl group. Specific examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a thirteen group, a tetradecyl group, a hexadecyl group, and a decyl group. Octa, 2-chloroethyl, 2-bromoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, 2-bromopropyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 2-hexenyl, 4-methyl-2-hexenyl, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2 -naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl, dimethoxybenzyl, cyclohexyl, 2-cyclohexylethyl, 2-cyclopentylethyl, bicyclo[3.2.1]oct-2-yl, 1-adamantyl, dimethylaminopropyl, ethylaminoethyl and N,N-di Butylaminomethylmercaptomethyl and the like. Among such alkyl groups, an unsubstituted alkyl group, a halogen atom, an aryl group or an alkyl group which may be substituted by a hydroxyl group is preferred, and an unsubstituted group is particularly preferred.

通式(2)的Q所示之-COOR75 中的R75 所示之芳基亦可具有取代基，以碳原子數6～20的芳基為佳，以碳原子數6～12的芳基為特佳。芳基的取代基可舉出例如鹵素原子、烷基、烯基、烷氧基、烷氧基羰基及醯胺等。此種芳基的具體例可舉出苯基、萘基、甲苯基、二甲苯基、丙基苯基、丁基苯基、辛基苯基、十二基苯基、甲氧基苯基、乙氧基苯基、丁氧基苯基、癸氧基苯基、氯苯基、二氯苯基、溴苯基、甲氧基羰基苯基、乙氧基羰基苯基、丁氧基羰基苯基、乙醯胺基苯基、丙醯胺基苯基及十二烷醯胺苯基等。此種芳基之中，以未取代芳基、或被鹵素原子、烷基、或烷氧基取代的芳基為佳，以被烷基取代的芳基為佳。The aryl group represented by R 75 in -COOR 75 represented by Q in the general formula (2) may have a substituent, preferably an aryl group having 6 to 20 carbon atoms, and an aromatic group having 6 to 12 carbon atoms. The base is especially good. The substituent of the aryl group may, for example, be a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group or a decylamine. Specific examples of such an aryl group include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a propylphenyl group, a butylphenyl group, an octylphenyl group, a dodecylphenyl group, and a methoxyphenyl group. Ethoxyphenyl, butoxyphenyl, nonyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylbenzene Base, acetaminophen phenyl, acrylamidophenyl and dodecyl decyl phenyl. Among such aryl groups, an unsubstituted aryl group or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group is preferred, and an aryl group substituted with an alkyl group is preferred.

此種R75 之中，以氫原子、碳原子數1～22的烷基為佳，以氫原子、碳原子數1～12的烷基為佳。Among such R 75 , a hydrogen atom or an alkyl group having 1 to 22 carbon atoms is preferred, and a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferred.

在枝部具有至少此種通式(2)所示構成單位之接枝型高分子的枝部具體例，可舉出聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸甲酯與(甲基)丙烯酸苄酯之共聚物、(甲基)丙烯酸甲酯與苯乙烯之共聚物、(甲基)丙烯酸甲酯與(甲基)丙烯酸之共聚物、(甲基)丙烯酸甲酯與丙烯腈之共聚物等。Specific examples of the branch portion of the graft type polymer having at least the constituent unit represented by the above formula (2) in the branch portion include methyl (meth) acrylate and n-butyl (meth) acrylate. Isobutyl (meth)acrylate, copolymer of methyl (meth)acrylate and benzyl (meth)acrylate, copolymer of methyl (meth)acrylate and styrene, methyl (meth)acrylate and A copolymer of (meth)acrylic acid, a copolymer of methyl (meth)acrylate and acrylonitrile, and the like.

合成在枝部具有至少通式(2)所示構成單位之接枝型高分子亦可使用眾所周知的方法。A well-known method can also be used for synthesizing a graft type polymer having a constituent unit represented by the formula (2) in the branch portion.

具體上，可舉出具有至少通式(2)所示構成單位之大分子單體、和能夠與該大分子單體共聚合的乙烯性不飽和單體進行共聚合。Specifically, a macromonomer having at least a structural unit represented by the formula (2) and an ethylenically unsaturated monomer copolymerizable with the macromonomer may be copolymerized.

具有至少通式(2)所示構成單位之大分子單體之中，以下述通式(3)所示者為佳。Among the macromonomers having at least the structural unit represented by the formula (2), those represented by the following formula (3) are preferred.

通式(3)中，R76 係表示氫原子或碳原子數1～8的烷基，W係表示單鍵或選目In the formula (3), R 76 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W represents a single bond or a selection.

(Z1 及Z2 係各目獨立地表示氫原子、鹵素原子、碳原子數1～6的烷基、氰基或羥基，Z3 係表示氫原子、碳原子敷1～18的烷基，或碳原子數6～20的芳基)等的原子團之單獨的連結基或任意的組合所構成之達結基，A係表示至少具有前述通式(2)所示構成單位之基。(Z 1 and Z 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group or a hydroxyl group, and Z 3 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. A single linking group or an arbitrary combination of atomic groups such as an aryl group having 6 to 20 carbon atoms may be used as a substituent, and A may be a group having at least a structural unit represented by the above formula (2).

此種通式(3)所示之大分子單體的具體例可舉出以下者。Specific examples of the macromonomer represented by the above formula (3) include the following.

在前述結構之A係在前述通式(3)之A同義。The A structure of the above structure is synonymous with A of the above formula (3).

能夠以市售品的方式取得之大分子單體可舉出例如一末端甲基丙烯醯化之聚甲基丙烯酸甲酯低聚物(Mn=6,000、商品名：AA-6、東亞合成化學工基(股)(TOAGOSEICo.,Ltd)製)及一末端甲基丙烯醯化之聚甲基丙烯酸丁酯低聚物(Mn：6,000、商品名：AB-6、東亞合成化學工基(股)製)、一末端甲基丙烯醯化之聚苯乙烯低聚物(Mn：6,000、商品名：AS-6、東亞合成化學工基(股)製)。The macromonomer which can be obtained as a commercial product is, for example, a polymethacrylic acid oligomer having a terminal methacrylic acid (Mn=6,000, trade name: AA-6, East Asian synthetic chemical Base (stock) (manufactured by TOAGOSEIC., Ltd.) and a terminal methacrylic acid butyl methacrylate oligomer (Mn: 6,000, trade name: AB-6, East Asia Synthetic Chemical Industry Group) A polystyrene oligomer having a terminal methacrylic acid (Mn: 6,000, trade name: AS-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.).

上述大分子單體之換算成聚苯乙烯的數量平均分子量(Mn)以1,000～20,000為佳，以2,000～15,000為更佳。數量平均分子量在上述範圍內時，能夠更有效地得到作為顏料分散劑之立體排斥效果。The number average molecular weight (Mn) of the above macromonomer in terms of polystyrene is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000. When the number average molecular weight is within the above range, the steric repulsion effect as a pigment dispersant can be more effectively obtained.

能夠與上述所記載之大分子單體共聚合之乙烯性不飽和單體，為了提升顏料的分散性及分散安定性，以使用「構成吸附顏料嵌段之單體」為佳，又，亦可與前述「構成未吸附顏料嵌段之單體」共聚合作為其他的共聚合成分。In order to improve the dispersibility and dispersion stability of the pigment, the ethylenically unsaturated monomer copolymerizable with the macromonomer described above may preferably be a "monomer constituting the adsorbed pigment block", or may be used. Copolymerization with the above-mentioned "monomer constituting the unadsorbed pigment block" as another copolymerization component.

上述接枝型高分子的重量平均分子量沒有特別限制，以3,000～100,000的範圍為佳，以5,000～50,000的範圍為更佳。數量平均分子量為3,000以上時，能夠更有效地得到安定化效果，又，重量平均分子量為100,000以下時，能夠更有效地吸附而發揮良好的分散性。The weight average molecular weight of the graft type polymer is not particularly limited, and is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the number average molecular weight is 3,000 or more, the stabilization effect can be more effectively obtained, and when the weight average molecular weight is 100,000 or less, it is possible to adsorb more effectively and exhibit good dispersibility.

前述接枝型高分子的市售品可舉出SOLSPERSE 24000、同28000、同32000、同38500、同39000、同55000(以上、Lubrizol Japan Ltd.)、Disperbyk-161、同171、同-174(以上、BYK-Chemie公司製)等。Commercial products of the graft type polymer include SOLSPERSE 24000, 28000, 32000, 38500, 39000, 55000 (above, Lubrizol Japan Ltd.), Disperbyk-161, 171, and -174 ( The above, BYK-Chemie company, etc.).

末端改性型高分子Terminal modified polymer

末端改性型高分子可舉出例如特開平9-77994號公報或特開2002-273191號公報所記載之在聚合物的末端具有官能基之高分子。The terminal-modified polymer may, for example, be a polymer having a functional group at the terminal of the polymer described in JP-A-H09-77994 or JP-A-2002-273191.

合成在聚合物的末端具有官能基之高分子之方法沒有特別限定，可舉出例如以下的方法及組合該等而成之方法等。The method of synthesizing the polymer having a functional group at the terminal of the polymer is not particularly limited, and examples thereof include the following methods and methods in which these are combined.

1.使用含有官能基的聚合引發劑並藉由聚合(例如自由基聚合、陰離子聚合、陽離子聚合等)來合成之方法。A method of synthesizing by using a polymerization initiator containing a functional group and polymerizing (for example, radical polymerization, anionic polymerization, cationic polymerization, or the like).

2.使用含有官能基的鏈轉移劑並藉由自由基聚合來合成之方法。2. A method of synthesizing by using a chain transfer agent containing a functional group and by radical polymerization.

在此所導入的官能基可舉出選自具有有機色素結構、雜環結構、酸性基、鹼性基之基、脲基、胺基甲酸酯基、具有配位性氧原子、碳數4以上的烴基、烷氧基矽烷基、環氧基、異氰酸酯基、羥基及離子性官能基之部位。又，能夠在該等吸附部位衍生之官能基亦無妨。The functional group introduced here may be selected from the group consisting of an organic dye structure, a heterocyclic structure, an acidic group, a basic group, a urea group, a urethane group, a coordinating oxygen atom, and a carbon number of 4. A moiety of the above hydrocarbon group, alkoxyalkyl group, epoxy group, isocyanate group, hydroxyl group, and ionic functional group. Further, the functional groups which can be derived at the adsorption sites may be used.

能夠在聚合物末端導入官能基鏈轉移劑的例子，可舉出例如氫硫基(mercapto)化合物(例如巰乙酸、硫代蘋果酸(thiomaleate)、硫柳酸、2-氫硫基丙酸、3-氫硫基丙酸、3-氫硫基丁酸、N-(2-氫硫基丙醯基)甘胺酸、2-氫硫基菸鹼酸、3-[N-(2-氫硫基乙基)胺基甲醯基]丙酸、3-[N-(2-氫硫基乙基)胺基]丙酸、N-(3-氫硫基丙醯基)丙胺酸、2-氫硫基乙磺酸、3-氫硫基丙磺酸、4-氫硫基丁磺酸、2-氫硫基乙醇、3-氫硫基-1,2-丙二醇、1-氫硫基-2-丙醇、3-氫硫基-2-丁醇、氫硫基苯酚、2-氫硫基乙胺、2-氫硫基咪唑、2-氫硫基-3-吡啶酚、苯硫酚、甲苯硫酚、氫硫基乙醯苯、萘硫酚、萘甲硫醇等)、或該等硫醇化合物的氧化劑之二硫醚化合物、及鹵素化合物(例如2-碘乙磺酸、3-碘丙磺酸等)。Examples of the functional chain transfer agent capable of introducing a terminal at the polymer include, for example, a mercapto compound (for example, indole acetic acid, thiomaleate, thiosislic acid, 2-hydrothiopropionic acid, 3-hydrothiopropionic acid, 3-hydrothiobutyric acid, N-(2-hydrothiopropyl decyl)glycine, 2-hydrothionicotinic acid, 3-[N-(2-hydrogen) Thioethyl)aminomercapto]propionic acid, 3-[N-(2-hydrothioethyl)amino]propionic acid, N-(3-hydrothiopropyl) alanine, 2 -Hexylthioethanesulfonic acid, 3-hydrothiopropanesulfonic acid, 4-hydrothiobutanesulfonic acid, 2-hydrothioethanol, 3-hydrothio-1,2-propanediol, 1-hydrogenthio 2-propanol, 3-hydrothio-2-butanol, hydrothiophenol, 2-hydrothioethylamine, 2-hydrothioimidazole, 2-hydrothio-3-pyridinol, benzene sulfide a bisphenol compound of an oxidizing agent such as phenol, toluene thiol, thioethyl thiobenzene, naphthol thiol, naphthyl mercaptan, or the like, and a halogen compound (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

又，能夠將官能基導入至聚合物末端之聚合引發劑可舉出例如2,2’-偶氮雙(2-氰基丙醇)、2,2’-偶氮雙(2-氰基丙醇)、4,4’-偶氮雙(4-氰基戊酸)、4,4’-偶氮雙(4-氰基戊醯氯)、2,2’-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]、2,2’-偶氮雙[2-(3,4,5,6-四氫嘧啶-2-基)丙烷]、2,2’-偶氮雙{2-[1-(2-羥乙基)-2-咪唑啉-2-基]丙烷}、2,2’-偶氮雙[2-甲基-N-(2-羥乙基)-丙醯胺]等或該等的衍生物等。Further, the polymerization initiator capable of introducing a functional group to the terminal of the polymer may, for example, be 2,2'-azobis(2-cyanopropanol) or 2,2'-azobis(2-cyanopropane). Alcohol), 4,4'-azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanopentyl chloride), 2,2'-azobis[2-( 5-methyl-2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[ 2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane], 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazoline-2 -yl]propane}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide] or the like, or the like.

可用於聚合之單體，例如可使用上述「構成未吸附顏料嵌段之單體」作為自由基之聚合性單體。As the monomer which can be used for the polymerization, for example, the above-mentioned "monomer constituting the unadsorbed pigment block" can be used as a radical polymerizable monomer.

上述末端改性型高分子的重量平均分子量以1,000～50,000為佳。上述重量平均分子量為1,000以上時，能夠更有效地得到作為顏料分散劑之立體排斥效果，50,000以下時能夠更有效地抑制立體效果，且能夠更縮短吸附於顏料之時間。The terminal modified polymer preferably has a weight average molecular weight of 1,000 to 50,000. When the weight average molecular weight is 1,000 or more, the steric repulsion effect as a pigment dispersant can be more effectively obtained, and when it is 50,000 or less, the steric effect can be more effectively suppressed, and the time of adsorption to the pigment can be further shortened.

前述末端改性型高分子的市售品可舉出例如SOLSPERSE 3000、同17000、同27000(以上、Lubrizol公司製)等。The commercially available product of the terminal-modified polymer may, for example, be SOLSPERSE 3000, the same 17000, the same 27000 (above, manufactured by Lubrizol), or the like.

分散劑以特定高分子化合物、接枝型高分子、末端改性型高分子為佳，其中以含有來自具有有機色素結構或雜環結構的單體之共聚合單位之接枝型高分子、或具有有機色素結構、雜環結構、酸性基、鹼性氮原子之基、脲基、或胺基甲酸酯基作為末端基之末端改性型高分子為特佳。The dispersing agent is preferably a specific polymer compound, a graft type polymer, or a terminally modified type polymer, and a graft type polymer containing a copolymerization unit derived from a monomer having an organic dye structure or a heterocyclic structure, or A terminal-modified polymer having an organic dye structure, a heterocyclic structure, an acidic group, a basic nitrogen atom group, a urea group, or a urethane group as a terminal group is particularly preferable.

相對於加工顏料，分散劑係高分子分散劑時的添加量以0.5～100質量%為佳，以3～100質量%為更佳，以5～80質量%為特佳。顏料的分散劑之量在前述範圍內時，能夠得到充分的顏料分散效果。但是分散劑的最佳添加量能夠按照使用顏料的種類、溶劑的種類等的組合等而適當地調整。The amount of the dispersant-based polymer dispersant added is preferably from 0.5 to 100% by mass, more preferably from 3 to 100% by mass, even more preferably from 5 to 80% by mass, based on the processing pigment. When the amount of the dispersant of the pigment is within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimum amount of the dispersant to be added can be appropriately adjusted depending on the type of the pigment to be used, the type of the solvent, and the like.

被覆顏料之特定高分子化合物與分散劑之比例沒有特別限制，分散劑為特定高分子分散劑時(特定高分子化合物/分散劑)以10/90～90/10質量比為佳，以20/80～80/20質量比為特佳。The ratio of the specific polymer compound to the dispersing agent to be coated with the pigment is not particularly limited, and when the dispersing agent is a specific polymer dispersing agent (specific polymer compound/dispersant), the mass ratio of 10/90 to 90/10 is preferably 20/20. The mass ratio of 80 to 80/20 is particularly good.

顏料分散組成物的調製Modulation of pigment dispersion composition

本發明的較佳態樣之顏料分散組成物係包含使用樹脂被覆處理而成的加工顏料及溶劑，而且亦按照必要含有顏料衍生物、或分散劑。The pigment dispersion composition of a preferred aspect of the present invention comprises a processed pigment and a solvent which are coated with a resin, and also contains a pigment derivative or a dispersant as necessary.

添加本發明的加工顏料、溶劑，及按照必要之分散劑或鹼可溶性樹脂，並進行混煉及分散。分散係主要使用縱型或橫型的砂磨機(sand grinder)、針盤式碾機機(pin mill)、狹縫碾磨機(slit mill)、超音波分散機等，且使用以0.01～1毫米粒徑的玻璃或鋯等製成的珠粒進行微分散處理，來得到顏料分散組成物。在進行珠粒分散之前，亦可使用二輥磨機(two-roll mill)、三輥磨機(three-roll mill)、球磨機(ball mill)、轉筒篩碾磨機(trommel)、分散器(disperser)、揑合器(kneader)、共揑合器(co-kneader)、均化器(homogenizer)、摻合器(blender)、單軸或雙軸的擠壓機(uniaxial or biaxial extruder)等，邊施加強烈的剪切力邊進行混煉分散處理。The processing pigment, the solvent, and the necessary dispersing agent or alkali-soluble resin of the present invention are added, and kneaded and dispersed. The dispersion system mainly uses a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, etc., and is used at 0.01~. A bead made of glass or zirconium having a particle diameter of 1 mm is subjected to a fine dispersion treatment to obtain a pigment dispersion composition. A two-roll mill, a three-roll mill, a ball mill, a trummel mill, and a disperser can also be used before bead dispersion. (disperser), kneader, co-kneader, homogenizer, blender, uniaxial or biaxial extruder, etc. The kneading and dispersing treatment is performed while applying a strong shearing force.

又，關於混煉及分散之詳細，係記載於T.C. Patton著“塗料流動及顏料分散；Paint Flow and Pigment Dispersion"(1964年John Wiley and Sons公司發行)等。Further, the details of kneading and dispersion are described in T.C. Patton, "Paint Flow and Pigment Dispersion; Published by John Wiley and Sons, 1964".

本發明的顏料分散物可適合使用製造彩色濾光片所使用的著色感光性組成物。The pigment dispersion of the present invention can be suitably used in the coloring photosensitive composition used for producing a color filter.

著色感光性組成物Coloring photosensitive composition

本發明的著色感光性組成物係含有前述本發明的顏料分散組成物、光聚合性化合物及光聚合引發劑，亦可按照必要更含有鹼可溶性樹脂。又，關於本發明的顏料分散組成物之詳細係如前述。以下，詳述各成分。The coloring photosensitive composition of the present invention contains the pigment dispersion composition, the photopolymerizable compound, and the photopolymerization initiator of the present invention, and may further contain an alkali-soluble resin as necessary. Further, the details of the pigment dispersion composition of the present invention are as described above. Hereinafter, each component will be described in detail.

本發明的感光性組成物能夠藉由例如將前述使用特定高分子化合物被覆處理所得到的加工顏料、光聚合性化合物及光聚合引發劑(較佳是與溶劑同時)混合，且按照必要在此混合鹼可溶性樹脂等添加劑，並使用各種混合機或分散機且經由混合分散之混合分散製程來調製造。The photosensitive composition of the present invention can be mixed, for example, by a process pigment, a photopolymerizable compound, and a photopolymerization initiator (preferably at the same time as a solvent) obtained by coating the above-mentioned specific polymer compound, and if necessary, An additive such as an alkali-soluble resin is mixed and adjusted by a mixing and dispersing process using various mixers or dispersers.

光聚合性化合物Photopolymerizable compound

光聚合性化合物的例子係以具有至少1個能夠加成聚合的乙烯性不飽和基，且在常溫之沸點100℃以上之化合物為佳，其中以4官能以上的丙烯酸酯化合物為更佳。The photopolymerizable compound is preferably a compound having at least one ethylenically unsaturated group capable of addition polymerization and having a boiling point of 100 ° C or higher at a normal temperature, and more preferably an acrylate compound having 4 or more functional groups.

前述具有至少1個能夠加成聚合的乙烯性不飽和基，且在常溫之沸點100℃以上之化合物的例子，可舉出例如聚乙二醇一(甲基)丙烯酸酯、聚丙二醇一(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯等的單官能的丙烯酸酯或甲基丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯、三羥甲基乙烷(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三羥甲基丙烷三(丙烯醯氧基丙基)醚、三(丙烯醯氧基乙基)三聚異氰酸酯、使甘油或三羥甲基乙烷等的多官能醇加添環氧乙烷或環氧丙烷後加以(甲基)丙烯酸酯化而成之化合物、聚(甲基)丙烯酸酯化新戊四醇或二新戊四醇而成之化合物、特公昭48-14708號公報、特公昭50-6034號公報、特公昭51-37193號公報所記載之胺基甲酸酯類、特公昭48-64183號公報、特公昭49-43191號公報、特公昭52030490號公報所記載之聚酯型丙烯酸酯類、環氧樹脂與(甲基)丙烯酸的反應生成物之環氧丙烯酸酯類等多官能的丙烯酸酯及甲基丙烯酸酯。Examples of the compound having at least one ethylenically unsaturated group capable of addition polymerization and having a boiling point of 100 ° C or higher at normal temperature include, for example, polyethylene glycol mono(meth)acrylate and polypropylene glycol (a) Monofunctional acrylate or methacrylate such as acrylate, phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane (methyl) Acrylate, neopentyl glycol di(meth)acrylate, neopentyl alcohol tri(meth)acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol hexa(meth)acrylic acid Ester, hexanediol (meth) acrylate, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene methoxyethyl) trimer isocyanate, glycerol or trimethylolethane The polyfunctional alcohol is added with ethylene oxide or propylene oxide and then compounded with (meth) acrylate, poly(meth)acrylated neopentyl alcohol or dipentaerythritol. The urethanes and special public sulphates described in the Japanese Patent Publication No. Sho. No. Sho. Polyester acrylates, and epoxy acrylates of reaction products of epoxy resin and (meth)acrylic acid, etc., are described in JP-A-49-43191 Functional acrylates and methacrylates.

而且，亦可使用日本黏著協會刊物(日本黏著協會期刊；Journal of the Adhesion Society of Japan)第20卷、第7期、第300～308頁介紹作為光硬化性單體及低聚物者。Further, as a photocurable monomer and oligomer, the Japanese Adhesive Society Journal (Journal of the Adhesion Society of Japan), Vol. 20, No. 7, and pages 300 to 308 can also be used.

又，亦能夠使用在特開平10-62986公報與通式(1)及(2)之具體例一同記載之在前述多官能醇加添環氧乙烷或或環氧丙烷後加以(甲基)丙烯酸酯化而成之化合物。Further, it is also possible to add (meth) to the polyfunctional alcohol after adding ethylene oxide or propylene oxide as described in the above-mentioned specific examples of the general formulas (1) and (2). Acrylate compound.

其中，以二新戊四醇(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯及該等的丙烯醯基透過乙二醇殘基或丙二醇殘基而成之結構為佳。亦可使用該等的低聚物型。Among them, it is preferred to use dipentaerythritol (meth) acrylate, dipentaerythritol hexa(meth) acrylate, and the propylene sulfonate group to pass through an ethylene glycol residue or a propylene glycol residue. . These oligomer types can also be used.

光聚合性化合物可單獨使用1種，亦可組合使用2種以上。The photopolymerizable compound may be used alone or in combination of two or more.

光聚合性化合物在光硬化性組成物中之含量，係相對於該組成物的總固體成分100質量份，以3～55質量份為佳，以10～50質量份為更佳。光聚合性化合物的含量在前述範圍內時，硬化反應能夠充分地進行。The content of the photopolymerizable compound in the photocurable composition is preferably from 3 to 55 parts by mass, more preferably from 10 to 50 parts by mass, per 100 parts by mass of the total solid content of the composition. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently carried out.

光聚合引發劑Photopolymerization initiator

光聚合引發劑的例子，可舉出例如特開平57-6096號公報所記載之鹵甲基二唑、特公昭59-1281號公報、特開昭53-133428號公報等所記載之鹵甲基-s-三等活性鹵素化合物、美國專利第4318791、歐洲專利公開EP-88050A等的各說明書所記載之縮酮、縮醛或苯偶姻烷基醚類等的芳香族羰基化合物、美國專利第4199420說明書所記載之二苯基酮類等的芳香族酮化合物、法國專利發明2456741說明書所記載之(噻)呫噸酮系或吖啶系化合物、特開平10-62986號公報所記載之香豆素系或二咪唑系化合物、特開平8-015521號公報等的鋶有機硼錯合物等等。An example of the photopolymerization initiator is, for example, a halomethyl group described in JP-A-57-6096. Halomethyl-s-three described in the oxadiazole, Japanese Patent Publication No. 59-1281, and JP-A-53-133428 An aromatic carbonyl compound such as a ketal, an acetal or a benzoin alkyl ether described in each specification of the above-mentioned active halogen compound, US Pat. No. 4,318,791, and European Patent Publication No. EP-88050A, and the description of the specification of US Patent No. 4199420 An aromatic ketone compound such as a diphenyl ketone or a coumarin compound or an acridine compound described in the specification of the patent application No. 2,546, 741, and a coumarin system or a succinct described in JP-A-10-62986 An imidazole-based compound, a bismuth organoboron complex such as JP-A-8-015521, and the like.

前述光聚合引發劑以乙醯苯(acetonphenone)系、縮酮系、二苯基酮系、苯偶姻系、苯甲醯系、呫噸酮系、活性鹵素化合物(例如、三系、鹵甲基二唑系或香豆素系化合物)、吖啶系、二咪唑系及肟酯(oxime ester)系等的引發劑為佳。The photopolymerization initiator is an acetonphenone system, a ketal system, a diphenylketone system, a benzoin system, a benzamidine system, a xanthone system, or an active halogen compound (for example, three). Halomethyl An initiator such as an oxadiazole-based or coumarin-based compound, an acridine-based compound, a diimidazole-based compound or an oxime ester-based compound is preferred.

前述乙醯苯系光聚合引發劑的例子，可適合舉出例如2,2-二乙氧基乙醯苯、對二甲胺基乙醯苯、2-羥基-2-甲基-1-苯基-丙烷-1-酮、對二甲胺基乙醯苯、4’-異丙基-2-羥基-2-甲基-丙醯苯、1-羥基-環己基-苯基-酮、2-苄基-2-二甲胺基-1-(4-嗎啉苯基)-丁酮-1、2-甲苯基-2-二甲胺基-1-(4-嗎啉苯基)-丁酮-1及2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉丙酮-1等。Examples of the phthalic acid-based photopolymerization initiator include, for example, 2,2-diethoxyethyl benzene, p-dimethylamino acetophenone, and 2-hydroxy-2-methyl-1-benzene. Base-propan-1-one, p-dimethylaminoethyl benzene, 4'-isopropyl-2-hydroxy-2-methyl-propenyl benzene, 1-hydroxy-cyclohexyl-phenyl-one, 2 -benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-tolyl-2-dimethylamino-1-(4-morpholinylphenyl)- Butanone-1 and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinone-1 and the like.

前述縮酮系光聚合引發劑的例子，可適合舉出例如苄基二甲基縮酮、苄基-β-甲氧基乙基縮酮等。Examples of the ketal-based photopolymerization initiator include, for example, benzyldimethylketal, benzyl-β-methoxyethylketal, and the like.

前述二苯基酮系光聚合引發劑的例子，可適合舉出例如二苯基酮、4,4’-(雙二甲胺基)二苯基酮、4,4’-(雙二乙胺基)二苯基酮、4,4’-二氯二苯基酮。Examples of the diphenylketone-based photopolymerization initiator include diphenyl ketone, 4,4'-(bisdimethylamino)diphenyl ketone, and 4,4'-(didiethylamine). Diphenyl ketone, 4,4'-dichlorodiphenyl ketone.

前述苯偶姻系或苯甲醯系光聚合引發劑的例子，可適合舉出例如苯偶姻異丙基醚、苯偶姻異丁基醚、苯偶姻甲基醚及鄰苯甲醯基苯甲酸甲酯等。Examples of the benzoin-based or benzamidine-based photopolymerization initiators include, for example, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and o-benzamide. Methyl benzoate and the like.

前述呫噸酮系光聚合引發劑的例子，可適合舉出例如二乙基噻噸酮、二異丙基噻噸酮、一異丙基噻噸酮及氯噻噸酮等。Examples of the xanthone-based photopolymerization initiator include, for example, diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, and chlorothioxanthone.

前述活性鹵素化合物(例如、三系、二唑系、或香豆素系化合物)的例子，2,4-雙(三氯甲基)-6-對甲氧基苯基-s-三、2,4-雙(三氯甲基)-6-對甲氧基苯乙烯基-s-三、2,4-雙(三氯甲基)-6-(1-對二甲胺基苯基)-1,3-丁二烯基-s-三、2,4-雙(三氯甲基)-6-聯苯基-s-三、2,4-雙(三氯甲基)-6-(對甲基聯苯基)-s-三、對羥基乙氧基苯乙烯基-2,6-二(三氯甲基)-s-三、甲氧基苯乙烯基-2,6-二(三氯甲基)-s-三、3,4-二甲氧基苯乙烯基-2,6-二(三氯甲基)-s-三、4-苯并氧雜戊環-2,6-二(三氯甲基)-s-三、4-(鄰溴-對N,N-(二乙氧基碳醯胺基)-苯基)-2,6-二(氯甲基)-s-三、4-(對N,N-(二乙氧基碳醯胺基)-苯基)-2,6-二(氯甲基)-s-三、2-三氯甲基-5-苯乙烯基-1,3,4-二唑、2-三氯甲基-5-(萘-1-基)-1,3,4-二唑、2-三氯甲基-5-(4-苯乙烯基)苯乙烯基-1,3,4-二唑、3-甲基-5-胺基-((s-三-2-基)胺基)-3-苯基香豆素、3-氯-5-二乙胺基-((s-三-2-基)胺基)-3-苯基香豆素及3-丁基-5-二甲胺基-((s-三-2-基)胺基)-3-苯基香豆素等。The aforementioned active halogen compound (for example, three system, An example of a diazole or coumarin compound, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-three , 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-three , 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-three 2,4-bis(trichloromethyl)-6-biphenyl-s-three , 2,4-bis(trichloromethyl)-6-(p-methylbiphenyl)-s-three P-hydroxyethoxystyryl-2,6-di(trichloromethyl)-s-three Methoxystyryl-2,6-di(trichloromethyl)-s-three 3,4-dimethoxystyryl-2,6-di(trichloromethyl)-s-three 4-benzooxacyclo-5,6-di(trichloromethyl)-s-three , 4-(o-bromo-p-N,N-(diethoxycarbamoyl)-phenyl)-2,6-di(chloromethyl)-s-three , 4-(p-N,N-(diethoxycarbamoyl)-phenyl)-2,6-di(chloromethyl)-s-three 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(naphthalen-1-yl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-styryl)styryl-1,3,4- Diazole, 3-methyl-5-amino-((s-three) -2-yl)amino)-3-phenylcoumarin, 3-chloro-5-diethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin and 3-butyl-5-dimethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin.

前述吖啶系光聚合引發劑的例子，可適當地舉出例如9-苯基吖啶、1,7-雙(9-吖啶基)庚烷等。Examples of the acridine photopolymerization initiator include, for example, 9-phenyl acridine and 1,7-bis(9-acridinyl)heptane.

前述二咪唑系光聚合引發劑的例子，可適當地舉出例如2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚物等。Examples of the diimidazole-based photopolymerization initiator include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-methoxyphenyl)-4. , 5-diphenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, and the like.

上述以外，1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、O-苯甲醯基-4’-(苯并氫硫基)苯甲醯基-己基-酮肟、2,4,6-三甲基苯基羰基-二苯基膦醯氧及六氟偶磷基(phosphoro)-三烷基苯基鏻鹽等。In addition to the above, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, O-benzylidene-4'-(benzohydrothio)benzimidyl-hexyl a ketone oxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonium oxime, a hexafluorophospho-trialkylphenyl sulfonium salt, and the like.

本發明未限定於以上的光聚合引發劑，亦可使用其他眾所周知的光聚合引發劑。可舉出例如美國專利第2,367,660號說明書所記載之vicinal polyketol aldonyl化合物、美國專利第2,367,661號及2,367,670號說明書所記載之α-羰基化合物、美國專利第2,448,828號說明書所記載之偶姻醚(acyloin ether)、美國專利第2,722,512號說明書所記載之被α-烴取代之芳香族偶姻醚化合物、美國專利第3,046,127號及2,951,758號說明書所記載之多核醌化合物、美國專利第3,549,367號說明書所記載之三烯丙基咪唑二聚物/對胺基苯基酮的組合、特公昭51-48516號公報所記載之苯并噻唑系化合物/三鹵甲基-s-三系化合物、J.C.S. Perkin II(1979)1653-1660、J.C.S. Perkin II(1979)156-162、光聚合物科學及技術期刊(Journal of Photopolymer Science and Technology(1995)202-232、特開2000-66385號公報所記載之肟酯(oxime ester)化合物等。The present invention is not limited to the above photopolymerization initiator, and other well-known photopolymerization initiators may be used. For example, the vicinal polyketol aldonyl compound described in the specification of U.S. Patent No. 2,367,660, the α-carbonyl compound described in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, and the acyloin ether described in the specification of U.S. Patent No. 2,448,828 (acyloin ether) The aromatic allylate ether compound substituted by an α-hydrocarbon described in the specification of U.S. Patent No. 2,722,512, the polynuclear ruthenium compound described in the specification of U.S. Patent Nos. 3,046,127 and 2,951,758, and the third of the specification of U.S. Patent No. 3,549,367. Combination of allyl imidazole dimer/p-aminophenyl ketone, benzothiazole compound/trihalomethyl-s-three described in Japanese Patent Publication No. Sho 51-48516 Compounds, JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A-2000-66385 An oxime ester compound or the like described in the publication.

又，亦可並用該等光聚合引發劑。Further, these photopolymerization initiators may be used in combination.

光聚合引發劑在光硬化性組成物中的含量，係相對於該組成物的總固體成分，以0.1～10.0質量份為佳，以0.5～5.0質量份為更佳。光聚合性化合物的含量在前述範圍內時，硬化反應能夠充分地進行而能夠形成良好的膜。The content of the photopolymerization initiator in the photocurable composition is preferably from 0.1 to 10.0 parts by mass, more preferably from 0.5 to 5.0 parts by mass, based on the total solid content of the composition. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently carried out to form a favorable film.

增感色素Sensitized pigment

增感色素係例如藉由能夠吸收的波長進行曝光時用以促進光聚合引發劑產生自由基反應及藉此之聚合性化合物的聚合反應。此種增感色素的例子可舉出眾所周知的分光增感色素或染料或吸收光而與光聚合引發劑相互作用之染料或顏料。The sensitizing dye is used to promote a radical reaction of a photopolymerization initiator and a polymerization reaction of a polymerizable compound by exposure at a wavelength that can be absorbed, for example. Examples of such a sensitizing dye include a well-known spectral sensitizing dye or dye or a dye or pigment which absorbs light and interacts with a photopolymerization initiator.

分光增感色素或染料Spectrophotosensitive pigment or dye

作為增感色素之較佳的分光增感色素或染料可舉出例如多核芳香族環(例如、芘、苝(perylene)、三鄰亞苯)、呫噸類(例如、螢光素(fluorescein)、曙紅(eosin)、紅黴素(erythrosine)、若丹明(rhodamine)B、玫瑰紅(rosebengal)、花青苷(例如、噻碳花青、碳花青)、部花青素類(例如、部花青素、碳部花青素)、噻類(例如、硫僅(thionine)、亞甲藍(methylene blue)、甲苯胺藍(toluidine blue)、吖啶類(例如、吖啶橙、氯黃素(chloroflavin)、吖啶黃(acriflavin)、酞菁類(例如、酞菁、金屬酞菁)、卟啉(porphyrin)類(例如、四苯基卟啉、中心金屬取代呤啉)、葉綠素類(例如葉綠素、葉綠酸、中心金屬取代葉綠素)、金屬錯合物(例如、下述化合物)、蒽醌類(例如、蒽醌)及角鯊鎓類(例如、角鯊鎓)等。Preferred spectral sensitizing dyes or dyes for sensitizing dyes include, for example, polynuclear aromatic rings (for example, perylene, tri-ortylene), xanthene (for example, fluorescein). , eosin, erythrosine, rhodamine B, rosebengal, anthocyanin (eg, thiocarbocyanine, Carbonic cyanine), genus anthocyanins (eg, anthocyanins, carbon anthocyanins), thiazide Classes (eg, thionine, methylene blue, toluidine blue, acridine (eg, acridine orange, chloroflavin, acriflavin, Phthalocyanines (eg, phthalocyanines, metal phthalocyanines), porphyrins (eg, tetraphenylporphyrins, central metal-substituted porphyrins), chlorophylls (eg, chlorophyll, chlorophyllin, central metal-substituted chlorophyll) ), metal complexes (for example, the following compounds), terpenoids (for example, hydrazine), and horned sharks (for example, squalane).

更佳的分光增感色素或染料係如下所示。A more preferred spectral sensitizing dye or dye is as follows.

特公平37-13034號公報所記載之苯乙烯系色素；特開昭62-143044號公報所記載之陽離子染料；特公昭59-24147號公報所記載之喹啉鎓鹽；特開昭64-33104號公報所記載之新亞甲藍化合物；特開昭64-56767號公報所記載之蒽醌類；特開平2-1714號公報所記載之苯并呫噸染料；特開平2-226148號公報及特開平2-226149號公報所記載之吖啶類；特公昭40-28499號公報所記載之吡喃鎓(pyrilium)鹽類；特公昭46-42363號公報所記載之花青苷類；特開平2-63053號公報之苯并呋喃色素；特開平2-85858號公報、特開平2-216154號公報之共軛酮色素；特開昭57-10605號公報所記載之色素；特公平2-30321號公報所記載之偶氮亞桂皮基衍生物(azo cinnamilidene)衍生物；特開平1-287105號公報所記載之花青苷系色素；特開昭62-31844號公報、特開昭62-31848號公報、特開昭62-143043號公報所記載之呫噸系色素；特公昭59-28325號公報所記載之胺基苯乙烯基酮；特開平2-179643號公報所記載之色素；特開平2-244050號公報所記載之部花青素色素；特公昭59-28326號公報所記載之部花青素色素；特開昭59-89303號公報所記載之部花青素色素；特開平8-129257號公報所記載之部花青素色素及特開平8-334897號公報所記載之苯并吡喃系色素。a styrene-based dye described in Japanese Patent Publication No. 37-13034, and a cation dye described in JP-A-62-143044; The phthalocyanine salt; the phthalocyanine compound described in the Unexamined-Japanese-Patent No. 64-56767; the benzoxanthene described in JP-A-2-1714 The acridines described in the Unexamined-Japanese-Patent No. 2-226149 and the Unexamined-Japanese-Patent No. 2-226149, and the pyrilium salts described in Japanese Patent Publication No. Sho 40-28499; Japanese Patent Publication No. SHO 46-42363 Japanese Patent Publication No. Hei 2-63053, conjugated ketone dyes of JP-A-2-85858, JP-A-2-216154, and JP-A-57-10605 The azo cinnamilidene derivative described in Japanese Patent Publication No. Hei 2-30321, and the anthocyanin-based dye described in JP-A-1-287105; The xanthene-based dye described in JP-A-62-143043, JP-A-62-143043, and the aminostilbene ketone described in JP-A-59-28325; a pigment described in the publication No. 179643; an anthocyanin dye described in JP-A-2-244050; An anthocyanin dye described in Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The benzopyran-based dye described in the publication.

在350～450奈米具有極大吸收波長之色素a pigment having a maximum absorption wavelength of 350 to 450 nm

增感色素之其他較佳態樣可舉出例如屬於以下化合物群且在350～450奈米具有極大吸收波長之色素。Other preferred aspects of the sensitizing dye include, for example, those having the following compound groups and having a maximum absorption wavelength of from 350 to 450 nm.

例如，多核芳香族類(例如、芘、苝、三鄰亞苯)、呫噸類(例如、螢光素、曙紅、紅黴素、若丹明B、玫瑰紅)、花青苷類(例如噻花青苷、花青苷)、部花青素類(例如、部花青素、碳部花青素)、噻類(例如、硫僅、亞甲藍、甲苯胺藍)、吖啶類(例如、吖啶橙、氯黃素、吖啶黃)、蒽醌類(例如、蒽醌)及角鯊鎓類(例如、角鯊鎓)等。For example, polynuclear aromatics (eg, hydrazine, hydrazine, tri-o-phenylene), xanthene (eg, luciferin, eosin, erythromycin, rhodamine B, rose red), anthocyanins ( For example, tialoside, Anthocyanins), genus anthocyanins (eg, anthocyanins, anthocyanins), thiazide Classes (eg, sulfur only, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavonoids, acridine yellow), terpenoids (eg, guanidine), and squalane ( For example, horn sharks, etc.

更佳之增感色素可舉出下述通式(XIV)～(XVIII)所示之化合物。More preferably, the sensitizing dyes include compounds represented by the following formulae (XIV) to (XVIII).

(通式(XIV)中，A1 係表示硫原子或NR50 ，R50 係表示烷基或芳基，L2 係表示鄰接碳原子A1 及鄰接碳原子共同形成色素的鹼性核之非金屬原子團，R51 及R52 係各自獨立地表示氫原子或一價的非金屬原子團，R51 及R52 亦可以互相鍵結而形成的色素的酸性核。W係表示氧原子或硫原子)(In the formula (XIV), A 1 represents a sulfur atom or NR 50 , R 50 represents an alkyl group or an aryl group, and L 2 represents a non-basic nucleus in which a carbon atom A 1 and a adjacent carbon atom together form a dye. a metal atom group, R 51 and R 52 each independently represent a hydrogen atom or a monovalent non-metal atomic group, and R 51 and R 52 may be bonded to each other to form an acid nucleus of a dye. W is an oxygen atom or a sulfur atom)

以下，顯示通式(XIV)所示化合物之較佳具體例[(F-1)～(F-5)]。Preferred examples of the compound represented by the formula (XIV) [(F-1) to (F-5)] are shown below.

(通式(XV)中，Ar1 及Ar2 係各自獨立地表示芳基且透過-L3 -之鍵來連結。在此，L3 係表示-O-或-S-。又，W係與在通式(XIV)所示者同義)(In the general formula (XV), Ar 1 and Ar 2 each independently represent an aryl group and are linked by a bond of -L 3 -. Here, L 3 means -O- or -S-. Further, W system Same as those shown in the general formula (XIV)

通式(XV)所示化合物之較佳例子，可舉出以下的(F-6)～(F-8)。Preferred examples of the compound represented by the formula (XV) include the following (F-6) to (F-8).

(通式(XVI)中，A2 係表示硫原子或NR59 ，L4 係表示鄰接的A2 及碳原子共同形成色素的鹼性核之非金屬原子團，R53 、R54 、R55 、R56 、R57 及R58 係各自獨立地表示一價的非金屬原子團，R59 係表示烷基或芳基)(In the formula (XVI), A 2 represents a sulfur atom or NR 59 , and L 4 represents a non-metal atomic group of a basic core in which adjacent A 2 and a carbon atom together form a dye, and R 53 , R 54 and R 55 , R 56 , R 57 and R 58 each independently represent a monovalent non-metal atomic group, and R 59 represents an alkyl group or an aryl group)

通式(XVI)所示化合物之較佳例子，可舉出以下的(F-9)～(F-11)。Preferable examples of the compound represented by the formula (XVI) include the following (F-9) to (F-11).

(通式(XVII)中，A3 及A4 係各自獨立地表示-S-或-NR63 ，R63 係表示取代或未取代的烷基或取代或未取代的芳基，L5 及L6 係各自獨立地表示鄰接的A3 或A4 及鄰接碳原子共同形成色素的鹼性核之非金屬原子團，R61 及R62 係各自獨立地表示一價的非金屬原子團或是亦可互相鍵結而形成脂肪性或芳香族性的環)(In the formula (XVII), A 3 and A 4 each independently represent -S- or -NR 63 , and R 63 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, L 5 and L 6 is a non-metal atomic group which independently represents adjacent A 3 or A 4 and a basic nucleus which forms a dye together with adjacent carbon atoms, and R 61 and R 62 each independently represent a monovalent non-metal atomic group or may also mutually Bonding to form a fatty or aromatic ring)

通式(XVII)所示化合物的較佳例子可舉出以下的(F-12)～(F-15)。Preferable examples of the compound represented by the formula (XVII) include the following (F-12) to (F-15).

又，此外，本發明所使用的較佳增感色素可舉出下述式(XVIII)所示者。Further, the preferred sensitizing dye used in the present invention is exemplified by the following formula (XVIII).

(通式(XVIII)中，A係表示亦可具有取代基之芳香族環或雜環，X係表示氧原子、硫原子、或-N(R1 )-，Y係表示氧原子或-N(R1 )-。R1 、R2 及R3 係各自獨立地表示氫原子或一價的非金屬原子團，R1 、R2 及R3 各自能夠與A鍵結而形成脂肪族性或芳香族性的環。(In the formula (XVIII), A represents an aromatic ring or a heterocyclic ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or -N(R 1 )-, and Y represents an oxygen atom or -N (R 1 )-. R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent non-metal atomic group, and each of R 1 , R 2 and R 3 can bond with A to form an aliphatic or aromatic group. Ethnic ring.

在此，R1 、R2 或R3 係表示一價的非金屬原子團時，較佳係表示取代或未取代的烷基或芳基Here, when R 1 , R 2 or R 3 represents a monovalent non-metal atomic group, it preferably represents a substituted or unsubstituted alkyl or aryl group.

接著，敘述R1 、R2 及R3 之較佳具體例。較佳烷基之例子可舉出碳原子數1～20之直鏈狀、分枝狀及環狀的烷基，其具體例可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十六基、十八基、二十基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、1-甲基丁基、異己基、2-乙基己基、2-甲基己基、環己基、環戊基、2-降基等。此等之中，以碳原子數1至12之直鏈狀、碳原子數3至12之分枝狀的烷基、和碳原子數5至10之環狀的烷基為更佳。Next, preferred specific examples of R 1 , R 2 and R 3 will be described. Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. , hexyl, heptyl, octyl, decyl, decyl, eleven, twelve, thirteen, hexadecyl, octadecyl, octadecyl, isopropyl, isobutyl, second Base, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-lower Base. Among these, an alkyl group having a linear number of 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

取代烷基之取代基可使用除了氫以外之1價的非金屬原子團之基，較佳的例子可舉出鹵素原子(-F、-Br、-Cl、-I)、羥基、烷氧基、芳氧基、氫硫基、烷硫基、芳硫基、烷二硫基、芳二硫基、胺基、N-烷胺基、N,N-二烷胺基、N-芳胺基、N,N-二芳胺基、N-烷基-N-芳胺基、醯氧基、胺基甲醯氧基、N-烷基胺基甲醯氧基、N-芳基胺基甲醯氧基、N,N-二烷基胺基甲醯氧基、N,N-二芳基胺基甲醯氧基、N-烷基-N-芳基胺基甲醯氧基、烷基亞磺醯(alkyl sulfoxy)基、芳基亞磺醯(aryl sulfoxy)基、醯氧基醯硫(acylthio)基、醯胺基、N-烷基醯胺基、N-芳基醯胺基、脲基、N-烷脲基、N，N-二烷脲基、N-芳脲基、N,N-二芳脲基、N-烷基-N-芳脲基、N-烷脲基、N-芳脲基、N-烷基-N-烷脲基、N-烷基-N-芳脲基、N,N-二烷基-N-烷脲基、N,N-二烷基-N-芳脲基、N-芳基-N-烷脲基、N-芳基-N-芳脲基、N,N-二芳基-N-烷脲基、N,N-二芳基-N-芳脲基、N-烷基-N-芳基-N-烷脲基、N-烷基-N-芳基-N-芳脲基、烷氧基碳醯胺基、芳氧基碳醯胺基、N-烷基-N-烷氧基碳醯胺基、N-烷基-N-芳氧基碳醯胺基、N-芳基-N-烷氧基碳醯胺基、N-芳基-N-芳氧基碳醯胺基、甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺基甲醯基、N-烷基胺基甲醯基、N,N-二烷基胺基甲醯基、N-芳基胺基甲醯基、N,N-二芳基胺基甲醯基、N-烷基-N-芳基胺基甲醯基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、磺酸基(-SO3 H)及其共軛鹼基(以下稱為磺酸根基)、烷氧基磺醯基、芳氧基磺醯基、胺亞磺醯基、N-烷基胺亞磺醯基、N,N-二烷基胺亞磺醯基、N-芳基胺亞磺醯基、N,N-二芳基胺亞磺醯基、N-烷基-N-芳基胺亞磺醯基、胺磺醯基、N-烷基胺磺醯基、N,N-二烷基胺磺醯基、N-芳基胺磺醯基、N,N-二芳基胺磺醯基、N-烷基-N-芳基胺磺醯基、膦酸基(-PO3 H2 )及其共軛鹼基(以下稱為膦酸根基)、二烷基膦酸基(-PO3 (烷基)2 )、二芳基膦酸基(-PO3 (芳基)2 )、烷基芳基膦酸基(-PO3 (烷基)(芳基))、一烷基膦酸基(-PO3 H(烷基))及其共軛鹼基(以下稱為烷基膦酸根基)、一芳基膦酸基(-PO3 H(芳基))及其共軛鹼基(以下稱為芳基膦酸根基)、膦醯氧基(-OPO3 H2 )及其共軛鹼基(以下稱為膦酸根氧基)、二烷基膦醯氧基(-OPO3 (烷基)2 )、二芳基膦醯氧基(-OPO3(芳基)2 )、烷基芳基膦醯氧基(-OPO3 (烷基)(芳基))、一烷基膦醯氧基(-OPO3 H(烷基))及共軛鹼基(以下稱為烷基膦酸根氧基基)、一芳基膦醯氧基(-OPO3 H(芳基))及共軛鹼基(以下稱為芳基膦酸根氧基)、氰基、硝基、芳基、雜芳基、烯基、炔基及矽烷基。The substituent of the substituted alkyl group may be a group of a monovalent non-metal atomic group other than hydrogen, and preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, Aryloxy, thiol, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamino, N,N-dialkylamino, N-arylamino, N,N-diarylamino, N-alkyl-N-arylamino, decyloxy, aminomethyl methoxy, N-alkylaminomethyl methoxy, N-arylamino formazan Oxy, N,N-dialkylaminomethyl methoxy, N,N-diarylaminomethyl methoxy, N-alkyl-N-arylaminomethyl methoxy, alkyl An alkyl sulfoxy group, an aryl sulfoxy group, an acylthio group, an anthranyl group, an N-alkyl decylamino group, an N-aryl decylamino group, a urea , N-alkylureido, N,N-dialkylureido, N-arylureido, N,N-diarylureido, N-alkyl-N-arylureido, N-alkylureido, N -Arylurea, N-alkyl-N-alkylureido, N-alkyl-N-arylureido, N,N-dialkyl-N-alkylureido, N,N-dialkyl-N -Arylurea, N-aryl-N-alkylureido, N-aryl-N-arylureido, N,N-diaryl-N-alkylureido, N,N -diaryl-N-arylureido, N-alkyl-N-aryl-N-alkylureido, N-alkyl-N-aryl-N-arylureido, alkoxycarbenyl , aryloxycarbamoylamine, N-alkyl-N-alkoxycarbamoylamine, N-alkyl-N-aryloxycarbenylamine, N-aryl-N-alkoxycarbon Amidino, N-aryl-N-aryloxycarbamicinyl, indolyl, fluorenyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, aminomethylindenyl, N-alkylamino Mercapto, N,N-dialkylaminomethyl fluorenyl, N-arylaminomethyl fluorenyl, N,N-diarylaminomethyl fluorenyl, N-alkyl-N-arylamine A thiol group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonic acid group (-SO 3 H), and a conjugated base thereof (hereinafter referred to as Sulfonate), alkoxysulfonyl, aryloxysulfonyl, amine sulfinyl, N-alkylamine sulfinyl, N,N-dialkylamine sulfinyl, N- Arylamine sulfinyl, N,N-diarylamine sulfinyl, N-alkyl-N-arylamine sulfinyl, amine sulfonyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine sulfonyl, N,N-diarylamine sulfonyl, N-alkyl-N-arylamine Acyl, a phosphonic acid group (-PO 3 H 2) and its conjugate base (referred to hereinafter phosphonate), a dialkyl phosphonic acid group (-PO 3 (alkyl) 2), diaryl acid a group (-PO 3 (aryl) 2 ), an alkylarylphosphonic acid group (-PO 3 (alkyl) (aryl)), a monoalkylphosphonic acid group (-PO 3 H(alkyl)), and a conjugated base (hereinafter referred to as an alkylphosphonate group), an arylphosphonic acid group (-PO 3 H (aryl)), and a conjugated base thereof (hereinafter referred to as an arylphosphonate group), a phosphine Alkoxy (-OPO 3 H 2 ) and its conjugated base (hereinafter referred to as phosphonateoxy), dialkylphosphinomethoxy (-OPO 3 (alkyl) 2 ), diarylphosphonium oxychloride Base (-OPO3(aryl) 2 ), alkylarylphosphinomethoxy (-OPO 3 (alkyl)(aryl)), monoalkylphosphinomethoxy (-OPO 3 H(alkyl)) And a conjugated base (hereinafter referred to as an alkylphosphonateoxy group), an arylphosphonium oxy group (-OPO 3 H(aryl)), and a conjugated base (hereinafter referred to as an arylphosphonateoxy group) ), cyano, nitro, aryl, heteroaryl, alkenyl, alkynyl and decyl.

在此等取代基，烷基的具體例可舉出前述烷基，此等亦可更具有取代基。Specific examples of the alkyl group in the above substituents include the above alkyl group, and these may further have a substituent.

又，芳基的具體例可舉出苯基、聯苯基、萘基、甲苯基、二甲苯基、基、異丙苯基、氯苯基、溴苯基、氯甲基苯基、羥苯基、甲氧基苯基、乙氧基苯基、苯氧基苯基、乙醯氧基苯基、苯甲醯氧基苯基、甲硫基苯基、苯硫基苯基、甲胺基苯基、二甲胺基苯基、乙醯胺基苯基、羧苯基、甲氧基羰基苯基、乙氧基羰基苯基、苯氧基羰基苯基、N-苯基胺基甲醯基苯基、苯基、氰基苯基、磺酸基苯基、磺酸根基苯基、膦酸基苯基及膦酸根基苯基等。Further, specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. Base, cumyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, Benzyloxyphenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethylaminophenyl, carboxyphenyl, methoxycarbonylphenyl , ethoxycarbonylphenyl, phenoxycarbonylphenyl, N-phenylaminoformamidophenyl, phenyl, cyanophenyl, sulfonylphenyl, sulfonylphenyl, phosphonic acid Phenyl and phosphonate phenyl groups, and the like.

雜芳基可舉出含有從氮原子、氧原子、硫原子中之至少一者之單環或多環芳香族環衍生之基。特佳之雜芳基中的雜芳基環之例子，可舉出例如噻吩、噻蒽(thiathrene)、呋喃、吡喃、異苯并呋喃、色烯(chromene)、呫噸、啡 、吡咯、吡唑、異噻唑、異唑、吡、嘧啶、嗒、吲哚、異吲哚、吲哚基(indoyl)、吲唑、嘌呤(purine)、喹、異喹、酞、萘啶、喹唑啉、shinorine、喋啶(pteridine)、咔唑、咔啉(carboline)、菲(phenanthrine)、吖啶、啶(perimidine)、啡啉、酞、啡唑啶(phenalzadine)及呋呫等，此等可以更進行苯并環縮，又，亦可以具有取代基。The heteroaryl group may be a group derived from a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the heteroaryl ring in the particularly preferred heteroaryl group include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, and brown. , pyrrole, pyrazole, isothiazole, different Oxazole, pyridyl Pyrimidine 吲哚 Heterogeneous , indoyl, carbazole, purine, quinine Isoquine 酞 , naphthyridine, quinazoline, shinorine, pteridine, carbazole, carboline, phenanthrine, acridine, Perimidine, morpholine, anthraquinone , phenalzadine and furazan, etc., which may further undergo benzo ring condensation, and may also have a substituent.

又，烯基可舉出例如乙烯基、1-丙烯基、1-丁烯基、肉桂基、2-氯-1-乙烯基等。炔基可舉出例如乙炔基、1-丙炔基、1-丁炔基、三甲基矽烷基乙炔基等。醯基(G1 CO-)之G1 可舉出例如氫及上述的烷基、芳基。該等取代基中，更佳的例子可舉出鹵素原子(-F、-Br、-Cl、-I)、烷氧基、芳氧基、烷硫基、芳硫基、N-烷胺基、N,N-二烷胺基、醯氧基、N-烷基胺基甲醯氧基、N-芳基胺基甲醯氧基、醯胺基、甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺基甲醯基、N-烷基胺基甲醯基、N,N-二烷基胺基甲醯基、N-芳基胺基甲醯基、N-烷基-N-芳基胺基甲醯基、磺酸基、磺酸根基、胺磺醯基、N-烷基胺磺醯基、N,N-二烷基胺磺醯基、N-芳基胺磺醯基、N-烷基-N-芳基胺磺醯基、膦酸基、膦酸根基、二烷基膦酸基、二芳基膦酸基、一烷基膦酸基、烷基膦酸根基、一芳基膦酸基、芳基膦酸根基、膦醯氧基、膦酸根氧基、芳基、烯基、亞烷基(亞甲基等)。Further, examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-vinyl group. The alkynyl group may, for example, be an ethynyl group, a 1-propynyl group, a 1-butynyl group or a trimethyldecyl ethynyl group. Acyl group (G 1 CO-) include, for example, of the hydrogen G 1 and said alkyl, aryl. Among the substituents, preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an N-alkylamino group. , N,N-dialkylamino, decyloxy, N-alkylaminomethyl methoxy, N-arylaminomethyl methoxy, decyl, decyl, decyl, carboxy, alkane Oxycarbonyl, aryloxycarbonyl, aminomethyl fluorenyl, N-alkylaminomethyl fluorenyl, N,N-dialkylaminomethyl fluorenyl, N-arylaminomethyl fluorenyl, N- Alkyl-N-arylaminocarbazinyl, sulfonate, sulfonate, sulfonyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-aryl Amine sulfonyl, N-alkyl-N-arylamine sulfonyl, phosphonic acid, phosphonate, dialkylphosphonic acid, diarylphosphonic acid, monoalkylphosphonic acid, alkane Phosphonate, monoarylphosphonate, arylphosphonate, phosphinyloxy, phosphonateoxy, aryl, alkenyl, alkylene (methylene, etc.).

另一方面，在取代烷基之伸烷基可舉出例如從前述碳數1~20之烷基上脫除氫原子中之任一個，而成為2價的有機殘基之物。較佳可舉出碳原子數1至12之直鏈狀、碳原子數3~12之分枝狀及碳原子數5~10之環狀的伸烷基。On the other hand, the alkylene group of the substituted alkyl group may, for example, be a compound having a divalent organic residue obtained by removing any one of hydrogen atoms from the alkyl group having 1 to 20 carbon atoms. Preferable examples thereof include a linear chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms.

藉由組合上述取代基與伸烷基而得到之R1 、R2 或R3 ，較佳取代烷基之具體例可舉出氯甲基、溴甲基、2-氯乙基、三氟甲基、甲氧基甲基、甲氧基乙氧基乙基、芳氧基甲基、苯氧基甲基、甲硫基甲基、甲苯硫基甲基、乙胺基乙基、二乙胺基丙基、嗎啉丙基、乙醯氧基甲基、苯甲醯氧基甲基、N-環己基胺基甲醯氧基乙基、N-苯基胺基甲醯氧基、乙醯胺基乙基、N-甲基苯甲醯胺基丙基、2-側氧乙基、2-側氧丙基、羧丙基、甲氧基羰基乙基、芳氧基羰基丁基、氯苯氧基羰基甲基、胺基甲醯基甲基、N-甲基胺基甲醯基乙基、N,N-二丙基胺基甲醯基甲基、N-(甲氧基苯基)胺基甲醯基乙基、N-甲基-N-(磺酸基苯基)胺基甲醯基甲基、磺酸基丁基、磺酸根基丙基、磺酸根基丁基、胺亞磺醯基丁基、N-乙基胺磺醯基甲基、N,N-二丙基胺磺醯基丙基、N-三胺磺醯基丙基、N-甲基-N-(膦酸基苯基)胺磺醯基辛基、膦酸基丁基、膦酸根基己基、二乙基膦酸基丁基、二苯基膦酸基丙基、甲基膦酸基丁基、甲基膦酸根基丁基、甲苯基膦酸基己基、甲苯基膦酸根己基、膦醯氧基丙基、膦酸根氧基丁基、苄基、苯乙基、α-甲基苄基、1-甲基-1-苯基乙基、對甲基苄基、肉桂基、烯丙基、1-丙烯基甲基、2-丁烯基、2-甲基烯丙基、2-甲基丙烯基甲基、2-丙炔基、2-丁炔基、3-丁炔基等。R 1 , R 2 or R 3 obtained by combining the above substituent with an alkyl group, and preferred examples of the substituted alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, and a trifluoromethyl group. , methoxymethyl, methoxyethoxyethyl, aryloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl, ethylaminoethyl, diethylamine Propyl, morpholinylpropyl, ethoxymethyloxymethyl, benzhydryloxymethyl, N-cyclohexylaminomethyloxyethyl, N-phenylaminomethyloxy, ethyl hydrazine Aminoethyl, N-methylbenzimidylpropyl, 2-sided oxyethyl, 2-sided oxypropyl, carboxypropyl, methoxycarbonylethyl, aryloxycarbonylbutyl, chloro Phenoxycarbonylmethyl, aminomethylmethylmethyl, N-methylaminomethylmethyl, N,N-dipropylaminomethylmethyl, N-(methoxyphenyl) Aminomethylmethyl, N-methyl-N-(sulfonylphenyl)aminomethylmethylmethyl, sulfonylbutyl, sulfonylpropyl, sulfonylbutyl, amine Sulfosylbutyl, N-ethylaminesulfonylmethyl, N,N-dipropylaminesulfonylpropyl, N-triaminesulfonylpropyl, N-methyl-N-( phosphine Alkyl phenyl sulfonyl octyl, phosphonic butyl, phosphonic hexyl, diethylphosphonic butyl, diphenylphosphonyl propyl, methylphosphonic butyl, methyl Phosphonate butyl, cresylphosphonylhexyl, tolylphosphonate, phosphinomethoxypropyl, phosphonityloxybutyl, benzyl, phenethyl, alpha-methylbenzyl, 1-methyl 1-phenylethyl, p-methylbenzyl, cinnamyl, allyl, 1-propenylmethyl, 2-butenyl, 2-methylallyl, 2-methylpropenyl Base, 2-propynyl, 2-butynyl, 3-butynyl and the like.

在R1 、R2 或R3 之較佳的芳基的具體例，可舉出1個至3個苯環形成稠環而成之物、苯環與5員不飽和環形成稠環而成之物，具體例可舉出苯基、萘基、蒽基、菲基、茚基、苊基、茀基，此等之中，以苯基、萘基為更佳。Specific examples of preferred aryl groups for R 1 , R 2 or R 3 include those in which one to three benzene rings form a fused ring, and a benzene ring forms a fused ring with a 5-membered unsaturated ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, a fluorenyl group, and a fluorenyl group. Among them, a phenyl group or a naphthyl group is more preferable.

R1 、R2 或R3 之較佳取代芳基的具體例，能夠使用在上述未取代芳基的環形成碳原子上具有-價的非金屬原子團作為取代基(氫原子以外的)。較佳取代基之例子可舉出前述的烷基、取代烷基、及在前述取代烷基作為取代基所示者。此種取代芳基之較佳具體例，可舉出聯苯基、甲苯基、二甲苯基、基、異丙苯基、氯苯基、溴苯基、氟苯基、氯甲基苯基、三氟甲基苯基、羥苯基、甲氧基苯基、甲氧基乙氧基苯基、烯丙氧基苯基、苯氧基苯基、甲硫基苯基、甲苯硫基苯基、乙胺基苯基、二乙胺基苯基、嗎啉苯基、乙醯氧基苯基、苯甲醯氧基苯基、N-環己基胺基甲醯氧基苯基、N-苯基胺基甲醯氧基苯基、乙醯胺基苯基、N-甲基苯甲醯胺基苯基、羧苯基、甲氧基羰基苯基、芳氧基羰基苯基、氯苯氧基羰基苯基、胺基甲醯基苯基、N-甲基胺基甲醯基苯基、N,N-二丙基胺基甲醯基苯基、N-(甲氧基苯基)胺基甲醯基苯基、N-甲基-N-(磺酸基苯基)胺基甲醯基苯基、磺酸基苯基、磺酸根基苯基、胺磺醯基苯基、N-乙基胺磺醯基苯基、N,N-二丙基胺磺醯基苯基、N-甲苯基胺磺醯基苯基、N-甲基-N-(膦酸基苯基)胺磺醯基苯基、膦酸基苯基、膦酸根基苯基、二乙基膦酸基苯基、二苯基膦酸基苯基、甲基膦酸基苯基、甲基膦酸根基苯基、甲苯基膦酸基苯基、甲苯基膦酸根基苯基、烯丙基苯基、1-丙烯基甲基苯基、2-丁烯基苯基、2-甲基烯丙基苯基、2-甲基丙烯基苯基、2-丙炔基苯基、2-丁炔基苯基、3-丁炔基苯基等。As a specific example of the preferable substituted aryl group of R 1 , R 2 or R 3 , a non-metal atomic group having a valence at the ring-forming carbon atom of the above unsubstituted aryl group can be used as a substituent (other than a hydrogen atom). Examples of preferred substituents include the above-mentioned alkyl group, substituted alkyl group, and the above-mentioned substituted alkyl group as a substituent. Preferred examples of such a substituted aryl group include a biphenyl group, a tolyl group, and a xylyl group. Base, cumyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl , allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinylphenyl, ethoxylated phenyl , benzyl methoxy phenyl, N-cyclohexylaminomethyl methoxy phenyl, N-phenylaminomethyl methoxy phenyl, acetaminophen phenyl, N-methyl benzyl amide Phenylphenyl, carboxyphenyl, methoxycarbonylphenyl, aryloxycarbonylphenyl, chlorophenoxycarbonylphenyl, aminomethylphenylphenyl, N-methylaminoformamidophenyl, N,N-dipropylaminopyristylphenyl, N-(methoxyphenyl)aminocarbamidophenyl, N-methyl-N-(sulfophenyl)aminocarbamidine Phenylphenyl, sulfonylphenyl, sulfonylphenyl, sulfonylphenyl, N-ethylaminesulfonylphenyl, N,N-dipropylaminesulfonylphenyl, N- Tolylamine sulfonylphenyl, N-methyl-N-(phosphonophenyl)amine sulfonylphenyl, phosphonic phenyl, phosphonate phenyl, diethylphosphonic phenyl Diphenylphosphonic phenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolylphosphonyl phenyl, allyl phenyl, 1-propene Methylphenyl, 2-butenylphenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propynylphenyl, 2-butynylphenyl, 3 - Butynylphenyl and the like.

又，R2 及R3 的更佳例子，可舉出取代或未取代的烷基。又，R1 的更佳例子可舉出取代或未取代的基。雖然其理由不明確，推測藉由具有此種取代基，光吸收所產生的電子激發狀態與引發劑化合物的相互作為變為特別大，而提高引發劑化合物產生自由基、酸或鹼的效率之緣故。Further, as a more preferable example of R 2 and R 3 , a substituted or unsubstituted alkyl group is exemplified. Further, a more preferable example of R 1 is a substituted or unsubstituted group. Although the reason is not clear, it is presumed that by having such a substituent, the mutual excitation of the electron-excited state and the initiator compound by light absorption becomes particularly large, and the efficiency of generating an initiator, a compound, or an alkali by an initiator is improved. reason.

接著，說明通式(XVIII)之A。A係表示亦可具有取代基之芳香族環或雜環，亦可具有取代基之芳香族環或雜環的具體例，可舉出在前述說明對通式(XVIII)之R1 、R2 或R3所例示者同樣之物。Next, A of the formula (XVIII) will be described. A is a specific example of an aromatic ring or a hetero ring which may have a substituent, and may have an aromatic ring or a hetero ring which may have a substituent, and R 1 and R 2 of the formula (XVIII) are mentioned above. Or the same as that exemplified in R3.

其中，較佳的A可舉出具有烷氧基、硫烷基或胺基之芳基，特佳的A可舉出具有胺基之芳基。Among them, preferred A is an aryl group having an alkoxy group, a sulfanyl group or an amine group, and particularly preferably A is an aryl group having an amine group.

接著，說明通式(XVIII)之Y。Y係表示上述的A及鄰接碳原子數共同形成雜環時所必要的非金屬原子團。此種雜環可舉出亦可具有稠環之5、6、7員的含氮、或含硫雜環，以5、6員的雜環為佳。Next, Y of the formula (XVIII) will be described. Y is a non-metal atomic group necessary for the above-mentioned A and the number of adjacent carbon atoms to form a hetero ring. Examples of such a heterocyclic ring include a nitrogen-containing or sulfur-containing heterocyclic ring which may have 5, 6 or 7 members of the fused ring, and a heterocyclic ring of 5 or 6 members is preferred.

舉出含氮雜環的例子時，可適合使用任一種在L.G. Brooker等人著美國化學協會期刊(J. Am. Chem.Soc.)第73卷(1951年)、第5326-5358頁及參考文獻所記載之已知構成部花青素色素類的鹼性核者。In the case of a nitrogen-containing heterocyclic ring, any one may be suitably used in LG Brooker et al., J. Am. Chem. Soc., vol. 73 (1951), pages 5326-5358, and references. The basic nucleus of the anthocyanin pigments of the known constituents described in the literature.

具體例可舉出噻唑類(例如噻唑、4-甲基噻唑、4-苯基噻唑、5-甲基噻唑、5-苯基噻唑、4,5-二甲基噻唑、4,5-二苯基噻唑、4,5-二(對甲氧基苯基噻唑)、4-(2-噻吩基)噻唑、4,5-二(2-呋喃基)噻唑等)；苯并噻唑類(例如、苯并噻唑、4-氯苯并噻唑、5-氯苯并噻唑、6-氯苯并噻唑、7-氯苯并噻唑、4-甲基苯并噻唑、5-甲基苯并壓唑、6-甲基苯并噻唑、5-溴苯并噻唑、4-苯基苯并噻唑、5-苯基苯并噻唑、4-甲氧基苯并噻唑、5-甲氧基苯并噻唑、6-甲氧基苯并噻唑、5-碘苯并噻唑、6-碘苯并噻唑、4-乙氧基苯并噻唑、5-乙氧基苯并噻唑、四氫苯并噻唑、5,6-二甲氧基苯并噻唑、5,6-二羥基亞甲基苯并噻唑、5-羥基苯并噻唑、6-羥基苯并噻唑、6-二甲胺基苯并噻唑、5-乙氧基羰基苯并噻唑等)；萘并噻唑類(例如、萘并[1,2]噻唑、萘并[2,1]噻唑、5-甲氧基萘并[2,1]噻唑、5-乙氧基萘并[2,1]噻唑、8-甲氧基萘并[1,2]噻唑、7-甲氧基萘并[1,2]噻唑等)；硫環烷基-7,6,4,5-噻唑類(例如，4-甲氧基硫環烷基-7,6,4,6-噻唑等)；唑類(例如、4-甲基唑、5-甲基唑、4-苯基唑、4,5-二苯基唑、4-乙基唑、4,5-二甲基唑、5-苯基唑等)；苯并唑類(苯并唑、5-氯苯并唑、5-甲基苯并唑、5-苯基苯并唑、6-甲基苯并唑、5,6-二甲基苯并唑、4,6-二甲基苯并唑、6-甲氧基苯并唑、5-甲氧基苯并唑、4-乙氧基苯并唑、5-氯苯并唑、6-甲氧基苯并唑、5-羥基苯并唑、6-羥基苯并唑等)；Specific examples thereof include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenyl). Thiazole, 4,5-di(p-methoxyphenylthiazole), 4-(2-thienyl)thiazole, 4,5-di(2-furyl)thiazole, etc.; benzothiazoles (for example, Benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzoxazole, 6 -methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6- Methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-di Methoxybenzothiazole, 5,6-dihydroxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonyl Benzothiazole, etc.; naphthylthiazoles (for example, naphtho[1,2]thiazole, naphtho[2,1]thiazole, 5-methoxynaphtho[2,1]thiazole, 5-ethoxyl Naphtho[2,1]thiazole, 8-methoxynaphtho[1,2]thiazole, 7-methoxynaphtho[1,2]thiazole, etc.; thiocycloalkyl-7,6,4,5-thiazoles (eg, 4- Methoxythiocycloalkyl-7,6,4,6-thiazole, etc.); Azole (eg, 4-methyl) Azole, 5-methyl Azole, 4-phenyl Azole, 4,5-diphenyl Azole, 4-ethyl Azole, 4,5-dimethyl Azole, 5-phenyl Azole, etc.; benzo Azole Oxazole, 5-chlorobenzo Azole, 5-methylbenzo Oxazole, 5-phenylbenzo Azole, 6-methylbenzo Oxazole, 5,6-dimethylbenzo Oxazole, 4,6-dimethylbenzo Oxazole, 6-methoxybenzo Oxazole, 5-methoxybenzo Oxazole, 4-ethoxybenzo Oxazole, 5-chlorobenzo Oxazole, 6-methoxybenzo Azole, 5-hydroxybenzo Azole, 6-hydroxybenzo Azole, etc.);

萘并噻唑類(例、如萘并[1,2]唑、萘并[2,1]唑等)；哂唑類(例如、4-甲基哂唑、4-苯基哂唑等)；苯并哂唑類(例如、苯并哂唑、5-氯苯并哂唑、5-甲氧基苯并哂唑、5-羥基苯并哂唑、四氫苯并哂唑等)；萘并哂唑類(例如、萘并[1,2]哂唑、萘并[2,1]哂唑等)；噻唑啉類(例如、噻唑啉、4-甲基噻唑啉、4,5-二甲基噻唑啉、4-苯基噻唑啉、4,5-二(2-呋喃基)噻唑啉、4,5-二苯基噻唑啉、4,5-二(對甲氧基苯基)噻唑啉等)：2-喹啉類(例如、喹啉、3-甲基喹啉、5-甲基喹啉、7-甲基喹啉、8-甲基喹啉、6-氯喹啉、8-氯喹啉、6-甲氧基喹啉、6-乙氧基喹啉、6-羥基喹啉、8-羥基喹啉等)；4-喹啉類(例如、喹啉、6-甲氧基喹啉、7-甲基喹啉、8-甲基喹啉等)；1-異喹啉類(例如、異喹啉、3,4-二氫異喹啉等)；3-異喹啉類(例如、異喹啉等)；苯并咪唑類(例如、1,3-二甲基苯并咪唑、1,3-二乙基苯并咪唑、1-乙基-3-苯基苯并咪唑等)；3,3-二烷基假吲哚(indolenine)類(例如、3,3-二甲基假吲哚、3,3,5-三甲基假吲哚、3,3,7-三甲基假吲哚等)；2-吡啶類(例如、吡啶、5-甲基吡啶等)；4-吡啶(例如、吡啶等)等。又，該等的環之取代基之間亦可鍵結而形成環。Naphthylthiazoles (eg, such as naphtho[1,2] Azole, naphtho[2,1] Oxazole, etc.; oxazoles (eg, 4-methylcarbazole, 4-phenyloxazole, etc.); benzoxazoles (eg, benzoxazole, 5-chlorobenzoxazole, 5-A) Oxylbenzoxazole, 5-hydroxybenzoxazole, tetrahydrobenzoxazole, etc.); naphtolocarbazoles (for example, naphtho[1,2]carbazole, naphtho[2,1]fluorene Azole or the like; thiazolines (for example, thiazoline, 4-methylthiazoline, 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-bis(2-furyl)thiazoline , 4,5-diphenylthiazoline, 4,5-di(p-methoxyphenyl)thiazoline, etc.): 2-quinoline (eg, quinoline, 3-methylquinoline, 5-a) Quinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline or the like; 4-quinoline (for example, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.); 1-isoquinoline ( For example, isoquinoline, 3,4-dihydroisoquinoline, etc.; 3-isoquinolines (eg, isoquinolines, etc.); benzimidazoles (eg, 1,3-dimethylbenzimidazole) , 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.; 3,3-dialkylhypothylene (indolenine) (eg, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.); 2-pyridine (e.g., pyridine, 5-methylpyridine, etc.); 4-pyridine (e.g., pyridine, etc.), and the like. Further, the substituents of the rings may be bonded to each other to form a ring.

又，含硫雜環的例子可舉出例如特開平3-296759號所記載的色素類之二硫醇部分結構。Further, examples of the sulfur-containing heterocyclic ring include a dithiol partial structure of a dye described in JP-A No. 3-296759.

具體例可舉出例如苯并二硫醇類(例如、苯并二硫醇、5-第三丁基苯并二硫醇、5-甲基苯并二硫醇等)；萘并二硫醇類(例如、萘并[1,2]二硫醇、萘并[2,1]二硫醇等)；二硫醇類(例如、4,5-二甲基二硫醇類、4-苯基二硫醇類、4-甲氧基二硫醇類、4,5-二甲氧基羰基二硫醇類、4-甲氧基羰基二硫醇類、4,5-二甲氧基羰基二硫醇類、4,5-二乙氧基二硫醇類、4,5-雙三氟甲基二硫醇、4,5-二氰基二硫醇類、4-甲氧基羰基甲基二硫醇類及4-羧基甲基二硫醇類等)等。Specific examples thereof include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.); naphthodithiols. Classes (eg, naphtho[1,2]dithiol, naphtho[2,1]dithiol, etc.); dithiols (eg, 4,5-dimethyldithiol, 4-benzene) Dithiols, 4-methoxydithiols, 4,5-dimethoxycarbonyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyl Dithiols, 4,5-diethoxydithiols, 4,5-bistrifluoromethyldithiols, 4,5-dicyanodithiols, 4-methoxycarbonyl Dithiols, 4-carboxymethyldithiols, etc.).

在上述之通式(XVIII)，Y係上述的A及鄰接碳原子共同形成之含氮或含硫雜環的例子之中，因為能夠提供具有高增感性能且保存安定性非常優良的感光性組成物，以具有下述通式(XVIII-2)的部分結構式所示結構之色素為特佳。具有下述通式(XVIII-2)的部分結構式所示結構之色素係新穎化合物，係在特願2003-311253說明書所詳細記載之化合物。In the above-mentioned general formula (XVIII), Y is an example of a nitrogen-containing or sulfur-containing hetero ring formed by the above-mentioned A and a contiguous carbon atom, and it is possible to provide a photosensitive property having high sensitization performance and excellent storage stability. The composition is particularly preferably a pigment having a structure represented by a partial structural formula of the following formula (XVIII-2). A novel dye-based compound having a structure represented by a partial structural formula of the following formula (XVIII-2), which is described in detail in the specification of Japanese Patent Application No. 2003-311253.

(通式(XVIII-2)中，A係表示亦可具有取代基之芳香族環或雜環，X係表示氧原子、硫原子、或-N(R1 )-。R1 、R4 、R5 及R6 係各自獨立地表示氫原子或一價的非金屬原子團，R1 、R4 、R5 及R6 各自能夠與A鍵結而形成脂肪族性或芳香族性的環)(In the formula (XVIII-2), A represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or -N(R 1 )-. R 1 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a monovalent non-metal atomic group, and each of R 1 , R 4 , R 5 and R 6 can be bonded to A to form an aliphatic or aromatic ring)

在通式(XVIII-2)中，A及R1 係與在通式(XVIII)所示者同義)，R4 係與在通式(XVIII)所示之R2 同義，R5 係與在通式(XVIII)所示之R3 同義，R6 係與在通式(XVIII)所示之R1 同義。In the formula (XVIII-2), A and R 1 are the same as those represented by the formula (XVIII), and R 4 is synonymous with R 2 represented by the formula (XVIII), and R 5 is R 3 represented by the formula (XVIII) is synonymous, and R 6 is synonymous with R 1 represented by the formula (XVIII).

接著，說明本發明所使用之通式(XVIII)所示化合物的較佳態樣亦即通式(XVIII-3)所示之化合物。Next, a preferred embodiment of the compound of the formula (XVIII) used in the present invention, that is, a compound of the formula (XVIII-3), will be described.

前述通式(XVIII-3)中，A係表示亦可具有取代基之芳香族環或雜環，X係表示氧原子、硫原子、或-N(R1 )-。R1 、R4 及R5 係各自獨立地表示氫原子或一價的非金屬原子團，R1 、R4 及R5 各自能夠與A鍵結而形成脂肪族性或芳香族性的環。Ar係表示具有取代基之芳香族環或雜環。但是，Ar骨架上的取代基之哈曼特(Hammett’s)值的總和為大於0。在此，哈曼特值的總和大於0係指可以具有1個取代基且該取代基的哈曼特值為大於0，亦可以具有複數個取代基且該取代基的哈曼特值的總和為大於0。In the above formula (XVIII-3), A represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents an oxygen atom, a sulfur atom or -N(R 1 )-. R 1 , R 4 and R 5 each independently represent a hydrogen atom or a monovalent non-metal atomic group, and each of R 1 , R 4 and R 5 may be bonded to A to form an aliphatic or aromatic ring. The Ar system represents an aromatic ring or a heterocyclic ring having a substituent. However, the sum of the Hammett's values of the substituents on the Ar skeleton is greater than zero. Here, the sum of the Hammant values greater than 0 means that the substituent may have one substituent and the Hammant value of the substituent is greater than 0, and may have a plurality of substituents and the sum of the Hammant values of the substituents. Is greater than 0.

通式(XVIII-3)中，A及R1 係與在通式(XVIII)所示者同義，R4 係與在通式(XVIII)所示之R2 同義，R5 係與在通式(XVIII)所示之R3 同義。Ar係表示具有取代基之芳香族環或雜環，具體例可同樣地舉出前面說明通式(XVIII)之A所記載者之中，具有取代基之芳香族環或雜環之具體例。但是，在通式(XVIII-3)之Ar能夠導入的取代基，其哈曼特值的總和必須為0以上。此種取代基的例子可舉出三氟甲基、羰基、酯基、鹵素原子、硝基、氰基、亞碸基、醯胺基及羧基等。該等取代基的哈曼特值係如下所示。三氟甲基(-CF3 、m：0.43、p：0.54)、羰基(例如-COH、m：0.36、p：0.43)、酯基(-COOCH3 、m：0.37、p：0.45)、鹵素原子(例如Cl、m：0.37、p：0.23)、氰基(-CN、m：0.56、p：0.66)、亞碸基(例如-SOCH3 、m：0.52、p：0.45)、醯胺基(例如-NHCOCH3 、m：0.21、p：0.00)、羧基(-COOH、m：0.37、p：0.45)等。括弧內係表示在該取代基的芳基骨架之導入位置及其哈曼特值。例如(m：0.50)係指該取代基係導入間位時，哈曼特值為0.50)。在此之中，Ar的較佳例子可舉出具有取代基之苯基，Ar骨架上的較佳取代基之例子可舉出酯基及氰基。取代位置以在Ar骨架上的鄰位為特佳。In the general formula (XVIII-3), A and R 1 are based in the general formula (XVIII) are shown synonymous, R 4 R in line with the formula (XVIII) of FIG synonymous 2, R 5 in the general formula based R 3 represented by (XVIII) is synonymous. The Ar system is an aromatic ring or a hetero ring which has a substituent, and a specific example of the aromatic ring or the hetero ring which has a substituent among the above-described description of the formula (XVIII) A can be similarly mentioned. However, the substituent which can be introduced into Ar of the formula (XVIII-3) must have a total Harmant value of 0 or more. Examples of such a substituent include a trifluoromethyl group, a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a fluorenylene group, a decylamino group, and a carboxyl group. The Hammant values of the substituents are as follows. Trifluoromethyl (-CF 3 , m: 0.43, p: 0.54), carbonyl (eg, -COH, m: 0.36, p: 0.43), ester group (-COOCH 3 , m: 0.37, p: 0.45), halogen Atom (for example, Cl, m: 0.37, p: 0.23), cyano (-CN, m: 0.56, p: 0.66), anthracenylene (for example, -SOCH 3 , m: 0.52, p: 0.45), amidino group (e.g., -NHCOCH 3 , m: 0.21, p: 0.00), a carboxyl group (-COOH, m: 0.37, p: 0.45), and the like. The parentheses indicate the introduction position of the aryl skeleton of the substituent and its Hammant value. For example, (m: 0.50) means that the substituent is introduced into the meta position, and the Hammant value is 0.50). Among the preferred examples of Ar, a phenyl group having a substituent is exemplified, and examples of preferred substituents on the Ar skeleton include an ester group and a cyano group. Substitution of positions to the ortho position on the Ar skeleton is particularly preferred.

以下，顯示在本發明之通式(XVIII)所示增感色素的較佳具體例[例示化合物(F1)～例示化合物(F56)]，但是本發明未限定於該等。In the following, preferred examples of the sensitizing dye represented by the formula (XVIII) of the present invention [exemplary compound (F1) to exemplary compound (F56)] are shown, but the present invention is not limited thereto.

在本發明能夠應用之前述的增感色素之中，從深部硬化性的觀點，以前述通式(XVIII)所示之化合物為佳。Among the above-mentioned sensitizing dyes which can be used in the present invention, the compound represented by the above formula (XVIII) is preferred from the viewpoint of deep curing property.

關於上述增感色素，為了改良著色感光性組成物的特性，能夠進行如以下的各種化學改性。例如將增感色素及加成聚合性化合物結構(例如，丙烯醯基或甲基丙烯醯基)藉由共價鍵、離子鍵、或氫鍵等方法使其鍵結，能夠得到交聯硬化膜的高強度化、或提升抑制色素從交聯硬化膜之不需要的析出。The sensitizing dye can be subjected to various chemical modifications as follows in order to improve the characteristics of the colored photosensitive composition. For example, a sensitizing dye and an addition polymerizable compound structure (for example, an acrylonitrile group or a methacryl oxime group) can be bonded by a covalent bond, an ionic bond, or a hydrogen bond to obtain a crosslinked cured film. The increase in strength or the suppression of unwanted precipitation of the dye from the crosslinked cured film.

相對於著色感光性組成物的總固體成分，增感色素的含量以0.01～20質量%為佳，以0.01～10質量%為較佳，以0.1～5質量%為更佳。The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.1 to 5% by mass, based on the total solid content of the coloring photosensitive composition.

藉由增感色素在該範圍，對超高壓水銀燈的曝光波長具有高敏感度，能夠得到膜深部硬化性，同時從顯像餘裕度、圖案形成性而言，乃是較佳。When the sensitizing dye is in this range, the exposure wavelength of the ultrahigh pressure mercury lamp is highly sensitive, and the film deep hardenability can be obtained, and it is preferable from the development margin and the pattern formation property.

鹼可溶性樹脂Alkali soluble resin

鹼可溶性樹脂係線形有機高分子聚合物，能夠適當地選自在分子(較佳是丙烯酸系共聚物、或是以苯乙烯系共聚物作為主鏈之分子)中至少具有1個促進鹼可溶性之基(例如羧基、磷酸基或磺酸基等)之鹼可溶性樹脂中。該等之中，更佳是可溶於有機溶劑且能夠藉由弱鹼性水溶液來顯像者。The alkali-soluble resin-based linear organic high molecular polymer can be appropriately selected from a group having at least one alkali-suppressing base in a molecule (preferably an acrylic copolymer or a molecule having a styrene copolymer as a main chain). (e.g., a carboxyl group, a phosphate group, a sulfonic acid group, etc.) in an alkali-soluble resin. Among these, it is more preferable that it is soluble in an organic solvent and can be imaged by a weakly alkaline aqueous solution.

製造鹼可溶性樹脂例如能夠應用眾所周知的自由基聚合法之方法。藉由自由基聚合法製造鹼可溶性樹脂時之溫度、壓力、自由基引發劑的種類及其量、溶劑的種類等等的聚合條件係該業者能夠容易地設定，且亦能夠實驗地決定條件。The method for producing an alkali-soluble resin can be applied, for example, to a well-known radical polymerization method. The polymerization conditions in the case of producing an alkali-soluble resin by a radical polymerization method, such as the temperature, the pressure, the type and amount of the radical initiator, the kind of the solvent, and the like, can be easily set by the manufacturer, and the conditions can be experimentally determined.

上述的線狀有機高分子聚合物以在側鏈具有羧酸之聚合物為佳。可舉出例如特開昭59-44615號、特公昭54-34327號、特公昭58-12577號、特公昭54-25957號、特開昭59-53836號、特開昭59-71048號的各公報所記載之甲基丙烯酸共聚物、丙烯酸共聚物、伊康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化(partially esterified)順丁烯二酸共聚物等，及對在側鏈具有羧酸之酸性纖維素衍生物、具有羥基之聚合物加添酸酐而成者等，而且亦可舉出的較佳例子係在側鏈具有(甲基)丙烯醯基之高分子聚合物。The above linear organic high molecular polymer is preferably a polymer having a carboxylic acid in a side chain. For example, each of JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, JP-A-54-25957, JP-A-59-53836, and JP-A-59-71048 a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, etc., as described in the publication, and A method in which an acid anhydride having a carboxylic acid in a side chain or a polymer having a hydroxyl group is added with an acid anhydride, and a preferred example is also a case where the side chain has a high (meth) acrylonitrile group. Molecular polymer.

該等之中，以由(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、及(甲基)丙烯酸苄酯/(甲基)丙烯酸/其他單體所構成的多元共聚物為特佳。Among these, a multicomponent copolymer composed of a benzyl (meth)acrylate/(meth)acrylic acid copolymer and a benzyl (meth)acrylate/(meth)acrylic acid/other monomer is particularly preferred. .

此外，使甲基丙烯酸2-羥基乙酯共聚合而成者等亦是可舉出的有用例子。該聚合物能夠以任意量混合使用。Further, a method of copolymerizing 2-hydroxyethyl methacrylate or the like is also a useful example. The polymer can be used in combination in any amount.

上述以外，可舉出特開平7-140654號公報所記載之(甲基)丙烯酸2-羥基丙酯/聚苯乙烯大分子單體/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/聚甲基丙烯酸甲酯大分子單體/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/聚苯乙烯大分子單體/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/聚苯乙烯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。In addition to the above, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer and acrylic acid 2-described in JP-A-7-140654 Hydroxy-3-phenoxypropyl ester/polymethyl methacrylate macromer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/ Methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

關於鹼可溶性樹脂之具體的構成單位，以(甲基)丙烯酸和能夠與其共聚合的其他單體之共聚物為特佳。在此，(甲基)丙烯酸係合併丙烯酸及甲基丙烯酸之總稱，以下亦同樣地，(甲基)丙烯酸酯係丙烯酸酯及甲基丙烯酸酯之總稱。The specific constituent unit of the alkali-soluble resin is particularly preferably a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith. Here, the general term for (meth)acrylic acid-based acrylic acid and methacrylic acid is the same as the general term of (meth)acrylate-based acrylate and methacrylate.

前述能夠與(甲基)丙烯酸共聚合的其他單體可舉出例如(甲基)丙烯酸烷酯、(甲基)丙烯酸芳酯、乙烯系化合物等。在此，烷基及芳基的氫原子亦可被取代基取代。Examples of the other monomer copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

前述(甲基)丙烯酸烷酯及(甲基)丙烯酸芳酯的具體例可舉出(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)丙烯酸萘酯及(甲基)丙烯酸環己酯等。Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate 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, and the like.

前述乙烯系化合物可舉出可舉出苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲基丙烯酸環氧丙酯、丙烯腈、乙酸乙烯酯、N-乙烯基吡咯啶酮、甲基丙烯酸四氫糠酯、聚苯乙烯大分子單體及聚甲基丙烯酸甲酯大分子、CH2 =CR1 R2 及CH2 =C(R1 )(COOR3 )[在此，R1 係表示氫原子或碳數1~5的烷基，R2 係表示碳數6～10的芳香族烴環，R3 係表示碳數1～8的烷基或碳數6～12的芳烷基]等。Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, and methacrylic acid. Tetrahydrofurfuryl ester, polystyrene macromonomer and polymethyl methacrylate macromolecule, CH 2 =CR 1 R 2 and CH 2 =C(R 1 )(COOR 3 ) [here, R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 2 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms; and R 3 represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms] Wait.

該等能夠共聚合之其他單體可單獨使用1種，亦可組合使用2種以上。能夠共聚合之較佳的其他單體可舉出例如選自CH2 =CR1 R2 、CH2 =C(R1 )(COOR3 )、(甲基)丙烯酸苯酯及(甲基)丙烯酸苄酯之至少1種，以CH2 =CR1 R2 及或CH2 =C(R1 )(COOR3 )為特佳。These other monomers which can be copolymerized may be used alone or in combination of two or more. Preferred other monomers capable of copolymerization include, for example, a compound selected from the group consisting of CH 2 =CR 1 R 2 , CH 2 =C(R 1 )(COOR 3 ), phenyl (meth)acrylate, and (meth)acrylic acid. At least one of the benzyl esters is particularly preferably CH 2 =CR 1 R 2 and or CH 2 =C(R 1 )(COOR 3 ).

鹼可溶性樹脂在光硬化性組成物中含量係相對於該組成物的總固體成分，以1～15質量%為佳，以2～12質量%為更佳，以3～10質量%為特佳。The content of the alkali-soluble resin in the photocurable composition is preferably from 1 to 15% by mass, more preferably from 2 to 12% by mass, even more preferably from 3 to 10% by mass, based on the total solid content of the composition. .

溶劑Solvent

本發明的著色感光性組成物通常能夠與上述成分一同使用溶劑而適當地調製。The colored photosensitive composition of the present invention can be usually appropriately prepared by using a solvent together with the above components.

溶劑的例子，酯類有例如乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、烷酯類、乳酸甲酯、乳酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、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、及3-羥基丙酸甲酯、3-羥基丙酸乙酯等的3-羥基丙酸烷酯類；3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯及3-乙氧基丙酸乙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基丙酸丙酯、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-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、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、2-酮基丁酸甲酯、2-酮基丁酸乙酯；醚類有例如二甘醇二甲基醚、四氫呋喃、乙二醇一甲基醚、乙二醇單乙基醚、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯(ethyl cellosolve acetate)、二甘醇一甲基醚、二甘醇一乙基醚、二甘醇一丁基醚、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯等；酮類有例如甲基乙基酮、環己酮、2-庚酮及3-庚酮等；芳香族烴類有例如甲苯、二甲苯等。此等之中，以3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基賽路蘇乙酸酯、乳酸乙酯、二甘醇二甲基醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯及丙二醇甲基醚乙酸酯等為佳。溶劑可單獨使用，亦可組合2種以上而使用。Examples of the solvent, esters are, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyrate B Ester, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, methoxy 3-hydroxypropionic acid alkyl esters such as butyl acetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, and methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate; 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxypropionic acid Ester, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropanoate , 2-ethoxy-2-methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetamidine Methyl ester, ethyl acetate, methyl 2-ketobutyrate, ethyl 2-ketobutyrate; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, methyl sarbuta acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3 - heptanone or the like; aromatic hydrocarbons such as toluene, xylene, and the like. Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Preferably, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol methyl ether acetate are preferred. The solvent may be used singly or in combination of two or more.

其他成分Other ingredients

在本發明的著色感光性組成物，亦可按照必要含有鏈轉移劑、氟系有機化合物、熱聚合引發劑、熱聚合成分、熱聚合抑制劑、其他填料、上述的鹼可溶性樹脂以外的高分子化合物、界面活性劑、黏附促進劑、抗氧化劑、紫外線吸收劑及防凝集劑等。In the colored photosensitive composition of the present invention, a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, another filler, or a polymer other than the above-described alkali-soluble resin may be contained as necessary. A compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and the like.

鏈轉移劑Chain transfer agent

鏈轉移劑可舉出例如N,N-二甲基胺基苯甲酸乙酯等的N,N-二烷基胺基苯甲酸烷酯、2-氫硫基苯并噻唑、2-氫硫基苯并唑、2-氫硫基苯并咪唑等具有雜環之氫硫基化合物及脂肪族多官能氫硫基化合物。The chain transfer agent may, for example, be an N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester, 2-hydrothiobenzothiazole or 2-hydrogenthio group. Benzo A heterocyclic hydrogenthio compound and an aliphatic polyfunctional thiol compound such as azole or 2-hydrothiobenzimidazole.

鏈轉移劑可單獨使用1種，亦可並用2種以上。The chain transfer agent may be used singly or in combination of two or more.

氟系有機化合物Fluorine organic compound

藉由含有氟系有機化合物，能夠改善將本發明的著色感光性組成物作為塗布液時之液特性(特別是流動性)，且能夠改善塗布厚度的均勻性及省液性。亦即，因為藉由降低被塗布物與塗布液之界面張力，能夠改善對被塗布物之潤濕性且能夠改善對被塗布物的塗布性，即便使用少量的液量來形成數微米左右的薄膜時，就能夠形成厚度不均少亦即厚度均勻的膜而言係有效的。By containing a fluorine-based organic compound, the liquid property (particularly fluidity) when the coloring photosensitive composition of the present invention is used as a coating liquid can be improved, and the uniformity of coating thickness and liquid-saving property can be improved. In other words, by reducing the interfacial tension between the object to be coated and the coating liquid, it is possible to improve the wettability to the object to be coated and to improve the applicability to the object to be coated, even if a small amount of liquid is used to form a few micrometers. In the case of a film, it is effective to form a film having a small thickness unevenness, that is, a film having a uniform thickness.

氟系有機化合物的氟含有率以3～40質量%為佳，以5～30質量%為更佳，以7～25質量%為特佳。氟含有率在前述範圍內時，就塗布厚度勻勻性而言係有效的，且在組成物中的溶解性亦是良好的。The fluorine-based organic compound preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity, and the solubility in the composition is also good.

氟系有機化合物的例子，可舉出例如MEGAFAC F171、同F172、同F173、同F177、同F141、同142、同143、同144、同R30、同F437(以上、DIC Corporation)製、FLUORAD FC-430、同FC-431、同FC-171(以上、住友3M(股)(Sumitomo 3M Limited)製)、SURFLON S-382、同SC-101、同SC-103、同SC-104、同SC-105、同SC-1068、同SC-381、同SC-383、同S393、同KH-40(以上、矽硝子(股)(Asahi Glass Co.,Ltd)製)等。Examples of the fluorine-based organic compound include, for example, MEGAFAC F171, F172, F173, F177, F141, 142, 143, 144, R30, F437 (above, DIC Corporation), FLUORAD FC. -430, with FC-431, with FC-171 (above, Sumitomo 3M Limited), SURFLON S-382, same SC-101, same SC-103, same SC-104, same SC -105, the same as SC-1068, the same SC-381, the same SC-383, the same S393, the same KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

氟系化合物作為氟系界面活性劑能夠適合使用在末端、主鏈及側鏈的至少任一部位具有氟烷基或氟伸烷基之化合物，具體上的市售品之例子，可舉出例如MEGAFAC F142D、同F172、同F173、同F176、同F177、同F183、同780、同781、同R30、同R08、同F-472SF、同BL20、同R-61、同R-90(DIC Corporation)製、FLUORAD FC-135、同FC-170C、同FC-430、同FC-431、Novec FC-4430(住友3M(股)製)、Asahi Guard AG7105、7000、950、7600、SURFLON S-112、同S-113、同S-131、同S-141、同S-145、同S-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(矽硝子(股)製)、EFTOP EF351、同352、同801、同802(JEMCO(股)製)等。Fluorine-based compound A compound having a fluoroalkyl group or a fluoroalkyl group in at least a part of the terminal, the main chain and the side chain can be suitably used as the fluorine-based surfactant. Specific examples of the commercially available product include, for example, a commercially available product. MEGAFAC F142D, with F172, with F173, with F176, with F177, with F183, with 780, with 781, with R30, with R08, with F-472SF, with BL20, with R-61, with R-90 (DIC Corporation ), FLUORAD FC-135, with FC-170C, with FC-430, with FC-431, Novec FC-4430 (Sumitomo 3M (share) system), Asahi Guard AG7105, 7000, 950, 7600, SURFLON S-112 Same as S-113, same S-131, same S-141, same S-145, same S-382, same SC-101, same SC-102, same SC-103, same SC-104, same SC-105 It is the same as SC-106 (manufactured by 矽 子 ( 股), EFTOP EF351, 352, 801, 802 (JEMCO).

氟系有機化合物特別是防止將塗布膜薄化時的塗布不均或厚度不均係有效的。又，而且在容易產生液體中斷之狹縫塗布亦是有效的。The fluorine-based organic compound is particularly effective in preventing coating unevenness or thickness unevenness when the coating film is thinned. Moreover, it is also effective to apply a slit which is liable to cause liquid interruption.

氟系有機化合物的添加量係相對於光硬化性組成物的總質量，以0.001～2.0質量%為佳，以0.005～1.0質量%為更佳。The amount of the fluorine-based organic compound to be added is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable composition.

熱聚合引發劑Thermal polymerization initiator

在本發明的著色感光性組成物，使其含有熱聚合引發劑亦是有效的。熱聚合引發劑的例子，可舉出例如各種的偶氮系化合物、過氧化物系化合物，前述偶氮系化合物可舉出例如偶氮雙系化合物，前述過氧化物系化合物可舉出例如過氧化酮、過氧化縮酮、氫過氧化物、二烷基過氧化物、二醯基過氧化物、過氧化酯及過氧化二碳酸酯等。It is also effective to contain a thermal polymerization initiator in the colored photosensitive composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds, and examples of the azo compound include azobis compounds, and examples of the peroxide compounds include Oxide ketone, peroxy ketal, hydroperoxide, dialkyl peroxide, dimercapto peroxide, peroxyester and peroxydicarbonate.

熱聚合成分Thermal polymerization component

在本發明的著色感光性組成物，使其含有熱聚合成分亦是有效的。為了提升塗膜的強度，亦可按照必要添加環氧化合物。環氧化合物可舉出例如雙酚A型、甲酚酚醛清漆型、聯苯型、脂環族環氧化合物等的在分子中具有2個以上的環氧環之化合物。例如雙酚A型可舉出EPOTOHTOYD-115、YD-118T、YD-127、YD-128、YD-134、YD-8125、YD-7011R、ZX-1059、YDF-8170、YDF-170等(以上、東都化成(Tohto Kasei Co.,Ltd.)製)、DENACOL EX-1101、EX-1102、EX-1103等(以上、Nagase ChemteX Corporation)製)、PLACCEL GL-61、GL-62、G101、G102(以上、Daicel Chemical Industries Ltd.)製)等及其他類似之雙酚F型、雙酚S型環氧樹脂。又，亦能夠使用Ebecry1 3700、3701、600(以上、Daicel-Cytec Company Ltd.)製)等的環氧丙烯酸酯。甲酚酚醛清漆型可舉出EPOTOHTO YDPN-638、YDPN-701、YDPN-702、YDPN-703、YDPN-704等(以上、東都化成(股)製)、DENACOL EM-125等(以上、NagaseChemteX Corporation)製)、聯苯型可舉出3,5,3’,5’-四甲基-4,4’-二環氧丙基聯苯等、脂環族環氧化合物可舉出CELLOXIDE 2021、2081、2083、2085、EPOLEAD GT-301、GT-302、GT-401、GT403、EHPE-3150(以上、Daicel化學製)、SUNTOHTO ST-3000、ST-4000、ST-5080、ST-5100等(以上、東都化成(股)製)等。又，亦能夠使用1,1,2,2-肆(對環氧苯氧基苯基)乙烷、參(對環氧丙氧基苯基)甲烷、三環氧丙基參(羥乙基)三聚異氰酸酯、鄰酞酸二環氧丙酯、對酞酸二環氧丙酯、此外亦能夠使用其它胺型環氧樹脂之EPOTOHTO YH-434、YH-434L及在雙酚A型環氧樹脂的骨架中將二聚酸改性而成之環氧丙酯等。It is also effective to contain the thermopolymerizable component in the colored photosensitive composition of the present invention. In order to increase the strength of the coating film, an epoxy compound may be added as necessary. Examples of the epoxy compound include compounds having two or more epoxy rings in the molecule, such as a bisphenol A type, a cresol novolak type, a biphenyl type, and an alicyclic epoxy compound. For example, bisphenol A type may include EPOTOHTOYD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. , manufactured by Tohto Kasei Co., Ltd., DENACOL EX-1101, EX-1102, EX-1103, etc. (above, Nagase ChemteX Corporation), PLACCEL GL-61, GL-62, G101, G102 (The above, manufactured by Daicel Chemical Industries Ltd.) and the like and other similar bisphenol F type, bisphenol S type epoxy resin. Further, an epoxy acrylate such as Ebecry 1 3700, 3701, 600 (above, manufactured by Daicel-Cytec Company Ltd.) can also be used. Examples of the cresol novolak type include EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 (above, Dongdu Chemical Co., Ltd.), DENACOL EM-125, etc. (above, NagaseChemteX Corporation) The biphenyl type may, for example, be 3,5,3',5'-tetramethyl-4,4'-diepoxypropyl biphenyl, etc., and the alicyclic epoxy compound may be CELLOXIDE 2021. 2081, 2083, 2085, EPOLEAD GT-301, GT-302, GT-401, GT403, EHPE-3150 (above, manufactured by Daicel Chemical), SUNTOHVTO ST-3000, ST-4000, ST-5080, ST-5100, etc. Above, Dongdu Chemical (share) system, etc. Further, 1,1,2,2-indole (p-epoxyphenoxyphenyl)ethane, ginseng (p-glycidoxyphenyl)methane, triepoxypropyl ginseng (hydroxyethyl) can also be used. Tripolyisocyanate, diglycidyl phthalate, diglycidyl phthalate, EPOTOHTO YH-434, YH-434L and bisphenol A epoxy which can also be used with other amine epoxy resins A glycidyl ester obtained by modifying a dimer acid in a skeleton of a resin.

界面活性劑Surfactant

從改良塗布性的觀點，本發明的著色感光性組成物以含有各種界面活性劑為佳。界面活性劑除了能夠使用前述的氟系界面活性劑以外，亦可使用其它非離子系、陽離子系、陰離子系的各種界面活性劑。其中，以前述非離子系界面活性劑且具有全氟烷基之氟系界面活性劑、非離子系界面活性劑為佳。From the viewpoint of improving coatability, the coloring photosensitive composition of the present invention preferably contains various surfactants. As the surfactant, in addition to the above-described fluorine-based surfactant, various other nonionic, cationic or anionic surfactants can be used. Among them, a fluorine-based surfactant having a perfluoroalkyl group and a perfluoro-based surfactant and a nonionic surfactant are preferred.

非離子系界面活性劑的例子，例如以聚氧乙烯烷基醚類、聚氧乙烯烷基芳基醚類、聚氧乙烯烷酯類、山梨糖醇酐烷酯類及一甘油酯烷酯等的非離子系界面活性劑為佳。具體上，有聚氧乙烯月桂醚、聚氧丙烯硬脂醚、聚氧乙烯油醚等的聚氧化烯烷酯類；聚氧乙烯辛基苯基醚、聚氧乙烯聚苯乙烯化醚、聚氧乙烯三苄基苯基醚、聚氧乙烯-丙烯聚苯乙烯化醚、聚氧乙烯壬基苯基醚等的聚氧乙烯芳基醚類；聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等的聚氧化烯二烷酯、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯類、伸乙二胺聚氧乙烯-聚氧丙烯縮合物等的非離子系界面活性劑，該等能夠適當地使用來自花王(股)(Kao Corporation)、日本油脂(股)(NOF Corporation)、竹本油脂(股)(Takemoto Oil & Fat Co.,Ltd.)、ADEKA(股)(ADEKACorporation)、三洋化成(股)(Sanyo Chemical Industries Ltd.)等之市售品。除了上述以外，亦可使用前述的分散劑。Examples of the nonionic surfactant are, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. A nonionic surfactant is preferred. Specifically, there are polyoxyalkylene alkyl esters such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene polystyrene ether, and poly Polyoxyethylene aryl ethers such as oxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyrene ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate, polyoxyethylene A nonionic system such as a polyoxyalkylene dialkyl ester such as stearate, a sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, or an ethylenediamine polyoxyethylene-polyoxypropylene condensate. Surfactant, which can be suitably used from Kao Corporation, Japan Oils and Fats (NOF Corporation), Takemoto Oil & Fat Co., Ltd., ADEKA (shares) (Available from (ADEKA Corporation), Sanyo Chemical Industries Ltd., etc.). In addition to the above, the aforementioned dispersing agent can also be used.

除了上述以外，亦可在著色感光性組成物添加各種添加物。添加物的具體例係2-(3-第三丁基-5-甲基-2-羥苯基)-5-氯苯并***、烷氧基二苯基酮等的紫外線吸收劑、聚丙烯酸鈉等的防凝集劑、玻璃、氧化鋁等的填料；伊康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化之順丁烯二酸共聚物、酸性纖維素衍生物、在具有羥基之聚合物加添酸酐而成者、醇可溶性耐綸及由雙酚A與表氯醇所形成的環氧樹脂等的鹼可溶性樹脂等。In addition to the above, various additives may be added to the coloring photosensitive composition. Specific examples of the additive are ultraviolet absorbers such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxydiphenyl ketone, and poly Anti-agglomerating agent such as sodium acrylate, filler of glass, alumina, etc.; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acid cellulose A derivative, an alkali-soluble resin obtained by adding an acid anhydride to a polymer having a hydroxyl group, an alcohol-soluble nylon, and an epoxy resin formed of bisphenol A and epichlorohydrin.

又，為了促進未硬化部的鹼溶解性，謀求更提升著色感光性組成物的顯像性時，能夠在著色感光性組成物添加有機羧酸、較佳是分子量1000以下之低分子量有機羧酸。具體上可舉出例如甲酸、乙酸、丙酸、丁酸、戊酸、三甲基乙酸、己酸、二乙基乙酸、庚酸(enanthicacid)、辛酸等的脂肪族一羧酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸(suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、十三烷二酸(brassylic acid)、甲基丙二酸(methylmalonic acid)、乙基丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、檸康酸等脂肪族二羧酸；1,2,3-丙三甲酸(tricaballylic acid)、烏頭酸(aconitic acid)、降樟腦三酸(camphoronic acid)等脂肪族三羧酸；苯甲酸、苯乙酸(toluic acid)、異丙苯酸(cuminic acid)、2,3-二甲苯甲酸(hemellitic acid)、3,5-二甲基苯甲酸等芳香族一羧酸；酞酸、異酞酸、對酞酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5- 苯四甲酸(mellophanic acid)、 焦蜜石酸(pyro mellitic acid)等芳香族聚羧酸；苯基乙酸、氫阿托酸(hydratropic acid)、氫桂皮酸、苦杏仁酸(mandelic acid)、苯基琥珀酸、阿托酸(atropic acid)、桂皮酸、桂皮酸甲酯、桂皮酸苄酯、亞桂皮基乙酸、香豆酸、繖形酸(umbellic acid)等其他的羧酸。In addition, in order to promote the alkali solubility of the uncured portion and to improve the developability of the coloring photosensitive composition, it is possible to add an organic carboxylic acid to the colored photosensitive composition, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less. . Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, enanthic acid, and octanoic acid; oxalic acid and propylene; Diacid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, trisallic acid ), an aliphatic dicarboxylic acid such as methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid or citraconic acid; 1, 2, An aliphatic tricarboxylic acid such as tricalylic acid, aconitic acid or camphoronic acid; benzoic acid, phenylacetic acid (toluic) Acid), cuminic acid, hemellitic acid, 3,5-dimethylbenzoic acid and other aromatic monocarboxylic acids; citric acid, isophthalic acid, p-citric acid 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3,5- Mellophanic acid, pyrophyllin (pyro Mellitic acid) an aromatic polycarboxylic acid; phenylacetic acid, hydratropic acid, hydrogen cinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid Other carboxylic acids such as methyl cinnamate, benzyl cinnamate, cinnamyl acetic acid, coumaric acid, and umbellic acid.

熱聚合抑制劑Thermal polymerization inhibitor

在本發明的著色感光性組成物，除了上述以外，以進而預先添加熱聚合抑制劑為佳。該熱聚合抑制劑可舉出例如氫醌、對甲氧基苯酚、二-第三丁基-對甲酚、五倍子酚、第三丁基兒茶酚、苯醌、4,4’-硫代雙(3-甲基-6-第三丁基苯酚)、2,2’-亞甲基雙(4-甲基-6-第三丁基苯酚)及2-氫硫基苯并咪唑等。In addition to the above, in addition to the above, the coloring photosensitive composition of the present invention is preferably a thermal polymerization inhibitor added in advance. The thermal polymerization inhibitor may, for example, be hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, tert-butylcatechol, benzoquinone, 4,4'-thio Bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2-hydrothiobenzimidazole, and the like.

本發明的著色感光性組成物能夠具有例如用以形成彩色濾光片的著色區域等之各種目的。The colored photosensitive composition of the present invention can have various purposes such as a colored region for forming a color filter.

彩色濾光片Color filter

本發明的彩色濾光片係在基板上具有使用前述本發明的著色感光性組成物所形成的著色區域。在此，著色區域係包含2色、3色或4色的著色圖案(像素部)及黑色矩陣之雙方者。The color filter of the present invention has a colored region formed on the substrate using the coloring photosensitive composition of the present invention. Here, the colored region includes both a color pattern (pixel portion) of two colors, three colors, or four colors, and a black matrix.

說明本發明的彩色濾光片之製法。A method of producing the color filter of the present invention will be described.

首先，將本發明的著色感光性組成物直接或透過其他的層藉由旋轉塗布、狹縫塗布、流延塗布、輥塗布及棒塗布等的塗布方法塗布在基板上，來形成由著色感光性組成物所構成的塗膜(塗布製程)。隨後，透過規定的光罩圖案(mask pattern)對塗膜進行曝光(曝光製程)。曝光後，使用顯像液來顯像除去塗膜的未硬化膜(顯像製程)。經由該等製程來形成由各色(3色或4色)的像素所構成的著色圖案，能夠得到彩色濾光片。First, the colored photosensitive composition of the present invention is applied onto a substrate directly or through another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, or bar coating to form a color-sensitive photosensitive property. A coating film composed of a composition (coating process). Subsequently, the coating film is exposed (exposure process) through a prescribed mask pattern. After the exposure, the uncured film of the coating film was removed by development using a developing solution (developing process). A color filter composed of pixels of respective colors (three colors or four colors) is formed through these processes, and a color filter can be obtained.

依照此種方法，能夠以製程上的困難性較少、高品質且低成本的方式來製造液晶顯示元件或固體攝像元件所使用的彩色濾光片。According to this method, the color filter used for the liquid crystal display element or the solid-state image sensor can be manufactured in a manner that is less difficult in the process, high in quality, and low in cost.

以下，詳細地說明在各製程。Hereinafter, each process will be described in detail.

塗布製程Coating process

首先，說明在塗布製程所使用的基板。First, the substrate used in the coating process will be described.

本發明的彩色濾光片所使用的基板，可舉出例如液晶顯示元件等所使用的無鹼玻璃、鈉鈣玻璃、派勒斯(PYREX、註冊商標)玻璃、石英玻璃及在該等黏附透明導電膜而成者，或固體攝像元件等所使用的光電轉換元件基板、例如矽基板或塑膠基板。The substrate used for the color filter of the present invention includes, for example, an alkali-free glass, a soda-lime glass, a Pyrex (registered trademark) glass, a quartz glass, and the like which are used for a liquid crystal display element. A conductive film is used, or a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a germanium substrate or a plastic substrate.

在該等基板上，亦可形成用以隔離各像素之黑色矩陣，亦可設置用於促進黏附等之透明樹脂層。A black matrix for isolating each pixel may be formed on the substrates, and a transparent resin layer for promoting adhesion or the like may be provided.

又，塑膠基板係以在其表面具有阻障層(gas barrier)及/或耐溶劑性層為佳。Further, the plastic substrate preferably has a gas barrier and/or a solvent resistant layer on the surface thereof.

此外，可使用配置有薄膜電晶體(TFT)方式彩色液晶顯示裝置的薄膜電晶體(TFT)而成之驅動用基板(以下，稱為「TFT方式液晶驅動用基板」)，且在該驅動用基板上亦形成由本發明的著色感光性組成物所構成的著色圖案，來製造彩色濾光片。In addition, a driving substrate (hereinafter referred to as a "TFT-type liquid crystal driving substrate") in which a thin film transistor (TFT) of a thin film transistor (TFT) color liquid crystal display device is disposed can be used, and the driving is used for the driving. A coloring pattern composed of the coloring photosensitive composition of the present invention is also formed on the substrate to produce a color filter.

在TFT方式液晶驅動用基板之基板可舉出例如玻璃、矽、聚碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等。在該等的基板，亦可按照需要使用矽烷偶合劑(silane coupling agent)等預先施行藥品處理、電漿處理、離子噴鍍(ion plating)、濺鍍(sputtering)、氣相反應法、真空蒸鍍法等適當的前處理。例如能夠使用在TFT方式液晶驅動用基板的表面形成有氮化矽膜等的保護(passivation)膜而成之基板。Examples of the substrate of the TFT liquid crystal driving substrate include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine. In these substrates, a drug treatment, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum evaporation may be performed in advance using a silane coupling agent or the like as needed. Appropriate pretreatment such as plating. For example, a substrate in which a passivation film such as a tantalum nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

在塗布製程，將本發明的著色感光性組成物塗布在基板之方法沒有特別限定，以狹縫與旋轉塗布(slit-and-spin coating)法、未旋轉塗布法等使用狹縫噴嘴(slit nozzle)之方法(以下、稱為狹縫噴嘴塗布法)。In the coating process, the method of applying the colored photosensitive composition of the present invention to a substrate is not particularly limited, and a slit nozzle is used by a slit, a spin-and-spin coating method, a non-rotation coating method, or the like. The method (hereinafter referred to as a slit nozzle coating method).

在狹縫噴嘴塗布法，狹縫與旋轉塗布法及未旋轉塗布法係因塗布基板的大小而有不同的條件，例如使用未旋轉塗布法來塗布第五世代的玻璃基板(1100毫米×1250毫米)時，從狹縫噴嘴的著色感光性組成物吐出量通常為500～2000微升/秒，以為800～1500微升/秒為佳，又，塗布速度通常為50～300毫米/秒，以100～200毫米/秒為佳。In the slit nozzle coating method, the slit, the spin coating method, and the non-spin coating method differ depending on the size of the coated substrate, and for example, the fifth generation glass substrate (1100 mm × 1250 mm) is applied by a non-rotation coating method. When the coloring photosensitive composition from the slit nozzle is discharged, the amount is usually 500 to 2000 μl/sec, preferably 800 to 1500 μl/sec, and the coating speed is usually 50 to 300 mm/sec. 100 to 200 mm / sec is preferred.

又，在塗布製程所使用的著色感光性組成物的固體成分通常為10～20%，以13～18%為佳。Further, the solid content of the colored photosensitive composition used in the coating process is usually 10 to 20%, preferably 13 to 18%.

使用本發明著色感光性組成物在基板上形成塗膜時，該塗膜的厚度(預烘烤(pre-baking)處理後)，通常為0.3～5.0微米，以0.5～4.0微米為佳，以0.5～3.0微米為最佳。When the coating film is formed on the substrate by using the colored photosensitive composition of the present invention, the thickness of the coating film (after pre-baking treatment) is usually 0.3 to 5.0 μm, preferably 0.5 to 4.0 μm. 0.5 to 3.0 microns is preferred.

又，固體攝像元件用的彩色濾光片時，塗膜厚度(預烘烤處理後)以0.5～5.0微米的範圍為佳。Further, in the case of a color filter for a solid-state image sensor, the thickness of the coating film (after the prebaking treatment) is preferably in the range of 0.5 to 5.0 μm.

在塗布製程，通常在塗布後施行預烘烤處理。亦可按照必要在預烘烤之前施行真空處理。In the coating process, a prebaking treatment is usually performed after coating. Vacuum treatment may also be carried out before prebaking as necessary.

真空乾燥的條件係真空度通常為0.1～1.0托(torr)，以0.2～0.5托左右為佳。The vacuum drying condition is usually 0.1 to 1.0 Torr (torr) and preferably 0.2 to 0.5 Torr.

又，預烘烤處理能夠使用熱板(hot plate)、烘箱(oven)等，並在50～140℃的溫度範圍、較佳是以70～110℃左右，10～300秒的條件進行。又，在預烘烤處理亦可並用高頻處理等。高頻處理亦可單獨使用。Further, the prebaking treatment can be carried out using a hot plate, an oven or the like at a temperature of 50 to 140 ° C, preferably about 70 to 110 ° C, for 10 to 300 seconds. Further, in the prebaking treatment, high frequency processing or the like may be used in combination. High frequency processing can also be used alone.

曝光製程Exposure process

曝光製程係對如前述進行所形成之由著色感光性組成物所構成的塗膜，透過規定的光罩圖案來進行曝光。The exposure process is performed by exposing a coating film composed of the colored photosensitive composition formed as described above through a predetermined mask pattern.

曝光時所使用的放射線以g射線、h射線、i射線、j射線等的紫外線為特佳。The radiation used for exposure is particularly excellent in ultraviolet rays such as g-rays, h-rays, i-rays, and j-rays.

而且，在製造液晶顯示裝置用的彩色濾光片時，以藉由接近式曝光(proximity exposure)機、鏡投射(mirror projection)曝光機，且主要使用h射線、i射線之曝光為佳。Further, in the production of a color filter for a liquid crystal display device, exposure by a proximity exposure machine or a mirror projection machine, and mainly using h-rays and i-rays is preferable.

又，在製造固體攝像元件用的彩色濾光片時，以藉由步進機(stepper)曝光機，且主要使用i射線之曝光為佳。Further, in the case of manufacturing a color filter for a solid-state image sensor, it is preferable to use a stepper exposure machine and mainly use i-ray exposure.

而且，使用TFT方式液晶驅動用基板來製造彩色濾光片時，所使用的光罩(photomask)能夠使用除了用以形成像素(著色圖案)之圖案以外，亦設置有用以形成通孔(through-hole)或字型(重直剖面為矩形)的凹下之圖案者。Further, when a color filter is manufactured using a TFT-type liquid crystal driving substrate, a photomask can be used to form a via hole in addition to a pattern for forming a pixel (colored pattern). Hole) or A concave pattern of a font (a straight cross section is a rectangle).

顯像製程Imaging process

顯像製程係使曝光後的塗膜之未硬化部溶出至顯像液，而只有使硬化部殘留於基板上。In the developing process, the uncured portion of the exposed coating film is eluted to the developing liquid, and only the hardened portion remains on the substrate.

顯像溫度通常為20～30℃，顯像時間為20～90秒。The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

顯像液若是能夠溶解在未硬化部之著色感光性組成物的塗膜，且另一方面不會溶解硬化部者，可使用任何物。Any developer can be used if it is a coating film which can be dissolved in the colored photosensitive composition of the uncured portion and does not dissolve the hardened portion.

具體上，能夠使用各種有機溶劑的組合或鹼性水溶液。Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used.

顯像所使用的有機溶劑，可舉出在調製本發明的著色感光性組成物時能夠使用之前述的溶劑。The organic solvent to be used for development includes the above-mentioned solvent which can be used when preparing the colored photosensitive composition of the present invention.

又，鹼性水溶液的例子，可舉出例如將氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉、氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲銨、氫氧化四乙銨、膽鹼、吡咯、哌啶、1,8-二氧雜環-[5.4.0]-7-十一烯等的鹼性化合物，以濃度成為0.001~10質量%、較佳是0.01~1質量%的方式溶解而成之鹼性水溶液。Further, examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, and dimethylethanolamine. a basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dioxane-[5.4.0]-7-undecene, etc. An alkaline aqueous solution obtained by dissolving in an amount of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.

在鹼性水溶液，亦可適量添加甲醇或乙醇等的水溶性有機溶劑或界面活性劑等。A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution in an appropriate amount.

顯像方式可以是浸漬(dipping)方式、噴淋(shower)方式、噴霧(spray)方式等之任一者，亦在該等組合搖擺(swing)方式、旋轉(spin)方式、超音波方式等。亦能夠在接觸顯像液之前預先使用水等濕潤被顯像面，來防止顯示不均。又，亦可使基板傾斜而進行顯像。The development method may be any one of a dipping method, a shower method, a spray method, and the like, and also a combination of a swing method, a spin method, an ultrasonic method, and the like. . It is also possible to moisten the imaged surface with water or the like before contact with the developer to prevent uneven display. Further, the substrate may be tilted to perform development.

又，在製造固體攝像元件用的彩色濾光片時，亦可使用浸置式(paddle)顯像。Further, in the case of manufacturing a color filter for a solid-state image sensor, paddle development can also be used.

顯像處理後係經由沖洗處理用以洗淨除去剩餘的顯像液，並施行乾燥後，施行加熱處理(後烘烤)用以使硬化完全。After the development treatment, the remaining developing liquid is removed by washing, and after drying, heat treatment (post-baking) is performed to complete the hardening.

沖洗處理通常係使用純水來進行，為了省液亦可使用在最後洗淨使用純水而在洗淨初期係使用使用過的純水，又，或是使基板傾斜而洗淨，或是並用超音波照射之方法。The rinsing treatment is usually carried out using pure water. In order to save the liquid, it is also possible to use pure water in the final washing and use the used pure water in the initial stage of washing, or to wash the substrate obliquely, or to use it in combination. The method of ultrasonic irradiation.

沖洗處理除去水並乾燥後，通常係進行約200℃～250℃的加熱處理。After the water is removed by the rinsing treatment and dried, it is usually subjected to a heat treatment at about 200 ° C to 250 ° C.

該加熱處理(後烘烤(post-baking))能夠對顯像後的塗膜使用熱板、對流式烘箱(convection oven)(熱風循式乾燥機)、或高頻加熱機等加熱裝置，以成為上述條件的方式藉由連續式或分批(batch)式進行。The heat treatment (post-baking) can use a heating plate such as a hot plate, a convection oven (hot air drying dryer), or a high frequency heating device for the coating film after development. The manner of achieving the above conditions is carried out by continuous or batch type.

藉由配合需要的色相數且各色每色依照順序重複進行以上的各製程，能夠製造形成有複數色著色而成的硬化膜(著色圖案)之彩色濾光片。By repeating the above respective processes in accordance with the number of required hue and the respective colors for each color, it is possible to manufacture a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.

本發明的著色感光性組成物的用途，主要是以彩色濾光片的著色圖案的用途為中心進行說明，但是亦能夠應用於形成黑色矩陣用以隔離構成彩色濾光片之著色圖案(像素)。The use of the colored photosensitive composition of the present invention is mainly described with the use of the coloring pattern of the color filter, but can also be applied to form a black matrix for isolating the colored pattern (pixel) constituting the color filter. .

基板上的黑色矩陣能夠使用含有碳黑、鈦黑等黑色顏料的加工顏料之著色感光性組成物，並經由塗布、曝光及顯像各製程，隨後，按照必要藉由後烘烤來形成。The black matrix on the substrate can be formed using a colored photosensitive composition containing a black pigment such as carbon black or titanium black, and subjected to coating, exposure, and development processes, followed by post-baking as necessary.

液晶顯示元件及固體攝像元件Liquid crystal display element and solid-state imaging element

本發明的液晶顯示元件及固體攝像元件係具備本發明的彩色濾光片而構成者。更具體地，例如藉由在彩色濾光片的內面側形成配向膜，並使其與電極基板相對，且在其間隙間充滿液晶而密封，能夠得到本發明的液晶顯示元件之面板。又，例如藉由在受光元件上形成彩色濾光片，能夠得到本發明的固體攝像元件。The liquid crystal display element and the solid-state imaging element of the present invention are provided with the color filter of the present invention. More specifically, for example, a panel of a liquid crystal display element of the present invention can be obtained by forming an alignment film on the inner surface side of the color filter and facing the electrode substrate, and filling the gap between the gaps to fill the liquid crystal. Further, for example, a solid-state imaging element of the present invention can be obtained by forming a color filter on a light receiving element.

[實施例][Examples]

以下，藉由實施例更具體地說明本發明，但是本發明只要未脫離其宗旨，未限定於以下的實施例。又，若未事先告知，「份」係質量基準。Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as they do not deviate from the gist thereof. Also, "parts" are quality standards without prior notice.

實施例1及比較例1Example 1 and Comparative Example 1 特定高分子化合物P-1的合成Synthesis of specific polymer compound P-1

在經氮氣取代的三口燒瓶導入27.0克M-1、126.0克MMA(甲基丙烯酸甲酯)、27.0克MAA(甲基丙烯酸甲酯)及420.0克1-甲氧基-2-丙醇，使用攪拌機(新東科學(股)(Shinto Scientific Co.,Ltd.)：THREE-ONE MOTOR)攪拌。邊將氮氣流入燒瓶內邊加熱且升溫至90℃。在此添加1.69克2,2-偶氮雙(2,4-二甲基戊腈)(和光純藥(股)(Wako Pure Chemical Industries Ltd)製V-65)，且在90℃進行加熱攪拌2小時。2小時後，進而添加1.69克V-65且加熱攪拌3小時，結果得到特定高分子化合物P-1的30%溶液。27.0 g of M-1, 126.0 g of MMA (methyl methacrylate), 27.0 g of MAA (methyl methacrylate) and 420.0 g of 1-methoxy-2-propanol were introduced into a three-necked flask substituted with nitrogen. The mixer (Shinto Scientific Co., Ltd.: THREE-ONE MOTOR) was stirred. Nitrogen gas was introduced into the flask while heating and the temperature was raised to 90 °C. Here, 1.69 g of 2,2-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries Ltd.) was added, and heating and stirring were carried out at 90 °C. 2 hours. After 2 hours, 1.69 g of V-65 was further added and stirred under heating for 3 hours, and as a result, a 30% solution of a specific polymer compound P-1 was obtained.

使用以聚苯乙烯作為標準物質之凝膠滲透色譜法(GPC(Gel Permeation Chromatography)測定所得到聚合物的重量平均分子量，結果為2.0萬。The weight average molecular weight of the obtained polymer was measured by gel permeation chromatography (GPC (Gel Permeation Chromatography) using polystyrene as a standard material, and it was 20,000.

又，使用氫氧化鈉滴定，結果特定高分子化合物的平均固體成分的酸價為98mgKOH/g。Further, titration with sodium hydroxide revealed that the acid value of the average solid content of the specific polymer compound was 98 mgKOH/g.

特定高分子化合物P-2的合成Synthesis of specific polymer compound P-2

在經氮氣取代的三口燒瓶導入27.0克M-5、126.0克MMA、27.0克MAA及420.0克1-甲氧基-2-丙醇，使用攪拌機(新東科學(股)(Shinto Scientific Co.,Ltd.)：THREE-ONE MOTOR)攪拌。邊將氮氣流入燒瓶內邊加熱且升溫至90℃。在此添加1.80克2,2-偶氮雙(2,4-二甲基戊腈)(和光純藥(股)製V-65)，且在90℃進行加熱攪拌2小時。2小時後，進而添加1.80克V-65且加熱攪拌3小時，結果得到特定高分子化合物P-2的30%溶液。27.0 g of M-5, 126.0 g of MMA, 27.0 g of MAA, and 420.0 g of 1-methoxy-2-propanol were introduced into a nitrogen-substituted three-necked flask using a stirrer (Shinto Scientific Co., Ltd.). Ltd.): THREE-ONE MOTOR) Stir. Nitrogen gas was introduced into the flask while heating and the temperature was raised to 90 °C. Here, 1.80 g of 2,2-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred under heating at 90 ° C for 2 hours. After 2 hours, 1.80 g of V-65 was further added and stirred under heating for 3 hours, and as a result, a 30% solution of a specific polymer compound P-2 was obtained.

使用以聚苯乙烯作為標準物質之凝膠滲透色譜法(GPC(Gel Permeation Chromatography)測定所得到聚合物的重量平均分子量，結果為2.1萬。The weight average molecular weight of the obtained polymer was measured by gel permeation chromatography (GPC (Gel Permeation Chromatography) using polystyrene as a standard material, and it was 21,000.

又，使用氫氧化鈉滴定，結果特定高分子化合物的平均固體成分的酸價為99mgKOH/g。Further, titration with sodium hydroxide revealed that the acid value of the average solid content of the specific polymer compound was 99 mgKOH/g.

特定高分子化合物P-3～P-23的合成Synthesis of specific polymer compounds P-3～P-23

依照表1之組成，與上述特定高分子化合物P-1同樣地進行，來合成特定高分子化合物P-3～P-23。The specific polymer compounds P-3 to P-23 were synthesized in the same manner as in the above-described specific polymer compound P-1 according to the composition of Table 1.

又，各單體的簡稱如下。Moreover, the abbreviation of each monomer is as follows.

MAA：甲基丙烯酸MAA: Methacrylic acid

MMA：甲基丙烯酸甲酯MMA: Methyl methacrylate

BzMA：甲基丙烯酸苄酯BzMA: benzyl methacrylate

加工顏料的製造Manufacture of processed pigments

依照表2～表7，在不鏽鋼製1加侖揑合器(井上製作所(Inoue Manufacturing Co.,Ltd)製)，添加50克顏料、500克氯化鈉、25克高分子化合物的溶液及100克二甘醇，並混煉9小時。接著，將該混合物投入約3升的水中，且使用高速攪拌機攪拌約1小時後，過濾及水洗來除去氯化鈉及溶劑並乾燥，而得到被高分子化合物被覆而成的加工顏料。According to Table 2 to Table 7, a stainless steel 1 gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) was added with 50 g of a pigment, 500 g of sodium chloride, 25 g of a polymer compound solution, and 100 g of a solution. Glycol and mix for 9 hours. Next, the mixture was poured into about 3 liters of water, and stirred for about 1 hour using a high-speed stirrer, and then filtered and washed with water to remove sodium chloride and a solvent, and dried to obtain a processed pigment which was coated with a polymer compound.

加工顏料的平均一次粒徑之測定Determination of average primary particle size of processed pigments

所得到加工顏料的平均粒徑係使用透射型電子顯微鏡(TEM(Transmission electron microscope)觀察，並測量在粒子未凝集位置之100個粒子的尺寸，且算出平均值而求得。顏料的被覆度之評價The average particle diameter of the obtained processed pigment was determined by using a transmission electron microscope (TEM (Transmission Electron Microscope), and the size of 100 particles at the non-aggregated position of the particles was measured, and the average value was calculated. The coverage of the pigment was determined. Evaluation

將10克所得到的加工顏料投入100毫升1-甲氧基-2-丙醇中，並使用振盪機振盪3小時。隨後，使用離心分離機並以80,000rpm、8小時來使顏料沈降。並藉由乾燥後求最上部澄清液的固體成分。求取從顏料游離之高分子化合物的量，並從與處理時所使用的的高分子化合物之比，算出游離率(%)。游離率越小係表示對顏料的被覆度越高。Ten grams of the obtained processed pigment was placed in 100 ml of 1-methoxy-2-propanol and shaken for 3 hours using a shaker. Subsequently, the pigment was sedimented using a centrifugal separator and at 80,000 rpm for 8 hours. And by drying, the solid content of the uppermost clear liquid is obtained. The amount of the polymer compound released from the pigment was determined, and the ratio (%) was calculated from the ratio of the polymer compound used in the treatment. The smaller the liberation rate, the higher the coverage of the pigment.

又，表2～表7所記載之的顏料及高分子化合物的詳細係如以下。Further, the details of the pigments and polymer compounds described in Tables 2 to 7 are as follows.

-顏料--pigment-

PR254：　C.I.顏料紅254PR254: C.I. Pigment Red 254

PR177：　C.I.顏料紅177PR177: C.I. Pigment Red 177

PG36：　C.I.顏料綠36PG36: C.I. Pigment Green 36

PY150：　C.I.顏料黃150PY150: C.I. Pigment Yellow 150

PB15：6：　C.I.顏料藍15：6PB15:6: C.I. Pigment Blue 15:6

PV23：　C.I.顏料紫23PV23: C.I. Pigment Violet 23

高分子化合物Polymer compound

Q-1：甲基丙烯酸甲酯/甲基丙烯酸=85/15質量%的共聚物(重量平均分子量=2萬、酸價=98mgKOH/g)Q-1: a copolymer of methyl methacrylate/methacrylic acid = 85/15% by mass (weight average molecular weight = 20,000, acid value = 98 mgKOH/g)

Q-2：加氫松香酯(荒川化學公司(Arakawa Chemical Industries,Ltd.)製「酯樹膠(Ester gum)HP」Q-2: Hydrogenated rosin ester (Ester gum HP manufactured by Arakawa Chemical Industries, Ltd.)

Q-3：三羥甲基丙烷三丙烯酸酯Q-3: Trimethylolpropane triacrylate

Q-4：甲基丙烯酸環己酯/甲基丙烯酸=85/15質量%的共聚物(重量平均分子量=2萬、酸價=98mgKOH/g)Q-4: cyclohexyl methacrylate/methacrylic acid = 85/15% by mass of copolymer (weight average molecular weight = 20,000, acid value = 98 mgKOH/g)

從上述結果，得知本實施例的加工顏料與比較例比較，游離率低。From the above results, it was found that the processed pigment of the present example was low in liberation ratio as compared with the comparative example.

實施例2及比較例2Example 2 and Comparative Example 2 顏料分散組成物的調製Modulation of pigment dispersion composition

依照表8的組成，混合下述組成(1)的成分並使用均化器(homogenizer)，以旋轉數3,000r.p.m攪拌3小時進行混合，來調製含有顏料之混合溶液。In accordance with the composition of Table 8, the components of the following composition (1) were mixed and mixed with a homogenizer at a rotation number of 3,000 r.p.m for 3 hours to prepare a mixed solution containing a pigment.

組成(1)Composition (1)

‧加工顏料(表8記載的加工顏料)　95份‧Processing pigments (processed pigments shown in Table 8) 95 parts

‧衍生物A(下述結構)　5份‧Derivative A (structure below) 5 parts

‧分散劑(表8記載分散劑的30%乙酸1-甲氧基-2-丙酯溶液)　表8記載的量‧ Dispersing agent (Table 8 describes a 30% acetic acid 1-methoxy-2-propyl acetate solution of the dispersing agent)

‧乙酸1-甲氧基-2-丙酯　750份‧ 1-methoxy-2-propyl acetate 750 parts

接著，將上述所得到的混合溶液，進而使用0.3毫米Φ鋯粒，藉由珠分散機DISPERMAT(GETZMANN公司製)進行分散處理6小時。隨後，使用附帶減壓機構高壓分散機NANO-3000-10((股)美粒(Beryu Co.,Ltd)製)，在2,000公斤/立方公分的壓力下以流量500克/分鐘進行分散處理。重複該分散處理10次，來得到表8的顏料分散組成物。顏料分散組成物的評價Then, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours by a bead disperser DISPERMAT (manufactured by GETZMANN Co., Ltd.) using 0.3 mm Φ zirconium particles. Subsequently, a dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2,000 kg/cm 3 using a high-pressure dispersing machine with a pressure-reducing mechanism, NANO-3000-10 (manufactured by Beryu Co., Ltd.). This dispersion treatment was repeated 10 times to obtain the pigment dispersion composition of Table 8. Evaluation of pigment dispersion composition

對所得到的顏料分散組成物進行以下的評價。結果如表8所示。The following pigment dispersion composition was evaluated as follows. The results are shown in Table 8.

(1)黏度的測定及評價(1) Determination and evaluation of viscosity

對所得到的顏料分散組成物，使用E型黏度計(20rpm、30℃、東京計器公司(Tokyo Keiki Kogyo Co.,Ltd.)製)，測定剛分散後的顏料分散組成物之黏度η1、及分散後(在室溫)經過1星期後的顏料分散組成物之黏度η2，來評價增黏的程度。在此，黏度低係指能夠抑制起因於分散劑之黏度上升，且表示顏料的分散性及分散安定性良好。The obtained pigment dispersion composition was measured for viscosity η1 of the pigment dispersion composition immediately after dispersion using an E-type viscometer (20 rpm, 30 ° C, manufactured by Tokyo Keiki Kogyo Co., Ltd.). The degree of viscosity increase was evaluated by the viscosity η2 of the pigment dispersion composition after one week of dispersion (at room temperature). Here, the low viscosity means that the viscosity of the dispersant is suppressed from increasing, and the dispersibility and dispersion stability of the pigment are good.

(2)對比的測定及評價(2) Measurement and evaluation of comparison

將所得到的顏料分散組成物塗布在玻璃基板上，以乾燥後的塗布膜厚度為1微米之方式製造試樣。在2片偏光板之間放置經塗布的基板，且使用BM-5亮度計(TOPCON公司製)測定偏光板平行時的亮度及正交時的亮度，並求取平行時的亮度除以正交時之亮度所得到的值作為對比(對比=平行時的亮度/正交時的亮度)。對比高係因為顏料高度被微細化狀態且均勻地分散，顯示透射率亦即著色力高。The obtained pigment dispersion composition was applied onto a glass substrate, and a sample was produced so that the thickness of the coating film after drying was 1 μm. The coated substrate was placed between two polarizing plates, and the brightness of the polarizing plates in parallel and the brightness at the time of orthogonality were measured using a BM-5 luminance meter (manufactured by TOPCON Co., Ltd.), and the luminance in parallel was divided by orthogonal. The value obtained by the brightness of the time is used as a comparison (contrast = brightness in parallel/luminance in orthogonal). In contrast to the high system, since the pigment height is finely dispersed and uniformly dispersed, the transmittance, that is, the coloring power is high.

(3)析出性的評價(3) Evaluation of precipitation

在100毫米×100毫米的玻璃基板(商品名：1737 Corning公司製)上，以膜厚度為2.0微米的方式塗布所得到的顏料分散組成物，並使用90℃的烘箱乾燥60秒。隨後，使用230℃的烘箱對塗布膜施行加熱處理30分鐘(後烘烤)，並使光學顯微鏡(Olympus公司製)，以倍率10確認硬化膜上有無析出物。重複後烘烤並每次觀察，點數越高，表示越不容易析出，著色圖案的透明性越良好。The obtained pigment dispersion composition was applied to a glass substrate of 100 mm × 100 mm (trade name: manufactured by 1737 Corning Co., Ltd.) so as to have a film thickness of 2.0 μm, and dried in an oven at 90 ° C for 60 seconds. Subsequently, the coating film was subjected to heat treatment for 30 minutes (post-baking) using an oven at 230 ° C, and an optical microscope (manufactured by Olympus Co., Ltd.) was used to confirm the presence or absence of precipitates on the cured film at a magnification of 10. The post-baking was repeated and observed each time. The higher the number of dots, the less likely it was to precipitate, and the better the transparency of the colored pattern.

4：在後烘烤第4次產生析出4: The fourth generation of precipitation after post-baking

3：在後烘烤第3次產生析出3: The third generation of precipitation after post-baking

2：在後烘烤第2次產生析出2: The second generation of precipitation after post-baking

1：在後烘烤第1次產生析出1: The first occurrence of precipitation after post-baking

如果如上述，得知本實施例與比較例比較，係對比高且在後烘烤不容易析出，而且在經時的增黏較小之顏料分散組成物。As described above, it was found that the present example was compared with the comparative example, and was a pigment dispersion composition which was high in contrast and which was not easily precipitated in post-baking, and which had a small viscosity increase over time.

顏料分散組成物的調製Modulation of pigment dispersion composition

依照表9的組成，混合下述組成(2)的成分並使用均化器(homogenizer)，以旋轉數3,000r.p.m攪拌3小時進行混合，來調製含有顏料之混合溶液。The composition of the following composition (2) was mixed according to the composition of the following Table (2), and the mixture was stirred for 3 hours at a rotation number of 3,000 r.p.m using a homogenizer to prepare a mixed solution containing a pigment.

組成(2)Composition (2)

‧加工顏料(表9記載的加工顏料)　100份‧Processing pigments (processed pigments listed in Table 9) 100 parts

‧分散劑(表9記載分散劑的30%乙酸1-甲氧基-2-丙酯溶液)　表9記載的量‧ Dispersing agent (Table 9 describes the 30% acetic acid 1-methoxy-2-propyl acetate solution of the dispersing agent)

‧乙酸1-甲氧基-2-丙酯　750份‧ 1-methoxy-2-propyl acetate 750 parts

接著，將上述所得到的混合溶液，進而使用0.3毫米Φ鋯粒，藉由珠分散機DISPERMAT(GETZMANN公司製)進行分散處理6小時。隨後，使用附帶減壓機構高壓分散機NANO-3000-10((股)美粒(Beryu Co.,Ltd)製)，在2,000公斤/立方公分的壓力下以流量500克/分鐘進行分散處理。重複該分散處理10次，來得到表9的顏料分散組成物。Then, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours by a bead disperser DISPERMAT (manufactured by GETZMANN Co., Ltd.) using 0.3 mm Φ zirconium particles. Subsequently, a dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2,000 kg/cm 3 using a high-pressure dispersing machine with a pressure-reducing mechanism, NANO-3000-10 (manufactured by Beryu Co., Ltd.). This dispersion treatment was repeated 10 times to obtain the pigment dispersion composition of Table 9.

顏料分散組成物的評價Evaluation of pigment dispersion composition

對所得到的顏料分散組成物進行以下的評價。實驗方法及評價方法係與組成(1)所進行的方法相同。結果如表9所示。The following pigment dispersion composition was evaluated as follows. The experimental method and the evaluation method are the same as those performed in the composition (1). The results are shown in Table 9.

(1)黏度的測定及評價(1) Determination and evaluation of viscosity

(2)對比的測定及評價(2) Measurement and evaluation of comparison

(3)析出性的評價(3) Evaluation of precipitation

因為對比的絕對值係依照色相而異，所以比較綠色之間、藍色之間。依照上述結果，得知本實施例與比較例，係能夠抑制感光性組成物經時的增黏，而且對比高且在後烘烤不容易析出。Because the absolute value of the contrast varies according to the hue, it is compared between green and blue. According to the above results, it was found that the present examples and the comparative examples were able to suppress the adhesion of the photosensitive composition over time, and the contrast was high and it was not easily precipitated after post-baking.

實施例3及比較例3Example 3 and Comparative Example 3 顏料分散組成物的調製Modulation of pigment dispersion composition

混合下述組成(3)的成分並使用均化器(homogenizer)，以旋轉數3,000r.p.m攪拌3小時進行混合，來調製含有顏料之混合溶液。The components of the following composition (3) were mixed and mixed with a homogenizer at a rotation number of 3,000 r.p.m for 3 hours to prepare a mixed solution containing a pigment.

組成(3)Composition (3)

‧加工顏料(表10記載的加工顏料)　120份‧Processing pigments (processed pigments listed in Table 10) 120 parts

‧分散劑(表10記載分散劑的30%乙酸1-甲氧基-2-丙酯溶液)　250份‧ Dispersant (Table 10 describes 30% acetic acid 1-methoxy-2-propyl acetate solution) 250 parts

‧乙酸1-甲氧基-2-丙酯　750份‧ 1-methoxy-2-propyl acetate 750 parts

接著，將上述所得到的混合溶液，進而使用0.3毫米Φ鋯粒，藉由珠分散機DISPERMAT(GETZMANN公司製)進行分散處理6小時。隨後，使用附帶減壓機構高壓分散機NANO-3000-10((股)美粒(Beryu Co.,Ltd)製)，在2,000公斤/立方公分的壓力下以流量500克/分鐘進行分散處理。重複該分散處理10次，來得到表10的顏料分散組成物。Then, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours by a bead disperser DISPERMAT (manufactured by GETZMANN Co., Ltd.) using 0.3 mm Φ zirconium particles. Subsequently, a dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2,000 kg/cm 3 using a high-pressure dispersing machine with a pressure-reducing mechanism, NANO-3000-10 (manufactured by Beryu Co., Ltd.). This dispersion treatment was repeated 10 times to obtain the pigment dispersion composition of Table 10.

著色感光性組成物的調製Modulation of coloring photosensitive composition

使用所得到的顏料分散組成物，來調製下述的著色感光性組成物。Using the obtained pigment dispersion composition, the following coloring photosensitive composition was prepared.

‧顏料分散液(表11所記載之顏料分散液)2000份‧ Pigment dispersion (the pigment dispersion described in Table 11) 2000 parts

‧二新戊四醇五-六丙烯酸酯80份‧ dipentaerythritol penta-hexaacrylate 80 parts

(光聚合性化合物)(photopolymerizable compound)

‧4-[鄰溴-對N,N-(二乙氧基碳醯胺基)-苯基]-2,6-二(氯甲基)-s-三30份‧4-[o-bromo-p-N,N-(diethoxycarbamoyl)-phenyl]-2,6-di(chloromethyl)-s-three 30 copies

(光聚合引發劑)(photopolymerization initiator)

‧甲基丙烯酸苄酯/甲基丙烯酸(=75/25[質量比])共聚物(重量平均分子量：12,000)的丙二醇一甲基醚乙酸酯溶液(固體成分30%)　300份(鹼可溶性樹脂)‧ Benzyl methacrylate / methacrylic acid (= 75 / 25 [mass ratio]) copolymer (weight average molecular weight: 12,000) propylene glycol monomethyl ether acetate solution (solid content 30%) 300 parts (alkali soluble Resin)

‧乙酸1-甲氧基-2-丙酯　390份‧ 1-methoxy-2-propyl acetate 390 parts

使用著色感光性組成物而成之彩色濾光片的調製Modulation of color filters using colored photosensitive compositions

將所得到的著色感光性組成物(彩色光阻液；color resist)在100毫米×100毫米的玻璃基板(1737、Corning公司製)上，以實施例3-1至3-10及比較例3-1及3-2成為色濃度指標x值為0.650的方式塗布，以實施例3-11至3-12及比較例3-3及3-4成為色濃度指標y值為0.600的方式塗布，又，以實施例3-13至3-14及比較例3-5及3-6成為色濃度指標y值為0.100的方式塗布，並使用90℃的烘箱使其乾燥60秒間(預烘烤)。隨後，在塗膜的全面使用200mJ/cm2 (照度20mW/cm2 )曝光，並將曝光後的塗膜使用鹼性顯像液CDK-1(FUJIFILM Electronic Materials,Co.,Ltd.製)的1%水溶液被覆，且靜止60秒鐘。靜止後，將純水以噴淋狀撒布來洗掉顯像液。而且，將經如上述施行過曝光及顯像過的塗膜，以220℃的烘箱加熱處理1小時(後烘烤)，並在玻璃基板上形成彩色濾光片用著色圖案(著色樹脂被膜)，來製造著色濾光片基板(彩色濾光片)。彩色濾光片的評價The obtained colored photosensitive composition (color resist) was placed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning), and Examples 3-1 to 3-10 and Comparative Example 3 were used. -1 and 3-2 were applied so that the color density index x value was 0.650, and they were applied so that the color density index y value of the examples 3-11 to 3-12 and the comparative examples 3-3 and 3-4 was 0.600. Further, Examples 3-13 to 3-14 and Comparative Examples 3-5 and 3-6 were applied so that the color density index y value was 0.100, and dried in an oven at 90 ° C for 60 seconds (prebaking). . Subsequently, the coating film was exposed to a total of 200 mJ/cm 2 (illuminance: 20 mW/cm 2 ), and the exposed coating film was made of an alkaline developing solution CDK-1 (manufactured by FUJIFILM Electronic Materials, Co., Ltd.). The 1% aqueous solution was coated and allowed to stand for 60 seconds. After standing, the pure water is sprayed to wash off the developing solution. Further, the coating film subjected to exposure and development as described above was heat-treated in an oven at 220 ° C for 1 hour (post-baking), and a coloring pattern for a color filter (colored resin film) was formed on the glass substrate. To manufacture a colored filter substrate (color filter). Color filter evaluation

對所製造的著色濾光片基板(彩色濾光片)，如此進行來進行評價。結果如表11所示。The produced color filter substrate (color filter) was evaluated in this manner. The results are shown in Table 11.

(1)對比(1) Comparison

將上述所得到的著色濾光片基板的著色樹脂被膜的上面，放置偏光板並夾住著色樹脂被膜，且使用BM-5亮度計(TOPCON公司製)測定偏光板平行時的亮度及正交時的亮度，並求取平行時的亮度除以正交時之亮度所得到的值(平行時的亮度/正交時的亮度)作為用以評價對比之指標。值越大係表示高對比。The polarizing plate was placed on the upper surface of the colored resin film of the color filter substrate obtained above, and the colored resin film was sandwiched, and the brightness and the orthogonality when the polarizing plates were parallel were measured using a BM-5 luminance meter (manufactured by TOPCON Co., Ltd.). The brightness is obtained by dividing the brightness in parallel by the brightness in the orthogonal direction (brightness in parallel/brightness in orthogonal) as an index for evaluating the contrast. A larger value indicates a high contrast.

(2)鹼性顯像液可溶性(2) Alkaline imaging solution solubility

在150毫升燒杯，測量100克鹼性顯像液CDK-1(富士FILM ELECTRONIC MATERIALS(股)製)的10%水溶液。在100毫米×100毫米的玻璃基板(商品名：1737 Corning公司製)上，以膜厚度為2.5微米的方式塗布前述光硬化性組成物，並將使用90℃的烘箱乾燥60秒(預烘烤)而成的玻璃基板，以25毫米×100毫米的方式切斷玻璃，且將其中2片以塗布面為外側的方式使其重疊。將其浸漬於預先準備的上述顯像液中，並重疊進行拉取之上下動作20次，且目視判斷未硬化性的溶解性及鹼性顯像液中是否有懸浮物。點數越高表示鹼溶解性良好。In a 150 ml beaker, 100 g of an alkaline developing solution CDK-1 (manufactured by Fuji FILM ELECTRONIC MATERIALS Co., Ltd.) was measured for a 10% aqueous solution. The photocurable composition was applied to a glass substrate of 100 mm × 100 mm (trade name: manufactured by 1737 Corning Co., Ltd.) at a film thickness of 2.5 μm, and dried in an oven at 90 ° C for 60 seconds (prebaking) The glass substrate was cut into glass at 25 mm × 100 mm, and two of them were overlapped so that the coated surface was outside. This was immersed in the above-described developing liquid prepared above, and was superposed and pulled up and down 20 times, and the solubility of the uncured property and the suspended matter in the alkaline developing solution were visually judged. The higher the number of dots, the better the alkali solubility.

*判定法*Judgement

5：上下動1～10次而未硬化膜完全溶解且鹼性顯像液無懸浮物5: Move up and down 1 to 10 times without the hardened film completely dissolved and the alkaline imaging liquid has no suspended matter

4：上下動11～20次而未硬化膜完全溶解且鹼性顯像液無懸浮物4: Move up and down 11 to 20 times while the unhardened film is completely dissolved and the alkaline imaging liquid has no suspended matter.

3：上下動1～10次而未硬化膜完全溶解，但是鹼性顯像液有懸浮物3: Move up and down 1 to 10 times and the unhardened film is completely dissolved, but the alkaline imaging solution has a suspended matter.

2：上下動11～20次而未硬化膜完全溶解，但是鹼性顯像液有懸浮物2: 11 to 20 times up and down and the unhardened film is completely dissolved, but the alkaline imaging solution has a suspension.

1：即便上下動20次未硬化膜亦不溶解1: Even if the unhardened film is moved up and down 20 times, it will not dissolve.

(3)析出性評價(3) Precipitation evaluation

在100毫米×100毫米的玻璃基板(商品名：1737 Corning公司製)上，以膜厚度為2.0微米的方式塗布所得到的顏料分散組成物，並使用90℃的烘箱乾燥60秒(預烘烤)。隨後，使用具有20微米線寬之光罩進行100mJ/cm2 的曝光(照度為20mW/cm2 )，且使用鹼性顯像液CDK-1(富士FILM ELECTRONICS MATERIALS(股)製)的1%水溶液在25℃顯像。The obtained pigment dispersion composition was applied to a glass substrate of 100 mm × 100 mm (trade name: manufactured by 1737 Corning Co., Ltd.) in a film thickness of 2.0 μm, and dried in an oven at 90 ° C for 60 seconds (prebaking) ). Subsequently, exposure was performed at 100 mJ/cm 2 (illuminance of 20 mW/cm 2 ) using a photomask having a line width of 20 μm, and 1% of an alkaline developing solution CDK-1 (manufactured by Fuji FILM ELECTRONICS MATERIALS Co., Ltd.) was used. The aqueous solution was developed at 25 °C.

如上述，將經施行過曝光及顯像過的塗膜，以230℃的烘箱加熱處理30分鐘(後烘烤)，並使用光學顯微鏡確認圖案上有無析出。並將其進而重複3次並進行同樣的評價。點數越高係表示越不容易析出。As described above, the applied and developed coating film was heat-treated in an oven at 230 ° C for 30 minutes (post-baking), and the presence or absence of precipitation on the pattern was confirmed using an optical microscope. This was repeated three more times and the same evaluation was performed. The higher the number of points, the less likely it is to precipitate.

在後烘烤第4次產生析出：4The fourth time after the post-baking produces precipitation: 4

在後烘烤第3次產生析出：3The third time after the post-baking produces precipitation: 3

在後烘烤第2次產生析出：2The second occurrence of precipitation after post-baking: 2

在後烘烤第1次產生析出：1The first occurrence of precipitation in post-baking: 1

彩色濾光片的色相係依照測試水準而異。特別是對比不同的色相之間係無法比較的。因此係在同一色相之間亦即DR之間、DG之間、DB之間進行比較。從上述結果，得知本實施例與比較例比較，能夠得到對比高且鹼性顯像液可溶性良好，而且在後烘烤不容易析出之彩色濾光片。The hue of the color filter varies according to the test level. In particular, it is incomparable to compare different hue. Therefore, comparison is made between the same hue, that is, between DR, between DG, and between DBs. From the above results, it was found that the present embodiment can obtain a color filter which is high in contrast and which is excellent in solubility in an alkaline developing solution and which is not easily precipitated after post-baking.

實施例4及比較例4Example 4 and Comparative Example 4 顏料分散組成物的調製Modulation of pigment dispersion composition

依照下述組成(4)的成分並使用均化器，以旋轉數3,000r.p.m攪拌3小時進行混合，來調製含有顏料之混合溶液。The mixture of the following composition (4) was mixed with a homogenizer at a rotation number of 3,000 r.p.m for 3 hours to prepare a mixed solution containing a pigment.

組成(4)Composition (4)

‧加工顏料(表12記載的加工顏料)　110份‧Processing pigments (processed pigments described in Table 12) 110 parts

‧分散劑D-3(30%乙酸1-甲氧基-2-丙酯溶液)　250份‧Dispersant D-3 (30% acetic acid 1-methoxy-2-propyl ester solution) 250 parts

‧顏料衍生物B(下述結構)　20份‧Pigment Derivative B (structure below) 20 parts

‧乙酸1-甲氧基-2-丙酯　750份‧ 1-methoxy-2-propyl acetate 750 parts

接著，將上述所得到的混合溶液，進而使用0.3毫米Φ鋯粒，藉由珠分散機DISPERMAT(GETZMANN公司製)進行分散處理6小時。隨後，使用附帶減壓機構高壓分散機NANO-3000-10((股)美粒(Beryu Co.,Ltd)製)，在2,000公斤/立方公分的壓力下以流量500克/分鐘進行分散處理。重複該分散處理10次，來得到表12的顏料分散組成物。Then, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours by a bead disperser DISPERMAT (manufactured by GETZMANN Co., Ltd.) using 0.3 mm Φ zirconium particles. Subsequently, a dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2,000 kg/cm 3 using a high-pressure dispersing machine with a pressure-reducing mechanism, NANO-3000-10 (manufactured by Beryu Co., Ltd.). This dispersion treatment was repeated 10 times to obtain the pigment dispersion composition of Table 12.

著色感光性組成物的調製Modulation of coloring photosensitive composition

使用所得到的顏料分散組成物，來調製下述的著色感光性組成物。Using the obtained pigment dispersion composition, the following coloring photosensitive composition was prepared.

‧顏料分散液(表13所記載之顏料分散液)　2100份‧Pigment dispersion (pigment dispersion described in Table 13) 2100 parts

‧二新戊四醇五-六丙烯酸酯　90份(光聚合性化合物)‧ dipentaerythritol penta-hexaacrylate 90 parts (photopolymerizable compound)

‧4-[鄰溴-對N,N-(二乙氧基碳醯胺基)-苯基]-2,6-二(氯甲基)-s-三　30份(光聚合引發劑)‧4-[o-bromo-p-N,N-(diethoxycarbamoyl)-phenyl]-2,6-di(chloromethyl)-s-three 30 parts (photopolymerization initiator)

．甲基丙烯酸苄酯/甲基丙烯酸(=75/25[質量比])共聚物(重量平均分子量：10,000)的丙二醇一甲基醚乙酸酯溶液(固體成分30%)　300份. Benzyl methacrylate/methacrylic acid (=75/25 [mass ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 30%) 300 parts

．乙酸1-甲氧基-2-丙酯　390份. 1-methoxy-2-propyl acetate 390 parts

使用著色感光性組成物而成之彩色濾光片的調製Modulation of color filters using colored photosensitive compositions

將所得到的著色感光性組成物(彩色光阻液)在100毫米×100毫米的玻璃基板(1737，Corning公司製)上，以實施例4-1至4-3及比較例4-1及4-2成為色濃度指標x值為0.650的方式塗布，以實施例4-4至4-6及比較例4-3及4-4成為色濃度指標y值為0.600的方式塗布，又，以實施例4-7至4-9及比較例4-5及4-6成為色濃度指標y值為0.100的方式塗布，並使用90℃的烘箱使其乾燥60秒間(預烘烤)。隨後，在塗膜的全面使用200mJ/cm2 (照度20mW/cm2 )曝光，並將曝光後的塗膜使用鹼性顯像液CDK-1(富士FILM ELECTRONIC MATERIALS(股)製)的1%水溶液被覆，且靜止60秒鐘。靜止後，將純水以噴淋狀撒布來洗掉顯像液。而且，將經如上述施行過曝光及顯像過的塗膜，以220℃的烘箱加熱處理1小時(後烘烤)，並在玻璃基板上形成彩色濾光片用著色圖案(著色樹脂被膜)，來製造著色濾光片基板(彩色濾光片)。The obtained colored photosensitive composition (color resist liquid) was placed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning), and Examples 4-1 to 4-3 and Comparative Example 4-1 and 4-2 was applied so that the color density index x value was 0.650, and the coatings of Examples 4-4 to 4-6 and Comparative Examples 4-3 and 4-4 were coated so that the color density index y value was 0.600, and Examples 4-7 to 4-9 and Comparative Examples 4-5 and 4-6 were applied so that the color density index y value was 0.100, and dried in an oven at 90 ° C for 60 seconds (prebaking). Subsequently, the coating film was exposed to a total of 200 mJ/cm 2 (illuminance: 20 mW/cm 2 ), and the exposed coating film was subjected to 1% of an alkaline developing solution CDK-1 (manufactured by Fuji FILM ELECTRONIC MATERIALS Co., Ltd.). The aqueous solution was coated and allowed to stand for 60 seconds. After standing, the pure water is sprayed to wash off the developing solution. Further, the coating film subjected to exposure and development as described above was heat-treated in an oven at 220 ° C for 1 hour (post-baking), and a coloring pattern for a color filter (colored resin film) was formed on the glass substrate. To manufacture a colored filter substrate (color filter).

彩色濾光片的評價Color filter evaluation

對所製造的著色濾光片基板(彩色濾光片)，如此進行來進行評價。結果如表13所示。The produced color filter substrate (color filter) was evaluated in this manner. The results are shown in Table 13.

(1)對比(1) Comparison

(2)鹼性顯像液可溶性(2) Alkaline imaging solution solubility

(3)電壓保持率(3) Voltage retention rate

在附帶ITO(Indium Tin Oxide)電極的玻璃基板(1737，Corning公司製)上，以膜厚度為2.0微米的方式塗布光硬化性組成物，並在90℃的烘箱乾燥60秒(預烘烤)。隨後，未透過光罩而進行100mJ/cm2 的曝光(照度為20mW/cm2)，並使用鹼性顯像液(商品名：CDK-1、富士FILM ELECTRONIC MATERIALS(股)製)的1%水溶液在25℃顯像，且使用230℃的烘箱對塗布膜施加乾燥處理30分鐘(後烘烤)。接著，將形成有該像素之基板與只有依照規定形狀蒸鍍ITO電極而成之基板，以混合有5微米的玻璃珠而成的密封劑貼合後，注入MERCK(股)公司製液晶MJ971189(商品名)，來製造液晶胞。The photocurable composition was applied to a glass substrate (1737, manufactured by Corning) equipped with an ITO (Indium Tin Oxide) electrode so as to have a film thickness of 2.0 μm, and dried in an oven at 90 ° C for 60 seconds (prebaking). . Subsequently, exposure to 100 mJ/cm 2 (illuminance: 20 mW/cm 2 ) was carried out without using a mask, and a 1% aqueous solution of an alkaline developing solution (trade name: CDK-1, manufactured by Fuji FILM ELECTRONIC MATERIALS Co., Ltd.) was used. The image was developed at 25 ° C, and the coating film was subjected to a drying treatment for 30 minutes (post-baking) using an oven at 230 ° C. Then, the substrate on which the pixel was formed and the substrate on which the ITO electrode was vapor-deposited in a predetermined shape were bonded together with a sealing agent in which 5 μm of glass beads were mixed, and then injected into a liquid crystal MJ971189 manufactured by MERCK Co., Ltd. ( Product name), to make liquid crystal cells.

接著，將液晶胞放入70℃的恆溫槽48小時後，藉由東陽Technica(股)(Toyo Corporation)製的液晶電壓保持率測定系統VHR-1A型(商品名)來測定液晶胞的電壓保持率。點數越高，係表示電壓保持率高且電氣特性良好。測定條件Then, the liquid crystal cell was placed in a thermostat at 70 ° C for 48 hours, and the voltage retention of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system VHR-1A (trade name) manufactured by Toyo Corporation (Toyo Corporation). rate. The higher the number of dots, the higher the voltage holding ratio and the better electrical characteristics. Measuring condition

‧電極間距離：約5微米‧ Distance between electrodes: about 5 microns

‧施加電壓脈衝(pulse)振幅：5V‧Apply voltage pulse amplitude: 5V

‧施加電壓脈衝頻數：60Hz‧Apply voltage pulse frequency: 60Hz

‧施加電壓脈衝寬度：16.67msec‧Applied voltage pulse width: 16.67msec

*電壓保持率：16.7毫秒後的液晶胞電位差/0毫秒施加後的* Voltage holding ratio: liquid crystal cell potential difference after 16.7 milliseconds / 0 milliseconds after application

電壓之值*判定法Voltage value*

90%以上：5More than 90%: 5

85～90%以上：485 to 90% or more: 4

80～85%以上：380 to 85% or more: 3

75～80%以上：275 to 80% or more: 2

小於75%：1Less than 75%: 1

彩色濾光片的色相係依照測試水準而異。特別是對比不同的色相之間係無法比較的。因此係在同一色相之間亦即DL之間、DY之間、DV之間進行比較。從上述結果，得知本實施例與比較例比較，能夠得到對比高且鹼性顯像液可溶性良好，且電壓保持率高的彩色濾光片。The hue of the color filter varies according to the test level. In particular, it is incomparable to compare different hue. Therefore, comparison is made between the same hue, that is, between DL, between DY, and between DV. From the above results, it was found that the present embodiment can obtain a color filter which is high in contrast and which is excellent in solubility in an alkaline developing solution and has a high voltage holding ratio as compared with the comparative example.

實施例5及比較例5Example 5 and Comparative Example 5 著色感光性組成物的調製Modulation of coloring photosensitive composition

使用所得到的顏料分散組成物，來調製下述的著色感光性組成物。Using the obtained pigment dispersion composition, the following coloring photosensitive composition was prepared.

‧顏料分散液A(表14A所記載之顏料分散液)2000份‧ Pigment Dispersion A (Pigment Dispersion in Table 14A) 2000 parts

‧顏料分散液B(表14B所記載之顏料分散液)1000份‧ Pigment Dispersion B (Pigment Dispersion in Table 14B) 1000 parts

‧二新戊四醇五-六丙烯酸酯　120份(光聚合性化合物)‧ dipentaerythritol penta-hexaacrylate 120 parts (photopolymerizable compound)

‧4-[鄰溴-對N,N-(二乙氧基碳醯胺基)-苯基]-2,6-二(氯甲基)-s-三　50份(光聚合引發劑)‧4-[o-bromo-p-N,N-(diethoxycarbamoyl)-phenyl]-2,6-di(chloromethyl)-s-three 50 parts (photopolymerization initiator)

‧甲基丙烯酸苄酯/甲基丙烯酸(=75/25[質量比])共聚物(重量平均分子量：10,000)的丙二醇一甲基醚乙酸酯溶液(固體成分30%)　300份(鹼可溶性樹脂)‧ Benzyl methacrylate / methacrylic acid (= 75 / 25 [mass ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 30%) 300 parts (alkali soluble Resin)

‧乙酸1-甲氧基-2-丙酯　390份使用著色感光性組成物而成之彩色濾光片的調製‧ 1-methoxy-2-propyl acetate 390 parts of color filter prepared by coloring photosensitive composition

將所得到的著色感光性組成物(彩色光阻液)在100毫米×100毫米的玻璃基板(1737，Corning公司製)上，以實施例5-1至5-2及比較例5-1成為色濃度指標x值為0.650的方式塗布，以實施例5-3至5-4及比較例5-2成為色濃度指標y值為0.600的方式塗布，又，以實施例5-5、5-6及比較例5-3成為色濃度指標y值為0.100的方式塗布，並使用90℃的烘箱使其乾燥60秒間(預烘烤)。隨後，在塗膜的全面使用200mJ/cm2 (照度20mW/cm2 )曝光，並將曝光後的塗膜使用鹼性顯像液CDK-1(富士FILM ELECTRONIC MATERIALS(股)製)的1%水溶液被覆，且靜止60秒鐘(。靜止後，將純水以噴淋狀撒布來洗掉顯像液。而且，將經如上述施行過曝光及顯像過的塗膜，以220℃的烘箱加熱處理1小時(後烘烤)，並在玻璃基板上形成彩色濾光片用著色圖案(著色樹脂被膜)，來製造著色濾光片基板(彩色濾光片)。The obtained colored photosensitive composition (color resist liquid) was formed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning Co., Ltd.), and Examples 5-1 to 5-2 and Comparative Example 5-1 were used. The color density index x was applied as a value of 0.650, and the coatings of Examples 5-3 to 5-4 and Comparative Example 5-2 were applied so that the color density index y value was 0.600, and further, Examples 5-5 and 5- were used. 6 and Comparative Example 5-3 were applied so that the color density index y value was 0.100, and dried in an oven at 90 ° C for 60 seconds (prebaking). Subsequently, the coating film was exposed to a total of 200 mJ/cm 2 (illuminance: 20 mW/cm 2 ), and the exposed coating film was subjected to 1% of an alkaline developing solution CDK-1 (manufactured by Fuji FILM ELECTRONIC MATERIALS Co., Ltd.). The aqueous solution was coated and allowed to stand for 60 seconds. (After standing, the pure water was sprayed to wash off the developing solution. Further, the coating film which had been exposed and developed as described above was oven at 220 ° C. The heat treatment was performed for 1 hour (post-baking), and a colored filter coloring pattern (colored resin film) was formed on the glass substrate to produce a colored filter substrate (color filter).

彩色濾光片的評價Color filter evaluation

對所製造的著色濾光片基板(彩色濾光片)，如此進行來進行評價。結果如表14所示。The produced color filter substrate (color filter) was evaluated in this manner. The results are shown in Table 14.

(1)對比(1) Comparison

(2)鹼性顯像液可溶性(2) Alkaline imaging solution solubility

(3)結晶析出性(3) Crystal precipitation

在附帶ITO(Indium Tin Oxide)電極的玻璃基板(商品名：1737 Corning公司製)上，以膜厚度為2.0微米的方式塗布光硬化性組成物，並使用90℃的烘箱乾燥60秒(預烘烤)。隨後，未透過光罩而進行100mJ/cm2 的曝光(照度為20mW/cm2 )，且使用鹼性顯像液CDK-1(富士FILM ELECTRONIC MATERIALS(股)製)的1%水溶液並在25℃顯像，並對塗布膜以230℃的烘箱加熱處理30分鐘(後烘烤)。接著，在形成有該像素之基板及以規定形狀蒸鍍ITO電極而成之基板，放入70℃、濕度80%的恆溫槽72小時後，目視評價基板上的結晶分析性，並整理如表14。點數越高係表示越不容易產生結晶析出，著色圖案具有透明性。The photocurable composition was applied to a glass substrate (trade name: 1737 Corning Co., Ltd.) equipped with an ITO (Indium Tin Oxide) electrode so as to have a film thickness of 2.0 μm, and dried in an oven at 90 ° C for 60 seconds (prebaking) grilled). Subsequently, exposure to 100 mJ/cm 2 (illuminance: 20 mW/cm 2 ) was carried out without passing through a photomask, and a 1% aqueous solution of an alkaline developing solution CDK-1 (manufactured by Fuji FILM ELECTRONIC MATERIALS Co., Ltd.) was used and at 25 The image was developed at ° C, and the coated film was heat-treated in an oven at 230 ° C for 30 minutes (post-baking). Next, the substrate on which the pixel was formed and the substrate on which the ITO electrode was vapor-deposited in a predetermined shape were placed in a thermostat at 70° C. and a humidity of 80% for 72 hours, and then the crystal analysis property on the substrate was visually evaluated and consolidated. 14. The higher the number of dots, the less likely that crystal precipitation occurs, and the colored pattern has transparency.

3：未觀察到結晶析出3: No crystal precipitation was observed

2：觀察到少許結晶析出2: A little crystal precipitation was observed

1：在基板面全體觀察到結晶析出1: crystal precipitation was observed on the entire substrate surface

彩色濾光片的色相係依照測試水準而異。特別是對比不同的色相之間係無法比較的。因此係在同一色相之間亦即DR之間、DG之間、DB之間進行比較。從上述結果，得知本實施例與比較例比較，能夠得到對比高且鹼性顯像液可溶性良好，而且在後烘烤不容易析出之彩色濾光片。The hue of the color filter varies according to the test level. In particular, it is incomparable to compare different hue. Therefore, comparison is made between the same hue, that is, between DR, between DG, and between DBs. From the above results, it was found that the present embodiment can obtain a color filter which is high in contrast and which is excellent in solubility in an alkaline developing solution and which is not easily precipitated after post-baking.

實施例中之其他的化合物如以下。Other compounds in the examples are as follows.

D-1：M-1/A-1/MAA=20/65/15質量%的聚合物(重量平均分子量2.3萬、酸價100mgKOH/g)D-1: M-1/A-1/MAA=20/65/15% by mass of polymer (weight average molecular weight: 23,000, acid value: 100 mgKOH/g)

D-2：M-2/A-1/BzMAA/MAA=10/58/20/12質量%的聚合物(重量平均分子量2.3萬、酸價100mgKOH/g)D-2: M-2/A-1/BzMAA/MAA=10/58/20/12% by mass of polymer (weight average molecular weight: 23,000, acid value: 100 mgKOH/g)

D-3：Lubrizol公司製「SOLSPERSE 24000」D-3: "SOLSPERSE 24000" manufactured by Lubrizol

D-4：St/MAA=75/15質量%的聚合物(重量平均分子量2.0萬、酸價100mgKOH/g)D-4: St/MAA=75/15% by mass of polymer (weight average molecular weight: 20,000, acid value: 100 mgKOH/g)

D-5：M-1/BzMA/MAA=20/65/15質量%的聚合物(重量平均分子量2.0萬、酸價100mgKOH/g)D-5: M-1/BzMA/MAA=20/65/15% by mass of polymer (weight average molecular weight: 20,000, acid value: 100 mgKOH/g)

D-6：St/A-1/MAA=30/55/15質量%的聚合物(重量平均分子量2.5萬、酸價100mgKOH/g)D-6: St/A-1/MAA=30/55/15% by mass of polymer (weight average molecular weight 25,000, acid value 100 mgKOH/g)

A-1：末端甲基丙烯醯化聚甲基丙烯酸甲酯(數量平均分子量6,000)A-1: terminal methacrylic acid polymethyl methacrylate (quantitative average molecular weight 6,000)

MAA：甲基丙烯酸MAA: Methacrylic acid

BzMA：甲基丙烯酸苄酯BzMA: benzyl methacrylate

St：苯乙烯St: Styrene

Claims (13)

一種加工顏料，其係含有顏料及高分子化合物，該高分子化合物係用以被覆該顏料，且該高分子化合物在側鏈具有選自由醯胺基、胺基甲醯基及脲基所組成群組之至少一種，而且重量平均分子量為1,000~100,000，其在將高分子化合物所含有的全部聚合單位作為100質量%時，含有5質量%以上60質量%以下之來自下述通式(1)所示單體之聚合單位，並且含有來自具有羧基之單體之聚合單位，而且含有50~200mgKOH/g的範圍之羧基， 通式(1)中，R1 係表示氫原子、或是取代或未取代的烷基，R1 所示之烷基的取代基係選自羥基及烷氧基；R2 係表示單鍵、或2價的連結基，該2價的連結基係選自伸烷基、透過雜原子連結2個以上而成之伸烷基、及伸苯基，或係選自在伸烷基之末端具有選自-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-及-NHCO-之雜原子或含有雜原子之部分結構，且透過該雜原子或含有雜原子 之部分結構與Z連結之連結基；Y係表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-或伸苯基；Z係表示-O-、-CONH-、-O(CO)NH-或-NHCONH-；Z係表示-O-時，R3 為表示氫原子，Z係表示-O-以外時，R3 為表示未取代的烷基、或取代或未取代的芳基，R3 所示之芳基的取代基係選自經羥基或烷氧基取代之烷基、烷基、羥基及烷氧基。A processed pigment comprising a pigment and a polymer compound for coating the pigment, and the polymer compound has a group selected from the group consisting of a mercaptoamine group, an aminomethylmercapto group and a urea group in a side chain. At least one of the group, and the weight average molecular weight is from 1,000 to 100,000, and when the total polymerization unit contained in the polymer compound is 100% by mass, the content is from 5% by mass to 60% by mass based on the following general formula (1). a polymerization unit of the monomer shown, and containing a polymerization unit derived from a monomer having a carboxyl group, and having a carboxyl group in the range of 50 to 200 mgKOH/g, In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group, and the substituent of the alkyl group represented by R 1 is selected from a hydroxyl group and an alkoxy group; and R 2 represents a single bond, Or a divalent linking group, wherein the divalent linking group is selected from an alkyl group, an alkyl group which is bonded to two or more hetero atoms, and a phenyl group, or is selected from the group consisting of an alkyl group at the end of the alkyl group. From -O-, -S-, -C(=O)O-, -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)O-, -NHC(=O) a hetero atom of S-, -OC(=O)-, -OCONH-, and -NHCO- or a partial structure containing a hetero atom, and a linking structure through which the hetero atom or a partial structure containing a hetero atom is bonded to Z; Represents -CO-, -C(=O)O-, -CONH-, -OC(=O)- or phenyl; Z series means -O-, -CONH-, -O(CO)NH- or - When NH-H-; Z represents -O-, R 3 represents a hydrogen atom, and Z represents a group other than -O-, and R 3 represents an unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R 3 represents The substituent of the aryl group is selected from the group consisting of an alkyl group substituted with a hydroxyl group or an alkoxy group, an alkyl group, a hydroxyl group, and an alkoxy group. 如申請專利範圍第1項之加工顏料，其中該顏料係選自由偶氮顏料及多環顏料所組成群組之至少1種。 The processing pigment according to claim 1, wherein the pigment is at least one selected from the group consisting of an azo pigment and a polycyclic pigment. 如申請專利範圍第1項之加工顏料，其中該顏料係選不溶性偶氮系、二系顏料、酞菁系顏料、二酮吡咯并吡咯系顏料、蒽醌系顏料、喹吖酮系顏料及苝系顏料所組成群組之至少1種。For example, in the processing pigment of claim 1, wherein the pigment is selected from insoluble azo and At least one of a group consisting of a pigment, a phthalocyanine pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, a quinophthalone pigment, and an anthraquinone pigment. 如申請專利範圍第1項之加工顏料，其中平均1次粒徑為5~25奈米。 For example, in the processing pigment of the first item of the patent scope, the average primary particle diameter is 5 to 25 nm. 如申請專利範圍第1項之加工顏料，其中使用1-甲氧基-2-丙醇洗淨該加工顏料後時，該高分子化合物的游離基為30質量%以下。 The process pigment according to claim 1, wherein when the process pigment is washed with 1-methoxy-2-propanol, the radical of the polymer compound is 30% by mass or less. 如申請專利範圍第1項之加工顏料，其係在該顏料的微細化製程添加該高分子化合物來製造。 The processed pigment of the first aspect of the patent application is produced by adding the polymer compound to the finening process of the pigment. 一種顏料分散組成物，其係含有如申請專利範圍第1至6項中任一項之加工顏料及用以分散該加工顏料之有機溶劑。 A pigment dispersion composition comprising the processed pigment according to any one of claims 1 to 6 and an organic solvent for dispersing the processed pigment. 如申請專利範圍第7項之顏料分散組成物，其中更含有顏料分散劑。 The pigment dispersion composition of claim 7, which further contains a pigment dispersant. 如申請專利範圍第7項之顏料分散組成物，其係使用於形成彩色濾光片之著色區域。 A pigment dispersion composition according to claim 7 of the patent application, which is used for forming a colored region of a color filter. 一種著色感光性組成物，其係含有如申請專利範圍第7項之顏料分散組成物、光聚合性化合物及光聚合引發劑。 A colored photosensitive composition containing the pigment dispersion composition, the photopolymerizable compound, and the photopolymerization initiator according to claim 7 of the patent application. 一種彩色濾光片，其係含有基板及在該基板上使用如申請專利範圍第10項之著色感光性組成物所形成的著色區域。 A color filter comprising a substrate and a colored region formed on the substrate using the colored photosensitive composition of claim 10 of the patent application. 一種液晶顯示元件，其係具備如申請專利範圍第11項之彩色濾光片。 A liquid crystal display element comprising a color filter as in claim 11 of the patent application. 一種固體攝像元件，其係具備如申請專利範圍第11項之彩色濾光片。 A solid-state imaging device comprising a color filter as in claim 11 of the patent application.
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