TWI437280B - Compound, photosensitive composition, curable composition, curable composition for forming color filter, color filter, and method for manufacturing the same - Google Patents

Description

化合物、感光性組成物、硬化性組成物、彩色濾光片用硬化性組成物、彩色濾光片及其製法Compound, photosensitive composition, curable composition, curable composition for color filter, color filter, and preparation method thereof

本發明係有關於一種能夠用於液晶顯示元件(LCD)或固體攝像元件(CCD、CMOS等)之彩色濾光片用硬化性組成物、彩色濾光片用硬化性組成物、彩色濾光片及其製法。The present invention relates to a curable composition for a color filter that can be used for a liquid crystal display element (LCD) or a solid-state imaging device (CCD, CMOS, etc.), a curable composition for a color filter, and a color filter. And its method of production.

彩色濾光片係在液晶顯示器不可缺少的構成零件。A color filter is an indispensable component of a liquid crystal display.

液晶顯示器作為顯示裝置與CRT比較時因為較為小巧，且具有同級以上的性能，所以逐漸取代CRT作為電視畫面、個人電腦畫面、及其他顯示裝置。又，近年來，液晶顯示裝置的開發動向係從畫面較小面積之先前的監視器用途，逐漸朝向要求大型畫面且高畫質之TV用途。When the liquid crystal display is used as a display device and compared with a CRT, it is relatively small and has the same level or higher performance, so it gradually replaces the CRT as a television screen, a personal computer screen, and other display devices. Further, in recent years, the development trend of liquid crystal display devices has been gradually shifting from the use of previous monitors having a small screen area to the use of TVs requiring large screens and high image quality.

TV用途的液晶顯示器與先前監視器用途之液晶顯示器相比，要求更高的畫質。亦即，對比及色純度提升。因為對比提升，關於製造彩色濾光片用之硬化性組成物所使用之著色劑(有機頻料等)的粒子大小，要求使用更微小之粒子。A liquid crystal display for TV use requires higher image quality than a liquid crystal display for a previous monitor. That is, the contrast and color purity are improved. Because of the increase in contrast, it is required to use finer particles for the particle size of the coloring agent (organic material, etc.) used for the production of the curable composition for a color filter.

又，為了提升色純度，在彩色濾光片製造用硬化性組成物的固體成分中著色劑(有機顏料)所佔有的含有率，要求更高之含有率。Moreover, in order to improve the color purity, the content ratio of the coloring agent (organic pigment) in the solid content of the curable composition for color filter production requires a higher content rate.

另一方面，在固體攝像元件用彩色濾光片方面，希望更高精密化。On the other hand, in the case of a color filter for a solid-state image sensor, it is desired to have higher precision.

但是，應用先前的顏料分散系而成之硬化性組成物，因為顏料的粒子比較粗大，而有產生顏色不均的問題，欲謀求更提高解像度係有困難的，不適用於如固體攝像元件要求微細圖案之用途。因此，有提案(例如參照特開平2－127602號)揭示一種技術，係使用有機溶劑可溶性染料代替顏料作為著色劑。However, since the curable composition obtained by the prior pigment dispersion system is used, since the particles of the pigment are relatively coarse and there is a problem of uneven color, it is difficult to seek to improve the resolution, and it is not suitable for a solid-state image sensor. The use of fine patterns. Therefore, there is a proposal (for example, refer to JP-A No. 2-127602) to disclose a technique in which an organic solvent-soluble dye is used instead of a pigment as a colorant.

又，在固體攝像元件用途的彩色濾光片亦要求著色圖案的薄膜化，為了以與先前相同色濃度的方式薄膜化，要求提高在彩色濾光片製造用硬化性組成物之著色劑的含有率。In addition, in the color filter used for the solid-state image sensor, the coloring pattern is required to be thinned, and in order to form a film having the same color density as before, it is required to improve the coloring agent of the curable composition for color filter production. rate.

如上述，在液晶顯示器用、固體攝像元件中任一種情況，因為彩色濾光片製造用硬化性組成物係含有著色劑，用以使該硬化性組成物硬化之必要成分之光聚合引發劑及光聚合性單體的含量受到限制，因強度不充分、或是硬化性不充分而有與基材之硬質表面無法得到充分的黏附性等問題。As described above, in the case of the liquid crystal display or the solid-state imaging device, the curable composition for producing a color filter contains a coloring agent, and a photopolymerization initiator which is an essential component for curing the curable composition and The content of the photopolymerizable monomer is limited, and the strength is insufficient or the curability is insufficient, and there is a problem that sufficient adhesion to the hard surface of the substrate is not obtained.

而且，近年來，隨著基板尺寸的擴大，要求在顯像步驟時即便在顯像液中長時間亦能夠維持圖案形狀、且圖案無欠缺或剝落之高敏感度的硬化性組成物。Further, in recent years, as the size of the substrate is enlarged, a highly sensitive curable composition capable of maintaining the pattern shape and having no pattern or peeling off in the pattern even in the developing liquid for a long period of time is required.

關於彩色濾光片製造用硬化性組成物，正嘗試開發敏感度更高的光聚合引發劑，用以在基板上塗布該組成物並進行曝光硬化時，即使在塗布膜底部附近亦能夠充分地達成硬化反應。In the case of a curable composition for producing a color filter, attempts have been made to develop a photopolymerization initiator having higher sensitivity, and to apply the composition on a substrate and perform exposure hardening, even in the vicinity of the bottom of the coating film. A hardening reaction is achieved.

先前，作為彩色濾光片製造用硬化性組成物，例如使用組合含有羧基之黏合劑聚合物與新戊四醇六丙烯酸酯等多官能性丙烯酸酯、及光聚合引發劑而成的感放射性組成物，在此種感放射性組成物作為高敏感度的光聚合引發劑，例如有提案(例如參照特開平6－75372號及特開平6－75373號)，揭示2,2’雙(2－氯苯基)－4,4’,5,5’－四苯基二咪唑、2,2’－雙(2,3－二氯苯基)－4,4’,5,5’－四苯基二咪唑等。In the past, as a curable composition for producing a color filter, for example, a radioactive composition composed of a binder polymer containing a carboxyl group and a polyfunctional acrylate such as pentaerythritol hexaacrylate and a photopolymerization initiator is used. In the case of such a sensitizing radioactive composition, as a high-sensitivity photopolymerization initiator, for example, there is a proposal (for example, refer to JP-A-6-75372 and JP-A No. 6-75373) to disclose 2,2' bis(2-chloro Phenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyl Diimidazole and the like.

又，能夠應用於硬化性組成物之光聚合引發劑，能夠應用於使用在印刷版或光阻劑等之感放射性組成物之光聚合引發劑，有提案(例如參照特公昭48－38403號及特開昭62－174204號)，揭示2,2’－雙(2－氯苯基)－4,4’,5,5’－四苯基二咪唑、2,2’－雙(2－氯苯基)－4,4’,5,5’－四(烷氧基苯基)二咪唑、2,2’－雙(2－氯苯基)－4,4’,5,5’－四(二烷氧基苯基)二咪唑、2,2’－雙(2－氯苯基)－4,4’,5,5’－四(三烷氧基苯基)二咪唑等。又，為了提升彩色濾光片用硬化性組成物(光聚合性組成物)的敏感度，有嘗試在含有聚合引發劑、敏化劑等之聚合引發劑系組成物中含有特定化合物(例如參照特開2002－221791號)。Moreover, it can be applied to a photopolymerization initiator which is a curable composition, and can be applied to a photopolymerization initiator which is used for a radiation-sensitive composition such as a printing plate or a photoresist, and is proposed (for example, see Japanese Patent Publication No. 48-38403 and JP-A-62-174204, discloses 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra (Dialkyloxyphenyl) diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)diimidazole, and the like. In addition, in order to improve the sensitivity of the curable composition (photopolymerizable composition) for a color filter, it is attempted to contain a specific compound in a polymerization initiator composition containing a polymerization initiator, a sensitizer, or the like (for example, reference) Special opening 2002-221791).

但是，上述中任一硬化性組成物，都是尚未滿足敏感度之程度，在使其硬化時，必須照射高能量的放射線。使用此種硬化性組成物來形成彩色濾光片的著色圖案時，若照射量不足時，會導致圖案脫落、缺損、殘膜率或像素強度下降等問題。進而在所得到彩色濾光片的著色圖案，會產生解像力及與支撐體的黏附性下降之問題。However, any of the above-mentioned curable compositions is not yet satisfactory in sensitivity, and it is necessary to irradiate high-energy radiation when it is hardened. When such a curable composition is used to form a colored pattern of a color filter, if the amount of irradiation is insufficient, problems such as loss of pattern, defect, residual film rate, or decrease in pixel intensity are caused. Further, in the colored pattern of the obtained color filter, there is a problem that the resolution and adhesion to the support are lowered.

如上述，即便高濃度地含有著色劑，亦要求以高敏感度硬化、具有良好圖案形成性之彩色濾光片製造用硬化性組成物，但是現狀尚未提供。As described above, even if a coloring agent is contained in a high concentration, a curable composition for color filter production which is cured with high sensitivity and has good pattern formability is required, but the present state of the art has not yet been provided.

本發明係鑒於前述先前的問題而完成。The present invention has been made in view of the foregoing prior problems.

亦即，本發明係提供一種對硬化性組成物的高敏感度化有用的新穎化合物、感光性組成物、硬化性組成物、彩色濾光片用硬化性組成物，該硬化性組成物即便高濃度地含有著色劑，亦能夠高敏感度地硬化，形成具有良好的圖案、且與支撐體的黏附性優良之著色圖案。In other words, the present invention provides a novel compound, a photosensitive composition, a curable composition, and a curable composition for a color filter which are useful for high sensitivity of a curable composition, and the curable composition is high even if the curable composition is high. When the coloring agent is contained in a concentration, it can be hardened with high sensitivity, and a colored pattern having a good pattern and excellent adhesion to a support can be formed.

而且，本發明係提供一種彩色濾光片，其具備解像力及與支撐體的黏附性優良之著色圖案(使用本發明的彩色濾光片用硬化性組成物所構成)，及提供能夠高生產力地製造該彩色濾光片之方法。Further, the present invention provides a color filter comprising a coloring pattern excellent in resolution and adhesion to a support (using the curable composition for a color filter of the present invention), and providing high productivity A method of manufacturing the color filter.

本發明者進行專心研究之結果，發現藉由含有特定化合物之彩色濾光片用硬化性組成物，能夠解決前述課題而完成了本發明。亦即，為了解決前述課題之手段如下。As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by a curable composition for a color filter containing a specific compound. That is, the means for solving the above problems are as follows.

一種彩色濾光片用硬化性組成物，其特徵係含有：選自由下述通式(1－I)所示之化合物、通式(1－II)所示之化合物、下述通式(2－I)所示之化合物、及通式(3－I)所示之化合物所組成群組中至少1種化合物；光聚合引發劑；聚合性化合物；及著色劑， A curable composition for a color filter, comprising: a compound represented by the following formula (1-I), a compound represented by the formula (1-II), and a formula (2) At least one compound selected from the group consisting of a compound represented by -I) and a compound represented by the formula (3-I); a photopolymerization initiator; a polymerizable compound; and a color former;

通式(1－I)及通式(1－II)中，R¹¹ 及R¹² 係各自獨立地表示一價的取代基；R¹³ 、R¹⁴ 、R¹⁵ 、及R¹⁶ 係各自獨立地表示氫原子或一價的取代基；n係表示0~5的整數；n’係表示0~5的整數；n及n’之不可雙方都為0；n為2以上時，複數存在之R¹¹ 各自可相同亦可不同；n’為2以上時，複數存在之R¹² 各自可相同亦可不同； In the formula (1-I) and the formula (1-II), R ¹¹ and R ¹² each independently represent a monovalent substituent; and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent; n represents an integer from 0 to 5; n' represents an integer from 0 to 5; n and n' are both non-zero; and when n is 2 or more, a complex number exists in R ¹¹ Each of them may be the same or different; when n' is 2 or more, the plurality of R ¹² present in the plural may be the same or different;

通式(2－I)中，A係表示亦可具有取代基之芳香族環或雜環；R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 係各自獨立地表示氫原子或一價的非金屬原子團；A、R²² 、R²³ 、及R²⁴ 亦可各自互相鍵結而形成脂肪族性或芳香族性的環； In the formula (2-I), A represents an aromatic ring or a heterocyclic ring which may have a substituent; and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent group. a non-metal atomic group; A, R ²² , R ²³ , and R ²⁴ may each be bonded to each other to form an aliphatic or aromatic ring;

通式(3－1)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(R³³ )－；Y係表示氧原子、硫原子或－N(R³³ )－；R³¹ 、R³² 、及R³³ 係各自獨立地表示氫原子或一價的非金屬原子團；A、R³¹ 、R³² 、及R³³ 亦可各自互相鍵結而形成脂肪族性或芳香族性的環。In the formula (3-1), 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 ³³ )-; and Y represents an oxygen atom or a sulfur atom. Or -N(R ³³ )-; R ³¹ , R ³² , and R ³³ each independently represent a hydrogen atom or a monovalent non-metal atom; A, R ³¹ , R ³² , and R ³³ may each be bonded to each other. An aliphatic or aromatic ring is formed.

本發明的較佳態樣包括下述態樣<1>~<18><1>一種彩色濾光片用硬化性組成物，含有至少一種選自如前述通式(1－I)或前述通式(1－II)所示之化合物、光聚合引發劑、聚合性化合物及著色劑。The preferred embodiment of the present invention includes the following aspects <1> to <18> <1> A curable composition for a color filter containing at least one selected from the group consisting of the above formula (1-I) or the above formula A compound represented by (1-II), a photopolymerization initiator, a polymerizable compound, and a color former.

<2>如前述<1>之彩色濾光片用硬化性組成物，其中在前述通式(1－I)或通式(1－II)，n係表示1~5的整數，R11中之至少一個為烷基、烷氧基、或二烷胺基。<2> The curable composition for a color filter according to the above <1>, wherein in the above formula (1-I) or formula (1-II), n represents an integer of 1 to 5, and R11 At least one is an alkyl group, an alkoxy group, or a dialkylamine group.

<3>如前述<1>或<2>之彩色濾光片用硬化性組成物，其中更含有硫醇化合物。<3> The curable composition for a color filter according to <1> or <2> above, which further contains a thiol compound.

<4>如前述<1>至<3>中任一項之彩色濾光片用硬化性組成物，其中含有二咪唑系化合物作為前述光聚合引發劑。The hardenable composition for color filters of any one of the above-mentioned <1> which contains a diimidazole type compound as the said photo-polymerization initiator.

<5>一種彩色濾光片，其特徵係具有在支撐體上使用前述<1>至<4>中任一項之彩色濾光片用硬化性組成物而構成之著色圖案。<5> A color filter comprising a coloring pattern formed by using the curable composition for a color filter according to any one of the above <1> to <4> on the support.

<6>一種彩色濾光片之製法，包含以下步驟：在支撐體上塗布前述<1>至<4>中任一項之彩色濾光片用硬化性組成物來形成著色硬化性組成物層之步驟；透過光罩對前述著色硬化性組成物層進行曝光之步驟；及對曝光後的前述著色硬化性組成物層進行顯像來形成著色圖案之步驟。<6> A method of producing a color filter, comprising the step of: forming a colored curable composition layer by applying a curable composition for a color filter according to any one of <1> to <4> on a support; a step of exposing the colored curable composition layer through a photomask; and a step of developing the colored curable composition layer after exposure to form a colored pattern.

<7>一種化合物，係如前述通式(2－I)所示。<7> A compound which is represented by the above formula (2-I).

<8>一種感光性組成物，其特徵係含有前述通式(2－I)所示之化合物。<8> A photosensitive composition characterized by containing a compound represented by the above formula (2-I).

<9>一種硬化性組成物，係含有前述通式(2－I)所示之化合物、光聚合引發劑、聚合性化合物、及著色劑。<9> A curable composition containing a compound represented by the above formula (2-I), a photopolymerization initiator, a polymerizable compound, and a color former.

<10>如前述<9>之硬化性組成物，其中含有二咪唑系化合物作為前述光聚合引發劑。<10> The curable composition according to the above <9>, which contains a diimidazole-based compound as the photopolymerization initiator.

<11>一種彩色濾光片用硬化性組成物，其特徵係含有前述通式(2－I)所示之化合物、光聚合引發劑、聚合性化合物、及著色劑。<11> A curable composition for a color filter, which comprises a compound represented by the above formula (2-I), a photopolymerization initiator, a polymerizable compound, and a color former.

<12>如前述<11>之彩色濾光片用硬化性組成物，其中含有二咪唑系化合物作為前述光聚合引發劑。<12> The curable composition for a color filter according to the above <11>, which comprises a diimidazole-based compound as the photopolymerization initiator.

<13>一種彩色濾光片，其特徵係在支撐體上具有藉由前述<11>或<12>之彩色濾光片用硬化性組成物所形成之著色圖案。<13> A color filter comprising a colored pattern formed of the curable composition for a color filter of the above <11> or <12> on a support.

<14>一種彩色濾光片之製法，包含以下步驟：支撐體上塗布前述<11>或<12>之彩色濾光片用硬化性組成物來形成著色硬化性組成物層之步驟；透過光罩對前述著色硬化性組成物層進行曝光之步驟；及對曝光後的前述著色硬化性組成物層進行顯像來形成著色圖案之步驟。<14> A method of producing a color filter comprising the steps of: applying a curable composition for color filters of <11> or <12> on a support to form a colored curable composition layer; a step of exposing the colored curable composition layer by a cover; and a step of developing the colored curable composition layer after exposure to form a colored pattern.

<15>一種彩色濾光片用硬化性組成物，其特徵係含有前述通式(3－1)所示之化合物、光聚合引發劑、聚合性化合物、及著色劑。<15> A curable composition for a color filter, which comprises a compound represented by the above formula (3-1), a photopolymerization initiator, a polymerizable compound, and a color former.

<16>如前述<15>之彩色濾光片用硬化性組成物，其中含有二咪唑系化合物作為前述光聚合引發劑。<16> The curable composition for a color filter according to the above <15>, which contains a diimidazole-based compound as the photopolymerization initiator.

<17>一種彩色濾光片，其特徵係在支撐體上具有使用前述<15>或<16>之彩色濾光片用硬化性組成物而構成之著色圖案。<17> A color filter comprising a colored pattern formed using the curable composition for a color filter of the above <15> or <16> on a support.

<18>一種彩色濾光片之製法，包含以下步驟：在支撐體上塗布前述<15>或<16>之彩色濾光片用硬化性組成物來形成著色硬化性組成物層之步驟；透過光罩對前述著色硬化性組成物層進行曝光之步驟；及對曝光後的前述著色硬化性組成物層進行顯像來形成著色圖案之步驟。<18> A method of producing a color filter, comprising the steps of: applying a curable composition for color filters of <15> or <16> to a support to form a colored curable composition layer; a step of exposing the colored curable composition layer to the photomask; and a step of developing the colored curable composition layer after exposure to form a colored pattern.

本發明鑒於上述之情況所達成，其可抑制薄膜於機械方向上之不均勻厚度及薄膜中的條紋，本發明的一目的為提供一具有均勻光學性質之熱塑性樹脂薄膜，其可作為高品質之功能膜及其製造方法。The present invention has been made in view of the above circumstances, which can suppress uneven thickness of a film in a machine direction and streaks in a film, and an object of the present invention is to provide a thermoplastic resin film having uniform optical properties, which can be used as a high quality product. Functional film and its method of manufacture.

以下，詳細地說明本發明使用的化合物、感光性組成物、硬化性組成物、彩色濾光片用硬化性組成物、及使用該彩色濾光片用硬化性組成物而構成之彩色濾光片及其製法。Hereinafter, the compound used in the present invention, a photosensitive composition, a curable composition, a curable composition for a color filter, and a color filter formed using the curable composition for a color filter will be described in detail. And its method of production.

彩色濾光片用硬化性組成物Hardening composition for color filters

本發明之彩色濾光片用硬化性組成物其特徵係含有(A)選自前述通式(1－I)、通式(1－II)所示之化合物、下述通式(2－I)所示之化合物、及通式(3－1)所示之化合物中之至少1種(以下，簡稱「特定敏化劑」)、(B)聚合性組成物、(C)聚合引發劑、及(D)著色劑。The curable composition for a color filter of the present invention is characterized by containing (A) a compound selected from the above formula (1-I), formula (1-II), and a formula (2-I) At least one of the compound shown in the formula (3-1) (hereinafter referred to as "specific sensitizer"), (B) a polymerizable composition, (C) a polymerization initiator, And (D) a colorant.

以下，依順序說明在本發明的彩色濾光片用硬化性組成物(以下，亦有簡稱「聚合性組成物」的情況)所含有之各成分。In the following, each component contained in the curable composition for a color filter of the present invention (hereinafter, simply referred to as "polymerizable composition") will be described in order.

<(A)特定敏化劑><(A) Specific sensitizer>

本發明之硬化性組成物、彩色濾光片用硬化性組成物係含有選自下述通式(1－I)所示之化合物、通式(1－II)所示之化合物、下述通式(2－I)所示之化合物、及下述通式(3－1)所示之化合物中至少1種化合物。The curable composition of the present invention and the curable composition for a color filter contain a compound represented by the following formula (1-I), a compound represented by the formula (1-II), and the following At least one compound of the compound represented by the formula (2-I) and the compound represented by the following formula (3-1).

前述通式(1－I)、通式(1－II)、通式(2－I)、或通式(3－1)所示之化合物係為具有敏化劑作用之化合物。其作用機構雖然尚未明確，可認為係藉由在本發明的硬化性組成物等含有此等化合物，來提升所照射活性放射線的吸收效率、提升組成物的硬化敏感度。可認為前述通式(1－I)、通式(1－II)、通式(2－I)、或通式(3－1)所示之化合物，因為能夠在吸收活性放射線、特別是紫外線後激發成高能量性狀態，而有效率地往聚合引發劑進行電子移動或能量移動，使聚合引發劑生成活性聚合引發種，而能夠使硬化性組成物的硬化反應高敏感度化。The compound represented by the above formula (1-I), formula (1-II), formula (2-I), or formula (3-1) is a compound having a sensitizer function. The action mechanism is not clear, and it is considered that the absorption efficiency of the irradiated actinic radiation is improved by the inclusion of these compounds in the curable composition of the present invention, and the hardening sensitivity of the composition is improved. The compound represented by the above formula (1-I), formula (1-II), formula (2-I), or formula (3-1) can be considered to be capable of absorbing active radiation, particularly ultraviolet rays. After the excitation is carried out in a high-energy state, the polymerization initiator is efficiently moved to the electrons or the energy is moved to form a living polymerization initiator, and the curing reaction of the curable composition is highly sensitive.

首先，詳細地說明通式(1－I)及通式(1－II)。First, the general formula (1-I) and the general formula (1-II) will be described in detail.

通式(1－I)或通式(1－II)中，R¹¹ 及R¹² 係各自獨立地表示一價的取代基，R¹³ 、R¹⁴ 、R¹⁵ 、及R¹⁶ 係各自獨立地表示氫原子或一價的取代基。n係表示0~5的整數，n’係表示0~5的整數，n及n’之不可雙方都為0。n為2以上時，複數存在之R¹¹ 各自可相同亦可不同。n’為2以上時，複數存在之R¹² 各自可相同亦可不同。In the formula (1-I) or the formula (1-II), R ¹¹ and R ¹² each independently represent a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent A hydrogen atom or a monovalent substituent. n is an integer from 0 to 5, n' is an integer from 0 to 5, and n and n' are both zero. When n is 2 or more, R ^{11 which is} present in plural may be the same or different. When n' is 2 or more, R ¹² existing in plural may be the same or different.

在通式(1－I)或通式(1－II)中，R¹¹ 及R¹² 係各自獨立地表示一價的取代基，n為2以上時，複數存在之R¹¹ 各自可相同亦可不同。n’為2以上時，複數存在之R¹² 各自可相同亦可不同。In the formula (1-I) or the formula (1-II), R ¹¹ and R ¹² each independently represent a monovalent substituent, and when n is 2 or more, each of R ¹¹ may be the same or may be the same. different. When n' is 2 or more, R ¹² existing in plural may be the same or different.

n為2以上時，複數存在之R¹¹ 之間可互相鍵結而形成環。n’為2以上時，複數存在之R¹² 之間可互相鍵結而形成環。When n is 2 or more, R ¹¹ which is present in plural may be bonded to each other to form a ring. When n' is 2 or more, the plural R ¹² existing may be bonded to each other to form a ring.

又，R¹¹ 及/或R¹² 亦可與R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 中至少一個互相鍵結而形成環。Further, R ¹¹ and/or R ¹² may be bonded to at least one of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ to form a ring.

在R¹¹ 及R¹² 之一價的取代基沒有特別限制，可舉出例如鹵素原子(包含氟原子、氯原子、溴原子、碘原子)、烷基(包含環烷基、二環烷基、三環烷基)、烯基(包含環烯基、二環烯基)、炔基、芳基、複合環基(亦稱為雜環基)、氰基、羥基、硝基、羧基、烷氧基、芳氧基、矽烷氧基、雜環氧基、醯氧基、胺基甲醯氧基、烷氧基羰基氧基、芳氧基羰基氧基、胺基(包含二烷胺基、烷胺基、二芳胺基、芳胺基、苯胺基)、銨基、醯胺基、胺基羰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、胺磺醯胺基、烷基及芳基磺醯胺基、氫硫基、烷硫基及芳硫基、雜環硫基、胺磺醯基、磺酸基、烷基及芳基亞磺醯基、烷基及芳基磺醯基、醯基、芳氧基羰基、烷氧基羰基、胺基甲醯基、芳基及雜環偶氮基、醯亞胺基、膦基、氧膦基、氧膦基氧基、氧膦基胺基、膦酸基、矽烷基、肼基、脲基、硼酸基(－B(OH)₂ )、磷酸基(－OPO(OH)₂ )、硫酸基(－OSO₃ H)等。The substituent of one of R ¹¹ and R ^{12 is} not particularly limited, and examples thereof include a halogen atom (including a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and the like). Tricycloalkyl), alkenyl (including cycloalkenyl, bicycloalkenyl), alkynyl, aryl, complex cyclic (also known as heterocyclyl), cyano, hydroxy, nitro, carboxy, alkoxy , aryloxy, decyloxy, heterocyclic oxy, decyloxy, aminomethyl methoxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amine (including dialkylamino, alkane Amino, diarylamine, arylamino, anilino), ammonium, decylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkane And arylsulfonylamino, thiol, alkylthio and arylthio, heterocyclic thio, sulfonyl, sulfonate, alkyl and arylsulfinyl, alkyl and aryl Sulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminomethylindenyl, aryl and heterocyclic azo, quinone imido, phosphino, phosphinyl, phosphinyloxy, Phosphoxylamino, phosphonic acid, decyl, Group, a ureido group, a boronic acid group (-B (OH) _2), a phosphoric acid group (-OPO (OH) _2), sulfuric acid group (-OSO ₃ H) and the like.

n為2以上時複數存在之R¹¹ 之間、或是n’為2以上時複數存在之R¹² 之間能夠互相鍵結而形成環(芳香族、或非芳香族的烴環、或雜環。此等可進而組合而成為多環稠環)。能夠形成的環，具體上可舉出例如苯環、萘環、蒽環、菲環、茀環、聯三伸苯環、稠四苯環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、唑環、噻唑環、吡啶環、吡環、嘧啶環、嗒環、吲哚環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹環、喹啉環、酞環、萘啶環、喹啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、烯環、環、啡噻環、啡噻環、啡環。When n is 2 or more, when R ¹¹ is present in plural, or when n' is 2 or more, R ^{12 which} is present in plural may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring). These can be combined to form a polycyclic fused ring). Specific examples of the ring which can be formed include, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a benzene ring, a condensed tetraphenyl ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, Imidazole ring, Oxazole ring, thiazole ring, pyridine ring, pyridyl Ring, pyrimidine ring, anthracene Ring, 吲哚 Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quin Ring, quinoline ring, anthracene Ring, naphthyridine ring, quin a porphyrin ring, a quinazoline ring, an isoquinoline ring, an oxazole ring, a pyridine ring, an acridine ring, a phenanthroline ring, a thiophene ring, Olefin, Ring, thiophene Ring, thiophene Ring, brown ring.

R¹¹ 及R¹² 以鹵素原子、烷基(包含環烷基、二環烷基、三環烷基)、烯基(包含環烯基、二環烯基)、炔基、芳基、氰基、羥基、硝基、羧基、烷氧基、芳氧基、矽烷氧基、醯氧基、胺基甲醯氧基、胺基(包含二烷胺基、烷胺基、二芳胺基、芳胺基、苯胺基)、醯胺基、胺基碳醯胺基、烷氧基碳醯胺基、芳氧基碳醯胺基、胺磺醯胺基、烷基或芳基磺醯胺基、烷硫基、芳硫基、胺磺醯基、烷基及芳基磺醯基、芳氧基羰基、烷氧基羰基、胺基甲醯基、醯亞胺基、矽烷基、或脲基為佳。R ¹¹ and R ^{12 are} a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group, a bicycloalkenyl group), an alkynyl group, an aryl group, or a cyano group. , hydroxy, nitro, carboxy, alkoxy, aryloxy, decyloxy, decyloxy, aminomethyl methoxy, amine (including dialkylamino, alkylamino, diarylamine, aromatic Amine, anilino), anthranyl, aminocarbinium, alkoxycarbenylamine, aryloxycarbamoylamine, aminesulfonylamino, alkyl or arylsulfonylamino, An alkylthio group, an arylthio group, an amine sulfonyl group, an alkyl group and an arylsulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aminomethyl fluorenyl group, a fluorenylene group, a decyl group, or a ureido group is good.

R¹¹ 及R¹² 以鹵素原子、烷基(包含環烷基、二環烷基、三環烷基)、烷氧基、芳氧基、烷硫基、芳硫基、或胺基(包含二烷胺基、烷胺基、二芳胺基、芳胺基)為更佳。R ¹¹ and R ^{12 are} a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an amine group (including two More preferably, an alkylamino group, an alkylamino group, a diarylamine group, or an arylamine group).

R¹¹ 及R¹² 所示之一價的取代基能夠導入時，亦可更具有取代基。When one of the substituents represented by R ¹¹ and R ¹² can be introduced, it may have a more substituent.

R¹³ 、R¹⁴ 、R¹⁵ 、及R¹⁶ 係各自獨立地表示氫原子或一價的取代基，R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 亦可互相鍵結而形成環。又，R¹³ 、R¹⁴ 、R¹⁵ 、及R¹⁶ 亦可與R¹¹ 及/或R¹² 互相鍵結而形成環。R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring. Further, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to each other with R ¹¹ and/or R ¹² to form a ring.

R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 之一價取代基沒有特別限制，可舉出例如鹵素原子、烷基(包含環烷基、二環烷基、三環烷基)、烯基(包含環烯基、二環烯基)、炔基、芳基、複合環基(亦稱為雜環基)、氰基、羥基、硝基、羧基、烷氧基、芳氧基、矽烷氧基、雜環氧基、醯氧基、胺基甲醯氧基、烷氧基羰基氧基、芳氧基羰基氧基、胺基(包含苯胺基)、銨基、醯胺基、胺基羰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、胺磺醯胺基、烷基及芳基磺醯胺基、氫硫基、烷硫基、芳硫基、雜環硫基、胺磺醯基、磺酸基、烷基及芳基亞磺醯基、烷基及芳基磺醯基、醯基、芳氧基羰基、烷氧基羰基、胺基甲醯基、芳基及雜環偶氮基、醯亞胺基、膦基、氧膦基、氧膦基氧基、氧膦基胺基、膦酸基、矽烷基、肼基、脲基、硼酸基(－B(OH)₂ )、磷酸基(－OPO(OH)₂ )、硫酸基(－OSO₃ H)等。The one-valent substituent of R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 is} not particularly limited, and examples thereof include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), and an alkenyl group (including Cycloalkenyl, bicycloalkenyl), alkynyl, aryl, complex cyclic (also known as heterocyclyl), cyano, hydroxy, nitro, carboxy, alkoxy, aryloxy, decyloxy, Heterocyclic oxy, decyloxy, aminomethyl methoxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amine (including anilino), ammonium, amidino, aminocarbonylamino , alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkyl and arylsulfonylamino, thiol, alkylthio, arylthio, heterocyclic thio, amine sulfonate Sulfhydryl, sulfonate, alkyl and arylsulfinylene, alkyl and arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminomethylindenyl, aryl and heterocyclic Azo, guanidino, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, phosphonic, decyl, decyl, ureido, boronic acid (-B(OH) ₂ ), a phosphate group (-OPO(OH) ₂ ), a sulfate group (-OSO ₃ H), or the like.

R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 能夠互相鍵結而形成環(芳香族、或非芳香族的烴環、或雜環。此等可進而組合而成為多環稠環)。R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring (an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring. These may be further combined to form a polycyclic fused ring).

又，R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 能夠與R¹¹ 及/或R¹² 互相鍵結而形成環(芳香族、或非芳香族的烴環、或雜環。此等可進而組合而成為多環稠環)。能夠形成的環，具體上可舉出例如苯環、萘環、蒽環、菲環、茀環、聯三苯環、稠四苯環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、唑環、噻唑環、吡啶環、吡環、嘧啶環、嗒環、吲哚環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹環、喹啉環、酞環、萘啶環、喹啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、烯環、環、啡噻環、啡噻環、啡環等。Further, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to R ¹¹ and/or R ¹² to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These may be further combined. Become a polycyclic fused ring). Specific examples of the ring which can be formed include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a terphenyl ring, a condensed tetraphenyl ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, and an imidazole. ring, Oxazole ring, thiazole ring, pyridine ring, pyridyl Ring, pyrimidine ring, anthracene Ring, 吲哚 Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quin Ring, quinoline ring, anthracene Ring, naphthyridine ring, quin a porphyrin ring, a quinazoline ring, an isoquinoline ring, an oxazole ring, a pyridine ring, an acridine ring, a phenanthroline ring, a thiophene ring, Olefin, Ring, thiophene Ring, thiophene Ring, brown Ring and so on.

R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 以氫原子、鹵素原子、烷基(包含環烷基、二環烷基、三環烷基)、烯基(包含環烯基、二環烯基)、炔基、芳基、氰基、羥基、羧基、烷氧基、芳氧基、醯氧基、胺基甲醯氧基、醯胺基、胺基羰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、胺磺醯胺基、烷基或芳基磺醯胺基、烷硫基、芳硫基、胺磺醯基、烷基或芳基磺醯基、芳氧基羰基、烷氧基羰基、胺基甲醯基、醯亞胺基、矽烷基、或脲基為佳。R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are} a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group). , alkynyl, aryl, cyano, hydroxy, carboxy, alkoxy, aryloxy, decyloxy, aminomethyl methoxy, decylamino, aminocarbonylamino, alkoxycarbonylamino, An aryloxycarbonylamino group, an amine sulfonylamino group, an alkyl or arylsulfonylamino group, an alkylthio group, an arylthio group, an aminesulfonyl group, an alkyl or arylsulfonyl group, an aryloxycarbonyl group, An alkoxycarbonyl group, an aminomethyl sulfonyl group, a quinone imine group, a decyl group, or a ureido group is preferred.

R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 以氫原子、或烷基(包含環烷基、二環烷基、三環烷基)為更佳。R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are more} preferably a hydrogen atom or an alkyl group (including a cycloalkyl group, a bicycloalkyl group or a tricycloalkyl group).

R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 所示之一價的取代基能夠導入時，亦可更具有取代基。When one of the substituents represented by R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ can be introduced, it may have a more substituent.

通式(1－I)所示之化合物，R¹¹ 係烷基(包含環烷基、二環烷基、三環烷基)、烷氧基、胺基(包含二烷胺基、烷胺基、二芳胺基、芳胺基)、烷硫基、芳硫基，R¹² 係烷基(包含環烷基、二環烷基、三環烷基)、烷氧基、胺基(包含二烷胺基、烷胺基、二芳胺基、芳胺基)、烷硫基、芳硫基，R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 係氫、烷基，較佳是n為0~3，n’為1~3。a compound of the formula (1-I), R ¹¹ alkyl (including cycloalkyl, bicycloalkyl, tricycloalkyl), alkoxy, amine (containing dialkylamino, alkylamino) , diarylamino, arylamino), alkylthio, arylthio, R ¹² alkyl (including cycloalkyl, bicycloalkyl, tricycloalkyl), alkoxy, amine (including two alkylamino, alkylamino, dialkylamino aryl group, an aryl group), an alkylthio group, an arylthio ^{group, R 13, R 14, R} 15 and R ¹⁶ lines hydrogen, alkyl, preferably n is 0 ~ 3, n' is 1~3.

又，通式(1－II)所示之化合物，R¹¹ 係烷基(包含環烷基、二環烷基、三環烷基)、烷氧基、胺基(包含二烷胺基、烷胺基、二芳胺基、芳胺基)、烷硫基、芳硫基，R¹² 係烷基(包含環烷基、二環烷基、三環烷基)、烷氧基、胺基(包含二烷胺基、烷胺基、二芳胺基、芳胺基)、烷硫基、芳硫基，R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 係氫、烷基，較佳是n為0~3，n’為1~3。Further, a compound represented by the formula (1-II), an R ¹¹ -alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), an alkoxy group, an amine group (including a dialkylamino group, an alkane) Amino, diarylamino, arylamino), alkylthio, arylthio, R ¹² alkyl (including cycloalkyl, bicycloalkyl, tricycloalkyl), alkoxy, amine ( Containing a dialkylamino group, an alkylamino group, a diarylamino group, an arylamino group, an alkylthio group, an arylthio group, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, an alkyl group, preferably n is 0~3, n' is 1~3.

在本發明，n係表示1~5的整數時，從光吸收效率及溶劑溶解性的觀點，在通式(1－I)或通式(1－II)之R¹¹ 中，以至少一個為烷基、烷氧基、或二烷胺基為佳。In the present invention, when n is an integer of 1 to 5, at least one of R ¹¹ in the formula (1-I) or the formula (1-II) is at least one from the viewpoint of light absorption efficiency and solvent solubility. An alkyl group, an alkoxy group or a dialkylamine group is preferred.

n係表示1~5的整數時，R¹¹ 所示之烷基可舉出例如甲基、乙基、丙基、第二丁基、第三丁基、正丁基、庚基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、環己基、2－乙基己基。此等烷基之中，以甲基、乙基、丙基、第二丁基、第三丁基、正丁基、庚基、己基、2－乙基己基為佳。When n is an integer of 1 to 5, the alkyl group represented by R ¹¹ may, for example, be a methyl group, an ethyl group, a propyl group, a second butyl group, a tert-butyl group, a n-butyl group, a heptyl group, a hexyl group or a geno group. Base, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , cyclohexyl, 2-ethylhexyl. Among these alkyl groups, a methyl group, an ethyl group, a propyl group, a second butyl group, a tert-butyl group, a n-butyl group, a heptyl group, a hexyl group or a 2-ethylhexyl group are preferred.

n係表示1~5的整數時，R¹¹ 所示之烷基可舉出例如甲氧基、乙氧基、丙氧基、異丙氧基、第二丁氧基、第三丁氧基、正丁氧基、庚氧基、己氧基、辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十八烷氧基、環己氧基、2－乙基己氧基、CH₃ OC₂ H₄ O－、C₂ H₅ OC₂ H₄ O－、CH₃ OC₂ H₄ OC₂ H₄ O－、CH₃ OC₂ H₄ OC₂ H₄ OC₂ H₄ O－、CH₃ OC₂ H₄ OC₂ H₄ OC₂ H₄ OC₂ H₄ O－、CH₃ OC₃ H₆ O－、C₂ H₅ OC₃ H₆ O－、CH₃ OC₃ H₄ OC₃ H₆ O－、CH₃ OC₃ H₆ OC₃ H₆ OC₃ H₆ O－。此等烷氧基之中，較佳是甲氧基、乙氧基、異丙氧基、丙氧基、第二丁氧基、第三丁氧基、正丁氧基、庚氧基、己氧基、2－乙基己氧基、CH₃ OC₂ H₄ O－、C₂ H₅ OC₂ H₄ O－、CH₃ OC₂ H₄ O C₂ H₄ O－。When n represents an integer of 1 to line 5, the alkyl group represented by ¹¹ R may include for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, n-Butoxy, heptyloxy, hexyloxy, octyloxy, decyloxy, nonyloxy, undecyloxy, dodecyloxy, octadecyloxy, cyclohexyloxy, 2- Ethylhexyloxy, CH ₃ OC ₂ H ₄ O-, C ₂ H ₅ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₃ H ₆ O-, C ₂ H ₅ OC ₃ H ₆ O-, CH ₃ OC ₃ H ₄ OC ₃ H ₆ O-, CH ₃ OC ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆ O-. Among these alkoxy groups, preferred are methoxy, ethoxy, isopropoxy, propoxy, second butoxy, tert-butoxy, n-butoxy, heptyloxy, and Oxyl, 2-ethylhexyloxy, CH ₃ OC ₂ H ₄ O-, C ₂ H ₅ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-.

n係表示1~5的整數時，R¹¹ 所示之二烷胺基可舉出例如二甲胺基、二乙胺基、二丙胺基、二丁胺基、二庚胺基、二己胺基、二辛胺基、二癸胺基、啉基、哌啶基、喹基。此等二烷胺基之中，以二甲胺基、二乙胺基、二丙胺基、啉基、哌啶基、喹基為佳。When n is an integer of 1 to 5, the dialkylamine group represented by R ¹¹ may, for example, be a dimethylamino group, a diethylamino group, a dipropylamine group, a dibutylamine group, a diheptylamino group or a dihexylamine. Base, dioctylamino, diammonium, Lolinyl, piperidinyl, quin base. Among these dialkylamine groups, dimethylamino, diethylamino, dipropylamine, Lolinyl, piperidinyl, quin The base is good.

從含有敏感度及著色劑時之著色劑的觀點，通式(1－I)所示之化合物以下述通式(1－III)所示之化合物為佳。 From the viewpoint of the coloring agent containing the sensitivity and the coloring agent, the compound represented by the formula (1-I) is preferably a compound represented by the following formula (1-III).

在通式(1－III)，R¹⁷ 係表示甲氧基、烷氧基、或二烷胺基。R¹¹ 及R¹² 係各自獨立地表示一價的取代基，R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 係各自獨立地表示氫原子或一價的取代基，n係表示0~4的整數、n’係表示0~5的整數。n為2以上時，複數存在之R¹¹ 各自可相同亦可不同；n’為2以上時，複數存在之R¹² 各自可相同亦可不同。又，在通式(1－III)，雙鍵之異構物未限定於任一種。In the formula (1-III), R ¹⁷ represents a methoxy group, an alkoxy group or a dialkylamino group. R ¹¹ and R ¹² each independently represent a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent, and n represents an integer of 0 to 4, The n' system represents an integer from 0 to 5. When n is 2 or more, R ^{11 which is} present in plural may be the same or different; and when n' is 2 or more, R ^{12 which is} present in plural may be the same or different. Further, in the general formula (1-III), the isomer of the double bond is not limited to any one.

在通式(1－III)，R¹¹ 及R¹² 所示之一價的取代基係與在前述通式(1－I)之R¹¹ 及R¹² 所示之一價的取代基同義，較佳範圍亦同樣。The substituents represented by the formula (1-III), R ¹¹ and R ^{12 are} synonymous with the substituents represented by R ¹¹ and R ^{12 of the} above formula (1-I), The same is true for the best range.

R¹⁷ 係烷基、烷氧基、或二烷胺基。藉由R¹⁷ ，即此等取代基，通式(1－III)所示之化合物具有優良的光吸收效率及溶劑溶解性。R ¹⁷ is an alkyl group, an alkoxy group or a dialkylamino group. By R ^17, i.e. these substituents, the compound of formula (1-III) have shown excellent in the light absorption efficiency and solvent solubility.

R¹⁷ 所示之烷基可舉出例如甲基、乙基、丙基、第二丁基、第三丁基、正丁基、庚基、己基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、環己基、2－乙基己基。此等烷基之中，以甲基、乙基、丙基、第二丁基、第三丁基、正丁基、庚基、己基、2－乙基己基為佳。The alkyl group represented by R ¹⁷ may, for example, be a methyl group, an ethyl group, a propyl group, a second butyl group, a tert-butyl group, a n-butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group, a decyl group or an eleven group. Alkyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclohexyl, 2-ethylhexyl. Among these alkyl groups, a methyl group, an ethyl group, a propyl group, a second butyl group, a tert-butyl group, a n-butyl group, a heptyl group, a hexyl group or a 2-ethylhexyl group are preferred.

R¹⁷ 所示之烷氧基可舉出例如甲氧基、乙氧基、丙氧基、異丙氧基、第二丁氧基、第三丁氧基、正丁氧基、庚氧基、己氧基、辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十八烷氧基、環己氧基、2－乙基己氧基、CH₃ OC₂ H₄ O－、C₂ H₅ OC₂ H₄ O－、CH₃ OC₂ H₄ OC₂ H₄ O－、CH₃ OC₂ H₄ OC₂ H₄ OC₂ H₄ O－、CH₃ OC₂ H₄ OC₂ H₄ OC₂ H₄ OC₂ H₄ O－、CH₃ OC₃ H₆ O－、C₂ H₅ OC₃ H₆ O－、CH₃ OC₃ H₄ OC₃ H₆ O－、CH₃ OC₃ H₆ OC₃ H₆ OC₃ H₆ O－。此等烷氧基之中，較佳是甲氧基、乙氧基、異丙氧基、丙氧基、第二丁氧基、第三丁氧基、正丁氧基、庚氧基、己氧基、2－乙基己氧基、CH₃ OC₂ H₄ O－、C₂ H₅ OC₂ H₄ O－、CH₃ OC₂ H₄ OC₂ H₄ O－。The alkoxy group represented by R ¹⁷ may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a second butoxy group, a third butoxy group, a n-butoxy group or a heptyloxy group. Hexyloxy, octyloxy, decyloxy, decyloxy, undecyloxy, dodecyloxy, octadecyloxy, cyclohexyloxy, 2-ethylhexyloxy, CH ₃ OC ₂ H ₄ O-, C ₂ H ₅ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₃ H ₆ O-, C ₂ H ₅ OC ₃ H ₆ O-, CH ₃ OC ₃ H ₄ OC ₃ H ₆ O- _{, CH 3 OC 3 H 6 OC} 3 H 6 OC 3 H 6 O-. Among these alkoxy groups, preferred are methoxy, ethoxy, isopropoxy, propoxy, second butoxy, tert-butoxy, n-butoxy, heptyloxy, and Oxyl, 2-ethylhexyloxy, CH ₃ OC ₂ H ₄ O-, C ₂ H ₅ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-.

R¹⁷ 所示之二烷胺基可舉出例如二甲胺基、二乙基胺基、二丙胺基、二丁胺基、二庚胺基、二己胺基、二辛胺基、二癸胺基、啉基、哌啶基、喹基。此等二烷基胺基之中，以二甲胺基、二乙胺基、啉基、哌啶基、喹基為佳。The dialkylamine group represented by R ¹⁷ may, for example, be a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diheptylamino group, a dihexylamino group, a dioctylamino group or a dioxime. Amine, Lolinyl, piperidinyl, quin base. Among these dialkylamine groups, dimethylamino, diethylamino, Lolinyl, piperidinyl, quin The base is good.

通式(1－III)所示之化合物，n為0，R¹² 係烷基、二烷胺基、二芳胺基、或烷氧基，R¹⁷ 係烷氧基，n’以0~3的整數為佳。a compound of the formula (1-III), wherein n is 0, R ¹² is an alkyl group, a dialkylamino group, a diarylamino group or an alkoxy group, and the R ¹⁷ alkoxy group, n' is 0 to 3 The integer is better.

通式(1－I)或通式(1－II)所示之化合物，在波長365奈米之莫耳吸光係數ε以500mol^－1 ．L．cm^－1 以上為佳，在波長365奈米之莫耳吸光係數ε以3000mol^－1 ．L．cm^－1 以上為更佳，在波長365奈米之莫耳吸光係數ε以20000mol^－1 ．L．cm^－1 以上為最佳。從光吸收效率的觀點，在各波長之莫耳吸光係數ε的值在上述範圍時提升敏感度之效果高，乃是較佳。The compound represented by the formula (1-I) or the formula (1-II) has a molar absorption coefficient ε of 500 mol ^-1 at a wavelength of 365 nm. L. It is preferably above cm ^-1 , and the molar absorption coefficient ε at a wavelength of 365 nm is 3000 mol ^-1 . L. More preferably, cm ^-1 or more, and the molar absorption coefficient ε at a wavelength of 365 nm is 20,000 mol ^-1 . L. Cm ^-1 or more is the best. From the viewpoint of light absorption efficiency, it is preferable that the effect of increasing the sensitivity at the value of the Mohr absorbance coefficient ε at each wavelength in the above range is high.

從吸收波長的觀點，R¹¹ 及R¹² 在前述一價的取代基之中，以烷氧基、芳氧基、胺基、烷胺基、二烷胺基、芳胺基、及二芳胺基為佳。From the viewpoint of absorption wavelength, R ¹¹ and R ¹² among the above monovalent substituents are an alkoxy group, an aryloxy group, an amine group, an alkylamino group, a dialkylamino group, an arylamine group, and a diarylamine. The base is good.

而且，R¹¹ 及R¹² 以烷氧基(此時，n及n’以2以上為更佳)、二烷胺基、二芳胺基為佳，以二芳胺基為最佳。Further, R ¹¹ and R ¹² alkoxide (in this case, n and n 'is more preferably not less than 2), dialkylamino, arylamino preferably two to optimal diarylamino group.

以下例示通式(1－I)及通式(1－II)所示之化合物的較佳具體例，但是本發明未限定於此等。Preferred specific examples of the compound represented by the formula (1-I) and the formula (1-II) are exemplified below, but the invention is not limited thereto.

又，在本說明書，化學式係藉由簡略結構式記載，特別是未標明元素或取代基之實線等係表示烴基。又，在下述具體例，Me係表示甲基，Et係表示乙基，Bu係表示丁基、n－Bu係表示正丁基，Ph係表示苯基。Further, in the present specification, the chemical formula is represented by a schematic structural formula, and particularly a solid line which does not indicate an element or a substituent, etc., represents a hydrocarbon group. Further, in the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents a n-butyl group, and Ph represents a phenyl group.

在本發明的硬化性組成物，通式(1－I)或通式(1－II)所示之化合物可以使用單獨1種，亦可並用2種以上，又，亦可各自並用選自通式(1－I)所示之化合物、及選自通式(1－II)所示之化合物。In the curable composition of the present invention, the compound represented by the formula (1-I) or the formula (1-II) may be used singly or in combination of two or more kinds, or may be used in combination with each other. A compound represented by the formula (1-I) and a compound represented by the formula (1-II).

接著，詳細地說明通式(2－1)所示之化合物。Next, the compound represented by the formula (2-1) will be described in detail.

在通式(2－I)中，A係表示亦可具有取代基之芳香族環或雜環。R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 係各自獨立地表示氫原子或一價的非金屬原子團，A、R²² 、R²³ 、及R²⁴ 亦可各自互相鍵結而形成脂肪族性或芳香族性的環。In the formula (2-I), A represents an aromatic ring or a heterocyclic ring which may have a substituent. R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent non-metal atomic group, and A, R ²² , R ²³ and R ²⁴ may each bond to each other to form a fat. A family or aromatic ring.

認為本發明之通式(2－I)所示之化合物會具有立體異構物(起因於碳原子間之雙鍵的軸固定)的情況。該化合物的化學結構未限定於特定的立體異構物，可以是任何的幾何異構物。It is considered that the compound represented by the formula (2-I) of the present invention has a stereoisomer (an axis which is caused by a double bond between carbon atoms). The chemical structure of the compound is not limited to a particular stereoisomer and may be any geometric isomer.

詳細地說明通式(2－I)所示之化合物。The compound represented by the formula (2-I) will be described in detail.

在通式(2－I)，R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 係各自獨立地表示氫原子或一價的非金屬原子團。R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 係表示一價的非金屬原子團時，以取代或未取代的烷基、取代或未取代的芳基、取代或未取代的烯基、取代或未取代的芳香族雜環殘基、取代或未取代的烷氧基、取代或未取代的烷硫基、羥基、鹵素原子為佳。In the general formula (2-I), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent non-metal atomic group. When R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ represent a monovalent non-metal atomic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom are preferred.

具體地敘述在通式(2－I)，R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳例子。Specific examples of the general formula (2-I), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are specifically described.

R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示未取代的烷基之較佳例子可舉出例如碳原子數1至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。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、及碳原子數5至10之環狀的烷基為更佳。Preferable examples of the unsubstituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ include, for example, a linear, branched and cyclic alkyl group having 1 to 20 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, fluorenyl group, undecyl group, dodeca group, thirteen group, and hexadecene. Base, octadecyl, icosyl, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethyl Hexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-lower base. Among these, an alkyl group having a linear chain of 1 to 12 carbon atoms, a branched chain of 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms is more preferable.

R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代烷基之伸烷基(烷基部分)，可舉出脫除上述碳數1~20之烷基上的氫原子中任一個，而成為2價的有機殘基之物，適合舉出的有碳數1~12之直鏈狀、碳原子數3至12之分枝狀及碳原子數5至10之環狀的烷基。The alkylene group (alkyl moiety) of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ may be any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. One which is a divalent organic residue, and is preferably a linear one having a carbon number of 1 to 12, a branched carbon number of 3 to 12, and a cyclic alkane having 5 to 10 carbon atoms. base.

R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代烷基之取代基，可舉出脫除氫之一價的非金屬原子團，適合舉出的例子有鹵素原子(－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、烷基亞磺醯基、芳基亞磺醯基、醯硫基、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、烷氧基羰基胺基、芳氧基羰基胺基、N－烷基－N－烷氧基羰基胺基、N－烷基－N－芳氧基羰基胺基、N－芳基－N－烷氧基羰基胺基、N－芳基－N－芳氧基羰基胺基、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))及其共軛鹼基(以下稱為烷基膦酸根氧基基)、一芳基膦醯氧基(－OPO₃ H(芳基))及其共軛鹼基(以下稱為芳基膦酸根氧基)、烷基、氰基、硝基、芳基、雜芳基、烯基、炔基。Examples of the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ include a non-metal atomic group in which one valence of hydrogen is removed, and a halogen atom (-F, a suitable example) is exemplified. -Br, -Cl, -I), hydroxy, alkoxy, aryloxy, thiol, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamine , N,N-dialkylamino, N-arylamino, N,N-diarylamino, N-alkyl-N-arylamino, decyloxy, aminomethyl methoxy, N-alkane Aminomethylmethoxymethyl, N-arylaminomethylmethoxy, N,N-dialkylaminomethyloxy, N,N-diarylaminomethyloxy, N-alkane --N-arylaminomethyl methoxy group, alkyl sulfinyl group, aryl sulfinyl group, sulfonylthio group, decylamino group, N-alkyl guanylamino group, N-aryl decylamino group , ureido, N'-alkylureido, N', N'-dialkylurea, N'-arylureido, N', N'-diarylureido, N'-alkyl-N'-aryl Urea, N-alkylureido, N-arylureido, N'-alkyl-N-alkylureido, N'-alkyl-N-arylureido, N',N'-dialkyl-N -Alkylureido, N',N'-dialkyl-N-aryl , 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, alkoxycarbonylamino , aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-Aryl-N-aryloxycarbonylamino, indolyl, fluorenyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, aminocarbamimidyl, N-alkylaminocarbamyl, N , N-dialkylaminomethyl fluorenyl, N-arylaminomethyl fluorenyl, N,N-diarylaminomethyl fluorenyl, N-alkyl-N-arylaminomethyl fluorenyl, 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 a sulfonate group), Alkoxysulfonyl, aryloxysulfonyl, amine sulfinylene, N-alkylamine sulfinyl, N,N-dialkylamine sulfinyl, N-arylamine sulfin Mercapto, N,N-diarylamine Sulfonyl, N-alkyl-N-arylamine sulfinyl, amine sulfonyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine Sulfonyl, N,N-diarylaminesulfonyl, N-alkyl-N-arylaminesulfonyl, phosphonic acid (-PO ₃ H ₂ ) and conjugated bases thereof (hereinafter referred to as Phosphonate), dialkylphosphonic acid group (-PO ₃ (alkyl) ₂ ), diarylphosphonic acid group (-PO ₃ (aryl) ₂ ), alkyl arylphosphonic acid group (-PO ₃ (alkyl)(aryl)), monoalkylphosphonic acid group (-PO ₃ H(alkyl)) and conjugated base thereof (hereinafter referred to as alkylphosphonate group), monoarylphosphonic acid group ( -PO ₃ H(aryl)) and its conjugated base (hereinafter referred to as arylphosphonate), phosphinomethoxy (-OPO ₃ H ₂ ) and its conjugated base (hereinafter referred to as phosphonate oxygen) , dialkylphosphonium oxy (-OPO ₃ (alkyl) ₂ ), diarylphosphonium oxy (-OPO ₃ (aryl) ₂ ), alkyl aryl phosphinooxy (-OPO) ₃ (alkyl)(aryl)), monoalkylphosphinomethoxy (-OPO ₃ H(alkyl)) and conjugated bases thereof (hereinafter referred to as alkylphosphonoxy groups), monoaryl acyl phosphine group (-OPO ₃ H (aryl)) and its conjugate base (referred to hereinafter aryl Phosphonate group), an alkyl group, a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group.

在此等具有取代烷基之取代基，烷基的具體例可舉出前述R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示作為未取代的烷基之烷基。Specific examples of the alkyl group-substituted substituents include an alkyl group represented by the above-mentioned R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ as an unsubstituted alkyl group.

在此等具有取代烷基之取代基，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、羥基苯基、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、羧基苯基、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、膦酸根基苯基等。Specific examples of the aryl group in the substituent having a substituted alkyl 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, phosphonate phenyl, and the like.

在此等具有取代烷基之取代基，雜芳基可舉出含有氮原子、氧原子、硫原子中之至少一者之單環或多環芳香族環。在雜芳基之雜芳基環的特佳例子，可舉出例如噻吩、噻蒽、呋喃、吡喃、異苯并呋喃、烯、、啡、吡咯、吡唑、異噻唑、異唑、吡、嘧啶、嗒、吲哚、異吲哚、吲哚基、吲唑、嘌呤、喹、異喹、酞、萘啶、喹唑啉、、喋啶、咔唑、咔啉、菲(phenanthrene)、吖啶、啶、啡啉、酞、啡吡、啡、呋咱等，此等可以更進行苯環縮，又，亦可以具有取代基。The substituent having a substituted alkyl group may, for example, be a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples of the heteroaryl ring of the heteroaryl group include, for example, thiophene, thiazide, furan, pyran, isobenzofuran, Alkene, ,coffee , pyrrole, pyrazole, isothiazole, different Oxazole, pyridyl Pyrimidine 吲哚 Heterogeneous , mercapto, carbazole, anthracene, quinine Isoquine 酞 , naphthyridine, quinazoline, , acridine, carbazole, porphyrin, phenanthrene, acridine, Pyridine, phenanthroline, anthracene Morphine ,coffee , furazan, etc., these may be more benzene ring shrinkage, and may also have a substituent.

在此等具有取代烷基之取代基，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。Examples of the substituent having a substituted alkyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-vinyl group.

在此等具有取代烷基之取代基，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。Examples of the substituent having a substituted alkyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethyldecyl ethynyl group and the like.

在此等具有取代烷基之取代基，在醯基(G₁ CO－)之G₁ ，可舉出氫原子、及上述的烷基、芳基。In such a substituted alkyl group having the substituent in the acyl group (G ₁ CO-) of G _1, include a hydrogen atom, and said alkyl group, an aryl group.

此等取代基中，更佳之物可舉出鹵素原子(－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)。Among these substituents, preferred are halogen atoms (-F, -Br, -Cl, -I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N,N-dialkylamino, decyloxy, N-alkylaminomethyl methoxy, N-arylaminomethyl methoxy, decyl, decyl, decyl, carboxy, alkoxy Carbonyl group, aryloxycarbonyl group, aminomethyl fluorenyl group, N-alkylaminomethyl fluorenyl group, N,N-dialkylaminomethyl fluorenyl group, N-arylaminomethyl fluorenyl group, N-alkane -N-arylaminomethyl fluorenyl, sulfonate, sulfonate, sulfonyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-aryl Aminesulfonyl, N-alkyl-N-arylamine sulfonyl, phosphonic acid, phosphonate, dialkylphosphonic acid, diarylphosphonic acid, monoalkylphosphonic acid, alkyl Phosphonate, monoarylphosphonate, arylphosphonate, phosphinyloxy, phosphonateoxy, aryl, alkenyl, alkylene (methylene, etc.).

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳取代烷基可舉出上述取代基與伸烷基(烷基部分)組合而成之物，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、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。The preferred substituted alkyl group for R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be a combination of the above substituent and an alkylene group (alkyl moiety), and specific examples thereof include a chloromethyl group. , bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, aryloxymethyl, phenoxymethyl, methylthiomethyl, toluene Thiomethyl, ethylaminoethyl, diethylaminopropyl, Phenylpropyl, ethoxymethyloxymethyl, benzhydryloxymethyl, N-cyclohexylaminomethyloxyethyl, N-phenylaminomethyloxy, ethylaminoethyl, N-methylbenzimidylpropyl, 2-sided oxyethyl, 2-sided oxypropyl, carboxypropyl, methoxycarbonylethyl, aryloxycarbonylbutyl, chlorophenoxycarbonyl Base, aminomethylmethylmethyl, N-methylaminomethylmethyl, N,N-dipropylaminomethylmethyl, N-(methoxyphenyl)aminocarbamidine Ethyl ethyl, N-methyl-N-(sulfophenyl)aminomercaptomethyl, sulfonylbutyl, sulfonylpropyl, sulfonylbutyl, amine sulfinamide Base, N-ethylaminesulfonylmethyl, N,N-dipropylaminesulfonylpropyl, N-triaminesulfonylpropyl, N-methyl-N-(phosphonophenyl) Aminesulfonyloctyl, phosphonic butyl, phosphonic hexyl, diethylphosphonic butyl, diphenylphosphonic propyl, methylphosphonic butyl, methylphosphonate Butyl, tolylphosphonylhexyl, tolylphosphonate hexyl, phosphinomethoxypropyl, phosphonateoxybutyl, benzyl, phenyl , α-methylbenzyl, 1-methyl-1-phenylethyl, p-methylbenzyl, cinnamyl, allyl, 1-propenylmethyl, 2-butenyl, 2-methyl Allyl, 2-methylpropenylmethyl, 2-propynyl, 2-butynyl, 3-butynyl and the like.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳未取代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，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 unsubstituted aryl groups of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include those in which one to three benzene rings form a fused ring, a benzene ring and a 5-membered unsaturated group. Examples of the ring-forming fused ring 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.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 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一價的非金屬原子團作為取代基之物。較佳取代基之例子可舉出前述的烷基及取代烷基、及在前述取代烷基作為取代基所示之物。R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示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、羥基苯基、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、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、羧基苯基、甲氧基羰基苯基、烯丙氧基羰基苯基、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。Specific examples of the preferred substituted aryl group of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ can be used as a substituent having a monovalent non-metal atom group on a ring-forming carbon atom of the above unsubstituted aryl group. Things. Examples of preferred substituents include the above-mentioned alkyl group and substituted alkyl group, and those represented by the above-mentioned substituted alkyl group. Preferable specific examples of the substituted aryl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ 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, Phenanylphenyl, ethoxylated phenyl, benzhydryloxyphenyl, N-cyclohexylaminomethyloxyphenyl, N-phenylaminomethyloxyphenyl, acetaminophen , N-methylbenzimidylphenyl, carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, aminomethylphenylphenyl, N -Methylaminopyristylphenyl, N,N-dipropylaminocarbamidophenyl, N-(methoxyphenyl)aminocarbamidophenyl, N-methyl-N- (sulfonylphenyl)aminomercaptophenyl, sulfonylphenyl, sulfonylphenyl, amidoximinophenyl, N-ethylaminesulfonylphenyl, N,N-di Propylsulfonylphenyl, N-methylphenylsulfonylphenyl, N-methyl-N-(phosphonophenyl)amine sulfonylphenyl, phosphophenyl, phosphonate Phenyl, diethylphosphonic phenyl, diphenylphosphonic phenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolylphosphonate Phenyl, allylphenyl, 1-propenylmethylphenyl, 2-butenylphenyl, 2-methylallylphenyl, 2- Phenyl-propenyl group, 2-propynyl group, a 2-butynyl group, a 3-butynyl group and the like.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳未取代烯基的具體例可舉出乙烯基、1－丙烯基等。Specific examples of the preferred unsubstituted alkenyl group of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a vinyl group and a 1-propenyl group.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳取代芳基的具體例可舉出在上述未取代烯基上，具有脫除氫原子作為取代基之一價的非金屬原子團之物。Specific examples of the preferred substituted aryl group of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a non-metal atomic group having a hydrogen atom removed as a substituent on the above unsubstituted alkenyl group. Things.

取代烯基所具有的取代基係一價的非金屬原子團時，該取代基之較佳例子可舉出前述的烷基及取代烷基，在該取代烷基之取代基的例子，可舉出前述取代烷基所具有的取代基。When the substituent of the substituted alkenyl group is a monovalent non-metal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent of the substituted alkyl group include The substituent of the above substituted alkyl group.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳未取代芳香族雜環殘基的具體例可舉出吡啶、噻吩、苯并噻吩、二苯并噻吩、呋喃、苯并呋喃、二苯并呋喃、吡咯、吡唑、噻唑、唑、嘧啶、嗒、吖啶、咪唑、喹啉、***、吲哚、咔唑等。 ^{R 21, R 22, R 23} , R 24, and specific preferred embodiment ²⁵ of the unsubstituted aromatic heterocyclic residue R may include pyridine, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran , dibenzofuran, pyrrole, pyrazole, thiazole, Oxazole, pyrimidine, pyrene , acridine, imidazole, quinoline, triazole, hydrazine, carbazole and the like.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳取代芳香族雜環殘基的具體例可舉出在上述未取代芳香族雜環殘基上，具有脫除氫原子之一價的非金屬原子團作為取代基之物。Specific examples of the preferred substituted aromatic heterocyclic residue of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include one of the unsubstituted aromatic heterocyclic residues and one of the dehydrogenating atoms. A valence non-metal atomic group acts as a substituent.

取代芳香族雜環殘基所具有的取代基係一價的非金屬原子團時，該取代基之較佳例子可舉出前述的烷基及取代烷基，在該取代烷基之取代基的例子，可舉出前述取代烷基所具有的取代基。When the substituent of the substituted aromatic heterocyclic residue is a monovalent non-metal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent of the substituted alkyl group. The substituent which the said substituted alkyl group has is mentioned.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳未取代烷氧基的具體例可舉出甲氧基、乙氧基、丙氧基、丁氧基、己氧基、辛氧基、十二烷氧基、2－乙基己氧基等。Specific examples of the preferred unsubstituted alkoxy group for R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group and a octyl group. Oxyl, dodecyloxy, 2-ethylhexyloxy and the like.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳取代烷氧基的具體例可舉出在上述未取代烷氧基上，具有脫除氫原子之一價的非金屬原子團作為取代基之物。Specific examples of the preferred substituted alkoxy group for R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a non-metal atomic group having a valence of one hydrogen atom removed from the above unsubstituted alkoxy group. Substituent.

取代烷氧基所具有的取代基係一價的非金屬原子團時，該取代基之較佳例子可舉出前述的烷基及取代烷基，在該取代烷基之取代基的例子，可舉出前述取代烷基所具有的取代基。When the substituent of the alkoxy group is a monovalent non-metal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent of the substituted alkyl group include The substituent which the aforementioned substituted alkyl group has.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳未取代烷硫基的具體例可舉出甲硫氧基、乙硫氧基、丙硫氧基、丁硫氧基、己硫氧基、辛硫氧基、十二烷硫氧基等Specific examples of the preferred unsubstituted alkylthio group of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a hexyl group. Thiooxy, octylthiooxy, dodecylthiooxy, etc.

R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 之較佳取代烷硫基的具體例可舉出在上述未取代烷硫基上，具有脫除氫原子之一價的非金屬原子團作為取代基之物。Specific examples of the preferred substituted alkylthio group of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a non-metal atomic group having a valence of one hydrogen atom removed from the above unsubstituted alkylthio group. Substituent.

取代烷硫基所具有的取代基係一價的非金屬原子團時，該取代基之較佳例子可舉出前述的烷基及取代烷基，在該取代烷基之取代基的例子，可舉出前述取代烷基所具有的取代基。When the substituent of the substituted alkylthio group is a monovalent non-metal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent of the substituted alkyl group include The substituent which the aforementioned substituted alkyl group has.

接著，說明通式(2－I)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之具體例，可舉出例與通式(2－I)中的R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 所記載之相同之物。Next, A of the formula (2-I) 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 examples thereof include R ²¹ and R in the formula (2-I). ^22, R ^23, according to the same thing R ^24, R ^25, and Suo.

A之較佳芳香族環，具體例可舉出苯、甲氧基苯、二甲氧基苯、三甲氧基苯、二乙胺苯、二苯胺基苯、甲硫基苯、蒽、苯硫基苯、噻蒽、啡噻、喹、二苯并噻吩、二苯并呋喃、咔唑、二甲氧基苯基苯、三苯膦等。Preferred aromatic rings of A, specific examples thereof include benzene, methoxybenzene, dimethoxybenzene, trimethoxybenzene, diethylamine benzene, diphenylaminobenzene, methylthiobenzene, hydrazine, and benzene sulfide. Benzobenzene, thiazide, thiophene Quino , dibenzothiophene, dibenzofuran, carbazole, dimethoxyphenylbenzene, triphenylphosphine, and the like.

又，A之較佳雜環，具體上可舉出吡啶、苯并噻唑、苯并唑、苯并噻唑等。Further, a preferred hetero ring of A, specifically pyridine, benzothiazole, benzo Oxazole, benzothiazole and the like.

通式(2－I)所示之化合物，R²² 、R²³ 、R²⁴ 、及A係各自鍵結而形成脂肪族性及芳香族的環時，所形成的環可舉出環烷基環、氧雜環壬烷(oxonane)環、環氧乙烷環、噻喃環、哌啶環、吡啶酮環、吡咯啶環、吡咯啶酮環、內酯環、內醯胺環、噻唑啉酮環、苯環、萘環、蒽環、菲環、茀環、鄰三伸苯環、稠四苯環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、唑環、噻唑環、吡啶環、吡環、嘧啶環、嗒環、吲哚環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹環、喹啉環、酞環、萘啶環、喹啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、烯環、環、啡噻環、啡噻環、啡環等，更佳之物可舉出環烷基環、內酯環、吡咯環、呋喃環、吡喃環、吡啶環。When a compound represented by the formula (2-I) is bonded to each of R ²² , R ²³ , R ²⁴ and A to form an aliphatic or aromatic ring, the ring formed may be a cycloalkyl ring. , oxonane ring, oxirane ring, thiopyran ring, piperidine ring, pyridone ring, pyrrolidine ring, pyrrolidone ring, lactone ring, indole ring, thiazolinone Ring, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, anthracene ring, ortho-triphenyl ring, condensed tetraphenyl ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, Oxazole ring, thiazole ring, pyridine ring, pyridyl Ring, pyrimidine ring, anthracene Ring, 吲哚 Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quin Ring, quinoline ring, anthracene Ring, naphthyridine ring, quin a porphyrin ring, a quinazoline ring, an isoquinoline ring, an oxazole ring, a pyridine ring, an acridine ring, a phenanthroline ring, a thiophene ring, Olefin, Ring, thiophene Ring, thiophene Ring, brown The ring is preferably a cycloalkyl ring, a lactone ring, a pyrrole ring, a furan ring, a pyran ring or a pyridine ring.

在通式(2－I)所示化合物的R²¹ 、R²² 、R²³ 、R²⁴ 、R²⁵ 、及A，更佳組合用以達成高敏感度(本發明的課題之一)，可舉出R¹ 係碳原子數為1~20之直鏈狀、分枝狀、環狀的取代或未取代之烷基、取代或未取代之芳基、羧基，R²² 、R²³ 、及R²⁴ 係氫原子、碳原子數為1~20之直鏈狀、分枝狀、或環狀的取代或未取代之烷基，R⁵ 係碳原子數1~20之直鏈狀、分枝狀、或環狀的取代或未取代之烷氧基，A係取代或未取代之芳香族環、或雜環。In the compound of the formula (2-I), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and A are more preferably used in combination to achieve high sensitivity (one of the problems of the present invention). the system ¹ R & lt aryl group, a carboxyl group, R ^22, R ^23, and R ²⁴ linear carbon atoms of 1 to 20, branched, or cyclic alkyl group of a substituted or unsubstituted, the substituted or unsubstituted a hydrogen atom, a linear or branched, or cyclic substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a linear or branched R ⁵ carbon atom having 1 to 20 carbon atoms. Or a cyclic substituted or unsubstituted alkoxy group, A substituted or unsubstituted aromatic ring or heterocyclic ring.

又，在通式(2－I)所示之化合物，R²² 、R²³ 、R²⁴ 、及A係各自鍵結而形成脂肪族性及芳香族的環時，該環係R²¹ 、R²⁵ 、及A之較佳組合時，該環可舉出環烷基環、內酯環、苯環、吡咯環、呋喃環、吡喃環、吡啶環，R²¹ 係碳原子數1~20之直鏈狀、分枝狀、及環狀的取代或未取代之烷基、取代或未取代之芳基、羧基，R²⁵ 係碳原子數1~20之直鏈狀、分枝狀、或環狀的取代或未取代之烷基、取代或未取代之芳基、取代或未取代之烷氧基，A係取代或未取代之芳香族環、或雜環。Further, when a compound represented by the formula (2-I) is bonded to each of R ²² , R ²³ , R ²⁴ and A to form an aliphatic or aromatic ring, the ring system R ²¹ , R ²⁵ , and when A preferred combination of the ring include a cycloalkyl ring, lactone ring, a benzene ring, a pyrrole ring, a furan ring, a pyran ring, a pyridine ring, the number of R ²¹ lines 1 to 20 carbon atoms of straight a chain, a branched, or a cyclic substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a carboxyl group, and a R ²⁵ group having a linear, branched, or cyclic carbon number of 1 to 20 A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aromatic ring, or a heterocyclic ring.

通式(2－I)所示之化合物，更佳之態樣可舉出下述通式(2－II)。The compound represented by the formula (2-I) is more preferably a compound of the following formula (2-II).

通式(2－II)中，n係表示0~5之整數。R²⁶ 可舉出脫除氫之價的非金屬原子團。R²⁶ 之具體例可舉出與R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代烷基所具有取代基的例子之相同之物。In the formula (2-II), n represents an integer of 0 to 5. R ²⁶ may be a non-metal atomic group which is desorbed by hydrogen. Specific examples of R ²⁶ include the same examples as the substituents of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ .

R²¹ 、R²⁵ 所示之取代基，可舉出通式(2－I)所示化合物R²¹ 及R²⁵ 所示之取代基，R²¹ 及R²⁵ 以環己基為特佳。The substituent represented by R ²¹ and R ²⁵ may, for example, be a substituent represented by the compounds R ²¹ and R ²⁵ represented by the formula (2-I), and R ²¹ and R ²⁵ are particularly preferably a cyclohexyl group.

R²⁶ 所示之取代基以二苯胺基、二甲胺基、甲氧基為特佳。n以0~3為特佳。The substituent represented by R ²⁶ is particularly preferably a diphenylamino group, a dimethylamino group or a methoxy group. n is 0 to 3 is particularly good.

通式(2－II)所示之化合物中，以組合R²¹ 、R²⁵ 、R²⁶ 、及n之較佳態樣而成之化合物為特佳態樣。Among the compounds represented by the formula (2-II), a compound obtained by combining the preferred aspects of R ²¹ , R ²⁵ , R ²⁶ and n is a particularly preferable aspect.

通式(2－II)所示之化合物中，最佳例子可舉出藉由下述合成例2－1~合成例2－4、及合成例2－6所合成而成之化合物為特佳態樣。Among the compounds represented by the formula (2-II), preferred examples are those obtained by synthesizing the following Synthesis Examples 2-1 to 2-4 and Synthesis Examples 2-6. Aspect.

敘述通式(2－I)所示之化合物的合成方法。A method for synthesizing the compound represented by the formula (2-I) will be described.

通式(2－I)所示之化合物通常能夠藉由具有活性亞甲基之酸性原料、與取代或非取代芳香族環或雜環進行縮合應而得到，此等可參照特公昭59－28329號公報來合成。可舉出例如下述反應式(2－1)所示，利用酸性原料化合物、與在雜環上具有醛基或羰基之鹼性原料進行縮合反應之合成方法。縮合反應按照必要在鹼(base)存在下進行。鹼係沒有限制地能夠利用通常泛用之物，例如胺、吡啶類(三烷胺、二甲胺吡啶、二氮雜雙環十一烯DBU等)、胺基金屬類(二異丙基胺基鋰等)、烷醇金屬類(甲醇鈉、第三丁醇鉀等)、氫化金屬類(氫化鈉、氫化鉀等)。又，反應式(2－1)中，R²¹ 、R²² 、R²³ 、R²⁴ 、R²⁵ 、及A係與通式(2－I)所示之化合物中的R²¹ 、R²² 、R²³ 、R²⁴ 、R²⁵ 、及A相同。The compound represented by the formula (2-I) can be usually obtained by condensing an acidic starting material having an active methylene group with a substituted or unsubstituted aromatic ring or a heterocyclic ring, and these can be referred to Japanese Patent Publication No. 59-28329. No. bulletin to synthesize. For example, a synthesis method in which an acidic starting material compound and a basic raw material having an aldehyde group or a carbonyl group on a hetero ring are subjected to a condensation reaction, as shown in the following reaction formula (2-1), may be mentioned. The condensation reaction is carried out as necessary in the presence of a base. The alkali system can be used without any limitation, such as an amine, a pyridine (trialkylamine, dimethylamine pyridine, diazabicycloundecene DBU, etc.), an amine metal (diisopropylamino group). Lithium or the like, an alkanol metal (such as sodium methoxide or potassium t-butoxide) or a hydrogenated metal (sodium hydride or potassium hydride). Further, in the reaction formula (2-1), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and A are R ²¹ , R ²² and R in the compound represented by the formula (2-I). ²³ , R ²⁴ , R ²⁵ , and A are the same.

又，較佳之其他合成方法，可舉出藉由下述反應式(2－2)之方法。亦即，藉由使用在前述反應式(2－1)之酸性原料化合物，N－R⁵ 係硫原子之酸性原料化合物作為起始物質、與在雜環上具有醛基或羰基之鹼性原料進行縮合反應來色料先質之步驟為止，係與前述反應式(2－1)同樣地進行後，使該色料先質，進而與能夠與硫原子互相進行化學作用來形成金屬硫化物之金屬鹽及水或1級胺化合物(R－NH₂ ：在此R係表示一價的非金屬原子團)進行作用之反應。R所示之一價的非金屬原子團，以與前述R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 同樣的取代基為佳。反應式(2－2)中，R²¹ 、R²² 、R²³ 、R²⁴ 、R²⁵ 、及A係與通式(2－I)所示之化合物中的R²¹ 、R²² 、R²³ 、R²⁴ 、R²⁵ 、及A相同。Further, other preferred synthesis methods include the method of the following reaction formula (2-2). That is, by using the aforementioned reaction formula (2-1) The acidic starting compound, an acidic starting compound N-R ⁵ based sulfur atoms as a starting material having an aldehyde group or a carbonyl group of the alkaline material on the heterocycle The step of performing the condensation reaction to the color precursor is carried out in the same manner as in the above reaction formula (2-1), and the color material is allowed to undergo a chemical reaction with the sulfur atom to form a metal sulfide. A reaction in which a metal salt and water or a primary amine compound (R-NH ₂ : wherein R represents a monovalent non-metal atomic group) acts. The one-valent non-metal atom group represented by R is preferably the same substituent as the above R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ . In the reaction formula (2-2), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and A are R ²¹ , R ²² and R ²³ in the compound represented by the formula (2-I). R ²⁴ , R ²⁵ , and A are the same.

此等之中，反應式(2－2)所示反應之各反應的產率高，在合成效率上特佳，其中，合成通式(2－I)所示之新穎化合物時，反應式(2－2)所示之反應係有用的。Among these, the yield of each reaction of the reaction represented by the reaction formula (2-2) is high, and it is particularly preferable in terms of synthesis efficiency, wherein when the novel compound represented by the formula (2-I) is synthesized, the reaction formula ( The reaction shown in 2-2) is useful.

又，前述反應式(2－2)中，M^n＋ X_n 係表示能夠與硫羰基的硫原子互相進行化學作用來形成金屬硫化物之金屬鹽。具體上的化合物可舉出例如M為Al、Au、Ag、Hg、Cu、Zn、Fe、Cd、Cr、Co、Ce、Bi、Mn、Mo、Ga、Ni、Pd、Pt、Ru、Rh、Sc、Sb、Sr、Mg、Ti等，X為F、Cl、Br、I、NO₃ 、SO₄ 、NO₂ 、PO₄ 、CH₃ CO₂ 等之AgBr、AgI、AgF、AgO、AgCl、Ag₂ O、Ag(NO₃ )、AgSO₄ 、AgNO₂ 、Ag₂ CrO₄ 、Ag₃ PO₄ 、Hg₂ (NO₃ )₂ 、HgBr₂ 、Hg₂ Br₂ 、HgO、HgI₂ 、Hg(NO₃ )₂ 、Hg(NO₂ )₂ 、HgSO₄ 、Hg₂ I₂ 、Hg₂ SO₄ 、Hg(CH₃ CO₂ )₂ 、AuBr、AuBr₃ 、AuI、AuI₃ 、AuF₃ 、Au₂ O₃ 、AuCl、AuCl₃ 、CuCl、CuI、CuI₂ 、CuF₂ 、CuO、CuO₂ 、Cu(NO₃ )₂ 、CuSO₄ 、Cu₃ (PO₄ )₂ 之化合物。其中，從容易與硫原子互相進行化學作用而言，以使用銀鹽作為金屬鹽為最佳。In addition, the aforementioned reaction formula ^{(2-2), M n + X} n represents a line formed of a metal salt can be a metal sulfide chemistry with the sulfur atom of thiocarbonyl group to each other. Specific examples of the compound include, for example, M is Al, Au, Ag, Hg, Cu, Zn, Fe, Cd, Cr, Co, Ce, Bi, Mn, Mo, Ga, Ni, Pd, Pt, Ru, Rh, Sc, Sb, Sr, Mg, Ti, etc., X is AgBr, AgI, AgF, AgO, AgCl, Ag such as F, Cl, Br, I, NO ₃ , SO ₄ , NO ₂ , PO ₄ , CH ₃ CO _{2 ,} etc. ₂ O, Ag(NO ₃ ), AgSO ₄ , AgNO ₂ , Ag ₂ CrO ₄ , Ag ₃ PO ₄ , Hg ₂ (NO ₃ ) ₂ , HgBr ₂ , Hg ₂ Br ₂ , HgO, HgI ₂ , Hg (NO _{3 2} , Hg(NO ₂ ) ₂ , HgSO ₄ , Hg ₂ I ₂ , Hg ₂ SO ₄ , Hg(CH ₃ CO ₂ ) ₂ , AuBr, AuBr ₃ , AuI, AuI ₃ , AuF ₃ , Au ₂ O ₃ , A compound of AuCl, AuCl ₃ , CuCl, CuI, CuI ₂ , CuF ₂ , CuO, CuO ₂ , Cu(NO ₃ ) ₂ , CuSO ₄ , Cu ₃ (PO ₄ ) ₂ . Among them, from the viewpoint of easy chemical interaction with a sulfur atom, it is preferred to use a silver salt as a metal salt.

以下，在本發明的新穎化合物，舉出化合物合成的特佳例子及記載所得到化合物的鑑定數據。Hereinafter, in the novel compound of the present invention, a particularly preferred example of the synthesis of the compound and the identification data of the obtained compound are described.

在本發明之通式(2－I)所示之化合物，舉出作為特佳例子之化合物2－1~化合物2－6合成例，係如下所示。In the compound represented by the formula (2-I) of the present invention, a synthesis example of the compound 2-1 to the compound 2-6 which are particularly preferable examples is shown below.

(合成例2－1)(Synthesis Example 2-1)

將對二苯胺基肉桂醛(5.0克、0.0175莫耳)、亞胺基唑啉酮化合物(4.63克、0.0189莫耳)、及第三丁氧基鉀(0.983克、0.0088莫耳)，溶解在20毫升THF中，在50℃反應2小時。反應係藉由TLC每1小時追蹤。反應結束後使用1N－HClaq(1當量之氯化氫水溶液)(11毫升)調整為pH＝5後，使用乙酸乙酯萃取有機層，並進行減壓餾去。藉由甲醇再分散精製所得到的結晶，得到化合物1(產量3.94克、產率49%)。p-Diphenylamino cinnamaldehyde (5.0 g, 0.0175 mol), imine The oxazolinone compound (4.63 g, 0.0189 mol) and potassium third potassium hydride (0.983 g, 0.0088 mol) were dissolved in 20 ml of THF and reacted at 50 ° C for 2 hours. The reaction was followed by TLC every hour. After the completion of the reaction, the mixture was adjusted to pH = 5 using 1N-HClaq (1% aqueous hydrogen chloride) (11 ml), and the organic layer was extracted with ethyl acetate. The obtained crystal was re-dispersed by methanol to obtain Compound 1 (yield: 3.94 g, yield: 49%).

又，莫耳吸光係數(ε)為13773。Further, the molar absorption coefficient (ε) was 13773.

在此，莫耳吸光係數ε係將在1－甲氧基－2－丙醇溶液中以0.01克/升的濃度調整而成的色料溶液作為試料，測定在365奈米之試料透射光譜，藉由從試料的紫外－可見(UV－visible)吸收光譜求得吸光度而得到。測定裝置係使用Varian公司製UV－Vis－MR Spectrophotometer Cary5G型分光光度計。Here, the molar absorption coefficient ε is a colorant solution adjusted to a concentration of 0.01 g/liter in a 1-methoxy-2-propanol solution, and a sample transmission spectrum of 365 nm is measured. It is obtained by obtaining the absorbance from the UV-visible absorption spectrum of the sample. The measuring apparatus was a UV-Vis-MR Spectrophotometer Cary 5G spectrophotometer manufactured by Varian.

合成例2－1所示之化合物2－1係藉由NMR鑑定。化合物1之¹ H－NMR圖係如第1圖所示。又，測定條件及尖峰的鑑定係藉由¹ H－NMR(CDCL₃ )：a7.38－7.01(m,14H),6.90(dd,1H,J＝15.6,10.8Hz),6.78(d,1H,J＝15.6Hz),6.32(d,1H,J＝10.8Hz),4.06－3.98(m,1H),3.78－3.71(m,1H),2.32－2.22(m,2H),1.86－1.19(m,18H)進行。Compound 2-1 shown in Synthesis Example 2-1 was identified by NMR. The ¹ H-NMR chart of Compound 1 is shown in Figure 1. Also, measurement conditions and the identification of the peak line by _{^{1 H-NMR (CDCL 3)}} : a7.38-7.01 (m, 14H), 6.90 (dd, 1H, J = 15.6,10.8Hz), 6.78 (d, 1H , J = 15.6 Hz), 6.32 (d, 1H, J = 10.8 Hz), 4.06 - 3.98 (m, 1H), 3.78 - 3.71 (m, 1H), 2.32 - 2.22 (m, 2H), 1.86-1.19 ( m, 18H).

(合成例2－2)(Synthesis Example 2-2)

將對二甲胺基肉桂醛(3.30克、0.0189莫耳)、亞胺基唑啉酮化合物(5.00克、0.0189莫耳)、及第三丁氧基鉀(1.06克、0.00945莫耳)，溶解在20毫升THF中，在50℃反應2小時。反應係藉由TLC每1小時追蹤。反應結束後使用1N－HClaq(11毫升)調整為pH＝5後，使用乙酸乙酯萃取有機層，並進行減壓餾去。藉由甲醇再分散精製所得到的結晶，得到化合物2－2(產量3.94克、產率49%)。P-Dimethylaminocinnamaldehyde (3.30 g, 0.0189 mol), imine The oxazolinone compound (5.00 g, 0.0189 mol), and potassium third butoxide (1.06 g, 0.00945 mol) were dissolved in 20 ml of THF and reacted at 50 ° C for 2 hours. The reaction was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 using 1N-HClaq (11 ml). The obtained crystal was re-dispersed by methanol to obtain Compound 2-2 (yield: 3.94 g, yield: 49%).

又，莫耳吸光係數(ε)為17004。Further, the molar absorption coefficient (ε) was 17004.

合成例2－2所示之化合物2－2係藉由NMR鑑定。化合物2－2之¹ H－NMR圖係如第2圖所示。又，測定條件及尖峰的鑑定係藉由¹ H－NMR(CDCL₃ )：a7.40(d,2H,J＝9.2Hz),6.86－6.68(m,2H),6.69(d,2H,J＝9.2Hz),6.33(d,1H,J＝9.6Hz),4.05－3.99(m,1H),3.80－3.73(m,1H),3.01(s,6H),2.33－2.23(m,2H)、1.85－1.17(m,18H)進行。The compound 2-2 shown in Synthesis Example 2-2 was identified by NMR. The ¹ H-NMR chart of the compound 2-2 is shown in Fig. 2. Further, the measurement conditions and the identification of the spikes were by ¹ H-NMR (CDCL ₃ ): a 7.40 (d, 2H, J = 9.2 Hz), 6.86-6.68 (m, 2H), 6.69 (d, 2H, J). =9.2Hz), 6.33(d,1H,J=9.6Hz), 4.05-3.99(m,1H), 3.80-3.73(m,1H),3.01(s,6H),2.33-2.23(m,2H) , 1.85-1.17 (m, 18H).

(合成例2－3)(Synthesis Example 2-3)

將4－甲氧基肉桂醛(3.07克、0.0189莫耳)、亞胺基唑啉酮化合物(5.00克、0.0189莫耳)、及第三丁氧基鉀(1.06克、0.00945莫耳)，溶解在THF中，在50℃反應2小時。反應係藉由TLC每1小時追蹤。反應結束後，藉由TLC每1小時追蹤。反應結束後使用1N－HClaq(11毫升)調整為pH＝5後，使用乙酸乙酯萃取有機層，並進行減壓餾去。藉由甲醇再分散精製所得到的結晶，得到化合物2－3(產量4.27克、產率55%)。4-methoxycinnamaldehyde (3.07 g, 0.0189 mol), imine The oxazolinone compound (5.00 g, 0.0189 mol) and potassium third butoxide (1.06 g, 0.00945 mol) were dissolved in THF and reacted at 50 ° C for 2 hours. The reaction was followed by TLC every hour. After the reaction was completed, it was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 using 1N-HClaq (11 ml). The obtained crystal was re-dispersed by methanol to obtain Compound 2-3 (yield: 4.27 g, yield: 55%).

又，莫耳吸光係數(ε)為40814。Further, the Mohr absorption coefficient (?) was 40814.

合成例2－3所示之化合物2－3係藉由NMR鑑定。化合物3之¹ H－NMR圖係如第3圖所示。又，測定條件及尖峰的鑑定係藉由¹ H－NMR(CDCL₃ )：a7.45(d,2H,J＝8.8Hz),6.32(d,1H,J＝11.2Hz),4.05(m,1H),3.87(s,3H),2.25(m,2H),2.25－2.30(m,2H)、1.81－1.67(m,9H)、1.43－1.38(m,9H)進行。Compound 2-3 shown in Synthesis Example 2-3 was identified by NMR. The ¹ H-NMR chart of Compound 3 is shown in Figure 3. Further, the measurement conditions and the identification of the spikes were by ¹ H-NMR (CDCL ₃ ): a 7.45 (d, 2H, J = 8.8 Hz), 6.32 (d, 1H, J = 11.2 Hz), 4.05 (m, 1H), 3.87 (s, 3H), 2.25 (m, 2H), 2.25-2.30 (m, 2H), 1.81-1.67 (m, 9H), 1.43-1.38 (m, 9H).

(合成例2－4)(Synthesis Example 2-4)

將肉桂醛(2.49克、0.0189莫耳)、AM－6572B(5.00克、0.0189莫耳)、及第三丁氧基鉀(1.06克、0.00945莫耳)，溶解在20毫升THF中，在50℃反應2小時。反應係藉由TLC每1小時追蹤。反應結束後使用1N－HClaq(11毫升)調整為pH＝5後，使用乙酸乙酯萃取有機層，並進行減壓餾去。藉由甲醇再分散精製所得到的結晶，得到化合物2－4(產量3.96克、產率55%)。Cinnamaldehyde (2.49 g, 0.0189 mol), AM-6572B (5.00 g, 0.0189 mol), and potassium third potassium hydride (1.06 g, 0.00945 mol), dissolved in 20 mL THF at 50 ° C Reaction for 2 hours. The reaction was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 using 1N-HClaq (11 ml). The obtained crystal was re-dispersed by methanol to obtain Compound 2-4 (yield: 3.96 g, yield: 55%).

又，莫耳吸光係數(ε)為20363。Further, the molar absorption coefficient (ε) was 20,363.

合成例2－4所示之化合物2－4係藉由NMR鑑定。化合物2－4之¹ H－NMR圖係如第4圖所示。又，測定條件及尖峰的鑑定係藉由¹ H－NMR(CDCL₃ )：a7.50(d,2H,J＝7.6Hz),7.37(t,2H),7.31(d,1H,J＝7.2Hz),7.04(dd,1H,J＝11.6,15.6Hz),6.85(d,1H,J＝15.6Hz),6.33(d,1H,J＝11.6Hz),4.03(m,1H),3.75(m,1H),2.25－2.29(m,2H),1.64－1.85(m,9H)、1.29－1.64(m,9H)進行。Compounds 2-4 shown in Synthesis Examples 2-4 were identified by NMR. The ¹ H-NMR chart of the compound 2-4 is shown in Fig. 4. Further, the measurement conditions and the identification of the spikes were by ¹ H-NMR (CDCL ₃ ): a 7.50 (d, 2H, J = 7.6 Hz), 7.37 (t, 2H), 7.31 (d, 1H, J = 7.2). Hz), 7.04 (dd, 1H, J = 11.6, 15.6 Hz), 6.85 (d, 1H, J = 15.6 Hz), 6.33 (d, 1H, J = 11.6 Hz), 4.03 (m, 1H), 3.75 ( m, 1H), 2.25-2.29 (m, 2H), 1.64-1.85 (m, 9H), 1.29-1.64 (m, 9H).

(合成例2－5)(Synthesis Example 2-5)

將α－甲基肉桂醛(2.76克、0.0189莫耳)、亞胺基唑啉酮化合物(5.00克、0.0189莫耳)、及第三丁氧基鉀(1.06克、0.00945莫耳)，溶解在THF中，在50℃反應2小時。反應係藉由TLC每1小時追蹤。反應結束後，藉由TLC每1小時追蹤。反應結束後使用1N－HClaq(11毫升)調整為pH＝5後，使用乙酸乙酯萃取有機層，並進行減壓餾去。藉由甲醇再分散精製所得到的結晶，得到化合物2－5(產量3.96克、產率51%)。Α-methylcinnamaldehyde (2.76 g, 0.0189 mol), imine The oxazolinone compound (5.00 g, 0.0189 mol) and potassium third butoxide (1.06 g, 0.00945 mol) were dissolved in THF and reacted at 50 ° C for 2 hours. The reaction was followed by TLC every hour. After the reaction was completed, it was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 using 1N-HClaq (11 ml). The obtained crystal was re-dispersed by methanol to obtain Compound 2-5 (yield: 3.96 g, yield: 51%).

又，莫耳吸光係數(ε)為8045。Further, the molar absorption coefficient (ε) was 8045.

合成例2－5所示之化合物2－5係藉由NMR鑑定。化合物2－5之¹ H－NMR圖係如第5圖所示。又，測定條件及尖峰的鑑定係藉由¹ H－NMR(CDCL₃ )：a7.37(m,5H),6.84(s,1H),6.23(s,1H),4.03(m,1H),3.75(m,1H),2.27(s,3H),2.25－2.29(m,2H),1.67－1.85(m,9H),1.42－1.31(m,9H)進行。The compound 2-5 shown in Synthesis Example 2-5 was identified by NMR. The ¹ H-NMR chart of the compound 2-5 is shown in Fig. 5. Further, the measurement conditions and the identification of the peaks were determined by ¹ H-NMR (CDCL ₃ ): a 7.37 (m, 5H), 6.84 (s, 1H), 6.23 (s, 1H), 4.03 (m, 1H), 3.75 (m, 1H), 2.27 (s, 3H), 2.25-2.29 (m, 2H), 1.67-1.85 (m, 9H), 1.42-1.31 (m, 9H).

(合成例2－6)(Synthesis Example 2-6)

將2,3,4－三甲氧基肉桂醛(2.40克、0.0189莫耳)、亞胺基唑啉酮化合物(2.85克、0.0108莫耳)、及第三丁氧基鉀(0.61克、0.0054莫耳)，溶解在THF中，在50℃反應2小時。反應係藉由TLC每1小時追蹤。反應結束後，藉由TLC每1小時追蹤。反應結束後使用1N－HClaq(11毫升)調整為pH＝5後，使用乙酸乙酯萃取有機層，並進行減壓餾去。藉由甲醇再分散精製所得到的結晶，得到化合物2－6(產量2.63克、產率52%)。2,3,4-trimethoxycinnamaldehyde (2.40 g, 0.0189 mol), imine The oxazolinone compound (2.85 g, 0.0108 mol) and potassium third butoxide (0.61 g, 0.0054 mol) were dissolved in THF and reacted at 50 ° C for 2 hours. The reaction was followed by TLC every hour. After the reaction was completed, it was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 using 1N-HClaq (11 ml). The obtained crystal was re-dispersed by methanol to obtain Compound 2-6 (yield: 2.63 g, yield: 52%).

又，莫耳吸光係數(ε)為35366。Further, the molar absorption coefficient (ε) was 35,366.

合成例2－6所示之化合物2－6係藉由NMR鑑定。化合物2－6之¹ H－NMR圖係如第6圖所示。又，測定條件及尖峰的鑑定係藉由¹ H－NMR(CDCL₃ )：a6.91(dd,1H,J＝15.6,11.2Hz),6.77(d,1H,J＝15.6Hz),6.71(s,2H),6.32(d,1H,J＝12.0Hz),4.09－3.98(m,1H),3.92(s,6H),3.88(s,3H),3.81－3.74(m,1H),2.34－2.23(m,2H),1.87－1.22(m,18H)進行。The compound 2-6 shown in Synthesis Example 2-6 was identified by NMR. The ¹ H-NMR chart of the compound 2-6 is shown in Fig. 6. Further, the measurement conditions and the identification of the spikes were by ¹ H-NMR (CDCL ₃ ): a6.91 (dd, 1H, J = 15.6, 11.2 Hz), 6.77 (d, 1H, J = 15.6 Hz), 6.71 ( s, 2H), 6.32 (d, 1H, J = 12.0 Hz), 4.09-3.98 (m, 1H), 3.92 (s, 6H), 3.88 (s, 3H), 3.81-3.74 (m, 1H), 2.34 -2.23 (m, 2H), 1.87-1.22 (m, 18H).

通式(2－I)所示化合物的例子，藉由標記R²¹ ~R²⁵ 、及A，可舉出以下所示之化合物(1~46)。此等化合物能夠藉由與前述相同的流程來合成。Examples of the compound represented by the formula (2-I) include the compounds (1 to 46) shown below by the labels R ²¹ to R ²⁵ and A. These compounds can be synthesized by the same procedure as described above.

而且，通式(2－I)所示之化合物的例子，可舉出以下所示之化合物(47~73)。Further, examples of the compound represented by the formula (2-I) include the compounds (47 to 73) shown below.

從內部硬化性的觀點，通式(2－I)所示之化合物之莫耳吸光係數以5000~100000為佳，以10000~80000為更佳。From the viewpoint of internal hardenability, the molar absorption coefficient of the compound represented by the formula (2-I) is preferably from 5,000 to 100,000, more preferably from 10,000 to 80,000.

本發明之通式(2－I)所示之化合物在300奈米~450奈米的波長區域具有吸收波長。以在330奈米~450奈米的波長區域具有吸收波長為更佳。The compound of the formula (2-I) of the present invention has an absorption wavelength in a wavelength region of from 300 nm to 450 nm. It is more preferable to have an absorption wavelength in a wavelength region of 330 nm to 450 nm.

本發明之通式(2－I)所示之化合物亦可使用作為感光材料用的敏化劑、光學性增白劑及場致發光主要成分的聚合物狀發光材料。As the compound represented by the formula (2-I) of the present invention, a polymer luminescent material which is a sensitizer for a photosensitive material, an optical brightener, and a main component of electroluminescence can be used.

又，感光材料除了彩色濾光片以外，亦可利用於成形樹脂、澆鑄樹脂、光造形用樹脂、密封劑、齒科用聚合材料、印刷印墨、塗料、印刷版用感光性樹脂、印刷用標準顏色、黑色矩陣用光阻、印刷基板用光阻、半導體製造用光阻、微電子用光阻、微機械用零件製造用光阻、絕緣材、全息照像材料、波導路用材料、保護塗劑、接著劑、黏著劑、黏接著劑、剝離塗劑、UV硬化印墨、2光子吸收材料、藍色雷射用感光性組成物等。In addition to the color filter, the photosensitive material can also be used for molding resins, casting resins, photo-forming resins, sealants, dental polymer materials, printing inks, paints, photosensitive resins for printing plates, and printing. Standard color, photoresist for black matrix, photoresist for printed circuit board, photoresist for semiconductor manufacturing, photoresist for microelectronics, photoresist for manufacturing parts for micromachines, insulating material, holographic material, material for waveguide, protection A coating agent, an adhesive, an adhesive, an adhesive, a release coating agent, a UV-curable ink, a 2-photon absorption material, a photosensitive composition for blue laser, and the like.

而且，本發明之通式(2－I)所示之化合物，特別是使用於後述之硬化性組成物等的情況，藉由上述波長區域的光線曝光，能夠與在該硬化性組成物可以含有的光聚合引發劑產生電子移動、能量移動，能夠有效率地分解該光聚合引發劑，使其產生引發種。因此，本發明之通式(2－I)所示之化合物能得到高敏感度的硬化性組成物，即便增加著色劑的含量亦能夠得到與基材的黏附性等優良、對比、色純度優良的彩色濾光片。Further, the compound represented by the formula (2-I) of the present invention, particularly when used in a curable composition or the like described later, can be contained in the curable composition by exposure of light in the wavelength region. The photopolymerization initiator generates electron mobility and energy migration, and can efficiently decompose the photopolymerization initiator to generate an initiating species. Therefore, the compound represented by the formula (2-I) of the present invention can obtain a highly sensitive curable composition, and can be excellent in adhesion to a substrate, and excellent in color purity even when the content of the coloring agent is increased. Color filter.

本發明之通式(2－I)所示之化合物、及後述之本發明之通式(3－1)所示之化合物(特定敏化劑)，使用作為硬化性組成物，亦能夠進行各種化學改性用以改良該硬化性組成物敏感度、黏附性等特性。The compound represented by the formula (2-I) of the present invention and the compound (specific sensitizer) represented by the formula (3-1) of the present invention to be described later can be used as a curable composition. Chemical modification is used to improve the properties of the curable composition such as sensitivity and adhesion.

例如，使特定敏感劑、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、氫鍵等方法使其鍵結，能夠使曝光膜高強度化、或進行抑制特定敏化劑從曝光後的膜之不必要的析出。For example, a specific sensitizer and an addition polymerizable compound structure (for example, an acryloyl group or a methacryl oxime group) can be bonded by a covalent bond, an ionic bond, a hydrogen bond or the like to make the exposed film high. The strength is increased, or the unnecessary precipitation of the specific sensitizer from the exposed film is suppressed.

又，藉由特定敏化劑與後述光聚合引發劑之具有產生自由基性的部分結構(例如，烷基鹵化物、鎓鹽、過氧化物、咪唑、二咪唑等的還原分解部位、或硼酸鹽、胺、三甲基矽烷基甲基、羧甲基、羰基、亞胺等的氧化解裂性部位)的鍵結，特別是能夠在低引發系濃度的狀態，顯著地提高感光性。Further, a specific sensitizer and a photopolymerization initiator described later have a partial structure which generates radicals (for example, a reductive decomposition site of an alkyl halide, a phosphonium salt, a peroxide, an imidazole, a diimidazole, or the like, or a boric acid). The bonding of a salt, an amine, a trimethyldecylmethyl group, a carboxymethyl group, a carbonyl group, an oxidative desulfurization site of an imine or the like, in particular, can significantly improve the photosensitivity in a state of a low initiator concentration.

本發明之硬化性組成物在彩色濾光片用硬化性組成物，通式(2－I)所示之化合物可使用單獨1種亦可並用2種以上。接著，詳細地說明(3－I)所示之化合物。In the curable composition for a color filter of the present invention, the compound represented by the formula (2-I) may be used alone or in combination of two or more. Next, the compound represented by (3-I) will be described in detail.

通式(3－1)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(R³³ )－，Y係表示氧原子、硫原子、或－N(R³³ )－。R³¹ 、R³² 、及R³³ 係各自獨立地表示氫原子或一價的非金屬原子團，A、R³¹ 、R³² 、及R³³ 亦可各自互相鍵結而形成脂肪族性或芳香族性的環。In the formula (3-1), 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 ³³ )-, and Y represents an oxygen atom or sulfur. Atom, or -N(R ³³ )-. R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a monovalent non-metal atomic group, and A, R ³¹ , R ³² and R ³³ may each bond to each other to form an aliphatic or aromatic group. Ring.

詳細說明通述(3－1)所示之化合物。The compound represented by the general formula (3-1) will be described in detail.

在通式(3－1)，R³¹ 、R³² 、及R³³ 係各自獨立地表示氫原子或一價的非金屬原子團。R³¹ 、R³² 、及R³³ 係表示一價的非金屬原子團時，以取代或未取代烷基、取代或未取代芳基、取代或未取代烯基、取代或未取芳香族雜環殘基、取代或未取代烷氧基、取代或未取代烷硫基、羥基、鹵素原子為佳。In the general formula ^{(3-1), R 31, R} 32, and R ³³ each independently represent a line a hydrogen atom or a monovalent non-metallic atomic group. R ³¹ , R ³² , and R ³³ represent a monovalent non-metal atomic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic heterocyclic group A base, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom are preferred.

具體地敘述在通式(3－1)之R³¹ 、R³² 、及R³³ 的較佳例子。Preferred examples of R ³¹ , R ³² and R ³³ in the formula (3-1) are specifically described.

R³¹ 、R³² 、及R³³ 所示非取代烷基的較佳例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代基的烷基之較佳例子同樣。Preferred examples of the non-substituted alkyl group represented by R ³¹ , R ³² and R ^{33 are the} substituents represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the formula (2-I). Preferred examples of the alkyl group are the same.

在R³¹ 、R³² 、及R³³ 所示取代烷基之伸烷基(烷基部分)的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代烷基之伸烷基(烷基部分)的例子同樣。Examples of the alkylene group (alkyl moiety) of the substituted alkyl group represented by R ³¹ , R ³² and R ^{33 are the same} as R ²¹ , R ²² , R ²³ and R ²⁴ in the formula (2-I). The same is true for the alkyl group (alkyl moiety) of the substituted alkyl group represented by R ²⁵ .

在R³¹ 、R³² 、及R³³ 所示取代烷基所具有取代基的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代烷基所具有取代基的例子同樣。Examples of the substituent having a substituted alkyl group represented by R ³¹ , R ³² and R ^{33 are} as shown by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the formula (2-I). Examples of the substituent having a substituted alkyl group are the same.

在此等取代基，烷基的具體例可舉出在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示未取代烷基之前述烷基。Specific examples of the alkyl group in the above substituents include the above-mentioned alkyl group represented by an unsubstituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I).

在此等取代基，芳基的具體例可舉出在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之取代基之芳基的具體例同樣。Specific examples of the substituent in the above-mentioned substituents include an aryl group having a substituent of a substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). The specific example is the same.

在此等取代基，雜芳基的例子可舉出在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之取代基之雜芳基的例子同樣。Examples of the substituent, examples of the heteroaryl group include a heteroaryl group having a substituent of a substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). The example of the base is the same.

在此等取代基之烯基的例子可舉出乙烯基、1－丙烯基、1－丁烯基、肉桂基、2－氯－1－乙烯基等。Examples of the alkenyl group of these substituents include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-vinyl group.

在此等取代基之炔基的例子可舉出乙炔基、1－丙炔基、1－丁炔基、三甲基矽烷基乙炔基等。Examples of the alkynyl group of these substituents include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethyldecylalkylethynyl group and the like.

在醯基(G₁ CO－)之G₁ ，可舉出氫原子、及上述的烷基、芳基。In the acyl (G ₁ CO-) of G _1, include a hydrogen atom, and said alkyl group, an aryl group.

此等取代基之中，更佳例子係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之取代基的例子所舉出的更佳例子同樣。Among these substituents, a more preferred example is exemplified by a substituent having a substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). A better example is the same.

R³¹ 、R³² 、及R³³ 之較佳取代烷基的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示較佳取代烷基的例子同樣。Examples of the preferred substituted alkyl group of R ³¹ , R ³² and R ^{33 are} preferably substituted alkyl groups represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the formula (2-I). The example of the base is the same.

R³¹ 、R³² 、及R³³ 之較佳未取代芳基的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示較佳未取代芳基的例子同樣。Examples of the preferred unsubstituted aryl group of R ³¹ , R ³² and R ^{33 are} preferably as shown by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). The examples of the substituted aryl group are the same.

R³¹ 、R³² 、及R³³ 之較佳取代芳基的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示較佳取代芳基的例子同樣。Examples of the preferred substituted aryl group of R ³¹ , R ³² and R ^{33 are} preferably substituted with R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). The example of the base is the same.

R³¹ 、R³² 、及R³³ 之較佳未取代烯基的具體例，可舉出乙烯基、1－丙烯基等。Specific examples of the preferred unsubstituted alkenyl group for R ³¹ , R ³² and R ³³ include a vinyl group and a 1-propenyl group.

R³¹ 、R³² 、及R³³ 之較佳取代烯基的具體例，可舉出在上述的未取代烯基上具有脫除氫原子之一價的非金屬原子團作為取代基之物。Specific examples of the preferred substituted alkenyl group of R ³¹ , R ³² and R ³³ include a non-metal atomic group having a valence of one hydrogen atom removed as a substituent on the above unsubstituted alkenyl group.

R³¹ 、R³² 、及R³³ 之較佳未取代芳香族雜環殘基的具體例，可舉出噻吩、呋喃、吡咯、吡唑、噻唑、唑、嘧啶、嗒、咪唑、喹啉、***、吲哚、咔唑等。Specific examples of preferred unsubstituted aromatic heterocyclic residues of R ³¹ , R ³² and R ³³ include thiophene, furan, pyrrole, pyrazole, and thiazole. Oxazole, pyrimidine, pyrene , imidazole, quinoline, triazole, hydrazine, carbazole and the like.

R³¹ 、R³² 、及R³³ 之較佳取代芳香族雜環殘基的具體例，可舉出在上述的未取代芳香族雜環殘基上具有脫除氫原子之一價的非金屬原子團作為取代基之物。Specific examples of the preferable substituted aromatic heterocyclic residue of R ³¹ , R ³² and R ³³ include a non-metal atomic group having a valence of one hydrogen atom removed from the above unsubstituted aromatic heterocyclic residue. As a substituent.

R³¹ 、R³² 、及R³³ 之較佳取代或未取代烷氧基的例子，係各自與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示較佳取代或未取代烷氧基的例子同樣。Examples of the preferred substituted or unsubstituted alkoxy group of R ³¹ , R ³² and R ³³ are each independently of R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of} the formula (2-I). Examples of preferably substituted or unsubstituted alkoxy groups are the same.

R³¹ 、R³² 、及R³³ 之較佳取代或未取代烷硫基的具體例，係各自與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示較佳取代或未取代烷硫基的具體例同樣。Specific examples of the preferred substituted or unsubstituted alkylthio group of R ³¹ , R ³² and R ³³ are each independently of R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the formula (2-I). Specific examples of the preferred substituted or unsubstituted alkylthio group are shown in the same manner.

接著，說明在通式(3－1)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例如與在通式(3－1)之R³¹ 、R³² 、及R³³ 所記載之物同樣之物。Next, A in the general formula (3-1) will be described. Specific examples of the aromatic ring or the hetero ring which may have a substituent, and the aromatic ring or the hetero ring which may have a substituent, for example, may be, for example, R ³¹ and R ³² in the formula (3-1). And the same thing as that described in R ³³ .

A之較佳芳香族環具體上可舉出苯、甲氧基苯、二甲氧基苯、三甲氧基苯、二乙胺苯、二苯胺基苯、甲硫基苯、蒽、苯硫基苯、噻蒽、啡噻、喹、二苯并噻吩、二苯并呋喃、咔唑、二甲氧基苯基苯等。Specific preferred aromatic ring of A may, for example, be benzene, methoxybenzene, dimethoxybenzene, trimethoxybenzene, diethylamine benzene, diphenylaminobenzene, methylthiobenzene, anthracene or phenylthio. Benzene, thiazide, thiophene Quino , dibenzothiophene, dibenzofuran, carbazole, dimethoxyphenylbenzene, and the like.

又，A之較佳雜環，具體上可舉出吡啶、苯并噻唑、苯并唑、苯并噻唑等。Further, a preferred hetero ring of A, specifically pyridine, benzothiazole, benzo Oxazole, benzothiazole and the like.

在通式(3－1)之X係表示氧原子、硫原子、或－N(R³ )－，以氧原子為佳。X in the general formula (3-1) represents an oxygen atom, a sulfur atom or -N(R ³ )-, and an oxygen atom is preferred.

在通式(3－1)之Y係表示氧原子、硫原子、或－N(R³ )－，以－N(R³ )－為佳。Y in the general formula (3-1) represents an oxygen atom, a sulfur atom, or -N(R ³ )-, preferably -N(R ³ )-.

從提高光聚合引發劑分解效率而言，通式(3－1)所示之化合物的較佳態樣之一係下述通式(3－2)所示之化合物。One of the preferable aspects of the compound represented by the formula (3-1) is a compound represented by the following formula (3-2) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator.

通式(3－2)中，A係表示亦可具有取代基之芳香族環或雜環，Y係表示氧原子、硫原子、或－N(R³³ )－，R³¹ 、R³² 、及R³³ 係各自獨立地表示氫原子或一價的非金屬原子團，A、R³¹ 、R³² 、及R³³ 亦可各自互相鍵結而形成脂肪族性或芳香族性的環。In the formula (3-2), A represents an aromatic ring or a heterocyclic ring which may have a substituent, and Y represents an oxygen atom, a sulfur atom, or -N(R ³³ )-, R ³¹ and R ³² , and R ³³ each independently represents a hydrogen atom or a monovalent non-metal atomic group, and A, R ³¹ , R ³² and R ³³ may each bond to each other to form an aliphatic or aromatic ring.

在通式(3－2)之A、R³¹ 、R³² 、及R³³ 的詳細係與前述通式(3－1)之A、R³¹ 、R³² 、及R³³ 同樣。The details of A, R ³¹ , R ³² and R ³³ in the formula (3-2) are the same as those in the above formula (3-1), A, R ³¹ , R ³² and R ³³ .

通式(3－2)所示之化合物，例如以下面所示之化合物(3－2－1)~(3－2－35)為佳。The compound represented by the formula (3-2) is preferably, for example, the compound (3-2-1) to (3-2-35) shown below.

從提高光聚合引發劑分解效率而言，通式(3－1)所示之化合物的較佳態樣之一係下述通式(3－3)所示之化合物。One of the preferable aspects of the compound represented by the formula (3-1) is a compound represented by the following formula (3-3) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator.

通式(3－3)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(R³³ )－，R³³ 、R³⁴ 、及R³⁵ 係各自獨立地表示氫原子或一價的非金屬原子團，A、R³³ 、R³⁴ 、及R³⁵ 亦可各自互相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。其中，在Ar骨架上具有哈曼特(Hammett’s)值的總和大於0之取代基。In the formula (3-3), 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 ³³ )-, R ³³ and R ³⁴ , and R ³⁵ each independently represents a hydrogen atom or a monovalent non-metal atomic group, and A, R ³³ , R ³⁴ and R ³⁵ may each be bonded to each other to form an aliphatic or aromatic ring. The Ar system represents an aromatic ring or a heterocyclic ring having a substituent. Among them, a substituent having a Hammett's value greater than 0 on the Ar skeleton.

在通式(3－3)，A、R³³ 、R³⁴ 、及R³⁵ 係與在前述通式(3－1)之A、R³³ 、R³² 、及R³¹ 各自同義。In the formula (3-3), A, R ³³ , R ³⁴ and R ³⁵ are synonymous with each of A, R ³³ , R ³² and R ³¹ in the above formula (3-1).

Ar係表示具有取代基之芳香族環或雜環，其具體例能夠同樣地舉出在前述通式(3－1)之A的說明所記載之物中，具有取代基之芳香族環或雜環之具體例。The Ar system is an aromatic ring or a hetero ring which has a substituent, and a specific example thereof can be similarly described in the description of A of the above formula (3-1), and an aromatic ring or a hetero group having a substituent. Specific examples of the ring.

但是，在通式(3－3)，能夠在Ar導入之取代基的哈曼特值總和必須為0以上，此種取代基的可舉出例如三氟甲基、羰基、酯基、鹵素原子、硝基、氰基、亞碸基、胺基、羧基等。此等取代基的哈曼特值係如下所示。可舉出三氟甲基(－CF₃ 、m：0.43、p：0.54)、羧基(例如－COHm：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。在括弧內，係表示在該取代基芳基骨架之導入位置及其哈曼特值，(m：0.50)係指該取代基在間位導入時顯示之哈曼特值為0.50。However, in the general formula (3-3), the sum of the Hammant values of the substituent which can be introduced into Ar must be 0 or more, and examples of such a substituent include a trifluoromethyl group, a carbonyl group, an ester group, and a halogen atom. , nitro, cyano, fluorenylene, amine, carboxyl, and the like. The Hammant values of these substituents are as follows. Trifluoromethyl (-CF ₃ , m: 0.43, p: 0.54), carboxyl (for example, -COHm: 0.36, p: 0.43), ester group (-COOCH ₃ , m: 0.37, p: 0.45), Halogen atoms (for example, Cl, m: 0.37, p: 0.23), cyano groups (-CN, m: 0.56, p: 0.66), fluorenylene groups (for example, -SOCH ₃ , m: 0.52, p: 0.45), decylamine A group (for example, -NHCOCH ₃ , m: 0.21, p: 0.00), a carboxyl group (-COOH, m: 0.37, p: 0.45), or the like. In the brackets, the introduction position of the substituent aryl skeleton and its Hammant value are indicated, and (m: 0.50) means that the substituent exhibits a Hammant value of 0.50 when introduced in the meta position.

其中，Ar之較佳例子，可舉出具有取代基之苯基，Ar骨架上之較佳取代基係酯基、氰基。取代基的位置以位於Ar骨架上的鄰位為特佳。Among them, preferred examples of Ar include a phenyl group having a substituent, a preferred substituent ester group on the Ar skeleton, and a cyano group. The position of the substituent is particularly preferred as the ortho position on the Ar skeleton.

通式(3－3)所示化合物的較佳例子，可舉出以下所示之化合物(3－3－1)~(3－3－32)。Preferable examples of the compound represented by the formula (3-3) include the compounds (3-3-1) to (3-3-32) shown below.

而且，從提升光聚合引發劑的分解效率之觀點，通式(3－1)所示之化合物的較佳態樣之一係下述通式(3－4)所示之化合物。本發明之特定敏化劑以下述通式(3－4)所示之化合物為更佳。Further, from the viewpoint of enhancing the decomposition efficiency of the photopolymerization initiator, one of the preferable aspects of the compound represented by the formula (3-1) is a compound represented by the following formula (3-4). The specific sensitizer of the present invention is more preferably a compound represented by the following formula (3-4).

通式(3－4)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－NR⁶¹ －。R⁶¹ 、R⁶² 、R⁶³ 、及R⁶⁶ 係各自獨立地表示氫原子或一價的非金屬原子團，R⁶⁴ 、及R⁶⁵ 係各自獨立地表示一價的非金屬原子團；A、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 亦可各自互相鍵結而形成脂肪族性或芳香族性的環。In the formula (3-4), A represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents an oxygen atom, a sulfur atom or -NR ⁶¹ -. R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁶ each independently represent a hydrogen atom or a monovalent non-metal atomic group, and R ⁶⁴ and R ⁶⁵ each independently represent a monovalent non-metal atomic group; A, R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ may each be bonded to each other to form an aliphatic or aromatic ring.

在此，R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 係表示一價的非金屬原子團時，以表示取代或未取代的烷基或取代或未取代的芳基為佳。Here, when R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , and R ⁶⁶ represent a monovalent non-metal atomic group, it is preferred to represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. .

接著，敘述在通式(3－4)之R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 之較佳例子。Next, preferred examples of R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ in the formula (3-4) will be described.

R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 所示未取代烷基之較佳例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示之未取代烷基的較佳例子同樣。Preferred examples of the unsubstituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ^{66 are} R ²¹ , R ²² , R ²³ and R in the formula (2-I). Preferred examples of the unsubstituted alkyl group represented by ²⁴ or R ²⁵ are the same.

R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 所示取代烷基(烷基部分)的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代烷基之伸烷基(烷基部分)的例子同樣。Examples of the substituted alkyl group (alkyl moiety) represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ^{66 are} R ²¹ , R ²² and R ²³ in the formula (2-I). Examples of the alkylene group (alkyl moiety) of the substituted alkyl group represented by R ²⁴ or R ²⁵ are the same.

R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 所示取代烷基之取代基的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之取代基的例子同樣。Examples of the substituent of the substituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ^{66 are} R ²¹ , R ²² , R ²³ and R in the formula (2-I). Examples of the substituent having a substituted alkyl group represented by ²⁴ or R ²⁵ are the same.

在此等取代基之烷基的具體例，可舉出在R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 所示未取代烷基之前述烷基，此時亦可更具有取代基。Specific examples of the alkyl group of the substituent include the alkyl group represented by an unsubstituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ . Has a substituent.

在此等取代基，芳基的具體例係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之取代基之芳基的具體例同樣。In these substituents, specific examples of the aryl group are the aryl group having a substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). The specific example is the same.

在此等取代基，雜芳基的例子係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之取代基之雜芳基的具體例同樣。In these substituents, examples of the heteroaryl group are heteroaryl groups having a substituent having a substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). The specific example is the same.

烯基的例子可舉出乙烯基、1－丙烯基、1－丁烯基、肉桂基、2－氯－1－乙烯基等。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.

炔基的例子可舉出乙炔基、1－丙炔基、1－丁炔基、三甲基矽烷基乙炔基等。Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethyldecylalkylethynyl group and the like.

在醯基(G₁ CO－)之G₁ 可舉出氫、及上述的烷基、及芳基。In the acyl (G ₁ CO-) include a hydrogen of G _1, and said alkyl group and an aryl group.

該等取代基之中，更佳之例子，可舉出在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之取代基的例子之更佳例子同樣。Among the above-mentioned substituents, a more preferable example is a substituent having a substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 of the} formula (2-I). A better example is the same.

R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 所示取代烷基的例子，係與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示具有取代烷基之較佳例子同樣。Examples of the substituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ^{66 are} R ²¹ , R ²² , R ²³ , R ²⁴ in the formula (2-I) or Preferred examples of the substituted alkyl group represented by R ²⁵ are the same.

R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 所示取代或未取代芳基的較佳例子，係各自與在通式(2－I)之R²¹ 、R²² 、R²³ 、R²⁴ 、或R²⁵ 所示取代或未取代芳基之較佳例子同樣。Preferred examples of the substituted or unsubstituted aryl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are each independently of R ²¹ , R ²² and R in the formula (2-I). Preferred examples of the substituted or unsubstituted aryl group represented by ²³ , R ²⁴ or R ²⁵ are the same.

又，R⁶¹ 之更佳例子，可舉出取代或未取代的芳基，R⁶² 及R⁶⁶ 之更佳例子可舉出取代或未取代的烷基。R²² 之特佳例子可舉出脂環族烷基，具體上可舉出環己基、環丁基、及環辛基。又，R⁶³ 、R⁶⁴ 、R⁶⁵ 之較佳例子可舉出取代或未取代的芳基、或取代或未取代的烷基，特佳例子，R⁶³ 及R⁶⁴ 、或R⁶⁴ 及R⁶⁵ 、或R⁶³ 及R⁶⁵ 以2價的連結基鍵結時，具體上，以在R⁶³ 、R⁶⁴ 、R⁶⁵ 之間形成環烷基結構為佳。較佳的環烷基結構可舉出環己基結構、環丁基結構、環辛基結構、金剛烷基結構。Further, a more preferable example of R ⁶¹ is a substituted or unsubstituted aryl group, and a more preferable example of R ⁶² and R ⁶⁶ is a substituted or unsubstituted alkyl group. A particularly preferred example of R ²² is an alicyclic alkyl group, and specific examples thereof include a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Further, preferred examples of R ⁶³ , R ⁶⁴ and R ⁶⁵ include a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, particularly preferred examples, R ⁶³ and R ⁶⁴ , or R ⁶⁴ and R ^{65 .} When R ⁶³ and R ⁶⁵ are bonded by a divalent linking group, specifically, a cycloalkyl structure is formed between R ⁶³ , R ⁶⁴ and R ⁶⁵ . Preferred cycloalkyl structures include a cyclohexyl structure, a cyclobutyl structure, a cyclooctyl structure, and an adamantyl structure.

此等取代基之適當要因仍未明確，可認為係藉由具有此種取代基，光吸收所產生的電子激發狀態及與引發劑化合物的相互作用變為特別大，藉由提高引發劑化合物產生自由基、酸或鹼之效率(提高敏感度效果)、在亞胺結構導入鄰接且高體積結構，能夠抑制因加水分解、氧化分解等的亞胺結構分解而從感光膜消失(提高保存安定性效果)。The appropriate cause of such substituents is still unclear, and it is considered that by having such a substituent, the electron excitation state by light absorption and the interaction with the initiator compound become particularly large by increasing the generation of the initiator compound. Free radical, acid or alkali efficiency (improving sensitivity effect), introduction of adjacent and high-volume structure in imine structure, and suppression of disappearance of the imine structure due to decomposition of imine structure such as hydrolysis and oxidative decomposition (increasing preservation stability) effect).

接著，說明通式(3－4)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與在R⁶¹ 、R⁶² 、R⁶³ 、R⁶⁴ 、R⁶⁵ 、及R⁶⁶ 的說明所示之物同樣之物。Next, A of the formula (3-4) will be described. Specific examples of the aromatic ring or the hetero ring which may have a substituent, and the aromatic ring or the hetero ring which may have a substituent may be exemplified by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ^{65 .} And the same thing as the description of R ⁶⁶ .

其中，較佳之A可舉出具有烷氧基、烷硫基、及胺基之芳基，更佳之A可舉出具有胺基之芳基。特佳之具有胺基之芳基可舉出二烷胺基芳基、二芳胺基芳基，具體上可舉出二甲胺苯基、二乙胺苯基、哌啶基苯基、啉苯基、喹基、及二苯胺苯基。Among them, preferred A is an aryl group having an alkoxy group, an alkylthio group, and an amine group, and more preferably A is an aryl group having an amine group. Particularly preferred examples of the aryl group having an amine group include a dialkylamino aryl group and a diarylamino aryl group, and specific examples thereof include dimethylaminophenyl group, diethylaminophenyl group, and piperidinylphenyl group. Phenylphenyl, quinolin Base, and diphenylamine phenyl.

以下，顯示通式(3－1)所示之化合物(特定敏化劑)的較佳具體例(3－D1)~(3－D121)，但是本發明未限定於此等。又，對藉由雙鍵連結酸性原料與鹼性原料之異構物並未清楚明白，本發明未限定於任一種異構物。In the following, preferred specific examples (3-D1) to (3-D121) of the compound (specific sensitizer) represented by the formula (3-1) are shown, but the present invention is not limited thereto. Further, it is not clear that the isomers of the acidic raw material and the basic raw material are linked by a double bond, and the present invention is not limited to any one of the isomers.

敘述通式(3－1)所示之化合物的合成方法。A method for synthesizing the compound represented by the formula (3-1) will be described.

敘述通式(3－1)所示之化合物通常能夠藉由具有活性亞甲基之酸性原料、與取代或非取代芳香族或雜環進行縮合應而得到，此等可參照特公昭59－28329號公報來合成。The compound represented by the formula (3-1) can be usually obtained by condensing an acidic starting material having an active methylene group with a substituted or unsubstituted aromatic or heterocyclic ring, and these can be referred to Japanese Patent Publication No. 59-28329. No. bulletin to synthesize.

可舉出例如下述反應式(3－1)所示，利用酸性原料化合物、與在雜環上具有醛基或羰基之鹼性原料進行縮合反應之合成方法。縮合反應按照必要在鹼(base)存在下進行。鹼可利用通常泛用之物，例如胺、吡啶類(三烷胺、二甲胺吡啶、二氮雜雙環十一烯DBU等)、胺基金屬類(二異丙基胺基鋰等)、烷醇金屬類(甲醇鈉、第三丁醇鉀等)、氫化金屬類(氫化鈉、氫化鉀等)，但是沒有特別限制。For example, a synthesis method in which an acidic starting material compound and a basic raw material having an aldehyde group or a carbonyl group on a hetero ring are subjected to a condensation reaction, as shown in the following reaction formula (3-1), may be mentioned. The condensation reaction is carried out as necessary in the presence of a base. The base can be generally used, such as an amine, a pyridine (trialkylamine, dimethylamine pyridine, diazabicycloundecene DBU, etc.), an amine metal (diisopropylamino lithium, etc.), An alkanol metal (such as sodium methoxide or potassium t-butoxide) or a metal hydride (sodium hydride or potassium hydride), but is not particularly limited.

又，通式(3－1)所示之化合物之較佳其他合成方法，可舉出藉由下述反應式(3－2)之方法。亦即，藉由使用在前述反應式(3－1)之酸性原料化合物，Y係使用硫原子之酸性原料化合物作為起始物質，與在雜環上具有醛基或羰基之鹼性原料進行縮合反應來色料先質之步驟為止，係與前述反應式(3－1)同樣地進行後，使該色料先質，進而與能夠與硫原子互相進行化學作用來形成金屬硫化物之金屬鹽及水或1級胺化合物(R－NH₂ ：在此R係表示一價的非金屬原子團)進行作用之反應。Further, a preferred synthesis method of the compound represented by the formula (3-1) is exemplified by the following reaction formula (3-2). That is, by using the acidic starting material compound of the above reaction formula (3-1), Y is an acidic starting material compound using a sulfur atom as a starting material, and is condensed with an alkaline raw material having an aldehyde group or a carbonyl group on the hetero ring. After the reaction of the coloring matter is carried out in the same manner as in the above reaction formula (3-1), the coloring material is advanced, and further, a metal salt capable of chemically reacting with a sulfur atom to form a metal sulfide is formed. And a reaction in which water or a primary amine compound (R-NH ₂ : wherein R represents a monovalent non-metal atomic group) acts.

此等之中，反應式(3－2)所示反應之各反應的產率高，在合成效率上特佳，其中，合成通式(3－4)所示之化合物時，該反應式(3－2)所示之反應係有用的。Among these, the yield of each reaction of the reaction represented by the reaction formula (3-2) is high, and it is particularly preferable in terms of synthesis efficiency, wherein when the compound represented by the formula (3-4) is synthesized, the reaction formula ( The reaction shown in 3-2) is useful.

反應式(3－2)中，M^n＋ X_n 係表示與前述反應式(2－2)中的M^n＋ X_n 同樣的金屬鹽。In the reaction formula (3-2), M ⁿ⁺ X _n represents the same metal salt as M ⁿ⁺ X _n in the above reaction formula (2-2).

又，合成前述通式(3－4)所示之化合物時，在反應式(3－1)及(3－2)之R³¹ 、R³² 、及Y係各自對應通式(3－4)之R⁶⁶ 、R⁶² 、及N－C(R⁶³ )(R⁶⁴ )(R⁶⁵ )。Further, when the compound represented by the above formula (3-4) is synthesized, the R ³¹ , R ³² and Y groups in the reaction formulae (3-1) and (3-2) correspond to the formula (3-4). R ⁶⁶ , R ⁶² , and N-C(R ⁶³ )(R ⁶⁴ )(R ⁶⁵ ).

在本發明的硬化性組成物，通式(3－1)所示之化合物(特定敏化劑)可使用單獨1種，亦可並用2種以上。In the curable composition of the present invention, the compound (specific sensitizer) represented by the formula (3-1) may be used alone or in combination of two or more.

在本發明的硬化性組成物、及彩色濾光片用硬化性組成物之特定敏化劑的含量，以佔硬化性組成物的總固體成分中之0.1質量%~20質量%為佳，以0.2質量%~20質量%為更佳。The content of the specific sensitizer of the curable composition of the present invention and the curable composition for a color filter is preferably 0.1% by mass to 20% by mass based on the total solid content of the curable composition. 0.2% by mass to 20% by mass is more preferable.

特別是通式(2－I)所示化合物、及後述的本發明之通式(3－1)所示化合物，係在硬化性組成物之著色劑的濃度非常高、且所形成的著色圖案(感光層)的光透射率係極低時，具體上，係在未添加通式(2－I)所示化合物、或後述的本發明之通式(3－1)所示化合物而形成時之感光層在365奈米的光線透射率、及/或在405奈米的光線透射率為10%以下時添加，其效果能夠顯著地發揮。In particular, the compound represented by the formula (2-I) and the compound of the formula (3-1) of the present invention described later are very high in the concentration of the coloring agent in the curable composition, and the colored pattern formed is formed. When the light transmittance of the (photosensitive layer) is extremely low, specifically, when the compound represented by the formula (2-I) or the compound of the formula (3-1) of the present invention described later is not added, it is formed. The photosensitive layer is added at a light transmittance of 365 nm and/or when the light transmittance of 405 nm is 10% or less, and the effect can be remarkably exhibited.

<(B)光聚合引發劑><(B) Photopolymerization initiator>

本發明的硬化性組成物係藉由光線分解，來引發、促進後述聚合物化合物的聚合之化合物，以在波長300~500奈米的區域具有吸收之物為佳。又，光聚合引發劑可單獨或並用2種以上。The curable composition of the present invention is a compound which initiates and accelerates polymerization of a polymer compound described later by decomposition of light, and preferably has an absorption in a region having a wavelength of 300 to 500 nm. Further, the photopolymerization initiator may be used alone or in combination of two or more.

光聚合引發劑可舉出例如有機鹵化化合物、二唑化合物、羰基化合物、縮酮化合物、苯偶姻化合物、吖啶化合物、有機過氧化化合物、偶氮化合物、香豆素化合物、疊氮化合物、二茂金屬化合物、二咪唑系化合物、有機硼酸化合物、二磺酸化合物、肟酯化合物、鎓鹽化合物、醯基膦(氧化物)化合物。The photopolymerization initiator may, for example, be an organic halogenated compound. Diazole compound, carbonyl compound, ketal compound, benzoin compound, acridine compound, organic peroxidation compound, azo compound, coumarin compound, azide compound, metallocene compound, diimidazole compound, organic boric acid A compound, a disulfonic acid compound, an oxime ester compound, a phosphonium salt compound, or a mercaptophosphine (oxide) compound.

有機鹵化化合物具體上可舉出在若林等「Bull Chem.Soc Japan」42、2924(1969年)、美國專利第3,905,815號說明書、特公昭46－4605號、特開昭48－36281號、特開昭55－32070號、特開昭60－239736號、特開昭61－169835號、特開昭61－169837號、特開昭62－58241號、特開昭62－212401號、特開昭63－70243號、特開昭63－298339號、M.P.Hutt“雜環化學期刊(Journal of Heterocyclic Chemistry”1(第3期)，(1970年)」之文章所記載之化合物，特別是可舉出三鹵甲基取代之二唑化合物、及s－三化合物。Specific examples of the organic halogenated compound include "Bull Chem. Soc Japan" 42 and 2924 (1969), and the specification of U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, and JP-A-48-36281. No. 55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63 -70243, JP-A-63-298339, MP Hutt "Journal of Heterocyclic Chemistry" (No. 3), (1970), the compounds described in the article, in particular, trihalogen Methyl substituted Diazole compound, and s-three Compound.

s－三化合物更佳是至少1個單、雙、或三鹵素取代甲基鍵結於s－三環而成之s－三衍生物，具體上可舉出例如2,4,6－參(一氯甲基)－s－三、2,4,6－參(二氯甲基)－s－三、2,4,6－參(三氯甲基)－s－三、2－甲基－4,6－雙(三氯)－s－三、2－正丙基－4,6－雙(三氯甲基)－s－三、2－(α,α,β－三氯乙基)－4,6－雙(三氯甲基)－s－三、2－苯基－4,6－雙(三氯甲基)－s－三、2－(對甲氧基苯基)－4,6－雙(三氯甲基)－s－三、2－(3,4－乙氧基苯基)－4,6－雙(三氯甲基)－s－三、2－(對氯苯基)－4,6－雙(三氯甲基)－s－三、2－[1－(對甲氧基苯基)－2,4－丁二烯]－4,6－雙(三氯甲基)－s－三、2－苯乙烯基－4,6－雙(三氯甲基)－s－三、2－(對甲氧基苯乙烯基)－4,6－雙(三氯甲基)－s－三、2－(對異丙氧基苯乙烯基)－4,6－雙(三氯甲基)－s－三、2－(對甲苯基)－4,6－雙(三氯甲基)－s－三、2－(4－甲氧基丁基)－4,6－雙(三氯甲基)－s－三、2－苯硫基－4,6－雙(三氯甲基)－s－三、2－苄硫基－4,6－雙(三氯甲基)－s－三、2,4,6－參(二溴甲基)－s－三、2,4,6－參(三溴甲基)－s－三、2－甲基－4,6－雙(三氯甲基)－s－三、2－甲氧基－4,6－雙(三溴甲基)－s－三等。S-three More preferably, the compound is at least one mono-, di- or tri-halogen-substituted methyl bond to the s-three Ring made of s-three The derivative may specifically be, for example, 2,4,6-gin(monochloromethyl)-s-three , 2,4,6-gin (dichloromethyl)-s-three , 2,4,6-para (trichloromethyl)-s-three 2-methyl-4,6-bis(trichloro)-s-three 2-n-propyl-4,6-bis(trichloromethyl)-s-three , 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-three 2-phenyl-4,6-bis(trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(3,4-ethoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-three ,2-[1-(p-methoxyphenyl)-2,4-butadiene]-4,6-bis(trichloromethyl)-s-three 2-styryl-4,6-bis(trichloromethyl)-s-three , 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-three , 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-three , 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-three 2-(4-methoxybutyl)-4,6-bis(trichloromethyl)-s-three 2-phenylthio-4,6-bis(trichloromethyl)-s-three 2-Benzylthio-4,6-bis(trichloromethyl)-s-three , 2,4,6-parade (dibromomethyl)-s-three , 2,4,6-parade (tribromomethyl)-s-three 2-methyl-4,6-bis(trichloromethyl)-s-three 2-methoxy-4,6-bis(tribromomethyl)-s-three Wait.

二唑化合物可舉出2－三氯甲基－5－苯乙烯－1,3,4－二唑、2－三氯甲基－5－(氰基苯乙烯)－1,3,4－二唑、2－三氯甲基－5－(氰基苯乙烯)－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)苯乙烯－1,3,4－二唑等。 The oxadiazole compound is exemplified by 2-trichloromethyl-5-styrene-1,3,4- Diazole, 2-trichloromethyl-5-(cyanostyrene)-1,3,4- Diazole, 2-trichloromethyl-5-(cyanostyrene)-1,3,4- Diazole, 2-trichloromethyl-5-(naphthalen-1-yl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-styrene)styrene-1,3,4- Diazole and the like.

羰基化合物可舉出二苯基酮、米其勒酮、2－甲基二苯基酮、3－甲基二苯基酮、4－甲基二苯基酮、2－氯二苯基酮、4－溴二苯基酮、2－羧基二苯基酮等二苯基酮衍生物、2,2－二甲氧基－2－苯基乙醯苯、2,2－二乙氧基乙醯苯、1－羥基環己基苯基酮、α－羥基－2－甲基苯基丙酮、1－羥基－1－甲基乙基－(對異丙基苯基)酮、1－羥基－1－(對十二烷基苯基)酮、2－甲基－(4’－(甲硫基)苯基)－2－啉－1－丙酮、1,1,1－三氯甲基－(對丁基苯基)酮、2－苄基－2－二甲胺－4－啉丁醯苯等乙醯苯衍生物、噻噸酮、2－乙基噻噸酮、2－異丙基噻噸酮、2－氯噻噸酮、2,4－二甲基噻噸酮、2,4－二乙基噻噸酮、2,4－二異丙基噻噸酮等噻噸酮衍生物、對二甲胺苯甲酸酯、對二乙胺苯甲酸酯等苯甲酸酯衍生物等。The carbonyl compound may, for example, be diphenyl ketone, michelitone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone or 2-chlorodiphenyl ketone. Diphenyl ketone derivatives such as 4-bromodiphenyl ketone and 2-carboxydiphenyl ketone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2-diethoxy acetamidine Benzene, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-(4'-(methylthio)phenyl)-2- Phenyl-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)one, 2-benzyl-2-dimethylamine-4- Anthraquinone derivatives such as phenylbutazone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, a thioxanthone derivative such as 2,4-diethylthioxanthone or 2,4-diisopropylthioxanthone, benzoic acid such as p-dimethylamine benzoate or p-diethylamine benzoate Ester derivatives and the like.

縮酮化合物可舉出苄基甲基縮酮、苄基－β－甲氧基乙基縮醛等。The ketal compound may, for example, be a benzyl methyl ketal or a benzyl-β-methoxyethyl acetal.

苯偶姻化合物可舉出間苯偶姻丙基醚、苯偶姻異丁基醚、苯偶姻乙基醚、甲基鄰苯甲醯基苯甲酸酯等。Examples of the benzoin compound include m-benzoin propyl ether, benzoin isobutyl ether, benzoin ethyl ether, and methyl phthalyl benzoyl benzoate.

吖啶化合物可舉出9－苯基啶、1,7－雙(9－吖啶基)庚烷等。Examples of the acridine compound include 9-phenylpyridine and 1,7-bis(9-acridinyl)heptane.

有機過氧化化合物可舉出例如過氧化三甲基環己烷、過氧化醯基丙酮、1,1－雙(第三丁基過氧)－3,3,5－三甲基環己烷、1,1－雙(第三丁基過氧)環己烷、2,2－雙(第三丁基過氧)丁烷、第三丁基過氧化氫、氫過氧化枯烯、二異丙基過氧化氫、2,5－二甲基己烷－2,5－二過氧化氫、1,1,3,3－四甲基丁基過氧化氫、過氧化第三丁基異丙苯、過氧化二異丙苯、2,5＝二甲基－2,5－二(第三丁基過氧)己烷、2,5－過氧化烷醯(2,5－oxanoyl peroxide)、過氧化琥珀酸、過氧化苯偶姻、過氧化2,4－二氯苯甲醯、二異丙基過氧化二碳酸酯、二－2－乙基己基過氧化二碳酸酯、二－2－乙氧基己基過氧化二碳酸酯、二甲氧基異丙基過氧化二碳酸酯、二(3－甲基－3－甲氧基丁基)過氧化二碳酸酯、第三丁基過氧化乙酸酯、第三丁基過氧化三甲基乙酸酯、第三丁基過氧化新癸酸酯、第三丁基過氧化辛酸酯、第三丁基過氧化月桂酸酯、第三碳酸酯、3,3’,4,4’－四－(第三丁基過氧化羰基)二苯基酮、3,3’,4,4’－四－(第三己基過氧化羰基)二苯基酮、3,3’,4,4’－四－(對異丙基異丙苯基過氧化羰基)二苯基酮、羰基二(第三丁基過氧化二氫二酞酸酯)、羰基二(第三己基過氧化二氫二酞酸酯)等。The organic peroxidic compound may, for example, be trimethylcyclohexane peroxide, decyl propyl acetonate or 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropyl Hydrogen peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butyl cumene peroxide Dicumyl peroxide, 2,5=dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-peroxidation 2,5-oxanoyl peroxide, succinic acid peroxide, benzoin peroxide, 2,4-dichlorobenzidine peroxide, diisopropylperoxydicarbonate, di-2-ethyl Hexylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, dimethoxyisopropyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl) Oxidized dicarbonate, t-butyl peroxyacetate, t-butyl peroxy trimethyl acetate, t-butyl peroxy neodecanoate, t-butyl peroxyoctanoate, Tributyl peroxylaurate, third carbonate, 3,3',4,4'-tetra-(t-butylperoxycarbonyl)diphenyl ketone, 3,3',4,4'- Tetra-(Third-hexylperoxycarbonyl)diphenyl ketone, 3,3',4,4'-tetra-(p-isopropylcumylperoxycarbonyl)diphenyl ketone, carbonyl di(third Butyl peroxydiphthalate), carbonyl di(trihexylperoxydicarboxylate), and the like.

偶氮化合物可舉出例如特開平8－108621號公報所記載之偶氮化合物等。The azo compound, for example, an azo compound described in JP-A-H08-108621.

香豆素化合物可舉出例如3－甲基－5－胺基－((s－三－2－基)胺基)－3－苯基香豆素、3－氯－5－二乙基胺基－((s－三－2－基)胺基)－3－苯基香豆素、3－丁基－5－二乙基胺基－((s－三－2－基)胺基)－3－苯基香豆素等。The coumarin compound may, for example, be 3-methyl-5-amino-((s-three) -2-yl)amino)-3-phenylcoumarin, 3-chloro-5-diethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin, 3-butyl-5-diethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin.

偶氮化合物可舉出例如美國專利第2848328號說明書、美國專利第2852379號說明書、及美國專利第2940853號說明書所記載之有機偶氮化合物、2,6－雙(4－疊氮亞苄基)－4－乙基環己酮(BAC－E)等。The azo compound may, for example, be an organic azo compound or 2,6-bis(4-azidobenzylidene) described in the specification of U.S. Patent No. 2,848,328, U.S. Patent No. 2,852,379, and U.S. Patent No. 2,940,853. 4-ethylcyclohexanone (BAC-E) and the like.

二茂金屬化合物可舉出特開昭59－152396號公報、特開昭61－151197號公報、特開昭63－41484號公報、特開平2－249號公報、特開平2－4705號公報、特開平5－83588號公報所記載之各種二茂鈦化合物、例如二環戊二烯－Ti－聯苯、二環戊二烯－Ti－雙－2,6－二氟苯－1－基、二環戊二烯－Ti－雙－2,4－二氟苯－1－基、二－環戊二烯－Ti－雙－2,4,6－三氟苯－1－基、二－環戊二烯－Ti－雙2,3,5,6－四氟苯－1－基、二－環戊二烯－Ti－雙－2,3,4,5,6－五氟苯－1－基、二－甲基環戊二烯－Ti－雙－2,6－二氟苯－1－基、二－甲基環戊二烯－Ti－雙－2,4,6－三氟苯－1－基、二－甲基環戊二烯－Ti－雙－2,3,5,6－四氟苯－1－基、二－甲基環戊二烯－Ti－雙－2,3,4,5,6－五氟苯－1－基、特開平1－304453號公報、特開平1－152109號公報所記載之鐵－芳烴錯合物等。The dimetallocene compound is disclosed in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705 Various titanocene compounds described in JP-A-H05-83588, for example, dicyclopentadiene-Ti-biphenyl, dicyclopentadiene-Ti-bis-2,6-difluorophenyl-1-yl, Dicyclopentadiene-Ti-bis-2,4-difluorophenyl-1-yl, di-cyclopentadiene-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclo Pentadiene-Ti-bis 2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadiene-Ti-bis-2,3,4,5,6-pentafluorobenzene-1- , bis-methylcyclopentadiene-Ti-bis-2,6-difluorophenyl-1-yl, bis-methylcyclopentadiene-Ti-bis-2,4,6-trifluorobenzene- 1-yl, di-methylcyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadiene-Ti-bis-2,3, An iron-aromatic hydrocarbon complex or the like described in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei.

二咪唑系化合物例如以六芳基二咪唑化合物等為佳。The diimidazole-based compound is preferably, for example, a hexaaryldiimidazole compound or the like.

六芳基二咪唑化合物可舉出例如特公平6－29285號公報、美國專利第3,479,185號、同第4,311,783號、同第4,622,286號等各說明書所記載之各種化合物，具體上可舉出2,2’－雙(鄰氯苯基)－4,4’,5,5’－四苯基二咪唑、2,2’－雙(鄰溴苯基))4,4’,5,5’－四苯基二咪唑、2,2’－雙(鄰,對溴二氯苯基))4,4’,5,5’－四苯基二咪唑、2,2’－雙(鄰氯苯基))4,4’,5,5’－肆(間甲氧基苯基)二咪唑、2,2’－雙(鄰,鄰二氯苯基))4,4’,5,5’－四苯基二咪唑、2,2’－雙(鄰硝基苯基)－4,4’,5,5’－四苯基二咪唑、2,2’－雙(鄰甲基苯基)－4,4’,5,5’－四苯基二咪唑、2,2’－雙(鄰三氟苯基)－4,4’,5,5’－四苯基二咪唑等。Examples of the hexaaryldiimidazole compound include various compounds described in the respective specifications, such as JP-A-6-29285, U.S. Patent No. 3,479,185, the entire disclosure of which is incorporated herein by reference. '-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'-four Phenyldiimidazole, 2,2'-bis(o-,p-bromodichlorophenyl))4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-chlorophenyl) 4,4',5,5'-肆(m-methoxyphenyl)diimidazole, 2,2'-bis(o-o-dichlorophenyl))4,4',5,5'-four Phenyldiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, and the like.

有機硼酸鹽化合物可舉出的具體例，例如特開昭62－143044號、特開昭62－150242號、特開平9－188685號、特開平9－188686號、特開平9－188710號、特開2000－131837號、特開2002－107916號、特許第2764769號、特願2000－310808號等各公報、及Kunz,Martin“Rad Tech’98.Proceeding April 19－22,1998年,Chicago”等所記載之有機硼酸鹽、特開平6－157623號公報、特開平6－175564號公報、特開平6－175561號公報所記載之有機硼鋶錯合物或有機硼氧鋶錯合物、特開平6－175554號公報、特開平6－175553號公報所記載之有機硼碘鎓錯合物、特開平9－188710號公報所記載之有機硼鋶錯合物、特開平6－348011號公報、特開平7－128785號公報、特開平7－140589號公報、特開平7－306527號公報、特開平7－292014號公報等之有機硼過渡金屬配位錯合物等。Specific examples of the organic borate compound include, for example, JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, Publications Nos. 2000-131837, JP-A-2002-107916, No. 2764769, and Specials 2000-310808, and Kunz, Martin "Rad Tech'98. Proceeding April 19-22, 1998, Chicago", etc. The organoboron oxime complex or the organoboron oxime complex described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The organoboron iodine complex described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. An organoboron transition metal complexing complex or the like, which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei.

二磺酸化合物可舉出例如特開昭61－166544號公報、特開2002－328465說明書等所記載之化合物等。Examples of the disulfonic acid compound include a compound described in, for example, JP-A-61-166544, JP-A-2002-328465, and the like.

肟酯化合物可舉出例如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年)202－232、特開2000－66385號公報、特開2000－80068號公報、特表2004－534797號公報所記載之化合物。The oxime ester compound can be exemplified by, for example, JCS Perkin II (1979) 1653-1660), JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232. The compounds described in JP-A-2000-66385, JP-A-2000-80068, and JP-A-2004-534797.

鎓鹽化合物可舉出例如S.I.Schlesinger,Photogr.Sci.Eng.,18,387(1974年)、T.S.Bal等人，Polymer,21,423(1980年)所記載之二唑鎓鹽、美國專利第4,069,055號說明書、特開平4－365049號等所記載之銨鹽、美國專利第4,069,055號、同4,069,056號的各說明書所記載之鎓鹽、歐洲專利第104、143號、美國專利第339,049號、同第410,201號之各說明書、特開平2－150848號公報、特開平2－296514號公報之各公報所記載之碘鎓鹽等。Examples of the onium salt compound include, for example, SISchlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBal et al., Polymer, 21, 423 (1980), and the specification of U.S. Patent No. 4,069,055. The ammonium salt described in Japanese Patent Laid-Open No. Hei 4-365049, No. 4, 069, 055, and the specification of the Japanese Patent No. 4, 069, 056, the European Patent No. 104, 143, the US Patent No. 339, 049, the same as the 410, 201 The iodonium salt described in each of the publications of JP-A No. 2-150848 and JP-A No. 2-296514.

本發明之適合使用的碘鎓鹽係二芳基碘鎓鹽，從安定性的觀點，以被2個以上烷基、烷氧基、芳氧基等電子給予性基取代為佳。又，其他較佳之碘鎓鹽形態，以三芳基碘鎓鹽之一個取代基具備鎓鹽的形態，且在300奈米以上具有吸收之碘鎓鹽等為佳。The iodonium salt-based diaryliodonium salt which is suitably used in the present invention is preferably substituted with an electron-donating group such as two or more alkyl groups, alkoxy groups or aryloxy groups from the viewpoint of stability. Further, in another preferred form of the iodonium salt, a sulfonium salt is preferably used as a substituent of the triaryl iodonium salt, and an iodonium salt having an absorption of 300 nm or more is preferred.

本發明適合使用之鋶鹽可舉出歐洲專利第370,693號、同390,214號、同233,567號、同297,443號、同297,442號、美國專利第4,933,377號、同161,811號、同410,201號、同339,049號、同4,760,013號、同4,734,444號、同2,833,827號、德國專利第2,904,626號、同3,604,580號、同3,604,581號之各說明書所記載之鎓鹽，從安定性的敏感度而言，以被電子吸引性基取代為佳。電子吸引性基之哈曼特值大0為佳。較佳之電子吸引性基可舉出鹵素原子、及羧酸等。The hydrazine salt suitable for use in the present invention is exemplified by European Patent No. 370, 693, 390, 214, 233, 567, 297, 443, 297, 442, U.S. Patent No. 4,933, 377, 161, 811, 410, 201, 339, 049. The sulfonium salts described in the specification of the same specification, which are described in the specification of 4,760,013, 4,734, 444, 2, 833, 827, German Patent No. 2, 904, 626, 3, 604, 580, and 3, 604, 581, are replaced by electron-attracting groups in terms of stability sensitivity. It is better. The Hammant value of the electron attracting base is preferably 0. Preferred examples of the electron attracting group include a halogen atom and a carboxylic acid.

又，其他較佳鋶鹽可舉出三芳基鋶鹽之一個取代基具有香豆素、蒽結構，在300奈米以上具有吸收之鋶鹽。另外之較佳鋶鹽可舉出三芳基鋶鹽具有烯丙氧基、芳硫基作為取代基之在300奈米以上具有吸收之鋶鹽。Further, as another preferred onium salt, a substituent of a triarylsulfonium salt has a coumarin and an anthracene structure, and has an absorption of an onium salt at 300 nm or more. Further, preferred sulfonium salts include sulfonium salts having an allylic oxy group and an arylthio group as a substituent having an absorption of 300 nm or more.

又，鎓鹽化合物可舉出J.V.Crivello等人，Macromolecules,10(6),1307(1977年)、J.V.Crivello等人，J.Polymer Sci.,Polymer Chem Ed.,17,1047(1979年)所記載之硒鎓鹽、C.S.Wen等人，Teh,Proc.Conf.Rad.Curing ASIA,第478頁Tokyo,10月(1988年)所記載之砷鎓鹽等鎓鹽。Further, the onium salt compound can be exemplified by JVCrivello et al., Macromolecules, 10 (6), 1307 (1977), JVCrivello et al., J. Polymer Sci., Polymer Chem Ed., 17, 1047 (1979). The selenium salts such as the selenium salts described in the Selenium Salt, CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, page 478, Tokyo, October (1988).

醯基膦(氧化物)化合物可舉出CIBA SPECIALTY CHEMICAL公司製之IRGACURE819、DAROCURE 4265、DAROCURE TPO等。Examples of the mercaptophosphine (oxide) compound include IRGACURE 819, DAROCURE 4265, and DAROCURE TPO manufactured by CIBA SPECIALTY CHEMICAL CO., LTD.

從高感度化的觀點，本發明所使用的光聚合引發劑以選自三鹵甲基三系化合物、二咪唑系化合物、肟系化合物所組成群組中至少一種化合物為佳，以二咪唑系化合物為最佳。From the viewpoint of high sensitivity, the photopolymerization initiator used in the present invention is selected from trihalomethyl three At least one of the group consisting of a compound, a diimidazole compound, and an anthraquinone compound is preferred, and a diimidazole compound is preferred.

相對於硬化性組成物的總固體成分，在本發明的硬化性組成物所含有光聚合引發劑的含量為0.1~50質量%為佳，以0.1~30質量%為更佳，以0.3~20質量%為特佳。在此範圍能夠得到良好的敏感度及圖案形成性。The content of the photopolymerization initiator contained in the curable composition of the present invention is preferably from 0.1 to 50% by mass, more preferably from 0.1 to 30% by mass, even more preferably from 0.3 to 20, based on the total solid content of the curable composition. The mass % is particularly good. Good sensitivity and pattern formation can be obtained in this range.

又，從引發劑的分解效率觀點，在本發明之(B)光聚合引發劑及(A)特定敏感劑的質量比[(B)/(A)]以0.1以上10以下為佳，以0.3以上5以下為較佳，以0.5以上3以下為更佳。Further, from the viewpoint of the decomposition efficiency of the initiator, the mass ratio [(B)/(A)] of the (B) photopolymerization initiator of the present invention and (A) the specific sensitizer is preferably 0.1 or more and 10 or less, and 0.3. The above 5 or less is preferable, and more preferably 0.5 or more and 3 or less.

<(C)聚合性化合物><(C) Polymerizable Compound>

本發明能夠使用之聚合性化合物係含有至少一個乙烯性不飽和雙鍵之加成聚合性化合物，能夠選自具有至少1個、較佳是具有2以上末端乙烯性不飽和鍵之化合物。此種化合物群在該產業領域係廣被知悉之物，在本發明，此等沒有特別限定而可以使用。此等具有例如單體、預聚物、亦即二聚物、三聚物及低聚物、或此等的混合物及此等的共聚物等化學形態。單體及其共聚物的例子能夠舉出不飽羧酸(例如，丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、異巴豆酸、順丁烯二酸等)、其酯類、醯胺類，較佳是使用不飽和羧酸與脂肪族多元醇化合物之酯、不飽和羧酸與脂肪族多元胺化合物之醯胺類。又，具有羥基或胺基、氫硫基等親核性取代基之不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類加成反應物，及與單官能或多官能羧酸之脫水縮合反應物等亦適合使用。又，具有異酸酯基或環氧基等親電子性取代基之不飽和羧酸酯或醯胺類與單官能或多官能的醇類、胺類、硫醇類之加成反應物，而且具有鹵素基、或對甲苯磺醯氧基等脫離性取代基之不飽和羧酸酯或醯胺類與單官能或多官能醇類、胺類、硫醇類之取代反應物亦適合。又，其他例子亦能夠使用不飽和磺酸、苯乙烯、乙烯醚等取代上述不飽和羧酸而成的化合物群。The polymerizable compound which can be used in the present invention is an addition polymerizable compound containing at least one ethylenically unsaturated double bond, and can be selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and in the present invention, it is not particularly limited and can be used. These have chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of the monomer and the copolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and guanamines. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. Further, an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group, and a monofunctional or polyfunctional isocyanate or epoxy addition reactant, and a monofunctional or polyfunctional group A dehydration condensation reaction product of a functional carboxylic acid or the like is also suitably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isoester group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol, A substituted carboxylic acid ester having a halogen group or a destructive substituent such as p-toluenesulfonyloxy group or a decylamine and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable. Further, in other examples, a compound group obtained by substituting an unsaturated carboxylic acid, styrene, vinyl ether or the like with the above unsaturated carboxylic acid can be used.

脂肪族多元醇化合物與不飽和羧酸之酯之單體的具體例，丙烯酸酯有乙二醇二丙烯酸酯、三甘醇二丙烯酸酯、1,3－丁二醇二丙烯酸酯、伸丁二醇二丙烯酸酯、丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三羧甲基三丙烯酸酯、三羧甲基丙烷三(丙烯醯氧基丙基)醚、三羧甲基乙烷三丙烯酸酯、己二醇二丙烯酸酯、1,4－環己二醇二丙烯酸酯、伸丁二醇二丙烯酸酯、四甘醇二丙烯酸酯、新戊四醇二丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇二丙烯酸酯、二新戊四醇六丙烯酸酯、山梨糖醇三丙烯酸酯、山梨糖醇四丙烯酸酯、山梨糖醇五丙烯酸酯、山梨糖醇六丙烯酸酯、三(丙烯醯氧基乙基)三聚異氰酸酯、聚酯型丙烯酸酯低聚物、三聚異氰酸EO改性三丙烯酸酯等。Specific examples of the monomer of the aliphatic polyol compound and the ester of an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and dibutyl Alcohol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, tricarboxymethyl triacrylate, tricarboxymethylpropane tris(propylene methoxypropyl) ether, tricarboxymethyl ethane triacrylate Ester, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, butanediol diacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate Ester, neopentyl alcohol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbus Sugar alcohol hexaacrylate, tris(propylene methoxyethyl) trimeric isocyanate, polyester acrylate oligomer, trimeric isocyanate EO modified triacrylate, and the like.

甲基丙烯酸酯有伸丁二醇二甲基丙烯酸酯、三甘醇二甲基丙烯酸酯、新戊二醇二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、三羥甲基乙烷三甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、1,3－丁二醇二甲基丙烯酸酯、己二醇二甲基丙烯酸酯、新戊四醇二甲基丙烯酸酯、新戊四醇三甲基丙烯酸酯、新戊四醇四甲基丙烯酸酯、二新戊四醇二甲基丙烯酸酯、二新戊四醇六甲基丙烯酸酯、山梨糖醇三甲基丙烯酸酯、山梨糖醇四甲基丙烯酸酯、雙[對－(3－甲基丙烯醯氧基－2－羥基丙氧基)苯]甲基甲烷、雙－[對(甲基丙烯醯氧基乙氧基)苯基]二甲基甲烷等。Methacrylates are butanediol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol B Alkenyl trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, neopentyl alcohol dimethacrylate, neopentyl Tetraol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbus Sugar alcohol tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)benzene]methylmethane, bis-[p-(methacryloxyethoxy) Phenyl] dimethylmethane and the like.

伊康酸酯有乙二醇二伊康酸酯、丙二醇二伊康酸酯、1,3－丁二醇二伊康酸酯、1,4－丁二醇二伊康酸酯、伸丁二醇二伊康酸酯、新戊四醇二伊康酸酯、山梨糖醇四伊康酸酯等。巴豆酸酯有乙二醇二巴豆酸酯、伸丁二醇二巴豆酸酯、新戊四醇二巴豆酸酯、山梨糖醇四巴豆酸酯等。異巴豆酸酯有乙二醇二異巴豆酸酯、新戊四醇二異巴豆酸酯、山梨糖醇四異巴豆酸酯等。順丁烯二酸酯有乙二醇二順丁烯二酸酯、三甘醇二順丁烯二酸酯、新戊四醇二順丁烯二酸酯、山梨糖醇四順丁烯二酸酯等。Ikonic acid esters include ethylene glycol diconconate, propylene glycol diconconate, 1,3-butanediol diconconate, 1,4-butanediol diconconate, and dibutyl Alcohol diconconate, neopentyl alcohol diconconate, sorbitol tetraconate, and the like. The crotonate is ethylene glycol dicrotonate, butanediol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate, and the like. The isocrotonate includes ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like. Maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol di maleate, sorbitol tetramaleic acid Ester and the like.

其他的酯之例子，例如有特公昭51－47334、特開昭57－196231所記載之脂肪族醇系酯類、或特開昭59－5240、特開昭59－5241、特開平2－226149所記載之具有芳香族系骨架之物、特開平1－165613所記載之含有胺基之物等。而且，前述酯單體亦能夠以混合物的形式使用。Examples of the other esters include, for example, the aliphatic alcohol esters described in JP-A-51-47334 and JP-A-57-196231, or JP-A-59-5240, JP-A-59-5241, JP-A-2-226149 The article having an aromatic skeleton, the amine group-containing product described in JP-A-1-156613, and the like. Moreover, the aforementioned ester monomers can also be used in the form of a mixture.

又，脂肪族多元胺化合物與不飽和羧酸之醯胺的單體之具體例有亞甲基雙丙烯醯胺、亞甲基雙甲基丙烯醯胺、1,6－伸己基雙丙烯醯胺、1,6－伸己基雙甲基丙烯醯胺、二伸乙三胺三丙烯醯胺、苯二甲基雙丙烯醯胺、苯二甲基雙甲基丙烯酸酯等。其他的較佳醯胺系單體可舉出例如特公昭54－21726號公報所記載之具有環己烯結構之物。Further, specific examples of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis acrylamide, methylene bis methacrylamide, and 1,6-exexyl bis acrylamide. 1,6-extended bis methacrylamide, diethylenetriamine propylene amide, benzodimethyl bis decylamine, benzene dimethyl methacrylate, and the like. Other preferable examples of the amide-based monomer include those having a cyclohexene structure described in JP-A-54-21726.

又，使用異氰酸酯與羥基的加成反應而製成的胺基甲酸酯系加成聚合性化合物亦佳，此種具體例可舉出例如特公昭48－41708號公報中所記載之對在1分子具有2個以上異氰酸酯基之聚異氰酸酯化合物，加添下述通式(A)所示之含有羥基之乙烯單體而成之在1分子中具有2個以上聚合物乙烯基之乙烯基胺基甲酸酯化合物等。In addition, a urethane-based addition polymerizable compound prepared by an addition reaction of an isocyanate and a hydroxyl group is also preferable, and a specific example thereof is described in JP-A-48-41708. A polyaminoisocyanate compound having two or more isocyanate groups, and a vinylamine group having two or more polymer vinyl groups in one molecule, which is a hydroxyl group-containing ethylene monomer represented by the following formula (A). Formate compound, etc.

CH₂ ＝C(R⁴ )COOCH₂ CH(R⁵ )OH (A)(但是，通式(A)中，R⁴ 及R⁵ 係表示H或CH₃ )CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH (A) (however, in the formula (A), R ⁴ and R ⁵ represent H or CH ₃ )

又，特開昭51－37193號、特公平2－32293號、及特公平2－16765號所記載之丙烯酸胺基甲酸酯類、特公昭58－49860號、特公昭56－17654號、特公昭62－39417號、及特公昭62－39418號所記載之具有環氧乙烷系骨架之胺基甲酸酯化合物類亦佳。而且藉由使用特開昭63－277653號、特開昭63－260909號、及特開平1－105238號所記載之在分子內具有胺基結構或硫醚結構之加成聚合性化合物，能夠得到感光速度非常優良之光聚合性組成物。In addition, the urethane urethanes described in JP-A-53-37193, JP-A No. 2-32293, and JP-A No. 2-16765, JP-A-58-49860, JP-A-56-17654, and TEL A urethane compound having an ethylene oxide-based skeleton described in No. 62-39417 and Japanese Patent Publication No. 62-39418 is also preferred. In addition, it is possible to obtain an addition polymerizable compound having an amine structure or a thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-10-15238. A photopolymerizable composition having a very excellent photospeed.

其他的例子，可舉出例如特開昭48－64183號、特公昭49－43191號、及特公昭52－30490號各公報所記載之聚酯型丙烯酸酯類、及環氧樹脂與(甲基)丙烯酸而成之環氧丙烯酸酯類等多官能丙烯酸酯或甲基丙烯酸酯。又，亦可舉出例如特公昭46－43946號、特公平1－40337號、及特公平1－40336號各公報所記載之特定不飽和化合物、或特開平2－25493號所記載之乙烯基磺酸系化合物。又，某種情況下，特開昭61－22048號所記載之含有全氟烷基結構係適合使用的。而且，亦可使用日本黏著協會刊物第20卷、第7期、第300~308頁(1984年)介紹作為光硬化性單體及低聚物之物。Other examples include polyester acrylates, epoxy resins, and (methyl groups) described in each of JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate. In addition, the specific unsaturated compound described in each of the publications of Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. A sulfonic acid compound. Further, in some cases, the perfluoroalkyl group-containing structure described in JP-A-61-22048 is suitably used. Moreover, it is also possible to introduce a photocurable monomer and an oligomer by using the Journal of the Japan Adhesive Society, Vol. 20, No. 7, and pages 300 to 308 (1984).

此等加成聚合性化合物之結構、單獨使用或並用、添加量使用方法之詳細能夠配合硬化性組成物最後性能設計而任意設定。例如，能夠從以下觀點選擇。The details of the structure of the addition polymerizable compound, the use alone or in combination, and the method of using the addition amount can be arbitrarily set in accordance with the final performance design of the curable composition. For example, it can be selected from the following points of view.

從敏感度而言，以每1分子之不飽和基含量多的結構為佳，多半情況係以2官能基以上為佳。又，為了提高硬化膜的強度，以3官能基以上之物為更佳，而且，藉由並用不同官能基數、不同聚合性基(例如丙烯酸酯、甲基丙烯酸酯、苯乙烯系化合物、乙烯基醚系化合物)，來調節敏感度及強度雙方的方法亦是有效的。From the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferred, and most of the cases are preferably a bifunctional group or more. Further, in order to increase the strength of the cured film, a trifunctional or higher group is more preferable, and a different functional group or a different polymerizable group (for example, acrylate, methacrylate, styrene compound, vinyl) is used in combination. The ether compound) is also effective in adjusting both sensitivity and strength.

又，對於與在硬化性組成物及感光性組成物所含有的其他成分(例如，光聚合引發劑、著色劑(顏料、染料)等、黏合劑聚合物等)之相溶性、分散性，加成聚合化合物的選擇、使用方法係重要因素，例如藉由使用低純度化合物或並用2種以上，能夠提升相溶性。又，為了提高與基板等的黏附性之目的，亦能夠選擇特定結構。In addition, compatibility and dispersibility with other components (for example, a photopolymerization initiator, a colorant (pigment, dye), a binder polymer, etc.) contained in the curable composition and the photosensitive composition are added. The selection and use method of the polymerized compound are important factors, and for example, by using a low-purity compound or a combination of two or more types, compatibility can be improved. Further, in order to improve adhesion to a substrate or the like, a specific structure can be selected.

<(D)著色劑><(D) colorant>

本發明之硬化性組成物含有著色劑。The curable composition of the present invention contains a colorant.

在本發明之硬化性組成物所含有的著色劑沒有特別限制，能夠使用1種或混合2種以上先前眾所周知的各種染料或顏料。從耐光性的觀點而言，該著色劑以顏料為佳。The coloring agent contained in the curable composition of the present invention is not particularly limited, and one type or a mixture of two or more kinds of previously known various dyes or pigments can be used. From the viewpoint of light resistance, the colorant is preferably a pigment.

本發明的硬化性組成物能夠使用先前已知的各種無機顏料或有機顏料。考慮無機顏料或有機顏料以高透射率為佳時，以盡可能使用較細之物為佳，考慮處理性時，上述顏料的平均粒徑以0.01微米~0.1微米為佳，以0.01微米~0.05微米為更佳。又，上述無機顏料可舉出金屬氧化、金屬錯合物等所示之金屬化合物。具體上可舉出鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等金屬氧化物及前述金屬的複合氧化物。The curable composition of the present invention can use various inorganic pigments or organic pigments previously known. When it is considered that the inorganic pigment or the organic pigment has a high transmittance, it is preferable to use a finer substance as much as possible. When considering the handleability, the average particle diameter of the above pigment is preferably 0.01 μm to 0.1 μm, and 0.01 μm to 0.05 μm. Micron is better. Further, the inorganic pigment may be a metal compound represented by metal oxidation or a metal complex. Specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

有機顏料可舉出例如C.I.顏料黃11、24、31、53、83、93、99、108、109、110、138、139、147、150、151、154、155、167、180、185、199；C.I.顏料橙36、38、43、71；C.I.顏料紅81、105、122、149、150、155、171、175、176、177、209、220、224、242、254、255、264、270；C.I.顏料紫19、23、32、39；C.I.顏料藍1、2、15、15：1、15：3、15：6、16、22、60、66；C.I.顏料綠7、36、37；C.I.顏料棕25、28；C.I.顏料黑1、7；碳黑等。The organic pigment may, for example, be CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199. CI Pigment Orange 36, 38, 43, 71; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270 CI Pigment Violet 19, 23, 32, 39; CI Pigment Blue 1, 2, 15, 15:1, 15:3, 15:6, 16, 22, 60, 66; CI Pigment Green 7, 36, 37; CI pigment brown 25, 28; CI pigment black 1, 7; carbon black and the like.

本發明特別在顏料的結構式中以使用具有鹼性的N原子之物為佳。具有此時鹼性的N原子之顏料在本發明的組成物中顯示良好的分散性。其原因雖未充分地解釋明白，可推定係感光性聚合成分與顏料的親和性良好之影響。The present invention is particularly preferably used in the structural formula of the pigment to use a substance having a basic N atom. The pigment having the N atom which is basic at this time exhibits good dispersibility in the composition of the present invention. Although the reason for this is not fully explained, it is estimated that the affinity of the photosensitive polymerizable component and the pigment is good.

在本發明之能夠使用的較佳顏料，能夠舉出以下之。但是本發明未限定於此等。Preferred pigments which can be used in the present invention include the following. However, the present invention is not limited to this.

有機顏料可舉出例如C.I.顏料黃11、24、108、109、110、138、139、150、151、154、167、180、185；C.I.顏料橙36、71；C.I.顏料紅122、150、171、175、177、209、224、242、254、255、264；C.I.顏料紫19、23、32；C.I.顏料藍15：1、15：3、15：6、16、22、60、66；C.I.顏料黑1；此等有機顏料可單獨或是組合各種使用來提高色純度。上述組合的具體例如以下所示。例如，例如紅顏料可舉出蒽醌系顏料、苝系顏料、二氧代吡咯系顏料單獨或其等之中至少一種與二重氮系黃色顏料、異吲哚滞系黃色顏料、喹啉黃系黃色顏料或苝系紅色顏料的混合等。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，氧代吡咯系顏料可舉出C.I.顏料紅254，從色再現性而言，以與C.I.顏料黃139混合為佳。又，紅色顏料及黃色顏料的質量比以100：5~100：50為佳。100：4以下時會有因抑制從400奈米至500奈米的光透射率困難，而難以提高色純度的情形。又，100：51以上時，因主波長變為短波長，會有從NTSC目標色相偏移大的情形。特別是上述質量比以100：10~100：30的範圍為最佳。又，組合紅色顏料之間時，能夠配向色度來調整。The organic pigment may, for example, be CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36, 71; CI Pigment Red 122, 150, 171 , 175, 177, 209, 224, 242, 254, 255, 264; CI Pigment Violet 19, 23, 32; CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; CI Pigment Black 1; these organic pigments can be used singly or in combination to improve color purity. Specific examples of the above combinations are as follows. For example, examples of the red pigment include at least one of an anthraquinone pigment, an anthraquinone pigment, a dioxopyrrole pigment alone or the like, a diazo yellow pigment, an isoindole yellow pigment, and quinoline yellow. It is a mixture of a yellow pigment or a lanthanide 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 exemplified as oxo pigment, and color reproducibility is used. It is better to mix with CI Pigment Yellow 139. Further, the mass ratio of the red pigment to the yellow pigment is preferably from 100:5 to 100:50. When it is 100:4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm, and it is difficult to increase the color purity. Further, when 100:51 or more, since the dominant wavelength becomes a short wavelength, there is a case where the color shift from the NTSC target is large. In particular, the above mass ratio is preferably in the range of 100:10 to 100:30. Further, when the red pigments are combined, the chromaticity can be adjusted to adjust.

又，綠色顏料能夠單獨使用鹵化酞青系顏料或是混合使用其與二重氮系黃色顏料、奎酞酮系黃色顏料、甲亞胺或異吲哚滿系黃色顏料。例如，此種例子以混合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為佳。綠顏料與黃色顏料的質量比以100：5~100：150為佳。上述質量比小於100：5時，會有因抑制從400奈米至450奈米的光透射率困難，而難以提高色純度的情形。又，大於100：150以上時，因主波長變為長波長，會有從NTSC目標色相偏移大的情形。特別是上述質量比以100：30~100：120的範圍為最佳。Further, the green pigment can be used alone or in combination with a diazo yellow pigment, a quinacone yellow pigment, a methylimine or an isoindane yellow pigment. 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 green pigment to yellow pigment is preferably from 100:5 to 100:150. When the mass ratio is less than 100:5, it is difficult to suppress the light transmittance from 400 nm to 450 nm, and it is difficult to increase the color purity. Moreover, when it is more than 100:150 or more, since the dominant wavelength becomes a long wavelength, there is a case where the color shift from the NTSC target is large. In particular, the above mass ratio is preferably in the range of 100:30 to 100:120.

藍色顏料能夠單獨使用酞青系顏料、或是混合使用其與二系紫色顏料。例如混合C.I.顏料藍15：6與C.I.顏料紫23為佳。藍色顏料與紫色顏料的質量比以100：0~100：30為佳，以100：10以下為更佳。Blue pigment can be used alone or in combination with two It is a purple pigment. For example, it is preferred to mix CI Pigment Blue 15:6 with CI Pigment Violet 23. The mass ratio of the blue pigment to the purple pigment is preferably 100:0 to 100:30, and more preferably 100:10 or less.

又，黑色矩陣用顏料能夠單獨或混合使用碳黑、鈦黑、氧化鐵、氧化鈦，以組合碳黑及鈦黑為佳。又，碳黑與鈦黑的質量比以100：0~100：60的範圍為佳。100：61以上時，會有分散安定性下降的情形。Further, the black matrix pigment can be used alone or in combination of carbon black, titanium black, iron oxide, or titanium oxide, and carbon black and titanium black are preferably combined. 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, the dispersion stability may be lowered.

在本發明，著色劑係染料時，能夠在組成物中均勻地溶解而得到硬化性組成物。In the case of the coloring agent-based dye of the present invention, the composition can be uniformly dissolved to obtain a curable composition.

在本發明的硬化性組成物中能夠含有而使用作為著色劑之染料沒有特別限制，能夠使用先前作為彩色濾光片用而眾所周知的染料。能夠使用例如特開昭64－90403號公報、特開昭64－91102號公報、特開平1－94301號公報、特開平6－11614號公報、特登2592207號公報、美國專利第4,808,501明書、美國專利第5,667920號說明書、美國專利第5,059,500號說明書、特開平5－333207號公報、特開平6－35183號公報、特開平6－51115號公報、特開平6－194828號公報、特開平8－211599號公報、特開平4－249549號公報、特開平10－123316號公報、特開平11－302283號公報、特開平7－286107號公報、特開2001－4823號公報、特開平8－15522號公報、特開平8－29771號公報、特開平8－146215號公報、特開平11－343437號公報、特開平8－62416號公報、特開2002－14220號公報、特開2002－14221號公報、特開2002－14222號公報、特開2002－14223號公報、特開平8－302224號公報、特開平8－73758號公報、特開平8－179120號公報、及特開平8－151531號公報所揭示之色料。The dye which can be contained in the curable composition of the present invention and used as a coloring agent is not particularly limited, and a dye which has been conventionally used as a color filter can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A No. 2,592,207, and US Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. Hei. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The color material disclosed.

化學結構能夠使用吡唑偶氮系、苯胺基偶氮系、三苯基甲烷系、蒽醌系、蒽吡啶酮系、亞苄基系、桑醇系、吡唑***偶氮系、吡啶酮偶氮系、花青苷系、啡噻系、吡咯吡咯偶氮甲川系、系、酞青系、苯并吡喃系、及靛藍系等染料。The chemical structure can use a pyrazole azo system, an anilino azo system, a triphenylmethane system, a guanidine system, an anthrapyridone system, a benzylidene group, Mulcan alcohol, pyrazole triazole azo, pyridone azo, anthocyanin, thiophene Department, pyrrolizirazo azomethine, Dyes such as phthalocyanine, indigo, benzopyran, and indigo.

又，進行水或鹼顯像之光阻系時，從藉由顯像來完全地除去光未照射部分的黏合劑及/或染料之觀點，會有酸性染料及/或其衍生物係適合使用之情形。Further, when performing a light-resistance system of water or alkali development, an acid dye and/or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and/or the dye in the unirradiated portion by development. The situation.

此外，使用直接染料、鹼性染料、媒染染料、酸性媒染染料、偶氮染料、分散染料、油溶染料、食品染料、及/或此等的衍生物等亦是有用的。Further, it is also useful to use a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azo dye, a disperse dye, an oil-soluble dye, a food dye, and/or such a derivative.

酸性染料未特別限定於具有磺酸或羧酸等酸性基之物，可考慮在有機溶劑或顯像液中的溶解性、與鹼性化合物之鹽形成性、吸光度、與組成物中之其他成分的互相作用、耐光性及耐熱性等全部必要的性能來選擇。The acid dye is not particularly limited to a substance having an acidic group such as a sulfonic acid or a carboxylic acid, and is considered to have solubility in an organic solvent or a developing solution, salt formability with a basic compound, absorbance, and other components in the composition. The choice of all necessary properties such as interaction, light resistance and heat resistance.

以下舉出酸性染料的具體例，但是未限定於此等。例如可舉出酸性茜素紫N(acid alizarin violet N)；酸性黑(acid black)1、2、24、48；酸性藍1、7、9、15、18、23、25、27、29、40、45、62、70、74、80、83、86、87、90、92、103、112、113、120、129、138、147、158、171、182、192、243、324：1；酸性鉻紫K；酸性品紅；酸性綠1、3、5、9、16、25、27、50；酸性橙6、7、8、10、12、50、51、52、56、63、74、95；酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、183、198、211、215、216、217、249、252、257、260、266、274；酸性紫6B、7、9、17、19；酸性黃1、3、7、9、11、17、23、25、29、34、36、42、54、72、73、76、79、98、99、111、112、114、116、184、243；食品黃3及此等染料的衍生物。Specific examples of the acid dye are listed below, but are not limited thereto. For example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324:1; Acid chrome violet K; acid fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87 , 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249 , 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54 , 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; food yellow 3 and derivatives of such dyes.

此等之中，酸性染料以酸性黑24；酸性藍23、25、29、62、80、86、87、92、138、158、182、243、324：1；酸性橙8、51、56、63、74；酸性紅1、4、8、34、37、42、52、57、80、97、114、143、145、151、183、217；酸性紫7；酸性黃17、25、29、34、42、72、76、99、111、112、114、116、184、243；酸性綠25等染料及此等染料的衍生物為佳。Among these, acid dyes are acid black 24; acid blues 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324:1; acid oranges 8, 51, 56, 63, 74; acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217; acid purple 7; acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; dyes such as acid green 25 and derivatives of such dyes are preferred.

又，上述以外之偶氮系、系、酞青系的酸性染料亦佳，C.I.溶劑藍44、38；C.I.溶劑橙45；使用若丹明B、若丹明110等酸性染料及此等染料的衍生物亦佳。Moreover, the azo system other than the above, The acid dyes of the system and the indigo are also good, CI solvent blue 44, 38; CI solvent orange 45; acid dyes such as rhodamine B, rhodamine 110 and derivatives of such dyes are also preferred.

其中，(D)著色劑以選自三烯丙基甲烷系、蒽醌系、次甲基偶氮系、亞苄基系、桑醇系、花青苷系、啡噻系、吡咯吡唑甲亞胺系、系、酞青系、苯并吡喃系、靛藍系、吡唑偶氮系、苯胺基偶氮系、吡唑***偶氮系、吡啶酮偶氮系、蒽吡啶酮系之著色劑為佳。Wherein (D) the colorant is selected from the group consisting of triallyl methane, lanthanide, methine azo, benzylidene, Mulberry alcohol, anthocyanin, thiophene Department, pyrrolidazole-methylimine, a coloring agent of a system, a phthalocyanine, a benzopyran, an indigo, a pyrazole azo, an anilino azo, a pyrazole triazole azo, a pyridone azo, or an anthrapyridone .

在本發明能夠使用的著色劑以染料、或是以平均粒徑r(單位奈米)為20≦r≦300、較佳是125≦r≦250、特佳是30≦r≦200之顏料為佳。藉由使用此種平均粒徑r的顏料，能夠得到高對比、且高光透射率的紅色或綠色的像素。在此「平均粒徑」係意指顏料的一次粒徑(單微結晶)聚集而成的二次粒子之平均粒徑。The coloring agent which can be used in the present invention is a dye or a pigment having an average particle diameter r (unit nm) of 20 ≦r ≦ 300, preferably 125 ≦r ≦ 250, particularly preferably 30 ≦ r ≦ 200. good. By using such a pigment having an average particle diameter r, a red or green pixel having high contrast and high light transmittance can be obtained. Here, the "average particle diameter" means the average particle diameter of the secondary particles obtained by aggregating the primary particle diameter (single microcrystal) of the pigment.

又，在本發明能夠使用之顏料的二次粒子的粒徑分布(以下簡稱「粒徑分布」)，在(平均粒徑±100)奈米之二次粒子以佔整體70質量%以上、較佳是80質量%以上為佳。Moreover, in the particle size distribution of the secondary particles of the pigment which can be used in the present invention (hereinafter referred to as "particle size distribution"), the secondary particles of (average particle diameter ± 100) nm account for 70% by mass or more of the total. Preferably, it is preferably 80% by mass or more.

具有前述的平均粒徑及粒徑分布之顏料能夠藉由將市售的顏料、與依情況而使用之其他顏料(平均粒徑通常大於300奈米)一同，較佳是與分散液及溶劑混合成為顏料混合液的方式，使用例如球磨機、輥磨機等粉碎機，邊粉碎邊混合、分散來進行調製。如此進行所得到的顏料通常具有顏料分散液的形態。The pigment having the above average particle diameter and particle size distribution can be mixed with a dispersion and a solvent by using a commercially available pigment together with other pigments (having an average particle diameter of usually more than 300 nm) as the case may be. The method of forming the pigment mixture liquid is prepared by mixing and dispersing while pulverizing using a pulverizer such as a ball mill or a roll mill. The pigment obtained in this manner usually has a form of a pigment dispersion liquid.

相對於硬化性組成物的總固體成分，在本發明的硬化性組成物所含有的(D)著色劑的含量以25~95質量%為佳，以30~90質量%為較佳，以40~80質量%為更佳。The content of the (D) coloring agent contained in the curable composition of the present invention is preferably from 25 to 95% by mass, preferably from 30 to 90% by mass, based on the total solid content of the curable composition. ~80% by mass is more preferred.

著色劑太少時，藉由本發明的硬化性組成物製造彩色濾光片時會有無法得到適當色度之傾向。另一方面，太多時會有因光硬化無法充分進行而使膜強度降低、又，會有在鹼顯像時顯像範圍變窄的傾向，但是因為本發明之特定敏化劑之光吸收率高，即便在硬化性組成物中高濃度地含有，亦能夠發揮顯著地提高敏感度之效果。When the amount of the coloring agent is too small, when a color filter is produced by the curable composition of the present invention, an appropriate chromaticity tends not to be obtained. On the other hand, when it is too much, the film hardening may not be sufficiently performed, and the film strength may be lowered, and the development range may be narrowed during alkali development. However, the light absorption of the specific sensitizer of the present invention is caused. The rate is high, and even if it is contained in a high concentration in the curable composition, the effect of remarkably improving the sensitivity can be exerted.

本發明之硬化性組成物按照必要亦能夠與上述說明之(A)特定敏化劑、(B)光聚合引發劑、(C)聚合性化合物、及(D)著色劑一同，更含有以下所詳述的任意成分。以下，說明在本發明之硬化性組成物能夠含有之任意成分。The curable composition of the present invention may further contain the following (A) specific sensitizer, (B) photopolymerization initiator, (C) polymerizable compound, and (D) colorant, as described above, Any ingredients detailed. Hereinafter, any component which can be contained in the curable composition of the present invention will be described.

<(E)分散劑><(E) Dispersant>

本發明的硬化性組成物含有顏料作為(D)著色劑時，從提高該顏料的分散性之觀點，以添加(E)分散劑為佳。When the curable composition of the present invention contains a pigment as the coloring agent (D), it is preferred to add the (E) dispersant from the viewpoint of improving the dispersibility of the pigment.

本發明能夠使用的分散劑(顏料分散劑)可舉出高分子分散劑[例如聚醯胺胺(polyamide amine)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、烷醇胺、顏料衍生物等。The dispersing agent (pigment dispersing agent) which can be used in the present invention is exemplified by a polymer dispersing agent [for example, polyamide amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, and a modified poly Carbamate, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate, polyoxygen A vinyl alkylamine, an alkanolamine, a pigment derivative or the like.

高分子分散劑能夠分類成直鏈狀高分子、末端改性高分子、接枝型高分子、及嵌段型高分子。The polymer dispersant can be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer.

高分子分散劑係吸著於顏料表面，其作用能夠防止再凝聚。為了此目的可舉出之較佳結構有對顏料表面具有固定部位之末端改性型高分子、接枝型高分子、及嵌段型高分子。另一方面，顏料衍生物藉由改質而具有促進高分子分散劑的吸附之效果。The polymer dispersant is adsorbed on the surface of the pigment to prevent re-agglomeration. A preferred structure for this purpose is a terminal-modified polymer having a fixed portion on the surface of the pigment, a graft-type polymer, and a block-type polymer. On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modification.

本發明能夠使用之顏料分散劑的具體例可舉出BYK Chemie公司製「Disperbyk－101(聚醯胺胺磷酸鹽)、107(羧酸酯)、110(含酸基之共聚物)、130(聚醯胺)、161、162、163、164、165、166、170(高分子共聚物)」、「BYK－P104、P105(高分子量不飽和聚羧酸)、EFKA公司製「EFKA4047、4050、4010、4165(聚胺基甲酸酯系)、EFKA4330、4340(嵌段共聚物)、4400、4402(改性聚丙烯酸酯)、5010(聚酯型醯胺)、5765(高分子量聚羧酸鹽)、6220(脂肪酸聚酯)、6745(酞青衍生物)、6750(偶氮顏料衍生物)」、AJINOMOTO FINETECHNO公司製「AJISPAR PB821、PB822」、共榮社化學公司製「FROLEN TG－710(胺基甲酸酯低聚物)」、「POLYFRO No.50E、No.300(丙烯酸系共聚物)」、楠本化成公司製「DISPARON KS－860、873SN、874、#2150(脂肪族多元羧酸)、#7004(聚醚酯)、DA－703－50、DA－705、DA－725」、花王公司製「DEMOL RN、N(萘磺酸福馬林縮聚物)、MS、C、SN－B(芳香族磺酸福馬林縮聚物)」、「HOMOGENOL L－18(高分子多元羧酸)」、「EMAGEN920、930、935、985(聚氧乙烯壬基苯基醚)」、「ACETAMINE 86(硬脂醯胺乙酸酯)」、LUBRIZOL公司製「SOLUSPARS 5000(酞青衍生物)、22000(偶氮顏料衍生物)、13240(聚酯型胺)、3000、17000、27000(在末端具有功能部之高分子)、24000、28000、32000、38500(接枝型高分子)」、NIKKO CHEMICAL公司製「NIKKOL T106(聚氧乙烯山梨糖醇酐一油酸酯)、MYS－IEX(聚氧乙烯一硬脂酸酯)」等。Specific examples of the pigment dispersant which can be used in the present invention include "Disperbyk-101 (polyammoniumamine phosphate), 107 (carboxylate), 110 (acid group-containing copolymer), 130 (manufactured by BYK Chemie Co., Ltd.). Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA 4047, 4050, EFKA) 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylic acid) Salt), 6220 (fatty acid polyester), 6745 (anthracene derivative), 6750 (azo pigment derivative), "AJISPAR PB821, PB822" manufactured by AJINOMOTO FINETECHNO Co., Ltd., "FROLEN TG-710" manufactured by Kyoeisha Chemical Co., Ltd. (Amino acid ester oligomer), "POLYFRO No. 50E, No. 300 (acrylic copolymer)", "Nanmoto Chemical Co., Ltd." "DISPARON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylate) Acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation "DEMOL RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN- B (aromatic sulfonate fumarate polycondensate), "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMAGEN920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMINE 86" (stearylamine acetate)", "SOLUSPARS 5000 (indigo derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 manufactured by LUBRIZOL Co., Ltd. (at the end) "polymer of functional parts", 24000, 28000, 32000, 38500 (graft type polymer)", "NIKKOL T106 (polyoxyethylene sorbitan monooleate) manufactured by NIKKO CHEMICAL Co., Ltd., MYS-IEX (polyoxygen) Ethylene monostearate) and the like.

該等分散劑可單獨使用、亦可組合使用2種以上。These dispersing agents may be used singly or in combination of two or more.

在本發明，以組合使用顏料衍生物及高分子分散劑為特佳。In the present invention, it is particularly preferred to use a pigment derivative and a polymer dispersant in combination.

相對於顏料，在本發明之分散劑的含量以1~80質量%為佳，以5~70質量%為較佳，以10~60質量%為更佳。The content of the dispersant in the present invention is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, even more preferably from 10 to 60% by mass, based on the pigment.

具體上，使用高分子分散劑時，相對於顏料其使用量以5~100質量%的範圍為佳，以10~80質量%的範圍為更佳。Specifically, when a polymer dispersant is used, the amount of the pigment used is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass.

使用顏料衍生物時，相對於顏料其使用量以1~30質量%的範圍為佳，以3~20質量%的範圍為更佳，以5~15質量%的範圍為特佳。When a pigment derivative is used, the amount thereof is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, even more preferably from 5 to 15% by mass.

在本發明，使用顏料及分散劑作為著色劑時，從硬化敏感度、色濃度的觀點，相對於構成硬化性組成物之總固體成分，顏料及分散劑之含量的總和，以30質量%以上90質量%以下的範圍為佳，以40質量%以上85質量%以下的範圍為較佳，以50質量%以上80質量%以下的範圍為更佳。In the present invention, when a pigment or a dispersing agent is used as the coloring agent, the total content of the pigment and the dispersing agent is 30% by mass or more based on the total solid content of the curable composition from the viewpoint of the curing sensitivity and the color density. A range of 90% by mass or less is preferable, and a range of 40% by mass or more and 85% by mass or less is preferable, and a range of 50% by mass or more and 80% by mass or less is more preferable.

<(F)黏合劑聚合物><(F) binder polymer>

本發明之硬化性組成物為了提升皮膜特性等目的，亦可按照必要更使用黏合劑聚合物。黏合劑以使用線形有機聚合物為佳。此種「線形有機聚合物」，能夠任意地使用眾所周知之物。為了能夠進行水顯像或弱鹼水顯像，以選自在水或弱鹼水中具有可溶性或潤脹性之線形有機聚合物為佳。線形有機聚合物不僅是作為皮膜形成劑，亦能夠按照用途選擇使用水、弱鹼水或有機溶劑顯像劑。例如使用水可溶性有機聚合物時能夠進行水顯像。此種線形有機聚合物可舉出在側鏈具有羧酸基之自由基聚合體，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54－92723號、特開昭59－53836號、特開昭59－71048號所記載之物，亦即單獨或共聚合具有羧基之單體而成之樹脂、將單獨或共聚合具有酸酐之單體而成之酸酐單元加水分解或半酯化或半醯胺化而成之樹脂、使用不飽和單羧酸及酸酐將環氧樹脂改性而成之環氧丙烯酸酯等。具有羧基之單體可舉出丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、順丁烯二酸、酞酸、及4－羧基苯乙烯等，具有酸酐之單體可舉出順丁烯二酸酐等。The curable composition of the present invention may further use a binder polymer as necessary for the purpose of improving film properties and the like. The binder is preferably a linear organic polymer. Such a "linear organic polymer" can be arbitrarily used as a well-known thing. In order to enable water development or weak alkaline water development, it is preferred to select a linear organic polymer which is soluble or swellable in water or weakly alkaline water. The linear organic polymer is not only used as a film forming agent, but also water, weak alkaline water or an organic solvent developing agent can be selected depending on the application. For example, water development can be performed when a water-soluble organic polymer is used. Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain, for example, JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, and JP 59-25957 No. 54-92723, JP-A-59-53836, JP-A-59-71048, which is a resin obtained by polymerizing a monomer having a carboxyl group alone or in combination. An acid anhydride unit obtained by polymerizing a monomer having an acid anhydride, a resin obtained by hydrolyzing or semi-esterifying or semi-esterifying, and an epoxy acrylate obtained by modifying an epoxy resin using an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, citric acid, and 4-carboxystyrene. The monomer having an acid anhydride may be exemplified by methacrylic acid. Anhydride, etc.

又，同樣地有在側鏈具有羧酸基之酸性纖維素衍生物。此外，在具有羥基之聚合物加添環狀酸酐而成之物等係有用的。Further, similarly, there is an acidic cellulose derivative having a carboxylic acid group in a side chain. Further, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group.

使用鹼可溶性樹脂作為共聚物時，共聚合化合物亦能夠使用前述所舉出單體之外的單體。其他單體可舉出例如下述(1)~(12)之化合物。When an alkali-soluble resin is used as the copolymer, the copolymerizable compound can also use a monomer other than the above-mentioned monomers. The other monomer may, for example, be a compound of the following (1) to (12).

(1)丙烯酸2－羥基乙酯、丙烯酸2－羥基丙酯、丙烯酸3－羥基丙酯、丙烯酸4－羥基丙酯、甲基丙烯酸2－羥基乙酯、甲基丙烯酸2－羥基丙酯、甲基丙烯酸3－羥基丙酯、甲基丙烯酸4－羥基丁酯等具有脂肪族羥基之丙烯酸酯類、及甲基丙烯酸酯類。(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, A An acrylate having an aliphatic hydroxy group such as 3-hydroxypropyl acrylate or 4-hydroxybutyl methacrylate, and a methacrylate.

(2)丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸異丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸2－乙基己酯、丙烯酸辛酯、丙烯酸苄酯、丙烯酸－2－氯乙酯、丙烯酸甘油酯、丙烯酸3,4－環氧環己基甲酯、丙烯酸乙烯酯、丙烯酸2－苯基乙烯酯、丙烯酸1－丙烯酯、丙烯酸烯丙酯、丙烯酸2－丙烯醯氧基乙酯、及丙烯酸炔丙酯等丙烯酸烷酯。(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid - 2-chloroethyl ester, glyceryl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-propene acrylate An alkyl acrylate such as oxyethyl ester or propargyl acrylate.

(3)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2－乙基己酯、甲基丙烯酸環己酯、甲基丙烯酸苄酯、甲基丙烯酸2－氯乙酯、甲基丙烯酸環氧丙酯、甲基丙烯酸3,4－環氧環己基甲酯、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、及甲基丙烯酸炔丙酯等甲基丙烯酸烷酯。(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, methacrylic acid 2 -ethylhexyl ester, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, Vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate An alkyl methacrylate.

(4)丙烯醯胺、甲基丙烯醯胺、N－羥甲基丙烯醯胺、N－乙基丙烯醯胺、N－己基甲基丙烯醯胺、N－環己基丙烯醯胺、N－羥基乙基丙烯醯胺、N－苯基丙烯醯胺、N－硝基苯基丙烯醯胺、N－乙基－N－苯基丙烯醯胺、乙烯基丙烯醯胺、乙烯基甲基丙烯醯胺、N,N－二烯丙基丙烯醯胺、N,N－二烯丙基甲基丙烯醯胺、烯丙基丙烯醯胺、及烯丙基甲基丙烯醯胺等丙烯醯胺或甲基丙烯醯胺。(4) acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyl Ethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide , N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, and allyl methacrylamide, etc. Acrylamide.

(5)乙基乙烯基醚、2－氯乙基乙烯基醚、羥基乙基乙烯基醚、丙基乙烯基醚、丁基乙烯基醚、辛基乙烯基醚、及苯基乙烯基醚等乙烯基醚類。(5) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether, etc. Vinyl ethers.

(6)乙酸乙烯酯、氯乙酸乙烯酯、丁酸乙烯酯、及苯甲酸乙烯酯等乙烯酯類。(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(7)苯乙烯、α－甲基苯乙烯、甲基苯乙烯、氯甲基苯乙烯、及對乙醯氧苯乙烯等苯乙烯類。(7) Styrene such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-ethoxyphenol.

(8)甲基乙烯基酮、乙基乙烯基酮、丙基乙烯基酮、及苯基乙烯基酮等乙烯基酮。(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(9)乙烯、丙烯、異丁烯、丁二烯、及異戊二烯等烯烴類。(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10)N－乙烯基吡咯啶酮、丙烯腈、及甲基丙烯腈等。(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like.

(11)順丁烯二醯亞胺、N－丙烯醯基丙烯醯胺、N－乙醯基甲基丙烯醯胺、N－丙醯甲基丙烯醯胺、N－(對氯苯甲醯基)甲基丙烯醯等不飽和醯亞胺。(11) maleimide, N-propylene decyl acrylamide, N-ethyl decyl methacrylamide, N-propion methacrylamide, N-(p-chlorobenzoyl amide An unsaturated quinone imine such as methacryl oxime.

(12)在α位有雜原子鍵結之甲基丙烯酸系單體。可舉出例如特願2001－115595號說明書、及特願2001－115598號說明書所記載之化合物。(12) A methacrylic monomer having a hetero atom bond at the α position. For example, the compounds described in the specification of Japanese Patent Application No. 2001-115595 and the specification of Japanese Patent Application No. 2001-115598 can be mentioned.

此等之中，在側鏈具有烯丙基或乙烯酯基及羧基之(甲基)丙烯酸樹脂及在特開2000－187322號公報、特開2002－62698號公報所記載之在側鏈具有雙鍵之鹼可溶性樹脂、或特開2001－242612號公報所記載之在側鏈具有醯胺基之鹼可溶性樹脂，因為膜強度、敏感度、顯像性之平衡性優良，乃是合適的。Among these, a (meth)acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and a double chain in the side chain described in JP-A-2000-187322 and JP-A-2002-62698 The alkali-soluble resin having a guanamine group in the side chain described in JP-A-2001-242612 is suitable because it has excellent balance between film strength, sensitivity, and developability.

又，特公平7－12004號公報、特公平7－120041號公報、特公平7－120042號公報、特公平8－12424號公報、特開昭63－287944號公報、特開昭63－287947號公報、特開平1－271741號公報、特願平10－116232號公報所記載之在側鏈含有酸基之胺基甲酸酯系黏合劑聚合物、或特開2002－107918公報所記載之在側鏈具有酸基及雙鍵之胺基甲酸酯系黏合劑聚合物，因為強度非常優良，就耐刷性、低曝光適合性而言乃是有利的。Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. Hei 8-12424, Japanese Patent Publication No. SHO63-287944, No. 63-287947 The urethane-based adhesive polymer containing an acid group in a side chain described in Japanese Patent Application Laid-Open No. Hei No. Hei 10-116232, or the Japanese Patent Publication No. 2002-107918 The urethane-based binder polymer having an acid group and a double bond in the side chain is excellent in strength, and is advantageous in terms of brush resistance and low exposure suitability.

又，歐洲專利993966、歐洲專利1204000、特開2001－318463號等所記載之具有酸基之縮醛改性聚乙烯醇黏合劑聚合物，因為膜強度、顯像性之平衡性優良，乃是合適的。In addition, the acetal-modified polyvinyl alcohol binder polymer having an acid group described in the European Patent No. 993966, the European Patent No. PCT Publication No. 2001-318463, etc., is excellent in the balance of film strength and imaging properties. suitable.

而且，其他的水溶性線形有機聚合物例如聚乙烯基吡咯啶酮或聚環氧乙烯等係有用的。又，為了提升硬化皮膜的強度，醇可溶性耐綸或2,2－雙－(4－羥基苯基)－丙烷與表氯醇之聚酯等亦是有用的。Further, other water-soluble linear organic polymers such as polyvinylpyrrolidone or polyethylene oxide are useful. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyester of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin is also useful.

本發明能夠使用的黏合劑聚合物之重量平均分子量以5,000以上為佳，以1萬~30萬的範圍為更佳，數量平均分子量以1,000以上為佳，以2,000~25萬的範圍為更佳。多分散度(重量平均分子量/數量平均分子量)以1以上為佳，以1.1~10的範圍為更佳。The weight average molecular weight of the binder polymer which can be used in the present invention is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, and more preferably in the range of 2,000 to 250,000. . The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10.

此等黏合劑聚合物，可以是無規聚合物、嵌段聚合物、及接枝聚合物等中任一者。These binder polymers may be any of a random polymer, a block polymer, and a graft polymer.

在本發明能夠使用的黏合劑聚合物，能夠藉由先前眾所周知的方法來合成。合成時所使用的溶劑可舉出例如四氫呋喃、二氯乙烷、環己酮、甲基乙基酮、丙酮、甲醇、乙醇、乙二醇一甲基醚、乙二醇一乙基醚、乙酸2－甲氧基乙酯、二甘醇二甲基醚、1－甲氧基－2－丙醇、乙酸1－甲氧基－2－丙酯、N,N－二甲基甲醯胺、N,N－二甲基乙醯胺、甲苯、乙酸乙酯、乳酸甲酯、乳酸乙酯、二甲基亞碸、水等。此等溶劑可單獨或混合使用2種以上。The binder polymer which can be used in the present invention can be synthesized by a previously known method. Examples of the solvent used in the synthesis include tetrahydrofuran, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and acetic acid. 2-methoxyethyl ester, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethylhydrazine, water, and the like. These solvents may be used alone or in combination of two or more.

合成本發明能夠使用的黏合劑聚合物時可使用的自由基聚合引發劑可舉出偶氮系引發劑、過氧化物引發劑等眾所周知的化合物。A known compound which can be used for the synthesis of the binder polymer which can be used in the present invention is a known compound such as an azo initiator or a peroxide initiator.

<(G)共敏化劑><(G) co-sensitizer>

本發明之硬化性組成物含有共敏化劑亦佳。在本發明之共敏化劑具有更提高敏化色料或引發劑對活性放射線的敏感度，或是抑制氧對聚合性化合物聚合之阻礙等之作用。It is also preferred that the curable composition of the present invention contains a co-sensitizer. The co-sensitizer of the present invention has an effect of further increasing the sensitivity of the sensitizing colorant or the initiator to the active radiation, or suppressing the inhibition of the polymerization of the polymerizable compound by oxygen.

此種共敏化劑之例子可舉出例如M.R.Sander等人著「聚合物協會期刊(Journal of Polymer Society」第10卷第3173頁(1972年)、特公昭44－20189號公報、特開昭51－82012號公報、特開昭52－134692號公報、特開昭59－138205號公報、特開昭60－84305號公報、特開昭62－18537號公報、特開昭64－33104號公報所記載之化合物等、Research Disclosure 33825號所記載之化合物等，具體上，可舉出三乙醇胺、對二甲基胺基苯甲酸乙酯、對甲醯基二甲基苯胺、對甲硫基二甲基苯胺等。Examples of such a co-sensitizer include, for example, MRSander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), U.S. Patent No. 44-20189, and JP-A Zhao Japanese Unexamined Patent Publication No. Publication No. Publication No. JP-A No. No. No. No. No. Nos. Nos. Nos. Nos. Nos. Nos. The compound and the like described in Research Disclosure No. 33825, and the like, specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-nonyldimethylaniline, p-methylthiodi Methyl aniline and the like.

共敏化劑之另外例子可舉出硫醇及硫化物類，例如特開昭53－702號公報、特公昭55－500806號公報、特開平5－142772號公報所記載之硫醇化合物、特開昭56－75643號公報之二硫化物等，具體上，可舉出2－氫硫基苯并噻唑、2－氫硫基苯并唑、2－氫硫基苯并咪唑、2－氫硫基－4(3H)－喹唑啉、β－氫硫基萘等。The thiol compound and the thiol compound described in JP-A-53-500806, JP-A-H05-500806, JP-A-5-142772, and the like. JP-A-56-75643 discloses a disulfide or the like, and specifically, 2-hydrothiobenzothiazole and 2-hydrothiobenzophenone Oxazole, 2-hydrothiobenzimidazole, 2-hydrothio-4(3H)-quinazoline, β-hydrothionaphthalene, and the like.

又，共敏化劑的另外例子可舉出例如胺基酸化合物(例如，N－苯基甘胺酸等)、特公昭48－42965號公報所記載之有機金屬化合物(例如，乙酸三丁基錫等)、特公昭55－34414號公報所記載之氫給予體、特開平6－308727號公報所記載之鋶化合物(例如，三聚甲硫醛等)等。In addition, examples of the co-sensitizer include, for example, an amino acid compound (for example, N-phenylglycine), and an organometallic compound described in JP-A-48-42965 (for example, tributyltin acetate, etc.) The hydrogen donor according to JP-A-55-34414, and the ruthenium compound (for example, trimethylthio aldehyde) described in JP-A-6-308727.

從藉由聚合成長速度與鏈轉移的平衡來提升硬化速度的觀點，相對於硬化性組成物的總固體成分的質量，該等共敏化劑之含量以0.1~30質量%的範圍為佳，以1~25質量%的範圍為較佳，以0.5~20質量%的範圍為更佳。From the viewpoint of increasing the curing rate by the balance between the polymerization growth rate and the chain transfer, the content of the co-sensitizer is preferably in the range of 0.1 to 30% by mass based on the mass of the total solid content of the curable composition. It is preferably in the range of 1 to 25% by mass, more preferably in the range of 0.5 to 20% by mass.

硫醇化合物Thiol compound

本發明之硬化性組成物以含有硫醇化合物作為共敏化劑為佳。在本發明之硬化性組成物能夠含有的硫醇化合物以下述通式(1－IV)所示之化合物為佳。The curable composition of the present invention preferably contains a thiol compound as a co-sensitizer. The thiol compound which can be contained in the curable composition of the present invention is preferably a compound represented by the following formula (1-IV).

通式(1－IV)中，X係表示硫原子、氧原子、或－N(R⁴³ )，R⁴³ 係表示氫原子碳數1~5之烷基、或碳數6~13的芳基。R⁴¹ 及R⁴² 係表示氫原子、碳數1~5的烷基、碳數1~3的羥基烷基、亦可被碳數1~8的烷氧基取代之苯基、硝基、具有碳數1~8的烷基之烷氧基羰基、苯氧基羰基、醯基、或羰基，又，亦可合併R⁴¹ 、R⁴² 、及此等鍵結而成雙鍵來形成苯環，R⁴¹ 、R⁴² 鍵結而成的雙鍵亦可加以氫化。In the formula (1-IV), X represents a sulfur atom, an oxygen atom or -N(R ⁴³ ), and R ⁴³ represents an alkyl group having 1 to 5 carbon atoms of a hydrogen atom or an aryl group having 6 to 13 carbon atoms. . R ⁴¹ and R ^{42 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a phenyl group or a nitro group which may be substituted by an alkoxy group having 1 to 8 carbon atoms, and An alkoxycarbonyl group having an alkyl group having 1 to 8 carbon atoms, a phenoxycarbonyl group, a fluorenyl group or a carbonyl group, or a combination of R ⁴¹ and R ⁴² and a double bond to form a benzene ring. The double bonds bonded by R ⁴¹ and R ⁴² may also be hydrogenated.

又，硫醇化合物的例子可舉出例如特開昭53－702號公報、特公昭55－500806號公報、特開平5－142772號公報所記載之化合物。In addition, examples of the thiol compound include the compounds described in JP-A-53-702, JP-A-55-500806, and JP-A-5-142772.

而且，硫醇化合物以下述通式(1－V)所示之物為佳。共敏化劑具有能夠更提升敏化劑或引發劑對活性放射線的敏感度、或是抑制氧對聚合性化合物聚合之阻礙等之作用。Further, the thiol compound is preferably represented by the following formula (1-V). The co-sensitizer has an effect of further increasing the sensitivity of the sensitizer or the initiator to actinic radiation or suppressing the inhibition of oxygen on the polymerization of the polymerizable compound.

通式(1－V)中，R係表示烷基或表示芳基，A係表示與N＝C－N一同形成雜環之原子團。In the formula (1-V), R represents an alkyl group or an aryl group, and A represents an atomic group which forms a hetero ring together with N=C-N.

在通式(1－V)，R係表示烷基或芳基。In the formula (1-V), R represents an alkyl group or an aryl group.

前述烷基可舉出碳原子數1~20之直鏈狀、分枝狀或環狀烷基，以碳原子數1~12之直鏈狀、碳原子數3~12之分枝狀、及碳原子數5~10之環狀烷基為更佳。Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, 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 is more preferred.

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。Specific examples thereof 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, a thirteen group, and a hexadecyl group. , octadecyl, icosyl, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl , 2-methylhexyl, cyclohexyl, cyclopentyl, 2-lower Base.

前述芳基係除了單環結構以外，並且1~3個苯環亦形成稠環而成之物，可舉出苯環與5員不飽和環形成稠環而成之物等，具體例可舉出苯基、萘基、蒽基、菲基、茚基、苊基、茀基等，此等之中以苯基、萘基為更佳。The aryl group is a monocyclic structure, and one or three benzene rings are also formed into a fused ring, and a benzene ring and a 5-membered unsaturated ring are formed into a fused ring, and the like. A phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthryl group, a fluorenyl group, a fluorenyl group or the like is exemplified, and among these, a phenyl group or a naphthyl group is more preferable

此等烷基或芳基亦可更具有取代基，能夠導入之取代基可舉出碳原子數1~20之直鏈狀、分枝狀或環狀的烷基、碳原子數2~20之直鏈狀、分枝狀或環狀烯基、碳原子數2~20之炔基、碳原子數6~20之芳基、碳原子數1~20的烷氧基、碳原子數2~20的烷氧基碳醯氧基、碳原子數7~20之芳氧基碳醯氧基、碳原子數1~20之胺基甲醯氧基、碳原子數1~20之碳醯胺基、碳原子數1~20之磺醯胺基、碳原子數1~20之胺磺醯基、碳原子數1~20之烷氧基、碳原子數6~20之芳氧基、碳原子數7~20之芳氧基羰基、碳原子數2~20烷氧基羰基、碳原子數1~20之N－醯基胺磺醯基、碳原子數1~20之N－胺磺醯基胺基甲醯基、碳原子數1~20之烷基磺醯基、碳原子數6~20之芳基磺醯基、碳原子數2~20之烷氧基碳醯胺基、碳原子數7~20之芳氧基碳醯胺基、胺基、碳原子數1~20之取代胺基、碳原子數1~20之亞胺基、碳原子數3~20之銨基、羧基、磺酸基、氧基、氫硫基、碳數1~20之烷基亞磺醯基、碳原子數6~20之芳基亞磺醯基、碳原子數1~20之烷硫基、碳原子數6~20之芳硫基、碳原子數1~20之脲基、碳原子數2~20之雜環基、碳原子數1~20之醯、胺磺醯基胺基、碳原子數1~2之取代胺磺醯基胺基、碳原子數2~20之矽烷基、異氰酸酯基、異氰化物基、鹵素原子(例如，氟原子、氯原子、溴原子等)、氰基、硝基、鎓基等。These alkyl or aryl groups may further have a substituent, and examples of the substituent which can be introduced include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and a carbon number of 2 to 20. a linear, branched or cyclic alkenyl group, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms Alkoxycarbenyloxy group, aryloxycarbenyloxy group having 7 to 20 carbon atoms, aminomethylmethoxyl group having 1 to 20 carbon atoms, carbon sulfonium group having 1 to 20 carbon atoms, a sulfonium amino group having 1 to 20 carbon atoms, an amine sulfonyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 7 carbon atoms ~20 aryloxycarbonyl group, carbon atom number 2-20 alkoxycarbonyl group, N-mercaptoamine sulfonyl group having 1 to 20 carbon atoms, N-amine sulfonylamino group having 1 to 20 carbon atoms A mercapto group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, an alkoxycarbenol group having 2 to 20 carbon atoms, and a carbon number of 7~ 20 aryloxycarbaguanyl, an amine group, a substituted amino group having 1 to 20 carbon atoms, an imido group having 1 to 20 carbon atoms, and a carbon number of 3 to 20 a group, a carboxyl group, a sulfonic acid group, an oxy group, a hydrogenthio group, an alkylsulfinyl group having 1 to 20 carbon atoms, an arylsulfinylene group having 6 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms Sulfur group, arylthio group having 6 to 20 carbon atoms, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, anthracene having 1 to 20 carbon atoms, and aminesulfonylamino group a substituted sulfonylamino group having 1 to 2 carbon atoms, an alkylene group having 2 to 20 carbon atoms, an isocyanate group, an isocyanate group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), Cyano, nitro, thiol and the like.

又，在通式(1－V)，A係表示與N＝C－N一同形成雜環之原子團。Further, in the formula (1-V), A represents an atomic group which forms a hetero ring together with N=C-N.

構成該原子之原子可舉出例如碳原子、氮原子、氫原子、硫原子、硒原子等。Examples of the atom constituting the atom include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.

又，A與N＝C－N所形成的雜環，以具更有取代基為佳，能夠導入的取代基可舉出與能夠在上述烷基或芳基導入之取代基同樣之物。Further, the hetero ring formed by A and N=C-N is preferably a more substituent, and the substituent which can be introduced may be the same as the substituent which can be introduced into the above alkyl group or aryl group.

又，硫醇化合物以下述通式(1－VI)或通式(1－VII)所示之物為更佳。Further, the thiol compound is more preferably represented by the following formula (1-VI) or formula (1-VII).

通式(1－VI)中，R⁵¹ 係表示芳基，X係表示氫原子、鹵素原子、烷氧基、烷基、或芳基。In the formula (1-VI), R ⁵¹ represents an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

通式(1－VII)中，R⁵² 係表示烷基、或芳基，X係表示氫原子、鹵素原子、烷氧基、烷基、或芳基。In the formula (1-VII), R ⁵² represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group or an aryl group.

在通式(1－VI)及(1－VII)之鹵素原子以氟原子、氯原子、溴原子、及碘原子為佳。The halogen atom of the formulae (1-VI) and (1-VII) is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

在通式(1－VI)及(1－VII)之烷氧基，可舉出甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、戊氧基、己氧基、十二烷氧基、苄氧基、烯丙氧基、苯乙氧基、羧基乙氧基、甲氧基羰基乙氧基、乙氧基羰基乙氧基、甲氧基乙氧基、苯氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、啉乙氧基、啉丙氧基、烯丙氧基乙氧基乙氧基、苯氧基、甲苯氧基、二甲苯氧基、氧基、枯烯氧基(cumenyloxy)、甲氧基苯氧基、乙氧基苯氧基、氯苯氧基、溴苯氧基、醯氧基、苯甲醯氧基、萘氧基等。Examples of the alkoxy group of the formulae (1-VI) and (1-VII) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. , dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxyethoxy, methoxycarbonylethoxy, ethoxycarbonylethoxy, methoxyethoxy, benzene Oxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, Oleto ethoxylate, Phenylpropoxy, allyloxyethoxyethoxy, phenoxy, tolyloxy, xyloxy, An oxy group, a cumenyloxy group, a methoxyphenoxy group, an ethoxyphenoxy group, a chlorophenoxy group, a bromophenoxy group, a decyloxy group, a benzamidineoxy group, a naphthyloxy group or the like.

在通式(1－VI)及(1－VII)之烷基，係與通式(1－V)的R所示之烷基同義，其較佳範圍亦同樣。The alkyl groups of the formulae (1-VI) and (1-VII) are synonymous with the alkyl group represented by R of the formula (1-V), and the preferred ranges thereof are also the same.

又，在通式(1－VI)及(1－VII)之芳基，係與通式(1－V)的R所示之芳基同義，其較佳範圍亦同樣。Further, the aryl groups of the formulae (1-VI) and (1-VII) are synonymous with the aryl group represented by R of the formula (1-V), and the preferred ranges thereof are also the same.

在(1－VI)及(1－VII)之各基亦可更具有取代基，該取代基係與通式(1－V)的R所示之在烷基或芳基能夠導入的取代基同樣。Each of (1-VI) and (1-VII) may further have a substituent which is a substituent which can be introduced at the alkyl group or the aryl group represented by R of the formula (1-V). same.

通式(1－VI)及(1－VII)中，從PGMEA溶解性的觀點，X以氫原子為更佳。In the general formulae (1-VI) and (1-VII), X is more preferably a hydrogen atom from the viewpoint of solubility of PGMEA.

通式(1－VI)中，從敏感度及PGMEA溶解性的觀點，R⁵¹ 以苯基為最佳。In the general formula (1-VI), R ^{51 is} preferably a phenyl group from the viewpoint of sensitivity and PGMEA solubility.

通式(1－VII)中，從敏感度及PGMEA溶解性的觀點，R⁵² 以甲基、乙基、苯基、及苄基為更佳。In the general formula (1-VII), R ^{52 is more} preferably a methyl group, an ethyl group, a phenyl group or a benzyl group from the viewpoints of sensitivity and PGMEA solubility.

通式(1－VI)及(1－VII)中，從PGMEA溶解性的觀點，以通式(1－VII)所示之化合物為最佳。In the general formulae (1-VI) and (1-VII), the compound represented by the formula (1-VII) is preferred from the viewpoint of solubility of PGMEA.

以下，顯示本發明所使用之硫醇化合物之較佳具體例，但是本發明未限定於此等。Hereinafter, preferred specific examples of the thiol compound used in the present invention are shown, but the present invention is not limited thereto.

又，在本說明書，化學式係以簡略結構式記載，特別是未標示元素或取代基之實線，係表示烴基。又，在下述具體例，Me係表示甲基。Further, in the present specification, the chemical formula is described by a schematic structural formula, and particularly, a solid line having no element or a substituent is a hydrocarbon group. Further, in the following specific examples, Me represents a methyl group.

從塗膜均勻性的觀點，此等硫醇化合物在PGMEA溶劑中之溶解度以20克/升以上為佳，以20克/升以上~50克/升以下為較佳，以20克/升以上~40克/升以下為更佳。From the viewpoint of uniformity of the coating film, the solubility of the thiol compound in the PGMEA solvent is preferably 20 g/L or more, preferably 20 g/L or more and 50 G/L or less, and more preferably 20 g/L or more. ~40 g / liter or less is more preferred.

－溶解度測定方法－- Solubility measurement method -

在本說明書，硫醇化合物溶解度係如下定義。In the present specification, the solubility of a thiol compound is defined as follows.

在5毫升丙二醇一甲基醚乙酸酯(PGMEA)添加特定硫醇化合物，以在25℃攪拌1小時後的時候，特定硫醇即將變為不溶解的量作為溶解度。When a specific thiol compound was added to 5 ml of propylene glycol monomethyl ether acetate (PGMEA) to stir at 25 ° C for 1 hour, the specific thiol was about to become insoluble as the solubility.

此等硫醇化合物能夠藉由J.Appl.Chem.,34、2203－2207(1961年)所記載之方法合成。These thiol compounds can be synthesized by the method described in J. Appl. Chem., 34, 2203-2207 (1961).

硫醇化合物可單獨使用1種，亦可共用2種以上。The thiol compound may be used alone or in combination of two or more.

並用硫醇化合物時，可只有並用前述通式中任一者所示化合物2種以上，亦可並用不同通式所示化合物(例如，並用選自通式(1－VI)所示化合物、及通式(1－VII)所示化合物之態樣)。When a thiol compound is used in combination, two or more kinds of the compounds represented by any one of the above formulas may be used in combination, and a compound of a different formula (for example, a compound selected from the group consisting of the formula (1-VI) may be used in combination, and The aspect of the compound represented by the formula (1-VII).

本發明之硫醇化合物含有硫醇化合物時，從藉由聚合成長速度與鏈轉移之平衡來提升硬化速度的觀點，相對於硬化性組成物的總固體成分的質量，其含量以0.5~30質量%的範圍為佳，以1~25質量%的範圍為較佳，以3~20質量%的範圍為更佳。When the thiol compound of the present invention contains a thiol compound, the content of the total solid content of the curable composition is 0.5 to 30 by mass from the viewpoint of increasing the curing rate by the balance between the polymerization growth rate and the chain transfer. The range of % is preferably in the range of 1 to 25% by mass, more preferably in the range of 3 to 20% by mass.

<(H)其他敏化劑><(H) Other sensitizers>

本發明之硬化性組成物在不損害本發明效果的範圍，為了提高自由基引發劑的產生效率、及感光波長的長波長化之目的，亦可含有特定敏化劑以外之(H)其他敏化劑。The curable composition of the present invention may contain other sensitive agents other than the specific sensitizer for the purpose of improving the efficiency of generating the radical initiator and increasing the wavelength of the photosensitive wavelength, without impairing the effects of the present invention. Chemical agent.

本發明能夠使用之其他敏化劑以能夠藉由電子轉移機構或能量轉移機構能使自由基引發劑敏化之物為佳。Other sensitizers which can be used in the present invention are preferably those which can sensitize the radical initiator by an electron transfer mechanism or an energy transfer mechanism.

在本發明能夠使用之其他敏化劑可舉出屬於以下所列舉的化合物、且在300奈米~450奈米的波長範圍具有吸收波長之物。Other sensitizers which can be used in the present invention include those which are exemplified below and which have an absorption wavelength in a wavelength range of from 300 nm to 450 nm.

較佳之其他敏化劑的例子，能夠舉出屬於以下化合物類、且在330奈米~450奈米的波長範圍具有吸收波長之物。Examples of other preferable sensitizers include those belonging to the following compounds and having an absorption wavelength in a wavelength range of from 330 nm to 450 nm.

其他敏化劑可舉出例如多環芳香族類(例如，菲、蒽、芘、苝、聯三伸苯、9,10－二烷氧基蒽)、類(例如，螢光素、曙紅、紅黴素、若丹明B、玫瑰紅)、噻噸酮類(異丙基噻噸酮、二乙基噻噸酮、氯噻噸酮)、花青苷類(例如噻喹啉藍色素、喹啉藍色素)、部花青素類(如部花青、碳部花青素)、酞青類、噻類(例如噻嚀、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)、角鯊鎓類(例如角鯊鎓)、香豆素類(例如，7－二乙胺基－4－甲基香豆素)、氧代香豆素、啡噻類、啡類、苯乙烯基苯類、偶氮化合物、二苯基甲烷、三苯基甲烷、二苯乙烯苯類、咔唑類、紫菜鹼、螺化合物、喹酮、靛藍、苯乙烯、吡啶鎓化合物、甲撐吡咯化合物、吡唑***化合物、苯并噻唑化合物、巴比妥酸衍生物、硫代巴比妥酸衍生物、乙醯苯、二苯基酮、噻噸酮、米其勒酮等芳香族酮化合物、及N－芳基－唑烷酮等雜環化合物等。Other sensitizers include, for example, polycyclic aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, hydrazine, 9,10-dialkoxyfluorene), Classes (eg, luciferin, eosin, erythromycin, rhodamine B, rose red), thioxanthone (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), flowers Alanines (eg thiaquinoline blue pigment, Quinoline blue pigment), procyanidins (such as merocyanine, carbon anthocyanins), indigo, thiophene Classes (such as thiazide, methylene blue, toluidine blue), acridines (such as acridine orange, chlorferrin, acridine yellow), terpenoids (such as guanidine), horned sharks (such as horn sharks)鎓), coumarins (eg, 7-diethylamino-4-methylcoumarin), oxocoumarin, thiophene Class, brown , styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, stilbene benzenes, oxazoles, laverine, spiro compounds, quinolones, indigo, styrene, pyridinium compounds, A azole pyrrole compound, a pyrazole triazole compound, a benzothiazole compound, a barbituric acid derivative, a thiobarbituric acid derivative, an acetophenone benzene, a diphenyl ketone, a thioxanthone, a mitone, etc. Aromatic ketone compounds, and N-aryl groups - a heterocyclic compound such as an oxazolone or the like.

相對於特定敏化劑，其他敏化劑的含量以0.1~20質量%為佳，以0.5~10質量%為更佳。The content of the other sensitizer is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the specific sensitizer.

<(1)聚合抑制劑><(1) Polymerization inhibitor>

在本發明，為了阻止在硬化性組成物的製造中或保存中具有能夠聚合的乙烯性不飽和雙鍵之化合物進行不要的熱聚合，以添加少量的熱聚合抑制劑為佳。In the present invention, in order to prevent unnecessary thermal polymerization of a compound having a polymerizable ethylenically unsaturated double bond during the production or storage of the curable composition, it is preferred to add a small amount of a thermal polymerization inhibitor.

在本發明，能夠使用的熱聚合抑制劑可舉出氫醌、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N－亞硝基苯基羥胺亞鈰鹽等。In the present invention, examples of the thermal polymerization inhibitor which can be used include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, tert-butylcatechol, benzoquinone, 4, 4 '-Thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitroso Phenylhydroxylamine sulfonium salt and the like.

相對於全組成物的質量，熱聚合抑制劑的添加量以0.01質量%~5質量%為佳。又，按照必要為了防止氧阻礙聚合，亦可添加如蘿酸或蘿醯胺之高級脂肪酸衍生物，並使其在塗布後的乾燥過程偏存在於感光層表面。高級脂肪酸衍生物的添加量，以佔全組成物的約0.5質量%~約10質量%為佳。The amount of the thermal polymerization inhibitor added is preferably 0.01% by mass to 5% by mass based on the mass of the total composition. Further, if necessary, in order to prevent oxygen from inhibiting polymerization, a higher fatty acid derivative such as rosin or lysine may be added, and the drying process after coating may be partially present on the surface of the photosensitive layer. The amount of the higher fatty acid derivative to be added is preferably from about 0.5% by mass to about 10% by mass based on the total composition.

<(J)黏附提升劑><(J) Adhesion Lifting Agent>

在本發明，為了提高與基材之硬質表面(基板)的黏附性，以添加黏附提升劑為佳。黏附提升劑可舉出矽烷系偶合劑、鈦系偶合劑、及鋁系偶合劑等。In the present invention, in order to improve the adhesion to the hard surface (substrate) of the substrate, it is preferred to add an adhesion enhancer. Examples of the adhesion-improving agent include a decane-based coupling agent, a titanium-based coupling agent, and an aluminum-based coupling agent.

矽烷系偶合劑可舉出例如γ－(2－胺基乙基)胺基丙基三甲氧基矽烷、γ－(2－胺基乙基)胺基丙基二甲氧基矽烷、β－(3,4－乙氧基環己基)乙基三甲氧基矽烷、γ－胺基丙基三甲氧基矽烷、γ－胺基丙基三乙氧基矽烷、γ－甲基丙烯醯氧丙基三甲氧基矽烷、γ－甲基丙烯醯氧丙基三乙氧基矽烷、γ－丙烯醯氧丙基三甲氧基矽烷、γ－丙烯醯氧丙基三乙氧基矽烷、γ－異氰酸酯丙基三甲氧基矽烷、γ－異氰酸酯丙基三乙氧基矽烷、N－β－(N－乙烯苄基胺基乙基)－γ－胺基丙基三氧基矽烷－鹽酸鹽、γ－環氧丙氧基丙基三甲氧基矽烷、γ－環氧丙氧基丙基三乙氧基矽烷、胺基矽烷、γ－氫硫基丙基三甲氧基矽烷、γ－氫硫基丙基三乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、γ－氯丙基三甲氧基矽烷、六甲基二矽氮烷、γ－苯胺基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(β－甲氧基乙氧基)矽烷、氯化十八基二甲基[3－(三甲氧基矽烷基)丙基]銨、γ－氯丙基甲基二甲氧基矽烷、γ－氫硫基丙基甲基二甲氧基矽烷、甲基三氯矽烷、二甲基二氯矽烷、三甲基氯矽烷、2－(3,4－乙氧基氯己基)乙基三甲氧基矽烷、雙烯丙基三甲氧基矽烷、四乙氧基矽烷、雙(三甲氧基矽烷基)己烷、苯基三甲氧基矽烷、N－(3－丙烯醯氧基－2－羥基丙基)－3－胺基丙基三乙氧基矽烷、N－(3－甲基丙烯醯氧基－2－羥基丙基)－3－胺基丙基三氧基矽烷、(甲基丙烯醯氧基甲基)甲基二乙氧基矽烷、及(丙烯醯氧基甲基)甲基二甲氧基矽烷等。The decane coupling agent may, for example, be γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-(2-aminoethyl)aminopropyldimethoxydecane, β-( 3,4-ethoxycyclohexyl)ethyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropenyloxypropyltrimethyl Oxydecane, γ-methacryloxypropyltriethoxydecane, γ-propylene methoxypropyltrimethoxydecane, γ-propylene methoxypropyltriethoxy decane, γ-isocyanate propyltrimethyl Oxydecane, γ-isocyanate propyl triethoxy decane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrioxydecane-hydrochloride, γ-epoxy Propoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, aminodecane, γ-hydrothiopropyltrimethoxydecane, γ-hydrothiopropyltriethyl Oxydecane, methyltrimethoxydecane, methyltriethoxydecane, vinyltriethoxydecane, gamma-chloropropyltrimethoxydecane, hexamethyldiazepine, gamma-anilino C Trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (β-methoxyethoxy) decane, octadecyl dimethyl [3-(trimethoxy)矽alkyl)propyl]ammonium, γ-chloropropylmethyldimethoxydecane, γ-hydrothiopropylmethyldimethoxydecane, methyltrichlorodecane, dimethyldichlorodecane, three Methylchlorodecane, 2-(3,4-ethoxychlorohexyl)ethyltrimethoxydecane, bisallyltrimethoxydecane, tetraethoxydecane, bis(trimethoxydecyl)hexane Phenyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, N-(3-methylpropenyloxy-2 -hydroxypropyl)-3-aminopropyltrimethoxydecane, (methacryloxymethyl)methyldiethoxydecane, and (propylene methoxymethyl)methyldimethoxy Decane and so on.

其中，以γ－甲基丙烯醯氧丙基三甲氧基矽烷、γ－甲基丙烯醯氧丙基三乙氧基矽烷、γ－丙烯醯氧丙基三甲氧基矽烷、γ－丙烯醯氧丙基三乙氧基矽烷、γ－氫硫基丙基三甲氧基矽烷、γ－胺基丙基三乙氧基矽烷、及苯基三甲氧基矽為佳，以γ－甲基丙烯醯氧丙基三甲氧基矽烷為最佳。Among them, γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, γ-acryloxypropyltrimethoxydecane, γ-acryloyloxypropane Triethoxy decane, γ-hydrothiopropyltrimethoxy decane, γ-aminopropyltriethoxy decane, and phenyltrimethoxyanthracene, preferably γ-methyl propylene oxime Trimethoxy decane is preferred.

鈦系偶合劑可舉出例如四－異丙氧基鈦、四－正丁氧基鈦、肆(2－乙基己氧基)鈦、四硬脂醯氧基鈦、二異丙氧基－雙(乙醯基丙酮酸酯)鈦、二－正丁氧基－雙(胺化三乙醇)鈦、二羥基－雙(丙醇酸酯)鈦、肆(2－乙基己烷二羥聯)鈦、三－正丁氧基鈦一硬脂酸酯、異丙基三異硬脂醯基鈦酸酯、異丙基三－十二烷基苯磺醯基鈦酸酯、異丙基參(二辛基焦磷酸酯)鈦酸酯、四異丙基雙(二辛基磷酸酯)鈦酸酯、四辛基雙(二－十三烷基磷酸酯)鈦酸酯、肆(2,2－二芳氧基甲基－1－丁基)雙(二－十三烷基)磷酸酯鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸酯鈦酸酯、雙(二辛基焦磷酸酸酯)伸乙基酞酸酯、異丙基三辛醇鈦酸酯、異丙基二甲基丙烯酸基異硬脂醯基鈦酸酯、異丙基異硬脂醯基二丙烯酸基鈦酸酯、異丙基參(二辛基磷酸酯)鈦酸酯、異丙基三異丙苯基苯基鈦酸酯、異丙基三(N－胺基乙基－胺基乙基)鈦酸酯、二異苯丙基苯氧基乙酸酯鈦酸酯、及二異硬脂醯基伸乙基鈦酸酯等。The titanium coupling agent may, for example, be tetra-isopropoxytitanium, tetra-n-butoxytitanium, cerium (2-ethylhexyloxy)titanium, tetrastearyloxytitanium, diisopropoxy- Bis(acetylthiopyruvate) titanium, di-n-butoxy-bis(aminated triethanol) titanium, dihydroxy-bis(propionate) titanium, bismuth (2-ethylhexane dihydroxyl Titanium, tri-n-butoxytitanium monostearate, isopropyl triisostearate titanate, isopropyl tri-dodecylbenzenesulfonate titanate, isopropyl ginseng (dioctyl pyrophosphate) titanate, tetraisopropylbis(dioctyl phosphate) titanate, tetraoctylbis(di-tridecyl phosphate) titanate, bismuth (2, 2-Diaryloxymethyl-1-butyl)bis(di-tridecyl)phosphate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, double (two Octyl pyrophosphate) ethyl phthalate, isopropyl trioctanol titanate, isopropyl dimethacrylate isostearyl decyl titanate, isopropyl isostearyl fluorenyl Acrylate titanate, isopropyl ginseng (dioctyl phosphate) titanate, isopropyl triisopropylphenyl phenyl titanate, isopropyl (N- aminoethyl - aminoethyl) titanate, di-iso-phenylpropyl dimethoxyphenoxy acetate titanate, and diisostearyl acyl extending ethyl titanate and the like.

鋁系偶合劑之鋁偶合劑可舉出例如異丙酸鋁(aluminium isopropylate)、二異丙酸一第二丁氧基鋁、第二－丁酸鋁、乙酸鋁、乙基乙醯乙酸二異丙酸鋁、參(乙基乙醯乙酸)鋁、烷基乙醯乙酸二異丙酸鋁、一乙醯乙酸雙(乙基乙醯乙酸)鋁、參(乙醯丙酮酸)鋁、及二異丙酸環狀氧化鋁等。The aluminum coupling agent of the aluminum coupling agent may, for example, be aluminum isopropylate, diisopropyl acid-second butoxide aluminum, second-butyric acid aluminum, aluminum acetate or ethyl acetoacetate. Aluminum propionate, ginseng (ethyl acetoacetate) aluminum, alkyl acetoacetic acid aluminum diisopropylate, acetoacetic acid bis(ethyl acetonitrile) aluminum, ginseng (acetyl acetonate) aluminum, and two Isopropyl acid cyclic alumina and the like.

黏附提升劑的添加量以佔硬化性組成物的總固體成分中之0.5~30質量%為佳，以0.7~20質量%為更佳。The amount of the adhesion-improving agent to be added is preferably from 0.5 to 30% by mass based on the total solid content of the curable composition, and more preferably from 0.7 to 20% by mass.

<其他添加劑><Other additives>

而且，在本發明，亦可添加用以改良硬化皮膜的物性之無機填料、或可塑劑、用以提高感光層表面之印墨著墨厚度性之感脂化劑等眾所周知的添加劑。Further, in the present invention, a well-known additive such as an inorganic filler for improving the physical properties of the cured film, or a plasticizer, and a sensory agent for increasing the thickness of the ink on the surface of the photosensitive layer may be added.

可塑劑有例如酞酸二辛酯、酞酸二－十二烷酯、三甘醇二辛酸酯、酞酸二甲基乙二酯、磷酸三環氧丙酯、己二酸二辛酯、癸二酸二丁酯、及三乙醯甘油等，使用結合劑時，相對於具有乙烯性不飽和雙鍵之化合物及結合劑的合計質量，可添加10質量%以下。Plasticizers are, for example, dioctyl phthalate, di-dodecyl phthalate, triethylene glycol dicaprylate, dimethylethylene citrate, triglycidyl phosphate, dioctyl adipate, When the binder is used, the amount of the compound having an ethylenically unsaturated double bond and the total amount of the binder may be 10% by mass or less.

<稀釋劑><diluent>

本發明之硬化性組成物在製造彩色濾光片時，於塗布在支撐體上時，亦可溶解在各種有機溶劑中而提供使用。When the color filter is produced in the production of a color filter, the curable composition of the present invention can be used by being dissolved in various organic solvents when applied to a support.

在此所使用的有機溶劑有丙酮、甲基乙基酮、環己烷、乙酸乙酯、二氯乙烷、四氫呋喃、甲苯、乙二醇一甲基醚、乙二醇一乙基醚、乙二醇二甲基醚、丙二醇一甲基醚、丙二醇一乙基醚、乙醯丙酮、環己酮、二丙酮醇、乙二醇一甲基醚乙酸酯、乙二醇乙基醚乙酸酯、乙二醇一異丙基醚、乙二醇一丁基醚乙酸酯、3－甲氧基丙醇、甲氧基甲氧基乙醇、二甘醇一甲基醚、二甘醇一乙基醚、二甘油二甲基醚、二甘醇二乙基醚、丙二醇一甲基醚乙酸酯、丙二醇一乙基醚乙酸酯、3－甲氧基丙基乙酸酯、N,N－二甲基甲醯胺、二甲基亞碸、γ－丁內酯、乳酸甲酯、乳酸乙酯等。The organic solvents used herein are acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and B. Glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetamidine acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate Ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol Ethyl ether, diglycerin dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl hydrazine, γ-butyrolactone, methyl lactate, ethyl lactate, and the like.

此等溶劑可單獨或混合使用。有機溶劑中的固體成分的濃度以2~60質量%為佳。These solvents may be used singly or in combination. The concentration of the solid component in the organic solvent is preferably 2 to 60% by mass.

本發明之彩色濾光片用硬化性組成物係高敏感度硬化、且保存安定性良好。又，顯示對應用硬化性組成物之基板等硬質材料表面具有高黏附性。The curable composition for a color filter of the present invention is highly sensitive and hard to be cured, and has good storage stability. Further, it is shown that the surface of the hard material such as the substrate to which the curable composition is applied has high adhesion.

[彩色濾光片及其製法][Color filter and its preparation method]

接著，說明本發明的彩色濾光片及其製法。Next, a color filter of the present invention and a method for producing the same will be described.

本發明的彩色濾光片其特徵係在支撐體上具有使用本發明的彩色濾光片用硬化性組成物所構成的著色圖案。The color filter of the present invention is characterized in that it has a colored pattern formed using the curable composition for a color filter of the present invention on a support.

以下對於本發明的彩色濾光片，通過其製法(本發明的彩色濾光片之製法)來加以詳述。Hereinafter, the color filter of the present invention will be described in detail by the production method thereof (the method for producing a color filter of the present invention).

本發明的彩色濾光片之製法其特徵係係包含以下步驟：在支撐體上塗布本發明的彩色濾光片用硬化性組成物來形成著色硬化性組成物層之步驟(以下簡稱「硬化性組成物層形成步驟」)；透過光罩使前述著色硬化性組成物層曝光之步驟(以下簡稱「曝光步驟」)；及將曝光後之前述硬化性組成物層顯像來形成著色圖案之步驟(以下簡稱「顯像步驟」)。The method for producing a color filter according to the present invention includes the step of forming a colored curable composition layer by applying a curable composition for a color filter of the present invention to a support (hereinafter referred to as "hardenability". a composition layer forming step"); a step of exposing the colored curable composition layer through a photomask (hereinafter referred to as "exposure step"); and a step of developing the colored layer after exposing the exposed curable composition layer (hereinafter referred to as "development step").

具體上，係將本發明的硬化性組成物直接或使其他的層介於中間而塗布在支撐體(基板)上，來形成光聚合性組成層(形成著色硬化性組成物層之步驟)，再透過規定的光罩圖案進行曝光，使已光照射的塗布膜部分硬化(曝光步驟)；再藉由顯像液進行顯像(顯像步驟)，來形成由各色(3色或4色)的像素所構成的圖案狀皮膜；藉由以上步驟能夠製造本發明的彩色濾光片。Specifically, the curable composition of the present invention is applied to a support (substrate) directly or with another layer interposed therebetween to form a photopolymerizable constituent layer (step of forming a colored curable composition layer). Further, exposure is performed through a predetermined mask pattern to partially cure the light-irradiated coating film (exposure step); and development is performed by a developing solution (development step) to form each color (3 colors or 4 colors). The patterned film formed by the pixels; the color filter of the present invention can be manufactured by the above steps.

以下說明本發明的製法之各步驟。The respective steps of the production method of the present invention will be described below.

<形成著色硬化性組成物層之步驟><Step of forming color hardening composition layer>

形成著色硬化性組成物層之步驟係在支撐體上塗布本發明的硬化性組成物，來形成著色硬化性組成物層。The step of forming the colored curable composition layer is to apply the curable composition of the present invention to the support to form a colored curable composition layer.

在本步驟可使用的支撐體，可舉出例如液晶顯示元件等所使用之鈉鈣玻璃、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之物，或攝像元件等所使用之電變換元件基板例如矽基板等、或互補金屬氧化膜半導體(CMOS)等。此等基板亦有形成黑色矩陣用以將各像素隔離之情形。Examples of the support which can be used in the present step include soda lime glass, Pyrex (registered trademark) glass, quartz glass, and the like which adhere to the transparent conductive film. An electric conversion element substrate used for an imaging element or the like, for example, a germanium substrate or the like, or a complementary metal oxide film semiconductor (CMOS) or the like. These substrates also have a black matrix to isolate each pixel.

又，在此等支撐體上，亦可按照必要設置底塗層用以改良與上部層之黏附、防止物質擴散或使基板表面平坦化。Further, on these supports, an undercoat layer may be provided as necessary to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate.

在支撐體上塗布本發明的硬化性組成物之塗布方法，能夠應用狹縫塗布、噴墨塗布、旋轉塗布、流延塗布、輥塗布、網版印刷法等各種塗布方法。The coating method of applying the curable composition of the present invention to the support can be applied to various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing.

硬化性組成物之塗布厚度以0.1~10微米為佳，以0.2~5微米為較佳，以0.2~3微米為更佳。The coating thickness of the curable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and more preferably 0.2 to 3 μm.

在支撐體所塗布的硬化性組成物，通常係在70~110℃、乾燥2~4分鐘左右的條件下，來形成著色硬化性組成物層。The curable composition applied to the support is usually dried at 70 to 110 ° C for 2 to 4 minutes to form a colored curable composition layer.

<曝光步驟><Exposure step>

曝光步驟係透過光罩將在前述形成著色硬化性組成物層之步驟所形成的著色硬化性組成物層進行曝光，只有使光照射過的塗布膜部分硬化。In the exposure step, the colored curable composition layer formed in the step of forming the colored curable composition layer is exposed through a photomask, and only the coating film irradiated with light is partially cured.

曝光以藉由照射放射線來進行為佳，曝光時所使用的放射線以使用g射線、i射線等紫外線為特佳，以高壓水銀燈為更佳。照射強度以5mJ~1500mJ為佳，以10mJ~1000mJ為更佳，以10mJ~800mJ為最佳。The exposure is preferably performed by irradiating radiation, and the radiation used for the exposure is preferably ultraviolet rays such as g-rays or i-rays, and more preferably a high-pressure mercury lamp. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

<顯像步驟><Exposure step>

接著曝光步驟，進行鹼顯像處理(顯像步驟)，來使在曝光步驟之光未照射部分溶出在鹼水溶液中。藉此，只有經光硬化過的部分殘留。Next, in the exposure step, an alkali development process (development step) is performed to dissolve the unexposed portion of the light in the exposure step in the aqueous alkali solution. Thereby, only the light-hardened portion remains.

顯像液以不會對下層的電路產生損傷之有機鹼顯像液為佳。顯像溫度通常為20℃~30℃，顯像時間為20~90秒。The developing solution is preferably an organic alkali developing solution which does not cause damage to the underlying circuit. The development temperature is usually 20 ° C ~ 30 ° C, and the development time is 20 ~ 90 seconds.

顯像液所使用的鹼，能夠使用例如將氨水、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、1,8－二氧雜雙環－[5.4.0]－7－十一烯等有機鹼性化合物，使用純水稀釋成濃度為0.001~10質量%、較佳是0.01~1質量%而成的鹼性水溶。又，使用由此種鹼性水溶液所構成之顯像液時，通常係在顯像後使用純水進行洗滌(rinse)。As the base to be used for the developing liquid, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8- can be used. An organic basic compound such as dioxabicyclo-[5.4.0]-7-undecene is diluted with pure water to an alkaline water solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Further, when a developing liquid composed of such an alkaline aqueous solution is used, it is usually washed with pure water after development.

又，在本發明的製法，進行上述形成硬化性組成物層步驟、曝光步驟、及顯像步驗後，亦可按照必要含有藉由對所形成的著色圖案進行加熱及/或曝光，來進行硬化之硬化步驟。Further, in the production method of the present invention, after the step of forming the curable composition layer, the exposing step, and the development step, the heating and/or exposure of the formed coloring pattern may be carried out as necessary. Hardening step of hardening.

如上述說明，藉由依照需要色相數目重複進行形成著色硬化性組成物層之步驟、曝光步驟、及顯像步驟(進而按照必要之硬化步驟)，能夠製造由需要的色相所構成之彩色濾光片。As described above, by repeating the step of forming the colored curable composition layer, the exposing step, and the developing step (and further the necessary hardening step) in accordance with the required number of hue, it is possible to manufacture a color filter composed of a desired hue. sheet.

因為本發明之彩色濾光片係使用前述本發明之硬化性組成物，所形成的著色圖案顯示與支撐體基板具有高黏附性，因為硬化的組成物之耐顯像性優良，曝光感度優良、曝光部與基板的黏附性良好、且能夠形成賦予需要剖面形狀之高解像度的圖案。因此,能夠適合使用於液晶顯示元件或CCD等固體攝像元件，特別是適合於超過100萬像素之高解像度CCD元件或CMOS等。本發明的彩色濾光片例如能夠使用作為配置於構成CCD之各像素的受光部與微透鏡(用以聚光)之間。Since the color filter of the present invention uses the above-described curable composition of the present invention, the colored pattern formed exhibits high adhesion to the support substrate, because the cured composition is excellent in display resistance and excellent in exposure sensitivity. The adhesion between the exposed portion and the substrate is good, and a pattern having a high resolution that requires a cross-sectional shape can be formed. Therefore, it can be suitably used for a solid-state imaging element such as a liquid crystal display element or a CCD, and is particularly suitable for a high-resolution CCD element, CMOS, or the like exceeding 1 million pixels. The color filter of the present invention can be used, for example, between a light receiving portion and a microlens (for collecting light) disposed in each pixel constituting the CCD.

[實施例][Examples]

以下，藉由實施例更具體地說明本發明。又，若無預先告知時，「%」、「份」係質量基準。Hereinafter, the present invention will be more specifically described by way of examples. Also, "%" and "parts" are quality standards without prior notice.

<特定敏化劑的合成>藉由以下所示之合成例1－1~1－18各自合成本發明之通式(1－I)所示之化合物、或是通式(1－II)所示之化合物1－1－~1－18。<Synthesis of Specific Sensitizer> The compound represented by the formula (1-I) of the present invention or the compound of the formula (1-II) can be synthesized by each of Synthesis Examples 1-1 to 1-18 shown below. Shown as compound 1-1-~1-18.

(合成例1－1)在300毫升三口燒瓶添加4－甲氧基苄基氯(0.19莫耳、1eq)、三苯基膦(PPh₃ )(0.19莫耳、1eq)、及N－甲基吡咯啶酮(NMP)(100毫升)，並在140℃加熱攪拌4小時。隨後投入水中，添加KPF₆ (0.23莫耳、1.2eq)，在室溫攪拌1小時的時候，因為有固體析出，進而以水洗條並使其乾燥，得到到鏻鹽A。產率為94%。(Synthesis Example 1-1) 4-methoxybenzyl chloride (0.19 mol, 1 eq), triphenylphosphine (PPh ₃ ) (0.19 mol, 1 eq), and N-methyl group were added to a 300 ml three-necked flask. Pyrrolidone (NMP) (100 ml) was stirred with heating at 140 °C for 4 hours. Subsequently, it was poured into water, and KPF ₆ (0.23 mol, 1.2 eq) was added thereto, and when it was stirred at room temperature for 1 hour, the solid was precipitated, and the strip was washed with water and dried to obtain cerium salt A. The yield was 94%.

在500毫升三口燒瓶添加鏻鹽A(30.8毫莫耳、1eq)、四氫呋喃(THF)(100毫升)，並在冰浴上攪拌。慢慢地對其添加氫化鈉(NaH)(46.2毫莫耳、1.5eq)/THF(20毫升)，添加結束後，在冰浴上攪拌15分鐘，隨後恢復至室溫。對其添加4－甲氧基桂皮酸醛(30.8毫莫耳、1eq)、並使其加熱回流4小時。隨後，投入冰水中時有固體析出，進行過濾，進而藉由進行甲醇洗滌而得到化合物1－1。產率為40%。In a 500 ml three-necked flask, hydrazine salt A (30.8 mmol, 1 eq), tetrahydrofuran (THF) (100 ml) was added and stirred on an ice bath. Sodium hydride (NaH) (46.2 mmol, 1.5 eq) / THF (20 mL) was slowly added, and after stirring, the mixture was stirred for 15 minutes on an ice bath and then returned to room temperature. 4-methoxycinnamic acid (30.8 mmol, 1 eq) was added thereto, and the mixture was heated under reflux for 4 hours. Subsequently, solids were precipitated when it was poured into ice water, filtered, and the compound 1-1 was obtained by washing with methanol. The yield was 40%.

(合成例1－2)在500毫升三口燒瓶添加鏻鹽A(37.8毫莫耳、1eq)、四氫呋喃(THF)(100毫升)，並在冰浴上攪拌。慢慢地對其添加氫化鈉(NaH)(56.7毫莫耳、1.5eq)/THF(20毫升)，添加結束後，在冰浴上攪拌15分鐘，隨後恢復至室溫。對其添加反式肉桂醛(37.8毫莫耳、1eq)、並使其加熱回流4小時。隨後，投入冰水中時有固體析出，進行過濾，進而藉由進行甲醇洗滌而得到化合物1－2。產率為45%。(Synthesis Example 1-2) To a 500 ml three-necked flask was added hydrazine salt A (37.8 mmol, 1 eq), tetrahydrofuran (THF) (100 ml), and stirred on an ice bath. Sodium hydride (NaH) (56.7 mmol, 1.5 eq) / THF (20 mL) was slowly added, and after stirring, the mixture was stirred for 15 minutes on an ice bath and then returned to room temperature. Trans-cinnamaldehyde (37.8 mmol, 1 eq) was added thereto and heated to reflux for 4 hours. Subsequently, a solid was precipitated when it was poured into ice water, and it was filtered, and the compound 1-2 was obtained by washing with methanol. The yield was 45%.

(合成例1－3)在300毫升三口燒瓶添加α－溴－對二甲苯(0.14莫耳、1eq)、三苯基膦(0.14莫耳、1eq)、及NMP(100毫升)，並在140℃加熱攪拌2小時(在反應溶液中，目的物產生結晶析出)。隨後投入水中，在冰浴中攪拌1小時，隨後過濾，進而以水洗條並使其乾燥，得到到鏻鹽B。產率為87%。(Synthesis Example 1-3) In a 300 ml three-necked flask, α-bromo-p-xylene (0.14 mol, 1 eq), triphenylphosphine (0.14 mol, 1 eq), and NMP (100 ml) were added, and at 140 The mixture was heated and stirred at ° C for 2 hours (in the reaction solution, the target product was crystallized). Subsequently, it was poured into water, stirred in an ice bath for 1 hour, and then filtered, and the strip was washed with water and dried to obtain a cerium salt B. The yield was 87%.

在500毫升三口燒瓶添加鏻鹽B(37.8毫莫耳、1eq)、THF(100毫升)，並在冰浴上攪拌。慢慢地對其添加氫化鈉(NaH)(56.7毫莫耳、1.5eq)/THF(20毫升)，添加結束後，在冰浴上攪拌15分鐘，隨後恢復至室溫。對其添反式肉桂醛(37.8毫莫耳、1eq)、並使其加熱回流3小時。隨後，投入冰水中時有固體析出，進行過濾，進而藉由進行甲醇再分散而得到化合物1－3。產率為60%。To a 500 ml three-necked flask was added hydrazine B (37.8 mmol, 1 eq), THF (100 mL) and stirred on ice. Sodium hydride (NaH) (56.7 mmol, 1.5 eq) / THF (20 mL) was slowly added, and after stirring, the mixture was stirred for 15 minutes on an ice bath and then returned to room temperature. Cinnamaldehyde (37.8 mmol, 1 eq) was added thereto and heated to reflux for 3 hours. Subsequently, solids were precipitated when it was poured into ice water, filtered, and then re-dispersed by methanol to obtain a compound 1-3. The yield was 60%.

(合成例1－4)在500毫升三口燒瓶添加鏻鹽B(34.2毫莫耳、1eq)、四氫呋喃(THF)(100毫升)，並在冰浴上攪拌。慢慢地對其添加氫化鈉(NaH)(51.3毫莫耳、1.5eq)/THF(40毫升)，添加結束後，在冰浴上攪拌15分鐘，隨後恢復至室溫。對其添加α－甲基肉桂醛(34.2毫莫耳、1eq)、並使其加熱回流3小時。隨後，投入冰水中時有固體析出，進行過濾，進而藉由進行甲醇再分散而得到化合物1－4。產率為40%。(Synthesis Example 1-4) To a 500 ml three-necked flask was added hydrazine salt B (34.2 mmol, 1 eq), tetrahydrofuran (THF) (100 ml), and stirred on an ice bath. Sodium hydride (NaH) (51.3 mmol, 1.5 eq) / THF (40 mL) was slowly added, and after stirring, the mixture was stirred for 15 minutes on an ice bath and then returned to room temperature. Α-methylcinnamaldehyde (34.2 mmol, 1 eq) was added thereto, and the mixture was heated under reflux for 3 hours. Subsequently, solids were precipitated when it was poured into ice water, filtered, and then re-dispersed by methanol to obtain a compound 1-4. The yield was 40%.

(合成例1－5)在500毫升三口燒瓶添加NaH(78.6毫莫耳、1.5eq)、鏻鹽C(52.4毫莫耳、1eq)、四氫呋喃(THF)(100毫升)，並在冰浴上攪拌。慢慢地對其添加鋶鹽(52.4毫莫耳、1eq)，添加結束後，在冰浴上攪拌15分鐘，隨後恢復至室溫。對其添加反式肉桂醛(52.4毫莫耳、1eq)、並使其加熱回流3小時。隨後，投入冰水中時有固體析出，進行過濾，進而藉由進行甲醇再分散而得到化合物1－5。產率為40%。(Synthesis Example 1-5) NaH (78.6 mmol, 1.5 eq), hydrazine salt C (52.4 mmol, 1 eq), tetrahydrofuran (THF) (100 ml) was added to a 500 ml three-neck flask, and on an ice bath. Stir. The cerium salt (52.4 mmol, 1 eq) was slowly added thereto, and after the addition was completed, the mixture was stirred on an ice bath for 15 minutes, and then returned to room temperature. Trans-cinnamaldehyde (52.4 mmol, 1 eq) was added thereto and heated to reflux for 3 hours. Subsequently, when it was poured into ice water, solids were precipitated, filtered, and then re-dispersed by methanol to obtain a compound 1-5. The yield was 40%.

(合成例1－6)在500毫升三口燒瓶添加NaH(78.6毫莫耳、1.5eq)、鏻鹽D(52.4毫莫耳、1eq)、四氫呋喃(THF)(100毫升)，並在冰浴上攪拌。慢慢地對其添加NaH(52.4毫莫耳、1eq)，添加結束後，在冰浴上攪拌15分鐘，隨後恢復至室溫。對其添加反式肉桂醛(52.4毫莫耳、1eq)、並使其加熱回流3小時。隨後，投入冰水中時有固體析出，過濾固體後，將濾液濃縮，使用矽膠柱層析法(己烷：乙酸乙酯＝10：1)精製而得到化合物1－6。產率為5%。(Synthesis Example 1-6) NaH (78.6 mmol, 1.5 eq), phosphonium salt D (52.4 mmol, 1 eq), tetrahydrofuran (THF) (100 ml) were added to a 500 ml three-necked flask, and on an ice bath. Stir. NaH (52.4 mmol, 1 eq) was slowly added thereto, and after the addition was completed, the mixture was stirred on an ice bath for 15 minutes, and then returned to room temperature. Trans-cinnamaldehyde (52.4 mmol, 1 eq) was added thereto and heated to reflux for 3 hours. Subsequently, solids were precipitated when poured into ice water, and after filtering the solid, the filtrate was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 10:1) to give compound 1-6. The yield was 5%.

(合成例1－7)在化合物1－5之合成例，除了使用下述鏻鹽E代替鏻鹽C以外，藉由同樣的方法得到下述化合物1－7。(Synthesis Example 1-7) In the synthesis example of the compound 1-5, the following compound 1-7 was obtained by the same method except that the above-mentioned onium salt E was used instead of the onium salt C.

(合成例1－8)在化合物1－5之合成例，除了使用下述鏻鹽F代替鏻鹽C以外，藉由同樣的方法得到下述化合物1－8。(Synthesis Example 1-8) In the synthesis example of the compound 1-5, the following compound 1-8 was obtained by the same method except that the above-mentioned onium salt F was used instead of the onium salt C.

(合成例1－9)在化合物1－5之合成例，除了使用下述鏻鹽G代替鏻鹽C以外，藉由同樣的方法得到下述化合物1－9。(Synthesis Example 1-9) In the synthesis example of the compound 1-5, the following compound 1-9 was obtained by the same method except that the above-mentioned onium salt G was used instead of the onium salt C.

(合成例1－10)在化合物1－5之合成例，除了使用下述鏻鹽H代替鏻鹽C以外，藉由同樣的方法得到下述化合物1－10。(Synthesis Example 1-10) In the synthesis example of the compound 1-5, the following compound 1-10 was obtained by the same method except that the above-mentioned onium salt H was used instead of the onium salt C.

(合成例1－11)在化合物1－5之合成例，除了使用下述鏻鹽I代替鏻鹽C以外，藉由同樣的方法得到下述化合物1－11。(Synthesis Example 1-11) In the synthesis example of the compound 1-5, the following compound 1-11 was obtained by the same method except that the above-mentioned onium salt I was used instead of the onium salt C.

(合成例1－12)在化合物1－5之合成例，除了使用下述鏻鹽J代替鏻鹽C以外，藉由同樣的方法得到下述化合物1－12。(Synthesis Example 1-12) In the synthesis example of the compound 1-5, the following compound 1-12 was obtained by the same method except that the above-mentioned onium salt J was used instead of the onium salt C.

(合成例1－13)在化合物1－5之合成例，除了使用下述鏻鹽K代替鏻鹽C以外，藉由同樣的方法得到下述化合物1－13。(Synthesis Example 1-13) In the synthesis example of the compound 1-5, the following compound 1-13 was obtained by the same method except that the above-mentioned onium salt K was used instead of the onium salt C.

(合成例1－14)在500毫升三口燒瓶添加鏻鹽L(16.9克、40.7毫莫耳)、四氫呋喃(THF)(100毫升)，並在冰浴上攪拌。慢慢地對其添加SM－28(NaOMe之28wt%MeOH溶液)(7.4克、38.4毫莫耳)，添加結束後，在冰浴上攪拌15分鐘，隨後恢復至室溫。對其添加對二苯基胺基苯甲醛10克(36.6毫莫耳)，並使其加熱回流2小時。隨後，投入冰水中時有固體析出，過濾固體後，而且進行甲醇洗滌而得到化合物1－14。產率為40%。(Synthesis Example 1-14) To a 500 ml three-necked flask was added hydrazine salt L (16.9 g, 40.7 mmol), tetrahydrofuran (THF) (100 ml), and stirred on an ice bath. SM-28 (NaOMe's 28 wt% MeOH solution) (7.4 g, 38.4 mmol) was slowly added thereto, and after the addition was completed, the mixture was stirred on an ice bath for 15 minutes, and then returned to room temperature. 10 g of p-diphenylaminobenzaldehyde (36.6 mmol) was added thereto and heated to reflux for 2 hours. Subsequently, solids were precipitated when placed in ice water, and the solid was filtered, and washed with methanol to give Compound 1-14. The yield was 40%.

(合成例1－15)在化合物1－14之合成例，除了使用二乙基胺基苯甲醛代替對二苯基胺基苯甲醛以外，藉由同樣的方法得到下述化合物1－15。(Synthesis Example 1-15) In the synthesis example of the compound 1-14, the following compound 1-15 was obtained by the same method except that diethylaminobenzaldehyde was used instead of p-diphenylaminobenzaldehyde.

(合成例1－16)在化合物1－14之合成例，除了使用3,4,5－三甲氧基苯甲醛代替對二苯基胺基苯甲醛以外，藉由同樣的方法得到下述化合物1－16。(Synthesis Example 1-16) In the synthesis example of the compound 1-14, the following compound 1 was obtained by the same method except that 3,4,5-trimethoxybenzaldehyde was used instead of p-diphenylaminobenzaldehyde. -16.

(合成例1－17)在化合物1－14之合成例，除了使用4－二乙基胺基－2－甲氧基苯甲醛代替對二苯基胺基苯甲醛以外，藉由同樣的方法得到下述化合物1－17。(Synthesis Example 1-17) A synthesis example of the compound 1-14 was obtained by the same method except that 4-diethylamino-2-methoxybenzaldehyde was used instead of p-diphenylaminobenzaldehyde. The following compounds 1-17.

(合成例1－18)在化合物1－14之合成例，除了使用2,4－二甲氧基苯甲醛代替對二苯基胺基苯甲醛以外，藉由同樣的方法得到下述化合物1－18。(Synthesis Example 1-18) In the synthesis example of the compound 1-14, the following compound 1- was obtained by the same method except that 2,4-dimethoxybenzaldehyde was used instead of p-diphenylaminobenzaldehyde. 18.

(合成例1－19)在化合物1－14之合成例，除了使用下述鏻鹽M代替鏻鹽L以外，藉由同樣的方法得到下述化合物1－19。(Synthesis Example 1-19) In the synthesis example of the compound 1-14, the following compound 1-19 was obtained by the same method except that the following sulfonium salt M was used instead of the sulfonium salt L.

又，合成例1－5~1－13所使用的鏻鹽C~K的合成，在合成例1－3所使用之鏻鹽B的合成，除了各自以適當的化合物代替α－溴－對二甲苯以外，係與合成鏻鹽B同樣。Further, in the synthesis of the onium salt C to K used in Synthesis Examples 1-5 to 1-13, the synthesis of the onium salt B used in Synthesis Example 1-3 was carried out except that the respective compounds were substituted for α-bromo-p-pair. The same as the synthetic sulfonium salt B except for toluene.

<莫耳吸光係數的測定>調製化合物1－1~1－19及比較化合物1－1~1－4(結構係如下述表3所示)之0.01克/升的1－甲氧基－2－丙醇溶液，使用Varian製cary－5 uv－vis－NIR SPECTROPHOTOMETERS來測定吸光度，測定在365奈米之莫耳吸光係數ε(mol^－1 ．L．cm^－1 )。<Measurement of Mohr Absorbance Coefficient> 0.01 g/L of 1-methoxy-2 of Compounds 1-1 to 1-19 and Comparative Compounds 1-1 to 1-4 (structure is shown in Table 3 below) The propanol solution was measured for absorbance using a Cary-5 uv-vis-NIR SPECTROPHOTOMETERS manufactured by Varian, and the molar absorption coefficient ε (mol ^-1 .L.cm ^-1 ) at 365 nm was measured.

化合物1－1~1－19的結構及在365奈米之莫耳吸光係數ε係整理記載於下述表1~2。又，在後述之比較例所使用之比較用化合物1－1~1－4的結構及在365奈米之莫耳吸光係數ε係記載於表3。The structures of the compounds 1-1 to 1-19 and the molar absorption coefficient ε at 365 nm are shown in Tables 1 and 2 below. Further, the structures of the comparative compounds 1-1 to 1-4 used in the comparative examples described later and the Mohr absorbance coefficient ε at 365 nm are shown in Table 3.

以下，藉由實施例更具體地說明本發明的硬化性組成物，但是只要未悖離本發明的主旨，未限定於以下的實施例。Hereinafter, the curable composition of the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples without departing from the spirit of the invention.

[實施例1－1－1][Example 1-1-1]

[1.著色硬化性組成物1－A－1的調製]在此，舉出調製含有著色劑(顏料)之著色硬化性組成物1－A－1(作為形成液晶顯示元件用途的彩色濾光片用)之例子，來進行說明。[1. Preparation of coloring curable composition 1-A-1] Here, a coloring-curable composition 1-A-1 containing a coloring agent (pigment) is prepared (as a color filter for forming a liquid crystal display element) The example of the film is used for explanation.

1－1.顏料分散液(P1)的調製將由作為顏料之40質量份C.I.顏料綠36與C.I.顏料黃219的30/70(質量比)混合物、作為分散劑之10質量份(換算固體成分約4.51質量份)BYK2001(Disper bky：BYK Chemie公司製、固體成分濃度45.1質量%)、及150質量份3－乙氧基丙酸乙酯所構成的混合液，藉由珠磨機混合分散15小時，來調製顏料分散液(P1)。1-1. Preparation of Pigment Dispersion Liquid (P1) A mixture of 40/70 (mass ratio) of 40 parts by mass of CI Pigment Green 36 and CI Pigment Yellow 219 as a pigment, and 10 parts by mass as a dispersant (converted solid content) 4.51 parts by mass) BYK2001 (Disper bky: manufactured by BYK Chemie Co., Ltd., solid concentration: 45.1% by mass) and 150 parts by mass of ethyl 3-ethoxypropionate were mixed and dispersed by a bead mill for 15 hours. To prepare the pigment dispersion (P1).

對所得到的顏料分散液(P1)，藉由動態光散射法測定顏料的平均粒徑時，為200奈米。When the average particle diameter of the pigment was measured by a dynamic light scattering method, the obtained pigment dispersion liquid (P1) was 200 nm.

1－2.著色硬化性組成物1－A－1(塗布液)的調製混合下述組成1－A－1的成分並溶解，來調製著色硬化性組成物1－A－1。1-2. Preparation of Colored Curable Composition 1-A-1 (Coating Liquid) The components of the following composition 1-A-1 were mixed and dissolved to prepare a colored curable composition 1-A-1.

[2.彩色濾光片的製造]2－1.硬化性組成物層的形成將藉由上述所得到含有顏料的著色硬化性組成物1－A－1作為光阻溶液，以下述條件狹縫塗布在550毫米×650毫米的玻璃基板上後，使其在此狀態下待機10分鐘，塗布在新的玻璃基板上，再施行真空乾燥及預烘焙(100℃ 80秒)，來形成著色硬化性組成物塗布膜(著色硬化性組成物層)。[2. Manufacture of a color filter] 2-1. Formation of a curable composition layer The coloring-curable composition 1-A-1 containing the pigment obtained above was used as a photoresist solution, and slits were formed under the following conditions. After coating on a 550 mm × 650 mm glass substrate, it was allowed to stand in this state for 10 minutes, coated on a new glass substrate, and subjected to vacuum drying and prebaking (100 ° C for 80 seconds) to form color hardening. The composition coating film (coloring curable composition layer).

(狹縫塗布條件)塗布頭前端開口部的間隙：50微米塗布速度：100毫米/秒基板與塗布頭之間隙：150微米塗布厚度(乾燥厚度)：2微米塗布溫度：23℃(Slit coating conditions) Gap of the opening end of the coating head: 50 μm Coating speed: 100 mm/sec Clearance between substrate and coating head: 150 μm coating thickness (dry thickness): 2 μm Coating temperature: 23 ° C

2－2曝光、顯像隨後，使用2.5kW之超高壓水銀燈將著色硬化性組成物塗布膜曝光成圖案狀，曝光後使用有機系顯像液(商品名：CD、Fuji Film Arch(股)製)之10%水溶液覆蓋塗布膜的全面，並靜止60秒。2-2 Exposure and development Subsequently, the colored curable composition coating film was exposed to a pattern using a 2.5 kW ultrahigh pressure mercury lamp, and an organic developing solution (trade name: CD, Fuji Film Arch Co., Ltd.) was used after exposure. The 10% aqueous solution covers the entire surface of the coating film and is still for 60 seconds.

2－3.加熱處理靜止後，噴淋狀地噴射純水來沖洗顯像液，在220℃的烘箱對施行過如此光硬化處理及顯像處理之塗布膜加熱1小時(後烘焙)。藉此，在玻璃基板上形成著色圖案而得到彩色濾光片。2-3. After the heat treatment was stopped, the pure water was sprayed in a shower form to rinse the developing liquid, and the coating film subjected to such photohardening treatment and development treatment was heated in an oven at 220 ° C for 1 hour (post-baking). Thereby, a colored pattern is formed on the glass substrate to obtain a color filter.

[3.性能評價]如下述進行評價上述所調製著色硬化性組成物1－A－1(塗布液)的保持安定性、及使用該著色硬化性組成物1－A－1在玻璃基板上所形成著色硬化性組成物塗布膜(著色層)的曝光敏感度、基板黏附、顯像性，及著色圖案的剖面形狀。結果如表4所示。[3. Performance Evaluation] The retention stability of the above-described colored curable composition 1-A-1 (coating liquid) was evaluated as follows, and the colored curable composition 1-A-1 was used on a glass substrate. The exposure sensitivity of the colored curable composition coating film (colored layer), the adhesion of the substrate, the developability, and the cross-sectional shape of the colored pattern are formed. The results are shown in Table 4.

3－1.著色硬化性組成物1－A－1的保存安定性在室溫保存著色硬化性組成物塗布液1個月，藉由目視依照以下基準評價異物的析出程度。3-1. Storage stability of the coloring curable composition 1-A-1 The colored curable composition coating liquid was stored at room temperature for one month, and the degree of precipitation of foreign matter was evaluated by visual observation according to the following criteria.

<判定基準>○：未認定有析出。<Judgment criterion> ○: No precipitation was confirmed.

△：認定有少許析出。△: It was confirmed that there was a little precipitation.

×：認定有析出。×: It is determined that there is precipitation.

3－2.塗布膜(著色層)的曝光敏感度將著色硬化性組成物1－A－1(塗布液)塗布在玻璃基板上，隨後乾燥使膜厚度為1.0微米。旋轉塗布條件係以300rpm 5秒後，以800rpm 20秒，乾燥條件係在100℃ 80秒。接著，使用線寬2.0微米之試驗用光罩，以10~1600mJ/cm² 之各種曝光量進行曝光。接著使用60%CD－2000(FUJI FILM ELECTRONICS MATERIALS公司製)顯像液，以25℃、60秒的條件進行顯像。隨後，以流水沖洗20秒後，噴霧乾燥而完成了圖案化。評價在曝光步驟經光照射後的區域之顯像後的膜厚度，將相對於曝光前的膜厚度100%，膜厚度為95%以上之最小曝光量作為曝光敏感度。曝光敏感度的值越小表示敏感度越高。3-2. Exposure Sensitivity of Coating Film (Colored Layer) The colored curable composition 1-A-1 (coating liquid) was coated on a glass substrate, followed by drying to a film thickness of 1.0 μm. The spin coating conditions were followed by 300 rpm for 5 seconds, 800 rpm for 20 seconds, and drying conditions at 100 ° C for 80 seconds. Next, exposure was performed at various exposure amounts of 10 to 1600 mJ/cm ² using a test mask having a line width of 2.0 μm. Next, development was carried out at 60 ° C for 60 seconds using a 60% CD-2000 (manufactured by FUJI FILM ELECTRONICS MATERIALS). Subsequently, after rinsing with running water for 20 seconds, spray drying was completed to complete the patterning. The film thickness after development of the region after the light irradiation in the exposure step was evaluated, and the minimum exposure amount with respect to the film thickness before exposure of 100% and the film thickness of 95% or more was taken as the exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity.

3－3.顥像性、圖案剖面形狀、基板黏附性藉由光學顯微鏡及SEM照相觀察，以通常的方法確認後烘焙後的基板表及剖面形狀，來進行評價顯像性、基板黏附性、及圖案剖面形狀。詳細評價方法如下。3-3. Visibility, pattern cross-sectional shape, and substrate adhesion are observed by optical microscopy and SEM observation, and the substrate and cross-sectional shape of the substrate after post-baking are confirmed by a usual method to evaluate the developability and substrate adhesion. And the shape of the profile. The detailed evaluation method is as follows.

<顯像性>觀察曝光步驟之光未照射的區域(未曝光部)有無殘渣，來評價顯像性。<Developing property> The presence or absence of residue in the region (unexposed portion) where the light was not irradiated in the exposure step was observed to evaluate the developability.

○：在未曝光部未確認有殘渣。○: No residue was observed in the unexposed portion.

△：在未曝光部確認有少許殘渣，但實用上沒有問題的程度。△: A small amount of residue was confirmed in the unexposed portion, but there was no problem in practical use.

×：在未曝光部確認有顯著的殘渣×: Significant residue was confirmed in the unexposed portion

<基板黏附性>評價基板黏附性係觀察是否產生圖案缺損。基於以下基準來評價此等評價項目。<Substrate Adhesion> The substrate adhesion was evaluated to see if a pattern defect occurred. These evaluation items are evaluated based on the following criteria.

○：未觀察到有圖案缺損。○: No pattern defect was observed.

△：大部分圖案未觀察到有缺損，但有一部分圖案觀察到缺損。△: No defects were observed in most of the patterns, but a part of the pattern was observed to be defective.

×：觀察到有顯著的圖案缺損×: A significant pattern defect was observed

<圖案剖面形狀>觀察所形成的圖案剖面形狀。圖案剖面形狀以順錐形為最佳，其次為矩形，以反錐形為不佳。<Pattern section shape> The pattern cross-sectional shape formed was observed. The shape of the cross-section of the pattern is preferably a straight cone, followed by a rectangle, and the reverse taper is not preferable.

[實施例1－1－2~1－1－26][Examples 1-1-2~1-1-26]

在實施例1－1－1，除了將調製著色硬化性組成物1－A－1所使用組成1－A－1中的特定敏化劑、光聚合引發劑、及共敏化劑各自變更為下述表4所示以外，全部與實施例1－1－1同樣地進行，來調製著色硬化性組成物1－A－2~A－26，得到具有使用其所構成的著色圖案之彩色濾光片。並進行與實施例1－1－1同樣的評價。結果如表4所示。In the example 1-1-1, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer in the composition 1-A-1 used in the preparation of the coloring curable composition 1-A-1 were each changed to In the same manner as in Example 1-1-1 except for the following Table 4, the colored curable compositions 1-A-2 to A-26 were prepared to obtain a color filter having a colored pattern formed using the same. Light film. The same evaluation as in Example 1-1-1 was carried out. The results are shown in Table 4.

[比較例1－1－1][Comparative Example 1-1-1]

在實施例1－1－1，除了將調製著色硬化性組成物1－A－1所使用組成1－A－1，變更為下述1－B－1以外，全部與實施例1－1－1同樣地進行，來調製著色硬化性組成物1－B－1，形成著色圖案而得到彩色濾光片。而且，進行與實施例1－1－1同樣的評價。結果如表4所示。In the example 1-1-1, except that the composition 1-A-1 used for the preparation of the coloring curable composition 1-A-1 was changed to the following 1-B-1, all were the same as those in the example 1-1- 1 is carried out in the same manner to prepare a colored curable composition 1-B-1, and a colored pattern is formed to obtain a color filter. Further, the same evaluation as in Example 1-1-1 was carried out. The results are shown in Table 4.

[比較例1－1－2~1－1－5][Comparative Example 1-1-2~1-1-5]

在實施例1－1－1，除了將調製著色硬化性組成物1－A－1所使用的特定敏化劑、光聚合引發劑、及共敏化劑各自變更為下述表4所示之比較化合物、光聚合引發劑、及共敏化劑以外，全部與實施例1－1－1同樣地進行，來調製比較用著色硬化性組成物層B－2~B－5，得到具有使用其所構成的著色圖案之彩色濾光片。並進行與實施例1－1－1同樣的評價。結果如表4所示。In the example 1-1-1, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer used for preparing the coloring curable composition 1-A-1 were each changed to the following Table 4. In the same manner as in Example 1-1-1 except that the comparative compound, the photopolymerization initiator, and the co-sensitizer were used, the coloring curable composition layers B-2 to B-5 for comparison were prepared and used. A color filter of a colored pattern formed. The same evaluation as in Example 1-1-1 was carried out. The results are shown in Table 4.

表4所示之光聚合引發劑D1~D3、共敏化劑F1~F3係以下所示之化合物。The photopolymerization initiators D1 to D3 and the co-sensitizers F1 to F3 shown in Table 4 are the compounds shown below.

D1：2,2’－雙(2－氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑D2：1－[4－(苯硫基)苯基]－2－(O－苯甲醯肟)D3：4－苯并氧雜環壬烷－2,6－二(三氯甲基)－s－三F1：2－氫硫基苯并咪唑F2：2－氫硫基苯并噻唑F3：4,4’－雙(二乙胺基)二苯基酮F4：N－苯基－2－氫硫基苯并咪唑D1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole D2: 1-[4-(phenylthio)benzene ]]-2-(O-benzhydrazide) D3: 4-benzoxanthracene-2,6-di(trichloromethyl)-s-three F1: 2-Homothiobenzimidazole F2: 2-Hydroxythiobenzothiazole F3: 4,4'-bis(diethylamino)diphenyl ketone F4: N-phenyl-2-hydrogenthio Benzimidazole

從表4的結果，得知含有特定敏化劑(化合物1－1~1－18)之各實施例的著色硬化性組成物係在其溶液狀態具有優良的保存安定性。又，得知使用該著色硬化性組成物在支撐體上形成著色圖案時，相對於未含有特定敏化劑或使用比較化合物1－1~1－4之各比較例，能夠得到曝光敏感度高、顯像性優良、同時基板黏附性、圖案剖面形狀都優良的彩色濾光片。From the results of Table 4, it was found that the color hardening composition of each of the examples containing the specific sensitizer (Compounds 1-1 to 1-18) had excellent storage stability in the solution state. Further, when it was found that a colored pattern was formed on the support using the colored curable composition, it was found that the exposure sensitivity was high with respect to each of the comparative examples in which the specific sensitizer was not contained or the comparative compounds 1-1 to 1-4 were used. A color filter that is excellent in image development, and has excellent substrate adhesion and pattern cross-sectional shape.

以下，舉出調製含有著色劑(染料)之硬化性組成物(作為形成固體攝像元件用途之彩色濾光片用)之例子，來進行說明。Hereinafter, an example in which a curable composition containing a colorant (dye) (for use as a color filter for forming a solid-state image sensor) is prepared will be described.

[實施例1－2－1][Example 1-2-1]

[1.光阻液的調製]混合溶解以下組成的成分，來調製光阻液。[1. Preparation of Photoresist] The components of the following composition were mixed and dissolved to prepare a photoresist.

[2.具底塗層之矽晶圓基板的製造]將6英吋矽晶圓於烘箱中在200℃加熱處理30分鐘。接著，在該矽晶圓上，以乾燥膜厚度為2微米的方式塗布前述光阻液，並且在220℃的烘箱中加熱乾燥1小時來形成塗布層，得到具有底塗層之矽晶圓基板。[2. Fabrication of undercoated silicon wafer substrate] A 6 inch wafer was heat-treated in an oven at 200 ° C for 30 minutes. Next, the photoresist liquid was applied to the tantalum wafer so as to have a dry film thickness of 2 μm, and dried by heating in an oven at 220 ° C for 1 hour to form a coating layer, thereby obtaining a tantalum wafer substrate having an undercoat layer. .

[3.著色硬化性組成物1－C－1的調製]混合溶解下述組成1－C－1的化合物，來調製著色感光性組成物1－C－1。[3. Preparation of Colored Curable Composition 1-C-1] The coloring photosensitive composition 1-C-1 was prepared by mixing and dissolving the compound of the following composition 1-C-1.

[4.著色硬化性組成物1－C－1(塗布液)的保存安定性評價]將著色硬化性組成物1－C－1保存在室溫1個月後，藉由目視依照以下基準評價異物的析出程度。[4. Evaluation of storage stability of the coloring curable composition 1-C-1 (coating liquid)] The colored curable composition 1-C-1 was stored at room temperature for one month, and then evaluated by visual observation according to the following criteria. The degree of precipitation of foreign matter.

<判定基準>○：未認定有析出。<Judgment criterion> ○: No precipitation was confirmed.

△：認定有少許析出。△: It was confirmed that there was a little precipitation.

×：認定有析出。×: It is determined that there is precipitation.

[5.使用著色硬化性組成物1－C－1製造彩色濾光片及評價]將前述3.所調製的著色感光性樹脂組成物1－C－1，塗布在前述2.所得到具有底塗層之矽晶圓基板的底塗層上，來形成光硬化性的塗布膜。隨後，以該塗布膜的乾燥膜厚度成為0.9微米的方式使用100℃的熱板進行加熱處理(預烘焙)120秒。[5. Production of color filter using coloring curable composition 1-C-1 and evaluation] The coloring photosensitive resin composition 1-C-1 prepared in the above 3. was applied to the above-mentioned 2. The coating is applied to the undercoat layer of the wafer substrate to form a photocurable coating film. Subsequently, heat treatment (prebaking) was performed for 120 seconds using a hot plate of 100 ° C so that the dried film thickness of the coating film became 0.9 μm.

接著，使用i射線步進曝光裝置FPA－3000i5＋(Canon(股)製)，藉由365奈米的波長透過圖案為2微米四方的島狀(Island)圖案光罩，以10~1600mJ/cm² 的曝光量進行照射。Next, using an i-ray stepwise exposure apparatus FPA-3000i5+ (manufactured by Canon), an island-shaped pattern mask having a pattern of 2 μm square is transmitted at a wavelength of 365 nm, and is 10 to 1600 mJ/cm ^{2 .} The exposure amount is irradiated.

隨後，將形成有已照射塗布膜之矽晶圓基板放置在旋轉噴淋顯像機(DW－30型、CHEMITRONICS(股)製)的水平旋轉平台上，使用CD－2000(FUJI FILM ELECTRONICS MATERIALS(股)製)，於23℃進行浸置式顯像60秒，在矽晶圓基板上形成著色圖案。Subsequently, the tantalum wafer substrate on which the irradiated coating film was formed was placed on a horizontal rotating platform of a rotary spray developing machine (DW-30 type, manufactured by CHEMITRONICS Co., Ltd.) using CD-2000 (FUJI FILM ELECTRONICS MATERIALS ( The system was subjected to dip-type development at 23 ° C for 60 seconds to form a colored pattern on the germanium wafer substrate.

將形成有著色圖案之矽晶圓基板，以真空處理方式固定在前述水平旋轉平台，邊藉由旋轉裝置以旋轉數50r.p.m使該矽晶圓基板旋轉、邊自該旋轉中心的上方，噴淋狀地供給來自噴嘴的純水，來進行沖洗處理，隨後進行噴霧乾燥而製得彩色濾光片。The silicon wafer substrate on which the colored pattern is formed is fixed to the horizontal rotating platform by vacuum processing, and the germanium wafer substrate is rotated by the rotating device at a rotation number of 50 r.pm, and is sprayed from above the rotating center. The pure water from the nozzle is supplied in a shower form to carry out a rinsing treatment, followed by spray drying to obtain a color filter.

<曝光敏感度>在曝光製程，光照射過的區域之顯像後的膜厚度，將相對於曝光前的膜厚度100%，膜厚度為95%以上之最小曝光量作為曝光敏感度。曝光敏感度的值越小表示敏感度越高。又，此時使用測長SEM「S－9260A」(HITACHI HITECHNOLOGIES(股)製)，來測定著色圖案的尺寸。圖案尺寸越接近2微米，表示硬化性充分且敏感度良好。<Exposure Sensitivity> In the exposure process, the film thickness after development of the light-irradiated region is the exposure sensitivity with respect to the film thickness before exposure of 100% and the film thickness of 95% or more. The smaller the value of the exposure sensitivity, the higher the sensitivity. In this case, the size of the colored pattern was measured using a length measuring SEM "S-9260A" (manufactured by HITACHI HITECHNOLOGIES Co., Ltd.). The closer the pattern size is to 2 μm, the sufficient hardenability and the good sensitivity.

測定評價結果如下述表5所示。The measurement evaluation results are shown in Table 5 below.

<基板黏附性>評價基板黏附性係觀察是否產生圖案缺損。基於以下基準來評價此等評價項目。<Substrate Adhesion> The substrate adhesion was evaluated to see if a pattern defect occurred. These evaluation items are evaluated based on the following criteria.

○：未觀察到有圖案缺損。○: No pattern defect was observed.

△：幾乎未觀察到有圖案缺損，但觀察到一部分缺損。△: A pattern defect was hardly observed, but a part of the defect was observed.

×：觀察到有顯著的圖案缺損。×: A significant pattern defect was observed.

<圖案剖面形狀>觀察所形成的圖案剖面形狀。圖案剖面形狀以順錐形為最佳，其次為矩形，以反錐形為不佳。<Pattern section shape> The pattern cross-sectional shape formed was observed. The shape of the cross-section of the pattern is preferably a straight cone, followed by a rectangle, and the reverse taper is not preferable.

[比較例1－2－1][Comparative Example 1-2-1]

在實施例1－2－1，除了將調製著色硬化性組成物1－C－1所使用組成1－C－1，變更為下述組成1－D－1以外，全部與實施例1－2－1同樣地進行，來調製比較用著色硬化性組成物D－1，同時得到形成有著色圖案之彩色濾光片。並進行與實施例1－2－1同樣的評價。結果如表5所示。In Example 1-2-1, except that the composition 1-C-1 used for the preparation of the coloring curable composition 1-C-1 was changed to the following composition 1-D-1, all and Example 1-2 were used. In the same manner, the coloring curable composition D-1 for comparison was prepared, and a color filter in which a colored pattern was formed was obtained. The same evaluation as in Example 1-2-1 was carried out. The results are shown in Table 5.

[實施例1－2－2~1－2－26、比較例1－2－2~1－2－5][Examples 1-2-2 to 1-2-26, Comparative Examples 1-2-2 to 1-2-5]

在實施例1－2－1，除了將調製著色感光性組成物1－C－1所使用組成1－C－1中的特定敏化劑、光聚合引發劑、及共敏化劑各自變更為下述表6所示以外，全部與實施例1－2－1同樣地進行，來調製著色感光性組成物1－C－2~1－C－26及比較用著色硬化性組成物1－C－27~1－C－30，同時形成著色圖案，並進行評價。結果如下述表5所示。In the example 1-2-1, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer in the composition 1-C-1 used in the preparation of the coloring photosensitive composition 1-C-1 were changed to In the same manner as in Example 1-2-1 except for the following Table 6, the coloring photosensitive composition 1-C-2 to 1-C-26 and the coloring curable composition for comparison 1-C were prepared. -27~1-C-30, at the same time forming a color pattern and evaluation. The results are shown in Table 5 below.

[實施例1－2－24][Example 1-2-24]

在實施例1－2－1，除了將調製著色感光性組成物1－C－1所使用組成1－C－1變更為下述組成1－E－1以外，全部與實施例1－2－1同樣地進行，來調製著色感光性組成物1－E－1，同時形成著色圖案而得到彩色濾光片。並且與實施例1－2－1同樣地進行評價。結果如表5所示。In Example 1-2-1, except that the composition 1-C-1 used for the coloring photosensitive composition 1-C-1 was changed to the following composition 1-E-1, all and Example 1-2- 1 was carried out in the same manner to prepare a coloring photosensitive composition 1-E-1, and a coloring pattern was formed to obtain a color filter. Further, evaluation was carried out in the same manner as in Example 1-2-1. The results are shown in Table 5.

[實施例1－2－25、比較例1－2－6][Examples 1-2-25, Comparative Examples 1-2-6]

在實施例1－2－24，除了將調製著色感光性組成物1－E－1所使用組成1－E－1中的特定敏化劑、光聚合引發劑、及共敏化劑各自變更為下述表5所示以外，全部與實施例1－2－24同樣地進行，來調製著色感光性組成物1－E－2及比較用著色硬化性組成物1－E－3，同時形成著色圖案，並進行評價。結果如下述表5所示。In the examples 1-2-24, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer in the composition 1-E-1 used in the preparation of the coloring photosensitive composition 1-E-1 were changed to In the same manner as in Example 1-2-24, except that the following Table 5 was used, the coloring photosensitive composition 1-E-2 and the comparative coloring curable composition 1-E-3 were prepared and colored. Pattern and evaluate. The results are shown in Table 5 below.

[比較例1－2－7][Comparative Example 1-2-7]

在實施例1－2－1，除了將調製著色感光性組成物1－C－1所使用組成1－C－1變更為下述組成1－F－1以外，全部與實施例1－2－1同樣地進行，來調製著色感光性組成物1－F－1，同時形成著色圖案而得到彩色濾光片。並且與實施例1－2－1同樣地進行評價。結果如表5所示。In Example 1-2-1, except that the composition 1-C-1 used for the coloring photosensitive composition 1-C-1 was changed to the following composition 1-F-1, all and Example 1-2- 1 was carried out in the same manner to prepare a coloring photosensitive composition 1-F-1, and a coloring pattern was formed to obtain a color filter. Further, evaluation was carried out in the same manner as in Example 1-2-1. The results are shown in Table 5.

如表5所示，光聚合引發劑D1~D3、共敏化劑F1~F3、比較化合物1－1~1－4係前述化合物。As shown in Table 5, the photopolymerization initiators D1 to D3, the co-sensitizers F1 to F3, and the comparative compounds 1-1 to 1-4 are the above compounds.

從表5的結果，得知含有特定敏化劑(化合物1－1~1－19)之實施例的各著色硬化性組成物在其溶液狀態之保存安定性優良，在支撐體上形成畫像時，相對於未含有特定敏化劑或使用比較化合物1－1~1－4之各比較例，能夠得到曝光敏感度高、顯像性優良、同時基板黏附性、圖案剖面形狀都優良的彩色濾光片。From the results of Table 5, it is understood that each of the colored curable compositions of the examples containing the specific sensitizer (compounds 1-1 to 1-19) has excellent storage stability in a solution state, and when a portrait is formed on the support. Compared with the comparative examples which do not contain a specific sensitizer or the comparative compound 1-1~1-4, it is possible to obtain a color filter which is excellent in exposure sensitivity, excellent in image formation, and excellent in substrate adhesion and pattern cross-sectional shape. Light film.

[實施例2－1－1][Example 2-1-1]

說明調製硬化性組成物2－A－1，並使用該硬化性組成物2－A－1來製造著色圖案塗布膜的例子。An example in which the curable composition 2-A-1 is prepared and the curable composition 2-A-1 is used to produce a colored pattern coating film will be described.

[1.硬化性組成物2－A－1(塗布液)的調製]將下述組成2－A－1的成分均勻地混合溶解，來調製硬化性組成物2－A－1。[1. Preparation of Curable Composition 2-A-1 (Coating Liquid)] The components of the following composition 2-A-1 were uniformly mixed and dissolved to prepare a curable composition 2-A-1.

<組成2－A－1>．光聚合引發劑(UV1－6992(DOW CHEMICAL製)) 0.08毫莫耳．聚合性化合物(新戊四醇四丙烯酸酯) 1克．黏合劑樹脂(聚甲基丙烯酸甲酯(Aldrich公司製試藥、Mw：c.a.996000) 1克．特定敏化劑(化合物2－1) 0.08毫莫耳．溶劑(環己酮) 16克<composition 2-A-1>. Photopolymerization initiator (UV1-6992 (manufactured by DOW CHEMICAL)) 0.08 millimolar. Polymeric compound (neopentitol tetraacrylate) 1 g. Adhesive resin (polymethyl methacrylate (tested by Aldrich, Mw: c.a.996000) 1 g. Specific sensitizer (Compound 2-1) 0.08 mmol. Solvent (cyclohexanone) 16 g

[2.硬化性組成物塗布膜的製造]將藉由上述所得到的硬化性組成物2－A－1作為光阻溶液，使用旋轉塗布器塗布在10公分×10公分的玻璃基板(旭硝子公司製：AN635)，在40℃乾燥10分鐘，來形成1.5微米膜厚度之硬化性組成物塗布膜。[2. Production of Curable Composition Coating Film] The curable composition 2-A-1 obtained above was used as a photoresist solution, and coated on a glass substrate of 10 cm × 10 cm using a spin coater (Asahi Glass Co., Ltd.) Preparation: AN635), dried at 40 ° C for 10 minutes to form a hardened composition coating film having a film thickness of 1.5 μm.

[3.性能評價]如下進行評價使用上述所得到的硬化性組成物2－A－1(塗布液)形成於玻璃基板上之硬化性組成物塗布膜的敏感度級數。結果如表13所示。[3. Performance Evaluation] The sensitivity level of the curable composition coating film formed on the glass substrate using the curable composition 2-A-1 (coating liquid) obtained above was evaluated as follows. The results are shown in Table 13.

－硬化性組成物塗布膜的敏感度級數－在如上述形成的硬化性組成物塗布膜上，放置21√ 2階段片(step tablet)(DAINIPPON SCREEN公司製灰階薄膜)，透過熱線截止濾片使USHIO電機公司製500mW之高壓水銀燈的光曝光30秒後，浸漬在甲苯中60秒來進行顯像處理，並將對應階段片之完全硬化而不溶化的級數作為敏感度而進行評價。級數越多表示敏感度越高。- Sensitivity level of the coating film of the curable composition - On the coating film of the curable composition formed as described above, a 21 √ 2 stage sheet (step film (DAINIPPON SCREEN company gray scale film) was placed, and the hot line cut filter was passed through The film was exposed to light of a high-pressure mercury lamp of 500 mW manufactured by USHIO Electric Co., Ltd. for 30 seconds, and then immersed in toluene for 60 seconds to carry out development processing, and the number of stages in which the corresponding stage sheets were completely hardened and insolubilized was evaluated as sensitivity. The greater the number of stages, the higher the sensitivity.

[實施例2－1－2~2－1－12、比較例2－1－1~2－1－7][Examples 21-2 to 2-1-12, Comparative Examples 2-1-1 to 2-1-7]

在實施例2－1－1，除了將特定敏化劑、及光聚合引發劑變更為下述表13所示以外，全部與實施例2－1－1同樣地進行，來調製硬化性組成物2－A－2~A－19，得到具有使用其所構成的硬化性組成物塗布膜之彩色濾光片。而且，與實施例2－1－1同樣地進行評價。結果如下述表13所示。In the case of Example 2-1-1, except that the specific sensitizer and the photopolymerization initiator were changed to the following Table 13, all of them were carried out in the same manner as in Example 2-1-1 to prepare a curable composition. 2-A-2 to A-19, a color filter having a coating film of a curable composition composed of the same is obtained. Further, evaluation was carried out in the same manner as in Example 2-1-1. The results are shown in Table 13 below.

表13所示之化合物1~化合物6、及比較化合物1~比較化合物3係表示表12所記載之化合物。又，表13所示之Irgacure OXE－01、化合物E、LD－5、及化合物I係表示以下所示之化合物。The compound 1 to the compound 6 shown in Table 13 and the comparative compound 1 to the comparative compound 3 are the compounds described in Table 12. Further, Irgacure OXE-01, Compound E, LD-5, and Compound I shown in Table 13 represent the compounds shown below.

從表13的結果，得知含有特定敏化劑(化合物2－1~2－6)之各實施例硬化性組成物，相對於使用比較化合物2－1~比較化合物2－3代替特定敏化劑之各比較例，曝光敏感度較高。From the results of Table 13, it was found that the hardening compositions of the respective examples containing the specific sensitizers (Compounds 2-1 to 2-6) were substituted for the specific sensitization with respect to Comparative Compound 2-1 to Comparative Compound 2-3. In each of the comparative examples, the exposure sensitivity was high.

[實施例2－1][Example 2-1]

接著，說明調製含有著色劑(顏料)之著色硬化性組成物層2－B－1，使用該著色硬化性組成物2－B－1來製造液晶顯示元件用途之彩色濾光片之例子。Next, an example of preparing a color-curable composition layer 2-B-1 containing a colorant (pigment) and using the colored curable composition 2-B-1 to produce a color filter for a liquid crystal display element will be described.

[1.著色硬化性組成物2－B－1的調製]1－1.顏料分散液(P1)的調製使用與在實施例1－1－1同樣地調製而成的顏料分散液。[1. Preparation of coloring curable composition 2-B-1] 1-1. Preparation of pigment dispersion liquid (P1) A pigment dispersion liquid prepared in the same manner as in Example 1-1-1 was used.

1－2.著色硬化性組成物2－B－1(塗布液)的調製混合溶解下述組成2－B－1的成分，來調製著色硬化性組成物2－B－1。1-2. Preparation and mixing of the coloring curable composition 2-B-1 (coating liquid) The component of the following composition 2-B-1 was dissolved to prepare a coloring curable composition 2-B-1.

[2.彩色濾光片的製造]除了使用著色硬化性組成物2－B－1代替著色硬化性組成物1－A－1以外，使用與實施例1－1－1同樣的方法，形成著色硬化性組成物塗布膜(著色硬化性組成物層)，並曝光、顯像、加熱處理，得到彩色濾光片。[2. Production of color filter] Coloring was carried out in the same manner as in Example 1-1-1 except that the colored curable composition 2-B-1 was used instead of the colored curable composition 1-A-1. The curable composition coating film (coloring curable composition layer) is exposed, developed, and heat-treated to obtain a color filter.

[3.性能評價]對上述所調製的著色硬化性組成物2－B－1(塗布液)，與實施例1－1－1同樣地進行評價。結果如表13所示。[3. Performance Evaluation] The coloring curable composition 2-B-1 (coating liquid) prepared above was evaluated in the same manner as in Example 1-1-1. The results are shown in Table 13.

[比較例2－1][Comparative Example 2-1]

在實施例2－2－1，除了使用下述所示之組成代替著色感光性組成物2－B－1以外，全部與實施例2－2－1同樣地進行，得到具有著色圖案之彩色濾光片。而且，進行與實施例2－2－1同樣的評價。結果如表14所示。In the same manner as in Example 2-2-1, except that the composition shown below was used instead of the colored photosensitive composition 2-B-1, a color filter having a colored pattern was obtained. Light film. Further, the same evaluation as in Example 2-2-1 was carried out. The results are shown in Table 14.

混合溶解下述組成2－B－11的成分，來調製著色硬化性組成物2－B－11。The coloring curable composition 2-B-11 was prepared by mixing and dissolving the component of the following composition 2-B-11.

[實施例2－2－2~2－10、比較例2－2－2~2－4][Example 2-2-2~2-10, Comparative Example 2-2-2~2-4]

在實施例2－2－1，除了將調製著色硬化性組成物2－B－1所使用組成2－B－1中的特定敏化劑、光聚合引發劑、及共敏化劑各自變更為下述表14所示以外，全部與實施例2－2－1同樣地進行，來調製著色感光性組成物2－B－2~2－B－10、2－B－12~2－B－14，得到具有使用其所構成的著色圖案之彩色濾光片。而且與實施例2－2－1同樣地進行評價。結果如下述表14所示。In the example 2-2-1, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer in the composition 2-B-1 used in the preparation of the coloring curable composition 2-B-1 were each changed to The coloring photosensitive compositions 2-B-2 to 2-B-10 and 2-B-12 to 2-B- were prepared in the same manner as in Example 2-2-1 except as shown in the following Table 14. 14. A color filter having a colored pattern formed using the same is obtained. Further, evaluation was carried out in the same manner as in Example 2-2-1. The results are shown in Table 14 below.

表14所示之光聚合引發劑D1~D4、共敏化劑A1及A2係以下所示之化合物。The photopolymerization initiators D1 to D4 and the co-sensitizers A1 and A2 shown in Table 14 are the compounds shown below.

D1：2,2’－雙(2－氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑D2：1－[4－(苯硫基)苯基]－2－(O－苯甲醯肟)D3：4－苯并氧雜環壬烷－2,6－二(三氯甲基)－s－三D4：Irgacure 784(ciba製)A1：氫硫基苯并噻唑A2：N－苯基氫硫基苯并咪唑D1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole D2: 1-[4-(phenylthio)benzene ]]-2-(O-benzhydrazide) D3: 4-benzoxanthracene-2,6-di(trichloromethyl)-s-three D4: Irgacure 784 (manufactured by ciba) A1: thiophanylbenzothiazole A2: N-phenyl thiothiobenzimidazole

從表14的結果，得知含有特定敏化劑(化合物2－1－~化合物2－6)之各實施例的著色硬化性組成物係在其溶液狀態具有優良的保存安定性。又，得知使用該著色硬化性組成物在支撐體上形成著色圖案時，相對於未含有特定敏化劑或使用比較化合物2－1~2－3之各比較例，能夠得到曝光敏感度高、顯像性優良、同時基板黏附性、圖案剖面形狀都優良的彩色濾光片。From the results of Table 14, it was found that the color hardening composition of each of the examples containing the specific sensitizer (Compound 2-1 to Compound 2-6) had excellent storage stability in the solution state. Moreover, when the coloring pattern was formed on the support using the colored curable composition, it was found that the exposure sensitivity was high with respect to each of the comparative examples in which the specific sensitizer was not contained or the comparative compounds 2-1 to 2-3 were used. A color filter that is excellent in image development, and has excellent substrate adhesion and pattern cross-sectional shape.

以下，舉出調製含有著色劑(顏料)之硬化性組成物(作為形成固體攝像元件用途之彩色濾光片用)之例子，來進行說明。Hereinafter, an example in which a curable composition containing a colorant (pigment) (for use as a color filter for forming a solid-state image sensor) is prepared will be described.

[實施例2－3－1][Example 2-3-1]

[1.光阻液的調製]與實施例1－2－1同樣地製造光阻液。[1. Preparation of Photoresist] A photoresist was produced in the same manner as in Example 1-2-1.

[2.具有底塗層之矽晶圓基板的製造]與在實施例1－2－1同樣地，得到具有底塗層之矽晶圓基板。[2. Production of ruthenium wafer substrate having undercoat layer] A ruthenium wafer substrate having an undercoat layer was obtained in the same manner as in Example 1-2-1.

[3.著色硬化性組成物2－C－1的調製]混合溶解下述組成2－C－1的化合物，來調製著色硬化性組成物2－C－1。[3. Preparation of Coloring Curable Composition 2-C-1] The coloring curable composition 2-C-1 was prepared by mixing and dissolving the compound of the following composition 2-C-1.

[4.著色硬化性組成物2－C－1(塗布液)的保存安定性評價]與在實施例1－2－1同樣地，將著色硬化性組成物2－C－1保存在室溫1個月而進行評價。測定評價的結果係如下述表15所示。[4. Evaluation of storage stability of the coloring curable composition 2-C-1 (coating liquid)] The colored curable composition 2-C-1 was stored at room temperature in the same manner as in Example 1-2-1. Evaluation was performed for 1 month. The results of the measurement evaluation are shown in Table 15 below.

[5.使用著色硬化性組成物2－C－1製造彩色濾光片及評價]除了使用著色感光性組成物2－C－1代替著色硬化性組成物1－C－1以外，與實施例1－2－1同樣地進行，來製造彩色濾光片。[5. Production of Color Filter Using Coloring Curable Composition 2-C-1 and Evaluation] Except that the coloring photosensitive composition 2-C-1 was used instead of the colored curable composition 1-C-1, and Examples 1-2-1 was carried out in the same manner to manufacture a color filter.

<曝光敏感度>與在實施例1－2－1同樣地評價曝光敏感度。測定評價的結果如下述表15所示.<Exposure Sensitivity> The exposure sensitivity was evaluated in the same manner as in Example 1-2-1. The results of the measurement evaluation are shown in Table 15 below.

<顯像性、基板黏附性、及圖案剖面形狀>顯像性、基板黏附性、及圖案剖面形狀係依據實施例2－2－1~實施例2－2－10所記載之評價基準來進行評價。測定評價結果係如下述表15所示。<Development property, substrate adhesion, and pattern cross-sectional shape> Development property, substrate adhesion, and pattern cross-sectional shape were performed based on the evaluation criteria described in Example 2-2-1 to Example 2-2-10. Evaluation. The measurement evaluation results are shown in Table 15 below.

[實施例2－3－2][Example 2-3-2]

在實施例2－3－1，除了使用下述所示之組成2－C－2代替著色感光性組成物2－C－1以外，全部與實施例2－3－1同樣地進行，來調製具有著色圖案之彩色濾光片。而且，進行與實施例2－3－1同樣的評價。結果如表15所示。In the example 2-3-1, except that the composition 2-C-2 shown below was used instead of the coloring photosensitive composition 2-C-1, all were carried out in the same manner as in Example 2-3-1. A color filter having a colored pattern. Further, the same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 15.

混合溶解下述組成2－C－2的成分，來調製著色硬化性組成物2－C－2。The coloring curable composition 2-C-2 was prepared by mixing and dissolving the component of the following composition 2-C-2.

[實施例2－3－3~實施例2－3－12][Example 2-3-3~ Example 2-3-12]

在實施例2－3－1，除了將調製著色感光性組成物2－C－1所使用組成2－C－1中的特定敏化劑、光聚合引發劑、及共敏化劑變更為下述表15所示以外，全部與實施例2－3－1同樣地進行，來調製著色感光性組成物2－C－3~2－C－12，得到具有使用其所構成之著色圖案之彩色濾光片。而且進行與實施例2－3－1同樣的評價。結果如下述表15所示。In Example 2-3-1, except for the specific sensitizer, photopolymerization initiator, and co-sensitizer in the composition 2-C-1 used for preparing the coloring photosensitive composition 2-C-1, In the same manner as in Example 2-3-1 except that the conditions shown in Table 15 were carried out, the coloring photosensitive composition 2-C-3 to 2-C-12 was prepared to obtain a color having a colored pattern formed using the same. Filter. Further, the same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 15 below.

[比較例2－3－1][Comparative Example 2-3-1]

在實施例2－3－1，除了將調製著色感光性組成物2－C－1所使用組成2－C－1，變更為下述組成2－C－13以外，全部與實施例2－3－1同樣地進行，來調製著色感光性組成物2－C－13，形成著色圖案而得到彩色濾光片。而且進行與實施例2－3－1同樣的評價。結果如下述表15所示。In Example 2-3-1, except that the composition 2-C-1 used for the preparation of the coloring photosensitive composition 2-C-1 was changed to the following composition 2-C-13, all were carried out in the same manner as in Example 2-3. In the same manner, the colored photosensitive composition 2-C-13 was prepared to form a colored pattern to obtain a color filter. Further, the same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 15 below.

[比較例2－3－5][Comparative Example 2-3-5]

在實施例2－3－1，除了將調製著色感光性組成物2－C－1所使用組成2－C－1，變更為下述組成2－C－17以外，全部與實施例2－3－1同樣地進行，來調製著色感光性組成物2－C－17，形成著色圖案而得到彩色濾光片。而且進行與實施例2－3－1同樣的評價。結果如下述表15所示。In Example 2-3-1, except that the composition 2-C-1 used for the coloring photosensitive composition 2-C-1 was changed to the following composition 2-C-17, all were carried out in the same manner as in Example 2-3. In the same manner, the colored photosensitive composition 2-C-17 was prepared to form a colored pattern to obtain a color filter. Further, the same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 15 below.

[比較例2－3－2~2－3－4、2－3－6][Comparative Example 2-3-2~2-3-4, 2-3-6]

在實施例2－3－1，除了將調製著色感光性組成物C－1所使用組成2－C－1中的特定敏化劑、光聚合引發劑、及共敏化劑變更為下述表9所示以外，全都與實施例2－3－1同樣地進行，來調製比較用著色感光性組成物2－C－14~2－C－16、2－C－18，同時在支撐體上形成著色圖案來製造彩色濾光片，而且進行評價。結果如下述表15所示。In the example 2-3-1, the specific sensitizer, photopolymerization initiator, and co-sensitizer in the composition 2-C-1 used in the preparation of the coloring photosensitive composition C-1 were changed to the following table. In the same manner as in Example 2-3-1, all of the coloring photosensitive compositions 2-C-14~2-C-16 and 2-C-18 for comparison were prepared while being on the support. A coloring pattern was formed to fabricate a color filter, and evaluation was performed. The results are shown in Table 15 below.

如表15所示之光聚合引發劑D1~D3、共敏化劑A1及A2、比較化合物2－1~2－3係上述之化合物。The photopolymerization initiators D1 to D3, the co-sensitizers A1 and A2, and the comparative compounds 2-1 to 2-3 shown in Table 15 are the above compounds.

從表15的結果，得知含有特定敏化劑(化合物2－1~2－6)之各實施例的著色硬化性組成物係在其溶液狀態具有優良的保存安定性。又，得知使用該著色硬化性組成物在支撐體上形成著色圖案時，相對於未含有特定敏化劑或使用比較化合物2－1~2－3之各比較例，能夠得到曝光敏感度高、顯像性優良、同時基板黏附性、圖案剖面形狀都優良的彩色濾光片。From the results of Table 15, it was found that the color hardening composition of each of the examples containing the specific sensitizer (compounds 2-1 to 2-6) had excellent storage stability in the solution state. Moreover, when the coloring pattern was formed on the support using the colored curable composition, it was found that the exposure sensitivity was high with respect to each of the comparative examples in which the specific sensitizer was not contained or the comparative compounds 2-1 to 2-3 were used. A color filter that is excellent in image development, and has excellent substrate adhesion and pattern cross-sectional shape.

而且，本發明之通式(3－1)所示化合物之化合物3－1~3－7的合成例係如下所示。Further, the synthesis examples of the compounds 3-1 to 3-7 of the compound of the formula (3-1) of the present invention are shown below.

(合成例3－1)將27克二苯基胺基苯甲醛、3.5克哌啶溶解在450毫升甲醇中後，邊回流1小時邊攪拌。接著，添加17克3－乙基－2－烯丙亞胺基－唑烷－4－酮並邊回流1小時邊攪拌。反應結束後，放冷至室溫時，有黃色結晶析出。過濾析出的結晶，添加1000毫升甲醇攪拌1小時。過濾結晶並乾燥，得到23克下述結構的化合物1(產率55%)。藉由¹ H－NMR(溶劑CDCl₃ )、紅外吸收光譜、質量分析頻譜、及元素分析進行鑑定。熔點(67℃)、電子吸收光譜(THF)：吸收極大波長388奈米、吸收極大莫耳吸光係數29400。氧化電位(CH₃ CN、vs Ag/AgCl)＋0.89V。(Synthesis Example 3-1) After dissolving 27 g of diphenylaminobenzaldehyde and 3.5 g of piperidine in 450 ml of methanol, the mixture was stirred under reflux for 1 hour. Next, add 17 grams of 3-ethyl-2-allylimidate - The oxazolidin-4-one was stirred while refluxing for 1 hour. After the completion of the reaction, when it was allowed to cool to room temperature, yellow crystals were precipitated. The precipitated crystals were filtered, and stirred with 1000 ml of methanol for 1 hour. The crystals were filtered and dried to give 23 g of Compound 1 (yield 55%) of the structure below. Identification was carried out by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass analysis spectrum, and elemental analysis. Melting point (67 ° C), electron absorption spectrum (THF): absorption maximum wavelength 388 nm, absorption maximum molar absorption coefficient 29400. Oxidation potential (CH ₃ CN, vs Ag/AgCl) + 0.89V.

(合成例3－2)將35克二苯基胺基苯甲醛、2.0克哌啶溶解在500毫升甲醇中後，邊回流1小時邊攪拌。接著，添加20克3－乙基－2－硫代－4－唑烷酮並邊回流4小時邊攪拌。反應結束後，放冷至室溫時，有黃色結晶析出。過濾析出的結晶，添加1000毫升甲醇攪拌1小時。過濾結晶並乾燥，得到48克下述結構的化合物3－2(產率91%)。藉由¹ H－NMR進行鑑定。(Synthesis Example 3-2) After dissolving 35 g of diphenylaminobenzaldehyde and 2.0 g of piperidine in 500 ml of methanol, the mixture was stirred under reflux for 1 hour. Next, add 20 g of 3-ethyl-2-thio-4- The oxazolidinone was stirred while refluxing for 4 hours. After the completion of the reaction, when it was allowed to cool to room temperature, yellow crystals were precipitated. The precipitated crystals were filtered, and stirred with 1000 ml of methanol for 1 hour. The crystals were filtered and dried to give 48 g of Compound 3-2 (yield: 91%). Identification by ¹ H-NMR.

接著將1.7克硝酸銀溶解在20毫升乙腈後，添加2.0克化合物2，在室溫攪拌0.5小時。接著，滴加1.0克苄胺並攪拌1.5小時後，滴加1.0克三乙胺，進而攪拌1.5小時。反應結束後，添加30毫升丙酮，使用矽藻土過濾分開析出的銀鹽，將濾液投入150毫升水中。過濾取得析出的結晶後，在甲醇中進行再分散，得到1.9克與合成例3－1所得到之物同樣的化合物3－1(產率88%)。藉由¹ H－NMR進行鑑定。Next, after dissolving 1.7 g of silver nitrate in 20 ml of acetonitrile, 2.0 g of Compound 2 was added, and the mixture was stirred at room temperature for 0.5 hour. Next, 1.0 g of benzylamine was added dropwise and stirred for 1.5 hours, and then 1.0 g of triethylamine was added dropwise, followed by stirring for 1.5 hours. After completion of the reaction, 30 ml of acetone was added, and the precipitated silver salt was separated by filtration using diatomaceous earth, and the filtrate was poured into 150 ml of water. The crystals which precipitated were collected by filtration, and then redispersed in methanol to obtain 1.9 g of the compound 3-1 (yield: 88%) which was obtained in the same manner as the compound obtained in the compound 3-1. Identification by ¹ H-NMR.

(合成例3－3)將20克2,3,6,7－四氫－1H,5H－吡啶并－[3,2,1－η]－喹啉－9－碳化醛、3.5克吡咯啶，溶解在400毫升甲醇後，邊回流1.5小時邊攪拌。接著，添加21克3－苯基乙基－1,3－唑烷－2,4－二酮並邊回流4小時邊攪拌。反應結束後，放冷至室溫時，有黃色結晶析出。過濾析出的結晶，添加800毫升甲醇攪拌1小時。過濾結晶並乾燥，得到33克下述結構的化合物3－3(產率85%)。藉由¹ H－NMR(溶劑CDCl₃ )、紅外吸收光譜、質量分析頻譜、及元素分析進行鑑定。熔點(162℃)、電子吸收光譜(THF)：吸收極大波長412奈米、吸收極大莫耳吸光係數35500。氧化電位(CH₃ CN、vs Ag/AgCl)＋0.64V。(Synthesis Example 3-3) 20 g of 2,3,6,7-tetrahydro-1H,5H-pyrido-[3,2,1-η]-quinoline-9-carbaldehyde, 3.5 g of pyrrolidine After dissolving in 400 ml of methanol, it was stirred while refluxing for 1.5 hours. Next, add 21 g of 3-phenylethyl-1,3- The oxazolidine-2,4-dione was stirred while refluxing for 4 hours. After the completion of the reaction, when it was allowed to cool to room temperature, yellow crystals were precipitated. The precipitated crystals were filtered, and added with 800 ml of methanol and stirred for 1 hour. The crystals were filtered and dried to give 33 g of Compound 3-3 (yield: 85%). Identification was carried out by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass analysis spectrum, and elemental analysis. Melting point (162 ° C), electron absorption spectrum (THF): absorption maximum wavelength 412 nm, absorption maximum molar absorption coefficient 35500. Oxidation potential (CH ₃ CN, vs Ag/AgCl) + 0.64V.

(合成例3－4)藉由與合成例3－2所記載的方法同樣的方法來合成化合物3－2。(Synthesis Example 3-4) Compound 3-2 was synthesized by the same method as the method of Synthesis Example 3-2.

接著，將2.8克硝酸銀溶解在40毫升乙腈後，添加3.0克化合物2，在室溫攪拌0.5小時。接著，滴加5克2,4,6－三甲基苯胺並攪拌1.5小時後，滴加1.0克三乙胺，進而在70℃攪拌1小時。反應結束後，添加60毫升丙酮，使用矽藻土過濾分開析出的銀鹽，將濾液投入300毫升水中。過濾取得析出的結晶後，在甲醇中進行再分散，得到3.5克下述結構的化合物3－4(產率92%)。藉由¹ H－NMR(溶劑CDCl₃ )、紅外吸收光譜、質量分析頻譜、及元素分析進行鑑定。熔點(117℃)、電子吸收光譜(THF)：吸收極大波長395奈米、吸收極大莫耳吸光係數30900。氧化電位(CH₃ CN、vs Ag/AgCl)＋0.82V。Next, after dissolving 2.8 g of silver nitrate in 40 ml of acetonitrile, 3.0 g of Compound 2 was added, and the mixture was stirred at room temperature for 0.5 hour. Next, 5 g of 2,4,6-trimethylaniline was added dropwise and stirred for 1.5 hours, and then 1.0 g of triethylamine was added dropwise, followed by stirring at 70 ° C for 1 hour. After completion of the reaction, 60 ml of acetone was added, and the precipitated silver salt was separated by filtration using diatomaceous earth, and the filtrate was poured into 300 ml of water. After the precipitated crystals were collected by filtration, they were redispersed in methanol to obtain 3.5 g of the compound 3-4 (yield: 92%). Identification was carried out by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass analysis spectrum, and elemental analysis. Melting point (117 ° C), electron absorption spectrum (THF): absorption maximum wavelength of 395 nm, absorption of the maximum Mohr absorption coefficient of 30,900. Oxidation potential (CH ₃ CN, vs Ag/AgCl) + 0.82V.

(合成例3－5)將1.8克二乙基胺基苯甲醛、0.7克哌啶、2.1克3－乙基－2－環己基亞胺基－唑烷－4－酮溶解在50毫升乙醇中後，邊回流8小時邊攪拌。反應結束後，放冷至室溫時，有黃色結晶析出。過濾析出的結晶，添加50毫升甲醇攪拌1小時。過濾結晶並乾燥，得到1.4克下述結構的化合物3－5(產率38%)。藉由¹ H－NMR(溶劑CDCl₃ )、紅外吸收光譜、質量分析頻譜、及元素分析進行鑑定。電子吸收光譜(THF)：吸收極大波長385奈米、吸收極大莫耳吸光係數37200。(Synthesis Example 3-5) 1.8 g of diethylaminobenzaldehyde, 0.7 g of piperidine, 2.1 g of 3-ethyl-2-cyclohexylimido- After the oxazolidine-4-one was dissolved in 50 ml of ethanol, it was stirred while refluxing for 8 hours. After the completion of the reaction, when it was allowed to cool to room temperature, yellow crystals were precipitated. The precipitated crystals were filtered, and added with 50 ml of methanol and stirred for 1 hour. The crystals were filtered and dried to give 1.4 g of Compound 3-5 (yield 38%) of the structure below. Identification was carried out by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass analysis spectrum, and elemental analysis. Electron absorption spectroscopy (THF): The absorption maximum wavelength is 385 nm, and the absorption maximum molar absorption coefficient is 37,200.

(合成例3－6)將17.7克二乙基胺基苯甲醛、1.0克哌啶溶解在250毫升甲醇中後，邊回流1小時邊攪拌。接著添加19.9克3－乙基－2－硫代－4－唑烷酮並邊回流4小時邊攪拌。反應結束後，放冷至室溫時，有黃色結晶析出。過濾析出的結晶，添加500毫升甲醇攪拌1小時。過濾結晶並乾燥，得到30.4克下述結構的化合物3－6(產率85%)。藉由¹ H－NMR進行鑑定。(Synthesis Example 3-6) After dissolving 17.7 g of diethylaminobenzaldehyde and 1.0 g of piperidine in 250 ml of methanol, the mixture was stirred under reflux for 1 hour. Then add 19.9 g of 3-ethyl-2-thio-4- The oxazolidinone was stirred while refluxing for 4 hours. After the completion of the reaction, when it was allowed to cool to room temperature, yellow crystals were precipitated. The precipitated crystals were filtered, and 500 ml of methanol was added and stirred for 1 hour. The crystals were filtered and dried to give 30.4 g of Compound 3-6 (yield: 85%). Identification by ¹ H-NMR.

(合成例3－7)將1.7克硝酸銀溶解在20毫升乙腈後，添加1.8克藉由與合成例3－6同樣的方法所得到的化合物3－6，在室溫攪拌0.5小時。接著，滴加1.0克環己胺並攪拌1.5小時後，滴加1.0克三乙胺，進而攪拌1.5小時。反應結束後，添加30毫升丙酮，使用矽藻土過濾分開析出的銀鹽，將濾液投入150毫升水中。過濾取得析出的結晶後，在甲醇中進行再分散，得到1.9克下述結構的化合物3－7(產率88%)。藉由¹ H－NMR(溶劑CDCl₃ )、紅外吸收光譜、質量分析頻譜、及元素分析進行鑑定。電子吸收光譜(THF)：吸收極大波長384奈米、吸收極大莫耳吸光係數38300。(Synthesis Example 3-7) After dissolving 1.7 g of silver nitrate in 20 ml of acetonitrile, 1.8 g of the compound 3-6 obtained by the same method as the synthesis of Example 3-6 was added, and the mixture was stirred at room temperature for 0.5 hour. Next, 1.0 g of cyclohexylamine was added dropwise and stirred for 1.5 hours, and then 1.0 g of triethylamine was added dropwise thereto, followed by stirring for 1.5 hours. After completion of the reaction, 30 ml of acetone was added, and the precipitated silver salt was separated by filtration using diatomaceous earth, and the filtrate was poured into 150 ml of water. The precipitated crystals were collected by filtration, and then redispersed in methanol to obtain 1.9 g of the compound 3-7 (yield: 88%) of the following structure. Identification was carried out by ¹ H-NMR (solvent CDCl ₃ ), infrared absorption spectrum, mass analysis spectrum, and elemental analysis. Electron absorption spectroscopy (THF): The absorption maximum wavelength is 384 nm, and the absorption maximum molar absorption coefficient is 38,300.

將化合物3－1~3－7結構整理記載於下述表16。又，在後述比較例所使用之比較化合物3－1~3－3的結構係記載於表17。The structural structuring of the compounds 3-1 to 3-7 is shown in Table 16 below. Moreover, the structures of the comparative compounds 3-1 to 3-3 used in the comparative examples described later are shown in Table 17.

以下藉由實施例更具體地說明本發明之彩色濾光片及其製法，但是只要未悖離本發明的主旨，未限定於以下的實施例。Hereinafter, the color filter of the present invention and the method for producing the same will be described more specifically by way of examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not deviated.

[實施例3－1－1][Example 3-1-1]

在此，調製含有著色劑(顏料)之著色硬化性組成物3－A－1，並使用該著色硬化性組成物3－A－1，來說明製造液晶顯示元件用途的彩色濾光片之例子。Here, an example of a color filter comprising a colorant (pigment) is prepared, and an example of a color filter for producing a liquid crystal display element is described using the colored curable composition 3-A-1. .

[1.著色硬化性組成物3－A－1的調製]1－1.顏料分散液(P1)的調製使用與在實施例1－1－1同樣地調製而成的顏料分散液。[1. Preparation of coloring curable composition 3-A-1] 1-1. Preparation of pigment dispersion liquid (P1) A pigment dispersion liquid prepared in the same manner as in Example 1-1-1 was used.

1－2.著色硬化性組成物3－A－1(塗布液)的調製混合下述組成3－A－1的成分並溶解，來調製著色硬化性組成物3－A－1。1-2. Preparation of coloring curable composition 3-A-1 (coating liquid) The following composition 3-A-1 was mixed and dissolved to prepare a coloring curable composition 3-A-1.

[2.彩色濾光片的製造]2－1.硬化性組成物層的形成除了使用著色硬化性組成物層3－A－1代替著色硬化性組成物1－A－1以外，藉由與實施例1－1－1同樣的方法，來形成著色硬化性組成物塗布膜(著色硬化性組成物層)，並曝光、顯像、加熱處理，得到彩色濾光片。[2. Manufacture of color filter] 2-1. Formation of a curable composition layer In addition to the coloring curable composition layer 3-A-1, instead of the coloring curable composition 1-A-1, In the same manner as in Example 1-1-1, a colored curable composition coating film (colored curable composition layer) was formed, and exposed, developed, and heat-treated to obtain a color filter.

[3.性能評價]對上述所調製的著色硬化性組成物3－A－1(塗布液)，進行與實施例1－1－1同樣的評價。結果如下述表18所示。[3. Performance Evaluation] The same evaluation as in Example 1-1-1 was carried out on the colored curable composition 3-A-1 (coating liquid) prepared above. The results are shown in Table 18 below.

[實施例3－1－2~3－1－10][Examples 3-1-2 to 3-1-10]

在實施例3－1－1，除了將調製著色硬化性組成物層3－A－1所使用的組成3－A－1中的特定敏化劑、及光聚合引發劑變更為下述表18所示以外，全部與實施例3－1－1同樣地進行，來調製硬化性組成物3－A－2~A－10，得到具有使用其所構成的著色圖案之彩色濾光片。而且，與實施例3－1－1同樣地進行評價。結果如下述表18所示。In the example 3-1-1, the specific sensitizer and the photopolymerization initiator in the composition 3-A-1 used for preparing the coloring curable composition layer 3-A-1 were changed to the following Table 18. In the same manner as in Example 3-1-1, the curable compositions 3-A-2 to A-10 were prepared to obtain a color filter having a colored pattern formed using the same. Further, evaluation was carried out in the same manner as in Example 3-1-1. The results are shown in Table 18 below.

[比較例1－1][Comparative Example 1-1]

在實施例3－1－1，除了將調製著色硬化性組成物3－A－1所使用組成3－A－1，變更為下述組成3－B－1以外，全部與實施例3－1－1同樣地進行，來調製比較用著色硬化性組成物B－1，形成著色圖案而得到彩色濾光片。而且進行與實施例3－1－1同樣的評價。結果如下述表18所示。In Example 3-1-1, except that the composition 3-A-1 used for the preparation of the coloring curable composition 3-A-1 was changed to the following composition 3-B-1, all of the examples and the examples 3-1 In the same manner, the coloring curable composition B-1 was prepared in the same manner to form a coloring pattern to obtain a color filter. Further, the same evaluation as in Example 3-1-1 was carried out. The results are shown in Table 18 below.

[比較例1－2~1－4][Comparative Example 1-2~1-4]

在實施例3－1－1所調製的著色硬化性組成物層3－A－1，除了將特定敏化劑、及光聚合引發劑、及共敏化劑變更為下述表18所示之比較化合物、光聚合引發劑、及共敏化劑以外，全部與實施例3－1－1同樣地進行，來調製比較用著色硬化性組成物3－B－2~3－B－4，得到具有使用其所構成的著色圖案之彩色濾光片。而且，與實施例3－1－1同樣地進行評價。結果如下述表18所示。In the colored curable composition layer 3-A-1 prepared in Example 3-1-1, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer were changed to those shown in Table 18 below. The comparative compound, the photopolymerization initiator, and the co-sensitizer were all prepared in the same manner as in Example 3-1-1 to prepare a comparative coloring curable composition 3-B-2 to 3-B-4. A color filter having a colored pattern formed using the same. Further, evaluation was carried out in the same manner as in Example 3-1-1. The results are shown in Table 18 below.

如表18所示之光聚合引發劑D1~D3、共敏化劑F1及F2係各自與表4所示之光聚合引發劑D1~D3、共敏化劑F1及F2相同。The photopolymerization initiators D1 to D3 and the co-sensitizers F1 and F2 shown in Table 18 are the same as the photopolymerization initiators D1 to D3 and the co-sensitizers F1 and F2 shown in Table 4, respectively.

從表18的結果，得知含有特定敏化劑(化合物3－1~3－7)之各實施例的著色硬化性組成物係在其溶液狀態具有優良的保存安定性。又，得知使用該著色硬化性組成物在支撐體上形成著色圖案時，相對於未含有特定敏化劑或使用比較化合物3－1~3－3之各比較例，能夠得到曝光敏感度高、顯像性優良、同時基板黏附性、圖案剖面形狀都優良的彩色濾光片。From the results of Table 18, it was found that the color hardening composition of each of the examples containing the specific sensitizer (compounds 3-1 to 3-7) had excellent storage stability in the solution state. Further, when it was found that a colored pattern was formed on the support using the colored curable composition, it was found that the exposure sensitivity was high with respect to each of the comparative examples in which the specific sensitizer was not contained or the comparative compounds 3-1 to 3-3 were used. A color filter that is excellent in image development, and has excellent substrate adhesion and pattern cross-sectional shape.

以下，說明調製含有固體攝像元件用途的著色劑(顏料)之著色硬化性組成物，使用該著色硬化性組成物來製造固體攝像元件用途的彩色濾光片之例子。Hereinafter, an example of a color filter having a coloring agent (pigment) containing a solid-state image sensor and preparing a color filter for use in a solid-state image sensor using the colored curable composition will be described.

[實施例3－2－1][Example 3-2-1]

[1.光阻液的調製]與實施例1－2－1同樣地進行光阻液調製。[1. Preparation of Photoresist] Photoresist liquid preparation was carried out in the same manner as in Example 1-2-1.

[2.具底塗層之矽晶圓基板的製造]與實施例1－2－1同樣地進行，得到具底塗層之矽晶圓基板。[2. Production of Undercoating Wafer Wafer Substrate] A primer wafer substrate having an undercoat layer was obtained in the same manner as in Example 1-2-1.

[3.著色硬化性組成物3－C－1的調製]混合溶解下述組成3－C－1的化合物，來調製著色硬化性組成物3－C－1。[3. Preparation of Colored Curable Composition 3-C-1] The colored curable composition 3-C-1 was prepared by mixing and dissolving the compound of the following composition 3-C-1.

[4.著色硬化性組成物3－C－1(塗布液)的保存安定性評價]與實施例1－2－1同樣地，將著色硬化性組成物3－C－1保存在室溫1個月後進行評價。[4. Evaluation of storage stability of the coloring curable composition 3-C-1 (coating liquid)] The colored curable composition 3-C-1 was stored at room temperature in the same manner as in Example 1-2-1. Evaluation is performed after one month.

[5.使用著色硬化性組成物3－C－1來製造彩色濾光片及評價]除了使用著色感光性組成物3－C－1代替著色硬化性組成物1－C－1以外，與實施例1－2－1同樣地進行，得到彩色濾光片。[5. Production of color filter using the coloring curable composition 3-C-1 and evaluation] In addition to using the colored photosensitive composition 3-C-1 instead of the colored curable composition 1-C-1, Example 1-2-1 was carried out in the same manner to obtain a color filter.

<曝光敏感度>與實施例1－2－1同樣地進行，來評價曝光敏感度、基板黏附性、及圖案剖面形狀。測定評價結果如下述表19所示。<Exposure Sensitivity> The exposure sensitivity, substrate adhesion, and pattern cross-sectional shape were evaluated in the same manner as in Example 1-2-1. The measurement evaluation results are shown in Table 19 below.

<顯像性>與實施例1－1－1同樣地進行評價。<Resonance> Evaluation was carried out in the same manner as in Example 1-1-1.

[比較例3－2－1][Comparative Example 3-2-1]

在實施例3－2－1，除了將調製著色硬化性組成物3－C－1所使用組成3－C－1，變更為下述組成3－D－1以外，全部與實施例3－2－1同樣地進行，來調製比較用著色硬化性組成物3－D－1，同時得到形成有著色圖案之彩色濾光片。並進行與實施例3－2－1同樣的評價。結果如表19所示。In Example 3-2-1, except that the composition 3-C-1 used for the preparation of the coloring curable composition 3-C-1 was changed to the following composition 3-D-1, all and Example 3-2 were used. In the same manner, the coloring curable composition 3-D-1 was prepared in the same manner, and a color filter in which a colored pattern was formed was obtained. The same evaluation as in Example 3-2-1 was carried out. The results are shown in Table 19.

[實施例3－2－2~2－10、比較例2－2~2－4][Example 3-2-2~2-10, Comparative Example 2-2~2-4]

在實施例3－2－1，除了將調製著色感光性組成物3－C－1所使用組成3－C－1中的特定敏化劑、光聚合引發劑、及共敏化劑各自變更為下述表19所示以外，全部與實施例3－2－1同樣地進行，來調製著色感光性組成物3－C－2~3－C－10及比較用著色硬化性組成物3－C－11~3－C－13，同時在支撐體上形成著色圖案來製造彩色濾光片，並進行評價。結果如下述表19所示。In the example 3-2-1, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer in the composition 3-C-1 used in the preparation of the coloring photosensitive composition 3-C-1 were changed to In the same manner as in Example 3-2-1 except for the following Table 19, the coloring photosensitive composition 3-C-2 to 3-C-10 and the coloring curable composition for comparison 3-C were prepared. -11~3-C-13, at the same time, a colored pattern was formed on the support to produce a color filter, and was evaluated. The results are shown in Table 19 below.

[實施例3－2－11][Example 3-2-11]

在實施例3－2－1，除了將調製著色感光性組成物3－C－1所使用組成3－C－1變更為下述組成3－E－1以外，全部與實施例3－2－1同樣地進行，來調製著色感光性組成物3－E－1，同時形成著色圖案而得到彩色濾光片。並且與實施例3－2－1同樣地進行評價。結果如表19所示。In Example 3-2-1, except that the composition 3-C-1 used for the preparation of the coloring photosensitive composition 3-C-1 was changed to the following composition 3-E-1, all and Example 3-2- 1 was carried out in the same manner to prepare a coloring photosensitive composition 3-E-1, and a coloring pattern was formed to obtain a color filter. Further, evaluation was carried out in the same manner as in Example 3-2-1. The results are shown in Table 19.

[實施例3－2－5][Example 3-2-5]

在實施例3－2－11，除了將調製著色感光性組成物3－E－1所使用組成3－E－1中的特定敏化劑、光聚合引發劑、及共敏化劑各自變更為下述表19所示以外，全部與實施例3－2－11同樣地進行，來調製著色感光性組成物3－E－2，同時形成著色圖案來製造彩色濾光片，並進行評價。結果如下述表19所示。In the example 3-2-11, the specific sensitizer, the photopolymerization initiator, and the co-sensitizer in the composition 3-E-1 used in the preparation of the coloring photosensitive composition 3-E-1 were changed to In the same manner as in Example 3-2-11, except that the coloring photosensitive composition 3-E-2 was prepared, and a colored pattern was formed, a color filter was produced and evaluated. The results are shown in Table 19 below.

[比較例3－2－6][Comparative Example 3-2-6]

在實施例3－2－1，除了將調製著色感光性組成物3－C－1所使用組成3－C－1變更為下述組成3－F－1以外，全部與實施例3－2－1同樣地進行，來調製比較用著色感光性組成物3－F－1，同時形成著色圖案而得到彩色濾光片。並且與實施例3－2－1同樣地進行評價。結果如表19所示。In Example 3-2-1, except that the composition 3-C-1 used for the preparation of the coloring photosensitive composition 3-C-1 was changed to the following composition 3-F-1, all and Example 3-2- 1 was carried out in the same manner to prepare a coloring photosensitive composition 3-F-1 for comparison, and a coloring pattern was formed to obtain a color filter. Further, evaluation was carried out in the same manner as in Example 3-2-1. The results are shown in Table 19.

如表19所示之光聚合引發劑D1~D3、共敏化劑F1及F2、及比較化合物3－1~3－3係前述的化合物。The photopolymerization initiators D1 to D3, the co-sensitizers F1 and F2, and the comparative compounds 3-1 to 3-3 shown in Table 19 are the aforementioned compounds.

由表19的結果，得知含有特定敏化劑(化合物3－1~3－7)之各實施例的著色硬化性組成物係在其溶液狀態具有優良的保存安定性。又，得知使用該著色硬化性組成物在支撐體上形成著色圖案時，相對於未含有特定敏化劑或使用比較化合物3－1~3－3之各比較例，能夠得到曝光敏感度高、顯像性優良、同時基板黏附性、圖案剖面形狀都優良的彩色濾光片。From the results of Table 19, it was found that the color hardening composition of each of the examples containing the specific sensitizer (compounds 3-1 to 3-7) had excellent storage stability in the solution state. Further, when it was found that a colored pattern was formed on the support using the colored curable composition, it was found that the exposure sensitivity was high with respect to each of the comparative examples in which the specific sensitizer was not contained or the comparative compounds 3-1 to 3-3 were used. A color filter that is excellent in image development, and has excellent substrate adhesion and pattern cross-sectional shape.

第1圖係化合物2－1之¹ H－NMR圖。Fig. ^{1 is a 1} H-NMR chart of Compound 2-1.

第2圖係化合物2－2之¹ H－NMR圖。Fig. 2 is a ¹ H-NMR chart of the compound 2-2.

第3圖係化合物2－3之¹ H－NMR圖。Figure 3 is a ¹ H-NMR chart of Compound 2-3.

第4圖係化合物2－4之¹ H－NMR圖。Figure 4 is a ¹ H-NMR chart of Compound 2-4.

第5圖係化合物2－5之¹ H－NMR圖。Fig. 5 is a ¹ H-NMR chart of the compound 2-5.

第6圖係化合物2－6之¹ H－NMR圖。Figure 6 is a ¹ H-NMR chart of compound 2-6.

Claims (13)

一種彩色濾光片用硬化性組成物，其特徵係含有：選自由下述通式(1-I)所示之化合物、通式(1-II)所示之化合物、及下述通式(2-I)所示之化合物所組成群組中的至少1種化合物；光聚合引發劑；聚合性化合物；及著色劑， 通式(1-I)及通式(1-II)中，R¹¹ 係表示烷基或烷氧基，R¹² 係各自獨立地表示一價的取代基；R¹³ 、R¹⁴ 、R¹⁵ 、及R¹⁶ 係各自獨立地表示氫原子或一價的取代基；n係表示1~5的整數；n’係表示0~5的整數；n及n’不可雙方都為0；n為2以上時，複數存在之R¹¹ 各自可相同亦可不同；n’為2以上時，複數存在之R² 各自可相同亦可不同； 通式(2-I)中，A係表示亦可具有取代基之芳香族環或雜環；R²¹ 、R²² 、R²³ 、R²⁴ 、及R²⁵ 係各自獨立地表示氫原子或一價的非金屬原子團；A、R²² 、R²³ 、及R²⁴ 亦可各自互相鍵結而形成脂肪族性或芳香族性的環；其中，選自由該通式(1-I)所示之化合物、通式(1-II)所示之化合物、及通式(2-I)所示之化合物所組成群組中的至少1種化合物的含量，相對於硬化性組成物的總固體成分為0.1質量%~20質量%；該光聚合引發劑的含量，相對於硬化性組成物的總固體成分為0.1質量%~50質量%；該著色劑的含量，相對於硬化性組成物的總固體成分為25質量%~95質量%。A curable composition for a color filter, comprising: a compound represented by the following formula (1-I), a compound represented by the formula (1-II), and the following formula ( At least one compound selected from the group consisting of compounds represented by 2-I); a photopolymerization initiator; a polymerizable compound; and a color former, In the formula (1-I) and the formula (1-II), R ¹¹ represents an alkyl group or an alkoxy group, and R ¹² each independently represents a monovalent substituent; R ¹³ , R ¹⁴ , R ¹⁵ , And R ¹⁶ each independently represents a hydrogen atom or a monovalent substituent; n represents an integer of 1 to 5; n' represents an integer of 0 to 5; n and n' are not both 0; n is 2 or more In the case where the plurality of R ¹¹ are present, they may be the same or different; when n′ is 2 or more, the R ² existing in the plural may be the same or different; In the formula (2-I), A represents an aromatic ring or a heterocyclic ring which may have a substituent; and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent group. a non-metal atomic group; A, R ²² , R ²³ , and R ²⁴ may each bond to each other to form an aliphatic or aromatic ring; wherein, a compound selected from the formula (1-I) The content of at least one compound in the group consisting of the compound represented by the formula (1-II) and the compound represented by the formula (2-I) is 0.1 based on the total solid content of the curable composition. % by mass to 20% by mass; the content of the photopolymerization initiator is from 0.1% by mass to 50% by mass based on the total solid content of the curable composition; and the content of the coloring agent is relative to the total solid content of the curable composition It is 25 mass% to 95 mass%. 如申請專利範圍第1項之彩色濾光片用硬化性組成物，其中含有該通式(1-I)或通式(1-II)所示之化合物。 The curable composition for a color filter according to the first aspect of the invention, which comprises the compound represented by the formula (1-I) or the formula (1-II). 如申請專利範圍第2項之彩色濾光片用硬化性組成物，其中在該通式(1-I)或通式(1-II)，n係表示1~5的整數，R¹¹ 中之至少一個為烷基或烷氧基。A hardening composition for a color filter according to the second aspect of the invention, wherein in the formula (1-I) or the formula (1-II), n represents an integer of 1 to 5, and R ¹¹ At least one is an alkyl group or an alkoxy group. 如申請專利範圍第2項之彩色濾光片用硬化性組成物，其中更含有相對於硬化性組成物的總固體成分為0.5質量%~30質量%的硫醇化合物。 The curable composition for a color filter according to the second aspect of the invention, further comprising a thiol compound in an amount of 0.5% by mass to 30% by mass based on the total solid content of the curable composition. 如申請專利範圍第1項之彩色濾光片用硬化性組成物，其中含有該通式(2-I)所示之化合物。 A curable composition for a color filter according to the first aspect of the invention, which comprises the compound represented by the formula (2-I). 如申請專利範圍第1至5項中任一項之彩色濾光片用硬 化性組成物，其中含有二咪唑系化合物作為該光聚合引發劑。 For example, the color filter of any one of claims 1 to 5 is hard. A chemical composition containing a diimidazole compound as the photopolymerization initiator. 如申請專利範圍第1項之彩色濾光片用硬化性組成物，其中該著色劑的含量，相對於硬化性組成物的總固體成分為40質量%~80質量%。 The curable composition for a color filter according to the first aspect of the invention, wherein the content of the colorant is 40% by mass to 80% by mass based on the total solid content of the curable composition. 如申請專利範圍第1項之彩色濾光片用硬化性組成物，其中(B)光聚合引發劑與(A)選自由通式(1-I)所示之化合物、通式(1-II)所示之化合物、及通式(2-I)所示之化合物所組成群組中的至少1種化合物的質量比[(B)/(A)]為0.5以上3以下。 The curable composition for a color filter according to the first aspect of the invention, wherein (B) the photopolymerization initiator and (A) are selected from the group consisting of a compound represented by the formula (1-I), and a formula (1-II) The mass ratio [(B)/(A)] of at least one compound in the group consisting of the compound shown by the formula and the compound represented by the formula (2-I) is 0.5 or more and 3 or less. 一種彩色濾光片，其特徵係具有在支撐體上使用如申請專利範圍第1~8項中任一項之彩色濾光片用硬化性組成物而構成之著色圖案。 A color filter comprising a colored pattern formed by using a curable composition for a color filter according to any one of claims 1 to 8 on a support. 如申請專利範圍第9項之彩色濾光片，其中該彩色濾光片用硬化性組成物含有二咪唑系化合物作為該光聚合引發劑。 The color filter of claim 9, wherein the curable composition for the color filter contains a diimidazole compound as the photopolymerization initiator. 一種彩色濾光片之製法，包含以下步驟：支撐體上塗布如申請專利範圍第9項之彩色濾光片用硬化性組成物來形成著色硬化性組成物層之步驟；透過光罩對該著色硬化性組成物層進行曝光之步驟；及對曝光後的該著色硬化性組成物層進行顯像來形成著色圖案之步驟。 A method for producing a color filter, comprising the steps of: coating a support layer with a curable composition for color filters according to claim 9 of the patent application to form a color hardening composition layer; a step of exposing the curable composition layer; and a step of developing the colored curable composition layer after exposure to form a colored pattern. 如申請專利範圍第11項之彩色濾光片之製法，其中該彩色濾光片用硬化性組成物含有二咪唑系化合物作為該 光聚合引發劑。 The method for producing a color filter according to claim 11, wherein the curable composition for the color filter contains a diimidazole compound as the Photopolymerization initiator. 一種化合物，係如該通式(2-I)所示， 通式(2-I)中，A係表示亦可具有取代基之苯環；R²¹ 係表示氫原子或一價的非金屬原子團，R²² 及R²⁴ 係各自表示氫原子，R²³ 係表示氫原子或甲基，R²⁵ 係表示亦可具有取代基之碳原子數5~10之環狀烷基。a compound as shown in the formula (2-I), In the formula (2-I), A represents a benzene ring which may have a substituent; R ²¹ represents a hydrogen atom or a monovalent non-metal atomic group, and R ²² and R ²⁴ each represent a hydrogen atom, and R ²³ represents A hydrogen atom or a methyl group, and R ²⁵ represents a cyclic alkyl group having 5 to 10 carbon atoms which may have a substituent.