TW202140594A - Photosensitive colored resin composition, cured product, color filter and display device - Google Patents

Abstract

A photosensitive colored resin composition comprising a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, wherein the dispersant contains a (meth)acrylate copolymer-based dispersant, and the photoinitiator contains a compound represented by the following general formula (A):

Description

Photosensitive colored resin composition, cured product, color filter, display device

The present invention relates to a photosensitive colored resin composition, a cured product, a color filter, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has continued to increase. The penetration rate of mobile displays (mobile phones, smart phones, and tablet PCs (personal computers, personal computers)) is also increasing, and the market for liquid crystal displays is expanding. Organic light-emitting display devices such as organic EL (Electroluminescence) displays with high visibility through self-luminescence are also attracting attention as next-generation image display devices. Color filters are used in these liquid crystal display devices or organic light emitting display devices. For example, regarding the formation of a color image in a liquid crystal display device, light passing through a color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. As the light source at this time, in addition to the previous cold cathode tube, an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light is sometimes used. In organic light emitting display devices, color filters are used for color adjustment and the like.

Here, the color filter generally has: a substrate; a colored layer, which is formed on the substrate, and includes colored patterns of the three primary colors of red, green, and blue; and a light-shielding portion, which is formed on the transparent substrate by dividing each colored pattern . Regarding the formation method of the colored layer in the color filter, for example, a binder resin, a photopolymerizable compound, and a photoinitiator are added to a color material dispersion liquid formed by dispersing the color material by a dispersant, etc. After the formed colored resin composition is coated on a glass substrate and dried, it is exposed using a photomask, developed to form a colored pattern, and heated to fix the pattern, thereby forming a colored layer. These steps are repeated for each color to form a color filter.

In recent years, as the requirements for higher brightness of color filters have increased, the concentration of color materials in the coloring layer of color filters has become higher than before, and the components required for photopolymerization have been relatively reduced, making it difficult Patterned. Furthermore, in order to improve the productivity of color filters, it is required to reduce the cumulative exposure required for patterning, and how to ensure the curability required for patterning has become a big problem.

In order to ensure the curability required for the patterning of the colored layer, in the colored resin composition for color filters, a relatively small molecular weight photoinitiator such as Irgacure 907 is used as a high-sensitivity photoinitiator, but the sublimation Cause pollution of the photomask or heating furnace, etc. Therefore, Patent Document 1 discloses a specific oxime ester compound as a high-sensitivity photopolymerization initiator that has excellent stability, low sublimability, and efficiently absorbs near ultraviolet light such as 365 nm to be activated. In addition, as a high-sensitivity photoinitiator, for example, in Patent Document 2, as a photoinitiator that is highly reactive, easy to synthesize, and easy to handle, a specific o-acyloxime compound is disclosed. Furthermore, in Patent Document 3, a specific oxime ester compound is disclosed as a high-sensitivity photoinitiator. Previous technical literature Patent literature

Patent Document 1: International Publication No. 2015/152153 Patent Document 2: Japanese Patent Laid-Open No. 2000-80068 Patent Document 3: Japanese Patent Laid-Open No. 2006-516246

[The problem to be solved by the invention]

Previously, color filters were formed on glass substrates, but in recent years, it has been required to directly form color filters on element substrates. The heat resistance of organic light-emitting devices and other devices is relatively low. Therefore, the heat treatment in the manufacturing step of directly forming the color filter on the device substrate is preferably performed at a temperature below 90°C. In the usual color filter manufacturing process, the colored layer is hardened by heating at about 230°C on the glass substrate. In contrast, it is difficult to harden the colored layer by heat in the heating process at 90°C or less. . Therefore, in order for the colored layer to have the solvent resistance required for subsequent steps, the colored layer must be sufficiently hardened by exposure. In order to promote the hardening of the colored layer by exposure, it is considered to use a high-sensitivity initiator. However, the high-sensitivity initiator tends to increase the offset of the line width. In the case of making fine line patterns, there is a problem that the size of the pattern is larger than the assumed pattern size. Furthermore, even if the colored layer contains a high-sensitivity initiator and is cured by exposure, the required solvent resistance may not necessarily be obtained by heat treatment at 90°C or less.

The present invention was completed in view of the above circumstances, and its object is to provide a photosensitive colored resin composition capable of forming a colored layer that suppresses line width deviation and has good solvent resistance under low-temperature heat treatment. In addition, an object of the present invention is to provide a color filter and a display device formed using the photosensitive colored resin composition. [Technical means to solve the problem]

The photosensitive colored resin composition of the present invention contains a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned dispersant contains a (meth)acrylate copolymer dispersant, The above-mentioned photoinitiator contains a compound represented by the following general formula (A).

(式中，R¹ 及R² 分別獨立地表示R¹¹ 、OR¹¹ 、COR¹¹ 、SR¹¹ 、CONR¹² R¹³ 或CN， R¹¹ 、R¹² 及R¹³ 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R¹¹ 、R¹² 及R¹³ 所表示之基之氫原子可進而被取代為R²¹ 、OR²¹ 、COR²¹ 、SR²¹ 、NR²² R²³ 、CONR²² R²³ 、-NR²² -OR²³ 、-NCOR²² -OCOR²³ 、NR²² COR²¹ 、OCOR²¹ 、COOR²¹ 、SCOR²¹ 、OCSR²¹ 、COSR²¹ 、CSOR²¹ 、羥基、硝基、CN或鹵素原子， R²¹ 、R²² 及R²³ 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R²¹ 、R²² 及R²³ 所表示之基之氫原子可進而被取代為羥基、硝基、CN、鹵素原子或羧基， R¹¹ 、R¹² 、R¹³ 、R²¹ 、R²² 及R²³ 所表示之基之伸烷基部分可於氧原子不相鄰之條件下包含1～5個-O-、-S-、-COO-、-OCO-、-NR²⁴ -、-NR²⁴ CO-、-NR²⁴ COO-、-OCONR²⁴ -、-SCO-、-COS-、-OCS-或-CSO-， R²⁴ 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R¹¹ 、R¹² 、R¹³ 、R²¹ 、R²² 、R²³ 及R²⁴ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基， R³ 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基，R³ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基，又，R³ 與R⁷ 、及R³ 與R⁸ 分別可一起形成環， R³ 所表示之基之氫原子可進而被取代為R²¹ 、OR²¹ 、COR²¹ 、SR²¹ 、NR²² R²³ 、CONR²² R²³ 、-NR²² -OR²³ 、-NCOR²² -OCOR²³ 、NR²² COR²¹ 、OCOR²¹ 、COOR²¹ 、SCOR²¹ 、OCSR²¹ 、COSR²¹ 、CSOR²¹ 、羥基、硝基、CN或鹵素原子， R⁴ 、R⁵ 、R⁶ 及R⁷ 分別獨立地表示R¹¹ 、OR¹¹ 、SR¹¹ 、COR¹⁴ 、CONR¹⁵ R¹⁶ 、NR¹² COR¹¹ 、OCOR¹¹ 、COOR¹⁴ 、SCOR¹¹ 、OCSR¹¹ 、COSR¹⁴ 、CSOR¹¹ 、羥基、CN或鹵素原子，R⁴ 與R⁵ 、R⁵ 與R⁶ 、及R⁶ 與R⁷ 分別可一起形成環， R¹⁴ 、R¹⁵ 及R¹⁶ 表示氫原子或碳原子數1～20之烷基，R¹⁴ 、R¹⁵ 及R¹⁶ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基，R⁸ 表示R¹¹ 、OR¹¹ 、SR¹¹ 、COR¹¹ 、CONR¹² R¹³ 、NR¹² COR¹¹ 、OCOR¹¹ 、COOR¹¹ 、SCOR¹¹ 、OCSR¹¹ 、COSR¹¹ 、CSOR¹¹ 、羥基、CN或鹵素原子， k表示0或1)[化1]

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom and the number of carbon atoms 1-20 alkyl, 6-30 aryl, 7-30 aralkyl, or 2-20 heterocyclic group, represented by R ¹¹ , R ¹² and R ¹³ The hydrogen atom of the group can be further substituted with R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN or halogen atom, R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom and a carbon atom number of 1-20 Alkyl group, aryl group with 6 to 30 carbon atoms, aralkyl group with 7 to 30 carbon atoms or heterocyclic group with 2 to 20 carbon atoms, hydrogen atom of the group represented by ^{R 21} , R ²² and R ²³ The alkylene moiety of the group represented by ^{R 11} , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, a CN, a halogen atom or a carboxyl group, and the oxygen atom may not be adjacent Under the conditions, it contains 1～5 -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO- ^{, -OCONR 24} -, -SCO-, -COS-, -OCS- or -CSO-, R ²⁴ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms or carbon A heterocyclic group having 2 to 20 atoms, ^{the alkyl portion of the group represented by R 11} , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl R ³ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, The alkyl part of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl group. In addition, R ³ and R ⁷ , and R ³ and R ⁸ may each form a ring together. The group represented by ^{R 3} The hydrogen atom can then be substituted into R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, CN or halogen atom, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ Together with R ⁷ can form a ring. R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group with 1 to 20 carbon atoms. The alkyl portion of the group represented by ^{R 14} , R ¹⁵ and R ^{16 can have a branch} The side chain can also be a cyclic alkyl group, R ⁸ represents R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , hydroxyl, CN or halogen atom, k represents 0 or 1)

The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the photosensitive coloring resin composition of the present invention.

The display device of the present invention has the above-mentioned color filter of the present invention. [Effects of the invention]

According to the present invention, it is possible to provide a photosensitive colored resin composition capable of forming a colored layer that suppresses the amount of line width deviation and has good solvent resistance even under low-temperature heat treatment. Furthermore, according to the present invention, it is possible to provide a color filter and a display device formed using the photosensitive colored resin composition.

Hereinafter, the photosensitive colored resin composition, cured product, color filter, and display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and further includes radiation, such as microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, (meth)acryloyl group means acryloyl group and methacryloyl group, (meth)acrylic acid means acrylic acid and methacrylic acid, and (meth)acrylate means acrylate and methacrylate. In addition, in this specification, "~" indicating a numerical range is used to include the numerical value described before and after it as the lower limit and the upper limit.

I. Photosensitive colored resin composition The photosensitive colored resin composition of the present invention contains a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned dispersant contains a (meth)acrylate copolymer dispersant, The above-mentioned photoinitiator contains a compound represented by the following general formula (A).

(式中，R¹ 及R² 分別獨立地表示R¹¹ 、OR¹¹ 、COR¹¹ 、SR¹¹ 、CONR¹² R¹³ 或CN， R¹¹ 、R¹² 及R¹³ 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R¹¹ 、R¹² 及R¹³ 所表示之基之氫原子可進而被取代為R²¹ 、OR²¹ 、COR²¹ 、SR²¹ 、NR²² R²³ 、CONR²² R²³ 、-NR²² -OR²³ 、-NCOR²² -OCOR²³ 、NR²² COR²¹ 、OCOR²¹ 、COOR²¹ 、SCOR²¹ 、OCSR²¹ 、COSR²¹ 、CSOR²¹ 、羥基、硝基、CN或鹵素原子， R²¹ 、R²² 及R²³ 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R²¹ 、R²² 及R²³ 所表示之基之氫原子可進而被取代為羥基、硝基、CN、鹵素原子或羧基， R¹¹ 、R¹² 、R¹³ 、R²¹ 、R²² 及R²³ 所表示之基之伸烷基部分可於氧原子不相鄰之條件下包含1～5個-O-、-S-、-COO-、-OCO-、-NR²⁴ -、-NR²⁴ CO-、-NR²⁴ COO-、-OCONR²⁴ -、-SCO-、-COS-、-OCS-或-CSO-， R²⁴ 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R¹¹ 、R¹² 、R¹³ 、R²¹ 、R²² 、R²³ 及R²⁴ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基， R³ 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基，R³ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基，又，R³ 與R⁷ 及R³ 與R⁸ 可分別一起形成環， R³ 所表示之基之氫原子可進而被取代為R²¹ 、OR²¹ 、COR²¹ 、SR²¹ 、NR²² R²³ 、CONR²² R²³ 、-NR²² -OR²³ 、-NCOR²² -OCOR²³ 、NR²² COR²¹ 、OCOR²¹ 、COOR²¹ 、SCOR²¹ 、OCSR²¹ 、COSR²¹ 、CSOR²¹ 、羥基、硝基、CN或鹵素原子， R⁴ 、R⁵ 、R⁶ 及R⁷ 分別獨立地表示R¹¹ 、OR¹¹ 、SR¹¹ 、COR¹⁴ 、CONR¹⁵ R¹⁶ 、NR¹² COR¹¹ 、OCOR¹¹ 、COOR¹⁴ 、SCOR¹¹ 、OCSR¹¹ 、COSR¹⁴ 、CSOR¹¹ 、羥基、CN或鹵素原子，R⁴ 與R⁵ 、R⁵ 與R⁶ 及R⁶ 與R⁷ 可分別一起形成環， R¹⁴ 、R¹⁵ 及R¹⁶ 表示氫原子或碳原子數1～20之烷基，R¹⁴ 、R¹⁵ 及R¹⁶ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基，R⁸ 表示R¹¹ 、OR¹¹ 、SR¹¹ 、COR¹¹ 、CONR¹² R¹³ 、NR¹² COR¹¹ 、OCOR¹¹ 、COOR¹¹ 、SCOR¹¹ 、OCSR¹¹ 、COSR¹¹ 、CSOR¹¹ 、羥基、CN或鹵素原子， k表示0或1)[化2]

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom and the number of carbon atoms 1-20 alkyl, 6-30 aryl, 7-30 aralkyl, or 2-20 heterocyclic group, represented by R ¹¹ , R ¹² and R ¹³ The hydrogen atom of the group can be further substituted with R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN or halogen atom, R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom and a carbon atom number of 1-20 Alkyl group, aryl group with 6 to 30 carbon atoms, aralkyl group with 7 to 30 carbon atoms or heterocyclic group with 2 to 20 carbon atoms, hydrogen atom of the group represented by ^{R 21} , R ²² and R ²³ The alkylene moiety of the group represented by ^{R 11} , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, a CN, a halogen atom or a carboxyl group, and the oxygen atom may not be adjacent Under the conditions, it contains 1～5 -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO- ^{, -OCONR 24} -, -SCO-, -COS-, -OCS- or -CSO-, R ²⁴ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms or carbon A heterocyclic group having 2 to 20 atoms, ^{the alkyl portion of the group represented by R 11} , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl R ³ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, The alkyl part of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl group. In addition, R ³ and R ⁷ and R ³ and R ⁸ may each form a ring together, and the group represented by ^{R 3} The hydrogen atom can be further substituted into R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, CN or halogen atom, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ^6, and R ⁶ and R ⁷ can form a ring together. R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group with 1 to 20 carbon atoms. The alkyl part of the group represented by ^{R 14} , R ¹⁵ and R ^{16 can have a branched side chain} , Can also be a cyclic alkyl group, R ⁸ represents R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , hydroxyl, CN or halogen atom, k represents 0 or 1)

The photosensitive colored resin composition of the present invention uses the above-mentioned (meth)acrylate copolymer dispersant as a dispersant, and contains the compound represented by the above-mentioned general formula (A) as a photoinitiator, so it can form a suppressed line width A coloring layer with good offset and solvent resistance even when low-temperature heat treatment is performed after exposure. Although it is not clear as to play such an effect, it is estimated as follows.

It is believed that in order to form a colored layer with good solvent resistance even under low-temperature heat treatment, the hardened state of the colored layer must be uniform in the colored layer, but the compatibility of the initiator and other components will affect the hardened state. In the photosensitive resin coloring composition, a dispersing agent is usually contained to uniformly disperse the color material. Even if the initiator used in the present invention is used, depending on the dispersant used, the line width shift may increase, or the coloring layer with sufficient solvent resistance cannot be obtained by low-temperature heating treatment. It is considered that if the compatibility of the initiator and other components is low, the initiator is likely to be concentrated on the surface of the colored layer, and further hardens on the surface of the colored layer, resulting in an increase in the line width deviation. On the other hand, in the photosensitive resin composition of the present invention, the (meth)acrylate copolymer-based dispersant is used as a dispersant, and the compound represented by the general formula (A) is contained as a photoinitiator, Therefore, the compatibility of the initiator and other components is good, and the initiator is easy to be uniformly present in the colored layer. Therefore, it is presumed to suppress the increase in the line width deviation caused by only the surface hardening, the uniform hardening of the colored layer reduces the unreacted components, and the internal stress of the colored layer also decreases, so the change of the colored layer when immersed in the solvent Become smaller. By combining the above-mentioned dispersant and photoinitiator, sufficient solvent resistance can be obtained even in low-temperature heat treatment. It is estimated that the main reason is the photoinitiator and photopolymerizable compound and dispersant, dispersant and photopolymerization The compatibility of sex compounds is relatively high. It is further estimated that when the above-mentioned (meth)acrylate copolymer dispersant is a solvent-affinity graft copolymer or a copolymer having an acid value, its compatibility with the initiator and other components is further improved. The improvement can uniformly and stably maintain the initiator in the film, and the solvent resistance is also improved.

The photosensitive colored resin composition of the present invention contains at least a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail in order starting from the dispersant and the photoinitiator that are the characteristic combination of the present invention.

＜Dispersant＞ In the present invention, a (meth)acrylate copolymer-based dispersant is used as the dispersant. The (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and contains at least a structural unit derived from (meth)acrylate. The (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a color material adsorption site and a structural unit that functions as a solvent affinity site, and preferably functions as a solvent affinity site The structural unit at least contains a structural unit derived from (meth)acrylate.

The structural unit that functions as the color material adsorption site can be, for example, a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with a structural unit derived from (meth)acrylate. The color material adsorption site may be a structural unit derived from an acidic group-containing ethylenic unsaturated monomer, or a structural unit derived from a basic group-containing ethylenic unsaturated monomer. As the structural unit derived from the basic group-containing ethylenically unsaturated monomer, from the viewpoint of excellent dispersibility, a structural unit represented by the following general formula (I) is preferred.

(通式(I)中，R⁴¹ 表示氫原子或甲基，A¹ 表示二價連結基，R⁴² 及R⁴³ 分別獨立地表示氫原子或可包含雜原子之烴基，R⁴² 及R⁴³ 可彼此鍵結而形成環結構)[化3]

(In the general formula (I), R ⁴¹ represents a hydrogen atom or a methyl group, A ¹ represents a divalent linking group, R ⁴² and R ⁴³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a heteroatom, R ⁴² and R ⁴³ may Bonded to each other to form a ring structure)

In the general formula (I), A ¹ is a divalent linking group. As the divalent linking group, for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group,- COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group) and combinations thereof, etc. Furthermore, in the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, -CO can be located on the carbon atom side of the main chain and -NH can be located on the nitrogen atom side of the side chain. Conversely, -NH can also be located on the carbon atom side of the main chain and -CO is located on the side of the nitrogen atom of the side chain. Among them, in terms of dispersibility, A ¹ in the general formula (I) is preferably a divalent linking group including -CONH- group or -COO- group, and more preferably includes -CONH- group or -COO- A divalent linking group of a group and an alkylene group having 1 to 10 carbon atoms.

The hydrocarbyl group in the hydrocarbyl group that may contain a hetero atom in R ⁴² and R ⁴³ may, for example, be an alkyl group, an aralkyl group, an aryl group, and the like. Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc. The number of carbon atoms in the alkyl group Preferably it is 1-18, and more preferably it is a methyl group or an ethyl group. As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example. The number of carbon atoms of the aralkyl group is preferably 7-20, and more preferably 7-14. Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. The number of carbon atoms of the aryl group is preferably 6-24, more preferably 6-12. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent. The heteroatom-containing hydrocarbon group has a structure in which the carbon atom in the above-mentioned hydrocarbon group is substituted with a heteroatom, or has a structure in which the hydrogen atom in the above-mentioned hydrocarbon group is substituted with a heteroatom-containing substituent. Examples of heteroatoms that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. In addition, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom.

R ⁴² and R ⁴³ are bonded to each other to form a ring structure means that R ⁴² and R ⁴³ form a ring structure via a nitrogen atom. The ring structure formed by R ⁴² and R ^{43 may contain heteroatoms.} The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, it is preferable that R ⁴² and R ⁴³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ⁴² and R ^{43 are} bonded to form a pyrrolidine ring or a piperidine ring , Morpholine ring.

As a monomer to derive the structural unit represented by the above general formula (I), for example: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, (methyl) ) (Meth)acrylates containing alkyl substituted amino groups such as diethylaminoethyl acrylate, diethylaminopropyl (meth)acrylate, etc.; dimethylaminoethyl (meth)propylene (Meth)acrylamide containing alkyl substituted amino groups such as dimethylaminopropyl (meth)acrylamide, etc. Among them, from the viewpoint of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl are preferably used. (Meth)acrylamide. In the polymer, the structural unit represented by the general formula (I) may include one type or two or more types.

In addition, as for the structural unit that functions as the color material adsorption site, at least a part of the nitrogen site of the structural unit represented by the general formula (I) may be at least selected from the group consisting of organic acid compounds and halogenated hydrocarbons One type forms a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer). The organic acid compound is preferably a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and the halogenated hydrocarbon is preferably a compound represented by the following general formula (2) Represents the compound. That is, as at least one selected from the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons, it is preferable to use one or more selected from the group consisting of the following general formulas (1) to (3) Compound.

(於通式(1)中，R^a 表示碳數1～20之直鏈、支鏈或環狀烷基、乙烯基、可具有取代基之苯基或苄基或者-O-R^e ，R^e 表示碳數1～20之直鏈、支鏈或環狀烷基、乙烯基、可具有取代基之苯基或苄基、或者經由碳數1～4之伸烷基之(甲基)丙烯醯基。於通式(2)中，R^b 、R^b' 及R^b'' 分別獨立地表示氫原子、酸性基或其酯基、可具有取代基之碳數1～20之直鏈、支鏈或環狀烷基、可具有取代基之乙烯基、可具有取代基之苯基或苄基或者-O-R^f ，R^f 表示可具有取代基之碳數1～20之直鏈、支鏈或環狀烷基、可具有取代基之乙烯基、可具有取代基之苯基或苄基、或者經由碳數1～4之伸烷基之(甲基)丙烯醯基，X表示氯原子、溴原子或碘原子。於通式(3)中，R^c 及R^d 分別獨立地表示氫原子、羥基、碳數1～20之直鏈、支鏈或環狀烷基、乙烯基、可具有取代基之苯基或苄基或者-O-R^e ，R^e 表示碳數1～20之直鏈、支鏈或環狀烷基、乙烯基、可具有取代基之苯基或苄基、或者經由碳數1～4之伸烷基之(甲基)丙烯醯基。其中，R^c 及R^d 之至少一者包含碳原子)[化4]

(In the general formula (1), Ra ^{represents a} linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent or -OR ^e , R ^e represents Linear, branched or cyclic alkyl groups with 1 to 20 carbons, vinyl groups, optionally substituted phenyl or benzyl, or (meth)acrylic groups via alkylenes with 1 to 4 carbons In the general formula (2), R ^b , R ^b'and R ^b” each independently represent a hydrogen atom, an acidic group or an ester group thereof, a linear or branched chain with 1 to 20 carbons that may have a substituent Or cyclic alkyl, optionally substituted vinyl, optionally substituted phenyl or benzyl or -OR ^f , R ^f represents optionally substituted straight chain, branched chain or ring with 1 to 20 carbons Alkyl groups, vinyl groups that may have substituents, phenyl or benzyl groups that may have substituents, or (meth)acrylic groups via alkylene groups with 1 to 4 carbon atoms, X represents a chlorine atom or a bromine atom Or iodine atom. In the general formula (3), R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, and optionally a substituent Phenyl or benzyl or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a substituted phenyl group or benzyl group, or a carbon number 1 (Meth)acrylic group of alkylene group of ~4. Among them, ^{at least one of R c} and R ^d contains a carbon atom)

Regarding the symbols in the above general formulas (1) to (3), they may be the same as those described in International Publication No. 2016/104493. From the viewpoint of excellent dispersibility and dispersion stability of the color material, the organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. As a specific example of the organic acid compound used for such a dispersing agent, the organic acid compound described in Unexamined-Japanese-Patent No. 2012-236882 etc. is suitable, for example. In addition, as the above-mentioned halogenated hydrocarbon, at least one of an allyl halide such as allyl bromide and benzyl chloride and a halogenated aralkyl group is preferred from the viewpoint of excellent dispersibility and dispersion stability of the color material.

Regarding the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons in the salt-type copolymer, based on the viewpoint of forming a salt with the terminal nitrogen portion of the structural unit represented by the general formula (I), The total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons with respect to the terminal nitrogen site of the structural unit represented by the general formula (I) is preferably 0.01 mol or more, more preferably 0.05 mol or more, more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. If it is more than the above lower limit value, it is easy to obtain the effect of improving the dispersibility of the color material by forming a salt. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. If it is equal to or less than the above upper limit value, the development adhesiveness and solvent resolubility can be excellent. In addition, at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When combining two or more types, it is preferable that the total content is within the above-mentioned range.

As a method of preparing the salt-type copolymer, the following method can be exemplified, that is, adding a solvent selected from the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons in a solvent in which the copolymer before the formation of the salt is dissolved or dispersed. At least one kind is stirred, and then heated as needed. Furthermore, the case where the terminal nitrogen site of the structural unit represented by the general formula (I) of the copolymer forms a salt with at least one selected from the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons and the ratio thereof For example, it can be confirmed by known methods such as NMR (nuclear magnetic resonance).

In terms of dispersibility and dispersion stability, the copolymer having the structural unit represented by the general formula (I) is more preferably at least one of a graft copolymer and a block copolymer, and the graft copolymer has The structural unit represented by the above general formula (I), and the graft polymer chain has a structural unit derived from (meth)acrylate, and the block copolymer has a structural unit including the structural unit represented by the above general formula (I) A block and B block containing structural units derived from (meth)acrylate. Hereinafter, the above-mentioned graft copolymer and the above-mentioned block copolymer will be described in order.

As the graft copolymer having the structural unit represented by the above-mentioned general formula (I) and the graft polymer chain having the structural unit derived from (meth)acrylate, the following graft copolymers and salt-type grafts can be exemplified At least one type of copolymer, the graft copolymer has a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (II), and the salt-type graft copolymer is the graft copolymer At least a part of the nitrogen site of the structural unit represented by the general formula (I) of the substance forms a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons.

(通式(II)中，R^41' 表示氫原子或甲基，A² 表示直接鍵結或二價連結基，Polymer表示聚合物鏈，該聚合物鏈之結構單元中包含源自(甲基)丙烯酸酯之結構單元)[化5]

(In the general formula (II), R ^41' represents a hydrogen atom or a methyl group, A ² represents a direct bond or a divalent linking group, and Polymer represents a polymer chain, and the structural unit of the polymer chain contains a structure derived from (methyl )The structural unit of acrylate)

In the above general formula (II), A ² is a direct bond or a divalent linking group. The ^{divalent linking group in A 2} is not particularly limited, as long as it can link the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. As the divalent linking group in ^{A 2} , for example, the same divalent linking group as the ^{above A 1 can be mentioned.} Among them, in terms of dispersibility, A ² in the general formula (II) is preferably a divalent linking group including -CONH- group or -COO- group, and more preferably includes -CONH- group or -COO- A divalent linking group of a group and an alkylene group having 1 to 10 carbon atoms.

In the above general formula (II), Polymer represents a polymer chain, and the structural unit of the polymer chain includes a structural unit derived from (meth)acrylate. The graft copolymer contains the structural unit represented by the above general formula (II) with a specific polymer chain, the solvent affinity is good, the dispersibility and dispersion stability of the color material are good, and it is compatible with the following photoinitiator Compatibility is also good. As the structural unit of the polymer chain, a structural unit represented by the following general formula (IV) can be exemplified.

(通式(IV)中，R^44'' 為氫原子或甲基，A⁴ 為二價連結基，R⁵⁰ 為氫原子或可包含雜原子之烴基)[化6]

(In the general formula (IV), R ^44" is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, and R ⁵⁰ is a hydrogen atom or a hydrocarbon group that may contain a hetero atom)

As the divalent linking group A ⁴ , for example, the same divalent linking group as in the ^{above A 1 can be mentioned.} In the present invention, as a structural unit derived from a (meth)acrylate, at least A ⁴ in the general formula (IV) is a structure represented by the general formula (IV) including a divalent linking group containing a -COO- group unit. In terms of solubility in organic solvents used for color filter applications, A ⁴ in the general formula (IV) may contain a divalent linking group including a -CONH- group.

The hydrocarbyl group in the hydrocarbyl group that may contain a hetero atom in R ⁵⁰ may be, for example, a combination of an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkyl substituted aryl group, and the like. As ^{the hydrocarbon group in the hydrocarbon group which may contain a hetero atom in R 50} , for example, an alkyl group having 1 to 18 carbons, an alkenyl group having 2 to 18 carbons, an aryl group, and an aralkyl group or an alkyl substituted aryl group may be mentioned. Base and other combinations. The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-nonane. Alkyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, 𦯉, iso𦯉, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc. The number of carbon atoms in the alkyl group is preferably 1-12, and more preferably 1-6. The aforementioned alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited. In terms of the reactivity of the obtained polymer, it is preferable that the end of the alkenyl group has a double bond. The carbon number of the alkenyl group is preferably 2-12, more preferably 2-8. The aryl group may, for example, be a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The carbon number of the aryl group is preferably 6-24, more preferably 6-12. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, and it may have a substituent further. The carbon number of the aralkyl group is preferably 7-20, and more preferably 7-14. In addition, a linear or branched alkyl group having 1 to 30 carbon atoms as a substituent may be bonded to an aromatic ring such as the above-mentioned aryl group or aralkyl group.

The hydrocarbon group in R ⁵⁰ is preferably selected from alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms in which the alkyl group may be substituted, and alkyl groups in terms of dispersion stability. One or more of the group consisting of optionally substituted aralkyl groups with 7 to 14 carbon atoms, more preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, One or more of the group consisting of n-lauryl, n-stearyl, phenyl whose alkyl may be substituted, and benzyl.

Examples of heteroatoms that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. As the hydrocarbon group that may contain heteroatoms, for example, a structure containing the following linking groups in the carbon chain of the hydrocarbon group: -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O -, -O-NH- etc. In addition, the hydrocarbon group may have a substituent within a range that does not hinder the dispersibility of the graft copolymer, etc., as the substituent, for example, a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, a nitro group, a cyano group, Epoxy, isocyanate, thiol, etc.

In addition, ^{the hydrocarbon group that may contain a hetero atom in R 50} may be a structure in which a polymerizable group such as an alkenyl group is added to the end via a link containing a hetero atom in the hydrocarbon group. For example, the structural unit represented by the general formula (IV) may be a structure obtained by reacting a structural unit derived from (meth)acrylic acid with glycidyl (meth)acrylate. ^{That is, the structure of -A 4} -R ⁵⁰ in the general formula (IV) can be the structure represented by -COO-CH ₂ CH(OH)CH ₂ -OCO-CR=CH ₂ (here, R is a hydrogen atom or methyl). In addition, the structural unit represented by the general formula (IV) may be a structure obtained by reacting a structural unit derived from hydroxyalkyl (meth)acrylate and 2-isocyanatoalkyl (meth)acrylate. ^{That is, R 50} in the general formula (IV) can be a structure represented by -R'-OCONH-R''-OCO-CR=CH ₂ (here, R'and R'' are each independently an alkylene group , R is a hydrogen atom or a methyl group).

As a monomer to derive the structural unit represented by the general formula (IV), for example, a monomer having a structural unit derived from the following compounds is preferred: methyl (meth)acrylate, ethyl (meth)acrylate, (formula) Base) isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) ) 2-ethoxyethyl acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, iso(meth)acrylate, (meth)acrylic acid Dicyclopentyl ester, adamantyl (meth)acrylate, (meth)acrylic acid, 2-methacryloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, (meth) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (meth) Phenoxy ethyl acrylate, methoxy polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and phenoxy ethylene with the number of repeating units in the ethylene oxide chain less than 19 Alcohol (meth)acrylate and the like. However, it is not limited to these.

In the present invention, as the above-mentioned R ⁵⁰ , it is preferable to use one having excellent solubility with the following organic solvents, as long as it is appropriately selected according to the organic solvent used in the color material dispersion liquid. Specifically, for example, when the above-mentioned organic solvent uses an organic solvent such as ether alcohol acetate, ether, ester, alcohol, etc., which are generally used as organic solvents for color material dispersions, the above R ^{50 is} preferably Methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxy polyethylene Glycol base, methoxy polypropylene glycol base, polyethylene glycol base, etc.

From the viewpoint of shortening the development time of the photosensitive resin composition and improving the solvent resistance of the cured product of the photosensitive colored resin composition, the graft copolymer is preferably a structural unit represented by the general formula (II) The structural unit of the polymer chain in includes at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (III) and the structural unit represented by the following general formula (III'). The structural unit represented by the following general formula (III) and the structural unit represented by the following general formula (III') are included in the structural unit represented by the above general formula (IV).

(通式(III)中，R⁴⁴ 為氫原子或甲基，A³ 為二價連結基，R⁴⁵ 為伸乙基或伸丙基，R⁴⁶ 為氫原子或烴基，m表示3以上80以下之數。  通式(III')中，R^44' 為氫原子或甲基，A^3' 為二價連結基，R⁴⁷ 係碳數為1～10之伸烷基，R⁴⁸ 係碳數為3～7之伸烷基，R⁴⁹ 為氫原子或烴基，n表示1以上40以下之數)[化7]

(In the general formula (III), R ⁴⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁴⁵ is an ethylene group or a propylene group, R ⁴⁶ is a hydrogen atom or a hydrocarbon group, and m represents 3 to 80 the number of 'in, R ⁴⁴ of formula ^(III)' is a hydrogen atom or a methyl group, A ^{3 'is} a divalent linking group, R ⁴⁷ based carbon atoms of the alkylene group having 1 to 10, R ⁴⁸ based carbon atoms 3-7 alkylene groups, R ⁴⁹ is a hydrogen atom or a hydrocarbon group, n represents a number of 1 to 40)

As the divalent linking group A ³ , for example, the same as the divalent linking group in ^{A 1} described above can be mentioned. Among them, in terms of solubility in organic solvents for color filters, A ³ in the general formula (III) is preferably a divalent linking group containing -CONH- group or -COO- group , More preferably -CONH- group or -COO- group, still more preferably -COO- group.

The above-mentioned m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more. Among them, from the viewpoint of suppressing the generation of water spots, it is preferably 19 or more, and more preferably 21 or more. Furthermore, water spots refer to the phenomenon that water seepage marks are produced after alkaline development is washed with pure water. Such water spots disappear after post-baking, so there is no problem for the product, but in the appearance inspection of patterning after development, it is detected as uneven and abnormal, which causes the problem that normal products and abnormal products cannot be distinguished. Therefore, if the inspection sensitivity of the inspection device is reduced during the appearance inspection, the yield of the final color filter product will be reduced as a result, which becomes a problem. As a cause of water spots in the cured film of the photosensitive resin composition, water absorption into the cured film can be mentioned. The alkali-soluble resin in the cured film has acidic groups such as carboxyl groups, so it is easy to absorb water. In addition, it is considered that the acidity is based on forming a metal salt with an alkali metal typically contained in an alkaline developer during development, and the water absorption is further improved. Oxygen atoms contained in the polyethylene oxide chain or the polypropylene oxide chain can be captured by complexing with metals such as alkali metals. It is speculated that as the number of repeating units of the polyethylene oxide chain or polypropylene oxide chain becomes larger, the complex constant increases, and the trapping ability of metal molecules increases. Therefore, the formation of alkali metal salts of alkali-soluble resins can be inhibited, and the hardening can be inhibited. Water absorption in the membrane. In addition, it is presumed that oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain interact with acidic groups such as the carboxyl group of the alkali-soluble resin contained in the photosensitive resin composition by hydrogen bonding, thereby suppressing Forms alkali metal salts of acidic bases and inhibits water absorption into the hardened film. In the case where m is 19 or more, as shown in FIG. 4, the graft copolymer 11 may contain a main component having a structural unit 21 represented by the general formula (I) and a structural unit 22 represented by the general formula (II) The chain part 12, and at least a part of the nitrogen site of the structural unit 21 represented by the above general formula (I) forms a salt with at least one 23 selected from the group consisting of organic acid compounds and halogenated hydrocarbons, the above general formula (II) The structural unit 22 represented by the polymer chain 24 contains the structural unit 25 represented by the general formula (III) including a polyethylene oxide chain or polypropylene oxide chain 26 having a specific repeating number. In the specific graft copolymer used in the present invention, the structural unit of the polymer chain 24 thus grafted contains a structural unit 25 including a polyethylene oxide chain or a polypropylene oxide chain having a specific repeating number. The branched polymer chain 24 itself has a branched structure. It is presumed that, as a result, the specific surface area of the metal capturing part of the dispersant becomes larger, and interacting with this, the metal capturing effect caused by the oxygen atom contained in the polyethylene oxide chain or the polypropylene oxide chain is obvious, which can improve water absorption Suppressive effect, suppress water spots caused by water absorption. It is inferred that the water-absorption inhibitory action in the hardened film can suppress the occurrence of water spots due to water absorption. On the other hand, the upper limit of m is 80 or less, and in terms of solubility in organic solvents used for color filters, it is preferably 50 or less.

The hydrocarbon group in R ⁴⁶ may be the same as the hydrocarbon group in ^{R 50 described above.} The hydrocarbon group in R ⁴⁶ is preferably selected from alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms in which the alkyl group may be substituted, in terms of dispersion stability or compatibility, And at least one of the group consisting of aralkyl groups having 7 to 14 carbon atoms in which the alkyl group may be substituted, more preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-butyl One or more of nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups whose alkyl groups may be substituted, and benzyl groups.

In addition, in the above general formula (III'), as the divalent linking group A ^3' , for example, the same as the divalent linking group in the ^{above A 1 can be exemplified.} Among them, in terms of solubility for the purposes of the use of organic solvents in the color filter of the formula (III ') in the A ^3' is preferably a divalent group of -CONH- group or a -COO- The linking group is more preferably a -CONH- group or a -COO- group, and even more preferably a -COO- group. In the above general formula (III'), R ⁴⁷ is an alkylene group having 1 to 10 carbon atoms, and among them, an alkylene group having 2 to 8 carbon atoms is preferred in terms of solvent resolubility. R ⁴⁸ is an alkylene group having 3 to 7 carbon atoms, and in terms of substrate adhesion, it is preferably an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms. alkyl. R ⁴⁹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group in the ^{above-mentioned R 49} may be the same as the hydrocarbon group in the ^{above-mentioned R 46.}

In the general formula (III'), n represents the number of repeating units of the ester chain and represents a number of 1 or more. Among them, from the viewpoint of shortening the development time and satisfying excellent solvent resistance, it is preferably 2 or more, and further Preferably it is 3 or more. On the other hand, the upper limit of n is 40 or less, and in terms of solubility in organic solvents for color filter applications, it is preferably 20 or less.

In the above-mentioned polymer chain, at least one structural unit selected from the group consisting of the structural unit represented by the above general formula (III) and the structural unit represented by the following general formula (III') may be used alone. , You can mix 2 or more kinds. From the viewpoint of making the solvent affinity part caused by oxygen atoms more obvious, shortening the development time of the photosensitive resin composition, and improving the solvent resistance, it is preferable that the polymer chain contains the above-mentioned general formula (III) Indicates the structural unit.

Among them, based on the viewpoints of enhancing the effect of inhibiting water spots, enhancing solvent resistance, and enhancing the effect of inhibiting development residues, the structural unit of the polymer chain in the structural unit represented by the general formula (II) is more preferably contained in combination At least one selected from the group consisting of structural units represented by the general formula (III) where m is 19 or more and 80 or less, and a structure represented by the general formula (III) where m is 3 or more and 10 or less At least one of the group consisting of the unit, and more preferably, the combination contains at least one selected from the group consisting of the structural unit represented by the general formula (III) whose m is 19 or more and 50 or less, and is selected from m is at least one of the group consisting of the structural unit represented by the general formula (III) in which m is 3 or more and 8 or less.

The structural unit of the polymer chain in the structural unit represented by the above general formula (II) contains at least 1 selected from the group consisting of the structural unit represented by the above general formula (III) whose m is 19 or more and 80 or less In this case, when all the structural units of the polymer chain are set to 100% by mass, the structural unit represented by the general formula (III) where m is 19 or more and 80 or less in terms of water spot suppression effect The total ratio of is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more. On the other hand, in terms of solvent resolubility and water spot suppression effect, it is preferably 75% by mass or less, more preferably 65% by mass or less, and still more preferably 50% by mass or less.

The combination of the structural units of the polymer chain in the structural unit represented by the above-mentioned general formula (II) contains at least one selected from the group consisting of the structural units represented by the above-mentioned general formula (III) whose m is 19 or more and 80 or less When one type and at least one type selected from the group consisting of structural units represented by the general formula (III) where m is 3 or more and 10 or less, set all the structural units of the polymer chain to 100 In the case of mass %, the total ratio of the structural units represented by the general formula (III) in which m is 3 or more and 10 or less is preferably 20 mass% or more. On the other hand, in terms of solvent re-solubility, when all the structural units of the polymer chain are set to 100% by mass, the polymer chain m is 3 or more and 10 or less in the above general formula (III) The total ratio of the structural units shown is preferably 80% by mass or less, and more preferably 60% by mass or less. In addition, the mixing ratio of the structural unit represented by the general formula (III) with m of 19 or more and 80 or less and the structural unit represented by the general formula (III) with m of 3 or more and 10 or less in the polymer chain is based on From the viewpoint of improving the effect of suppressing development residues, the sum of the structural units represented by the general formula (III) where m is 19 or more and 80 or less and the structural unit represented by the general formula (III) where m is 3 or more and 10 or less When it is 100 parts by mass, the total of the structural units represented by the general formula (III) whose m is 19 or more and 80 or less is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, and preferably 80 parts by mass or less , More preferably 60 parts by mass or less.

In terms of dispersion stability, high contrast, shortening of development time, and at the same time satisfying excellent solvent resistance, when all the structural units of the above polymer chain are set to 100% by mass, it is selected from the above general formula (III) The total ratio of at least one structural unit in the group consisting of the structural unit represented and the structural unit represented by the general formula (III') is preferably 1% by mass or more, more preferably 2% by mass or more, and still more Preferably, it is 4% by mass or more. In terms of solvent resolubility, when all the structural units of the polymer chain are set to 100% by mass, they are selected from the structural units represented by the above general formula (III) and those represented by the above general formula (III') The total ratio of at least one structural unit in the group consisting of the structural unit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

In the above polymer chain, the structural unit represented by the above general formula (IV) including the structural unit represented by the above general formula (III) and the structural unit represented by the above general formula (III') may be used alone, Two or more types can also be mixed. In terms of the dispersibility and dispersion stability of the color material, when all the structural units of the polymer chain are set to 100% by mass, the total ratio of the structural units represented by the general formula (IV) is preferably 70 Mass% or more, more preferably 90 mass% or more. On the other hand, in terms of dispersion stability and at the same time satisfying excellent solvent resistance, when all the structural units of the polymer chain are set to 100% by mass, the above-mentioned general formula (IV) in the above-mentioned polymer chain The total ratio of the structural units shown can be 100% by mass. Among them, in terms of dispersion stability, solvent resistance, and compatibility with the initiator, when all the structural units of the polymer chain are set to 100% by mass, the structure is derived from (meth)acrylate The total ratio of the units is preferably 60% by mass or more, and more preferably 80% by mass or more. On the other hand, in terms of dispersion stability and at the same time satisfying excellent solvent resistance, when all the structural units of the polymer chain are set to 100% by mass, the polymer chain is derived from (methyl) The total ratio of the structural units of the acrylate may be 100% by mass.

Among the structural units of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, except for the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') In addition to the structural unit represented by the above general formula (IV) of the structural unit shown, other structural units may also be included. As another structural unit, a structural unit derived from a monomer having an unsaturated double bond which can be copolymerized with the monomer deriving the structural unit represented by the general formula (IV) can be exemplified. Examples of monomers from which other structural units are derived include styrenes such as styrene and α-methylstyrene; vinyl ethers such as phenyl vinyl ether and the like.

In the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, in terms of the effect of the present invention, all the structural units of the polymer chain are set to 100% by mass At this time, the total ratio of other structural units is preferably 30% by mass or less, more preferably 10% by mass or less.

In terms of the dispersibility and dispersion stability of the color material, the mass average molecular weight Mw of the polymer chain in the Polymer is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, and even more preferably 15000 Hereinafter, it is more preferably 12,000 or less. By staying in the above range, the sufficient steric repulsion effect of the dispersant can be maintained, and the specific surface area of the solvent affinity part of the dispersant can be increased, and the solvent can be prevented from penetrating into the coating film or reaching the color material. In the case of ethylene oxide chain or polypropylene oxide chain, the interaction caused by oxygen atoms is obvious, which can shorten the development time and improve the solvent resistance, thereby suppressing the generation of water spots and the generation of development residues. The effect is good.

In addition, with regard to the polymer chain in Polymer, as a standard, it is preferable that the solubility in the organic solvent used in combination at 23° C. is 20 (g/100 g solvent) or more. The solubility of the polymer chain can be used as a standard when the raw material for introducing the polymer chain has the above solubility when preparing the graft copolymer. For example, when a polymer chain and a polymerizable oligomer (macromonomer) containing an ethylenically unsaturated double bond at the end is used to introduce the graft copolymer into the polymer chain, as long as the polymer chain is low It is only necessary for the polymer to have the above-mentioned solubility. In addition, after forming a copolymer from a monomer containing a group having an ethylenically unsaturated double bond, a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer is used to introduce the polymer chain In this case, as long as the polymer chain containing the reactive group has the above-mentioned solubility.

In the graft copolymer, the structural unit represented by the general formula (I) is preferably contained in a ratio of 3-60% by mass, more preferably 6-45% by mass, and still more preferably 9-30% by mass . If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity part to the color material in the graft copolymer is appropriate, and its dissolution in the organic solvent can be suppressed It has reduced properties, so it has good adsorption to color materials and can obtain excellent dispersibility and dispersion stability. On the other hand, in the above-mentioned graft copolymer, the structural unit represented by the above-mentioned general formula (II) is preferably contained in a ratio of 40 to 97% by mass, more preferably 55 to 94% by mass, and even more preferably 70 ～91% by mass. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent affinity part in the graft copolymer is appropriate, and the sufficient steric repulsion effect of the dispersant can be maintained and dispersed The specific surface area of the solvent affinity part of the agent becomes larger, which can prevent the solvent from penetrating into the coating film or reaching the color material, and when it contains a polyethylene oxide chain or a polypropylene oxide chain, it is caused by oxygen atoms The interaction is obvious, which can shorten the development time, improve the solvent resistance, and then have a good effect of inhibiting the generation of water spots and the generation of development residues.

The graft copolymer used in the present invention may have the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) within a range that does not impair the effects of the present invention, and further have Other structural units. Regarding other structural units, an ethylenically unsaturated double bond-containing monomer that can be copolymerized with the ethylenically unsaturated double bond-containing monomer that derives the structural unit represented by the general formula (I) can be appropriately selected and copolymerized. Import other structural units. As another structural unit copolymerized with the structural unit represented by the above general formula (I), for example, the structural unit represented by the above general formula (IV) and the like can be mentioned. Furthermore, the content ratio of the above-mentioned structural unit is based on the structural unit represented by the above-mentioned general formula (I), the structural unit represented by the above-mentioned general formula (II) and the above-mentioned general formula (IV) when the graft copolymer is synthesized during production. Calculate the added amount of monomers such as the indicated structural units.

Furthermore, in terms of dispersibility and dispersion stability, the mass average molecular weight Mw of the graft copolymer is preferably 4,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more. On the other hand, in terms of solvent resolubility, it is preferably 50,000 or less, and more preferably 30,000 or less. Furthermore, in the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). The measurement was carried out under the following conditions, namely, using Tosoh's HLC-8120GPC, the dissolution solvent was set to 0.01 mol/L of lithium bromide added N-methylpyrrolidone, and the calibration curve was based on polystyrene standards. Set to Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh), set the measuring column to TSK-GEL ALPHA-M×2 (manufactured by Tosoh).

(Manufacturing method of graft copolymer) In the present invention, the method for producing the graft copolymer is not particularly limited, as long as it can produce the graft copolymer having the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). The branch copolymer method is sufficient. In the case of producing a graft copolymer having the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II), for example, the following method can be exemplified: containing the following general formula (Ia) The indicated monomer, the polymer chain and the polymerizable oligomer (macromonomer) having a group having an ethylenically unsaturated double bond at the end thereof are copolymerized as a copolymerization component to produce a graft copolymer. Other monomers can be used as needed, and the graft copolymer can be produced by a well-known polymerization method.

(通式(Ia)中，R⁴¹ 、A¹ 、R⁴² 及R⁴³ 與通式(I)中之該等相同)[化8]

(In the general formula (Ia), R ⁴¹ , A ¹ , R ⁴² and R ⁴³ are the same as those in the general formula (I))

In addition, in the case of producing a graft copolymer having the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), the monomer represented by the general formula (Ia) can be used Addition polymerization with other monomers containing groups with ethylenically unsaturated double bonds to form copolymers, and then use polymer chains containing reactive groups capable of reacting with the reactive groups contained in the copolymer to introduce into the polymer chain. Specifically, for example, after synthesizing a copolymer having substituents such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, and a hydrogen bond forming group, it can be reacted with a copolymer containing the substituent The polymer chain of the functional group reacts and is introduced into the polymer chain. For example, a copolymer having a glycidyl group in the side chain can be reacted with a polymer chain having a carboxyl group at the end, or a copolymer having an isocyanate group in the side chain can be reacted with a polymer chain having a hydroxyl group at the end to introduce the polymer chain. Furthermore, in the above polymerization, additives generally used for polymerization, such as polymerization initiators, dispersion stabilizers, chain transfer agents, etc., can be used.

Next, a block copolymer having an A block including a structural unit represented by the above general formula (I) and a B block including a (meth)acrylate-derived structural unit will be described. In the present invention, the arrangement of each block of the block copolymer is not particularly limited. For example, it may be an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of excellent dispersibility, AB block copolymers or ABA block copolymers are preferred.

The A block is a block that functions as a color material adsorption site, and contains at least the structural unit represented by the above-mentioned general formula (I). The A block may be at least a part of the nitrogen site of the structural unit represented by the general formula (I) of the block copolymer to form a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons The resulting salt-type block copolymer. The A block can have a structural unit other than the structural unit represented by the general formula (I) within the scope of achieving the purpose of the invention, and the structural unit that can be copolymerized with the structural unit represented by the general formula (I) can contain . Specifically, for example, the structural unit represented by the above-mentioned general formula (IV) and the like can be exemplified. In the A block in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is preferably 50-100% by mass relative to the total mass of all structural units of the A block , More preferably 80-100% by mass, most preferably 100% by mass. The reason is that the higher the ratio of the structural units represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. In addition, the content ratio of the above-mentioned structural unit is calculated based on the added mass when synthesizing the A block having the structural unit represented by the general formula (I).

In addition, in the block copolymer before salt formation, based on the viewpoint of making the dispersibility and dispersion stability good, the total mass of all the structural units of the block copolymer is The content ratio is preferably from 5 to 60% by mass, more preferably from 10 to 50% by mass. In addition, the content ratio of each structural unit in the block copolymer is calculated based on the added mass when the block copolymer is synthesized before the salt is formed. Furthermore, the structural unit represented by the general formula (I) may be included as long as it has affinity with the color material, and may include one type or two or more types.

The B block is a block that functions as a solvent affinity site, and contains at least a structural unit derived from (meth)acrylate. Regarding the structural unit derived from (meth)acrylate, it may be the same as described above. As the B block, it is preferably selected from a monomer having an unsaturated double bond which can be copolymerized with the monomer deriving the structural unit represented by the general formula (I) to have solvent affinity and appropriately selected and used according to the solvent. . As a standard, it is preferable to introduce the B block in such a way that the solubility of the copolymer at 23° C. is 20 (g/100 g solvent) or more relative to the solvent used in combination. The structural unit constituting the B block portion may include one type or two or more types. As the structural unit contained in the B block, for example, the structural unit represented by the above-mentioned general formula (IV) and the like can be mentioned.

In the block copolymer used as the dispersant of the present invention, the ratio m of the unit number m of the structural unit represented by the general formula (I) to the unit number n of other structural units constituting the solvent affinity block part /n is preferably in the range of 0.01 or more and 1 or less, and in terms of the dispersibility and dispersion stability of the color material, it is more preferably in the range of 0.05 or more and 0.7 or less.

From the viewpoint of improving solvent resistance by combining with the specific initiator used in the present invention and suppressing the generation of development residues, it is preferable that the block copolymer used as the dispersant of the present invention contains the following block copolymer And at least one of salt-type block copolymers, the block copolymers containing the A block containing the structural unit represented by the general formula (I), and containing the structural unit derived from the carboxyl-containing monomer and derived from The B block of the structural unit of (meth)acrylate, the salt-type block copolymer is at least a part of the nitrogen part of the structural unit represented by the general formula (I) of the block copolymer and selected from organic At least one of the group consisting of an acid compound and a halogenated hydrocarbon forms a salt. At least one of the above block copolymers and salt-type block copolymers has an acid value of 1-18 mgKOH/g, glass transition temperature Above 30°C. In this case, the B block contains a structural unit derived from (meth)acrylate as an essential component, and may be the same as the B block in International Publication No. 2016/104493.

As the above-mentioned carboxyl group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxyl group can be used. Examples of such monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, butene Acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction of monomers with hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used物; ω-carboxy-polycaprolactone mono (meth)acrylate and so on. In addition, as the precursor of the carboxyl group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can be used. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxyl group-containing monomer is not particularly limited, as long as the acid value of the block copolymer is within the above-mentioned specific acid value range. However, with respect to the total mass of all the structural units of the block copolymer, it is preferably from 0.05% by mass to 4.5% by mass, and more preferably from 0.07% to 3.7% by mass. When the content ratio of the structural unit derived from the carboxyl group-containing monomer is more than the above lower limit, the development residue suppression effect can be expressed. By being below the above upper limit, it is possible to prevent deterioration of development adhesion or solvent resolubility. Difference. Furthermore, the structural unit derived from a carboxyl group-containing monomer should just have the said specific acid value, 1 type may be contained, and 2 or more types may be contained.

In addition, from the viewpoint of improving development adhesion, it is preferable that the B block of the block copolymer contains a structural unit derived from a hydroxyl group-containing monomer. When a structural unit derived from a hydroxyl-containing monomer is included in the B block, the development speed is also increased. Furthermore, the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the structural unit derived from the hydroxyl-containing monomer, a monomer that can be copolymerized with the monomer that derives the structural unit represented by the general formula (I) and contains an unsaturated double bond and a hydroxyl group can be used. As such a monomer, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4 (meth)acrylate -Hydroxybutyl ester, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate ε-caprolactone 1 mol adduct, ( 2-hydroxy-3-phenoxypropyl meth)acrylate and the like. From the viewpoint of improving development adhesion, among them, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate is preferred.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the hydroxyl-containing monomer relative to the total mass of all structural units of the block copolymer is preferably 1% by mass or more, more preferably 2% by mass % Or more, more preferably 3% by mass or more, and particularly preferably 4% by mass or more. If it is more than the above lower limit, the development adhesiveness can be made better. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is less than the above upper limit, the introduction ratio of other useful monomers can be increased, which is preferable. In addition, the content ratio of the above-mentioned structural unit is calculated based on the added mass when synthesizing the block copolymer before forming the salt.

Regarding the acid value of at least one of the above-mentioned block copolymers and salt type block copolymers, in terms of the effect of suppressing development residues, the lower limit is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g above. In addition, with regard to the acid value of at least one of the above-mentioned block copolymers and salt-type block copolymers, the upper limit is preferably 18 mgKOH/ from the viewpoint of preventing deterioration of development adhesion or deterioration of solvent resolubility g or less, more preferably 16 mgKOH/g or less, and still more preferably 14 mgKOH/g or less. The acid value of at least one of the above-mentioned block copolymers and salt-type block copolymers can be obtained by the method described in International Publication No. 2016/104493.

In terms of developing adhesion, the glass transition temperature of at least one of the above-mentioned block copolymers and salt-type block copolymers is preferably 30°C or higher, and among them, it is preferably 32°C or higher, and more preferably 35°C. above. On the other hand, in terms of operability during use such as easy and accurate weighing, it is preferably 200°C or lower. The glass transition temperature of at least one of the above-mentioned block copolymers and salt-type block copolymers is determined by measuring by differential scanning calorimetry (DSC) in accordance with JIS K7121. When two or more peaks representing the glass transition temperature are observed, the peak area, that is, the peak with the largest area of the part protruding from the reference line of the obtained graph, is set as the representative value of the glass transition temperature.

The mass average molecular weight Mw of the block copolymer is not particularly limited. From the viewpoint of improving the dispersibility and dispersion stability of the color material, it is preferably 1000 or more and 20000 or less, more preferably 2000 or more and 15000 or less, and still more preferably 3000 Above 12000 and below. Here, the mass average molecular weight (Mw) can be measured in the same manner as described above.

In addition, in terms of dispersion stability, solvent resistance, and compatibility with the initiator, when all the structural units in the B block in the block copolymer are set to 100% by mass, it is derived from (former The total ratio of the structural units of the base) acrylate is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. On the other hand, in terms of dispersion stability and satisfying excellent solvent resistance at the same time, when all the structural units in the B block are set to 100% by mass, the structure derived from (meth)acrylate The total ratio of the units can be 100% by mass. When the B block contains structural units derived from the above-mentioned carboxyl group-containing monomer, when all structural units in the B block that are different from the structural unit derived from the above-mentioned carboxyl group-containing monomer are set to 100% by mass, the source The total ratio of the structural units from (meth)acrylate may be 100% by mass.

In addition, in the block copolymer before salt formation, based on the viewpoint of improving the dispersibility of the color material, the content ratio of the structural unit represented by the above general formula (IV) relative to the total mass of all the structural units of the block copolymer It is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated based on the added mass when synthesizing the block copolymer before forming the salt.

From the viewpoint of good dispersibility, no precipitation of foreign matter when forming a coating film, and improvement of brightness and contrast, the (meth)acrylate copolymer containing the structural unit represented by the above general formula (I) preferably has an amine value of 40 The copolymer is above 120 mgKOH/g and below 120 mgKOH/g. When the amine value is within the above range, the viscosity with time stability or heat resistance is excellent, and the alkali developability or solvent resolubility is also excellent. In the present invention, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. On the other hand, in terms of solvent resolubility, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, more preferably Below 105 mgKOH/g. The amine value refers to the mg number of potassium hydroxide equivalent to the perchloric acid equivalent required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. In the case of measurement by this method, even if it is an amine group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so the block copolymer itself used as the dispersant can be measured. Amine value.

The content ratio (mole%) of each structural unit in the copolymer in the dispersant can be calculated based on the amount of raw materials added during production, and can be measured with an analysis device such as NMR. In addition, the structure of the dispersant can be measured using NMR, various mass analyses, and the like. In addition, the dispersant may be decomposed by thermal decomposition if necessary. For the obtained decomposed product, high performance liquid chromatography, gas chromatography mass spectrometry, NMR, elemental analysis, XPS/ESCA (X-ray photoelectron spectroscopy) /Electron Spectroscopy for Chemical Analysis, X-ray photoelectron spectroscopy/chemical analysis electronic spectroscopy) and TOF-SIMS (time of flight secondary ion mass spectrometry, time of flight secondary ion mass spectrometry) etc.

In the present invention, as a dispersant, at least one of the above-mentioned (meth)acrylate copolymer-based dispersants is used, and the content thereof is based on the type of color material used, and further based on the following photosensitive color resin composition The solid content concentration, etc. are appropriately selected. Regarding the content of the dispersant, relative to the total solid content of the photosensitive colored resin composition, it is preferably formulated at a ratio of 2% by mass to 30% by mass, and more preferably at a ratio of 3% by mass to 25% by mass. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of a photosensitive colored resin composition will be more excellent. Moreover, if it is less than the said upper limit, developability will become favorable. In particular, when forming a colored layer with a high color material concentration, the content of the dispersant is preferably 2% to 25% by mass, relative to the total solid content of the photosensitive colored resin composition, More preferably, it is blended at a ratio of 3% by mass to 20% by mass. Furthermore, in the present invention, the solid components are all components except the following solvents, and also include monomers dissolved in the solvents and the like.

＜Photoinitiator＞ The photoinitiator in the photosensitive colored resin composition of the present invention contains a compound represented by the following general formula (A). It is considered that since it contains a photoinitiator as a compound represented by the following general formula (A), by combining it with the above-mentioned specific dispersing agent, the initiator is likely to be uniformly present in the colored layer, and it is suppressed that only the surface is hardened. As a result, the line width deviation becomes larger, the colored layer is uniformly cured, and the curability of the coating film is improved, so that the cured product of the photosensitive colored resin composition has good solvent resistance.

(The compound represented by the following general formula (A)) The oxime ester compound represented by the following general formula (A) used in the present invention contains geometric isomers caused by the double bond of the oxime, but these are not distinguished. That is, in this specification, the compound represented by the following general formula (A) and the preferred form of the compound, namely the compound represented by the following general formula (B) and its exemplified compounds, mean a mixture of the two or Either one is not limited to showing the structure of an isomer.

(式中，R¹ 及R² 分別獨立地表示R¹¹ 、OR¹¹ 、COR¹¹ 、SR¹¹ 、CONR¹² R¹³ 或CN， R¹¹ 、R¹² 及R¹³ 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R¹¹ 、R¹² 及R¹³ 所表示之基之氫原子可進而被取代為R²¹ 、OR²¹ 、COR²¹ 、SR²¹ 、NR²² R²³ 、CONR²² R²³ 、-NR²² -OR²³ 、-NCOR²² -OCOR²³ 、NR²² COR²¹ 、OCOR²¹ 、COOR²¹ 、SCOR²¹ 、OCSR²¹ 、COSR²¹ 、CSOR²¹ 、羥基、硝基、CN或鹵素原子， R²¹ 、R²² 及R²³ 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R²¹ 、R²² 及R²³ 所表示之基之氫原子可進而被取代為羥基、硝基、CN、鹵素原子或羧基， R¹¹ 、R¹² 、R¹³ 、R²¹ 、R²² 及R²³ 所表示之基之伸烷基部分可於氧原子不相鄰之條件下包含1～5個-O-、-S-、-COO-、-OCO-、-NR²⁴ -、-NR²⁴ CO-、-NR²⁴ COO-、-OCONR²⁴ -、-SCO-、-COS-、-OCS-或-CSO-， R²⁴ 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基， R¹¹ 、R¹² 、R¹³ 、R²¹ 、R²² 、R²³ 及R²⁴ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基， R³ 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基，R³ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基，又，R³ 與R⁷ 及R³ 與R⁸ 可分別一起形成環， R³ 所表示之基之氫原子可進而被取代為R²¹ 、OR²¹ 、COR²¹ 、SR²¹ 、NR²² R²³ 、CONR²² R²³ 、-NR²² -OR²³ 、-NCOR²² -OCOR²³ 、NR²² COR²¹ 、OCOR²¹ 、COOR²¹ 、SCOR²¹ 、OCSR²¹ 、COSR²¹ 、CSOR²¹ 、羥基、硝基、CN或鹵素原子， R⁴ 、R⁵ 、R⁶ 及R⁷ 分別獨立地表示R¹¹ 、OR¹¹ 、SR¹¹ 、COR¹⁴ 、CONR¹⁵ R¹⁶ 、NR¹² COR¹¹ 、OCOR¹¹ 、COOR¹⁴ 、SCOR¹¹ 、OCSR¹¹ 、COSR¹⁴ 、CSOR¹¹ 、羥基、CN或鹵素原子，R⁴ 與R⁵ 、R⁵ 與R⁶ 及R⁶ 與R⁷ 可分別一起形成環， R¹⁴ 、R¹⁵ 及R¹⁶ 表示氫原子或碳原子數1～20之烷基，R¹⁴ 、R¹⁵ 及R¹⁶ 所表示之基之烷基部分可具有分支側鏈，亦可為環狀烷基，R⁸ 表示R¹¹ 、OR¹¹ 、SR¹¹ 、COR¹¹ 、CONR¹² R¹³ 、NR¹² COR¹¹ 、OCOR¹¹ 、COOR¹¹ 、SCOR¹¹ 、OCSR¹¹ 、COSR¹¹ 、CSOR¹¹ 、羥基、CN或鹵素原子， k表示0或1)[化9]

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom and the number of carbon atoms 1-20 alkyl, 6-30 aryl, 7-30 aralkyl, or 2-20 heterocyclic group, represented by R ¹¹ , R ¹² and R ¹³ The hydrogen atom of the group can be further substituted with R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN or halogen atom, R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom and a carbon atom number of 1-20 Alkyl group, aryl group with 6 to 30 carbon atoms, aralkyl group with 7 to 30 carbon atoms or heterocyclic group with 2 to 20 carbon atoms, hydrogen atom of the group represented by ^{R 21} , R ²² and R ²³ The alkylene moiety of the group represented by ^{R 11} , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, a CN, a halogen atom or a carboxyl group, and the oxygen atom may not be adjacent Under the conditions, it contains 1～5 -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO- ^{, -OCONR 24} -, -SCO-, -COS-, -OCS- or -CSO-, R ²⁴ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms or carbon A heterocyclic group having 2 to 20 atoms, ^{the alkyl portion of the group represented by R 11} , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl R ³ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, The alkyl part of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl group. In addition, R ³ and R ⁷ and R ³ and R ⁸ may each form a ring together, and the group represented by ^{R 3} The hydrogen atom can be further substituted into R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, CN or halogen atom, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ^6, and R ⁶ and R ⁷ can form a ring together. R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group with 1 to 20 carbon atoms. The alkyl part of the group represented by ^{R 14} , R ¹⁵ and R ^{16 can have a branched side chain} , Can also be a cyclic alkyl group, R ⁸ represents R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , hydroxyl, CN or halogen atom, k represents 0 or 1)

As the number of carbon atoms represented by ^{R 3} , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A), 1 to 20 The alkyl group, for example, can include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, isopentyl, tertiary pentyl , Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, third octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl Alkyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc.

As the aryl group having 6 to 30 carbon atoms represented ^{by R 3} , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ^23, and R ²⁴ in the above general formula (A), for example: Phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, phenyl substituted by one or more of the above alkyl groups, biphenyl, naphthyl, anthryl, etc.

As the aralkyl group having 7 to 30 carbon atoms represented ^{by R 3} , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A), for example, : Benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, etc.

As the heterocyclic group having 2 to 20 carbon atoms represented ^{by R 3} , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A), for example, : Pyridyl, pyrimidinyl, furanyl, thienyl, tetrahydrofuranyl, dioxolane, benzoazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, 5- to 7-membered heterocycles such as thiazolidinyl, isothiazolidinyl, azolidinyl, isoazolidinyl, piperidinyl, piperazinyl, and morpholinyl. ^{As the ring that R 4} and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ³ and R ^7, and R ³ and R ⁸ in the above general formula (A) can form together, for example, preferred ones can be Examples: 5- to 7-membered rings such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactone ring.

In addition, as ^{halogen atoms represented by R 4} , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above general formula (A), and substitutable R ³ , R ¹¹ , R ^{12 in the above general formula (A)} The halogen atoms of R ¹³ , R ²¹ , R ²² and R ²³ can be exemplified by fluorine, chlorine, bromine, and iodine.

^{The alkylene moiety of the group represented by R 11} , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the above general formula (A) can be represented by -O-, -S-, -COO-,- OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-, when the oxygen atoms are not adjacent Contains 1 to 5, and the divalent group contained in this case may be one or more than two groups, and in the case of a group that can be continuously contained, it may be consecutively contained two or more.

In addition, the alkyl (alkylene) portion of the group represented ^{by R 11} , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A) may have a branched side chain, or It can be a cyclic alkyl group. Among the compounds represented by the above general formula (A), those having an ^{aromatic ring that can be condensed by R 3} or the compounds represented by the following general formula (B) are more sensitive and easy to manufacture, so they are preferred.

(式中，R¹ 、R² 、R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 及k與上述通式(A)中之該等相同，R³¹ 、R³² 、R³³ 、R³⁴ 及R³⁵ 分別獨立地表示R¹¹ 、OR¹¹ 、SR¹¹ 、COR¹¹ 、CONR¹⁵ R¹⁶ 、NR¹² COR¹¹ 、OCOR¹¹ 、COOR¹⁴ 、SCOR¹¹ 、OCSR¹¹ 、COSR¹⁴ 、CSOR¹¹ 、羥基、硝基、CN或鹵素原子，R³¹ 與R³² 、R³² 與R³³ 、R³³ 與R³⁴ 及R³⁴ 與R³⁵ 可分別一起形成環)[化10]

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and k are the same as those in the above general formula (A), R ³¹ , R ³² , R ³³ , R ³⁴ And R ³⁵ independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl, nitrate Group, CN or halogen atom, R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ and R ³⁴ and R ³⁵ can respectively form a ring together)

As ^{examples of the ring formed by R 31} and R ³² , R ³² and R ³³ , R ³³ and R ^34, and R ³⁴ and R ³⁵ together, there can be mentioned as R ⁴ and R ⁵ , R ⁵ and R ⁶ , The examples of rings that R ⁶ and R ⁷ , R ³ and R ^7, and R ³ and R ⁸ can form together are the same as those exemplified.

In the above general formulas (A) and (B), R ¹ is an alkyl group with 1 to 12 carbon atoms or an aralkyl group with 7 to 15 ^{carbon atoms, and R 11} is an aryl group with 6 to 12 carbon atoms, The alkyl group with 1-8 carbon atoms is preferred because of its higher solvent solubility, and the one with R ² being methyl, ethyl or phenyl is preferred because of its higher reactivity. R ⁴ to R ⁷ are hydrogen An atom or a cyano group, especially a hydrogen atom, is easy to synthesize, so it is preferred. R ⁸ is a hydrogen atom, so it is easy to synthesize, so it is preferred. When k is 1, the sensitivity is higher, so it is preferred; in the above general formula ( In B), ^{at least one of R 31} to R ³⁵ is a nitro group, CN, a halogen atom, COR ^11, and R ¹¹ is an aryl group with 6 to 12 carbon atoms or an alkyl group with 1 to 8 carbon atoms. Sensitivity is higher, so it is preferable, and it is more preferable that ^{at least one of R 31} to R ³⁵ is a nitro group, CN or a halogen atom, and it is particularly ^{preferable that R 33} is a nitro group, CN or a halogen atom.

As a preferable specific example of the compound represented by the said general formula (A), the following compounds can be mentioned, for example. In addition, compounds No. 1 to No. 212 described in International Publication No. 2015/152153 can be cited.

[化11]

The compound represented by the above general formula (A) can be synthesized, for example, by referring to International Publication No. 2015/152153, and appropriately selecting a solvent, reaction temperature, reaction time, purification method, etc. according to the materials used. In addition, commercially available products can also be obtained and used appropriately.

系光起始劑、醯基氧化膦系光起始劑及巰基系鏈轉移劑所組成之群中之至少1種。即，於使用更高感度之光起始劑以形成著色層之情形時，產生自由基後，自由基轉移至未曝光部，難以保持位於曝光部分之內部之未曝光部之形狀，且於尺寸精度不變差之情況下形成未曝光部周邊部。不同於上述通式(A)所表示之化合物之選自由肟酯系光起始劑、α-胺基酮系光起始劑、聯咪唑系光起始劑、9-氧硫𠮿

系光起始劑、醯基氧化膦系光起始劑及巰基系鏈轉移劑所組成之群中之至少1種具有自塗膜之中間使深部硬化之性質，從而容易抑制僅於塗膜表面硬化。 因此，若除上述通式(A)所表示之化合物以外，進而組合含有不同於上述通式(A)所表示之化合物之選自由肟酯系光起始劑、α-胺基酮系光起始劑、聯咪唑系光起始劑、9-氧硫𠮿

系光起始劑、醯基氧化膦系光起始劑及巰基系鏈轉移劑所組成之群中之至少1種，則可維持良好之感度，且自塗膜之表面至深部平衡性較佳地硬化，可控制微孔之剖面形狀，微孔之剖面形狀之傾斜角(θ2)(參照圖6)未達90°，從而良好。 又，若除上述通式(A)所表示之化合物以外，進而組合含有不同於上述通式(A)所表示之化合物之選自由肟酯系光起始劑、α-胺基酮系光起始劑、聯咪唑系光起始劑、9-氧硫𠮿

系光起始劑、醯基氧化膦系光起始劑及巰基系鏈轉移劑所組成之群中之至少1種，則可將未曝光部之感度控制為良好，微孔內之顯影殘渣抑制效果變高。(Other photoinitiators) The photoinitiator in the photosensitive colored resin composition of the present invention contains the oxime ester-based photoinitiator represented by the above general formula (A), and is based on the viewpoint of adjusting the sensitivity to be more favorable. It may further contain a photoinitiator different from the compound represented by the above general formula (A). Furthermore, the other photoinitiator used in the photosensitive colored resin composition of the present invention contains a chain transfer agent in addition to the photopolymerization initiator. Among them, based on the viewpoint of suppressing the development residue in the micropores during the patterning of the coloring layer and forming the required micropores in the coloring layer, and making the cross-sectional shape of the micropores good, the photosensitive coloring resin composition of the present invention The photoinitiator is preferably in addition to the compound represented by the above general formula (A), and further contains a compound different from the compound represented by the above general formula (A) selected from the group consisting of oxime ester-based photoinitiators and α-amine groups. Ketone-based photoinitiator, biimidazole-based photoinitiator, 9-oxysulfur𠮿

It is at least one of the photoinitiator, phosphine oxide-based photoinitiator, and mercapto-based chain transfer agent. That is, in the case of using a more sensitive photoinitiator to form the coloring layer, after the free radicals are generated, the free radicals are transferred to the unexposed part, and it is difficult to maintain the shape of the unexposed part located inside the exposed part. The periphery of the unexposed part is formed while the accuracy is not deteriorated. The compound different from the compound represented by the above general formula (A) is selected from the group consisting of oxime ester-based photoinitiator, α-aminoketone-based photoinitiator, biimidazole-based photoinitiator, and 9-oxysulfur 𠮿

At least one of the photoinitiator, phosphine oxide-based photoinitiator, and mercapto-based chain transfer agent has the property of hardening the deep part from the middle of the coating film, so that it is easy to suppress only on the surface of the coating film. hardening. Therefore, if in addition to the compound represented by the above general formula (A), a combination containing a compound different from the compound represented by the above general formula (A) is selected from the group consisting of oxime ester-based photoinitiators and α-aminoketone-based photoinitiators. Starter, biimidazole-based photoinitiator, 9-oxysulfur 𠮿

At least one of the photoinitiator, phosphine oxide-based photoinitiator, and mercapto-based chain transfer agent can maintain good sensitivity and has better balance from the surface to the depth of the coating film The ground hardening can control the cross-sectional shape of the micro-holes. The inclination angle (θ2) (refer to Figure 6) of the cross-sectional shape of the micro-holes is less than 90°, which is good. In addition, if in addition to the compound represented by the above general formula (A), a combination containing a compound different from the compound represented by the above general formula (A) is selected from the group consisting of oxime ester-based photoinitiators and α-aminoketone-based photoinitiators. Starter, biimidazole-based photoinitiator, 9-oxysulfur 𠮿

At least one of the group consisting of photoinitiator, phosphine oxide photoinitiator and sulfhydryl chain transfer agent, the sensitivity of the unexposed part can be controlled to be good, and the development residue in the micropores can be suppressed The effect becomes higher.

When an oxime ester-based photoinitiator different from the compound represented by the above general formula (A) is used as another photoinitiator, the cross-sectional shape of the above-mentioned micropores is good, which has the effect of suppressing development residues, and further forms In the case of a thin line pattern, it is easy to make the cross-sectional shape good, which is preferable in this respect. As an oxime ester-based photoinitiator different from the compound represented by the above general formula (A), for example, it can be selected from 1,2-octanedion-1-[4-(phenylthio)phenyl]-,2- (O-benzyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-,1-(o-acetyl Oxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2010-527338, Japanese Patent Application Publication 2013- Among the oxime ester-based photoinitiators described in No. 041153, etc., an appropriate selection is made. As the oxime ester-based photoinitiator different from the compound represented by the above general formula (A), from the viewpoint of enhancing sensitivity, one having a carbazole skeleton, a diphenyl sulfide skeleton, or a sulphur skeleton is preferred. The oxime ester-based photoinitiator having a carbazole skeleton or a diphenyl sulfide skeleton can easily increase the sensitivity by combining with the compound represented by the above general formula (A), and it is also better in terms of the cross-sectional shape of the colored layer. good.

As an oxime ester-based photoinitiator having a carbazole skeleton, for example, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3- Group]-,1-(O-acetyl oxime) (e.g. Irgacure OXE02, manufactured by BASF Corporation), ketone, [8-[[(acetyloxy)imino][2-(2,2, 3,3-Tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-,(2,4,6- Trimethylphenyl) (e.g. Irgacure OXE-03, manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxy Phenoxy)-9H-carbazol-3-yl)-,1-(o-acetyloxime), ketone, (9-ethyl-6-nitro-9H-carbazol-3-yl)[ 4-(2-Methoxy-1-methylethoxy-2-methylphenyl]-, o-acetoxyoxime, 1-acetone, 3-cyclopentyl-1-[9-ethyl- 6-(2-Methylbenzyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (for example, TR-PBG-304, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1-Acetone, 3-cyclopentyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-,1-(o-acetyloxime), ethyl ketone, 2-ring Hexyl-1-[2-(2-pyrimidinyloxy)-9H-carbazol-3-yl]-,1-(o-acetyloxime), ethyl ketone, 2-cyclohexyl-1-[2-( 2-pyrimidinylthio)-9H-carbazol-3-yl]-,1-(o-acetyloxime), 1-octanone, 1-[4-[3-[1-[(acetoxy )Imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)sulfanyl]-2-methylbenzyl]-9H-carbazole-9- Phenyl]-,1-(o-acetyloxime) (e.g. EXTA-9, manufactured by UNION Chemical), ADEKA OPT-N-1919 (manufactured by ADEKA), Adeka Arkles NCI-831 ( Made by ADEKA company) and so on. As the oxime ester-based photoinitiator having a carbazole skeleton, it can be used alone or in combination of two or more. Among them, from the viewpoint of making the sensitivity higher, it is preferable to use 1-acetone, 3-cyclopentyl-1- [9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (e.g. TR-PBG-304, Changzhou Power Electronics New Materials Co., Ltd.), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime ) (E.g. Irgacure OXE02, manufactured by BASF) or ketone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4-(2-methoxy-1-methylethoxy 2-methylphenyl]-, o-acetyloxime.

As an oxime ester-based photoinitiator having a diphenyl sulfide skeleton, for example, an oxime ester compound represented by the following chemical formula (C-1), 1,2-octanedione, 1-[4- (Phenylthio)phenyl]-,2-(ortho-benzyl oxime) (e.g. Irgacure OXE01, manufactured by BASF Corporation), 1,2-propanedione, 3-cyclopentyl-1-[4-( Phenylthio)phenyl]-,2-(ortho-benzyl oxime) (e.g. TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclopentyl- 1-[4-[(2-Hydroxyethoxy)phenylthio]phenyl]-,2-(o-acetyloxime], 1-pentanone, 1-[4-[4-(2-benzene Phenylsulfanyl)phenyl)-4-methyl, 1-(o-acetyloxime), TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkles NCI-930 (manufactured by ADEKA), Irgacure OXE04 (manufactured by BASF), etc.

[化12]

Examples of the oxime ester-based photoinitiator having a stilbene skeleton include the oxime ester compound represented by the general formula (1) described in International Publication No. 2018/062105 (the oxime ester represented by the following general formula (D)) Compound). The oxime ester compound represented by the following general formula (D) may be the same as the oxime ester compound represented by the general formula (1) described in International Publication No. 2018/062105.

(於通式(D)中，R^a 及R^b 分別獨立地為氫原子或烷基，R^c 係可包含選自硫醚鍵(-S-)、醚鍵(-O-)及羰基鍵(-CO-)之至少1種二價連結基之烴基，Z為氫原子或-(C=O)R^d ，R^d 係可包含選自氧原子及硫原子之至少1種之烴基、或不包含氮原子，包含選自氧原子及硫原子之至少1種之雜環基，R^e 為碳數1～10之烴基)[化13]

(In the general formula (D), R ^a and R ^b are each independently a hydrogen atom or an alkyl group, and R ^c may include a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (-CO-) is a hydrocarbyl group of at least one divalent linking group, Z is a hydrogen atom or -(C=O)R ^d , R ^d may contain at least one hydrocarbyl group selected from oxygen atoms and sulfur atoms, or does not contain a nitrogen atom, selected from the group comprising an oxygen atom and a sulfur atom of at least one kind of the heterocyclic group, R ^e is a hydrocarbon group having a carbon number of 1 to 10)

As the oxime ester-based photoinitiator having a fluorine skeleton, a more suitable one may be a compound represented by the following compound (D-1). Moreover, as a commercially available product, for example, TR-PBG-365 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) can be mentioned.

[化14]

As the α-aminoketone photoinitiator, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (for example, Irgacure 907, BASF Company manufacture), 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone (e.g. Irgacure 369, manufactured by BASF Company), 2-(dimethylamino) Amino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF Corporation) and the like. As the α-aminoketone-based photoinitiator, it can be used alone or in combination of two or more. Among them, from the viewpoint of suppressing the development residue in the micropores and improving the cross-sectional shape of the micropores, 2-methyl is more preferred -1-(4-Methylthiophenyl)-2-morpholinopropane-1-one and 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl) -1-butanone.

As the biimidazole-based photoinitiator, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)- 1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-bi Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-bis Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4' ,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2' -Biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis( 2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like. As the biimidazole-based photoinitiator, it can be used alone or in combination of two or more. Among them, from the viewpoint of suppressing the development residue in the micropores and improving the cross-sectional shape of the micropores, it is preferable to use 2,2'-double (2-Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

系光起始劑，例如可例舉：2,4-異丙基9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、1-氯-4-丙氧基9-氧硫𠮿

、2,4-二氯9-氧硫𠮿

等。 作為9-氧硫𠮿

系光起始劑，可單獨使用或組合使用2種以上，其中，基於抑制微孔內之顯影殘渣，使微孔之剖面形狀良好之觀點，較佳為使用2,4-異丙基9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

。As 9-oxysulfur 𠮿

It is a photoinitiator, for example: 2,4-isopropyl 9-oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

, 1-chloro-4-propoxy 9-oxysulfur 𠮿

, 2,4-Dichloro 9-oxysulfur 𠮿

Wait. As 9-oxysulfur 𠮿

It is a photoinitiator, which can be used alone or in combination of two or more. Among them, it is preferable to use 2,4-isopropyl 9- from the viewpoint of suppressing the development residue in the micropores and improving the cross-sectional shape of the micropores. Oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

.

Phosphine oxide-based photoinitiators have the property of less yellowing caused by heat, so they are suitable for improving brightness, but generally have low sensitivity and sometimes fail to obtain sufficient curability. However, when combined with the compound represented by the above general formula (A), the overall coating film hardenability is improved, the development residue in the micropores is suppressed, and the cross-sectional shape of the micropores is improved, which is preferable in this respect. As the phosphine oxide-based photoinitiator, for example, benzyl-diphenylphosphine oxide, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, 2,3 ,5,6-Tetramethylbenzyl-diphenylphosphine oxide, 3,4-dimethylbenzyl-diphenylphosphine oxide, 2,4,6-trimethylbenzyl -Phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4 , 4-Trimethyl-pentyl phosphine oxide, bis(2,6-dimethylbenzyl)-ethyl phosphine oxide, etc. As the phosphine oxide-based photoinitiator, it can be used alone or in combination of two or more. Among them, from the viewpoint of improving the hardenability of the coating film, bis(2,4,6-trimethylbenzyl )-Phenyl phosphine oxide.

The sulfhydryl chain transfer agent has the properties of slower reaction free radicals to receive free radicals, accelerate the reaction, improve the overall coating film hardening, inhibit the development residue in the micropores, and make the cross-sectional shape of the micropores good. Better. As the mercapto-based chain transfer agent, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto -5-Methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutanoate Oxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione, three Hydroxymethylpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate) and tetraethyl Diol bis(3-mercaptopropionate) and the like. The mercapto-based chain transfer agent may be used singly or in combination of two or more types. Among them, from the viewpoint of increasing the reaction rate, 2-mercaptobenzothiazole is preferred.

The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, as long as the effects of the present invention are not impaired, relative to the total solid content of the photosensitive colored resin composition, Preferably it is 0.1 mass% or more and 12.0 mass% or less, More preferably, it is the range of 1.0 mass% or more and 8.0 mass% or less. If the content is more than the above lower limit, photocuring is sufficiently performed, the exposed part is prevented from eluting during development, and the solvent resistance is good. On the other hand, if the content is less than the above upper limit, the line width shift can be suppressed. Suppress the decrease in brightness caused by the yellowing of the obtained colored layer. Furthermore, the solid component is all components except the solvent, and also includes liquid polyfunctional monomers and the like. In addition, the total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is preferably 1% by mass to 20% by mass relative to the total of the alkali-soluble resin, polyfunctional monomer, and initiator. , More preferably, it is the range of 2 mass% or more and 15 mass% or less. If the content is more than the above lower limit, photocuring is sufficiently performed, the exposed part is prevented from eluting during development, and the solvent resistance is good. On the other hand, if the content is less than the above upper limit, the line width shift can be suppressed. Suppress the decrease in brightness caused by the yellowing of the obtained colored layer.

When the photoinitiator contains the compound represented by the general formula (A) and the other photoinitiator, the line width shift is suppressed, the solvent resistance is improved, and the development residue in the micropores is suppressed. In terms of the cross-sectional shape, relative to the total amount of the photoinitiator, the content of the compound represented by the general formula (A) is preferably 10% by mass or more and 98% by mass or less, more preferably 20% by mass or more and 95% by mass. Mass% or less, and more preferably 30% by mass or more and 95% by mass or less, it is more preferable in terms of suppressing line width deviation, improving solvent resistance, suppressing development residues in the micropores, and the cross-sectional shape of the micropores It is 50% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 90% by mass or less.

＜Color material＞ In the present invention, the color material is not particularly limited, as long as it can present the desired color when forming the coloring layer of the color filter. Various organic pigments, inorganic pigments, dispersible dyes, and salt-forming compounds of dyes can be used. Use alone or in a mixture of two or more. Among them, organic pigments have higher color rendering properties and higher heat resistance, so they are preferably used. As an organic pigment, for example, a compound classified as a pigment in the Dyestuff Index (CI; issued by The Society of Dyers and Colourists) can be mentioned. Specifically, there can be mentioned the following marked with a dye index (CI ) Numbered paint.

CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155 , 156, 166, 168, 175, 185 and CI Pigment Yellow 150 pigment derivatives; C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32 , 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57 : 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104 , 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180 , 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272 , 291; C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; C.I. Pigment Green 7, 36, 58, 59, 62, 63; C.I. Pigment Brown 23, 25; C.I. Pigment Black 1, 7.

In addition, specific examples of the above-mentioned inorganic pigments include: titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow plum, zinc yellow, iron plum (red iron oxide (III)), cadmium red, ultramarine blue , Iron blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc.

For example, when the color material dispersion of the present invention is made into the following photosensitive colored resin composition to form the pattern of the light-shielding layer on the substrate of the color filter, a black with higher light-shielding properties is blended in the ink pigment. As black pigments with high light-shielding properties, for example, inorganic pigments such as carbon black or ferroferric oxide; or organic pigments such as cyanine black can be used.

Examples of the above-mentioned dispersible dyes include dyes that can be dispersible by imparting various substituents to the dye, or by using it in combination with a solvent with low solubility. As a dye salt-forming compound, it refers to a compound in which the dye forms a salt with a counter ion. For example, it can be exemplified: a salt-forming compound of a basic dye and an acid, a salt-forming compound of an acid dye and a base, as well as the use of well-known lakes. (Salt formation) method, a lake pigment made by making solvent-soluble dyes insoluble in solvent. In the present invention, the dispersibility and dispersion stability of the color material can be improved by combining the color material containing at least one selected from the group consisting of dyes and dye salt-forming compounds and the above-mentioned dispersant of the present invention.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 再者，作為標準，若相對於10 g之溶劑(或混合溶劑)，染料之溶解量為10 mg以下，則可判定該染料能夠分散於該溶劑(或混合溶劑)中。As the above-mentioned dye, it can be suitably selected from previously known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, and

Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. Furthermore, as a standard, if the dissolved amount of the dye is 10 mg or less relative to 10 g of the solvent (or mixed solvent), it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

Among them, the color material contains diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salts of these dyes In the case of at least one of the group consisting of the compound, the use of the above-mentioned dispersant has a high effect of suppressing the sublimation or precipitation of the color material, and can form a high-brightness colored layer, which is preferable in this respect. Furthermore, as the above-mentioned color material, it is preferable to contain at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes. .

As the diketopyrrolopyrrole pigments, for example, CI Pigment Red 254, 255, 264, 272, 291 and the diketopyrrolopyrrole pigments represented by the following general formula (i) may be mentioned. Among them, the diketopyrrolopyrrole pigments are preferably selected from CI Pigment Reds 254, 272, 291 and the following general formula (i) where R ²¹ and R ²² are each 4-bromophenyl diketopyrrolopyrrole pigments.

(通式(i)中，R⁵¹ 及R⁵² 分別獨立地為4-氯苯基或4-溴苯基)[化15]

(In the general formula (i), R ⁵¹ and R ⁵² are each independently 4-chlorophenyl or 4-bromophenyl)

As the quinophthalone pigment, for example, C.I. Pigment Yellow 138 may, for example, be mentioned. Examples of copper phthalocyanine pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, CI Pigment Green 7, 36, etc. Preferably, it is CI Pigment Blue 15:6. As a zinc phthalocyanine pigment, C.I. Pigment Green 58, 59 etc. are mentioned, for example. As the quinophthalone dye, for example, C.I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. Solvent Yellow 114, 157, etc., and among them, C.I. Disperse Yellow 54 is preferred.

The average primary particle size of the color material used in the present invention is not particularly limited, as long as it can present the desired color when the coloring layer of the color filter is made, and it depends on the type of color material used. Different, preferably in the range of 10-100 nm, more preferably 15-60 nm. By making the average primary particle diameter of the color material within the above-mentioned range, a display device equipped with a color filter manufactured using the photosensitive colored resin composition of the present invention can be of high contrast and high quality.

In addition, the average dispersed particle diameter of the color material in the photosensitive colored resin composition differs depending on the type of color material used, and is preferably in the range of 10-100 nm, more preferably in the range of 15-60 nm Inside. The average dispersed particle diameter of the color material in the photosensitive colored resin composition is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. When the particle size is measured by a laser light scattering particle size distribution meter, the photosensitive color resin composition can be appropriately diluted (for example, 1000 times, etc.) to the particle size by laser light scattering with the solvent used in the photosensitive color resin composition The concentration that can be measured by the distribution meter is measured using a laser light scattering particle size distribution meter (for example, the Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.) by dynamic light scattering at 23°C. The average distribution particle size here is the volume average particle size.

The color material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt milling method. In addition, commercially available color materials can be refined and used.

In the photosensitive colored resin composition of the present invention, the content of the color material is not particularly limited. Regarding the content of the color material, in terms of dispersibility and dispersion stability, it is preferably 3% by mass to 65% by mass, more preferably 4% by mass relative to the total solid content of the photosensitive colored resin composition. %～60% by mass ratio. If it is more than the above lower limit, the coloring layer when the photosensitive colored resin composition is coated with a specific film thickness (usually 1.0 μm to 5.0 μm) has a sufficient color density. Moreover, if it is below the said upper limit, the coloring layer which is excellent in storage stability, and has sufficient hardness or adhesion to a substrate can be obtained. In particular, when forming a colored layer with a high color material concentration, the total content of the color material is preferably 15% by mass to 65% by mass relative to the total solid content of the photosensitive colored resin composition , It is better to mix at a ratio of 25% to 60% by mass.

＜Alkali-soluble resin＞ The alkali-soluble resin in the present invention has an acidic group and can be appropriately selected and used from those that function as a binder resin and are soluble in the alkaline developer used for pattern formation. In the present invention, the alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard.

As the alkali-soluble resin, a previously known alkali-soluble resin can be appropriately selected and used. For example, the alkali-soluble resin described in International Publication No. 2016/104493 can be appropriately selected and used. The preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxyl group. Specifically, it can be exemplified by acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups ; Epoxy (meth)acrylate resins with carboxyl groups, etc., acrylic resins such as acrylic copolymers with carboxyl groups and styrene-acrylic copolymers with carboxyl groups are suitably used. Particularly preferred among these are those having a carboxyl group in the side chain, and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. The reason is that by containing the photopolymerizable functional group, the film strength of the formed cured film is improved. In addition, acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more types.

The alkali-soluble resin used in the photosensitive colored resin composition may be used singly or in combination of two or more kinds. The content is not particularly limited, and is relative to the total solid content of the photosensitive colored resin composition The alkali-soluble resin is preferably 5% by mass to 60% by mass, and more preferably in the range of 10% by mass to 40% by mass. If the content of the alkali-soluble resin is more than the above lower limit value, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is less than the above upper limit value, film roughness or pattern defects during development can be suppressed.

＜Photopolymerizable compound＞ The photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, as long as it can be polymerized by the above-mentioned photoinitiator. Generally, a compound having two or more ethylenically unsaturated double bonds is suitably used. Particularly preferred is a multifunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups. As such a polyfunctional (meth)acrylate, what is necessary is just to select suitably from conventionally well-known ones, and use. As a specific example, for example, the one described in JP 2013-029832 A, etc. may be mentioned.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional (meth)acrylate preferably has three (trifunctional) or more polymerizable double The bond is preferably poly(meth)acrylates of trivalent or higher polyols or dicarboxylic acid-modified products thereof, specifically, trimethylolpropane tri(meth)acrylic acid is preferred Esters, pentaerythritol tri(meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Meth) acrylate, succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited. The photopolymerizable compound is preferably 5% to 60% by mass relative to the total solid content of the photosensitive colored resin composition. %, more preferably in the range of 10% by mass to 40% by mass. If the content of the photopolymerizable compound is more than the above lower limit, the photocuring can be carried out sufficiently, the exposed part can be prevented from eluting during development, the line width shift can be suppressed, and the solvent resistance is good. In addition, if the content of the photopolymerizable compound is When it is below the above upper limit value, the alkali developability is sufficient. Regarding the ratio of the content of the photopolymerizable compound used in the photosensitive colored resin composition to the content of the photoinitiator, based on the suppression of line width shift, the solvent resistance is improved, and the effect of suppressing development residues is improved. From the viewpoint of the cross-sectional shape of the hole, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 40 parts by mass relative to 100 parts by mass of the photopolymerizable compound. Parts or less, more preferably 30 parts by mass or less.

＜Solvent＞ The solvent used in the present invention is not particularly limited, as long as it is an organic solvent that does not react with each component in the photosensitive colored resin composition and can dissolve or disperse these. The solvent can be used alone or in combination of two or more kinds. Specific examples of solvents include, for example, alcoholic solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxyethanol, etc. Carbitol solvents such as oxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate Esters, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexyl acetate and other ester solvents; acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketone solvents; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-acetate Glycol ether acetate solvents such as butyl ester, 3-methoxybutyl acetate, and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol acetate solvents such as carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethyl Glycol ether solvents such as glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether ; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other aprotic amide solvents; γ-butyrolactone and other lactone-based solvents; tetrahydrofuran Cyclic ether solvents such as benzene, toluene, xylene, naphthalene and other unsaturated hydrocarbon solvents; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; aromatic hydrocarbons such as toluene and xylene Class and other organic solvents. Among these solvents, in terms of solubility of other components, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are suitably used. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol in terms of solubility of other components and coating suitability. BCA, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate More than species.

In the photosensitive colored resin composition of the present invention, the content of the solvent may be appropriately set within the range where the colored layer can be formed with high accuracy. With respect to the total amount of the photosensitive colored resin composition containing the solvent, it is generally preferably in the range of 55% by mass to 95% by mass, and more preferably in the range of 65% by mass to 88% by mass. When the content of the above-mentioned solvent is within the above-mentioned range, the coatability can be excellent.

＜Other ingredients＞ In the photosensitive colored resin composition of this invention, various additives may be contained as needed. Examples of additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters. As a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.

From the viewpoint of suppressing the amount of line width shift, the photosensitive colored resin composition of the present invention preferably further contains an antioxidant. The photosensitive colored resin composition of the present invention contains antioxidants in combination with the compound represented by the above general formula (A), does not impair the curability when forming a cured film, and can control excessive radical chain reactions, thereby forming fine lines When patterning, the linearity is further improved, or the ability to form fine line patterns according to the design of the mask line width is improved. In addition, heat resistance can be improved, and the decrease in brightness after exposure and post-baking can be suppressed, so the brightness can be improved. The antioxidant used in the present invention is not particularly limited, as long as it is appropriately selected from previously known ones. As specific examples of antioxidants, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc., the thin line pattern is formed according to the design of the mask line width From the aspect of improving the ability and the aspect of heat resistance, it is preferable to use a hindered phenol-based antioxidant. It can also be a potential antioxidant described in International Publication No. 2014/021023.

As a hindered phenol antioxidant, for example, pentaerythritol tetrakis[3-(3,5 di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX 1010, BASF Corporation) Manufacture), 1,3,5-tris(3,5 di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-tris( 4-hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methyl Phenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol tetra[3-(3,5 di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX 1010, manufactured by BASF Corporation).

Regarding the compounding amount of the antioxidant, the antioxidant is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 5.0 parts by mass relative to 100 parts by mass of all solid components in the colored resin composition. If it is more than the above lower limit, the ability to form a thin line pattern according to the design of the mask line width is improved, and the heat resistance is excellent. On the other hand, if it is not more than the above upper limit, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.

In addition, with regard to the compounding amount of the antioxidant, the antioxidant is preferably 1 part by mass to 250 parts by mass relative to 100 parts by mass of the total amount of the oxime ester-based photoinitiator containing the compound represented by the general formula (A) , More preferably 3 parts by mass to 80 parts by mass, and still more preferably 5 parts by mass to 45 parts by mass. If it is in the above-mentioned range, the effect of the above-mentioned combination is excellent.

Also, as the silane coupling agent, for example, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.), etc. Among them, in terms of the adhesiveness of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacryl group and an acrylic group are preferable.

Regarding the content of the silane coupling agent, relative to 100 parts by mass of all solid components in the photosensitive colored resin composition, the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass the following. If it is more than the said lower limit and less than the said upper limit, the board|substrate adhesiveness will be excellent.

<Method for manufacturing photosensitive colored resin composition> From the viewpoint of enhancing the contrast, the method for producing the photosensitive colored resin composition of the present invention is preferably a method containing a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and a visual Various additional components are required, and the color material can be uniformly dispersed in the solvent by the dispersant. The photosensitive colored resin composition of the present invention can be prepared by mixing using a known mixing method. As a preparation method of the resin composition, for example, the following methods can be exemplified: (1) First, a color material and a dispersant are added to a solvent to prepare a color material dispersion, and an alkali-soluble resin and photopolymerization are mixed in the dispersion. (2) Add color material, dispersant, alkali-soluble resin, photopolymerizable compound, photoinitiator and various additives as needed in the solvent at the same time (3) Add dispersant, alkali-soluble resin, photopolymerizable compound, photoinitiator and various additional components as needed in the solvent, after mixing, add color material and disperse it; ( 4) Add color material, dispersant, and alkali-soluble resin to the solvent to prepare a color material dispersion, and then add alkali-soluble resin, solvent, photopolymerizable compound, photoinitiator, and various as needed to the dispersion. Add ingredients and mix. Among these methods, the above-mentioned methods (1) and (4) are preferred based on the viewpoint that the color material can be effectively prevented from agglomerating and can be uniformly dispersed.

The method for preparing the color material dispersion can be appropriately selected and used from previously known dispersion methods. For example, the following methods can be exemplified: (1) Preliminarily mix the dispersant in a solvent, stir to prepare a dispersant solution, and then mix the organic acid compound as necessary to make the amine group of the dispersant and the organic acid compound form a salt, Mix it with the color material and other ingredients as needed, and use a known mixer or disperser to disperse it; (2) Mix the dispersant in a solvent, stir to prepare a dispersant solution, and then mix the color material and the The organic acid compound that needs to be used, and then mix other ingredients as needed, use a known mixer or disperser to disperse them; (3) Mix the dispersant in the solvent, stir, adjust the dispersant solution, and then mix the color materials And other ingredients used as needed, use a known mixer or disperser to make a dispersion, and then add organic acid compounds as needed.

Examples of dispersing machines used for dispersing treatment include: roller mills such as two-roll mills and three-roll mills; ball mills such as ball mills and vibrating ball mills; paint conditioners, continuous disc bead mills, and continuous ring beads Bead mills such as mills. Regarding the preferred dispersion conditions of the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

＜Use＞ The photosensitive colored resin composition of the present invention suppresses line width deviation and has good solvent resistance under low-temperature heat treatment. Therefore, it is suitable for color filter applications. Among them, it is particularly suitable for forming organic EL elements, etc. The use of forming color filters directly on the substrates of components with lower heat resistance, etc.

III. Color filter The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the photosensitive coloring resin composition of the present invention.

The color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light-shielding portion 2 and a coloring layer 3.

＜Colored layer＞ At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition of the present invention. The colored layer is usually formed in the opening of the light-shielding part on the following substrate, and is usually composed of a colored pattern of more than three colors. In addition, the arrangement of the colored layers is not particularly limited. For example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type can be used. In addition, the width and area of the colored layer can be arbitrarily set. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive colored resin composition, etc., and is generally preferably in the range of 1 to 5 μm.

This colored layer can be formed by the following method, for example. First, use spray coating method, dip coating method, bar coating method, roll coating method, spin coating method, die nozzle coating method and other coating methods to combine the photosensitive colored resin of the present invention. The material was applied on the following substrates to form a wet coating film. Among them, the spin coating method and the die nozzle coating method can be preferably used. Then, the wet coating film is dried using a hot plate, an oven, etc., and then exposed through a mask of a specific pattern, and an alkali-soluble resin, a polyfunctional monomer, etc. are subjected to photopolymerization to form a cured coating film. As the light source used for exposure, for example, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, etc., such as ultraviolet rays, electron beams, and the like can be cited. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film. Furthermore, after exposure, heat treatment may also be performed to promote the polymerization reaction. The heating conditions are appropriately selected according to the blending ratio of the components in the photosensitive colored resin composition used, the thickness of the coating film, and the like.

Next, a developing solution is used to perform a development process to dissolve and remove the unexposed part, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. In the alkaline solution, an appropriate amount of surfactants, etc. can also be added. In addition, a general method can be used for the development method. After the development process, the developer is usually washed, and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. Furthermore, after the development treatment, heat treatment may be performed to fully harden the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

＜Shading part＞ The light-shielding part in the color filter of the present invention is formed in a pattern on the following substrate, and can be the same as that used as the light-shielding part in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and for example, shapes such as a stripe shape and a matrix shape may be mentioned. The light-shielding part may be a metal thin film such as chromium formed by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding part may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin adhesive. In the case of a resin layer containing light-shielding particles, there are the following methods: a method of patterning by development using a photosensitive resist; a method of patterning using inkjet ink containing light-shielding particles; Resist thermal transfer method, etc.

The film thickness of the light-shielding part is set to about 0.2-0.4 μm in the case of a metal thin film, and set to about 0.5-2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

＜Substrate＞ As the substrate, the following transparent substrates can be used; silicon substrates; and those having aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the transparent substrate or silicon substrate. On these substrates, other color filter layers, resin layers, TFTs (thin-film transistors) and other transistors, circuits, etc. can be formed. The transparent substrate in the color filter of the present invention is not particularly limited, as long as it is a transparent substrate for visible light, and a transparent substrate used for general color filters can be used. Specifically, examples include: transparent rigid materials that are not flexible, such as quartz glass, alkali-free glass, and synthetic quartz plates; or transparent resin films, optical resin plates, flexible glass, and other flexible transparent materials. Flexible material. The thickness of the transparent substrate is not particularly limited. According to the use of the color filter of the present invention, for example, a transparent substrate of about 100 μm to 1 mm can be used. Furthermore, in addition to the above-mentioned substrate, light-shielding portion, and coloring layer, the color filter of the present invention may also be formed with an overcoat layer or a transparent electrode layer, and further formed with an alignment film or columnar spacers.

IV. Display device The display device of the present invention is characterized by having the above-mentioned color filter of the present invention. In the present invention, the structure of the display device is not particularly limited, and can be appropriately selected from previously known display devices. For example, a liquid crystal display device or an organic light-emitting display device can be mentioned.

[Liquid crystal display device] As the liquid crystal display device of the present invention, for example, the following liquid crystal display device can be exemplified, which has: the color filter of the present invention, a counter substrate, and a liquid crystal formed between the color filter and the counter substrate Floor. The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has: a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a color filter 10 and a counter substrate 20 formed between the color filter 10 and the counter substrate 20. Liquid crystal layer 30. In addition, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and a structure known to liquid crystal display devices generally using color filters can be adopted.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. As such a driving method, for example, TN (Twisted Nematic) method, IPS (in-plane switching, lateral electric field effect) method, OCB (optically compensated bend) method, and MVA (Multi -Domain Vertical Alignment, multi-domain vertical alignment) method, etc. In the present invention, any of these methods can be suitably used. In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention, and the like.

As a method of forming the liquid crystal layer, a method generally used as a method of producing a liquid crystal cell can be used, for example, a vacuum injection method or a liquid crystal dropping method can be mentioned. After the liquid crystal layer is formed by the above method, the liquid crystal cell is slowly cooled to normal temperature, thereby aligning the enclosed liquid crystal.

[Organic Light Emitting Display Device] As the organic light-emitting display device of the present invention, for example, an organic light-emitting display device having the above-mentioned color filter and organic light-emitting body of the present invention can be exemplified. The organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. As shown in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. There may be an organic protective layer 50 or an inorganic oxide film 60 between the color filter 10 and the organic light-emitting body 80.

As a layering method of the organic light-emitting body 80, for example, the following method can be exemplified: a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, and an electron injection layer 75 are sequentially formed on the upper surface of the color filter. And the method of the cathode 76; or the method of attaching the organic light-emitting body 80 formed on other substrates to the inorganic oxide film 60, etc. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75 and the cathode 76 in the organic light-emitting body 80, and other configurations can be appropriately used known ones. The organic light-emitting display device 100 manufactured in this manner can be applied to, for example, an organic EL display in a passive driving mode, and can also be applied to an organic EL display in an active driving mode. Furthermore, the organic light-emitting display device of the present invention is not limited to the structure shown in FIG. 3, and a structure known to organic light-emitting display devices generally using color filters can be adopted. [Example]

Hereinafter, examples will be shown to specifically describe the present invention. The present invention is not limited by these descriptions. The mass average molecular weight (Mw) of the copolymer before the salt is formed is determined by GPC (gel permeation chromatography) in accordance with the measurement method described in the specification of the present invention as a standard polystyrene conversion value.

(Synthesis example 1: Synthesis of block copolymer 1) Add 250 parts by mass of THF and 0.75 parts by mass of lithium chloride to a 500 mL round-bottomed four-neck separable flask equipped with a cooling tube, addition funnel, nitrogen gas inlet, mechanical stirrer, and digital thermometer, and fully perform nitrogen substitution. After cooling the reaction flask to -60°C, 6.1 parts by mass of butyllithium (15% by mass hexane solution), 1.4 parts by mass of diisopropylamine, and 1.2 parts by mass of methyl isobutyrate were injected using a syringe. Using an addition funnel, 9 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.4 parts by mass of n-butyl methacrylate (BMA), and methacrylic acid, which are monomers for the B block, were added dropwise over 60 minutes 7.5 parts by mass of benzyl ester (BzMA) and 47.5 parts by mass of methyl methacrylate (MMA). After 30 minutes, 22.6 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. It was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer 1 containing the structural unit represented by the above-mentioned general formula (I). (Amine value 95 mgKOH/g, acid value 0 mgKOH/g) The weight average molecular weight Mw is 7600.

(Synthesis Example 2: Synthesis of Block Copolymer 2) Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round-bottomed four-neck separable flask equipped with a cooling tube, addition funnel, nitrogen gas inlet, mechanical stirrer, and digital thermometer, and fully perform nitrogen substitution. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Using the addition funnel, dropwise add 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) and 2-(trimethylsilyloxy)ethyl methacrylate over 60 minutes as a monomer for the B block (TMSMA) 29.1 parts by mass, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass, n-butyl methacrylate (BMA) 13.7 parts by mass, benzyl methacrylate (BzMA) 9.5 parts by mass, methyl 17.5 parts by mass of methyl acrylate (MMA). After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solution of solid content. Add 32.5 parts by mass of water, heat up to 100°C, react for 7 hours, deprotect the structural unit derived from EEMA to obtain the structural unit derived from methacrylic acid (MAA), and deprotect the structural unit derived from TMSMA. A structural unit derived from 2-hydroxyethyl methacrylate (HEMA) is obtained. The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer 2 (amine value 95) containing the structural unit represented by the above general formula (I) mgKOH/g, acid value 8 mgKOH/g, Tg 38℃). The weight average molecular weight Mw is 7730.

(Synthesis example 3: Synthesis of salt type block copolymer 3) The block copolymer 1 was synthesized in the same manner as in Synthesis Example 1. 50 parts by mass of the obtained block copolymer was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and reacted at 90° C. for 12 hours to obtain a PGMEA solution of salt type block copolymer 3 (solid content 35%).

(Synthesis example 4: Synthesis of salt type block copolymer 4) The block copolymer 2 was synthesized in the same manner as in Synthesis Example 2. 50 parts by mass of the obtained block copolymer 2 was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and reacted at 90° C. for 12 hours to obtain a PGMEA solution of salt type block copolymer 4 (solid content 35%).

(Synthesis Example 5: Synthesis of graft copolymer 5) (1) Manufacture of macromonomer A in a reactor equipped with a cooling pipe, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer to add propylene glycol methyl ether Acetate (PGMEA) 70.0 parts by mass was heated to a temperature of 90°C while stirring under a nitrogen stream. The monomer with a PEG chain (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W) of the structural unit represented by the general formula (III) will be derived by dropping for 1.5 hours. R ⁴ in the general formula (III) is CH ₃ , A ³ is COO, R ⁵ is ethylene, R ⁶ is CH ₃ , m=22) 2.0 parts by mass, 98.0 parts by mass of methyl methacrylate (MMA), 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, α A mixed solution of 1.0 parts by mass of α'-azobisisobutyronitrile (AIBN) was further reacted for 3 hours. Next, the nitrogen flow was stopped, the reaction solution was cooled to 80°C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko Co., Ltd.), 0.125 g of dioctyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and PGMEA were added 30 parts by mass, stirred for 3 hours, thereby obtaining a 50% solution of the macromonomer A. The obtained macromonomer A was confirmed by GPC (Gel Permeation Chromatography) under the conditions of N-methylpyrrolidone/polystyrene standard added with 0.01 mol/L lithium bromide, the result was The weight average molecular weight (Mw) is 4000, and the molecular weight distribution (Mw/Mn) is 1.6.

(2) Synthesis of graft copolymer 5 Add 63.1 parts by mass of PGMEA to a reactor equipped with a cooling pipe, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, the temperature is heated to 85°C. 141 parts by mass of the above-mentioned macromonomer A solution (70.5 parts by mass of effective solid content), 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), and n-dodecyl were added dropwise over 1.5 hours A mixed solution of 1.24 parts by mass of mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN was heated and stirred for 3 hours, and a mixture of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes, and then matured at the same temperature. Hours, thereby obtaining a 35.0% by mass solution of graft copolymer A. GPC measurement of the obtained graft copolymer 5 showed that the weight average molecular weight (Mw) was 10,500. Furthermore, the amine value is 105 mgKOH/g.

(Synthesis Example 6: Synthesis of graft copolymer 6) (1) Manufacture of macromonomer B. Add propylene glycol methyl ether to a reactor equipped with a cooling pipe, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer Acetate (PGMEA) 70.0 parts by mass was heated to a temperature of 90°C while stirring under a nitrogen stream. A monomer with a PEG chain (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W), which derives the structural unit represented by the general formula (III), is added dropwise over 1.5 hours. R ⁴ in the general formula (III) is CH ₃ , A ³ is COO, R ⁵ is ethylene, R ⁶ is CH ₃ , m=22) 6.0 parts by mass, triethylene glycol monoethyl ether methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., m=3) 69.0 parts by mass, A mixed solution of 25.0 parts by mass of methyl acrylate (MMA), 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α,α'-azobisisobutyronitrile (AIBN) was further reacted for 3 hours. Next, the nitrogen flow was stopped, the reaction solution was cooled to 80°C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko Co., Ltd.), 0.125 g of dioctyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and PGMEA were added 30 parts by mass, stirred for 3 hours, thereby obtaining a 50% solution of the macromonomer B. The obtained macromonomer B was confirmed by GPC (Gel Permeation Chromatography) under the conditions of N-methylpyrrolidone/polystyrene standard added with 0.01 mol/L lithium bromide, the result The weight average molecular weight (Mw) is 5800, and the molecular weight distribution (Mw/Mn) is 1.6.

(2) Synthesis of graft copolymer 6 Add 63.1 parts by mass of PGMEA to a reactor equipped with a cooling pipe, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, the temperature is heated to 85°C. 141 parts by mass of the above-mentioned macromonomer A solution (70.5 parts by mass of effective solid content), 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), and n-dodecyl were added dropwise over 1.5 hours A mixed solution of 1.24 parts by mass of mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN was heated and stirred for 3 hours, and a mixture of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes, and then matured at the same temperature In 1 hour, a 35.0% by mass solution of graft copolymer 6 was thereby obtained. GPC measurement of the obtained graft copolymer 6 showed that the weight average molecular weight (Mw) was 10,000. Furthermore, the amine value is 105 mgKOH/g.

(Synthesis Example 7: Synthesis of graft copolymer 7) (1) Manufacturing of giant cell C Add 30.0 parts by mass of PGMEA to a reactor equipped with a cooling pipe, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, the temperature is heated to 90°C. 25.0 parts by mass of MMA, caprolactone-modified hydroxyethyl methacrylate (trade name: PLACCEL FM5, manufactured by Daicel Co., Ltd., caprolactone chain repeat number n=5) (PCL-FM5) 75.0 A mixed solution of 7.0 parts by mass of mercaptopropionic acid, and 1.0 parts by mass of AIBN was further reacted for 3 hours. After cooling, the reaction solution was diluted with 200 parts by mass of tetrahydrofuran (THF), and reprecipitated in 3000 parts by mass of hexane, thereby obtaining 106.0 parts by mass of white powder. Next, add 50.0 parts by mass of PGMEA, 3.7 parts by mass of glycidyl methacrylate (GMA), 0.15 parts by mass of N,N-dimethyldodecylamine, and p-methoxyphenol to 50.0 parts by mass of the white powder. 0.1 part by mass, while blowing air, stir at 110°C for 24 hours. After cooling, the reaction solution was reprecipitated in 3000 parts by mass of hexane, thereby obtaining 52.0 parts by mass of macromonomer C. The weight average molecular weight (Mw) of the obtained macromonomer C was 6,300, and the molecular weight distribution (Mw/Mn) was 1.6.

(2) Synthesis of graft copolymer 7 Add 63.1 parts by mass of PGMEA to a reactor equipped with a cooling pipe, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, the temperature is heated to 85°C. 141 parts by mass (effective solid content 70.5 parts by mass) of the above-mentioned macromonomer C dissolved in PGMEA and 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA) were added dropwise over 1.5 hours A mixed solution of 1.24 parts by mass of n-dodecyl mercaptan, 49.4 parts by mass of PGMEA, and 1.0 parts by mass of AIBN. After heating and stirring for 3 hours, a mixture of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes , And then matured at the same temperature for 1 hour, thereby obtaining a 35.0% by mass solution of graft copolymer 7. GPC measurement of the obtained graft copolymer 7 showed that the weight average molecular weight (Mw) was 13,000. Furthermore, the amine value is 105 mgKOH/g.

(Synthesis Example 8: Synthesis of Salt Type Graft Copolymer 8) The graft copolymer 5 was synthesized in the same manner as in Synthesis Example 5. The obtained graft copolymer 5, 50 parts by mass was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and reacted at 90° C. for 12 hours to obtain a PGMEA solution of salt type block copolymer 8 (solid content 35%).

(Synthesis Example 9: Synthesis of Salt Type Graft Copolymer 9) The graft copolymer 6 was synthesized in the same manner as in Synthesis Example 6. 50 parts by mass of the obtained graft copolymer 6 was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and reacted at 90° C. for 12 hours to obtain a PGMEA solution of salt type block copolymer 9 (solid content 35%).

(Synthesis Example 10: Synthesis of Salt Type Graft Copolymer 10) The graft copolymer 7 was synthesized in the same manner as in Synthesis Example 7. The obtained graft copolymer 750 parts by mass was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and reacted at 90° C. for 12 hours to obtain a PGMEA solution of salt type block copolymer 10 (solid content 35%).

(Preparation Example 1: Preparation of Alkali-soluble Resin A) 300 parts by mass of PGMEA was added to the polymerization tank, and after the temperature was raised to 100°C in a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, and methyl were continuously added dropwise over 1.5 hours. 36 parts by mass of acrylic acid (MAA), 6 parts by mass of PERBUTYLO (manufactured by NOF Corporation), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan). Thereafter, the reaction was continued at 100°C, and 2 hours after the completion of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor was added to terminate the polymerization. Next, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy-containing compound was added. After the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added, and the mixture was added at 110°C. The reaction was carried out for 15 hours to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass). Furthermore, regarding the above-mentioned method for measuring the weight average molecular weight, polystyrene is used as a standard substance, and THF is used as a eluent, and the weight average molecular weight is measured by Shodex GPC System-21H (Shodex GPC System-21H). In addition, the acid value measurement method is based on JIS K 0070.

(Production Example 1: Production of Color Material Dispersion Liquid R(1)) In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) of Preparation Example 1, and the PGMEA solution of block copolymer 1 of Synthesis Example 1 (solid content) 35 mass %) 9.2 parts by mass and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes. To this was added 9.6 parts by mass of CI Pigment Red 177 (PR177), 2.4 parts by mass of CI Pigment Red 254 (PR254), 100 parts by mass of zirconia beads with a particle size of 2.0 mm, using a paint shaker (manufactured by Asada Iron Works) It was shaken for 1 hour for pre-crushing, and then changed to 200 parts of zirconia beads with a particle size of 0.1 mm, and dispersed by a paint shaker for 4 hours to perform main crushing to obtain color material dispersion R(1). Furthermore, the block copolymer 1 becomes a salt-type block copolymer 1 by forming a salt with phenylphosphonic acid.

(Production Example 2: Production of Color Material Dispersion Liquid R(2)) Change the block copolymer 1 of synthesis example 1 in the production of the color material dispersion liquid R(1) of manufacture example 1 to the block copolymer 2 of synthesis example 2. In addition, use the same color material as the color material of manufacture example 1. The color material dispersion liquid R(2) is obtained in the same manner as the dispersion liquid R(1). Furthermore, in the color material dispersion liquid R(2), the block copolymer 2 forms a salt with phenylphosphonic acid, and becomes a salt type block copolymer 2.

(Production Example 3: Production of Color Material Dispersion Liquid R(3)) Change the block copolymer 1 of synthesis example 1 in the production of the color material dispersion liquid R(1) of manufacture example 1 to the graft copolymer 5 of synthesis example 5. In addition, use the same color material as the color material of manufacture example 1. The color material dispersion liquid R(3) is obtained in the same manner as the dispersion liquid R(1). Furthermore, in the color material dispersion liquid R(3), the graft copolymer 5 forms a salt with phenylphosphonic acid, and becomes the salt type graft copolymer 5.

(Production Example 4: Production of Color Material Dispersion Liquid R(4)) Change the block copolymer 1 of Synthesis Example 1 in the production of Color Material Dispersion Liquid R(1) of Preparation Example 1 to the graft copolymer 6 of Synthesis Example 6. Otherwise, the same as the color material of Preparation Example 1 The color material dispersion liquid R(4) is obtained in the same manner as the dispersion liquid R(1). Furthermore, in the color material dispersion liquid R(4), the graft copolymer 6 forms a salt with phenylphosphonic acid, and becomes the salt-type graft copolymer 6.

(Production Example 5: Production of Color Material Dispersion Liquid R(5)) Change the block copolymer 1 of synthesis example 1 in the production of the color material dispersion liquid R(1) of manufacture example 1 to the graft copolymer 7 of synthesis example 7. In addition, use the same color material as the color material of manufacture example 1. The color material dispersion liquid R(5) is obtained in the same manner as the dispersion liquid R(1). Furthermore, in the color material dispersion liquid R(5), the graft copolymer 7 forms a salt with phenylphosphonic acid, and becomes the salt type graft copolymer 7.

(Example 1: Production of photosensitive colored resin composition R-1) Add 35.7 parts by mass of the color material dispersion liquid R(1) obtained in Production Example 1, 3.52 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) obtained in Production Example 1, and a multifunctional monomer (commercial product) Name ARONIX M-305, manufactured by Toagosei Co., Ltd.) 5.64 parts by mass, 0.45 parts by mass of the oxime ester compound represented by the above chemical formula (A-1) (relative to the total of alkali-soluble resin, polyfunctional monomer and initiator) (6 mass %), 0.03 parts by mass of a fluorine-based surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), and 54.66 parts by mass of PGMEA, to obtain a photosensitive colored resin composition R-1.

(Examples 2-8: Production of photosensitive colored resin composition R-2 to R-8) As shown in Table 1, except for changing the type and amount of the initiator in Example 1, the photosensitive colored resin composition R-2 to R was obtained in the same manner as the photosensitive colored resin composition R-1. -8.

(Examples 9-12: Production of photosensitive colored resin composition R-9 to R-12) As shown in Table 1, the color material dispersion liquid R(1) in Example 1 was changed to color material dispersion liquid R(2), R(3), R(4) or R(5). Otherwise, In the same manner as the photosensitive colored resin composition R-1, photosensitive colored resin compositions R-9 to R-12 were obtained.

(Example 13: Production of photosensitive colored resin composition R-13) Add 35.7 parts by mass of the color material dispersion R(1) obtained in Production Example 1, 3.49 parts by mass of the alkali-soluble resin A solution obtained in Production Example 1, and a multifunctional monomer (trade name ARONIX M-305, East Asia Synthetic Co., Ltd. production) 5.58 parts by mass, 0.45 parts by mass of the oxime ester compound represented by the chemical formula (A-1), fluorine-based surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.) 0.03 parts by mass, antioxidant 0.07 parts by mass of Irganox 1010 (1.0% by mass relative to the total of the alkali-soluble resin, polyfunctional monomer, and initiator) and 54.68 parts by mass of PGMEA to obtain photosensitive colored resin composition R-13.

(Production Example 6: Production of Color Material Dispersion Liquid G(1)) Use CI Pigment Green 58 (PG58) 8.4 parts by mass and CI Pigment Yellow 138 (PY138) 3.6 parts by mass instead of 9.6 parts by mass of CI Pigment Red 177 (PR177) in the manufacture of the color material dispersion R(1) of Manufacturing Example 1, and Except for 2.4 parts by mass of CI Pigment Red 254 (PR254), a color material dispersion G(1) was obtained in the same manner as the color material dispersion R(1) of Production Example 1. In addition, in the color material dispersion liquid G(1), the block copolymer 1 is formed into a salt with phenylphosphonic acid, and becomes the salt type block copolymer 1.

(Production Examples 7-10: Production of Color Material Dispersion Liquids G(2)～G(5)) Change the block copolymer 1 of synthesis example 1 in the production of the color material dispersion liquid G(1) of manufacture example 6 to the block copolymer 2 of synthesis example 2 and the graft copolymer 5 of synthesis example 5, respectively. Except for the graft copolymer 6 of Example 6 or the graft copolymer 7 of Synthesis Example 7, the color material dispersion G(2), G(3), G(4) or G(5). Furthermore, in the color material dispersion liquids G(2) to G(5), the block copolymer 2, graft copolymers 5, 6, and 7 each form a salt with phenylphosphonic acid to form a salt-type block copolymer 2. Salt type graft copolymers 5, 6 and 7.

(Example 14: Production of photosensitive colored resin composition G-1) The color material dispersion liquid R(1) obtained in Production Example 1 in Example 1 was changed to the color material dispersion liquid G(1) obtained in Production Example 6, and otherwise combined with a photosensitive color resin The photosensitive colored resin composition G-1 was obtained in the same manner as the substance R-1.

(Examples 15-21: Production of photosensitive colored resin compositions G-2 to G-8) As shown in Table 2, except that the type and amount of the initiator in Example 14 were changed, photosensitive colored resin compositions G-2 to G were obtained in the same manner as photosensitive colored resin composition G-1. -8.

(Examples 22-25: Production of photosensitive colored resin compositions G-9 to G-12) As shown in Table 2, the color material dispersion G(1) in Example 14 was changed to the color material dispersion G(2), G(3), G(4) or G(5). Otherwise, In the same manner as the photosensitive colored resin composition G-1, photosensitive colored resin compositions G-9 to G-12 were obtained.

(Example 26: Production of photosensitive colored resin composition G-13) The color material dispersion liquid R(1) obtained in Production Example 1 in Example 13 was changed to the color material dispersion liquid G(1) obtained in Production Example 6, and otherwise combined with a photosensitive color resin The photosensitive colored resin composition G-13 was obtained in the same manner as the compound R-13.

(Production Example 11: Production of Color Material Dispersion Liquid B(1)) In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) of preparation example 1, and the PGMEA solution (solid form) of salt block copolymer 3 of synthesis example 3 were added. (35% by mass of the substance) 9.2 parts by mass and stirred. Add CI Pigment Blue 15:6 (PB15:6) 9.6 parts by mass, CI Pigment Violet 23 (PV23) 2.4 parts by mass, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm. Co., Ltd.) was shaken for 1 hour and pre-crushed, and then changed to 200 parts of zirconia beads with a particle size of 0.1 mm, and dispersed by a paint shaker for 4 hours to be crushed to obtain color material dispersion B ( 1).

(Production Examples 12-15: Production of Color Material Dispersion Liquids B(2)～B(5)) Change the PGMEA solution of the salt-type block copolymer 3 of Synthesis Example 3 in the production of the color material dispersion B(1) of Preparation Example 11 to the PGMEA solution of the salt-type block copolymer 4 of Synthesis Example 4, synthesis The PGMEA solution of salt type graft copolymer 8 of Example 8, the PGMEA solution of salt type graft copolymer 9 of Synthesis Example 9 or the PGMEA solution of salt type graft copolymer 10 of Synthesis Example 10, in addition to In the same manner as the color material dispersion liquid B(1) of Production Example 11, the color material dispersion liquid B(2), B(3), B(4) or B(5) was obtained.

(Example 27: Production of photosensitive colored resin composition B-1) The color material dispersion liquid R(1) obtained in Production Example 1 in Example 1 was changed to the color material dispersion liquid B(1) obtained in Production Example 11, and otherwise combined with a photosensitive color resin The photosensitive colored resin composition B-1 was obtained in the same manner as the substance R-1.

(Examples 28 to 34: Production of photosensitive colored resin compositions B-2 to B-8) As shown in Table 3, except for changing the type and amount of the initiator in Example 27, photosensitive colored resin compositions B-2 to B were obtained in the same manner as photosensitive colored resin composition B-1. -8.

(Examples 35 to 38: Production of photosensitive colored resin compositions B-9 to B-12) As shown in Table 3, the color material dispersion B(1) in Example 27 was changed to color material dispersion B(2), B(3), B(4), or B(5). Otherwise, In the same manner as the photosensitive colored resin composition B-1, photosensitive colored resin compositions B-9 to B-12 were obtained.

(Example 39: Production of photosensitive colored resin composition B-13) The color material dispersion liquid R(1) obtained in Production Example 1 in Example 1 was changed to the color material dispersion liquid B(1) obtained in Production Example 11, and otherwise combined with a photosensitive color resin The photosensitive colored resin composition B-13 was obtained in the same manner as the substance R-13.

(Examples 40 to 52: Production of photosensitive colored resin composition R-14 to R-26) As shown in Table 4, the oxime ester compounds represented by the above chemical formula (A-1) in Examples 1 to 13 were respectively changed to the oxime ester compounds represented by the above chemical formula (A-2), and in addition to In the same manner as the photosensitive colored resin compositions R-1 to R-13, photosensitive colored resin compositions R-14 to R-26 were obtained.

(Examples 53 to 65: Production of photosensitive colored resin compositions G-14 to G-26) As shown in Table 5, the oxime ester compounds represented by the above chemical formula (A-1) in Examples 14 to 26 were respectively changed to the oxime ester compounds represented by the above chemical formula (A-2). In the same manner as the photosensitive colored resin compositions G-1 to G-13, photosensitive colored resin compositions G-14 to G-26 were obtained.

(Examples 66 to 78: Production of photosensitive colored resin compositions B-14 to B-26) As shown in Table 6, the oxime ester compounds represented by the above chemical formula (A-1) in Examples 27 to 39 were changed to the oxime ester compounds represented by the above chemical formula (A-2), and in addition to In the same manner as the photosensitive colored resin compositions B-1 to B-13, photosensitive colored resin compositions B-14 to B-26 were obtained.

(Examples 79 to 84: Production of photosensitive colored resin compositions R-27 to R-32) As shown in Table 7, the oxime ester compounds represented by the above chemical formula (A-1) in Examples 1 and 9 to 13 were respectively changed to the oxime ester compounds represented by the above chemical formula (A-3), except for that, The photosensitive colored resin composition R-27-R-32 was obtained in the same manner as the photosensitive colored resin composition R-1 and R-9 to R-13.

(Examples 85 to 90: Production of photosensitive colored resin composition R-33 to R-38) As shown in Table 7, the oxime ester compounds represented by the above chemical formula (A-1) in Examples 1 and 9 to 13 were respectively changed to the oxime ester compounds represented by the above chemical formula (A-4), except for that, The photosensitive colored resin composition R-33-R-38 was obtained in the same manner as the photosensitive colored resin composition R-1 and R-9 to R-13.

(Comparative Examples 1 to 3: Production of photosensitive colored resin composition CR-1, CG-1 and CB-1) As shown in Table 7, the oxime ester compound represented by the above chemical formula (A-1) in Example 1, Example 14 or Example 27 was changed to an oxime ester-based photoinitiator and ethyl ketone having a carbazole skeleton ,1-[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (trade name Irgacure OXE02, BASF Company manufacture), except for this, the photosensitive colored resin composition CR-1, CG-1, and CB-1 were manufactured in the same manner as in Example 1, Example 14 or Example 27.

(Comparative Production Examples 1 and 2: Production of Color Material Dispersion Liquids CR(1) and CR(2)) As shown in Table 7, the block copolymer 1 of Synthesis Example 1 in the production of Color Material Dispersion Liquid R(1) of Manufacturing Example 1 was changed to Ajisper PB821 (PB821, manufactured by Ajinomoto Fine-Techno Co., Ltd., poly Ester-based dispersant, solid content 30% by mass) or Disperbyk-161 (BYK-161, manufactured by BYK-Chemie, urethane-based dispersant, solid content 30% by mass), based on solid content Use in the same way as block copolymer 1, without adding phenylphosphonic acid, adjust the amount of PGMEA so that the solid content of the dispersion is the same as that of Production Example 1, except for the color material dispersion of Production Example 1. The color material dispersion liquids CR(1) and CR(2) are obtained in the same way as R(1).

(Comparative Production Examples 3 and 4: Production of Color Material Dispersion Liquids CG(1) and CG(2)) As shown in Table 7, the block copolymer 1 of Synthesis Example 1 in the production of Color Material Dispersion Liquid G(1) of Manufacturing Example 6 was changed to Ajisper PB821 (PB821, manufactured by Ajinomoto Fine-Techno Co., Ltd., poly Ester-based dispersant, solid content 30% by mass) or Disperbyk-161 (BYK-161, manufactured by BYK-Chemie, urethane-based dispersant, solid content 30% by mass), based on solid content Used in the same manner as block copolymer 1, without adding phenylphosphonic acid, adjusting the amount of PGMEA so that the solid content of the dispersion is the same as that of Production Example 6, except for the color material dispersion of Production Example 6. The color material dispersion liquids CG(1) and CG(2) are obtained in the same way as G(1).

(Comparative Production Examples 5 and 6: Production of Color Material Dispersion Liquids CB(1) and CB(2)) As shown in Table 7, the PGMEA solution (solid content 35% by mass) of the salt-type block copolymer 3 in the synthesis example 3 in the production of the color material dispersion liquid B(1) of the production example 11 was changed to Ajisper PB821. (PB821, manufactured by Ajinomoto Fine-Techno Co., Ltd., polyester-based dispersant, solid content 30% by mass) or Disperbyk-161 (BYK-161, manufactured by BYK-Chemie, urethane-based dispersant, solid content 30% by mass), using the same solid content as the block copolymer 1. Adjust the amount of PGMEA so that the solid content of the dispersion is the same as in Production Example 11. Except for this, the same as in Production Example Color material dispersions CB(1) and CB(2) were obtained in the same manner as the color material dispersion B(1) of 11.

(Comparative Examples 4 to 5: Production of photosensitive colored resin composition CR-2, CR-3) As shown in Table 7, the color material dispersion liquid R(1) in Example 1 was changed to the color material dispersion liquid CR(1) or CR(2) respectively, except for this, it was manufactured in the same manner as Example 1 Photosensitive colored resin composition CR-2 or CR-3.

(Comparative Examples 6-7: Production of photosensitive colored resin composition CG-2, CG-3) As shown in Table 7, the color material dispersion liquid G(1) in Example 14 was changed to the color material dispersion liquid CG(1) or CG(2), respectively, except that it was produced in the same manner as in Example 14. Photosensitive colored resin composition CG-2 or CG-3.

(Comparative Examples 8-9: Production of photosensitive colored resin composition CB-2 and CB-3) As shown in Table 7, the color material dispersion liquid B(1) in Example 27 was changed to the color material dispersion liquid CB(1) or CB(2), except that it was produced in the same manner as in Example 27 Photosensitive colored resin composition CB-2 or CB-3.

[Evaluation method] Using a spin coater, the photosensitive colored resin composition obtained in each example and each comparative example was applied to a glass substrate so that the thickness of the cured coating film became 3.0 μm (NH TECHNO GLASS Co., Ltd. Made by the company, "NA35") After mounting, use a hot plate to dry at 80°C for 3 minutes to form a coating film on the glass substrate. Using ultra-high pressure mercury lamp, a patterned mask (chromium mask) with a 20 μm×20 μm chromium mask arranged in the center of an independent thin line with an opening size of 90 μm×300 μm, with 40 mJ/cm ² of ultraviolet light By exposing the coating film, a post-exposure coating film is formed on the glass substrate. Then, a 0.05 wt% potassium hydroxide aqueous solution was used as a developer for rotational development, and after being in contact with the developer for 60 seconds, it was rinsed with pure water to perform a development process to obtain a coating film with independent fine line patterns with micropores. Thereafter, post-baking in a dust-free oven at 90°C for 25 minutes, thereby forming a colored layer with independent fine line patterns with micropores. The following evaluation was performed on the obtained colored layer.

＜Evaluation of line width deviation＞ With an optical microscope, the width of the fine line pattern of the colored layer at the portion corresponding to the 90 μm opening width of the chrome mask used during exposure was measured at 5 locations, and the line width was evaluated based on the difference between the average line width and the target line width Offset. (Evaluation criteria for line width deviation) A: Relative to the target line width, the difference is within 1.5 μm B: Relative to the target line width, the difference exceeds 1.5 μm and is within 3.0 μm C: Relative to the target line width, the difference exceeds 3.0 μm and is within 4.0 μm D: Relative to the target line width, the difference exceeds 4.0 μm If the evaluation result is B, the line width deviation amount is good, and if the evaluation result is A, the line width deviation amount is excellent.

＜Evaluation of solvent resistance (PGME resistance)＞ After measuring the film thickness of the coloring layer obtained, it was immersed in propylene glycol monomethyl ether (PGME) for 10 minutes, then air-dried, and the film thickness was measured again. In addition, in the film thickness measurement, a stylus type stepped film thickness gauge "P-15Tencor" (manufactured by Instruments) was used. The film thickness after solvent immersion/film thickness before solvent immersion×100 was calculated as the residual film rate. (Evaluation criteria for solvent resistance) A: The residual film rate after solvent immersion is above 98% B: The residual film rate after solvent immersion is more than 96% and less than 98% C: The residual film rate after solvent immersion is above 94% and less than 96% D: The residual film rate after solvent immersion does not reach 94% If the evaluation result is B, the solvent resistance is good, and if the evaluation result is A, the solvent resistance is excellent.

<Evaluation of the cross-sectional shape of the colored layer with a fine line pattern> The cross-sectional shape of the colored layer in the thickness direction of the individual thin-line pattern-like colored layer was observed with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification 10000 times), and the cross-sectional shape of the colored layer was evaluated based on the following evaluation criteria The inclination angle (θ1) (refer to Figure 5) is evaluated. (Evaluation criteria for the cross-sectional shape of the patterned colored layer) A: The inclination angle (θ1) is 15 degrees or more and less than 70 degrees B: The inclination angle (θ1) is 70 degrees or more and less than 90 degrees C: The inclination angle (θ1) is 90 degrees or more and less than 100 degrees D: The inclination angle (θ1) is 100 degrees or more If the evaluation result is B, the cross-sectional shape of the colored layer is good, and if the evaluation result is A, the cross-sectional shape of the colored layer is excellent.

＜Cross-section shape of micropores＞ Observe the cross-sectional shape in the thickness direction of the colored layer of the above-mentioned micro-hole with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification 10000 times), and determine the inclination angle of the cross-sectional shape of the micro-hole based on the following evaluation criteria (θ2) (refer to Fig. 6) for evaluation. (Evaluation criteria for the cross-sectional shape of micropores) A: The inclination angle (θ2) is 15 degrees or more and less than 70 degrees B: The inclination angle (θ2) is 70 degrees or more and less than 90 degrees C: The inclination angle (θ2) is 90 degrees or more and less than 100 degrees D: The inclination angle (θ2) is 100 degrees or more If the evaluation result is B, the cross-sectional shape of the micropore is good, and if the evaluation result is A, the cross-sectional shape of the micropore is excellent.

＜Residue in the micropores＞ The micropores were observed with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification 5000 times), and the residues in the micropores were evaluated based on the following evaluation criteria. (Evaluation criteria for residue in micropores) A: No residue is observed at all. B: A little residue was observed only at the end of the hole. C: A little residue is observed in the whole hole D: Many residues are observed in the whole hole If the evaluation result is B, the residue in the micropores is good, and if the evaluation result is A, the residue in the micropores is excellent.

＜Evaluation of development residue suppression＞ Using a spin coater, the photosensitive colored resin compositions obtained in the examples and comparative examples were then baked to form a coloring layer with a thickness of 2.0 μm and applied to a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd.) , "NA35"), then use a hot plate to dry at 80°C for 3 minutes to form a colored layer on the glass substrate. The glass plate on which the above-mentioned colored layer was formed was subjected to spray development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then washed with pure water to perform development processing. After visually observing the formation part of the colored layer after development, it was wiped sufficiently with a lens cloth containing ethanol (manufactured by Toray Corporation, trade name Toraysee MK Clean Cloth), and the degree of coloration of the lens cloth was observed visually. (Evaluation Criteria for Suppression of Development Residue) A: No development residue is visually confirmed, and the lens cleaning cloth is not colored at all B: No development residue is visually confirmed, but the lens cleaning cloth is slightly stained C: A little development residue is visually confirmed, and the lens cleaning cloth is confirmed to be colored D: Visually confirm the development residue and the staining of the lens cloth If the evaluation result is B, the development residue suppression effect is good, and if the evaluation result is A, the development residue suppression effect is excellent.

<Evaluation of water spot suppression> Using a spin coater, the photosensitive colored resin composition obtained in the Examples and Comparative Examples was then baked to form a coloring layer with a thickness of 2.0 μm and coated on a glass substrate (NH Manufactured by TECHNO GLASS Co., Ltd., "NA35", thickness 0.7 mm, 100 mm×100 mm), then use a heating plate to dry at 60°C for 3 minutes, use an ultra-high pressure mercury lamp, and irradiate the entire surface without the light shield Ultraviolet rays of 30 mJ/cm ² form a colored layer on the glass substrate. Then, use 0.05 wt% potassium (KOH) as a developer for 60 seconds to spray and develop, and then wash with pure water to carry out the development process. The cleaned substrate is rotated for 10 seconds and centrifuged to remove the water. The contact angle of pure water was measured as follows to evaluate water spots. Regarding the measurement of the contact angle of pure water, a drop of 1.0 μL of pure water was added to the surface of the colored layer just after the water was removed by centrifugation, and the static contact angle after 10 seconds of attachment of the drop was measured according to the θ/2 method. The measurement was performed using the contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. as the measurement device. (Evaluation criteria for water spot suppression) A: The contact angle is 70 degrees or more B: The contact angle is 50 degrees or more and less than 70 degrees C: The contact angle is 30 degrees or more and less than 50 degrees D: The contact angle is less than 30 degrees if water If the spot suppression evaluation criterion is A or B, it can be used in terms of practicality, and if the evaluation result is A, the effect is more excellent.

系光起始劑，2,4-二乙基9-氧硫𠮿

(商品名DOUBLECURE DETX，Double BondChemical製造) ・起始劑7：醯基膦系光起始劑，苯基雙(2,4,6-三甲基苯甲醯基)氧化膦(商品名Irgacure 819，BASF公司製造)Furthermore, in Tables 1 to 7, the compound represented by the above general formula (A) and other initiators different from the compound represented by the above general formula (A) are respectively as follows. <The compound represented by the above general formula (A)> ・A-1: The compound represented by the above chemical formula (A-1) ・A-2: The compound represented by the above chemical formula (A-2) ・A-3: The above The compound represented by the chemical formula (A-3) ・A-4: The compound represented by the above chemical formula (A-4) <Other initiators> ・Initiator 1: an oxime ester-based photoinitiator with a carbazole skeleton , Trade name Adeka Arkles NCI-831, manufactured by ADEKA company ・Initiator 2: α-aminoketone-based photoinitiator, 2-benzyl-2-(dimethylamino)-1-(4-? (Aminophenyl)-1-butanone (trade name Irgacure 369, manufactured by BASF) ・Initiator 3: α-aminoketone-based photoinitiator, 2-methyl-1-(4-methylthio Phenyl)-2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by BASF Corporation) ・Initiator 4: Mercapto-based chain transfer agent, 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) ・Initiator 5: Biimidazole-based photoinitiator, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (black gold Made by Kasei Corporation) ・Initiator 6: 9-oxysulfur 𠮿

Department of photoinitiator, 2,4-diethyl 9-oxysulfur 𠮿

(Trade name DOUBLECURE DETX, manufactured by Double Bond Chemical) ・Initiator 7: Phosphine-based photoinitiator, phenyl bis(2,4,6-trimethylbenzyl) phosphine oxide (Trade name Irgacure 819 , Manufactured by BASF Corporation)

[Table 1] Table 1. sample Photosensitive colored resin composition Initiator (general formula (A)) Starting agent (general formula (A)) content Starter (other starter) Starter (other starter) content Antioxidants Dispersant Dispersions Line width offset Residual film rate of solvent resistance (%) Sectional shape of the colored layer Development residue suppression Water spot suppression The cross-sectional shape of the micropore Residues in the micropores Example 1 R-1 A-1 6% - - - Salt block 1 R(l) B B B B B B B Example 2 R-2 A-1 4% Initiator 1 1% - Salt block 1 R(l) B B A B B A A Example 3 R-3 A-1 5% Initiator 2 2% - Salt block 1 R(l) B B B B B A A Example 4 R-4 A-1 5% Initiator 3 2% - Salt block 1 R(l) B B B B B A A Example 5 R-5 A-1 5% Initiator 4 2% - Salt block 1 R(l) B B B B B A A Example 6 R-6 A-1 5% Starter 5 2% - Salt block 1 R(l) B B B B B A A Example 7 R-7 A-1 5% Starter 6 2% - Salt block 1 R(l) B B B B B A A Example 8 R-8 A-1 5% Starter 7 2% - Salt block 1 R(l) B B B B B A A Example 9 R-9 A-1 6% - - - Salt block 2 R(2) B A B A B B A Example 10 R-10 A-1 6% - - - Salt graft 5 R(3) B A B B A B B Example 11 R-11 A-1 6% - - - Salt grafting 6 R(4) B A B A A B A Example 12 R-12 A-1 6% - - - Salt grafting 7 R(5) B A B B B B B Example 13 R-13 A-1 8% - - 1.0% Salt block 1 R(l) A B B B B B B

[Table 2] Table 2. sample Photosensitive colored resin composition Initiator (general formula (A)) Starting agent (general formula (A)) content Starter (other starter) Starter (other starter) content Antioxidants Dispersant Dispersions Line width offset Residual film rate of solvent resistance (%) Sectional shape of the colored layer Development residue suppression Water spot suppression The cross-sectional shape of the micropore Residues in the micropores Example 14 G-1 A-1 6% - - - Salt block 1 G(l) B B B B B B B Example 15 G-2 A-1 4% Initiator 1 1% - Salt block 1 G(l) B B A B B A A Example 16 G-3 A-1 5% Initiator 2 2% - Salt block 1 G(l) B B B B B A A Example 17 G-4 A-1 5% Initiator 3 2% - Salt block 1 G(l) B B B B B A A Example 18 G-5 A-1 5% Initiator 4 2% - Salt block 1 G(l) B B B B B A A Example 19 G-6 A-1 5% Starter 5 2% - Salt block 1 G(l) B B B B B A A Example 20 G-7 A-1 5% Starter 6 2% - Salt block 1 G(l) B B B B B A A Example 21 G-8 A-1 5% Starter 7 2% - Salt block 1 G(l) B B B B B A A Example 22 G-9 A-1 6% - - - Salt block 2 G(2) B A B A B B A Example 23 G-10 A-1 6% - - - Salt graft 5 G(3) B A B B A B B Example 24 G-11 A-1 6% - - - Salt grafting 6 G(4) B A B A A B A Example 25 G-12 A-1 6% - - - Salt grafting 7 G(5) B A B B B B B Example 26 G-13 A-1 8% - - 1.0% Salt block 1 G(l) A B B B B B B

[table 3] table 3. sample Photosensitive colored resin composition Initiator (general formula (A)) Starting agent (general formula (A)) content Starter (other starter) Starter (other starter) content Antioxidants Dispersant Dispersions Line width offset Residual film rate of solvent resistance (%) Sectional shape of the colored layer Development residue suppression Water spot suppression The cross-sectional shape of the micropore Residues in the micropores Example 27 B-1 A-1 6% - - - Salt block 3 B(l) B B B B B B B Example 28 B-2 A-1 4% Initiator 1 1% - Salt block 3 B(l) B B A B B A A Example 29 B-3 A-1 5% Initiator 2 2% - Salt block 3 B(l) B B B B B A A Example 30 B-4 A-1 5% Initiator 3 2% - Salt block 3 B(l) B B B B B A A Example 31 B-5 A-1 5% Initiator 4 2% - Salt block 3 B(l) B B B B B A A Example 32 B-6 A-1 5% Starter 5 2% - Salt block 3 B(l) B B B B B A A Example 33 B-7 A-1 5% Starter 6 2% - Salt block 3 B(l) B B B B B A A Example 34 B-8 A-1 5% Starter 7 2% - Salt block 3 B(l) B B B B B A A Example 35 B-9 A-1 6% - - - Salt block 4 B(2) B A B A B B A Example 36 B-10 A-1 6% - - - Salt grafting 8 B(3) B A B B A B B Example 37 B-11 A-1 6% - - - Salt graft 9 B(4) B A B A A B A Example 38 B-12 A-1 6% - - - Salt grafting 10 B(5) B A B B B B B Example 39 B-13 A-1 8% - - 1.0% Salt block 3 B(l) A B B B B B B

[Table 4] Table 4. sample Photosensitive colored resin composition Initiator (general formula (A)) Starting agent (general formula (A)) content Starter (other starter) Starter (other starter) content Antioxidants Dispersant Dispersions Line width offset Residual film rate of solvent resistance (%) Sectional shape of the colored layer Development residue suppression Water spot suppression The cross-sectional shape of the micropore Residues in the micropores Example 40 R-14 A-2 6% - - - Salt block 1 R(l) B B B B B B B Example 41 R-15 A-2 4% Initiator 1 1% - Salt block 1 R(l) B B A B B A A Example 42 R-16 A-2 5% Initiator 2 2% - Salt block 1 R(l) B B B B B A A Example 43 R-17 A-2 5% Initiator 3 2% - Salt block 1 R(l) B B B B B A A Example 44 R-18 A-2 5% Initiator 4 2% - Salt block 1 R(l) B B B B B A A Example 45 R-19 A-2 5% Starter 5 2% - Salt block 1 R(l) B B B B B A A Example 46 R-20 A-2 5% Starter 6 2% - Salt block 1 R(l) B B B B B A A Example 47 R-21 A-2 5% Starter 7 2% - Salt block 1 R(l) B B B B B A A Example 48 R-22 A-2 6% - - - Salt block 2 R(2) B A B A B B A Example 49 R-23 A-2 6% - - - Salt graft 5 R(3) B A B B A B B Example 50 R-24 A-2 6% - - - Salt grafting 6 R(4) B A B A A B A Example 51 R-25 A-2 6% - - - Salt grafting 7 R(5) B A B B B B B Example 52 R-26 A-2 8% - - 1.0% Salt block 1 R(l) A B B B B B B

[table 5] table 5. sample Photosensitive colored resin composition Initiator (general formula (A)) Starting agent (general formula (A)) content Starter (other starter) Starter (other starter) content Antioxidants Dispersant Dispersions Line width offset Residual film rate of solvent resistance (%) Sectional shape of the colored layer Development residue suppression Water spot suppression The cross-sectional shape of the micropore Residues in the micropores Example 53 G-14 A-2 6% - - - Salt block 1 G(l) B B B B B B B Example 54 G-15 A-2 4% Initiator 1 1% - Salt block 1 G(l) B B A B B A A Example 55 G-16 A-2 5% Initiator 2 2% - Salt block 1 G(l) B B B B B A A Example 56 G-17 A-2 5% Initiator 3 2% - Salt block 1 G(l) B B B B B A A Example 57 G-18 A-2 5% Initiator 4 2% - Salt block 1 G(l) B B B B B A A Example 58 G-19 A-2 5% Starter 5 2% - Salt block 1 G(l) B B B B B A A Example 59 G-20 A-2 5% Starter 6 2% - Salt block 1 G(l) B B B B B A A Example 60 G-21 A-2 5% Starter 7 2% - Salt block 1 G(l) B B B B B A A Example 61 G-22 A-2 6% - - - Salt block 2 G(2) B A B A B B A Example 62 G-23 A-2 6% - - - Salt graft 5 G(3) B A B B A B B Example 63 G-24 A-2 6% - - - Salt grafting 6 G(4) B A B A A B A Example 64 G-25 A-2 6% - - - Salt grafting 7 G(5) B A B B B B B Example 65 G-26 A-2 8% - - 1.0% Salt block 1 G(l) A B B B B B B

[Table 6] Table 6. sample Photosensitive colored resin composition Initiator (general formula (A)) Starting agent (general formula (A)) content Starter (other starter) Starter (other starter) content Antioxidants Dispersant Dispersions Line width offset Residual film rate of solvent resistance (%) Sectional shape of the colored layer Development residue suppression Water spot suppression The cross-sectional shape of the micropore Residues in the micropores Example 66 B-14 A-2 6% - - - Salt block 3 B(l) B B B B B B B Example 67 B-15 A-2 4% Initiator 1 1% - Salt block 3 B(l) B B A B B A A Example 68 B-16 A-2 5% Initiator 2 2% - Salt block 3 B(l) B B B B B A A Example 69 B-17 A-2 5% Initiator 3 2% - Salt block 3 B(l) B B B B B A A Example 70 B-18 A-2 5% Initiator 4 2% - Salt block 3 B(1) B B B B B A A Example 71 B-19 A-2 5% Starter 5 2% - Salt block 3 B(l) B B B B B A A Example 72 B-20 A-2 5% Starter 6 2% - Salt block 3 B(l) B B B B B A A Example 73 B-21 A-2 5% Starter 7 2% - Salt block 3 B(l) B B B B B A A Example 74 B-22 A-2 6% - - - Salt block 4 B(2) B A B A B B A Example 75 B-23 A-2 6% - - - Salt grafting 8 B(3) B A B B A B B Example 76 B-24 A-2 6% - - - Salt graft 9 B(4) B A B A A B A Example 77 B-25 A-2 6% - - - Salt grafting 10 B(5) B A B B B B B Example 78 B-26 A-2 8% - - 1.0% Salt block 3 B(l) A B B B B B B

[Table 7] Table 7. sample Photosensitive colored resin composition Initiator (general formula (A)) Starting agent (general formula (A)) content Starter (other starter) Starter (other starter) content Antioxidants Dispersant Dispersions Line width offset Residual film rate of solvent resistance (%) Sectional shape of the colored layer Development residue suppression Water spot suppression The cross-sectional shape of the micropore Residues in the micropores Example 79 R-27 A-3 6% - - - Salt block 1 R(1) B B B B B B B Example 80 R-28 A-3 6% - - - Salt block 2 R(2) B A B A B B A Example 81 R-29 A-3 6% - - - Salt graft 5 R(3) B A B B A B B Example 82 R-30 A-3 6% - - - Salt grafting 6 R(4) B A B A A B A Example 83 R-31 A-3 6% - - - Salt grafting 7 R(5) B A B B B B B Example 84 R-32 A-3 8% - - 1.0% Salt block 1 R(l) A B B B B B B Example 85 R-33 A-4 6% - - - Salt block 1 R(l) B B B B B B B Example 86 R-34 A-4 6% - - - Salt block 2 R(2) B A B A B B A Example 87 R-35 A-4 6% - - - Salt graft 5 R(3) B A B B A B B Example 88 R-36 A-4 6% - - - Salt grafting 6 R(4) B A B A A B A Example 89 R-37 A-4 6% - - - Salt grafting 7 R(5) B A B B B B B Example 90 R-38 A-4 8% - - 1.0% Salt block 1 R(l) A B B B B B B Comparative example 1 CR-1 - - OXE02 6% - Salt block 1 R(l) D D D B B D C Comparative example 2 CG-1 - - OXE02 6% - Salt block 1 G(l) D D D B B D C Comparative example 3 CB-1 - - OXE02 6% - Salt block 3 B(1) D D D B B D C Comparative example 4 CR-2 A-1 6% - - - PB821 CR(1) C D C D B C D Comparative example 5 CR-3 A-1 6% - - - BYK-161 CR(2) C D C D B C D Comparative example 6 CG-2 A-1 6% - - - PB821 CG(1) C D C D B C D Comparative example 7 CG-3 A-1 6% - - - BYK-161 CG(2) C D C D B C D Comparative example 8 CB-2 A-1 6% - - - PB821 CB(1) C D C D B C D Comparative example 9 CB-3 A-1 6% - - - BYK-161 CB(2) C D C D B C D

系光起始劑、醯基氧化膦系光起始劑及巰基系鏈轉移劑所組成之群中之至少1種，則微孔之剖面形狀良好，微孔內之殘渣得到抑制。 又，顯示，若使用酸值為1～18 mgKOH/g且玻璃轉移溫度為30℃以上之(甲基)丙烯酸酯共聚物系分散劑作為分散劑，則藉由與上述通式(A)所表示之化合物組合而提昇耐溶劑性，且抑制產生顯影殘渣。 又，顯示，若使用為接枝共聚物且接枝聚合物鏈之結構單元中包含選自由通式(III)所表示之結構單元及下述通式(III')所表示之結構單元所組成之群中之至少1種結構單元的(甲基)丙烯酸酯共聚物系分散劑作為分散劑，則藉由與上述通式(A)所表示之化合物組合而提昇耐溶劑性。亦顯示，若其中接枝聚合物鏈之結構單元中包含上述通式(III)所表示之結構單元(其中，m表示19以上80以下之數)，則水斑產生抑制效果提昇。 亦顯示，若進而添加抗氧化劑，則線寬偏移量良好。[Summary of Results] In the comparative photosensitive colored resin compositions of Comparative Examples 1 to 3 that did not use the compound represented by the general formula (A) specified by the present invention as the photoinitiator, the amount of line width shift was large, The solvent resistance obtained by low-temperature heat treatment is poor. Comparison of Comparative Examples 4-9 in which the compound represented by the general formula (A) specified in the present invention is used as the photoinitiator, but the polyester-based dispersant or the urethane-based dispersant is used as the dispersant In the photosensitive colored resin composition, the amount of line width shift becomes large, and the solvent resistance obtained by low-temperature heat treatment is poor. It is shown that, in contrast to this, the photosensitive coloring of Examples 1 to 90 in which at least the compound represented by the general formula (A) is used as the photoinitiator and the (meth)acrylate copolymer dispersant is combined as the dispersant In the resin composition, it is possible to form a colored layer that suppresses the amount of line width deviation and has good solvent resistance under low-temperature heat treatment. The examples show that if the photoinitiator further contains a compound different from the compound represented by the above general formula (A) selected from the group consisting of oxime ester-based photoinitiator, α-aminoketone-based photoinitiator, and biimidazole-based photoinitiator. Initiator, 9-oxysulfur 𠮿

If at least one of the photoinitiator, phosphine oxide-based photoinitiator, and mercapto-based chain transfer agent is used, the cross-sectional shape of the micropores is good, and the residue in the micropores is suppressed. In addition, it is shown that if a (meth)acrylate copolymer-based dispersant with an acid value of 1-18 mgKOH/g and a glass transition temperature of 30°C or higher is used as a dispersant, it can be combined with the above general formula (A) The indicated compound combination improves solvent resistance and suppresses the development of residues. In addition, it is shown that if a graft copolymer is used and the structural unit of the grafted polymer chain includes a structural unit selected from the general formula (III) and the structural unit represented by the following general formula (III') The (meth)acrylate copolymer-based dispersant of at least one structural unit in the group is used as a dispersant, and the solvent resistance is improved by combining with the compound represented by the above-mentioned general formula (A). It has also been shown that if the structural unit of the grafted polymer chain contains the structural unit represented by the above-mentioned general formula (III) (wherein, m represents a number of 19 or more and 80 or less), the effect of inhibiting the occurrence of water spots is improved. It also shows that if an antioxidant is further added, the line width deviation is good.

1: substrate 2: Shading part 3: Coloring layer 5: Microporous 10: Color filter 11: graft copolymer 12: Main chain part 20: Opposite substrate 21: Structural unit represented by general formula (I) 22: Structural unit represented by general formula (II) 23: At least 1 selected from the group consisting of organic acid compounds and halogenated hydrocarbons 24: polymer chain 25: The structural unit represented by the general formula (III) (including the structural unit of the polyethylene oxide chain or the polypropylene oxide chain with a specific repeating number) 26: Polyethylene oxide chain or polypropylene oxide chain with specific repeating number 30: liquid crystal layer 40: Liquid crystal display device 50: Organic protective layer 60: Inorganic oxide film 71: Transparent anode 72: hole injection layer 73: hole transport layer 74: luminescent layer 75: electron injection layer 76: Cathode 80: organic light-emitting body 100: Organic light-emitting display device θ1: Tilt angle θ2: Tilt angle

Fig. 1 is a schematic diagram showing an example of the color filter of the present invention. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. Fig. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. Fig. 4 is a diagram schematically showing a part of an example of the structure of the graft copolymer used in the present invention. Fig. 5 is a schematic diagram illustrating the inclination angle (θ1) of the cross-sectional shape of the colored layer of the thin line pattern. Fig. 6 is a schematic diagram illustrating the inclination angle (θ2) of the cross-sectional shape of the micropores in the colored layer.

Claims (10)

A photosensitive colored resin composition containing a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and the dispersant contains a (meth)acrylate copolymer dispersant, The photoinitiator contains a compound represented by the following general formula (A); [化1]

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom and the number of carbon atoms 1-20 alkyl, 6-30 aryl, 7-30 aralkyl, or 2-20 heterocyclic group, represented by R ¹¹ , R ¹² and R ¹³ The hydrogen atom of the group can be further substituted with R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN or halogen atom, R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom and a carbon atom number of 1-20 Alkyl group, aryl group with 6 to 30 carbon atoms, aralkyl group with 7 to 30 carbon atoms or heterocyclic group with 2 to 20 carbon atoms, hydrogen atom of the group represented by ^{R 21} , R ²² and R ²³ The alkylene moiety of the group represented by ^{R 11} , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, a CN, a halogen atom or a carboxyl group, and the oxygen atom may not be adjacent Under the conditions, it contains 1～5 -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO- ^{, -OCONR 24} -, -SCO-, -COS-, -OCS- or -CSO-, R ²⁴ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms or carbon A heterocyclic group having 2 to 20 atoms, ^{the alkyl portion of the group represented by R 11} , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl R ³ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, The alkyl part of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl group. In addition, R ³ and R ⁷ , and R ³ and R ⁸ may each form a ring together. The group represented by ^{R 3} The hydrogen atom can then be substituted into R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, CN or halogen atom, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ Together with R ⁷ can form a ring. R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group with 1 to 20 carbon atoms. The alkyl portion of the group represented by ^{R 14} , R ¹⁵ and R ^{16 can have a branch} The side chain can also be a cyclic alkyl group, R ⁸ represents R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , hydroxyl, CN or halogen atom, k represents 0 or 1). The photosensitive colored resin composition of claim 1, wherein the photoinitiator further contains a compound different from the compound represented by the general formula (A) selected from the group consisting of oxime ester-based photoinitiators and α-aminoketone-based photoinitiators. Initiator, biimidazole-based photoinitiator, 9-oxysulfur 𠮿

It is at least one of the photoinitiator, phosphine oxide-based photoinitiator, and mercapto-based chain transfer agent. The photosensitive colored resin composition of claim 1 or 2, wherein the (meth)acrylate copolymer-based dispersant contains at least one of a graft copolymer and a salt-type graft copolymer, and the graft copolymer has The structural unit represented by the following general formula (I) and the structural unit represented by the following general formula (II), the above-mentioned salt-type graft copolymer is the structure represented by the general formula (I) of the graft copolymer At least a part of the nitrogen site of the unit forms a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons, and the polymer chain in the structural unit represented by the following general formula (II) The structural unit includes at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (III) and the structural unit represented by the following general formula (III'); [化2]

(In the general formula (I), R ⁴¹ represents a hydrogen atom or a methyl group, A ¹ represents a divalent linking group, R ⁴² and R ⁴³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a heteroatom, R ⁴² and R ⁴³ may Bonded to each other to form a ring structure; In the general formula (II), R ^41' represents a hydrogen atom or a methyl group, A ² represents a direct bond or a divalent linking group, and Polymer represents a polymer chain, the structural unit of the polymer chain Contains structural units derived from (meth)acrylate) [化3]

(In the general formula (III), R ⁴⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁴⁵ is an ethylene group or a propylene group, R ⁴⁶ is a hydrogen atom or a hydrocarbon group, and m represents 3 to 80 the number; apos, R ⁴⁴ of formula (III) ^'is a hydrogen atom or a methyl group, A ^3' is a divalent linking group, R ⁴⁷ based carbon atoms of the alkylene group having 1 to 10, R ⁴⁸ based carbon atoms In the alkylene group of 3-7, R ⁴⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number ranging from 1 to 40). The photosensitive colored resin composition of claim 1 or 2, wherein the (meth)acrylate copolymer-based dispersant contains at least one of a block copolymer and a salt-type block copolymer, and the block copolymer contains The A block containing the structural unit represented by the above general formula (I), and the B block containing the structural unit derived from the carboxyl group-containing monomer and the structural unit derived from (meth)acrylate; the above-mentioned salt type block The copolymer is formed by forming a salt with at least a part of the nitrogen sites of the structural unit represented by the above-mentioned general formula (I) of the block copolymer and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons ; At least one of the above-mentioned block copolymers and salt-type block copolymers has an acid value of 1-18 mgKOH/g, and a glass transition temperature of 30°C or higher. The photosensitive colored resin composition of claim 3, wherein in the (meth)acrylate copolymer-based dispersant, the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer The structural unit includes the structural unit represented by the above general formula (III). The photosensitive colored resin composition of claim 3, wherein in the (meth)acrylate copolymer-based dispersant, the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer The structural unit includes the structural unit represented by the general formula (III) (wherein, m represents a number of 19 or more and 80 or less). The photosensitive colored resin composition of claim 1 or 2, which further contains an antioxidant. A cured product, which is a cured product of the photosensitive colored resin composition according to any one of claims 1 to 7. A color filter is provided with at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claim 8. A display device having the above-mentioned color filter as claimed in claim 9.

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