TW202313742A - Photosensitive colored resin composition, color filter and display device - Google Patents

Abstract

Provided is a photosensitive colored resin composition, comprising a color material containing a phthalocyanine compound represented by the following general formula (1), a sulfonic acid group-containing dye derivative, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent:

Description

Photosensitive colored resin composition, color filter, and display device

The invention relates to a photosensitive colored resin composition, 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 been increasing. 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, electroluminescence) displays with high visibility due to 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 of 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 a light source at this time, in addition to the conventional cold cathode tube, an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light may be 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 formed on the substrate and including colored patterns of three primary colors of red, green, and blue; and a light shielding portion formed on the substrate to divide each colored pattern. Regarding the method of forming the colored layer in the color filter, for example, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator are added to a color material dispersion obtained by dispersing the color material with a dispersant, etc., and the resulting The formed photosensitive colored resin composition is coated on a glass substrate and dried, then exposed using a photomask, developed to form a colored pattern, and heated to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.

As a coloring material, pigments are generally used from the viewpoint of heat resistance and light resistance, but pigments cannot meet market demands especially in terms of high brightness. Therefore, dyes have been extensively studied. Due to the color purity of the dye itself and the vividness of the hue, the dye is excellent in improving the hue and brightness of the displayed image when displaying an image. On the other hand, dyes are generally poor in heat resistance and solvent resistance, and have low solubility in solvents, causing foreign matter to precipitate in the obtained colored layer, so it is considered difficult to put them into practical use. For a green coloring layer, studies have been conducted using specific phthalocyanine dyes as dyes (for example, refer to Patent Documents 1 to 3). prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2009-051896 Patent Document 2: Japanese Patent Laid-Open No. 2014-125460 Patent Document 3: Japanese Patent No. 2020-42263

[Problem to be solved by the invention]

For example, when forming the pattern of the colored layer during the manufacture of color filters, after exposing the coating film of the photosensitive colored resin composition, the non-exposed part is developed with a developing solution, but the photosensitive colored resin is contained in the developing waste solution. Components of the composition. Therefore, in a factory, a coagulant is usually added to the developing waste liquid to coagulate the components of the photosensitive colored resin composition including the color material, and then the coagulated matter is collected and the pH-adjusted water is discharged. Therefore, it is required that the filtrate after recovering the condensate does not contain a coloring material and is not colored. However, when a phthalocyanine-based dye is included in the color material like the photosensitive colored resin compositions described in Patent Documents 1 to 3 above, the problem that the waste developing liquid does not coagulate sufficiently even if an aggregating agent is added , The filtrate after recovering the condensate is colored as the color of phthalocyanine dye.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a photosensitive colored resin composition that can easily recover a color material during waste liquid treatment after development even when the color material contains a specific phthalocyanine dye. Moreover, the object of this invention is to provide the color filter and display apparatus formed using this photosensitive colored resin composition. [Technical means to solve the problem]

The photosensitive colored resin composition of the present invention contains: a coloring material comprising a phthalocyanine compound represented by the following general formula (1), a pigment derivative containing a sulfonic acid group, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator agents, and solvents.

(通式(1)中，X ¹～X ¹⁶分別獨立地表示氫原子、鹵素原子、或-Y-R ^D，-Y-表示-O-、-S-、或-NH-，R ^D表示一價有機基。其中，X ¹～X ¹⁶中之1個以上表示-Y-R ^D) [chemical 1]

(In the general formula (1), X ¹ to X ¹⁶ each independently represent a hydrogen atom, a halogen atom, or -YR ^D , -Y- represents -O-, -S-, or -NH-, R ^D represents a monovalent Organic group. Among them, one or more of X ¹ to X ¹⁶ represents -YR ^D )

The color filter of the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, at least one of the colored layers being a cured product of the photosensitive colored resin composition of the present invention. Furthermore, the present invention provides a display device having the above-mentioned color filter of the present invention. [Effect of Invention]

According to the present invention, even when the color material contains a specific phthalocyanine dye, it is possible to provide a photosensitive coloring resin composition in which the color material can be easily recovered at the time of waste liquid treatment after development. Also, according to the present invention, a color filter and a display device formed using the photosensitive colored resin composition can be provided.

Hereinafter, the photosensitive colored resin composition, the color filter, and the display device of the present invention will be described in detail sequentially. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and invisible regions, and further includes radiation, and radiation includes, for example, 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)acryl means each of acryl and methacryl, (meth)acryl means each of acrylic acid and methacryl, and (meth)acrylate means acrylate and methacryl. Acrylate each. In addition, in this specification, "-" which shows a numerical range is used in the meaning which includes the numerical value described before and after it as a lower limit and an upper limit.

I. Photosensitive colored resin composition The photosensitive colored resin composition of the present invention contains: a coloring material comprising a phthalocyanine compound represented by the following general formula (1), a pigment derivative containing a sulfonic acid group, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator agents and solvents.

(通式(1)中，X ¹～X ¹⁶分別獨立地表示氫原子、鹵素原子、或-Y-R ^D，-Y-表示-O-、-S-、或-NH-，R ^D表示一價有機基。其中，X ¹～X ¹⁶中之1個以上表示-Y-R ^D) [Chem 2]

(In the general formula (1), X ¹ to X ¹⁶ each independently represent a hydrogen atom, a halogen atom, or -YR ^D , -Y- represents -O-, -S-, or -NH-, R ^D represents a monovalent Organic group. Among them, one or more of X ¹ to X ¹⁶ represents -YR ^D )

The photosensitive coloring resin composition of the present invention can provide a color material containing a specific In the case of phthalocyanine dyes, it is also easy to recover the photosensitive colored resin composition of the color material during the waste liquid treatment after development. The color material contained in the conventional photosensitive colored resin composition is usually a pigment. The pigment is insoluble in the solvent and exists as particles, the particle size is larger than that of the dye, and it has a surface charge in the aqueous solution. In the case of a pigment that exists as particles in an aqueous solution and has a surface charge, by adding a coagulant with a charge to the developing waste liquid, it is easy to coagulate and recover together with other resin components. On the other hand, solvent-soluble dyes such as phthalocyanine compounds represented by the above general formula (1) tend to exist at the molecular level, and have weak or no surface charges even in aqueous solutions. Therefore, in the case of a photosensitive colored resin composition containing a phthalocyanine compound represented by the general formula (1) in the color material, it is estimated that even if an aggregating agent is added to the developing waste liquid, the aggregating agent is difficult to act on the phthalocyanine compound, Free phthalocyanine compounds are produced, and the filtrate after recovering the condensate is colored as the color of phthalocyanine compounds. On the other hand, it is speculated that if the above-mentioned specific phthalocyanine compound and a sulfonic acid group-containing pigment derivative are used in combination, the phthalocyanine compound and the sulfonic acid group-containing pigment derivative interact to give the surface of the phthalocyanine compound a Anionic. Therefore, when the photosensitive colored resin composition contains the above-mentioned specific phthalocyanine compound and a sulfonic acid group-containing pigment derivative, it is speculated that if an aggregating agent is added to the developing waste liquid, the aggregating agent is likely to act on the phthalocyanine compound. , It is easy to coagulate with other resin components, and it is not easy to produce free phthalocyanine compounds, so it is easy to recycle color materials.

Moreover, it also found that the photosensitive colored resin composition of this invention suppresses the residue after image development by using together the said specific phthalocyanine compound and the pigment derivative containing a sulfonic acid group. It is speculated that the phthalocyanine compound, which tends to become a residue during development, interacts with the pigment derivatives containing sulfonic acid groups, and is easily washed away by the developer solution during development, and is easily dissolved even after the coating film is formed.

The photosensitive colored resin composition of the present invention contains: a coloring material, a pigment derivative containing a sulfonic acid group, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, within the range that does not impair the effect of the present invention, It may further contain other components. Hereinafter, each component of the colored resin composition of this invention is demonstrated in detail sequentially.

[Color Material] In the present invention, the color material includes the phthalocyanine compound represented by the above general formula (1). In the phthalocyanine compound represented by the above general formula (1), X ¹ to X ¹⁶ each independently represent a hydrogen atom, a halogen atom, or -YR ^D , and -Y- represents -O-, -S-, or -NH -, R ^D represents a monovalent organic group. Among them, one or more of X ¹ to X ¹⁶ represents ^-YRD .

Among X ¹ to X ¹⁶ , the halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In addition, when there are two or more halogen atoms in said formula (1), each of these plural halogen atoms may be the same or different from each other. From the viewpoint of hue, the halogen atoms in X ¹ to X ¹⁶ preferably include at least fluorine atoms, more preferably all of them are fluorine atoms.

The number of halogen atoms in X ¹ to X ¹⁶ is preferably 4 or more, more preferably 6 or more, and still more preferably 7 or more from the viewpoint of high brightness. Also, the number of halogen atoms in X ¹ to X ¹⁶ is preferably 12 or less, more preferably 10 or less, and still more preferably 9 or less. The number of halogen atoms in X ¹ to X ¹⁶ may be 8. Among them, from the viewpoint of the color tone and the maximum absorption wavelength region, it is preferable that 6 to 10 of X ¹ to X ¹⁶ are fluorine atoms, especially 7 to 9 of them are fluorine atoms.

X ¹ to X ¹⁶ may also be hydrogen atoms. The number of hydrogen atoms in X ¹ to X ¹⁶ may be appropriately selected according to the adjustment of the color tone, and may be 0 to 8, 0 to 4, or 0 to 2.

-Y- in -YR ^D represents -O-, -S-, or -NH-, based on the viewpoint of obtaining the desired transmission spectrum, preferably -O-, or -S-, more preferably -O -. In addition, when there are two or more -YR ^D' s in said formula (1), each of these plural -YR ^D's may be the same or different from each other.

R ^D in -YR ^D is a monovalent organic group. Here, the organic group refers to a group containing carbon atoms. R ^D may, for example, be a hydrocarbon group or a heterocyclic group which may have a substituent. The hydrocarbon group may, for example, be a linear, branched, or cyclic aliphatic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. As a straight-chain or branched aliphatic hydrocarbon group, it can be a straight-chain or branched aliphatic hydrocarbon group with 1 to 10 carbons, and as a cyclic aliphatic hydrocarbon group, it can be an alicyclic hydrocarbon group with 3 to 20 carbons, The aromatic hydrocarbon group can be an aromatic hydrocarbon group with 6 to 20 carbon atoms, and the heterocyclic group can include nitrogen-containing heterocycles, sulfur-containing heterocycles, oxygen-containing heterocycles, etc. either.

Examples of linear or branched aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, etc., and examples of alicyclic hydrocarbon groups include cyclopentyl, cyclo Hexyl etc. Moreover, as an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group etc. are mentioned, for example. Also, as the heterocyclic group, for example, a furan ring having one free atomic valence, a thiophene ring, a pyrrole ring, a 2H-pyranyl ring, a 4H-thiopyranyl ring, a pyridine ring, and a 1,3-oxazole ring , Isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furoxane ring, pyryrazole ring, pyrimidine ring, pyridyl ring, etc.

When the hydrocarbon group or heterocyclic group of R ^D has a substituent, the substituent may, for example, be a halogen atom, -OR ^d0 , -COR ^d0 , -COOR ^d0 (here, R ^d0 is a hydrocarbon group or a heterocyclic ring base) etc. As -OR ^d0 , -COR ^d0 , -COOR ^d0 (here, R ^d0 is a hydrocarbon group or a heterocyclic group), specifically, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxy Carbonyl etc.

R ^D in -YR ^D is preferably an aromatic hydrocarbon group which may have a substituent, from the viewpoint of crystallinity control (precipitation suppression of foreign matter) and solubility impartation during coating film hardening (baking), It is preferably a valence group represented by the following formula (2).

(式(2)中，-W-為單鍵或-O-，R ^d1為可具有取代基之碳數1～10之脂肪族烴基、可具有取代基之碳數3～12之脂環式烴基、或可具有取代基之碳數6～20之芳香族烴基。R ^d2為鹵素原子、碳數1～4之烷基或碳數1～4之烷氧基。p為1～3之整數，q為0～2之整數。其中，於p為2或3之情形時，複數個W、R ^d1各自可相同亦可不同，於m為2之情形時，複數個R ^d2各自可相同亦可不同。 -Y-表示-O-、-S-、或-NH-，*表示與式(1)中之酞菁骨架之鍵結位置) [Chem 3]

(In formula (2), -W- is a single bond or -O-, R ^d1 is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that may have substituents, an alicyclic hydrocarbon group with 3 to 12 carbon atoms that may have substituents A hydrocarbon group, or an aromatic hydrocarbon group with 6 to 20 carbons that may have a substituent. R ^d2 is a halogen atom, an alkyl group with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons. p is an integer of 1 to 3 , q is an integer from 0 to 2. Wherein, when p is 2 or 3, the plurality of W and R ^d1 may be the same or different, and when m is 2, the plurality of R ^d2 may be the same or different. Can be different. -Y- represents -O-, -S-, or -NH-, * represents the bonding position with the phthalocyanine skeleton in formula (1))

In the above-mentioned formula (2), examples of the substituents for the above-mentioned aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group include an alkoxy group having 1 to 5 carbon atoms. R ^d1 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms. When R ^d1 is a substituted alkyl group, it is preferably a group having an alkoxy group having 1 to 5 carbon atoms as a substituent. p is preferably 1 or 2, more preferably 1. When p=1, -CO-WR ^d1 is preferably bonded at the 3-position or 4-position with respect to -Y-, more preferably bonded at the 4-position. In the case of p=2, the two -CO-WR ^d1 are preferably bonded to the 3,5 or 2,4 positions with respect to -Y-, more preferably bonded to the 3,5 positions. q is preferably 0 or 1, more preferably 0. As a preferable specific example of the group represented by said formula (2), the group represented respectively by following formula (2-1) - a formula (2-10) is mentioned, However, It is not limited to these.

(式(2-1)～式(2-10)中，-Y-表示-O-、-S-、或-NH-，*表示與式(1)中之酞菁骨架之鍵結位置) [chemical 4]

(In formula (2-1) ~ formula (2-10), -Y- represents -O-, -S-, or -NH-, * represents the bonding position with the phthalocyanine skeleton in formula (1))

From the viewpoint of obtaining the desired transmission spectrum (high brightness) and the crystallinity control (suppression of foreign matter precipitation) peculiar to phthalocyanine compounds when the coating film is cured (baking), the ^X1 to ^X16 The number of -YR ^D is preferably at least 4, more preferably at least 6, and still more preferably at least 7. In addition, the number of ^-YRD in X ¹ to X ¹⁶ is preferably 12 or less, more preferably 10 or less, further preferably 9 or less. The number of -YR ^D in X ¹ to X ¹⁶ may be 8. From the viewpoint of obtaining the desired transmission spectrum (high brightness), X ¹ to X ¹⁶ are preferably at least one of X ² , X ³ , X ⁶ , X ⁷ , X ¹⁰ , X ¹¹ , X ¹⁴ and X ¹⁵ More than 4 are ^-YRD , especially X ² , X ³ , X ⁶ , X ⁷ , X ¹⁰ , X ¹¹ , X ¹⁴ and X ¹⁵ are all groups ^-YRD , and the remaining (X ¹ , X ⁴ , X ⁵ , X ⁸ , X ⁹ , X ¹² , X ¹³ and X ¹⁶ ) are halogen atoms.

Preferable specific examples of the phthalocyanine compound represented by the general formula (1) include compounds represented by the following formulas (1-1) to (1-6), respectively, but are not limited thereto.

[chemical 5]

[chemical 6]

[chemical 7]

As a method for producing a halogenated phthalocyanine color material, a conventionally known production method can be appropriately selected and used. For example, it can be suitably used in a molten state or in an organic solvent to make a phthalonitrile compound and a metal salt undergo a cyclization reaction. For example, refer to Japanese Patent Laid-Open No. 2014-43556 or Japanese Patent Laid-Open No. 2020-42263 Bulletin to manufacture. The phthalonitrile compound used as the starting material can also be synthesized by appropriately selecting a conventionally known production method, or using a commercially available product.

In the present invention, the coloring material may further include other coloring materials in addition to the phthalocyanine compound represented by the above general formula (1). Other color materials are not particularly limited, as long as the required color development can be achieved, various organic pigments, inorganic pigments, dyes, salt-forming compounds of dyes, etc. can be used alone or in combination of two or more. Among them, organic pigments have high color rendering properties and high heat resistance, so they are suitable for use. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; issued by The Society of Dyers and Colourists, Inc.), and specifically, the appended Color Index (C.I.) as described below. Numbered.

Examples of yellow color materials include: C.I. 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, 231, and their derivative pigments and other yellow pigments; coumarin dyes, cyanine dyes, merocyanine dyes , Azo-based dyes, methine-based dyes, methine-azo-based dyes, quinophthalone-based dyes and other yellow dyes.

Among them, the yellow color material is preferably a quinophthalone-based color material from the viewpoint of good heat resistance and light resistance and high transmittance. Moreover, the quinophthalone-based color material is also preferable from the viewpoint of having a hue suitable for use in color filters. Quinophthalone-based color materials refer to the color materials synthesized by the condensation of quinadine and other quinoline derivatives with phthalic anhydride derivatives or naphthalic anhydride derivatives, which can be pigments, dyes, and dyes. Any of the salt compounds. As the quinophthalone pigment in the quinophthalone-based color material, C.I. Pigment Yellow 138 and the like may, for example, be mentioned. Examples of quinophthalone dyes include: C.I. Disperse Yellow 54, 64, 67, 134, 149, 160; C.I. Solvent Yellow 114, 157, etc.

Other green color materials include: C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 , 55, 58, 59, 62, 63 and other green pigments; squaraine, triarylmethane, anthraquinone, coumarin, cyanine, or azo dyes and other green dyes. A phthalocyanine green pigment is preferable as another green color material different from the above-mentioned halogenated phthalocyanine compound from the viewpoint of easy adjustment of chromaticity. As this phthalocyanine green pigment, C.I. pigment green 7, 36, 58, 59, 62, 63 etc. are mentioned, for example. From the viewpoint of easy brightness adjustment, the phthalocyanine green pigment is preferably C.I. Pigment Green 7, 58, 59, 62, or 63, preferably C.I. Pigment Green 58, 59, 62, or 63, and more preferably For C.I. Pigment Green 59.

Moreover, as an orange color material, for example: C.I. 71, 73; Examples of blue color materials include: C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60; Examples of purple color materials include C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like.

The phthalocyanine compound represented by the above-mentioned general formula (1) is usually green, so as other color materials, at least one selected from the group consisting of yellow color materials and other green color materials is preferably used.

In the photosensitive colored resin composition of the present invention, the content ratio of the phthalocyanine compound represented by the above-mentioned general formula (1) relative to the entire color material is not particularly limited, as long as it is appropriately adjusted according to the desired chromaticity, relative It can be 100 mass % in the whole color material containing the phthalocyanine compound represented by the said general formula (1). When other coloring materials are contained in the photosensitive colored resin composition of the present invention, from the viewpoint of adjusting to the desired chromaticity, compared to the coloring material containing the phthalocyanine compound represented by the above general formula (1), Overall, the phthalocyanine compound represented by the said general formula (1) may contain 30-95 mass %, may contain 40-85 mass %, and may contain 50-80 mass %.

When the photosensitive colored resin composition of the present invention contains a yellow coloring material, the yellow coloring material can be selected appropriately and used alone or as a mixture of two or more. In the photosensitive colored resin composition of the present invention, the content ratio of the yellow color material to the halogenated phthalocyanine color material of the present invention is not particularly limited, as long as it is appropriately adjusted according to the desired chromaticity. Among them, based on the viewpoint of required chromaticity adjustment, the yellow coloring material may contain 5 to 233 parts by mass, or 18 to 150 parts by mass, relative to 100 parts by mass of the phthalocyanine compound represented by the above general formula (1). parts, 25 to 100 parts by mass may be included.

In the case where the photosensitive colored resin composition of the present invention contains a green color material different from the phthalocyanine compound represented by the above general formula (1), it is different from the phthalocyanine compound represented by the above general formula (1). The green color materials can be selected appropriately, and used alone or in combination of two or more. In the photosensitive colored resin composition of the present invention, the content ratio of the green color material different from the phthalocyanine compound represented by the above general formula (1) relative to the phthalocyanine compound represented by the above general formula (1) is not particularly Limited, as long as it is properly adjusted to the desired chromaticity. Among them, based on the viewpoint of required chromaticity adjustment and brightness adjustment, with respect to 100 parts by mass of the phthalocyanine compound represented by the above-mentioned general formula (1), which is different from the phthalocyanine compound represented by the above-mentioned general formula (1) The green color material may contain 5-233 parts by mass, may contain 18-150 parts by mass, or may contain 25-100 parts by mass.

Moreover, when the photosensitive colored resin composition of the present invention further contains a green color material other than the phthalocyanine compound represented by the above-mentioned general formula (1), the phthalocyanine represented by the above-mentioned general formula (1) is included. The content ratio of the green color material of the compound relative to the entire color material is not particularly limited, as long as it is properly adjusted according to the required chromaticity. Among them, from the standpoint of required chromaticity adjustment and brightness adjustment, the green color material containing the phthalocyanine compound represented by the above general formula (1) preferably contains 30 to 95% by mass relative to the entire color material, More preferably, it contains 50-80 mass %. Also, the content ratio of the yellow color material to the green color material containing the halogenated phthalocyanine color material of the present invention is not particularly limited, as long as it is appropriately adjusted according to the desired chromaticity. Wherein, based on the viewpoint of required chromaticity adjustment and brightness adjustment, the yellow color material preferably contains 5 to 70 It is more preferable to contain 20-50 mass parts as a mass part.

Also, in the photosensitive colored resin composition of the present invention, within the range that does not impair the effect of the present invention, other color materials other than the green color material and yellow color material may be included in the color material. Overall, the total content of the green coloring material and the yellow coloring material including the phthalocyanine compound represented by the above general formula (1) may be 70-100% by mass, particularly 80-100% by mass.

In the photosensitive colored resin composition of the present invention, the content of the color material is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the total content of the color materials 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. When it is more than the said lower limit, the coloring layer at the time of apply|coating a photosensitive coloring resin composition to a specific film thickness (normally 1.0-5.0 micrometers) has sufficient color density. Moreover, it is excellent in storage stability as it is below the said upper limit, and the colored layer which has sufficient hardness and the adhesiveness with a board|substrate can be obtained. In particular, when forming a colored layer with a high concentration of coloring materials, the total content of coloring materials is preferably 15% by mass to 65% by mass, more preferably It is within the range of 25% by mass to 60% by mass. In addition, in this invention, solid content is all components except the following solvent, and also includes the monomer etc. which melt|dissolve in a solvent.

[Dye Derivatives Containing Sulfonic Acid Groups] The dye derivatives are compounds that have the function of imparting functional groups to the skeleton of the dye to add various functions to the dye. In the present invention, pigment derivatives having a sulfonic acid group (-SO ₃ H) can be used. The sulfonic acid group-containing pigment derivative is preferably a pigment skeleton having a color material such as various pigments that can be used in the coloring layer of a color filter.

Examples of the dye skeleton of the dye derivative used in the present invention include: phthalocyanine skeleton, quinophthalone skeleton, triarylmethane skeleton, dibenzopyran skeleton, coumarin skeleton, naphthol azo skeleton , diketopyrrolopyrrole skeleton, quinacridone skeleton, etc. The pigment skeleton of the pigment derivative used in the present invention is preferably a pigment skeleton having an aromatic ring from the viewpoint of easy interaction with the compound represented by the above-mentioned general formula (1) through π-π stacking. .

In the pigment derivatives with sulfonic acid group (-SO ₃ H), the sulfonic acid group (-SO ₃ H) can be directly bonded to the pigment skeleton, or for example -SO ₂ NH-(CH ₂ ) _m -SO ₃ H (where m is an integer of 1 to 6) or the like binds a sulfonic acid group to the dye skeleton via a linking group. The sulfonic acid group (-SO ₃ H) can be directly bonded to the dye skeleton from the viewpoint of easy action on the target component.

In addition, in the pigment derivative having a sulfonic acid group (-SO ₃ H), the number of substitutions of the sulfonic acid group in one molecule may be 1 to 4, preferably 1 to 2, based on the fact that the brightness is not likely to decrease From a viewpoint, 1 is preferable.

Since the color material containing the halogenated phthalocyanine color material represented by the above-mentioned general formula (1) is used to make the usual green coloring layer, the pigment skeleton as a pigment derivative preferably has a green color from the viewpoint of hue. A pigment derivative having a pigment skeleton of a blue color material, a pigment derivative having a pigment skeleton of a blue color material, or a pigment derivative having a pigment skeleton of a yellow color material.

As the pigment skeleton of the pigment derivative used in the present invention, from the viewpoint of hue and the viewpoint of easier interaction with the compound represented by the above general formula (1), phthalo Cyanine skeleton or quinophthalone skeleton.

Examples of dyes having a phthalocyanine skeleton include metal-free phthalocyanines, copper phthalocyanines, nickel phthalocyanines, aluminum phthalocyanines, cobalt phthalocyanines, and zinc phthalocyanines. The dye having a phthalocyanine skeleton may not have a substituent on the phthalocyanine, but may have a known substituent such as an alkyl group or a halogen atom on the phthalocyanine. The dye having a phthalocyanine skeleton is preferably a phthalocyanine dye or a copper phthalocyanine dye from the viewpoint of easy acquisition of raw materials, and may be a copper phthalocyanine dye.

On the other hand, examples of pigments having a quinophthalone skeleton include quinophthalone pigments such as C.I. Pigment Yellow 138, C.I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. Solvent Yellow 114, 157 and other quinophthalone dyes. As a pigment with a quinophthalone skeleton, C.I. Pigment Yellow 138 or Pigment Yellow 231 is preferable from the viewpoint of higher transmittance and higher brightness, and C.I. Pigment Yellow 138 can be used.

As a method of introducing a sulfonic acid group into a dye, it can be produced by using known sulfonation. When a sulfonic acid group is introduced into a dye, it can be produced, for example, by putting a dye such as copper phthalocyanine into concentrated sulfuric acid, oleum, chlorosulfonic acid, or a mixture thereof, and performing a sulfonation reaction. After the sulfonation reaction, the reaction solution is diluted with a large amount of water, and the obtained suspension is filtered, washed with an aqueous cleaning solution, and dried.

In the case of sulfonation by the above method, the amount of sulfonic acid groups introduced per molecule can be controlled by adjusting the concentration of the reaction solution, the reaction temperature, and the reaction time.

As the sulfonic acid group-containing pigment derivatives, one type may be used alone or two or more types may be used in combination. For example, two or more sulfonic acid group-containing dye derivatives having different positions or numbers of substitutions of sulfonic acid groups can be used in combination. Alternatively, two or more pigment derivatives having a pigment skeleton can also be used in combination, for example, a mixture of copper phthalocyanine derivatives containing sulfonic acid groups and C.I. Pigment Yellow 138 derivatives containing sulfonic acid groups.

In the present invention, the total content of the sulfonic acid group-containing pigment derivative is preferably 1% to 15% by mass, more preferably 2% to 10% by mass, based on the total content of the compounds represented by the general formula (1). %, and more preferably 3% by mass to 9% by mass. By using such a content, the hue will not be greatly changed, and even when the color material contains a specific phthalocyanine dye, it is easy to recover the color material during waste liquid treatment after development.

In the photosensitive colored resin composition of the present invention, the total content of the pigment derivatives containing sulfonic acid groups can be, for example, 0.03% by mass to 9.75% by mass relative to the total solid content of the photosensitive colored resin composition. It is 0.12 mass % - 9.0 mass %, Preferably it is 1.0 mass % - 5.0 mass %, More preferably, it exists in the range of 2.5 mass % - 3.5 mass %. When it is more than the said lower limit, even when a color material contains a specific phthalocyanine dye, it becomes easy to recover a color material at the time of waste liquid processing after image development. Moreover, when it is below the said upper limit, it will be hard to exert an influence on optical characteristics (brightness) or dye solubility.

[Alkali-soluble resin] The alkali-soluble resin used in the present invention has an acidic group, and can be appropriately selected from those that function as a binder resin and are soluble in an alkaline developer that can be 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 an acidic group which alkali-soluble resin has, a carboxyl group is mentioned, for example. As an alkali-soluble resin which has a carboxyl group, the epoxy (meth)acrylate resin etc. which have a carboxyl group containing copolymer which has a carboxyl group, or a carboxyl group are mentioned. As a carboxyl group-containing copolymer, (meth)acrylic-type copolymers, such as the (meth)acrylic-type copolymer which has a carboxyl group, and the styrene-(meth)acryl-type copolymer which has a carboxyl group, etc. are mentioned. In addition, these (meth)acrylic copolymers and (meth)acrylic copolymers such as styrene-(meth)acrylic copolymers having carboxyl groups, and epoxy (meth)acrylate resins may be used in combination. 2 or more.

(Meth)acrylic copolymers such as carboxyl group-containing (meth)acrylic copolymers and carboxyl group-containing styrene-(meth)acrylic copolymers, etc., can be obtained by making carboxyl group-containing vinyl non-toxic, for example, by a known method. A (co)polymer obtained by (co)polymerizing a saturated monomer and, if necessary, other copolymerizable monomers.

Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleic acid, fumaric acid, icon acid, crotonic acid, cinnamic acid, (meth)acrylic acid dimer, etc. Also, the addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used. substances; ω-carboxy-polycaprolactone mono(meth)acrylate, etc. Moreover, as a precursor of a carboxyl group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride can be used. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

It is preferable that the alkali-soluble resin further has a hydrocarbon ring from a viewpoint of being excellent in the adhesiveness with a board|substrate. The alkali-soluble resin has a hydrocarbon ring as a bulky group, so that the shrinkage during curing is suppressed, the peeling with the substrate is relaxed, and the adhesion to the substrate is improved. Moreover, it is also preferable from the standpoint of improving the solvent resistance of the obtained colored layer by using an alkali-soluble resin having a hydrocarbon ring as a bulky group, especially from the viewpoint of suppressing swelling of the colored layer. Examples of such hydrocarbon rings include cyclic aliphatic hydrocarbon rings which may have substituents, aromatic rings which may have substituents, and combinations thereof. The hydrocarbon rings may also have carbonyl, carboxyl, oxycarbonyl, Substituents such as amide groups.

Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, nor-alane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) , adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, stilbene and other aromatic hydrocarbon rings; biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene and other chain polycyclic rings; and Cardo structure ( 9,9-diaryl fluorine) and so on.

Among them, when an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance or the adhesiveness of the colored layer is improved, and the brightness of the obtained colored layer is improved, so it is preferable. Also, when the structure (Cardo structure) in which two benzene rings are bonded to the fennel skeleton is included, the curability of the colored layer is improved, the solvent resistance is improved, and the swelling in NMP is suppressed, so it is particularly good. The hydrocarbon ring may be included as a monovalent group, or may be included as a divalent or higher group.

Based on the viewpoint that it is easy to adjust the amount of each structural unit, and it is easy to increase the amount of the structural unit having the above-mentioned hydrocarbon ring to enhance the function of the structural unit, it is preferable to use a compound other than carboxyl in the alkali-soluble resin used in the present invention. In addition to the structural unit, the (meth)acrylic copolymer which has the structural unit of the said hydrocarbon ring is contained. The (meth)acrylic copolymer comprising a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer".

As the ethylenically unsaturated monomer having a hydrocarbon ring used in the alkali-soluble resin having a hydrocarbon ring, for example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth)acrylate, base) adamantyl acrylate, iso(meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, styrene, having the above Cardo structure and an ethylenically unsaturated group Monomers, etc., are more effective in suppressing the precipitation of foreign matter originating from coloring materials even after heat treatment, among them, cyclohexyl (meth)acrylate and dicyclopentanyl (meth)acrylate are preferable. , Adamantyl (meth)acrylate, benzyl (meth)acrylate, styrene, monomers having the above-mentioned Cardo structure and ethylenically unsaturated groups.

Moreover, it is preferable that the alkali-soluble resin used by this invention has an ethylenically unsaturated bond in a side chain. In the case of having an ethylenically unsaturated bond, the alkali-soluble resins, or the alkali-soluble resin and a polyfunctional monomer can form a crosslinking bond during the hardening step of the resin composition when producing a color filter. The film strength of the cured film is further improved, the development resistance is improved, and the heat shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent. Furthermore, the ethylenically unsaturated group means a radical-polymerizable group containing a carbon-carbon double bond, for example, a (meth)acryl group, a vinyl group, an allyl group, etc. are mentioned. The method for introducing an ethylenically unsaturated bond into the alkali-soluble resin can be appropriately selected from previously known methods. For example, a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule added to the carboxyl group of an alkali-soluble resin, such as glycidyl (meth)acrylate, etc., introduces ethylenically unsaturated bonds into the side chain The method of bonding; or the method of introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenically unsaturated bond in the molecule, and introducing an ethylenically unsaturated bond into a side chain, etc.

The alkali-soluble resin used in the present invention may further contain other structural units such as structural units having ester groups such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the photosensitive colored resin composition, but also functions as a component that increases solubility in a solvent and further improves solvent resolubility.

The alkali-soluble resin used in the present invention is preferably a (meth)acrylic copolymer comprising a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and a styrene-(meth)acrylic copolymer (meth) ) acrylic resin, more preferably a (meth)acrylic copolymer and a styrene-(meth)acrylic acid containing a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond (meth)acrylic resins such as copolymers.

The alkali-soluble resin used in the present invention can obtain the desired performance by properly adjusting the addition amount of monomers derived from each structural unit.

The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually not less than 5% by mass and not more than 50% by mass, preferably not less than 10% by mass and not more than 40% by mass. In this case, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is 5% by mass or more, the decrease in the solubility of the obtained coating film in an alkaline developing solution can be suppressed, making it easy to form a pattern. Moreover, when a copolymerization ratio is 50 mass % or less, the chipping of a pattern and the film roughness of a pattern surface are hard to generate|occur|produce when developing with an alkaline developing solution. In addition, the said copolymerization ratio is the value calculated from the addition amount of each monomer.

Also, (meth)acrylic copolymers and styrene-(meth)acrylic copolymers and other (meth)acrylic resins that are more suitable for use as alkali-soluble resins include structural units having ethylenically unsaturated bonds. Among them, the addition amount of monomers having both epoxy groups and ethylenically unsaturated bonds is preferably 10% by mass to 95% by mass, more preferably It is 15 mass % - 90 mass %.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000-50,000, more preferably 3,000-20,000. When the weight-average molecular weight of the carboxyl group-containing copolymer is 1,000 or more, sufficient curability of the coating film can be obtained, and if it is 50,000 or less, it is easy to form a pattern when developing with an alkaline developer. In addition, the weight average molecular weight (Mw) in this invention is calculated|required as the standard polystyrene conversion value by gel permeation chromatography (GPC).

As a specific example of the (meth)acrylic-type copolymer which has a carboxyl group, what was described in Unexamined-Japanese-Patent No. 2013-029832 is mentioned, for example.

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited. For example, an epoxy (meth)acrylate resin obtained by reacting an epoxy compound with an unsaturated group-containing monocarboxylic acid and an acid anhydride is suitable. Acrylate compound. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. As an epoxy (meth)acrylate resin having a carboxyl group, it is preferable to include in the molecule from the viewpoint of improving the effect of suppressing defects, improving the curability of the colored layer, and increasing the residual film rate of the colored layer. The aforementioned Cardo constructor.

The acid value of the alkali-soluble resin is more preferably 40 mgKOH/g or more from the viewpoint of developability (solubility) in the alkaline aqueous solution used for the developer. From the viewpoint of developability (solubility) in the alkaline aqueous solution used in the developer and the viewpoint of adhesion to the substrate, the acid value of the above-mentioned carboxyl group-containing copolymer is preferably 50 mgKOH/g or more and 300 mgKOH/g or less, more preferably 60 mgKOH/g or more and 280 mgKOH/g or less, still more preferably 70 mgKOH/g or more and 250 mgKOH/g or less. In addition, in this invention, an acid value can be measured based on JISK0070.

From the standpoint of improving the film strength of the cured film and further suppressing the precipitation of the color material, when the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferably 100 to 2000 The range is preferably between 140 and 1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, image development resistance and adhesiveness are excellent. Moreover, if it is 100 or more, since the ratio of other structural units, such as the structural unit which has the said carboxyl group or the structural unit which has a hydrocarbon ring, can increase relatively, it is excellent in developability and heat resistance. Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mol of ethylenically unsaturated bond in the above-mentioned alkali-soluble resin, and is represented by the following numerical formula (1).

Formula (1) Ethylenic unsaturated bond equivalent (g/mol)=W(g)/M(mol) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the molar number (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g))

The above-mentioned ethylenically unsaturated bond equivalent can be calculated, for example, by measuring the number of ethylenically unsaturated bonds contained in 1 g of alkali-soluble resin according to the test method of iodine value described in JIS K 0070:1992.

The alkali-soluble resin used for the photosensitive colored resin composition may be used individually by 1 type, and may use it in combination of 2 or more types. The content of the alkali-soluble resin is not particularly limited, but is, for example, preferably within a range of 5% by mass to 60% by mass, more preferably within a range of 10% by mass to 40% by mass, relative to the total solid content of the photosensitive colored resin composition . If the content of the alkali-soluble resin is more than the above lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is below the above upper limit, film roughness or pattern loss during development can be suppressed.

[Photopolymerizable compound] The photopolymerizable compound used in the photosensitive colored resin composition of this invention means the compound which has a photopolymerizable group in a molecule|numerator. The photopolymerizable group is not particularly limited as long as it can be polymerized by a photoinitiator, for example, an ethylenically unsaturated bond, such as a vinyl group, an allyl group, an acryl group or a methyl group. Acryloyl, etc. As the photopolymerizable group, an acryl group or a methacryl group is preferably used from the viewpoint of ultraviolet curability. From the viewpoint of curability, the photopolymerizable compound preferably contains a compound having two or more photopolymerizable groups in one molecule, and more preferably contains a compound having three or more photopolymerizable groups in one molecule. compound.

The photopolymerizable compound is not particularly limited, as long as it can be polymerized by the following photoinitiator, generally, a compound having two or more ethylenically unsaturated double bonds can be used, especially acrylic acid having two or more Multifunctional (meth)acrylates of methacryl or methacryl groups. As such a polyfunctional (meth)acrylate, what is necessary is just to select suitably from well-known thing beforehand, and to use it. As a specific example, what is described in Unexamined-Japanese-Patent No. 2013-029832, etc. are mentioned, for example.

These photopolymerizable compounds may be used alone or in combination of two or more. Also, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, it is preferable that the photopolymerizable compound has three or more (trifunctional) ethylenically unsaturated bonds that can be polymerized. It is preferably poly(meth)acrylates of polyhydric alcohols with a valence of more than three or their modified dicarboxylic acids, specifically, trimethylolpropane tri(meth)acrylate is preferred , pentaerythritol tri(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate base) acrylate, dipentaerythritol penta(meth)acrylate modified succinic acid, dipentaerythritol hexa(meth)acrylate, etc.

The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but is preferably 5% by mass to 60% by mass relative to the total solid content of the photosensitive colored resin composition, and further Preferably, it exists in the range of 10 mass % - 40 mass %. If the content of the photopolymerizable compound is more than the above-mentioned lower limit, the photocuring will be sufficiently carried out, and the dissolution of the exposed part during development can be suppressed. full.

等。作為光起始劑之具體例，可例舉：二苯甲酮、4,4'-雙二乙基胺基二苯甲酮、4-甲氧基-4'-二甲基胺基二苯甲酮等芳香族酮類；安息香甲醚等安息香醚類；乙基安息香等安息香；2-(鄰氯苯基)-4,5-苯基咪唑二聚物等聯咪唑類；2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-㗁二唑等鹵甲基㗁二唑化合物；2-(4-丁氧基-萘甲醯-1-基)-4,6-雙-三氯甲基-對稱三𠯤等鹵甲基-對稱三𠯤系化合物；2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-N-嗎啉基丙酮、1,2-苄基-2-二甲基胺基-1-(4-N-嗎啉基苯基)-丁酮-，、1-羥基環己基苯基酮、苯偶醯、苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯硫醚、苯偶醯二甲基縮酮、二甲基胺基苯甲酸酯、對二甲基胺基苯甲酸異戊酯、2-正丁氧基乙基-4-二甲基胺基苯甲酸酯、2-氯9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二甲基-9-氧硫𠮿

、異丙基9-氧硫𠮿

、4-苯甲醯基-甲基二苯硫醚、1-羥基環己基苯基酮、2-苄基-2-(二甲基胺基)-1-[4-(4-嗎啉基)苯基]-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯基雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-(4-嗎啉基)-1-丙酮、1-(9,9-二丁基-9H-茀-2-基)-2-甲基-2-(4-嗎啉基)-1-丙酮等。 其中，可較佳地使用2-甲基-1-[4-(甲硫基)苯基]-2-N-嗎啉基丙烷-1-酮、2-苄基-2-(二甲基胺基)-1-(4-嗎啉基苯基)-1-丁酮、4,4'-雙(二乙基胺基)二苯甲酮、二乙基9-氧硫𠮿

。基於調整感度，抑制水斑，提昇顯影耐性之觀點而言，進而較佳為將2-甲基-1-[4-(甲硫基)苯基]-2-N-嗎啉基丙烷-1-酮之類的α-胺基苯乙酮系起始劑與二乙基9-氧硫𠮿

之類的9-氧硫𠮿

系起始劑加以組合。 關於使用α-胺基苯乙酮系起始劑及9-氧硫𠮿

系起始劑之情形時之該等之合計含量，相對於感光性著色樹脂組合物之固形物成分總量，例如較佳為5質量%～15質量%。若為上限值以下，則製造製程中之昇華物減少，因此較佳。若為下限值以上，則改善水斑等、顯影耐性。 [Photoinitiator] Examples of photoinitiators include aromatic ketones, benzoin ethers, halomethyldiazole compounds, α-aminoketones, biimidazoles, N,N-dimethyl Aminobenzophenones, halomethyl-symmetrical tri-series compounds, 9-oxothiophenones

wait. Specific examples of photoinitiators include: benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminodiphenyl Aromatic ketones such as ketone; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer; 2-trichloro Methyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyl oxadiazole compounds; 2-(4-butoxy-naphthyl-1-yl) -4,6-bis-trichloromethyl-symmetrical tristannium and other halomethyl-symmetrical tristannium compounds; 2,2-dimethoxy-1,2-diphenylethane-1-one, 2- Methyl-1-[4-(methylthio)phenyl]-2-N-morpholinoacetone, 1,2-benzyl-2-dimethylamino-1-(4-N-morpholine phenyl)-butanone-,, 1-hydroxycyclohexyl phenyl ketone, benzoyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyl di Phenylsulfide, benzoyldimethylketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylamine Benzoate, 2-Chloro-9-Oxothio𠮿

, 2,4-Diethyl 9-oxosulfur 𠮿

, 2,4-Dimethyl-9-oxosulfur 𠮿

, Isopropyl 9-oxosulfur

, 4-benzoyl-methyl diphenyl sulfide, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) )phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[ 4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 1-(9,9-dibutyl-9H-fluorene-2-yl)-2-methyl- 2-(4-morpholino)-1-propanone, etc. Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-N-morpholinopropan-1-one, 2-benzyl-2-(dimethyl Amino)-1-(4-morpholinylphenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, diethyl 9-oxothiophenone

. From the viewpoint of adjusting sensitivity, suppressing water spots, and improving developing resistance, it is more preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-N-morpholinopropane-1 α-Aminoacetophenone-based initiators such as -ketones and diethyl 9-oxosulfur

9-oxosulfur

Department of starter to be combined. Regarding the use of α-aminoacetophenone-based initiators and 9-oxosulfur

In the case of an initiator, the total content of these is preferably, for example, 5% by mass to 15% by mass relative to the total solid content of the photosensitive colored resin composition. If it is below the upper limit, since the sublimation in the manufacturing process will decrease, it is preferable. If it is more than the lower limit, water spots etc. and image development resistance will be improved.

In the present invention, the photoinitiator preferably includes an oxime ester-based photoinitiator from the viewpoint of improving sensitivity. In addition, by using an oxime ester-based photoinitiator, it is easy to suppress the variation in line width in a plane when forming a thin line pattern. Furthermore, the use of an oxime ester-based photoinitiator tends to increase the remaining film rate and increase the effect of suppressing the occurrence of water spots. As the oxime ester-based photoinitiator, from the viewpoint of reducing pollution of the photosensitive colored resin composition or equipment pollution caused by decomposition products, those having an aromatic ring are preferred, and those containing an aromatic ring are more preferred. The one having a condensed ring is more preferably one having a condensed ring including a benzene ring and a heterocycle. As an oxime ester photoinitiator, it can be obtained from 1,2-octanedione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Properly select from the oxime ester-based photoinitiators described in JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, and JP-A-2013-041153. As commercially available products, Irgacure OXE-01, Adeka Arkles NCI-930, and TR-PBG-3057 having a diphenylsulfide skeleton; Irgacure OXE-02, Adeka Arkles NCI-831, and TR-PBG having a carbazole skeleton can be used. -304, TR-PBG-345; TR-PBG-365 with a fenugreek skeleton, etc. (Irgacure series are manufactured by BASF, Adeka Arkles series are manufactured by ADEKA, TR series are manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.). From the viewpoint of brightness, it is particularly preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a terpene skeleton. Also, from the viewpoint of high sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton. From the viewpoint of sensitivity and brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton and an oxime ester-based photoinitiator having a terpene skeleton in combination. Moreover, it is preferable to use together the oxime ester type photoinitiator which has a diphenyl sulfide skeleton, and the oxime ester type photoinitiator which has a carbazole skeleton from a viewpoint of sensitivity and brightness.

系起始劑，基於提昇亮度、殘膜率，容易調整感度，水斑產生抑制效果較高，提昇顯影耐性之觀點而言，可將2種以上之肟酯系光起始劑與9-氧硫𠮿

系起始劑加以組合。 Also, from the viewpoint of suppressing water spots and improving sensitivity, an oxime ester-based photoinitiator can be used in combination with a photoinitiator having a tertiary amine structure. The reason is that the photoinitiator with a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, so the free radicals generated from the initiator are not easily inactivated by oxygen, and the sensitivity can be improved. As a commercially available photoinitiator having the above-mentioned tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-N-morpholinopropane-1- Ketone (such as Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-N-morpholinophenyl)-1-butanone (such as Irgacure 369, manufactured by BASF manufactured by the company), 4,4'-bis(diethylamino)benzophenone (for example, Hicure ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like. In addition, based on the viewpoint of adjusting sensitivity, suppressing water spots, and improving developing resistance, the oxime ester-based photoinitiator can be combined with 9-oxosulfur

It is an initiator, based on the viewpoint of improving brightness, residual film rate, easy adjustment of sensitivity, high water spot suppression effect, and improving development resistance, two or more oxime ester photoinitiators can be combined with 9-oxo sulfur

Department of starter to be combined.

The content of the photoinitiator in the photosensitive colored resin composition is preferably, for example, 0.1% by mass to 15% by mass, more preferably 1% by mass to 10% by mass relative to the total solid content of the photosensitive colored resin composition. % range. When the content of the photoinitiator is more than the above-mentioned lower limit, curing will proceed sufficiently, and if the content of the photo-initiator is below the above-mentioned upper limit, side reactions can be suppressed and stability over time can be maintained.

[solvent] The solvent used in the present invention is not particularly limited as long as it is an organic solvent that can dissolve or disperse the components in the photosensitive colored resin composition without reacting. A solvent can be used individually or in combination of 2 or more types. As specific examples of solvents, for example, alcohol-based solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; Carbitol-based 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 Butyl, 3-methoxybutyl acetate, ethoxyethyl acetate and other glycol ether acetate solvents; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol acetate-based 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, dipropylene glycol dimethyl ether, etc. ; Aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.; Lactone-based solvents such as γ-butyrolactone; Tetrahydrofuran Cyclic ether solvents; benzene, toluene, xylene, naphthalene and other unsaturated hydrocarbon solvents; N-heptane, N-hexane, N-octane and other saturated hydrocarbon solvents; toluene, xylene and other aromatic hydrocarbons and other organic solvents. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are suitably used from the viewpoint of the solubility of other components. 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 from the viewpoint of solubility of other components and coating adaptability. Among the group consisting of acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate 1 or more.

In the present invention, since the acidic group-containing pigment derivative is contained, it is preferable to contain an alcoholic hydroxyl group-containing solvent as a solvent from the viewpoint of improving the solubility of the entire composition, suppressing the precipitation of foreign matter in the coating film, and improving the contrast. . As a solvent containing an alcoholic hydroxyl group, it is preferably an alkylene glycol monoalkyl ether, for example, it is preferably selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether. At least one of the group consisting of methyl ethers, among which propylene glycol monomethyl ether is more preferred. Among them, it is preferable to contain at least one of glycol ether acetate solvents, carbitol acetate solvents, and ester solvents, and at least one of alcoholic hydroxyl-containing solvents, and it is more preferable to contain two solvents. At least one kind of alcohol ether acetate-based solvent, and at least one kind of alcoholic hydroxyl group-containing solvent. The content of the alcoholic hydroxyl group-containing solvent may be within a range of preferably 15% by mass to 35% by mass, more preferably more than 20% by mass and 30% by mass or less with respect to the total amount of solvents.

In the photosensitive colored resin composition of this invention, content of a solvent can be set suitably within the range which can form a colored layer with high precision. The content of the solvent is usually preferably within a range of 55% by mass to 95% by mass, more preferably within a range of 65% by mass to 88% by mass, relative to the total amount of the photosensitive colored resin composition containing the solvent. By making content of the said solvent into the said range, applicability can be made excellent.

[optional ingredients added] In the photosensitive colored resin composition, various additives may be included as needed. Examples of additives include dispersants, sensitizers, antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoter etc. As a specific example of a surfactant and a plasticizer, what was described in Unexamined-Japanese-Patent No. 2013-029832 is mentioned, for example.

＜Dispersant＞ In the photosensitive colored resin composition of the present invention, when dispersing a color material, a dispersant may be further included from the viewpoint of color material dispersibility and color material dispersion stability. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants and used. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, polysiloxane, and fluorine can be used. Among the surfactants, polymer dispersants are preferred from the viewpoint of being able to disperse uniformly and finely.

Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; ) ammonium salts or (partial) alkylamine salts; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or their modified products; polyurethanes; unsaturated polyacrylates Amides; Polysiloxanes; Long-chain polyaminoamide phosphates; Polyethyleneimine derivatives (formed by reaction of poly(lower alkyleneimine) with free carboxyl-containing polyesters) obtained amides or bases thereof); polyallylamine derivatives (polyallylamine, polyamides selected from polyesters having free carboxyl groups, polyamides or cocondensates of esters and amides (polyesteramides) A reaction product obtained by reacting one or more compounds among three compounds), etc.

In the present invention, since the above-mentioned pigment derivatives containing sulfonic acid groups are included, as the polymer dispersant, for example, a polymer dispersant that contains nitrogen atoms in the main chain or side chain and has an amine value can be used. Among them, it can include Polymer dispersant containing polymers with repeating units of tertiary amines. In the present invention, since the above-mentioned sulfonic acid group-containing pigment derivatives are included, when the polymer dispersant containing nitrogen atoms in the main chain or the side chain and having an amine value is included, the coagulation agent is added to the coagulation waste liquid When the above-mentioned phthalocyanine compound aggregates more easily, it is easy to recover the color material from the developing waste liquid. As a polymer dispersant that contains nitrogen atoms in the main chain or side chain and has an amine value, based on the viewpoint that the main chain skeleton is not easily thermally decomposed and has high heat resistance, for example, the following dispersants can be used, such as Japan A polymer having a structural unit represented by the following general formula (I) described in Japanese Patent Laid-Open No. 2016-224447, or a polymer represented by the following general formula (I) as described in International Publication No. 2016/104493 At least one of a block copolymer and a salt-type block copolymer of structural units.

(通式(I)中，R ¹表示氫原子或甲基，A表示二價連結基，R ²及R ³分別獨立地表示氫原子、或可包含雜原子之烴基，R ²及R ³可相互鍵結而形成環結構) [chemical 8]

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ independently represent a hydrogen atom or a hydrocarbon group that may contain heteroatoms, R ² and R ³ may bonded to each other to form a ring structure)

In the general formula (I), A 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 arylylene group, -CONH- group, - COO-group, -NHCOO-group, ether group (-O-group), thioether group (-S-group), 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 includes -CONH-, -CO may be located on the carbon atom side of the main chain and -NH may be located on the nitrogen atom side of the side chain, and vice versa, -NH may be located on the carbon atom side of the main chain and -CO is located on the nitrogen atom side of the side chain. Among them, based on the viewpoint of dispersibility, A in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group and a divalent linking group of an alkylene group having 1 to 10 carbon atoms.

The hydrocarbon group in the hydrocarbon group that may contain heteroatoms in R ² and R ³ may, for example, be an alkyl group, an aralkyl group, an aryl group, or the like. As the alkyl group, for example, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc., the carbon number of the alkyl group is relatively small. Preferably it is 1-18, and among them, methyl or ethyl is more preferable. As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group etc. are mentioned, for example. The carbon number of an aralkyl group becomes like this. Preferably it is 7-20, More preferably, it is 7-14. Moreover, as an aryl group, a phenyl group, a biphenylyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. The carbon number of the aryl group is preferably 6-24, more preferably 6-12. Furthermore, the above preferred carbon number does not include the carbon number of the substituent. The heteroatom-containing hydrocarbon group has a structure in which carbon atoms in the above-mentioned hydrocarbon group are replaced by heteroatoms, or has a structure in which hydrogen atoms in the above-mentioned hydrocarbon group are replaced by substituents containing heteroatoms. Examples of heteroatoms that may be included in the hydrocarbon group include oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms. Moreover, the hydrogen atom in the hydrocarbon group may be substituted by a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

The fact that R ² and R ³ are bonded to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. The ring structure formed by R ² and R ³ 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 preferred that R ² and R ³ are independently hydrogen atoms, alkyl groups with 1 to 5 carbons, or phenyl groups, or that R ² and R ³ are bonded to form a pyrrolidine ring or a piperidine ring. , Morpholine ring.

As the monomer for deriving the structural unit represented by the above-mentioned general formula (I), for example: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, (methyl) ) Diethylaminoethyl acrylate, diethylaminopropyl (meth)acrylate and other (meth)acrylates containing alkyl-substituted amino groups; dimethylaminoethyl (meth)propylene Amide, dimethylaminopropyl (meth)acrylamide and other (meth)acrylamides containing alkyl-substituted amino groups, etc. Among them, from the viewpoint of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethyl Aminopropyl (meth)acrylamide. In a polymer, the structural unit represented by general formula (I) may contain 1 type, and may contain 2 or more types of structural units.

Also, regarding the structural unit functioning as a color material adsorption site, at least a part of the nitrogen site contained in the structural unit represented by the above general formula (I) and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons can be used. One type forms a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer). As the above-mentioned organic acid compound, preferably the compound represented by the following general formula (A) and the compound represented by the following general formula (C), as the above-mentioned halogenated hydrocarbon, which is preferably the following general formula (B ) represented by 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 selected from the group consisting of the following general formulas (A), (B) and (C). One or more compounds.

(於通式(A)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(B)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(C)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) [chemical 9]

(In the general formula (A), R ^a represents a straight-chain, branched or cyclic alkyl, vinyl, phenyl or benzyl that may have substituents or -OR ^e with 1 to 20 carbon atoms, and R ^e represents Straight chain, branched or cyclic alkyl, vinyl, phenyl or benzyl with 1 to 20 carbons, or (meth)acryloyl through alkylene with 1 to 4 carbons In the general formula (B), R ^b , R ^{b '} , and R ^{b ”} each independently represent a hydrogen atom, an acidic group or its ester group, and a straight chain or branched chain with 1 to 20 carbon atoms that may have substituents. or a cyclic alkyl group, a vinyl group that may have a substituent, a phenyl or benzyl group that may have a substituent, or -OR ^f , where R ^f represents a straight chain, branched chain or ring with 1 to 20 carbon atoms that may have a substituent An alkyl group, a vinyl group that may have a substituent, a phenyl or benzyl group that may have a substituent, or a (meth)acryl group via an alkylene group with 1 to 4 carbon atoms, X represents a chlorine atom or a bromine atom or an iodine atom. In the general formula (C), R ^c and R ^d independently represent a hydrogen atom, a hydroxyl group, a straight-chain, branched or cyclic alkyl group, vinyl group, or a substituent phenyl or benzyl or -OR ^e , R ^e represents straight chain, branched or cyclic alkyl, vinyl, phenyl or benzyl which may have substituents, or through carbon number 1 ~4 alkylene (meth)acryloyl groups. Wherein, at least one of R ^c and R ^d contains carbon atoms)

The respective symbols of the above-mentioned general formulas (A), (B) and (C) may be the same as the respective symbols of the general formulas (1), (2) and (3) of International Publication No. 2016/104493. From the viewpoint of excellent dispersibility and dispersion stability of the coloring material, it is preferable that the organic acid compound is an acidic organophosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. As a specific example of the organic acid compound used for such a dispersant, the organic acid compound described in Unexamined-Japanese-Patent No. 2012-236882 etc. is suitably mentioned, for example. In addition, the halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride, and halogenated aralkyl groups from the viewpoint of excellent dispersibility and dispersion stability of the coloring material. .

The content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons in the salt-type copolymer is based on the viewpoint of forming a salt with the terminal nitrogen site of the structural unit represented by the general formula (I). In other words, the total amount of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is preferably 0.01 mole or more relative to the terminal nitrogen site of the structural unit represented by the general formula (I), and more preferably It is preferably at least 0.05 mol, more preferably at least 0.1 mol, and most preferably at least 0.2 mol. When it is more than the said lower limit, the effect of improving color material dispersibility by forming a salt is easy to be acquired. Likewise, it is preferably at most 1 mole, more preferably at most 0.8 mole, still more preferably at most 0.7 mole, and especially preferably at most 0.6 mole. When it is below the said upper limit, image development adhesiveness and solvent re-dissolution property can be made excellent. In addition, at least 1 type selected from the group which consists of an organic acid compound and a halogenated hydrocarbon may be used individually by 1 type, and may combine 2 or more types. When combining 2 or more types, it is preferable that the total content exists in the said range.

As a method for preparing a salt-type copolymer, a method such as adding a compound selected from the group consisting of the above-mentioned organic acid compound and halogenated hydrocarbon to a solvent in which the copolymer before forming a salt is dissolved or dispersed is exemplified. At least 1 type is stirred, and it heats further as needed. In addition, 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 compound and halogenated hydrocarbon, and the ratio thereof For example, it can be confirmed by known methods such as NMR (nuclear magnetic resonance, nuclear magnetic resonance).

Based on the viewpoint of dispersibility and dispersion stability, the copolymer having the structural unit represented by the above-mentioned general formula (I) is more preferably at least one of a graft copolymer and a block copolymer, and the above-mentioned graft copolymer has The structural unit represented by the above-mentioned general formula (I) has a structural unit derived from (meth)acrylate on the graft polymer chain, and the above-mentioned block copolymer has a structural unit comprising the structural unit represented by the above-mentioned general formula (I). A block, and a B block containing a structural unit derived from (meth)acrylate. In the above-mentioned graft copolymer, as the graft polymer chain having a structural unit derived from (meth)acrylate, a conventionally known structure can be appropriately selected and used. For example, at least one of graft copolymers and salt-type graft copolymers described in International Publication No. 2021/006077 can be used. In addition, in the above-mentioned block copolymer, as the B block containing the structural unit derived from (meth)acrylate, a conventionally known structure can be selected suitably and used. For example, at least one of block copolymers and salt-type block copolymers described in International Publication No. 2016/104493 can be used.

From the point of view that the substrate adhesiveness and solvent resistance of the cured film become good even if it is heat-treated at a low temperature, and from the point of view of suppressing the generation of development residue, it is preferable to contain the following block copolymer and salt-type block copolymer At least one of the above-mentioned block copolymers and salt-type block copolymers has an acid value of 1 mgKOH/g to 18 mgKOH/g, a glass transition temperature of 30°C or higher, and the above-mentioned block copolymers are A block containing a structural unit represented by the above general formula (I) in a block copolymer used as a dispersant and a structural unit derived from a carboxyl group-containing monomer and a structure derived from (meth)acrylate The block copolymer of the B block of the unit, the above-mentioned salt-type block copolymer is at least a part of the nitrogen site of the structural unit represented by the above-mentioned general formula (I) of the corresponding block copolymer and selected from organic acid compounds and A salt-type block copolymer in which at least one member of the group consisting of halogenated hydrocarbons forms a salt. The B block in this case contains a (meth)acrylate-derived structural unit as an essential component, but may be the same as the B block of International Publication No. 2016/104493.

Based on the viewpoint of good dispersibility, no precipitation of foreign matter when forming a coating film, and improvement of brightness and contrast, the copolymer having the structural unit represented by the above general formula (I) preferably has an amine value of 40 mgKOH/g to 120 mgKOH /g. When the amine value is within the above range, the temporal stability of the viscosity and the heat resistance are excellent, and also the alkali developability and solvent resolubility are excellent. In the present invention, the amine value of the copolymer having the structural unit represented by the above general formula (I) is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. On the other hand, the amine value of the copolymer having the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less, from the viewpoint of solvent resolubility. The amine value refers to the number of mg of potassium hydroxide equivalent to the amount of perchloric acid 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 an organic acid compound in a dispersant, the organic acid compound usually dissociates, so the property of the block copolymer itself used as a dispersant can be measured. Amine value.

The content ratio (mole %) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials added at the time of production, and can be measured using an analysis device such as NMR. Moreover, the structure of a dispersing agent can be measured using NMR, various mass spectrometry, etc. Also, if necessary, the dispersant can be decomposed by thermal decomposition or the like, and the obtained decomposed products are subjected to 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 electron spectroscopy) and TOF-SIMS (time of flight secondary ion mass spectrometry, time of flight secondary ion mass spectrometry), etc.

In the photosensitive colored resin composition of the present invention, when using a dispersant, the content of the dispersant is not particularly limited, as long as the dispersibility and dispersion stability of the color material are selected to be excellent, but relative to the photosensitive colored resin The total amount of solids in the composition is, for example, preferably within a range of 2% by mass to 30% by mass, more preferably within a range of 3% by mass to 25% by mass. If it is more than the said lower limit, it will be excellent in the dispersibility and dispersion stability of a color material, and the storage stability of a photosensitive colored resin composition will be more excellent. Moreover, developability will become favorable as it is below the said upper limit. Especially in the case of forming a cured film with a high concentration of coloring material, the content of the dispersant relative to the total solid content of the photosensitive colored resin composition is, for example, preferably 2% by mass to 25% by mass, more preferably Within the range of 3% by mass to 20% by mass.

＜Sensitizer＞ In the present invention, since the phthalocyanine compound represented by the above general formula (1) diffused into the system easily absorbs the light of exposure, the free radicals generated from the initiator are lost, so from the viewpoint of making up for the above-mentioned situation , it is preferable to include a sensitizer in combination with the above-mentioned photoinitiator. Among them, from the viewpoint of good reactivity of the (meth)acrylic acid polymerization system, it is preferable to include a thiol-based sensitizer, and it is more preferable to include a thiol-based sensitizer in combination with the above-mentioned oxime ester-based initiator. .

Examples of the thiol-based sensitizer include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. Examples of monofunctional thiol compounds include: 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, and the like. Examples of polyfunctional thiol compounds include: 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3 ,5-tris-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate), etc.

In the photosensitive colored resin composition of the present invention, when the sensitizer is included, the content of the sensitizer is relative to the total amount of solid content of the photosensitive colored resin composition from the viewpoint of the curability improvement effect , For example, 0.5% by mass to 10% by mass can be used. When the sensitizer is included, the content of the sensitizer is more preferably 1% by mass to 6% by mass, more preferably 2% by mass to 5% by mass, based on the total solid content of the photosensitive colored resin composition % range.

＜Antioxidant＞ It is preferable that the photosensitive colored resin composition of this invention further contains an antioxidant from a viewpoint of suppressing a line width deviation. The photosensitive colored resin composition of the present invention contains an antioxidant in combination with the above-mentioned specific photoinitiator, and can control excessive free radical chain reaction without impairing curability when forming a cured film. Therefore, when forming a thin line pattern, The linearity is further improved, or the ability to form thin line patterns according to the design of the mask line width is improved. In addition, heat resistance can be improved, and brightness reduction after exposure and post-baking can be suppressed, so that brightness can be improved. The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from previously known ones. Specific examples of antioxidants include, for example, hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Fine line patterns are formed based on the design of masked line widths. From the viewpoint of improving the ability of the antioxidant and the viewpoint of heat resistance, it is preferable to use a hindered phenolic antioxidant. It can also be a potential antioxidant as described in International Publication No. 2014/021023.

As a hindered phenolic antioxidant, for example, pentaerythritol tetrakis [3-(3,5 di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX 1010, BASF Corporation manufactured), 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 phenylphenol) (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, pentaerythritol tetrakis [3-(3,5 di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX 1010, manufactured by BASF Corporation).

The content of the antioxidant is preferably within a range of 0.1% by mass to 10.0% by mass, more preferably within a range of 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive colored resin composition. If it is more than the said lower limit, the ability to form a thin line pattern according to the design of a mask line width improves, and it is excellent in heat resistance. On the other hand, if it is below the said upper limit, the photosensitive colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.

<Manufacturing method of photosensitive colored resin composition> In the method for producing the photosensitive colored resin composition of the present invention, the coloring material, sulfonic acid group-containing pigment derivative, alkali-soluble resin, photopolymerizable compound, photoinitiator, solvent, and visual Prepared by mixing the various additives required. As the preparation method of the resin composition, for example, the following methods can be exemplified: (1) First, add a color material, a sulfonic acid group-containing pigment derivative, and a dispersant if necessary to prepare a color material liquid in a solvent, Mix alkali-soluble resin, photopolymerizable compound, photoinitiator, and various additive components as needed in the color material liquid; (2) Add color material, sulfonic acid group-containing pigment derivatives, Optional dispersant, alkali-soluble resin, photopolymerizable compound, photoinitiator, and various additive components used as needed and mixed; (3) Add alkali-soluble resin, photopolymerizable compound, photostarter After mixing the starter, and various additional ingredients used if necessary, then add the color material and the pigment derivative containing sulfonic acid group and mix them; (4) Add the color material and the pigment derivative containing sulfonic acid group to the solvent The color material liquid is prepared by using a dispersant, an alkali-soluble resin if necessary, and an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additional components as needed are added to the color material liquid. to mix.

II. Color filter The color filter of the present invention includes 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 of the present invention.

Such a 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 , a color filter 10 of the present invention has a substrate 1 , a light shielding portion 2 and a colored layer 3 .

(shading 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 described above. The colored layer is usually formed in the opening of the light-shielding portion on the substrate described below, and usually includes colored patterns of three or more colors. Also, the arrangement of the colored layers is not particularly limited, and general arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type can be used, for example. In addition, the width, area, etc. of the colored layer can be set arbitrarily. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the photosensitive colored resin composition, etc., and is usually preferably in the range of 1-5 μm.

The said colored layer can be formed by the following method, for example. First, the above-mentioned photosensitive colored resin composition of the present invention is coated using a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, or die coating. Spread on the following substrate to form a wet coating film. Among them, a spin coating method and a die coating method can be suitably used. Then, after heating and drying the wet coating film using a heating plate or an oven, it is exposed through a mask with a specific pattern, and the alkali-soluble resin and photopolymerizable compound are photopolymerized to form a hardened coating. membrane. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, an electron beam, etc. are mentioned, for example. The exposure amount is properly adjusted according to the light source used or the thickness of the coating film. In addition, heat treatment may be performed after exposure to accelerate the polymerization reaction. The heating conditions are appropriately selected according to the compounding ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

Next, a developing treatment is performed using a developer to dissolve and remove unexposed parts, thereby forming a coating film in a desired pattern. As a developing solution, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. A suitable amount of surfactant and the like can be added to the alkaline solution. Also, as a developing method, a general method can be used. After the development treatment, the developing solution is usually washed away, 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 sufficiently harden the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film. The colored layer may be a colored layer of a fine pattern with a line width of 40 μm or less, or a colored layer of a fine pattern with a line width of 20 μm or less.

(shading part) The light-shielding portion in the color filter of the present invention is patterned on the substrate described below, and may be the same as that used as the light-shielding portion in a general color filter. It does not specifically limit as a pattern shape of this light shielding part, For example, shapes, such as a stripe shape and a matrix shape, are mentioned. The light-shielding portion may be a metal thin film of chromium or the like formed by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, and organic pigments in a resin binder. 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 an inkjet ink containing light-shielding particles; The method of thermal transfer printing of resist, etc.

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

(substrate) As the substrate, the following transparent substrates; silicon substrates; and those in which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the transparent substrate or silicon substrate can be used. On these substrates, other color filter layers, resin layers, transistors such as TFT (thin-film transistor, thin-film transistor), 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 transparent to visible light, and a transparent substrate used in general color filters can be used. Specifically, examples include: non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates; or flexible transparent materials such as transparent resin films, optical resin plates, and flexible glass. 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 colored layer, the color filter of the present invention may also be formed with an overcoat layer or a transparent electrode layer, and further be provided with an alignment film, alignment protrusions, and columnar spacers.

(Treatment of developing waste liquid in the manufacture of color filters) As mentioned above, when forming the pattern of a colored layer, after exposing the coating film of the photosensitive colored resin composition, it develops using a developing solution, and unexposed part is dissolved and removed. As a developing solution, an alkaline aqueous solution obtained by dissolving an alkali such as potassium hydroxide in an amount of about 0.02 to 0.5% by mass in water or a water-soluble solvent is usually used. The components of the photosensitive colored resin composition of the unexposed part are contained in the waste liquid of the developing liquid (development waste liquid) produced|generated by this process. Therefore, a coagulant is usually added to the developing waste liquid to coagulate the components of the photosensitive colored resin composition containing the coloring material, and the coagulated matter is collected by filtration, etc., the filtrate is neutralized, and the pH-adjusted water is discharged. . Conventionally, the developing waste liquid containing phthalocyanine dye has the following problems: even if a coagulant is added, it cannot be coagulated sufficiently, and the filtrate after recovering the coagulant is colored in the color of phthalocyanine dye. On the other hand, if the photosensitive colored resin composition of this invention is used, the filtrate after throwing in a flocculant and recovering an aggregate can contain no dye, and will not be colored. The coagulant is not particularly limited as long as it is a coagulant that can be generally used when treating waste developing liquid in a color filter factory. As the coagulant, for example, a cationic inorganic coagulant such as polyaluminum chloride or an anionic polymer coagulant such as polyacrylamide can be used. For example, a cationic inorganic coagulant such as polyaluminum chloride can also be used to coagulate the developing waste liquid, and after neutralizing the negative charges repelled by the colloidal surface existing in the waste liquid, the aggregate can be formed by an anionic polymer coagulant. Cross-linking and coarsening make the aggregates precipitate. For the filtrate after recovering the condensate, check whether there is any coloring or foreign matter. Specifically, for example, the presence or absence of components derived from the photosensitive colored resin composition remaining in the filtrate is confirmed using a liquid chromatography mass spectrometer. As the neutralizing agent for neutralizing the filtrate after recovering the condensate, for example, acid such as dilute hydrochloric acid can be used.

III. Display device A display device of the present invention is characterized by comprising the above-mentioned color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from previously known display devices, for example, a liquid crystal display device or an organic light-emitting display device.

[Liquid crystal display device] The liquid crystal display device of the present invention includes the above-mentioned color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the above-mentioned color filter and the above-mentioned target substrate. Such a 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 a 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 substrate 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 configuration shown in FIG. 2 , and a known configuration for a liquid crystal display device generally using a color filter can be employed.

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 used. As such a driving method, for example, a TN (Twisted Nematic) method, an IPS (in-plane switching, transverse electric field effect) method, an OCB (optically compensated bend) method, and an MVA (Multi -Domain Vertical Alignment, multi-domain vertical alignment) method, etc. In the present invention, any of these forms 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 and the like. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention and the like.

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

[Organic Light Emitting Display Device] The organic light-emitting display device of the present invention has the above-mentioned color filter of the present invention and an organic luminescent body. 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 an 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 . Between the color filter 10 and the organic light emitting body 80 , there may be an organic protection layer 50 or an inorganic oxide film 60 .

As a lamination method of the organic luminescent body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode are sequentially formed on the upper surface of a color filter. 76; or a method of attaching the organic luminescent body 80 formed on another substrate to the inorganic oxide film 60, etc. The transparent anode 71 , hole injection layer 72 , hole transport layer 73 , light emitting layer 74 , electron injection layer 75 , cathode 76 and other components in the organic luminescent body 80 can appropriately use known ones. The organic light emitting display device 100 fabricated in this way can be applied to, for example, a passively driven organic EL display, and can also be applied to an actively driven organic EL display. Furthermore, the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3 , and a known configuration for an organic light emitting display device generally using a color filter can be employed. [Example]

Hereinafter, an Example is shown and this invention is demonstrated concretely. The present invention is not limited by these descriptions. The intermediates of the halogenated phthalocyanine compounds were analyzed by LC-MS (liquid chromatography-mass spectrometry) (manufactured by Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity). Pigment derivatives such as sulfonic acid group-containing pigment derivatives and halogenated phthalocyanine compounds were analyzed by TOF-MS (Time of Flight Mass Spectrometer) (manufactured by Shimadzu Corporation, MALDI-8020).

(Synthesis Example 1: Synthesis of Phthalocyanine Compound 1) Put 5.0 g (25.0 mmol) of tetrafluorophthalonitrile, 6.91 g (50 mmol) of potassium carbonate, and 25 ml of acetone into a 500 ml eggplant-shaped flask, and stir at room temperature until dissolved. Then, 8.31 g (50.0 mmol) of ethyl 4-hydroxybenzoate dissolved in 25 ml of acetone was put into the previous eggplant-shaped flask using a dropping funnel for 1 hour, and stirred in an ice bath, and then After stirring for 1 hour. After the reaction was completed, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off with an evaporator to remove the solvent, and the obtained oily product was dissolved in dichloromethane, and liquid separation was performed with pure water. . The organic layer after liquid separation was recrystallized in isopropanol to obtain Intermediate 1. Intermediate 1 was analyzed by LC-MS, and it had the following structure. A representative chemical structural formula of Intermediate 1 is shown below.

[Chem. 10] Intermediate 1

Put 15.00 g (10.15 mmol) of the intermediate and 15.0 ml of benzonitrile into a 50 ml flask, dissolve at about 100°C, then add 0.97 g (3.05 mmol) of zinc iodide, and react while stirring at 140°C 15 hours. After cooling the reaction solution to room temperature, add the reaction solution dropwise to 150 ml of methanol, stir the resulting precipitate for 30 minutes, then use filter paper to recover it, use methanol to repeatedly stir and filter in the beaker and wash it . The obtained product was dried to obtain a halogenated phthalocyanine compound 1 . A representative chemical structural formula of the halogenated phthalocyanine compound 1 is shown below.

[chemical 11]

(Synthesis Example 2: Synthesis of Phthalocyanine Compound 2) Put 5.0 g (25.0 mmol) of tetrafluorophthalonitrile, 6.91 g (50 mmol) of potassium carbonate and 25 ml of acetone into a 500 ml eggplant-shaped flask, and stir at room temperature until dissolved. Then, 9.01 g (50.0 mmol) of n-propyl 4-hydroxybenzoate dissolved in 25 ml of acetone was dropped into the previous eggplant-shaped flask using a dropping funnel for 1 hour, and stirred in an ice bath. Stir for 1 hour after adding. After the reaction was completed, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off with an evaporator to remove the solvent, and the obtained oily product was dissolved in dichloromethane, and liquid separation was performed with pure water. . The organic layer after liquid separation was recrystallized in isopropanol to obtain Intermediate 2. Intermediate 2 was analyzed by LC-MS (manufactured by Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity), and as a result, it had the following structure. Furthermore, the representative chemical structural formula of the intermediate 2 is shown below.

[Chem. 12] Intermediate 2

Put 5.28 g (10.15 mmol) of intermediate 2 and 15.0 ml of benzonitrile into a 50 ml flask, dissolve at about 100°C, then add 0.97 g (3.05 mmol) of zinc iodide, and react while stirring at 140°C 15 hours. After cooling the reaction solution to room temperature, add the reaction solution dropwise to 150 ml of methanol, stir the resulting precipitate for 30 minutes, then use filter paper to recover it, use methanol to repeatedly stir and filter in the beaker and wash it . The obtained product was dried to obtain a halogenated phthalocyanine compound 2. Representative chemical structural formulas are shown below.

[chemical 13]

(Synthesis Example 3: Synthesis of Pigment Derivative A Containing Sulfonic Acid Group) After adding 10.0 parts by weight of copper phthalocyanine to 266.7 parts by weight of 100% sulfuric acid, it was stirred at 100° C. for 2 hours. After cooling to room temperature, the reaction liquid was added to 800 parts by weight of ice water, and the precipitate was filtered off. Then, it was washed twice with 800 parts by weight of water, and vacuum-dried at 80° C. to obtain a blue product. The mass analysis result of the blue product (pigment derivative A containing sulfonic acid group) obtained by TOF-MS is consistent with the molecular weight (Mw=656.14) of the monosulfonic acid derivative of copper phthalocyanine having the following structure.

[chemical 14]

(Synthesis Example 4: Synthesis of Pigment Derivative B Containing Sulfonic Acid Group) 374.76 parts by mass of 11 mass % oleum was stirred while being cooled to 10°C, and 74.96 parts by mass of C.I. Pigment Yellow 138 (PY138) was added. Then, it stirred at 90 degreeC for 6 hours. After adding the reaction liquid to 1600 parts by mass of ice water and stirring for 15 minutes, the precipitate was filtered off. The obtained wet filter cake was washed 3 times with 800 ml of water. The wet filter cake was vacuum-dried at 80° C. to obtain 81.55 parts by mass of a yellow product. The mass analysis result of the yellow product (pigment derivative B containing sulfonic acid group) obtained by TOF-MS is consistent with the molecular weight (Mw=774.0) of the monosulfonic acid derivative of PY138 having the following structure.

[chemical 15]

(Synthesis Example 5: Synthesis of Pigment Derivative C Containing Sulfonic Acid Group) Commercially available C.I. Pigment Red 254 (PR254) was added to 300 parts by mass of 20% oleum, 30 parts by mass, and reacted at 40° C. for 4 hours. After cooling, the reaction mixture was precipitated in 3,000 parts by mass of ice water, filtered and washed with water to obtain a water slurry. 26 parts by mass of a red product were obtained by drying the aqueous slurry. The mass analysis result of the red product (pigment derivative C containing sulfonic acid group) obtained by TOF-MS is consistent with the molecular weight (Mw=437.25) of the monosulfonic acid derivative of PR254 having the following structure.

[chemical 16]

(Synthesis Example 6: Synthesis of Pigment Derivative D Containing Sulfonamide Group) After adding 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine to the reaction container and completely dissolving them, 24 parts by mass of thionyl chloride was added, and the temperature was raised slowly to react at 101° C. for 3 hours. After injecting this reaction liquid into 9000 mass parts of ice waters and stirring, it filtered and washed with water. After the obtained press cake was made into a slurry with 300 parts by mass of water, 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, stirred at 65°C for 4 hours, and then Filter, wash with water, and dry to obtain a blue product. The mass analysis result of the blue product (pigment derivative D containing sulfonamide group) by TOF-MS is consistent with the molecular weight (Mw=768.35) of the sulfonamide derivative of copper phthalocyanine having the following structure.

[chemical 17]

(Synthesis Example 7: Synthesis of Alkali-Soluble Resin A Solution) Mix 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 3 parts by mass of azobisisobutyronitrile (AIBN) The liquid was dripped at 100° C. for 3 hours under a nitrogen stream into a polymerization tank charged with 150 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). After completion of the dropwise addition, it was further heated at 100° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7000. Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heated at 110° C. for 10 hours. This reacts the carboxylic acid groups of the main chain methacrylic acid with the epoxy groups of glycidyl methacrylate. During the reaction, air was blown through the reaction solution in order to prevent the polymerization of glycidyl methacrylate. Again, the reaction was followed by measuring the acid value of the solution. The obtained alkali-soluble resin A is a resin formed by using GMA to introduce a side chain having an ethylenic double bond into the main chain formed by the copolymerization of BzMA, MMA, and MAA. The acid value is 74 mgKOH/g, and the weight The average molecular weight is 12000. The solid content of the alkali-soluble resin A solution was 40% by mass.

(Example 1) (1) Manufacture of color material solution G1 As a dispersant, a dispersant b (salt type block copolymer) solution (solid matter) was prepared in the same manner as the preparation of dispersant b in Synthesis Example II-2 described in paragraph 0302 of International Publication No. 2016/104493. Ingredient 40% by mass). 8.13 parts by mass of the above-mentioned dispersant b solution as a dispersant, 11.96 parts by mass of a halogenated phthalocyanine compound as a coloring material, 1.04 parts by mass of a pigment derivative A containing a sulfonic acid group, and the alkali-soluble resin obtained in Synthesis Example 7 14.63 parts by mass of solution A, 64.25 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm were added to a mayonnaise bottle as pre-crushed, and vibrated by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 Hours, then take out the zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, similarly crush them, and disperse them with a paint shaker for 4 hours to obtain color material solution G1.

(2) Production of Photosensitive Colored Resin Composition G1 Add 43.43 parts by mass of the color material liquid G1 obtained in (1), 4.23 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 7, and a multifunctional monomer (trade name ARONIX M-403, Toya Gosei Co., Ltd.) Made by the company) 3.95 parts by mass, photoinitiator 1 (trade name TR-PBG-3057, manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 0.50 parts by mass, photoinitiator 2 (trade name Adeka Arkles NCI-831, manufactured by ADEKA company ) 0.50 parts by mass, sensitizer (pentaerythritol tetrakis (3-mercaptobutyrate), trade name Karenz MT-PE1, manufactured by Showa Denko) 0.13 parts by mass, fluorine-based surfactant (trade name MEGAFAC F559, DIC (stock) 0.03 parts by mass, 0.34 parts by mass of a silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones), 26.24 parts by mass of PGMEA, and 20.65 parts by mass of propylene glycol monomethyl ether (PGME), to obtain photosensitive colored resin composition G1.

(3) Formation of colored layer Using a spin coater, apply the photosensitive colored resin composition G1 obtained in (2) to a thickness of 0.7 mm on a glass substrate (NH TECHNO GLASS (NH TECHNO GLASS ( Co., Ltd., "NA35"), after drying on a heating plate at 80°C for 3 minutes, using an ultra-high pressure mercury lamp to irradiate 60 mJ/cm ² of ultraviolet rays, and then post-baking in a clean oven at 230°C for 30 minutes, In this way, the film thickness was adjusted to a film thickness of 2.5 μm to form the colored layer G1.

(Example 2) (1) Manufacture of color material solution G2 In addition to using the above-obtained sulfonic acid group-containing pigment derivative B in an equimolar amount to replace the sulfonic acid-group-containing pigment derivative A in (1) of Example 1, with the same method as in Example 1 (1) Color material solution G2 was obtained in the same manner. (2) Manufacture of photosensitive colored resin composition G2 The photosensitive colored resin composition G2 was obtained in the same manner as in (2) of Example 1, except that the above-mentioned color material liquid G2 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer G2 was obtained in the same manner as in (3) of Example 1 except that the photosensitive colored resin composition G2 described above was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(Example 3) (1) Manufacture of color material solution G3 In addition to using the pigment derivative C containing sulfonic acid group obtained above in an equimolar amount to replace the pigment derivative A containing sulfonic acid group in (1) of Example 1, with (1) of Example 1 Color material solution G3 was obtained in the same manner. (2) Manufacture of Photosensitive Colored Resin Composition G3 The photosensitive colored resin composition G3 was obtained in the same manner as in (2) of Example 1, except that the above-mentioned color material liquid G3 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer G3 was obtained in the same manner as in (3) of Example 1, except that the photosensitive colored resin composition G3 described above was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(Example 4) (1) Manufacture of color material solution G4 Obtained in the same manner as in (1) of Example 1, except that an equimolar amount of the obtained halogenated phthalocyanine compound 2 was used instead of the halogenated phthalocyanine compound 1 used as a color material in (1) of Example 1. Color material liquid G4. (2) Manufacture of Photosensitive Colored Resin Composition G4 The photosensitive colored resin composition G4 was obtained in the same manner as in (2) of Example 1, except that the above-mentioned color material liquid G4 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer G4 was obtained in the same manner as in (3) of Example 1 except that the photosensitive colored resin composition G4 described above was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(Example 5) (1) Manufacture of color material liquid G5 In addition to using the halogenated phthalocyanine compound 2 obtained above in an equimolar amount instead of the halogenated phthalocyanine compound 1 used as a color material in (1) of Example 1, and using the above obtained sulfonic acid in an equimolar amount Color material solution G5 was obtained in the same manner as in Example 1 (1) except that the pigment derivative B containing a sulfonic acid group was substituted for the pigment derivative A containing a sulfonic acid group. (2) Manufacture of Photosensitive Colored Resin Composition G5 The photosensitive colored resin composition G5 was obtained in the same manner as in (2) of Example 1, except that the above-mentioned color material liquid G5 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer G5 was obtained in the same manner as in (3) of Example 1, except that the photosensitive colored resin composition G5 described above was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(Example 6) (1) Manufacture of color material solution G6 In addition to using the halogenated phthalocyanine compound 2 obtained above in an equimolar amount instead of the halogenated phthalocyanine compound 1 used as a color material in (1) of Example 1, and using the above obtained sulfonic acid in an equimolar amount Color material liquid G6 was obtained in the same manner as in Example 1 (1) except that the pigment derivative C containing a sulfonic acid group was substituted for the pigment derivative A containing a sulfonic acid group. (2) Manufacture of Photosensitive Colored Resin Composition G6 The photosensitive colored resin composition G6 was obtained in the same manner as in (2) of Example 1, except that the above-mentioned color material liquid G6 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer G6 was obtained in the same manner as in (3) of Example 1 except that the above-mentioned photosensitive colored resin composition G6 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(Example 7) (1) Manufacture of color material liquid G7 In addition to using 12.87 parts by mass of halogenated phthalocyanine compound 1 as a color material and 0.26 parts by mass of pigment derivative A containing sulfonic acid groups in (1) of Example 1, with (1) of Example 1 Color material solution G7 was obtained in the same manner. (2) Manufacture of Photosensitive Colored Resin Composition G7 The photosensitive colored resin composition G7 was obtained in the same manner as in (2) of Example 1, except that the above-mentioned color material liquid G7 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer G7 was obtained in the same manner as in (3) of Example 1 except that the photosensitive colored resin composition G7 described above was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(Embodiment 8) (1) Manufacture of color material solution G8 In addition to using 11.70 parts by mass of halogenated phthalocyanine compound 1 as a color material in (1) of Example 1, and 1.30 parts by mass of the pigment derivative A containing sulfonic acid groups, with (1) of Example 1 Color material solution G8 was obtained in the same manner. (2) Manufacture of Photosensitive Colored Resin Composition G8 The photosensitive colored resin composition G8 was obtained in the same manner as in (2) of Example 1, except that the above-mentioned color material liquid G8 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer G8 was obtained in the same manner as in (3) of Example 1 except that the photosensitive colored resin composition G8 described above was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(comparative example 1) (1) Comparison of the production of color material liquid CG1 Except not using the pigment derivative A containing a sulfonic acid group in (1) of Example 1, the comparison color material liquid CG1 was obtained in the same manner as (1) of Example 1. (2) Production of Comparative Photosensitive Colored Resin Composition CG1 A comparative photosensitive colored resin composition CG1 was obtained in the same manner as in (2) of Example 1 except that the above-mentioned comparative color material liquid CG1 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer CG1 was obtained in the same manner as in (3) of Example 1, except that the above comparative photosensitive colored resin composition CG1 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(comparative example 2) (1) Production of Comparative Photosensitive Colored Resin Composition CG2 As a color material liquid, the comparative photosensitive colored resin composition which increased alkali-soluble resin content was prepared using comparative color material liquid CG1. Specifically, 43.43 parts by mass of the comparative color material liquid CG1 obtained in (1), 8.47 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 4, and a multifunctional monomer (trade name ARONIX M-403, East Asia Synthetic (Stock) Co., Ltd.) 2.26 parts by mass, photoinitiator (trade name TR-PBG-3057, manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 0.50 mass part, photoinitiator (trade name Adeka Arkles NCI-831, ADEKA company manufacture) 0.50 mass parts, sensitizer (pentaerythritol tetrakis (3-mercaptobutyrate), trade name Karenz MT-PE1, Showa Denko manufacture) 0.13 mass parts, fluorine-based surfactant (trade name MEGAFAC F559, DIC Co., Ltd.) 0.03 parts by mass, silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones) 0.34 parts by mass, PGMEA 23.70 parts by mass, propylene glycol monomethyl ether (PGME) 20.65 parts by mass to obtain a photosensitive coloring resin combination Object CG2. (2) Formation of colored layer Colored layer CG2 was obtained in the same manner as in (3) of Example 1 except that the comparative photosensitive colored resin composition CG2 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(comparative example 3) (1) Comparison of the production of color material liquid CG3 Except using the pigment derivative D containing sulfonamide group obtained above in an equimolar amount to replace the pigment derivative A containing sulfonic acid group in (1) of embodiment 1, with (1) of embodiment 1 ) in the same manner to obtain comparative color material liquid CG3. (2) Production of Comparative Photosensitive Colored Resin Composition CG3 A comparative photosensitive colored resin composition CG3 was obtained in the same manner as in (2) of Example 1 except that the above-mentioned comparative color material liquid CG3 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer CG3 was obtained in the same manner as in (3) of Example 1 except that the comparative photosensitive colored resin composition CG3 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(comparative example 4) (1) Comparison of the production of color material liquid CG4 In addition to using the halogenated phthalocyanine compound 2 obtained above in an equimolar amount instead of the halogenated phthalocyanine compound 1 as a color material in (1) of Example 1, and not using the pigment derivative A containing a sulfonic acid group, Comparative color material liquid CG4 was obtained in the same manner as in (1) of Example 1. (2) Production of Comparative Photosensitive Colored Resin Composition CG4 A comparative photosensitive colored resin composition CG4 was obtained in the same manner as in (2) of Example 1 except that the above-mentioned comparative color material liquid CG4 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer CG4 was obtained in the same manner as in (3) of Example 1, except that the above comparative photosensitive colored resin composition CG4 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

(comparative example 5) (1) Comparison of the production of color material liquid CG5 In addition to using the halogenated phthalocyanine compound 2 obtained above in an equimolar amount instead of the halogenated phthalocyanine compound 1 as a color material in (1) of Example 1, and using the above obtained sulfonyl in an equimolar amount A comparison color material liquid CG5 was obtained in the same manner as in Example 1 (1) except that the amino-group-containing pigment derivative D was substituted for the sulfonic-acid-group-containing pigment derivative A. (2) Production of Comparative Photosensitive Colored Resin Composition CG5 A comparative photosensitive colored resin composition CG5 was obtained in the same manner as in (2) of Example 1 except that the above-mentioned comparative color material liquid CG5 was used instead of the color material liquid G1 in (2) of Example 1. (3) Formation of colored layer Colored layer CG5 was obtained in the same manner as in (3) of Example 1, except that the above comparative photosensitive colored resin composition CG5 was used instead of the photosensitive colored resin composition G1 in (3) of Example 1.

[Evaluation method] (1) Developability Using a spin coater, the photosensitive colored resin compositions of Examples and Comparative Examples were coated on glass substrates with a thickness of 0.7 mm (manufactured by NH TECHNO GLASS Co., Ltd., "NA35 ")superior. Then, it heat-dried for 3 minutes on the hot plate of 80 degreeC. Using an ultra-high pressure mercury lamp, an independent fine-line pattern mask with a line width of 1 μm to 100 μm is used to expose the colored layer to 60 mJ/ ^cm2 of ultraviolet rays, thereby forming a colored layer with a thickness of 2.0 μm on the glass substrate. Next, a 0.05% by mass potassium hydroxide (KOH) aqueous solution was used as a developing solution, and rotational development was carried out. After contacting the developing solution, it was rinsed with pure water, developed, and patterned, and the developability was evaluated. In the above development process, the time (unit: second) until the unexposed portion was dissolved and removed was measured.

(2) Development residue evaluation Using a spin coater, the colored resin compositions of Examples and Comparative Examples were coated on glass substrates (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm, and then heated at 60 Drying was carried out at °C for 3 minutes to form a colored layer with a thickness of 2.5 μm. The glass plate on which the said colored layer was formed was shower-developed for 60 second using the 0.05 mass % potassium hydroxide aqueous solution which is an alkaline developing solution. The unexposed portion (50 mm×50 mm) of the glass substrate after the above-mentioned colored layer was formed was observed with an optical microscope at 200 times reflected light. (Development residue evaluation criteria) 〇: Observation with an optical microscope, no coloring residue was confirmed ×: Observation with an optical microscope, coloring residues were confirmed

(3) Evaluation of developing waste liquid The development treatment was carried out in the same manner as in the above-mentioned evaluation of developability. Add 1 g of a cationic inorganic coagulant (polyaluminum chloride, manufactured by Taki Chemical Co., Ltd.) to 500 mL of the coloring waste liquid (alkaline developer) after the development treatment, and stir for 30 minutes to agglomerate the contained components. 1 g of an anionic polymer flocculant (polyacrylamide, manufactured by Asada Chemical Industry Co., Ltd.) was further added to the colored waste liquid, and stirred for 30 minutes to coarsen aggregates and precipitate aggregates. Agglomerates were removed from the effluent by filtering the effluent containing coagulates with a 5 μm filter. A neutralizing agent (dilute hydrochloric acid) was added to the filtrate of the waste liquid, and neutralized until the pH value reached 7. After neutralization, filtration was performed with a 0.2 μm filter, whereby a filtrate was obtained. The presence or absence of coloration of the obtained filtrate was confirmed visually. Moreover, using a liquid chromatography mass spectrometer (LC/MS, manufactured by Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity), it was confirmed whether or not components of the photosensitive colored resin composition remained in the obtained filtrate. (Development Waste Liquid Evaluation Criteria) 〇: The filtrate is not colored, and the total content of solids derived from the photosensitive colored resin composition is less than 0.001% by mass ×: The filtrate is colored, and/or the total content of solids derived from the photosensitive colored resin composition is 0.001% by mass or more

[Table 1] Table 1 Implement No Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Color material liquid Color material solution G1 Color material solution G2 Color material solution G3 Color material liquid G4 Color material solution G5 Color material liquid G6 Color material liquid G7 Color material liquid G8 Color material solution CG1 Color material solution CG1 Color material liquid CG3 Color material liquid CG4 Color material liquid CG5 Evaluation composition Color material liquid 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 Basic resin A solution 4.23 4.23 4.23 4.23 4.23 4.23 4.23 4.23 4.23 8.47 4.23 4.23 4.23 multifunctional monomer 3.95 3.95 3.95 3.95 3.95 3.95 3.95 3.95 3.95 2.26 3.95 3.95 3.95 Photoinitiator 1 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Photoinitiator 2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 PGMEA 26.24 26.24 26.24 26.24 26.24 26.24 26.24 26.24 26.24 23.70 26.24 26.24 26.24 PGME 20.65 20.65 20.65 20.65 20.65 20.65 20.65 20.65 20.65 20.65 20.65 20.65 20.65 Sensitizer 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 Fluorinated Surfactant 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Silane coupling agent 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Evaluation results developing residual time 23 seconds 24 seconds 26 seconds 30 seconds 32 seconds 34 seconds 25 seconds 21 seconds 25 seconds 18 seconds 28 seconds 38 seconds 36 seconds Residue on glass substrate 〇 〇 〇 〇 〇 〇 〇 〇 x x x x x Waste liquid treatment after developing 〇 〇 〇 〇 〇 〇 〇 〇 x x x x x

[Summary of Results] The photosensitive colored resin compositions of Comparative Examples 1 to 5 that do not contain sulfonic acid group-containing pigment derivatives are not easy to recycle in the waste liquid treatment after development because of the specific phthalocyanine dye contained in the color material Color material, and the color material remains in the waste liquid (filtrate) after the condensate is recovered to be colored. Furthermore, since the photosensitive coloring resin composition of Comparative Examples 1-5 is easy to leave a phthalocyanine dye at the time of image development, coloring and development residue tends to remain. Even in Comparative Example 2 where the content of the alkali-soluble resin was increased, although the development time was not fast, the coloring material remained in the waste liquid (filtrate) after the aggregate was recovered and the coloring was caused, and the phthalocyanine dye was likely to be left during the development, thereby coloring and developing Residue is easy to remain. Even in Comparative Examples 3 and 5, which contain basic sulfonamide group-containing pigment derivatives, the coloring material remains in the waste liquid (filtrate) after the condensate is recovered, and the coloring is caused, and the phthalocyanine dye is easily left during development, so Coloring and development residues tend to remain. In contrast, the photosensitive colored resin compositions of Examples 1 to 8 containing the sulfonic acid group-containing pigment derivatives of the present invention can be recovered in the treatment of waste liquid after development, although the color material contains a specific phthalocyanine dye The color material and the waste liquid (filtrate) will not be colored, and the components of the photosensitive colored resin composition will not remain. Furthermore, since the photosensitive colored resin composition of Examples 1-8 is hard to leave a phthalocyanine dye at the time of image development, coloring development residue is hard to remain.

1: Substrate 2: shading part 3: coloring layer 10:Color filter 20: facing the substrate 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: luminous layer 75: Electron injection layer 76: Cathode 80: organic luminous body 100: Organic light-emitting display device

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 a liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of an organic light emitting display device of the present invention.

Claims (4)

A photosensitive colored resin composition, which contains: a color material comprising a phthalocyanine compound represented by the following general formula (1), a pigment derivative containing a sulfonic acid group, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator agent, and solvent, [Chemical 1]

(In the general formula (1), X ¹ to X ¹⁶ each independently represent a hydrogen atom, a halogen atom, or -YR ^D , -Y- represents -O-, -S-, or -NH-, R ^D represents a monovalent Organic group; wherein, one or more of X ¹ to X ¹⁶ represents -YR ^D ). The photosensitive colored resin composition according to claim 1, wherein the above-mentioned sulfonic acid group-containing pigment derivative contains a phthalocyanine skeleton or a quinophthalone skeleton as the pigment skeleton. A color filter comprising at least a substrate and a colored layer disposed on the substrate, and at least one of the colored layers is a hardened photosensitive colored resin composition according to claim 1 or 2. A display device having the color filter according to Claim 3.

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