Phthalocyanine compound and composition, colored resin composition, color filter, and image display device

Abstract

The present invention provides a phthalocyanine composition comprising a phthalocyanine compound that has a specific chemical structure, wherein the Fe atom content as measured by inductively coupled plasma optical emission spectrometry is 40 mass ppm or less.　The present invention makes it possible to provide a phthalocyanine composition that has excellent storage stability when used as a colored resin composition.

Description

Phthalocyanine compound and composition, colored resin composition, color filter, image display device

[0001] The present invention relates to a phthalocyanine compound and composition, a colored resin composition using the same, a color filter, and an image display device using the color filter.

[0002] Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods have been known as methods for producing color filters used in liquid crystal displays, etc. Among these, the pigment dispersion method is most widely adopted because it has excellent average properties in terms of spectral characteristics, durability, pattern shape, precision, etc.

[0003] In recent years, there has been a demand for color filters with higher brightness, higher contrast, and a wider color gamut. Pigments are generally used as coloring materials for determining the color of color filters, due to their heat resistance, light resistance, and other properties. However, pigments are no longer able to meet market demands, particularly for high brightness, and active research is underway into the use of dyes as coloring materials instead of pigments. For green pixels, the use of specific phthalocyanine dyes as dyes is being investigated (see, for example, Patent Documents 1 and 2).

[0004] The colored resin compositions described in Patent Documents 1 and 2 do not provide a practically sufficient brightness for the resulting color filter, and foreign matter is generated in the resulting pattern. In contrast, Patent Document 3 proposes a colored resin composition that is practically sufficient brightness and capable of forming a pattern in which the generation of foreign matter is suppressed. Patent Document 3 discloses a colored resin composition containing a colorant, a solvent, a binder resin, and a photopolymerization initiator, in which a phthalocyanine dye is used as the colorant.

[0005] Furthermore, with the recent diversification of devices, dyes with various absorption characteristics depending on the application are required. Phthalocyanine compounds are stable against light, heat, temperature, etc. and have excellent fastness, but it is difficult to control the absorption wavelength, and the majority of phthalocyanine compounds have been insoluble in solvents. Therefore, numerous studies have been conducted to control the absorption wavelength required depending on the application and to dissolve them in the solvent required depending on the application. For example, Patent Document 4 proposes a fluorine-containing phthalocyanine compound, and proposes a near-infrared absorbing material that has absorption in the near-infrared wavelength region and is highly soluble in solvents.

[0006] JP 2009-51896 A JP 2014-125460 A JP 2020-42263 A Japanese Patent No. 2812624 A

[0007] In Example 30 of Patent Document 4, 3,6-octafluoro-4,5-octakis(p-ethoxycarbonylphenoxy)zinc phthalocyanine is produced using 3,6-difluoro-4,5-bis(p-ethoxycarbonylphenoxy)phthalonitrile and zinc iodide, but no consideration is given to the Fe content in the raw materials and in the composition containing the resulting phthalocyanine compound and by-products such as its isomers (hereinafter referred to as the phthalocyanine composition). It is assumed that the Fe content in the phthalocyanine composition of Example 30 is high, which is likely to result in the presence of an isomer of the phthalocyanine compound and thus prevent the effects of the present invention from being achieved. It is known that the Fe content in commercially available raw materials used as raw materials (e.g., 99.5% pure zinc iodide (Nacalai Tesque)) is 100 ppm by mass. This is the same level as the compound of Comparative Example 1 described in the present specification.

[0008] Furthermore, in Synthesis Example 7 of Patent Document 3, intermediate G was purified during the synthesis of dye G, and an intermediate with a purification yield of 92% and a purity of 84% was obtained. However, a similar purification treatment was not performed in the subsequent process of reacting intermediate G with zinc iodide to obtain dye G. In other words, in Patent Document 3, the intermediate was merely purified as a normal operation, and it is clear that no consideration was given at all to the Fe content in the product phthalocyanine composition. The Fe content in zinc iodide is as described above.

[0009] As described above, it can be easily inferred that the colorant compositions disclosed in Patent Documents 3 and 4 are insufficient in terms of storage stability. Under the above circumstances, an object of the present invention is to provide a phthalocyanine composition that has excellent storage stability when made into a colored resin composition.

[0010] As a result of extensive research, the present inventors have found that controlling the content of iron (Fe), an impurity in a phthalocyanine compound, results in excellent storage stability when made into a colored resin composition. Furthermore, the inventors have found that a small amount of an isomer is by-produced in the process of producing the phthalocyanine compound, and have ascertained that this isomer is the cause of reduced storage stability of the colored resin composition. The present invention has been completed based on these findings. The present invention has the following aspects.

[0011] [1] A phthalocyanine composition comprising a phthalocyanine compound having a chemical structure represented by the following general formula (1), wherein the content of Fe atoms in the phthalocyanine composition is 40 ppm by mass or less:

[0012]

[0013] (In formula (1), A １ ~A １６ each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2): １ ~A １６ At least one of the groups represents a fluorine atom or a group represented by the following general formula (2):

[0014]

[0015] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

[0016] [2] A phthalocyanine composition having a chemical structure represented by the following general formula (1), wherein, when analyzed by high performance liquid chromatography under the following measurement conditions, the ratio of the total chart area of ​​peaks having peak tops at retention times of 16±0.5 minutes and 21±0.5 minutes to the chart area of ​​a peak having a peak top at a retention time of 19±0.5 minutes is less than 0.40%. <Measurement conditions> [Column] CHEMCOSORB ODS (particle size: 5 μm, size: 4.6 × 250 mm) [Eluent] water:MeOH:THF=17:43:40 (mass ratio) [Analysis time] 40 min [Flow rate] 1.0 mL / min [Column temperature] 45°C [Injection amount] 2 μL

[0017]

[0018] (In formula (1), A １ ~A １６ each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2): １ ~A １６ At least one of the groups represents a fluorine atom or a group represented by the following general formula (2):

[0019]

[0020] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

[0021] [3] In the formula (1), A １ ~A １６ At least one of A is a fluorine atom, and １ ~A １６ [4] The phthalocyanine composition according to any one of the above [1] to [3], wherein in formula (2), X is an oxygen atom or a sulfur atom. [5] The phthalocyanine composition according to the above [1] or [2], wherein in formula (1), A １ ~A １６The phthalocyanine composition according to any one of [1] to [4] above, wherein the halogen atom in formula (2) is a fluorine atom, and the benzene ring in formula (2) has an alkoxycarbonyl group as a substituent. [6] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the (A) colorant contains the phthalocyanine composition according to any one of [1] to [5] above. [7] The colored resin composition according to [6] above, wherein the content of the phthalocyanine composition is 5% by mass or more and 70% by mass or less based on the total solid content of the colored resin composition. [8] The colored resin composition according to [6] or [7] above, wherein the (D) photopolymerization initiator contains an oxime compound. [9] The colored resin composition according to any one of [6] to [8] above, wherein the (A) colorant contains a colorant other than the phthalocyanine composition.

[10] A color filter having pixels formed using the colored resin composition according to any one of [6] to [9] above.

[11] An image display device having the color filter according to

[10] above.

[0022] According to the present invention, it is possible to provide a phthalocyanine composition that has excellent storage stability when made into a colored resin composition.

[0023] FIG. 1 is a chart showing a high performance liquid chromatograph (HPLC) of the phthalocyanine compound of the present invention.

[0024] The phthalocyanine composition, colored resin composition, color filter, and image display device of the present invention will be described below as examples of embodiments of the present invention. However, the scope of the present invention is not limited to the embodiments described below. Note that "(meth)acrylic," "(meth)acrylate," and the like mean "acrylic and / or methacrylic," "acrylate and / or methacrylate," and the like. For example, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid." Furthermore, "total solids" means all components other than the solvent component contained in the pigment dispersion or colored resin composition.

[0025] [Phthalocyanine Composition] The phthalocyanine composition of the present invention has a phthalocyanine compound represented by the following general formula (1): Hereinafter, the phthalocyanine compound represented by the following general formula (1) will also be referred to as "phthalocyanine compound (1)".

[0026]

[0027] In formula (1), A １ ~A １６ A each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). Here, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, with a fluorine atom being preferred. １ ~A １６ Preferably, one or more of the fluorine atoms are fluorine atoms, more preferably four or more, and even more preferably eight or more. The presence of fluorine atoms suppresses aggregation of phthalocyanines. In addition, it is preferable that the phthalocyanine has a group represented by the following general formula (2). In particular, A １ ~A １６ At least one of A is a fluorine atom, and １ ~A １６ It is preferable that one or more of the above is a group represented by the following formula (2).

[0028]

[0029] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.

[0030] The phthalocyanine compound (1) contains a compound represented by the general formula (1), １ ~A １６Preferably, two or more of the groups represented by the general formula (2) are groups represented by the general formula (2). By having two or more groups, solubility in solvents and alkali-soluble resins is improved, and precipitation during curing is suppressed due to intermolecular steric repulsion between the groups represented by the general formula (2). From the above viewpoints, the number of groups represented by the general formula (2) is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and particularly preferably 7 or more. On the other hand, the number of groups represented by the general formula (2) is preferably 10 or less, more preferably 9 or less, and even more preferably 8. By setting the number to the above upper limit or less, compatibility with alkali-soluble resins having acid groups is improved, and phase separation is suppressed.

[0031] X in the general formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, but may be an oxygen atom, a sulfur atom, or —N(R ａ１ )-group. ａ１ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among these, from the viewpoint of stability of the phthalocyanine during baking, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0032] The optional substituent that the benzene ring in the general formula (2) may have is not particularly limited, but includes a halogen atom, an alkyl group, an alkoxy group (—OR Ａ group (where R Ａ represents an alkyl group, an alkoxycarbonyl group (—COOR Ａ group), an aryl group, an aryloxy group (—OR Ｂ group (where R Ｂ represents an aryl group), an aryloxycarbonyl group (—COOR Ｂ groups), and the alkyl groups (—R Ａ group) and aryl groups (-R Ｂ The alkoxycarbonyl group may be further substituted with one of these substituents. Among these, an alkoxycarbonyl group is preferred from the viewpoint of selective light transmission and solubility in a solvent.

[0033] In the present invention, to detect the Fe atom content in a phthalocyanine composition, the phthalocyanine composition is pretreated by acid decomposition in accordance with Japanese Industrial Standard JIS K 0116;2014, and the Fe atom content is measured by ICP atomic emission spectrometry. The Fe atomic weight was measured using ICP atomic emission spectrometry as follows: Approximately 0.2 g of a phthalocyanine composition sample was weighed out and subjected to microwave pressure decomposition with nitric acid in a sealed container. The sample was then recovered, its volume was measured, and quantitatively analyzed by ICP-MS. A Multiwave 7000 manufactured by Anton Paar was used as the microwave pretreatment device. An ELEMENT 2 manufactured by Thermo Fisher Scientific was used as the measurement device. The Fe atom content obtained by this method is referred to as the (α) total Fe atom content. Furthermore, 0.1 g of a phthalocyanine composition sample was weighed out, and 10 g of approximately 0.1 N hydrochloric acid was added, followed by stirring at room temperature for 20 minutes using a shaker. The sample was then centrifuged, and the supernatant was filtered through a 0.45 μm PTFE filter and measured by ICP-OES. The ICP-OES device used was an Agilent 5800 manufactured by Agilent Technologies. The Fe atom content obtained by this method was taken as the Fe atom content in the (β) extracted sample.

[0034] The Fe atom content in the phthalocyanine composition of the present invention is defined as follows: The difference obtained by subtracting the Fe atom content in the extracted sample (β) from the total Fe atom content (α) is defined as the Fe atom content in the phthalocyanine composition of the present invention.

[0035] In the phthalocyanine composition of the present invention, it is essential that the Fe atom content in the phthalocyanine composition calculated by the above method is 40 ppm by mass or less. By ensuring that the Fe atom content in the phthalocyanine composition is 40 ppm by mass or less, the minimum line width (CD: critical dimension) when formed into a resist can be made to be an appropriate width. Furthermore, changes over time can be minimized, and the line width of the developed resist does not narrow over time. Since the Fe contained in the organic composition undergoes reversible changes between divalent and trivalent states, if the initiator contained in the resist decomposes over time to generate radicals, a chain reaction is promoted, resulting in significant consumption of the initiator and a decrease in sensitivity. On the other hand, if the Fe content in the phthalocyanine composition is 40 ppm by mass or less, chain decomposition of the initiator is suppressed, and therefore, it is believed that the phthalocyanine composition has excellent storage stability. From the above viewpoints, the content of Fe atoms in the phthalocyanine composition is more preferably 30 ppm by mass or less, even more preferably 20 ppm by mass or less, even more preferably 15 ppm by mass or less, particularly preferably 10 ppm by mass or less, and most preferably 5 ppm by mass or less. The lower limit of the content of Fe atoms in the phthalocyanine composition is most preferably 0 ppm by mass, i.e., no Fe is present. However, even in cases where Fe is mixed in as an impurity due to constraints of the production method, the content is preferably about 1 ppm by mass. The impurity Fe may be present, for example, in the form of substituting Zn in the compound represented by the above formula (1).

[0036] As a method for reducing the Fe atom content in the phthalocyanine composition to 40 ppm by mass or less, there is a method of using Fe-free raw materials as raw materials for use in synthesizing the phthalocyanine composition. There is also a method of purifying the raw materials to reduce the Fe content. Still another method is to remove Fe that is mixed in during the synthesis of the phthalocyanine composition by purifying the phthalocyanine composition after synthesis.

[0037] The present inventors have also discovered that a small amount of an isomer is by-produced in the phthalocyanine composition of the present invention during its production process. They have also found that the isomer can be detected by high-performance liquid chromatography (hereinafter also referred to as "HPLC"), and that by reducing the content of the isomer, the phthalocyanine composition of the present invention exhibits excellent storage stability when used as a colored resin composition. While the reason why reducing the content of the isomer results in excellent storage stability when used as a colored resin composition is unclear, it is believed that the components contained in the isomer decompose the photopolymerization initiator contained in the colored resin composition over time, resulting in consumption of the photopolymerization initiator, resulting in a decrease in storage stability.

[0038] [Quantification by HPLC] The method for quantifying the content of isomers using HPLC is as follows. When analyzed by high-performance liquid chromatography under specific measurement conditions, an HPLC chart such as that shown in FIG. 1 is obtained. Peak (a) having a peak top at a retention time of 19±0.5 minutes is a peak derived from the phthalocyanine composition. In contrast to this peak, peak (b) observed at a retention time of 16±0.5 minutes and peak (c) observed at a retention time of 21±0.5 minutes are considered to be peaks derived from isomers. In the present invention, it is essential that the ratio of the total chart area of ​​peaks (b) and (c) to the chart area of ​​peak (a) is less than 0.40%. A ratio of less than 0.40% sufficiently reduces the content of by-products (isomers), resulting in the phthalocyanine composition of the present invention exhibiting sufficient effects. From the above perspectives, this ratio is preferably 0.38% or less, and more preferably 0.35% or less. The chart areas of peak (a) and peak (b) are the areas enclosed by the peak and retention time axes on the HPLC chart. On the other hand, peak (c) is a shoulder of peak (a), and the chart area of ​​peak (c) is the area enclosed by the background line drawn on peak (c) and the background line.

[0039] Although the specific compound of the by-product (isomer) generated in the production process of the phthalocyanine composition is not clear, it is conceivable that it is, for example, a compound in which Zn in phthalocyanine compound (1) is substituted with another metal such as Fe. Note that, since the content of this by-product is extremely small, it is difficult to separate it, and separating and identifying it is either impossible or requires a great deal of effort, making it impractical.

[0040] <HPLC Measurement Conditions> The HPLC measurement conditions are as follows: [Column] CHEMCOSORB ODS (particle diameter: 5 μm, size: 4.6 × 250 mm) [Eluent] Water: MeOH: THF = 17:43:40 (mass ratio) [Analysis time] 40 min [Flow rate] 1.0 mL / min [Column temperature] 45°C [Injection volume] 2 μL

[0041] [Method for Producing Phthalocyanine Compound (1)] As a method for producing the phthalocyanine compound (1) of the present invention, a method for cyclizing a phthalonitrile compound with a metal salt in a molten state or in an organic solvent can be preferably used, from the viewpoints of ease of synthesis, high yield, and facile reaction, by controlling the number of groups represented by formula (2) to be introduced. That is, the phthalocyanine compound (1) of the present invention can be produced by cyclizing a phthalonitrile compound represented by the following general formula (3) with one selected from metal halides, organic metals, metal carbonyls, etc.

[0042]

[0043] In formula (3), B １ ~B ４ each independently represents a group represented by formula (2) or a fluorine atom.

[0044] The phthalonitrile compound represented by formula (3) can be synthesized by a conventional method, such as the method disclosed in Japanese Patent Application Laid-Open No. 64-45474. For example, it can be synthesized by reacting tetrafluorophthalonitrile (hereinafter also abbreviated as "TFPN") with a nucleophilic substitution reagent (phenols, thiols, amines) for introducing the group represented by formula (2). As the organic solvent used in the synthesis, an inert solvent such as acetone or acetonitrile, or an aprotic polar solvent such as pyridine or N,N-dimethylformamide, can be used. The amount of organic solvent used is typically such that the TFPN concentration is 10 to 80 (w / v)%, preferably 20 to 50 (w / v)%. Furthermore, it is preferable to use an inorganic base such as potassium fluoride or potassium carbonate as a condensation agent when reacting TFPN with a nucleophilic substitution reagent.

[0045] The reaction conditions for the reaction of TFPN with the nucleophilic substitution reagent are not particularly limited as long as the reaction proceeds smoothly. However, in order to increase the reaction selectivity of the fluorine atoms at the 4- and 5-positions, the reaction temperature is preferably 0 to 80°C.

[0046] After the reaction is complete, the phthalonitrile compound represented by formula (3) can be precipitated by, for example, mixing the reaction mixture with an appropriate organic solvent and then isolated by filtration. There is a possibility that the phthalonitrile compound may contain fluorine atoms at the 4- or 5-positions that have not been completely substituted with the nucleophilic substitution reagent, with some fluorine atoms remaining. If this phthalonitrile compound is used as a raw material for the subsequent cyclization reaction, the number of groups represented by formula (2) contained per molecule of the final target phthalocyanine compound may decrease, which may affect physical properties such as solubility. Therefore, it is preferable to purify the phthalonitrile compound by recrystallization, column chromatography, or the like so that the selectivity (purity) of the phthalonitrile compound in which the fluorine atoms at the 4- and 5-positions have been substituted with groups represented by formula (2) is preferably 90% or more, more preferably 95% or more, in terms of area % by high-performance liquid chromatography analysis.

[0047] The cyclization reaction of the phthalonitrile compound represented by formula (3) can be carried out by a conventional method such as the method disclosed in JP-A-2016-17147. The metal salt to be reacted with the phthalonitrile compound is not particularly limited, but examples include halides such as zinc chloride, bromide, and iodide; organic acid zinc salts such as acetate; and zinc complex compounds such as zinc acetylacetonate. Among these, zinc halides are preferred, and zinc iodide is more preferred, from the viewpoint of high reactivity.

[0048] When the cyclization reaction between the metal salt to be reacted with phthalonitrile and the phthalonitrile compound represented by general formula (3) is carried out in an organic solvent, the organic solvent may be, for example, an inert solvent such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, or benzonitrile; or an aprotic polar solvent such as pyridine, N,N-dimethylformamide, N-methyl-2-pyrrolidinone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, dimethyl sulfone, or sulfolane. Of these, 1-chloronaphthalene, N-methyl-2-pyrrolidone, 1-methylnaphthalene, trimethylbenzene, benzonitrile, nitrobenzene, or ethylene glycol is preferred from the viewpoints of high boiling points and high solubility of phthalocyanine. Trimethylbenzene and benzonitrile are more preferred.

[0049] When an organic solvent is used in the cyclization reaction, the amount of the organic solvent used is preferably such that the concentration of the phthalonitrile compound represented by the general formula (3) is 1 to 50 mass %, more preferably 10 to 40 mass %.

[0050] The reaction temperature in the cyclization reaction may be set depending on the types of raw materials, the type of organic solvent, and other conditions, and is typically preferably 100 to 300°C. The temperature may also be increased stepwise to control the exothermic reaction. The reaction time is not particularly limited, but is typically 5 to 20 hours. The reaction may be carried out in an air atmosphere; however, depending on the type of metal salt to be reacted with the phthalonitrile compound, it is preferably carried out in an inert gas or oxygen-containing gas atmosphere, and more preferably under a flow of nitrogen gas, helium gas, argon gas, or an oxygen / nitrogen mixed gas. After the cyclization reaction, crystallization, column chromatography, filtration, washing, drying, and the like may be carried out according to conventionally known methods.

[0051] [Colored Resin Composition] The colored resin composition of the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator. Here, the (A) colorant contains the aforementioned phthalocyanine composition. That is, the colored resin composition contains a phthalocyanine compound having a chemical structure represented by the general formula (1) and having an Fe atom content of less than 45 ppm by mass as measured by ICP. Alternatively, the colored resin composition contains a phthalocyanine composition having a chemical structure represented by the general formula (1) and having an HPLC chromatographic chart area in which the ratio of the sum of the peak areas at retention times of 16±0.5 minutes and 21±0.5 minutes to the chart area of ​​the peak having a peak top at a retention time of 19±0.5 minutes, measured under the measurement conditions described above, is less than 0.40%.

[0052] <Colorant> The colored resin composition of the present invention contains a colorant (A), which contains the above-mentioned phthalocyanine composition. The content of the phthalocyanine composition is preferably 5% by mass or more and 70% by mass or less based on the total solid content of the colored resin composition. When the content of the phthalocyanine composition is 5% by mass or more, the colored resin composition can obtain sufficient brightness when used as a color filter and excellent durability when used as a resist. On the other hand, when the content of the phthalocyanine composition is 70% by mass or less, the other components (solid content) can be sufficiently contained, and pattern formability is improved. From the above viewpoints, the content of the phthalocyanine composition is more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 35% by mass or more. On the other hand, the upper limit is more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and particularly preferably 40% by mass or less.

[0053] <Other Colorants> The colorant (A) may contain other colorants in addition to the phthalocyanine composition. Examples of other colorants include pigments and dyes. In particular, when used for green pixel applications, it is preferable to use a green pigment, green dye, yellow pigment, yellow dye, etc., and it is more preferable to use a yellow pigment and / or yellow dye. Examples of green pigments include C.I. Pigment Green 7, 36, 58, 59, 62, and 63, and from the viewpoint of brightness, C.I. Pigment Green 58 and 59 are preferred. Examples of green dyes classified as dyes in the Color Index include C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 as C.I. Solvent dyes, and C.I. Acid dyes. Examples include C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109, and C.I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53. Among these, C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred from the viewpoint of suppressing dye decomposition during thermal baking.

[0054] Examples of yellow pigments include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 8 3, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 1 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and compounds in which other compounds are inserted into a 1:1 complex of azobarbituric acid with nickel represented by the following formula (i) or a tautomer thereof.

[0055]

[0056] Furthermore, examples of the other compounds include compounds represented by the following formula (ii).

[0057]

[0058] Among these, from the viewpoint of high brightness and wide color gamut, C.I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by formula (i) are preferred, and C.I. Pigment Yellow 83, 138, 139, 180, 185, and the nickel azo complex represented by formula (i) are more preferred.

[0059] Examples of yellow dyes include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples include the specific compounds described in JP 2010-168531 A. Among those classified as dyes in the Color Index, C.I. solvent dyes include C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163. C.I. acid dyes include C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 16 0, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and derivatives thereof. C.I. direct dyes include C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141 and the like.Furthermore, examples of C.I. Mordant dyes include C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65, and preferably C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162, and C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 and derivatives thereof. Among these, from the viewpoint of suppressing dye decomposition during thermal baking, at least one selected from the group consisting of C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162 and 163 is preferred.

[0060] <Solvent> The solvent, which is the component (B) of the colored resin composition of the present invention, has the function of dissolving or dispersing the colorant (A), the alkali-soluble resin (C), the photopolymerization initiator (D), and other components, and adjusting the viscosity. The solvent (B) is not particularly limited as long as it can dissolve or disperse each component.

[0061] Examples of such solvents include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0062] glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0063] Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0064] aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; and nitriles such as acetonitrile and benzonitrile.

[0065] Commercially available solvents that meet the above criteria include mineral spirits, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all trade names). These solvents may be used alone or in combination of two or more.

[0066] When forming color filter pixels by photolithography, it is preferable to select a solvent having a boiling point in the range of 100 to 200°C (under a pressure condition of 1013.25 [hPa]; the same applies hereinafter to boiling points). More preferably, it is a solvent having a boiling point of 120 to 170°C. Glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) are preferred because they have a good balance of coatability, surface tension, etc., and have a relatively high solubility of the components in the composition.

[0067] Furthermore, glycol alkyl ether acetates may be used alone or in combination with other solvents. Glycol monoalkyl ethers are particularly preferred as solvents to be used in combination. Among these, propylene glycol monomethyl ether (PGME) is particularly preferred from the viewpoint of solubility of the components in the composition. Glycol monoalkyl ethers have high polarity, and if added in excessive amounts, the pigment tends to aggregate, resulting in a decrease in storage stability, such as an increase in the viscosity of the resulting colored resin composition. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

[0068] It is also preferable to use a solvent with a boiling point of 150°C or higher in combination. The use of such a high-boiling solvent makes the colored resin composition less likely to dry, but also has the effect of preventing the destruction of the interrelationships of the pigment dispersion liquid due to rapid drying. The content of the high-boiling solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass, relative to the (B) solvent. By setting the content at or above the lower limit, it is easy to avoid, for example, the precipitation and solidification of colorant components at the tip of the slit nozzle, which can cause foreign matter defects. Setting the content at or below the upper limit tends to slow the drying rate of the composition, which can easily prevent problems such as poor tact time in the reduced-pressure drying process and pin marks during pre-baking. The solvent with a boiling point of 150°C or higher may be either a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to separately add a solvent with a boiling point of 150°C or higher. Preferred high-boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, triacetin, and the like, among the various solvents mentioned above.

[0069] When forming pixels of a color filter by an inkjet method, a solvent having a boiling point of typically 130°C or higher and 300°C or lower, preferably 150°C or higher and 280°C or lower, is suitable. By setting the boiling point at or above the lower limit, the uniformity of the resulting coating film tends to be improved, while by setting the boiling point at or below the upper limit, the amount of residual solvent during baking is easily reduced. Furthermore, from the viewpoint of the uniformity of the resulting coating film, the vapor pressure of the solvent that can be used is typically 10 mmHg or lower, preferably 5 mmHg or lower, and more preferably 1 mmHg or lower.

[0070] In color filter production using the inkjet method, the ink ejected from the nozzle is extremely fine, ranging from a few to several tens of picoliters. Therefore, before the ink lands around the nozzle or within the pixel bank, the solvent tends to evaporate, causing the ink to concentrate and dry out. To avoid this, a solvent with a high boiling point is preferred. Specifically, it is preferable to include a solvent with a boiling point of 180°C or higher. More preferably, the solvent contains a solvent with a boiling point of 200°C or higher, and particularly preferably a solvent with a boiling point of 220°C or higher. Furthermore, the high-boiling-point solvent with a boiling point of 180°C or higher preferably accounts for 50% by mass or more of the total solvents contained in the colored resin composition, more preferably 70% by mass or higher, and most preferably 90% by mass or higher. By ensuring that the content is equal to or greater than the above-mentioned lower limit, the effect of preventing solvent evaporation from the droplets is easily achieved.

[0071] Preferred high-boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, triacetin, and the like, among the various solvents mentioned above. Furthermore, in order to adjust the viscosity of the colored resin composition and the solubility of the solids, it is also effective to partially contain a solvent with a boiling point lower than 180°C. Such solvents are preferably those with low viscosity, high solubility, and low surface tension, and ethers, esters, ketones, and the like are preferred. Among these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferred.

[0072] On the other hand, if the solvent contains alcohols, the ejection stability in the ink-jet method may be deteriorated. Therefore, the alcohol content of the total solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0073] The content of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. By setting the content below the upper limit, it becomes easier to form a coating film. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 78% by mass or more, taking into account viscosity suitable for coating.

[0074] <Alkali-Soluble Resin> The alkali-soluble resin, which is the component (C) of the colored resin composition of the present invention, functions as a binder resin in the colored resin composition of the present invention. In addition, the alkali-soluble resin is suitable because it can form a pattern by alkaline development. As the alkali-soluble resin, for example, polymer compounds described in JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, etc. can be used. Among them, the following resins (C-1) to (C-5) are preferred.

[0075] (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups in a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction (hereinafter sometimes referred to as "resin (C-1)"). (C-2): A carboxyl group-containing linear alkali-soluble resin (hereinafter sometimes referred to as "resin (C-2)"). (C-3): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2). (C-4): A (meth)acrylic resin. (C-5): An epoxy acrylate resin having a carboxyl group.

[0076] Of these, resin (C-1) is particularly preferred. Resin (C-1) will be described in detail below. Resins (C-2) to (C-5) are not limited as long as they are dissolved in an alkaline developer and have solubility to the extent that the intended development process can be carried out, and are the same as those described in the same section of JP-A-2009-025813. Preferred aspects are also the same.

[0077] One particularly preferred resin for the resin (C-1) is a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol % of the epoxy groups in a copolymer of 5 to 90 mol % of an epoxy group-containing (meth)acrylate and 10 to 95 mol % of another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol % of the hydroxyl groups generated by the addition reaction.

[0078] Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among these, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

[0079] The other radically polymerizable monomer to be copolymerized with the epoxy group-containing (meth)acrylate is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include vinyl aromatics, dienes, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, and monomaleimides. Of these, mono(meth)acrylates are preferred.

[0080] The weight average molecular weight (Mw) of the alkali-soluble resin, measured by GPC (gel permeation chromatography) in terms of polystyrene, is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, even more preferably 15,000 or less, and particularly preferably 13,000 or less. A weight average molecular weight (Mw) within the above range is preferable in terms of good heat resistance, film strength, and solubility in a developer. Furthermore, as a measure of molecular weight distribution, the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) is preferably 2.0 to 5.0.

[0081] The acid value of the alkali-soluble resin is usually 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 25 mgKOH / g or more, and even more preferably 50 mgKOH / g or more, and is usually 200 mgKOH / g or less, preferably 150 mgKOH / g or less, and more preferably 100 mgKOH / g or less. By setting the acid value at least to the lower limit, the solubility in the developer tends to be good, and by setting the acid value at most to the upper limit, the occurrence of film roughening tends to be suppressed.

[0082] In the colored resin composition of the present invention, the content of the alkali-soluble resin (C) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more, based on the total solid content of the colored resin composition. Also, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. By setting it to the lower limit or more, intermolecular hydrophobic interaction with the phthalocyanine compound (1) tends to work efficiently, resulting in good pattern formability. By setting it to the upper limit or less, alkaline developability tends to be good, and residues on the substrate tend to be suppressed.

[0083] <Photopolymerization initiator> The colored resin composition of the present invention contains a photopolymerization initiator as component (D). By containing the photopolymerization initiator (D), film curability can be obtained by photopolymerization. The photopolymerization initiator (D) can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye that is added as needed. The photopolymerization initiation system is a component that has the function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction, thereby generating polymerization active radicals.

[0084] Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, hexaarylbiimidazole derivatives described in JP-A No. 10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other radical activators, α-aminoalkylphenone compounds, and oxime ester initiators described in JP-A No. 2000-80068.

[0085] Specific examples of the photopolymerization initiator that can be used in the present invention are listed below: halomethylated triazine derivatives such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine;

[0086] Halomethylated oxadiazole derivatives such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; Imidazole derivatives such as 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer; benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone;

[0087] Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone; thioxanthone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone;

[0088] Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone; dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6 -difluorophen-1-yl, dicyclopentadienyl-Ti-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadienyl-Ti-2,6-difluoro-3-(pyr-1-yl)-phenyl-1-yl and other titanocene derivatives;

[0089] α-aminoalkylphenone compounds such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone; Oxime ester compounds such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime).

[0090] Among these, from the viewpoint of sensitivity and surface properties, oxime compounds such as oxime ester compounds are preferred. Oxime compounds have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, and therefore have high sensitivity even in small amounts and are stable against thermal reactions, making it possible to design a colored resin composition that is highly sensitive even in small amounts. In particular, from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, oxime compounds having a carbazole ring that may have a substituent are preferred.

[0091] Commercially available oxime ester compounds include OXE-02, OXE-03, and OXE-04 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Strong Electronics Co., Ltd., and N-1919, NCI-930, and NCI-831 manufactured by ADEKA Corporation.

[0092] These photopolymerization initiators may be used singly or in combination of two or more.

[0093] In addition to the (D) photopolymerization initiator, a chain transfer agent may also be used. A chain transfer agent is a compound that has the function of receiving generated radicals and transferring the radicals to another compound. Various compounds having the above function can be used as the chain transfer agent, but examples include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a compound having a mercapto group because it tends to have a high chain transfer effect. This is thought to be because the small S-H bond energy makes bond cleavage more likely, facilitating hydrogen abstraction reactions and chain transfer reactions. This is effective for improving sensitivity and surface curability.

[0094] Examples of the mercapto group-containing compound include mercapto group-containing compounds having an aromatic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, and trishydroxybenzoates. Examples of the mercapto group-containing aliphatic compounds include ethyl tristhiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. From the viewpoint of surface smoothness, compounds having a plurality of mercapto groups are particularly preferred.

[0095] Of these, among the mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among the aliphatic mercapto group-containing compounds, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

[0096] From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, specifically, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred. These compounds may be used alone or in combination of two or more.

[0097] In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (D) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 4% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, particularly preferably 10% by mass or less, based on the total solid content of the colored resin composition. By making it equal to or more than the lower limit, patterning properties after development tend to be ensured, and by making it equal to or less than the upper limit, a decrease in transmittance due to excessive addition of the photopolymerization initiator tends to be suppressed.

[0098] When the colored resin composition of the present invention contains a chain transfer agent, its content is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, based on the total solid content of the colored resin composition. By keeping the content within the above range, storage stability and patterning ability during alkali development tend to be ensured.

[0099] <Other Solid Contents> The colored resin composition of the present invention may further contain solid contents other than the above-described components, as necessary. Examples of such components include photopolymerizable monomers, dispersants, dispersing aids, surfactants, etc.

[0100] (Photopolymerizable Monomer) The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular-weight compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as an "ethylenic compound") is preferred. The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and hardening under the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with actinic rays. The term "monomer" as used herein refers to a concept that is opposite to so-called polymeric substances, and includes not only monomers in the narrow sense but also dimers, trimers, and oligomers. In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds per molecule. The number of ethylenic double bonds possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually two or more, preferably four or more, more preferably five or more, and preferably eight or less, more preferably seven or less. Setting the number at or above the lower limit tends to result in high sensitivity, while setting the number at or below the upper limit tends to result in improved solubility in solvents.

[0101] Examples of the ethylenic compound include unsaturated carboxylic acids and esters thereof with monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification reactions of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl-containing hydroxy compound.

[0102] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Further examples include methacrylic acid esters in which the acrylic acid moiety of these acrylates is replaced with a methacrylic acid moiety, itaconic acid esters in which the itaconic acid moiety is replaced, crotonic acid esters in which the crotonic acid moiety is replaced, and maleic acid esters in which the maleic acid moiety is replaced, etc.

[0103] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polycarboxylic acid and a polyhydroxy compound is not necessarily a single substance, but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

[0104] Examples of ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate with (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, and 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

[0105] Other useful ethylenic compounds for use in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. The ethylenic compound may also be a monomer having an acid value. The monomer having an acid value is preferably a polyfunctional monomer obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to provide the unreacted hydroxyl group of the aliphatic polyhydroxy compound with an acid group. Particularly preferred is an ester in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

[0106] Although one of these monomers may be used alone, since using a single compound is difficult in production, two or more may be used in combination. Furthermore, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer. The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. By setting the acid value at or above the lower limit, development solubility characteristics tend to be improved, while by setting the acid value at or below the upper limit, production and handling tend to be improved and curing properties such as photopolymerization performance and pixel surface smoothness tend to be improved. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferable to adjust the acid group content of the entire polyfunctional monomer to fall within the above range.

[0107] In the present invention, a more preferred polyfunctional monomer having an acid group is a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinate ester of dipentaerythritol pentaacrylate, which is commercially available as TO1382 manufactured by Toagosei Co., Ltd. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Furthermore, those described in paragraphs

[0056] and

[0057] of JP 2013-140346 A can also be used.

[0108] In the present invention, from the viewpoint of improving the chemical resistance of pixels and the linearity of pixel edges, it is preferable to use the polymerizable monomers described in JP-A-2013-195971. From the viewpoint of achieving both high sensitivity of the coating film and a short development time, it is preferable to use the polymerizable monomers described in JP-A-2013-195974.

[0109] The content of these photopolymerizable monomers in the total solids content of the colored resin composition of the present invention is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 22% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less. Furthermore, the ratio relative to 100 parts by mass of the (A) colorant is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, particularly preferably 60 parts by mass or more, and usually 200 parts by mass or less, preferably 100 parts by mass or less, even more preferably 80 parts by mass or less. Setting the content at or above the lower limit tends to increase curability, while setting the content at or below the upper limit tends to suppress a decrease in developability.

[0110] (Dispersant, Dispersing Aid) When the colored resin composition of the present invention contains a pigment as the colorant (A), a dispersant can be contained for the purpose of stably dispersing the pigment. Among these, the use of a polymer dispersant is preferred because it provides excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants. Specific examples of these dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and those described in JP 2013-119568 A.

[0111] Among polymer dispersants, from the viewpoints of dispersibility and storage stability, block copolymers having a functional group containing a nitrogen atom are preferred, and acrylic block copolymers are more preferred. As the block copolymer having a functional group containing a nitrogen atom, A-B block copolymers and / or B-A-B block copolymers consisting of an A block having a quaternary ammonium salt group and / or an amino group in the side chain and a B block not having a quaternary ammonium salt group and / or an amino group are preferred.

[0112] Examples of the functional group containing a nitrogen atom include primary, secondary, or tertiary amino groups and quaternary ammonium salt groups. From the viewpoints of dispersibility and storage stability, it is preferable for the functional group to have a primary, secondary, or tertiary amino group, and it is more preferable for the functional group to have a tertiary amino group.

[0113] When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, relative to 100 parts by mass of the pigment, and is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, particularly preferably 30 parts by mass or less. By setting the content within the above range, it tends to be possible to obtain a colored resin composition that is excellent in dispersion stability and has high brightness.

[0114] Furthermore, when the colored resin composition of the present invention contains a pigment, it may contain a pigment derivative or the like as a dispersing aid to improve the pigment dispersibility and dispersion stability. Examples of pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, isoindoline-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based pigment derivatives. Examples of substituents on the pigment derivative include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, and amide groups bonded to the pigment skeleton directly or via alkyl groups, aryl groups, heterocyclic groups, and the like. Preferred are sulfonamide groups and quaternary salts thereof, and sulfonic acid groups, with sulfonic acid groups being more preferred. Furthermore, a single pigment skeleton may be substituted with a plurality of these substituents, or a mixture of compounds with different numbers of substitutions may be used. Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0115] (Surfactant) As the surfactant, various kinds of surfactants such as anionic, cationic, nonionic, amphoteric surfactants can be used, but it is preferable to use nonionic surfactants because they are less likely to have adverse effects on various properties.The content ratio of surfactant is generally 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and generally 10 mass% or less, preferably 1 mass% or less, even more preferably 0.5 mass% or less, most preferably 0.3 mass% or less, based on the total solid content of the colored resin composition.

[0116] <Preparation of Colored Resin Composition> Next, a method for preparing the colored resin composition (hereinafter, sometimes referred to as a resist) according to the present invention will be described.

[0117] When preparing a pigment-containing colorant, first, predetermined amounts of pigment, solvent, and dispersant are weighed, and then, in a dispersion treatment step, the pigment-containing pigment dispersion is prepared. In this dispersion treatment step, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like can be used. This dispersion treatment microparticulates the colorant, improving the coating properties of the colored resin composition and improving the transmittance of pixels in the finished color filter substrate.

[0118] When dispersing a pigment, it is preferable to use a dispersing aid or dispersing resin as described above. When dispersing using a sand grinder, it is preferable to use glass beads or zirconia beads with a diameter of 0.1 to several mm. The temperature during dispersion is set to a range of usually 0°C or higher, preferably room temperature or higher, and usually 100°C or lower, preferably 80°C or lower. The dispersion time must be adjusted appropriately, as the appropriate time varies depending on the composition of the pigment dispersion and the size of the sand grinder.

[0119] The pigment dispersion obtained by the above dispersion treatment is mixed with a solvent, a binder resin, a photopolymerization initiator, and, in some cases, other components to prepare a uniform dispersion solution. Note that, since fine dust particles may be mixed in during the dispersion treatment step and each mixing step, it is preferable to filter the obtained pigment dispersion using a filter or the like.

[0120] When a pigment is not used as a colorant, a homogeneous solution can be obtained by mixing a colorant, a solvent, a binder resin, a photopolymerization initiator, and, in some cases, other components, etc. The obtained solution is preferably filtered using a filter or the like.

[0121] [Color Filter] The color filter of the present invention has pixels formed using the above-described colored resin composition. <Transparent Substrate (Support)> The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass. Among these, glass or heat-resistant resins are preferred from the viewpoint of heat resistance.

[0122] To improve surface properties such as adhesiveness, the transparent substrate and the black matrix-formed substrate may be subjected to corona discharge treatment, ozone treatment, or thin-film formation treatment with a silane coupling agent or various resins such as urethane-based resins, as needed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When a thin-film formation treatment with various resins is performed, the thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

[0123] <Black Matrix> A color filter according to the present invention can be produced by providing a black matrix on the above-described transparent substrate and then forming pixel images, typically red, green, and blue. The colored resin composition is preferably used as a coating liquid for forming a green pixel (resist pattern) among the red, green, and blue pixels (hereinafter, sometimes abbreviated as "green resist"). The green resist is applied to a surface on which a resin black matrix is ​​formed on a transparent substrate, or to a surface on which a metal black matrix is ​​formed using a chromium compound or other light-shielding metal material, and the process of coating, heat drying, image exposure, development, and heat curing is carried out to form a pixel image.

[0124] The black matrix is ​​formed on a transparent substrate using a light-shielding metal thin film or a colored resin composition for a black matrix. Examples of light-shielding metal materials include metallic chromium, chromium oxide, chromium nitride, and other chromium compounds, and nickel-tungsten alloys, and these may be laminated in multiple layers. These metal light-shielding films are generally formed by sputtering. After forming a desired film pattern using a positive photoresist, the film is etched using an etching solution containing a mixture of ceric ammonium nitrate and perchloric acid and / or nitric acid for chromium, or an etching solution appropriate for the material for other materials. Finally, the positive photoresist is stripped using a dedicated stripper to form the black matrix.

[0125] In this case, a thin film of the metal or metal / metal oxide is first formed on a transparent substrate by vapor deposition, sputtering, or the like. Next, a coating film of a colored resin composition is formed on this thin film, and then the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, or triangles to form a resist image. Thereafter, the coating film is subjected to an etching treatment to form a black matrix.

[0126] When using a photosensitive colored resin composition for a black matrix, a black matrix is ​​formed using a colored resin composition containing a black colorant. For example, a colored resin composition containing a single or multiple black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or a mixture of red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes can be used to form the black matrix in the same manner as in the method for forming red, green, and blue pixel images described below.

[0127] <Pixels> The method of forming pixels varies depending on the type of colored resin composition used, but here, an example will be described in which a photopolymerizable composition is used as the colored resin composition. A colored resin composition of one of red, green, and blue colors is applied to a transparent substrate provided with a black matrix, and after drying, a photomask is placed on the coating film, and a pixel image is formed by image exposure through the photomask, development, and, if necessary, heat curing or photocuring. This operation is performed for each of the three colored resin compositions of red, green, and blue, thereby forming a color filter image.

[0128] The colored resin composition for a color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, etc. Among these, the die coating method is preferable from an overall viewpoint, since it can significantly reduce the amount of coating solution used, is completely free from the influence of mist or the like that adheres when using a spin coating method, and furthermore, it can suppress the generation of foreign matter.

[0129] If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell formation process becomes difficult, while if the thickness is too small, it becomes difficult to increase the pigment concentration and the desired color expression may become impossible. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less.

[0130] <Drying of coated film> After the colored resin composition is applied to the substrate, the coated film is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, the film is dried by heating again. The pre-drying conditions can be appropriately selected depending on the type of solvent component and the performance of the dryer used. The drying temperature and drying time are selected depending on the type of solvent component and the performance of the dryer used. Specifically, the drying temperature is usually 40°C or higher, preferably 50°C or higher, and usually 80°C or lower, preferably 70°C or lower, and the drying time is usually 15 seconds or higher, preferably 30 seconds or higher, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

[0131] The temperature conditions for reheating and drying are preferably higher than the pre-drying temperature, specifically, usually 50°C or higher, preferably 70°C or higher, and usually 200°C or lower, preferably 160°C or lower, particularly preferably 130°C or lower. The drying time, depending on the heating temperature, is usually 10 seconds or longer, preferably 15 seconds or longer, and usually 10 minutes or shorter, preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate, but if the temperature is too high, the binder resin may decompose, inducing thermal polymerization and resulting in poor development. The drying process for this coating film may also be performed using a reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without increasing the drying temperature.

[0132] <Exposure> Imagewise exposure is carried out by superimposing a negative matrix pattern on a coating film of the colored resin composition and irradiating the film with a light source of ultraviolet or visible light through this mask pattern. If necessary, an oxygen-blocking layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer before exposure in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen. The light source used for the imagewise exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. When using light of a specific wavelength, an optical filter can also be used.

[0133] <Development> The color filter according to the present invention can be produced by imagewise exposing a coating film using the colored resin composition according to the present invention to the light source described above, and then developing the film using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound, thereby forming an image on a substrate. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0134] Examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, as well as organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be a mixture of two or more.

[0135] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkylbetaines and amino acids.

[0136] Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent can be used alone or in combination with an aqueous solution. There are no particular restrictions on the conditions for development processing, but the development temperature is usually 10°C or higher, preferably 15°C or higher, and more preferably 20°C or higher, and usually 50°C or lower, preferably 45°C or lower, and more preferably 40°C or lower. The development method can be any method such as immersion development, spray development, brush development, or ultrasonic development.

[0137] <Thermal curing treatment> After development, the color filter is subjected to a thermal curing treatment. The thermal curing conditions are selected such that the temperature is usually 100°C or higher, preferably 150°C or higher, and usually 280°C or lower, preferably 250°C or lower, and the time is selected such that the time is 5 minutes or longer and 60 minutes or shorter. After this series of steps, the formation of a single-color patterned image is completed. This process is repeated sequentially to pattern black, red, green, and blue, thereby forming a color filter. Note that the order of patterning the four colors is not limited to the order described above.

[0138] <Formation of Transparent Electrode> The color filter according to the present invention is used as a part of a component of a color display, a liquid crystal display device, etc. by forming a transparent electrode such as ITO on the image as it is, but in order to improve surface smoothness and durability, a top coat layer of polyamide, polyimide, etc. can be provided on the image as needed. In addition, in some applications such as a planar alignment type driving system (IPS mode), a transparent electrode may not be formed.

[0139] [Image Display Device] Next, the image display device of the present invention will be described. The image display device of the present invention has the above-mentioned color filter. Hereinafter, as the image display device, a liquid crystal display device and an organic EL display device will be described in detail.

[0140] <Liquid Crystal Display Device> A method for manufacturing a liquid crystal display device according to the present invention will now be described. A liquid crystal display device according to the present invention is typically manufactured by forming an alignment film on the color filter according to the present invention, dispersing spacers on the alignment film, and then bonding it to a counter substrate to form a liquid crystal cell. Liquid crystal is then injected into the formed liquid crystal cell, and the cell is connected to the counter electrode to complete the device. A resin film such as polyimide is suitable for the alignment film. Gravure printing and / or flexographic printing are typically used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After hardening the alignment film by thermal baking, the surface is treated by ultraviolet irradiation or treatment with a rubbing cloth to create a surface state that allows adjustment of the tilt of the liquid crystal.

[0141] The spacers used should be of a size that corresponds to the gap (gap) with the opposing substrate, with a size of 2 to 8 μm being typically preferred. Transparent resin photospacers (PS) can be formed on the color filter substrate by photolithography and used instead of spacers. An array substrate is typically used as the opposing substrate, with a TFT (thin film transistor) substrate being particularly preferred.

[0142] The gap between the opposing substrate and the substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After bonding with the opposing substrate, the area other than the liquid crystal injection port is sealed with a sealant such as epoxy resin. The sealant is hardened by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed. The liquid crystal cell with the sealed periphery is cut into panel units, and then the pressure is reduced in a vacuum chamber. The liquid crystal injection port is immersed in liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The degree of pressure reduction in the liquid crystal cell is usually 1×10 －２ Pa or more, preferably 1×10 －３ Above, usually 1 x 10 －７ Pa or less, preferably 1×10 －６ The pressure is preferably in the range of 30° C. or higher, preferably 50° C. or higher, and is usually 100° C. or lower, preferably 90° C. or lower.

[0143] The heating and holding time during reduced pressure is usually within a range of 10 minutes to 60 minutes, after which the cell is immersed in liquid crystal. The liquid crystal cell into which the liquid crystal has been injected is sealed by curing a UV-curable resin at the liquid crystal injection port, completing a liquid crystal display device (panel). There are no particular limitations on the type of liquid crystal, and any of the conventionally known liquid crystals, such as aromatic, aliphatic, and polycyclic compounds, including lyotropic and thermotropic liquid crystals, may be used. Known thermotropic liquid crystals include nematic, smectic, and cholesteric liquid crystals, and any of these may be used.

[0144] <Organic EL Display Device> When producing an organic EL display device having the color filter of the present invention, for example, a multicolor organic EL element is produced by laminating an organic light-emitting body on a green color filter having pixels formed from the colored resin composition of the present invention on a transparent supporting substrate, via an organic protective layer and an inorganic oxide film.

[0145] Examples of methods for laminating organic light-emitting bodies include a method of sequentially forming a transparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer, and a cathode on the top surface of a color filter, and a method of laminating an organic light-emitting body formed on a separate substrate onto an inorganic oxide film. Organic EL elements fabricated in this manner can be applied to both passive-drive organic EL display devices and active-drive organic EL display devices.

[0146] The phthalocyanine composition and colored resin composition of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited in any way.

[0147] [Evaluation Method] <Fe Content in Phthalocyanine Composition> The Fe content in the phthalocyanine composition was measured using the above-mentioned ICP emission spectrometry.

[0148] <HPLC analysis> Measurements were performed under the conditions described in the present specification. When analyzed by high performance liquid chromatography under these measurement conditions, the areas represented by the intersections of the charts with the axes having peak tops at a retention time of 19±0.5 minutes (peak (a) in FIG. 1, RT19), 16±0.5 minutes (peak (b) in FIG. 1, RT16), and 21±0.5 minutes (peak (c) in FIG. 1, RT21) were calculated. For the peak area at a retention time of 21±0.5 minutes, the area above the shoulder of the chart having a peak at a retention time of 19±0.5 minutes was calculated.

[0149] <ΔCD> The colored resin composition immediately after preparation was applied by spin coating onto a 50 mm square, 0.5 mm thick glass substrate (AN100, manufactured by AGC). The rotation speed was adjusted so that the film thickness after heat curing would be 2.0 μm. Each coating film was pre-baked at 100° C. for 120 seconds. Then, a 2 kW high-pressure mercury lamp was used to apply 40 mJ / cm２ The film was exposed to light through an exposure mask having a 50 μm linear coating area at an exposure dose of 1 kg / cm. Thereafter, the film was developed using a 0.04 mass % aqueous potassium hydroxide solution at a developer temperature of 23° C. for 60 seconds. ２ The resulting pattern substrate A was subjected to a spray water washing treatment at a water pressure of 100 psi for 10 seconds. This was followed by a heat curing treatment at 230°C for 20 minutes to produce a pattern substrate A. The resulting pattern substrate A was measured for line widths (μm) at three locations in the linear portions of the pattern using an optical microscope, and the average was calculated. The calculated line width was taken as the line width immediately after preparation. The colored resin compositions were prepared and stored at 25°C for 1 day, 3 days, and 7 days, and the line widths (μm) of the linear portions of the pattern were measured in the same manner as above. The measured line widths were taken as the line width 1 day after preparation, the line width 3 days after preparation, and the line width 7 days after preparation, respectively, and ΔCD was calculated as the line width change after 1 day of storage ((line width 1 day after preparation) - (line width immediately after preparation)), the line width change after 3 days of storage ((line width 3 days after preparation) - (line width immediately after preparation)), and the line width change after 7 days of storage ((line width 7 days after preparation) - (line width immediately after preparation)).

[0150] <Synthesis of Phthalocyanine Compound> As a method for producing phthalocyanine compound (1), a method of cyclizing a phthalonitrile compound with a metal salt in a molten state or in an organic solvent can be preferably used, from the viewpoints of ease of synthesis by controlling the number of groups represented by formula (2) to be introduced, high yield, and ease of reaction. That is, the phthalocyanine compound (1) of the present invention can be produced by cyclizing a phthalonitrile compound represented by the following general formula (3) with one selected from metal halides, organic metals, metal carbonyls, etc.

[0151]

[0152] In formula (3), B １ ~B ４ each independently represents a group represented by formula (2) or a fluorine atom.

[0153] The phthalonitrile compound represented by formula (3) can be synthesized by a conventional method, such as the method disclosed in Japanese Patent Application Laid-Open No. 64-45474. For example, it can be synthesized by reacting tetrafluorophthalonitrile (hereinafter also abbreviated as "TFPN") with a nucleophilic substitution reagent (phenols, thiols, amines) for introducing the group represented by general formula (2). As the organic solvent used in the synthesis, an inert solvent such as acetone or acetonitrile, or an aprotic polar solvent such as pyridine or N,N-dimethylformamide can be used. The amount of organic solvent used is such that the concentration of TFPN is typically 10 to 80 (w / v)%, preferably 20 to 50 (w / v)%. Furthermore, it is preferable to use an inorganic base such as potassium fluoride or potassium carbonate as a condensation agent.

[0154] The reaction conditions for the reaction of TFPN with the nucleophilic substitution reagent are not particularly limited as long as the reaction proceeds smoothly. However, in order to increase the reaction selectivity of the fluorine atoms at the 4- and 5-positions, the reaction temperature is preferably 0 to 80°C.

[0155] After the reaction was completed, the reaction mixture was mixed with an appropriate organic solvent to precipitate the phthalonitrile compound represented by the formula (3), which was then separated by filtration.

[0156] The cyclization reaction of the phthalonitrile compound represented by formula (3) can be carried out by a conventional method such as the method disclosed in JP-A-2016-17147. The metal salt to be reacted with the phthalonitrile compound is not particularly limited, but examples include halides such as zinc chloride, bromide, and iodide; organic acid zinc salts such as acetate; and zinc complex compounds such as zinc acetylacetonate. Among these, zinc halides are preferred, and zinc iodide is more preferred, from the viewpoint of high reactivity.

[0157] When the cyclization reaction between the metal salt to be reacted with phthalonitrile and the phthalonitrile compound represented by general formula (3) is carried out in an organic solvent, the organic solvent may be, for example, an inert solvent such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, or benzonitrile; or an aprotic polar solvent such as pyridine, N,N-dimethylformamide, N-methyl-2-pyrrolidinone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, dimethyl sulfone, or sulfolane. Of these, 1-chloronaphthalene, N-methyl-2-pyrrolidone, 1-methylnaphthalene, trimethylbenzene, benzonitrile, nitrobenzene, or ethylene glycol is preferred from the viewpoints of high boiling points and high solubility of phthalocyanine. Trimethylbenzene and benzonitrile are more preferred.

[0158] When an organic solvent is used in the cyclization reaction, the amount of the organic solvent used is preferably such that the concentration of the phthalonitrile compound represented by the general formula (3) is 1 to 50% by mass.

[0159] The reaction temperature in the cyclization reaction may be set depending on the types of raw materials, the type of organic solvent, and other conditions, and is typically preferably 100 to 300°C. The temperature may also be increased stepwise to control the exothermic reaction. The reaction time is not particularly limited, but is typically 5 to 20 hours. The reaction may be carried out in the air, but is preferably carried out in an inert gas or oxygen-containing gas atmosphere depending on the type of metal salt to be reacted with the phthalonitrile compound, and more preferably in a stream of nitrogen gas, helium gas, argon gas, or an oxygen / nitrogen mixed gas. After the cyclization reaction, crystallization, column chromatography, filtration, washing, drying, and the like may be carried out according to conventional methods. In this manner, the following phthalocyanine compound A can be prepared.

[0160] Synthesis Example 1 Tetrafluorophthalonitrile (TFPN) was reacted with ethyl p-hydroxybenzoate to obtain difluoro-di(4-ethoxycarbonylphenoxy)phthalonitrile (DFPN) as an intermediate product. The obtained DFPN was subjected to a cyclization reaction using zinc iodide to obtain phthalocyanine compound A. The obtained phthalocyanine compound A is represented by the following formula. Measurement by ICP showed that the Fe content of TFPN was 20 ppm by mass, the Fe content of the intermediate product DFPN was 10 ppm by mass, the Fe content of zinc iodide was 5 ppm by mass, and the Fe content in the phthalocyanine composition of phthalocyanine compound A was 9.3 ppm by mass.

[0161]

[0162] Synthesis Example 2 A phthalocyanine composition B having an Fe content of 2.9 ppm by mass was obtained in the same manner as in Synthesis Example 1, except that the intermediate product DFPN had an Fe content of 5 ppm by mass and the zinc iodide had an Fe content of 3 ppm by mass.

[0163] Synthesis Example 3 A phthalocyanine composition C having an Fe content of 13.8 ppm by mass was obtained in the same manner as in Synthesis Example 1, except that the intermediate product DFPN had an Fe content of 20 ppm by mass and the zinc iodide had an Fe content of 10 ppm by mass.

[0164] Synthesis Example 4 The same preparation as in Synthesis Example 1 was carried out, except that the intermediate product DFPN had an Fe content of 50 ppm by mass and the zinc iodide had an Fe content of 30 ppm by mass, to obtain phthalocyanine composition D, which had an Fe content of 40.8 ppm by mass. Phthalocyanine compositions B to D are all represented by the above formula.

[0165] <Materials> (a) Dispersant A methacrylic AB block copolymer consisting of an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. The A block contains a repeating unit represented by the following formula (1a), and the B block contains a repeating unit represented by the following formula (2a). The content of the repeating unit represented by the following formula (1a) and the repeating unit represented by the following formula (2a) in the total repeating units is 33.3 mol% and 6.7 mol%, respectively. The amine value is 120 mgKOH / g, and the acid value is 0 mgKOH / g.

[0166] The content of the repeating unit represented by the general formula (2a) is 0 mol % relative to the total content of the repeating unit represented by the general formula (1a) and the repeating unit represented by the general formula (2a).

[0167]

[0168] (b) Alkali-soluble Resin A 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen and heated to 120°C. 7 parts by weight of styrene, 92 parts by weight of glycidyl methacrylate, and 62 parts by weight of a monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and stirring was continued for another 2 hours at 120°C. Next, the atmosphere in the reaction vessel was replaced with air, and 47 parts by weight of acrylic acid, 0.7 parts by weight of trisdimethylaminomethylphenol, and 0.12 parts by weight of hydroquinone were added, and the reaction was continued for 6 hours at 120°C. Thereafter, 39 parts by weight of succinic anhydride and 0.7 parts by weight of triethylamine were added, and the reaction was continued for 3.5 hours at 120°C. The weight average molecular weight (Mw) of the alkali-soluble resin A thus obtained, measured by GPC in terms of polystyrene, was approximately 5700, the acid value was 89 mgKOH / g, and the double bond equivalent was 430 g / mol.

[0169] (c-1) Solvent; PGMEA: propylene glycol monomethyl ether acetate (c-2) Solvent; PGME: propylene glycol monomethyl ether (d) Photopolymerizable monomer A: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) (e) Photopolymerizable initiator A: (methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate) (f) Surfactant A: Megafac F-554 (manufactured by DIC Corporation)

[0170] <Preparation of Dispersion> [Preparation Example 1] 9.90 parts by mass of the phthalocyanine composition A synthesized in Synthesis Example 1, 0.10 part by mass in terms of solid content of a dispersant, 72.0 parts by mass of propylene glycol monomethyl ether acetate and 18.0 parts by mass of propylene glycol monomethyl ether as solvents, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were charged into a stainless steel container, and the mixture was dispersed using a paint shaker for 6 hours to prepare dispersion 1.

[0171] Preparation Examples 2 to 4 Dispersions 2 to 4 were prepared in the same manner as in Preparation Example 1, except that the phthalocyanine composition A in Preparation Example 1 was replaced with other phthalocyanine compositions as shown in Table 1.

[0172]

[0173] Examples 1 to 4 and Comparative Example 1 <Preparation of Colored Resin Composition> Dispersions 1 to 4 prepared in Preparation Examples 1 to 4 above, alkali-soluble resin A, photopolymerizable monomer A, photopolymerization initiator A, and surfactant A were dispersed in PGMEA, a solvent, to the contents shown in Table 2. When mixing, the components were stirred for 10 minutes or more until they were thoroughly mixed, and then ultrasonically treated at 23°C for 10 minutes. Finally, the mixture was filtered through a 5 μm pore size filter to remove foreign matter. Example 4 is the colored resin composition of Example 2 to which Fe was later added.

[0174] <Evaluation> The results of evaluation of these colored resin compositions by the above-mentioned methods are shown in Tables 2 and 3.

[0175]

[0176]

[0177] The results in Tables 2 and 3 show that the colored resin composition using the phthalocyanine composition of the present invention can suppress a decrease in exposure sensitivity and maintain a suitable line width even after preparation and storage for several days. Furthermore, the results of Example 4 suggest that simply mixing iron oxide does not have a significant effect on the results, and that the effect is due to the influence of Fe in the phthalocyanine composition.

[0178] The phthalocyanine composition of the present invention has excellent brightness when used in a color filter, and also has excellent storage stability when made into a colored resin composition. The present invention is significant in that it achieves both of these properties, making it an industrially valuable invention. In particular, it can achieve high brightness as a green dye, and can be applied to color filters and image display devices using the color filter to produce excellent products.

Claims

1. A phthalocyanine composition having a phthalocyanine compound having a chemical structure represented by the following general formula (1), wherein the Fe atom content in the phthalocyanine composition is 40 ppm by mass or less. (In formula (1), A １ ~A １６ Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2): １ ~A １６ At least one of the groups represented by the following general formula (2) represents a fluorine atom or a group represented by the following general formula (2): (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have an arbitrary substituent. * represents a bond.) 2. A phthalocyanine composition having a chemical structure represented by the following general formula (1), in which, when analyzed by high performance liquid chromatography under the following measurement conditions, the ratio of the total chart area having peak tops at retention times of 16±0.5 minutes and 21±0.5 minutes to the chart area of ​​the peak having a peak top at a retention time of 19±0.5 minutes is less than 0.40%. <Measurement conditions> [Column] CHEMCOSORB ODS (particle size: 5 μm, size: 4.6×250 mm) [Eluent] Water:MeOH:THF=17:43:40 (mass ratio) [Analysis time] 40 min [Flow rate] 1.0 mL / min [Column temperature] 45° C. [Injection amount] 2 μL (In formula (1), A １ ~A １６ Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2): １ ~A １６ At least one of the groups represented by the following general formula (2) represents a fluorine atom or a group represented by the following general formula (2): (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have an arbitrary substituent. * represents a bond.) 3. In the formula (1), A １ ~A １６ At least one of A is a fluorine atom, and １ ~A １６ The phthalocyanine composition according to claim 1 or 2, wherein one or more of the following are groups represented by formula (2):

4. The phthalocyanine composition according to claim 1 or 2, wherein in said formula (2), X is an oxygen atom or a sulfur atom.

5. In the formula (1), A １ ~A １６ The phthalocyanine composition according to claim 1 or 2, wherein the halogen atom in the formula (2) is a fluorine atom, and the benzene ring in the formula (2) has an alkoxycarbonyl group as a substituent.

6. A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the colorant (A) comprises the phthalocyanine composition according to claim 1 or 2.

7. The colored resin composition according to claim 6, wherein the content of the phthalocyanine composition is 5% by mass or more and 70% by mass or less of the total solid content of the colored resin composition.

8. The colored resin composition according to claim 6, wherein the photopolymerization initiator (D) contains an oxime compound.

9. The colored resin composition according to claim 6, wherein the colorant (A) contains a colorant other than the phthalocyanine composition.

10. A color filter having pixels formed using the colored resin composition according to claim 6.

11. An image display device comprising the color filter according to claim 10.

Images