Novel composition for forming green coating film and method for producing the same

Abstract

To provide a composition for forming a green coating film which exhibits excellent dispersibility and demonstrates excellent brightness and contrast ratio upon formation of the green coating film.SOLUTION: A composition for forming a green coating film of the present invention comprises: C.I. Pigment Yellow 150 and / or a derivative thereof; a phthalocyanine-based green pigment; a derivative represented by formula 1; an acidic dispersant having an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less; and a solvent. R1 and R2 are independently hydrogen, an alkyl group, a benzyl group, a phenyl group, or the like.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for forming a green coating film, particularly suitable for forming green pixels in a color filter, and a method for producing the same. [Background technology]

[0002] Color filters are widely used as components of display devices such as liquid crystal displays (LCDs). LCDs are widely used in monitors, televisions, notebook computers, tablet computers, smartphones, etc., and high image quality is required for these display devices. On the other hand, in recent years, there has been an increasing demand for reduced power consumption from the perspective of protecting the global environment, and color filters are now required to have high brightness and high contrast.

[0003] Color filters are widely produced by forming a coating film by a photolithography process using a colored photosensitive composition in which colorants such as red, green and blue dyes and pigments are dissolved or dispersed in a photosensitive resin as a coating liquid. As described above, a method for improving the image quality of a color filter can be considered to improve color purity by increasing the concentration of the dye or pigment in the colored photosensitive composition. However, in this case, the transmittance of light from the backlight of the LCD decreases, so power consumption increases. In addition, in order to achieve high contrast, it can be considered to eliminate large-diameter particles of the pigment and disperse the pigment in the colored photosensitive composition as small-diameter particles equal to or smaller than the wavelength of light. However, the smaller the particle diameter of the pigment, the more likely it is that it will aggregate, and it tends to be difficult to disperse it uniformly in the colored photosensitive composition. Therefore, there is a demand for the development of a pigment that can realize a high-brightness, high-contrast color filter that can express the same brightness with less light than before without increasing the concentration of the pigment, etc.

[0004] Since there is a difference between the hue of a pigment and the color characteristics required for a liquid crystal display, a pigment for color matching is used in combination. For example, for green and red pigments, a small amount of yellow pigments such as CI Pigment Yellow 138, CI Pigment Yellow 139, and CI Pigment Yellow 150 are used as a pigment for color matching. In order to form good pixels in a color filter, it is desirable that the main pigment and the pigment for color matching have good dispersibility in the pigment dispersion.

[0005] Patent Document 1 discloses a pigment dispersant represented by the following chemical formula 2 as a pigment dispersant that improves the fluidity of pigment-containing inks, paints, etc. and prevents pigment particle aggregation. The pigment dispersant represented by chemical formula 2 is said to enable the production of colored articles that exhibit excellent gloss and clarity while preventing the generation of foreign matter.

[0006] [ka]

[0007] In Chemical Formula 2, X represents a residue of an aromatic compound or a heterocyclic compound which may have a substituent (wherein the bonding site to N=N- is an aromatic ring or a heterocyclic ring), Y represents a reactive residue of an aliphatic amine, alicyclic amine, or heteroalicyclic amine having 2 to 30 carbon atoms and a basic nitrogen atom (wherein the bond site to O2S- is a nitrogen atom), n represents a number from 0.2 to 3.

[0008] Patent Document 2 discloses a pigment dispersion for color filters having excellent viscosity stability, which contains a base-type triazine derivative and a resin-type dispersant having an acid value of 50 mgKOH / g or more and 100 mgKOH / g or less.

[0009] Patent Document 3 discloses a negative resist composition for color filters that can form a high-brightness, high-contrast color filter and has excellent alkaline developability. Patent Document 3 uses a sulfonic acid derivative of CI Pigment Yellow 138; and a pigment dispersant that is a block copolymer having repeating units (I) and (II), in which at least a part of the amino group of the repeating unit (I) forms a salt with an organic phosphoric acid compound. Patent Document 3 discloses a green pigment dispersion for color filters in which a yellow pigment, CI Pigment Yellow 150, is used to tone a green pigment, CI Pigment Green 58 (Example 1).

[0010] Patent Document 4 describes a colored curable composition in which the pigment is unlikely to remain as a residue after development, as follows: The composition contains a pigment, a pigment dispersant, a polymerizable compound having a specific structure, a photopolymerization initiator, and an organic solvent. As pigments, at least one of CI Pigment Green 36 and CI Pigment Green 58, CI Pigment Green 7, CI Pigment Yellow 139, Pigment Yellow 139 and CI Pigment Yellow 150 are included; The present invention discloses a colored curable composition, in which the total amount of CI Pigment Green 36 and CI Pigment Green 58 is 50 mass% or more of all pigments, and the mass ratio ((PG36+PG58) / (PY139+PY150)) of the total amount of CI Pigment Green 36 and CI Pigment Green 58 (PG36+PG58) to the total amount of CI Pigment Yellow 139 and CI Pigment Yellow 150 (PY139+PY150) is 1.5 to 4.0. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2016-169356 A [Patent Document 2] Patent Publication No. 2022-31725 [Patent Document 3] International Publication No. 2011 / 108496 [Patent Document 4] JP 2015-102612 A Summary of the Invention [Problem to be solved by the invention]

[0012] Both CI Pigment Green 58 and CI Pigment Green 59 are phthalocyanine green pigments that are widely used for forming green pixels in color filters. The present inventors have investigated derivatives of various dye structures in order to improve pigment dispersibility for green pigment dispersions for color filters containing such phthalocyanine green pigments and yellow pigment dispersions used for toning, and have focused on a hydroxyquinolinone structure commonly contained in yellow dyes such as CI Disperse Yellow 4 and CI Disperse Yellow 5, and CI Pigment Green 10.

[0013] For example, in Examples 1 to 6 of Patent Document 1, pigment dispersants (A) to (F) having a dihydroxyquinoline structure, which is a tautomer of hydroxyquinolinone, are used. However, the pigment dispersants (A) to (F) have a reddish color and are not suitable for pigment dispersions used to form coating films for green pixels, and there was a problem that the color characteristics of the green coating film were insufficient. Among them, the use of pigment dispersant (D) represented by chemical formula 3 improves the dispersibility of the pigment dispersion, but there was also a problem that the brightness and contrast ratio were insufficient when a green coating film was formed.

[0014] [ka]

[0015] An object of the present invention is to provide a composition for forming a green coating film which has excellent dispersibility and which, when a green coating film is formed, has excellent brightness and contrast ratio, and a method for producing the same. [Means for solving the problem]

[0016] The present inventors have continued to study a green coating film-forming composition that uses a phthalocyanine green pigment as the green pigment and uses a yellow pigment, CI Pigment Yellow 150, for color matching in order to solve the above problems. As a result, they have found that the above problems can be solved by using a specific derivative and dispersant, and have completed the present invention.

[0017] Specifically, the present invention provides Yellow pigment, A green pigment; A derivative represented by chemical formula 1, An acid type dispersant having an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less; A solvent; A green coating film-forming composition comprising: The yellow pigment is CI Pigment Yellow 150 and / or a derivative pigment of CI Pigment Yellow 150; The green pigment is a phthalocyanine green pigment. The present invention relates to a composition for forming a green coating film.

[0018] [ka]

[0019] In Chemical Formula 1, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or a group represented by -R3-NR4R5; R3 is an alkylene group having 1 to 6 carbon atoms; R4 and R5 each independently represent an alkyl group having 1 to 6 carbon atoms; At least one of R1 and R2 is a group represented by -R3-NR4R5.

[0020] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: preparing a dispersion of a yellow pigment; preparing a dispersion of a green pigment; mixing the yellow pigment dispersion with the green pigment dispersion, The yellow pigment dispersion is A derivative represented by chemical formula 1, An acid type dispersant having an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less; It contains a solvent, The yellow pigment is CI Pigment Yellow 150 and / or a derivative pigment of CI Pigment Yellow 150; The dispersion of the green pigment is A phthalocyanine green pigment; A resin type dispersant; A solvent is included. The present invention relates to a method for producing a composition for forming a green coating film.

[0021] The derivative used in the present invention is a derivative represented by Chemical Formula 1. This derivative is yellowish because it has a structure based on a yellow dye called Disperse Yellow 4, and is suitable for use in coating film-forming compositions for green pixels, particularly for use in dispersions of yellow pigments. On the other hand, the derivative disclosed in Patent Document 1 has a hydroxyquinolinone structure like the derivative represented by Chemical Formula 1, but is reddish and is not very suitable for use in green pixels.

[0022] The yellow pigment used in the present invention is CI Pigment Yellow 150 and / or a pigment derivative of CI Pigment Yellow 150. Here, the pigment derivative of CI Pigment Yellow 150 means a metal azo complex pigment in which a complex compound formed by complexing a ligand compound of CI Pigment Yellow 150 or a structural analogue thereof with a divalent or trivalent metal ion includes a guest compound as a host.

[0023] The dispersant used in the present invention is an acid type dispersant having an acid value of 40 mgKOH / g to 90 mgKOH / g. The acid value means the acid value per 1 g of the dispersant solid content, and can be determined by potentiometric titration in accordance with JIS K 0070 (1992) (unit: mgKOH / g).

[0024] The dispersant used in the present invention preferably has an amine value of 0 mgKOH / g. The amine value represents the amine value per 1 g of dispersant solid content, and is determined by potentiometric titration using a 0.1 N aqueous hydrochloric acid solution, and then converted into the equivalent amount of potassium hydroxide (unit: mgKOH / g).

[0025] The composition for forming a green coating film of the present invention is preferably used for forming green pixels of a color filter. Effect of the Invention

[0026] According to the present invention, the pigment dispersibility during preparation is high, and the contrast ratio and brightness are improved. excellent The present invention provides a method for producing a green coating film having a clear green color.

[0027] Hereinafter, an embodiment of the present invention will be described.

[0028] (Yellow pigment) The yellow pigment used in the present invention is CI Pigment Yellow 150 and / or a pigment derived from CI Pigment Yellow 150. The pigment derived from CI Pigment Yellow 150 means a metal azo complex pigment in which a complex compound formed by complexing a ligand compound of CI Pigment Yellow 150 or a structural analog thereof with a divalent or trivalent metal ion acts as a host to encapsulate a guest compound, specifically, a metal azo complex pigment in which a metal azo compound represented by Chemical Formula 4 or a tautomer thereof acts as a host to encapsulate a guest compound such as melamine. Examples of the derivative pigment of 150 include metal azo complex pigments disclosed in JP-A-2001-354869, JP-A-2007-025687, JP-A-2006-016506, JP-A-2007-033579, JP-A-2014-012838, JP-A-2016-180100, JP-A-2018-021204, JP-A-2021-119216, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, or JP-A-2017-197719. In particular, from the viewpoint of obtaining a coating film with good dispersibility and high brightness, R6 and R7 in Chemical Formula 4 are OH, R8 and R9 are O, and Me is Ni. 2+ A metal azo complex pigment in which melamine is encapsulated as a guest compound in a metal azo compound (CI Pigment Yellow 150) represented by the formula (4), or a metal azo complex pigment in which R6 and R7 are OH, R8 and R9 are O, and Me is Ni 2+ and Zn 2+ , Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ and Co 3+ 2 / 3A metal azo complex pigment is preferably used in which melamine is included as a guest compound in a metal azo compound containing at least one metal ion selected from the following: As the yellow pigment in the present invention, any one of CI Pigment Yellow 150 and / or a pigment derived from CI Pigment Yellow 150 may be used, or two or more of them may be used.

[0029] [ka]

[0030] (R6 and R7 are each independently OH or NR 10 R 11 is any of the groups represented by R8 and R9 are each independently O or NR 12 is any of the groups represented by R 10 , R 11 and R 12 are each independently either hydrogen or an alkyl group; Me represents at least one divalent or trivalent metal ion.

[0031] The yellow pigment used in the present invention preferably has an average primary particle diameter of 10 to 200 nm. The average primary particle diameter can be calculated, for example, as the arithmetic mean of the maximum width of a plurality of (for example, 50) primary particles in an image captured by a transmission electron microscope (TEM). The content of the yellow pigment in the composition for forming a green coating film is not particularly limited and may be appropriately adjusted according to the desired chromaticity of the green coating film. From the viewpoint of color reproducibility, the content is preferably 20 to 100% by mass relative to the mass of the phthalocyanine green pigment. In addition, when a yellow pigment dispersion is prepared before preparing the composition for forming a green coating film, the content of the yellow pigment in the yellow pigment dispersion is preferably 5% by mass or more and 30% by mass or less from the viewpoint of dispersibility.

[0032] (Green pigment) The green pigment used in the present invention may be any phthalocyanine green pigment, and is preferably a metal halide phthalocyanine green pigment. Specific examples include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, and CI Pigment Green 59, and are particularly preferably CI Pigment Green 58 or CI Pigment Green 59. The phthalocyanine green pigment may be used alone or in combination of two or more.

[0033] The green pigment used in the present invention preferably has an average primary particle diameter of 10 to 200 nm. The content of the green pigment in the composition for forming a green coating film is not particularly limited and may be appropriately adjusted according to the desired chromaticity of the green coating film. From the viewpoint of color reproducibility, the content is preferably 5 to 60 mass% based on the total solid content of the composition for forming a green coating film. In addition, when a green pigment dispersion is prepared before preparing the composition for forming a green coating film, the content of the green pigment in the green pigment dispersion is preferably 5 mass% or more and 30 mass% or less from the viewpoint of dispersibility.

[0034] (Acid-type dispersant) The acid type dispersant used in the present invention has an acidic group in its chemical structure and has an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less. The acidic group of the acid type dispersant includes, but is not limited to, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc. By having an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less, a pigment dispersion having excellent pigment dispersibility and a coating film having excellent alkali solubility can be obtained. As the acid type dispersant, polyacrylic polymers and polyester polymers can be suitably used, but polyacrylic polymers are preferred. In addition, as the acid type dispersant, any of random copolymers, block copolymers, and graft copolymers can be suitably used.

[0035] The molecular weight of these acid-type dispersants is preferably 1,000 or more and 30,000 or less in weight average molecular weight. By adjusting the molecular weight within this range, the dispersibility of the pigment and excellent alkali solubility are achieved. In addition, the acid-type dispersant used in the present invention preferably has an amine value of 0 mgKOH / g. The content of the acid-type dispersant in the green coating film-forming composition can be appropriately adjusted depending on the combination with the type of pigment used, and is not particularly limited. From the viewpoint of dispersibility, it is preferably 5% by mass or more and 100% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, based on the total mass of the yellow pigment, the green pigment, and the derivative represented by Chemical Formula 1. As such an acid-type dispersant, a commercially available product can be used.

[0036] (derivative) The derivative used in the present invention is a compound having a hydroxyquinolinone structure represented by Chemical Formula 1. In Chemical Formula 1, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or a group represented by -R3-NR4R5; R3 is an alkylene group having 1 to 6 carbon atoms; R4 and R5 each independently represent an alkyl group having 1 to 6 carbon atoms; At least one of R1 and R2 is a group represented by -R3-NR4R5.

[0037] The compound represented by chemical formula 1 can be easily obtained by diazotizing an aniline compound having a sulfonamide group and azo-coupling with hydroxyquinolinone. The aniline compound having a sulfonamide group can be easily prepared using 2-aminobenzenesulfonic acid (orthanilic acid), 3-aminobenzenesulfonic acid (metanilic acid), 4-aminobenzenesulfonic acid (sulfanilic acid), and derivatives thereof as raw materials. For example, commercially available 4-acetamidobenzenesulfonyl chloride can be reacted with N,N-dialkylaminoalkylamine such as N,N-diethylaminopropylamine, and then hydrolysis of the acetamide site can be performed using hydrochloric acid or the like. In this way, by introducing a tertiary amino group in advance into the aniline compound to be diazotized, there is an advantage that by-products are less likely to be generated.

[0038] The hydroxyquinolinone moiety of the compound represented by Chemical Formula 1 has tautomers as shown below. The compound represented by Chemical Formula 1 in the present invention includes such tautomeric structures.

[0039] [ka]

[0040] The content of the derivative represented by Chemical Formula 1 in the composition for forming a green coating film is preferably 3% by mass or more and 40% by mass or less with respect to the total mass of the yellow pigment, the green pigment, and the derivative represented by Chemical Formula 1. In addition, when a yellow pigment dispersion is prepared before preparing the composition for forming a green coating film, the content of the derivative represented by Chemical Formula 1 in the yellow pigment dispersion is preferably 5% by mass or more and 40% by mass or less with respect to the total mass of the yellow pigment and the derivative represented by Chemical Formula 1.

[0041] (solvent) As the solvent used in the present invention, various organic solvents such as aromatic, ketone, ester, glycol ether, alcohol, and aliphatic solvents can be used. Among them, from the viewpoint of the film forming property in the color filter application, a solvent selected from aromatic, ketone, ester, and glycol ether solvents is preferable. The organic solvent may be used alone or in combination of two or more kinds.

[0042] Examples of aromatic organic solvents include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

[0043] Examples of the ketone-based organic solvent include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetylacetone, isophorone, acetophenone, and cyclohexanone.

[0044] Examples of ester-based organic solvents include ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate (PMA), propylene glycol monoethyl ether acetate, propylene glycol methyl ether propionate, 3-methoxy-3-methyl-1-butyl acetate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and 1,3-butylene glycol diacetate.

[0045] Examples of glycol ether-based organic solvents include water-soluble glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; Examples of the glycol ethers include water-insoluble glycol ethers such as ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, diethylene glycol-2-ethylhexyl ether, and dipropylene glycol monobutyl ether.

[0046] Examples of the alcohol-based organic solvent include alkyl alcohols having 1 to 4 carbon atoms, such as ethanol, methanol, butanol, propanol, and isopropanol; Examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycols with a molecular weight of 2,000 or less, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, glycerin, mesoerythritol, and pentaerythritol.

[0047] Examples of the aliphatic organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.

[0048] From the viewpoint of ease of handling, the content of the solvent in the composition for forming a green coating film is preferably adjusted so that the solid content concentration including the pigment, etc. is 6 to 40 mass %. Furthermore, when preparing a composition for forming a green coating film using a green pigment dispersion and a yellow pigment dispersion, the content of the solvent in each pigment dispersion is preferably adjusted so that the solid content concentration including the pigment, etc. is 6 to 40 mass %.

[0049] The green coating film-forming composition of the present invention may contain other additives in addition to the above-mentioned components, as necessary. Examples of the other additives include colorants other than the above-mentioned yellow pigment and green pigment, antioxidants, anti-aggregation agents, surface conditioners (leveling agents), etc.

[0050] The green coating film-forming composition of the present invention preferably contains a polymer or a polymerizable component as a coating film-forming component. The polymer is preferably an alkali-soluble resin that is soluble in a solution in the alkaline range. From the viewpoint of developability, the weight average molecular weight of the polymer is preferably 5,000 to 50,000. As the alkali-soluble resin that can be used as a coating film-forming component, various resins are commercially available, and specific examples thereof are as follows, but are not limited to these. Resonac Corporation: Lipoxy (registered trademark) SPC-2000; Mitsubishi Chemical Corporation: Dianale (registered trademark) NR series, Osaka Organic Chemical Industry Co., Ltd.: Viscoat R-264, KS Resist 106, SOP-005, Daicel Corporation: Cyclomer (registered trademark) P series, Plaxel (registered trademark) CF200 series, Daicel-Allnex Corporation: Ebecryl (registered trademark) 3800, Manufactured by Soken Chemical Industries, Ltd.: Follett (registered trademark) ZAH-110.

[0051] As the polymerizable component, a photopolymerizable component is preferred because it is easy to apply patterning by development (negative development). Usable photopolymerizable components include photopolymerizable compounds and photopolymerization initiators. As such photopolymerizable compounds and photopolymerization initiators, for example, compounds described in JP-A-2009-179789 can be used.

[0052] These additives may be mixed with the above-mentioned components when preparing the green coating film-forming composition, or may be mixed in advance with the green pigment dispersion and the yellow pigment dispersion.

[0053] The green coating film forming composition of the present invention can be prepared, for example, by adding each of the above-mentioned components to a known dispersing machine such as a bead mill, a sand mill, or a disperser and dispersing them. There is no particular limitation on the way each component is added, and each component may be mixed at the same time and dispersed, or a green pigment dispersion and a yellow pigment dispersion may be prepared in advance and then mixed and dispersed again. Since the progress of dispersion differs for each pigment, from the viewpoint of the dispersibility of each pigment, it is preferable to prepare a green pigment dispersion and a yellow pigment dispersion in advance and then mix them and disperse again.

[0054] The green pigment dispersion contains a phthalocyanine green pigment, a resin-type dispersant, and a solvent, and may optionally contain the above-mentioned additives. The resin-type dispersant can be appropriately changed according to the phthalocyanine green pigment used, and is not particularly limited as long as it can disperse the phthalocyanine green pigment, but it is preferable that the acid value is 30 mgKOH / g or more and 135 mgKOH / g or less. The resin-type dispersant may have an amine value or may be 0 mgKOH / g. The above-mentioned solvents can be suitably used as the solvent contained in the green pigment dispersion.

[0055] The yellow pigment dispersion contains CI Pigment Yellow 150 and / or a pigment derivative of CI Pigment Yellow 150, an acid-type dispersant having an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less, and a solvent, and may optionally contain the above-mentioned additives, etc. As the solvent contained in the yellow pigment dispersion, the above-mentioned solvents can be suitably used.

[0056] <Production examples of derivatives> A derivative (Chemical Formula 5) encompassed by Chemical Formula 1 was produced using the following raw materials and production method.

[0057] [ka]

[0058] 240 parts by mass of water, 240 parts by mass of ethylene glycol, 19.2 parts by mass of N,N-diethylaminopropylamine, and 22.5 parts by mass of 4-acetamidobenzenesulfonyl chloride were mixed and reacted at 50°C for 1 hour. The temperature was raised to 85°C, and 33.6 parts by mass of 35% hydrochloric acid was added and reacted for 3 hours. After cooling to 5°C or less, 19.6 parts by mass of 40.5% aqueous sodium nitrite solution was added and reacted for 30 minutes. Furthermore, 10 parts by mass of 80% acetic acid and 10 parts by mass of sodium acetate were added and cooled to 1°C or less to obtain reaction liquid A.

[0059] 30 parts by mass of dipropylene glycol monomethyl ether, 15.5 parts by mass of 4-hydroxy-2-quinolinone (1 molar equivalent relative to 4-acetaminobenzenesulfonyl chloride), and 15 parts by mass of 30% aqueous sodium hydroxide solution were added to 100 parts by mass of water at 60°C and dissolved, and then 300 parts by mass of cold water was added to obtain reaction liquid B.

[0060] Reaction liquid B was added to reaction liquid A, and the mixture was reacted at 25° C. for 30 minutes, and then further reacted at 60° C. for 30 minutes. The pH was adjusted to 10 with sodium hydroxide, and then the mixture was filtered, washed with water, and dried to obtain 36 parts by mass of a compound represented by chemical formula 5.

[0061] Using an AXIMA CFR plus matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (Shimadzu Corporation), the molecular ion peak of the compound obtained was measured in positive ion mode using α-cyano-4-hydroxycinnamic acid (CHCA) as the matrix. As a result, a peak was observed at m / z = 458. This ion peak corresponds to the molecular weight of 457 of the compound represented by chemical formula 5.

[0062] Furthermore, according to the method described in Example 4 of Patent Document 1, a pigment dispersant (D) represented by Chemical Formula 3 was produced.

[0063] <Production Example 1 of Yellow Pigment Dispersion> 10.2 parts by mass of CI Pigment Yellow 150 (manufactured by Lanxess KK, Levascreen Yellow G 05) as a yellow pigment, 1.80 parts by mass of a compound represented by chemical formula 4 as a derivative, 12.0 parts by mass of Solsperse (registered trademark) 41000 (manufactured by Lubrizol Japan, acid value: 50 mg KOH / g, amine value: 0 mg KOH / g) as an acid-type dispersant in terms of solid content, 76.0 parts by mass of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 400 parts by mass of φ0.8 mm zirconia beads were placed in a container and dispersed for 30 minutes using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). After removing the φ0.8 mm zirconia beads, 400 parts by mass of φ0.1 mm zirconia beads were added and dispersed again for 60 minutes using a paint shaker. The φ0.1 mm zirconia beads were removed to obtain a yellow pigment dispersion PY-1.

[0064] <Production Example 2 of Yellow Pigment Dispersion> A yellow pigment dispersion PY-2 was obtained in the same manner as in Production Example 1, except that 1.80 parts by mass of the pigment dispersant (D) represented by Chemical Formula 3 was used instead of the compound represented by Chemical Formula 5 as the derivative.

[0065] <Production Example 3 of Yellow Pigment Dispersion> A yellow pigment dispersion PY-3 was obtained in the same manner as in Production Example 1, except that 12.0 parts by mass of HIPLAAD (registered trademark) ED-153 (manufactured by Kusumoto Chemicals Co., Ltd., acid value: 55 mg KOH / g, amine value: 0 mg KOH / g) was used in place of Solsperse (registered trademark) 41000 as the acid dispersant, calculated as a solid content.

[0066] <Production Example 4 of Yellow Pigment Dispersion> A yellow pigment dispersion PY-4 was obtained in the same manner as in Production Example 3, except that 1.80 parts by mass of the pigment dispersant (D) represented by Chemical Formula 3 was used instead of the compound represented by Chemical Formula 5 as the derivative.

[0067] <Production Example 5 of Yellow Pigment Dispersion> A yellow pigment dispersion PY-5 was obtained in the same manner as in Production Example 1, except that 12.0 parts by mass of Terplus (registered trademark) MD1100 (manufactured by Otsuka Chemical Co., Ltd., acid value: 85 mg KOH / g, amine value: 0 mg KOH / g) was used in place of Solsperse (registered trademark) 41000 as the acid dispersant, calculated as a solid content.

[0068] <Production Example 6 of Yellow Pigment Dispersion> A yellow pigment dispersion PY-6 was obtained in the same manner as in Production Example 5, except that 1.80 parts by mass of the pigment dispersant (D) represented by Chemical Formula 3 was used instead of the compound represented by Chemical Formula 5 as the derivative.

[0069] [Viscosity measurement of yellow pigment dispersion] The viscosity (25° C.) of the yellow pigment dispersions PY-1 to PY-6 immediately after preparation was measured using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.). The compositions and viscosities of the yellow pigment dispersions PY-1 to PY-6 are shown in Table 1. In Table 1, the values ​​for the yellow pigment, derivatives, and acid-type dispersants indicate the solid content (non-volatile content).

[0070] [Table 1]

[0071] Only the yellow pigment dispersion PY-4 gelled immediately after preparation. All the other yellow pigment dispersions had a viscosity that did not cause any problems when used as a coating film-forming composition. In other words, the yellow pigment dispersions other than the yellow pigment dispersion PY-4 had excellent pigment dispersibility.

[0072] <Green Pigment Dispersion Production Example 1> 12.0 parts by mass of CI Pigment Green 58 (DIC Corporation, FASTOGEN (registered trademark) GREEN A110) as a green pigment, 7.2 parts by mass of DISPERBYK (registered trademark)-2001 (BYK Japan Co., Ltd., acid value: 41 mg KOH / g, amine value: 63 mg KOH / g) as a dispersant, 2.4 parts by mass of Folet ZAH-110 (Soken Chemical Industries, Ltd., acid value: 96 mg KOH / g) as an alkali-soluble resin, 78.4 parts by mass of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 400 parts by mass of φ0.8 mm zirconia beads were placed in a container and dispersed for 20 minutes using a paint shaker (Asada Iron Works Co., Ltd.). After removing the φ0.8 mm zirconia beads, 400 parts by mass of φ0.1 mm zirconia beads were added and dispersed again for 30 minutes using a paint shaker. The 0.1 mm zirconia beads were removed to obtain a green pigment dispersion PG-1.

[0073] <Green Pigment Dispersion Production Example 2> 12.0 parts by mass of CI Pigment Green 59 (manufactured by DIC Corporation, FASTOGEN (registered trademark) GREEN C100) as a green pigment, 9.6 parts by mass of DISPERBYK (registered trademark)-2001 (manufactured by BYK Japan Co., Ltd., acid value: 41 mg KOH / g, amine value: 63 mg KOH / g) as a dispersant, 2.4 parts by mass of Folet ZAH-110 (manufactured by Soken Chemical Industries Co., Ltd., acid value: 96 mg KOH / g) as an alkali-soluble resin, 76.0 parts by mass of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 400 parts by mass of φ0.8 mm zirconia beads were placed in a container and dispersed for 20 minutes using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). After removing the φ0.8 mm zirconia beads, 400 parts by mass of φ0.1 mm zirconia beads were added and dispersed again for 30 minutes using a paint shaker. The 0.1 mm zirconia beads were removed to obtain a green pigment dispersion PG-2.

[0074] <Preparation of green coating film-forming composition> A green coating film-forming composition was prepared by mixing yellow pigment dispersion PY-1, PY-2, PY-5, or PY-6 with green pigment dispersion PG-1 or PG-2. The mass ratio of yellow pigment dispersion PY-2 or yellow pigment dispersion PY-6 was adjusted for the green coating film-forming composition containing yellow pigment dispersion PY-2 or yellow pigment dispersion PY-6, as shown in Tables 2 to 5 below, according to the chromaticity of the coating film prepared from the green coating film-forming composition containing yellow pigment dispersion PY-1 or yellow pigment dispersion PY-5. All coating film-forming compositions had a viscosity that did not cause any problems in coating film formation.

[0075] <Example 1> PG-1 and PY-1 were mixed in a mass ratio of 50:50, and Follett ZAH-110 was added so that the ratio of the total mass of the green pigment and yellow pigment in the mixture to the total mass of each dispersant (DISPERBYK®-2001 contained in PG-1 and Solsperse® 41000 contained in PY-1) and alkali-soluble resin was 1:1. Furthermore, PMA was added so that the solid content concentration of the resulting mixture was 20 mass %, and a green coating film-forming composition of Example 1 was obtained.

[0076] <Examples 2 to 4, Comparative Examples 1 to 4> Green coating film-forming compositions (solid content concentration: 20 mass%) of Examples 2 to 4 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1, except that the green pigment dispersion and the yellow pigment dispersion were changed as shown in Tables 2 to 5 described below.

[0077] <How to prepare the coating> For each green coating composition, three types of green coating films with different chromaticity were prepared. Specifically, the green coating composition was applied to a glass plate (thickness 1 mm, 100 mm square) using a spin coater (MS-150A, manufactured by Mikasa Co., Ltd.), pre-baked (90°C, 2.5 minutes), and then post-baked (230°C, 30 minutes) to form a green coating film. In addition, the thickness of the green coating film was changed by changing the rotation speed of the spin coater, and the chromaticity of the green coating film was adjusted.

[0078] The chromaticity of the three types of green coating films produced was such that one film had a chromaticity y value smaller than a specific value and the other film had a chromaticity y value larger than a specific value. The specific chromaticity y values ​​were those shown in Tables 2 to 5 described below.

[0079] [Evaluation method for green paint film] The chromaticity coordinates (x, y) and luminance Y of the prepared green coating film were measured using a colorimeter (MCPD-6800, manufactured by Otsuka Electronics Co., Ltd.). In addition, the contrast ratio (CR) was measured using a colorimeter (BM-5AS, manufactured by Topcon Technohouse Co., Ltd.). An approximate straight line (calibration curve) was created from the measured values ​​of three types of green coating films with different chromaticities, and the luminance and contrast ratio (CR) of each green coating film were obtained from this calibration curve. The luminance and contrast ratio of each green coating film were adopted as the luminance and contrast ratio at the chromaticity coordinates (x, y) listed in Tables 2 to 5. In addition, the film thickness was measured using a film thickness meter (F20-EXR, manufactured by FILMETRICS Co., Ltd.).

[0080] Tables 2 to 5 show the composition of the green coating film forming composition used for each green coating film, and the color coordinates (x, y), brightness (Y), contrast ratio (CR) and film thickness of the green coating film after post-baking.

[0081] [Table 2]

[0082] [Table 3]

[0083] [Table 4]

[0084] [Table 5]

[0085] From Tables 2 to 5, it was confirmed that the green coating films of Examples 1 to 4 were superior in brightness (Y) and contrast ratio (CR) to the green coating films of Comparative Examples 1 to 4, respectively. In addition, the thicknesses of the green coating films of Examples 1, 2, and 4 were comparable to those of Comparative Examples 1, 2, and 4, respectively. On the other hand, the thickness of the green coating film of Example 3 was significantly thinner than that of Comparative Example 3. That is, the green coating film of Example 3 had superior coloring power. From the above, it was confirmed that the green coating film-forming compositions used in Examples 1 to 4 had the same pigment dispersibility at the time of preparation as the green coating film-forming compositions of Comparative Examples 1 to 4 using the pigment dispersant (D) (chemical formula 3) used in Example 4 of Patent Document 1, and when a green coating film was produced, the brightness and contrast ratio were superior. [Industrial Applicability]

[0086] The green coating film-forming composition and its production method of the present invention are useful in technical fields such as displays, solid-state imaging devices, and infrared sensors.

Claims

1. Yellow pigment, A green pigment; A derivative represented by Chemical Formula 1, An acid type dispersant having an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less; A solvent; A green coating film-forming composition comprising: The yellow pigment is CI Pigment Yellow 150 and / or a derivative pigment of CI Pigment Yellow 150; The green pigment is a phthalocyanine green pigment. Composition for forming green paint film. 【Chemistry 1】 (R １ and R ２ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or -R ３ -NR ４ R ５ is any of the groups represented by R ３ is an alkylene group having 1 to 6 carbon atoms, R ４ and R ５ are each independently an alkyl group having 1 to 6 carbon atoms, R １ and R ２ At least one of the groups is -R ３ -NR ４ R ５ It is a group represented by the following formula:

2. For forming green pixels in color filters. The composition for forming a green coating film according to claim 1 .

3. preparing a dispersion of a yellow pigment; preparing a dispersion of a green pigment; mixing the yellow pigment dispersion with the green pigment dispersion, The yellow pigment dispersion is A derivative represented by Chemical Formula 1, An acid type dispersant having an acid value of 40 mgKOH / g or more and 90 mgKOH / g or less; It contains a solvent, The yellow pigment is CI Pigment Yellow 150 and / or a derivative pigment of CI Pigment Yellow 150; The dispersion of the green pigment is A phthalocyanine green pigment; A resin type dispersant; A solvent and A method for producing a green coating film-forming composition. 【Chemistry 2】 (R １ and R ２ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or -R ３ -NR ４ R ５ is any of the groups represented by R ３ is an alkylene group having 1 to 6 carbon atoms, R ４ and R ５ are each independently an alkyl group having 1 to 6 carbon atoms, R １ and R ２ At least one of the groups is -R ３ -NR ４ R ５ It is a group represented by the following formula:

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