Photosensitive coloring composition, color filter and display element

Abstract

The invention provides a photosensitive coloring composition, a color filter and a display element, wherein the photosensitive coloring composition can obtain a colored hardened film with high brightness, high contrast and excellent solvent resistance. The photosensitive coloring composition contains (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, the colorant (A) containing a dye represented by formula (1), and the photopolymerization initiator (D) containing an oxime initiator. (In formula (1), RX1-RX16 each independently represents a hydrogen atom, a halogen atom, or-ORP1, and RP1 represents a monovalent organic group. In the formula, at least one of RX1-RX16 represents a halogen atom, and at least one of RX1-RX16 represents-ORP1. > # imgabs0 #

Description

[0001] The present invention is a divisional application of the invention patent application with application number 2019108593116 filed on September 11, 2019 and invention name “Photosensitive coloring composition, color filter and display element”. Technical Field

[0002] The present invention relates to a photosensitive coloring composition, a color filter and a display element. Background Art

[0003] Colorants and dyes used in colored hardened films such as color filters have been widely studied. Dyes are excellent in improving the hue or brightness of displayed images when displaying images due to the color purity of the dye itself or the vividness of its hue. On the other hand, dyes generally have poor heat resistance or solvent resistance, and are low in solubility relative to solvents, and are considered difficult to be practical. Therefore, in the past, various dyes have been proposed for use as colorants for display elements, etc. (for example, refer to Patent Document 1 or Patent Document 2). Dyes with phthalocyanine skeletons are disclosed in Patent Document 1 and Patent Document 2.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2012-180519

[0007] [Patent Document 2] Japanese Patent Application Laid-Open No. 05-345861 Summary of the invention

[0008] [Problems to be solved by the invention]

[0009] Regarding display elements such as liquid crystal displays, large-screen and high-definition LCD TVs have become the mainstay. In addition, the popularization of small display terminals such as smart phones and tablet personal computers (PCs) has expanded their uses. In addition, as the use of display elements expands, further high-quality display elements are required. In order to achieve further high-quality display elements, it is expected that the high-quality coloring cured films such as color filters possessed by display elements can be achieved.

[0010] For example, color filters are required to achieve higher brightness and higher contrast. In addition, in color filters, other layers are sometimes formed after patterning, and resistance to solvents contained in other layers is required. Therefore, not only color characteristics but also solvent resistance needs to be sufficiently high.

[0011] The present invention has been made in view of the above-mentioned problems, and one object of the present invention is to provide a photosensitive coloring composition capable of obtaining a colored cured film having high brightness and high contrast and excellent solvent resistance.

[0012] [Technical means to solve the problem]

[0013] In order to solve the above-mentioned problems, according to the present invention, the following photosensitive coloring composition, color filter, and display element are provided.

[0014] [1] A photosensitive coloring composition comprising (A) a coloring agent, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the (A) coloring agent comprises a dye represented by the following formula (1), and the (D) photopolymerization initiator comprises an oxime initiator.

[0015] [Chemistry 1]

[0016]

[0017] (In formula (1), R X1 ~R X16 Each independently represents a hydrogen atom, a halogen atom or -OR P1 , R P1 represents a monovalent organic group. X1 ~R X16 At least one of them represents a halogen atom, and at least one represents -OR P1 . )

[0018] [2] The photosensitive coloring composition according to [1] above, wherein the colorant (A) further contains a yellow pigment.

[0019] [3] The photosensitive coloring composition according to [1] or [2], further comprising a polyfunctional thiol compound.

[0020] [4] The photosensitive coloring composition according to any one of [1] to [3], wherein the (E) solvent contains: a first solvent which is at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and 3-methoxybutyl acetate; and a second solvent which is at least one selected from the group consisting of water and an alcohol having 1 to 4 carbon atoms.

[0021] [5] The photosensitive coloring composition according to any one of [1] to [4], further comprising a dispersant.

[0022] [6] The photosensitive coloring composition according to any one of [1] to [5], further comprising (B) an alkali-soluble resin. The acid value of the alkali-soluble resin (B) is preferably 75 mgKOH / g to 200 mgKOH / g.

[0023] [7] A photosensitive coloring composition comprising (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the (A) colorant is contained in an amount of 15% to 45% by mass relative to the total solid content in the photosensitive coloring composition, wherein the (A) colorant comprises a dye having a zinc phthalocyanine structure, wherein a coating film is formed on a substrate using the photosensitive coloring composition, and a value obtained by calculating the color difference ΔEab before and after the coating film is heated at 230° C. for 20 minutes to a film thickness of 2.5 μm based on the International Commission on Illumination (CIE) 1976 standard is 5 to 30.

[0024] [8] The photosensitive coloring composition according to [7], wherein the colorant (A) contains a dye represented by the formula (1).

[0025] [9] The photosensitive coloring composition according to [8], wherein the colorant (A) further contains a yellow pigment.

[0026]

[10] The photosensitive coloring composition according to any one of [7] to [9], further comprising a polyfunctional thiol compound.

[0027]

[11] The photosensitive coloring composition according to any one of [7] to

[10] , further comprising a dispersant.

[0028]

[12] The photosensitive coloring composition according to any one of [7] to

[11] , further comprising (B) an alkali-soluble resin. The acid value of the alkali-soluble resin (B) is preferably 75 mgKOH / g to 200 mgKOH / g.

[0029]

[13] A photosensitive coloring composition comprising (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the solvent (E) comprises: a first solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methoxybutyl acetate; and a second solvent selected from the group consisting of water and an alcohol having 1 to 4 carbon atoms, wherein the second solvent is contained in an amount of 0.2% by mass to 2.0% by mass relative to the total solvent in the photosensitive coloring composition, wherein the colorant (A) comprises a compound satisfying the following necessary conditions (i) and (ii).

[0030] (i) The solubility at 25° C. in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate or methoxybutyl acetate, or a mixed solvent of two or more thereof is 10 g / L or less.

[0031] (ii) The solubility at 25° C. in water or a primary alcohol having 1 to 4 carbon atoms, or a mixed solvent of two or more thereof is 10 g / L or less.

[0032]

[14] The photosensitive coloring composition according to

[13] , wherein the colorant (A) contains a dye represented by the formula (1).

[0033]

[15] The photosensitive coloring composition according to

[14] , wherein the colorant (A) further contains a yellow pigment.

[0034]

[16] The photosensitive coloring composition according to any one of

[13] to

[15] , further comprising a polyfunctional thiol compound.

[0035]

[17] The photosensitive coloring composition according to any one of

[13] to

[16] , further comprising a dispersant.

[0036]

[18] The photosensitive coloring composition according to any one of

[13] to

[17] , further comprising (B) an alkali-soluble resin. The acid value of the alkali-soluble resin (B) is preferably 75 mgKOH / g to 200 mgKOH / g.

[0037]

[19] A color filter formed using the photosensitive coloring composition according to any one of [1] to

[18] .

[0038]

[20] A display element comprising the color filter according to

[19] .

[0039] [Effects of the Invention]

[0040] According to the photosensitive coloring composition containing the zinc phthalocyanine dye represented by formula (1) as the (A) coloring agent and the oxime initiator as the (D) photopolymerization initiator, a colored cured film having high brightness and high contrast and excellent solvent resistance can be obtained. DETAILED DESCRIPTION

[0041] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit.

[0042] <<First Implementation Method>>

[0043] [Photosensitive coloring composition]

[0044] The photosensitive coloring composition is a composition for forming a coloring layer such as each color pixel, black matrix, black spacer, etc. used in the color filter. The photosensitive coloring composition of the present embodiment (hereinafter referred to as "first photosensitive coloring composition") contains (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent.

[0045] <(A) Coloring agent>

[0046] The (A) coloring agent contained in the first photosensitive coloring composition contains a dye having a zinc phthalocyanine structure, and specifically, contains a compound represented by the following formula (1) (hereinafter, also referred to as “specific dye A”).

[0047] [Chemistry 2]

[0048]

[0049] (In formula (1), R X1 ~R X16 Each independently represents a hydrogen atom, a halogen atom or -OR P1 , R P1 represents a monovalent organic group. X1 ~R X16 At least one of them represents a halogen atom, and at least one represents -OR P1 . )

[0050] Regarding R in the formula (1) X1 ~R X16 As the halogen atom, for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be mentioned. Furthermore, when there are two or more halogen atoms in the formula (1), the plurality of halogen atoms may all be of the same type or may be of different types. X1~R X16 The halogen atoms present preferably include at least fluorine atoms, and particularly preferably all of them are fluorine atoms.

[0051] In terms of achieving high brightness, R X1 ~R X16 The number of halogen atoms in is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, and particularly preferably 8 or more. X1 ~R X16 The number of groups which are halogen atoms in the alkylene group is 15 or less, preferably 14 or less, more preferably 12 or less.

[0052] The group "-OR P1 "R" P1 Preferred are substituted or unsubstituted monovalent chain hydrocarbon groups having 1 to 10 carbon atoms, substituted or unsubstituted monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, or substituted or unsubstituted monovalent heterocyclic groups having 6 to 20 carbon atoms.

[0053] Here, in this specification, the so-called "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure on the main chain, but are composed only of a chain structure. Among them, it can be saturated or unsaturated. The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains the structure of alicyclic hydrocarbon as a ring structure and does not contain an aromatic ring structure. Among them, it is not necessary to be composed only of the structure of alicyclic hydrocarbons, and a hydrocarbon group having a chain structure in a part thereof is also included. The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessary to be composed only of the aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be contained in a part thereof. The so-called "heterocyclic group" is a group formed by removing n (n is an integer) hydrogen atoms from the ring part of the heterocycle.

[0054] In R P1 When the hydrocarbon group or heterocyclic group has a substituent, examples of the substituent include, in addition to halogen atoms and alkoxy groups, groups formed by combining a hydrocarbon group or heterocyclic group with -O-, -CO-, or -COO-. P1 In the case of a substituted or unsubstituted monovalent heterocyclic group, examples of the heterocyclic ring constituting the heterocyclic group include a nitrogen-containing heterocyclic ring, a sulfur-containing heterocyclic ring, and an oxygen-containing heterocyclic ring, and the heterocyclic ring may be either an aromatic ring or a non-aromatic ring.

[0055] Among these, the group "-OR P1 " is preferably a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Specifically, it is preferably a monovalent group represented by the following formula (2).

[0056] [Chemistry 3]

[0057]

[0058] (In formula (2), X 10 is a single bond or an oxygen atom, R 21 R is a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. 20 is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. k is an integer of 1 to 3, and m is an integer of 0 to 2. When k is 2 or 3, multiple X 10 , R 21 Each independently has the above definition, when m is 2, multiple R 20 Each independently has the above definition. "*" represents a bond to the aromatic ring in formula (1).

[0059] In the above formula (2), examples of the substituents of the chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group include alkoxy groups having 1 to 5 carbon atoms. 21 It is preferably a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms. 21 In the case of a substituted alkyl group, a group having an alkoxy group having 1 to 5 carbon atoms as a substituent is preferred.

[0060] k is preferably 1 or 2, more preferably 1. When k = 1, the group "-CO-X 10 -R 21 " is preferably bonded to the 3-position or 4-position relative to -O-, more preferably to the 4-position. When k = 2, the two groups "-CO-X 10 -R 21 " is preferably bonded to the 3,5-position or the 2,4-position relative to -O-, and more preferably bonded to the 3,5-position.

[0061] m is preferably 0 or 1, more preferably 0.

[0062] Preferred specific examples of the group represented by the formula (2) include groups represented by the following formulae (2-1) to (2-15), respectively.

[0063] [Chemistry 4]

[0064]

[0065] (In the formula, "*" represents a bond.)

[0066] In terms of the high improvement effect on solvent resistance and heat resistance, R X1 ~R X16 The group "-OR P1 The number of " is preferably 2 or more, more preferably 4 or more. In addition, the group "-OR P1 The number of " is 15 or less, preferably 14 or less, more preferably 12 or less, and further preferably 8 or less.

[0067] In terms of solvent resistance and heat resistance, R X1 ~R X16 Preferably R X2 , R X3 , R X6 , R X7 , R X10 , R X11 , R X14 and R X15 At least 4 of them are groups "-OR P1 ", especially preferably R X2 , R X3 , R X6 , R X7 , R X10 , R X11 , R X14 and R X15 All are groups "-OR P1 ”, and the rest (R X1 , R X4 , R X5 , R X8 , R X9 , R X12 , R X13 and R X16 ) is a halogen atom.

[0068] Preferred specific examples of the specific dye A include compounds represented by the following formula (1-1) to formula (1-6), respectively.

[0069] [Chemistry 5]

[0070]

[0071] [Chemistry 6]

[0072]

[0073] (In the formula, Me represents a methyl group, Et represents an ethyl group, and n-Bu represents a n-butyl group.)

[0074] (Other colorants)

[0075] In the first photosensitive coloring composition, the colorant (A) may contain the specific dye A alone, or may contain the specific dye A and a colorant different from the specific dye A (hereinafter also referred to as "other colorant") together. By further containing other colorants, a colored layer of desired chromaticity can be obtained.

[0076] As other coloring agents, there is no particular limitation, and color or kind can be appropriately selected according to purpose. As other coloring agents, dyes other than pigment and specific dye A and natural pigments can be used, but in order to obtain pixels with high brightness and color purity, at least any one of organic pigments and organic dyes is preferred.

[0077] Examples of organic pigments include compounds classified as pigments in the Color Index (CI (Color Index); issued by The Society of Dyers and Colourists), that is, compounds to which the following Color Index (CI) names are attached. The following organic pigments can be preferably used.

[0078] CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 61, CI Pigment Yellow 61:1, CI Pigment Yellow 62, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 100, CI Pigment Yellow 104, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 129, CI Pigment Yellow 133, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 140, CI Pigment Yellow 141, CI Pigment Yellow 142, CI Pigment Yellow 143, CI Pigment Yellow 144, CI Pigment Yellow 145, CI Pigment Yellow 146, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 149, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153 Yellow pigments such as CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 180, CI Pigment Yellow 183, CI Pigment Yellow 185, CI Pigment Yellow 191, CI Pigment Yellow 191:1, CI Pigment Yellow 206, CI Pigment Yellow 209, CI Pigment Yellow 209:1, CI Pigment Yellow 211, CI Pigment Yellow 212, CI Pigment Yellow 215, CI Pigment Yellow 231;

[0079] Green pigments such as CI Pigment Green 1, CI Pigment Green 4, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 63;

[0080] Blue pigments such as CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 79, CI Pigment Blue 80;

[0081] Orange pigments such as CI Pigment Orange 38;

[0082] Violet pigments such as CI Pigment Violet 19 and CI Pigment Violet 23.

[0083] When a pigment is used as another colorant, or when no pigment is used, it is preferred that a dispersant is contained in the photosensitive coloring composition. In addition, a dispersant and a dispersing aid may also be contained together. As the dispersant and the dispersing aid, known ones can be used. Specifically, as a dispersant, for example, a carbamate dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, a polyethylene glycol diester dispersant, a sorbitan fatty acid ester dispersant, a polyester dispersant, an acrylic dispersant, etc. can be listed; as a dispersing aid, for example, a pigment derivative can be listed.

[0084] As the organic dye, among compounds to which the Color Index (CI) name is attached, the following organic dyes can be preferably used.

[0085] Yellow dyes such as CI Acid Yellow 11, CI Direct Yellow 12, CI Reactive Yellow 2, CI Mordant Yellow 5, CI Acid Yellow 3, CI Acid Yellow 1, CI Basic Yellow 4, CI Solvent Yellow 33, CI Disperse Yellow 64, CI Disperse Yellow 42, CI Solvent Yellow 179, Disperse Yellow 201, etc.

[0086] Green dyes such as CI Direct Green 59, CI Direct Green 28, CI Acid Green 25, etc.

[0087] In addition, as the organic dye, in addition to the above, yellow dyes described in Japanese Patent Laid-Open No. 2015-044982, Japanese Patent Laid-Open No. 2017-207676, and Japanese Patent Laid-Open No. 2013-213208 can also be used.

[0088] The specific dye A is usually green. Therefore, the photosensitive coloring composition containing the specific dye A is preferably used to form a green pixel. In this case, the colorant (A) preferably contains the specific dye A and at least one selected from the group consisting of a green pigment, a green dye, a yellow pigment, and a yellow dye as other colorants. This photosensitive coloring composition more preferably contains at least a yellow pigment as another colorant, and more preferably contains at least a yellow pigment.

[0089] When the colorant (A) contains other colorants, the content ratio of the specific dye A in the colorant (A) is appropriately adjusted to obtain the desired chromaticity, preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more, and particularly preferably 20% by mass or more, relative to the total amount of the colorant (A). In addition, the content ratio of the specific dye A in the colorant (A) is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less, relative to the total amount of the colorant (A). Furthermore, the specific dye A and other colorants can be used alone or in combination of two or more.

[0090] From the viewpoint of forming pixels with high brightness and excellent color purity, or from the viewpoint of forming a black matrix with excellent light-shielding properties, the content ratio of the (A) colorant is generally 5% to 70% by mass relative to the total solid content of the photosensitive coloring composition. The content ratio of the (A) colorant is preferably 10% by mass or more, more preferably 12% by mass or more, and further preferably 15% by mass or more relative to the total solid content of the photosensitive coloring composition. In addition, the content ratio of the (A) colorant is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 45% by mass or less relative to the total solid content of the photosensitive coloring composition. In addition, in this specification, the so-called "solid content" refers to the components other than the (E) solvent contained in the photosensitive coloring composition. Therefore, the so-called "total solid content" refers to the components of the (A) colorant, (C) polymerizable compound, (D) photopolymerization initiator, and other components (including (B) alkali-soluble resin) other than (A) and (C) to (E) combined. For example, even if the photopolymerizable compound or additive components (such as surfactants) are in a liquid state, these are contained in the solid component.

[0091] <(B) Alkali-soluble resin>

[0092] The coloring composition preferably contains (B) an alkali-soluble resin. (B) The alkali-soluble resin is not particularly limited as long as it is soluble in an alkaline solution, and is preferably a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among these, (B) the alkali-soluble resin is preferably a polymer having a carboxyl group (hereinafter, also referred to as a "carboxyl-containing polymer"). As a carboxyl-containing polymer, for example, copolymers of ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter, also referred to as "unsaturated monomers (b1)") and ethylenically unsaturated monomers copolymerizable with the unsaturated monomer (b1) (hereinafter, also referred to as "unsaturated monomers (b2)").

[0093] Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(meth)acryloyloxyethyl] ester, ω-carboxy polycaprolactone mono(meth)acrylate, and p-vinylbenzoic acid. In addition, the term "(meth)acrylic acid" as used herein includes methacrylic acid and acrylic acid. The alkali-soluble resin (B) may have only one structural unit derived from the unsaturated monomer (b1), or may have two or more structural units in combination.

[0094] Examples of the unsaturated monomer (b2) include N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide;

[0095] Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthene;

[0096] Methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 2 ,6 ] decane-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane and the like (meth)acrylates;

[0097] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 2,6 ] vinyl ethers such as decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane;

[0098] Macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, polybutyl(meth)acrylate, and polysiloxane, etc. The alkali-soluble resin (B) may have only one structural unit derived from the unsaturated monomer (b2), or may have two or more structural units in combination.

[0099] In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5% to 50% by mass, more preferably 10% to 40% by mass. By having the unsaturated monomer (b1) component within this range, a photosensitive coloring combination having excellent alkali developability and storage stability can be obtained.

[0100] Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include copolymers disclosed in JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. In addition, as (B) an alkali-soluble resin, for example, as disclosed in Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095, etc., a carboxyl group-containing polymer having a polymerizable unsaturated bond (for example, a carbon-carbon double bond in a (meth)acryloyl group) in the side chain can also be used.

[0101] For (B) alkali-soluble resin, the weight average molecular weight (Mw) of polystyrene conversion measured by gel permeation chromatography (GPC) with the elution solvent set to tetrahydrofuran is generally 1,000 to 100,000. Mw is preferably 3,000 or more. In addition, Mw is preferably 50,000 or less. If Mw is within the range, the generation of dry foreign matter or the reduction of resolution during coating by a slit nozzle method can be suppressed, and the residual film rate, pattern shape, heat resistance and electrical properties of the film suitable for a color filter can be ensured.

[0102] The ratio (Mw / Mn) of the Mw of the alkali-soluble resin (B) to the number average molecular weight (Mn) is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. Mn is a polystyrene-equivalent value measured by GPC using tetrahydrofuran as the elution medium.

[0103] The acid value of the alkali-soluble resin (B) is preferably 75 mgKOH / g to 200 mgKOH / g. By setting the acid value of the alkali-soluble resin (B) to a value within the above range, it is preferred in that the contrast of the colored layer obtained using the photosensitive coloring composition of the present invention can be further improved. From the perspective of providing a higher contrast for the colored layer, the acid value is more preferably 100 mgKOH / g or more, and further preferably 120 mgKOH / g or more. In addition, the acid value is more preferably 190 mgKOH / g or less. Here, in this specification, the so-called "acid value" refers to the number of mg of KOH required to neutralize 1 g of the solid content of the alkali-soluble resin (B).

[0104] (B) Alkali-soluble resin can be produced by known methods. In addition, its structure or Mw and Mw / Mn can be controlled by methods disclosed in Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, International Publication No. 07 / 029871, etc. Furthermore, (B) alkali-soluble resin can be used alone or in combination of two or more.

[0105] In the photosensitive coloring composition, the content of the alkali-soluble resin (B) is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, relative to 100 parts by mass of the colorant (A). When the content of the alkali-soluble resin (B) is within the above range, it is possible to ensure appropriate alkali developability in the coating film formation process, sufficient storage stability as a product of the obtained coloring composition, and sufficient color density for the required film thickness as the obtained color filter.

[0106] <(C) Polymerizable compound>

[0107] (C) The polymerizable compound is a compound having preferably two or more polymerizable groups and functions as a crosslinking agent. The polymerizable group is preferably a group that can be subjected to free radical polymerization, for example, ethylenically unsaturated groups, oxacyclopropyl groups, oxetanyl groups, N-alkoxymethylamino groups, etc. Among these, the (C) polymerizable compound is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

[0108] Specific examples of the compound having two or more (meth)acryloyl groups include: polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional (meth)acrylic acid urethanes obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride.

[0109] As the compound having more than two N-alkoxymethylamino groups, for example, compounds having a melamine structure, a benzoguanamine structure, a urea structure, etc. can be cited. Furthermore, the so-called melamine structure and benzoguanamine structure refer to a chemical structure having one or more triazine rings or a triazine ring substituted with a phenyl group as a basic skeleton, and are concepts that also include melamine, benzoguanamine, or condensates thereof. Specific examples of compounds having more than two N-alkoxymethylamino groups include: N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl)glycoluril, etc.

[0110] Among these, as the (C) polymerizable compound, polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional (meth)acrylate urethanes, polyfunctional (meth)acrylates having a carboxyl group, N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, and N,N,N',N'-tetra(alkoxymethyl)benzoguanamine are preferred, and polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, polyfunctional (meth)acrylate urethanes, and polyfunctional (meth)acrylates having a carboxyl group are more preferred. Among the multifunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred in terms of high strength of the coloring layer, excellent surface smoothness of the coloring layer, and difficulty in causing stains and film residues on the substrate and the light-shielding layer of the unexposed portion. In addition, for the same reason, among the multifunctional (meth)acrylates having a carboxyl group, compounds obtained by reacting pentaerythritol triacrylate with succinic anhydride and compounds obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferred. (C) The polymerizable compound may be used alone or in combination of two or more.

[0111] The content of the (C) polymerizable compound in the photosensitive coloring composition is preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more, relative to 100 parts by mass of the (A) colorant. In addition, the content of the (C) polymerizable compound is preferably 1,000 parts by mass or less, and particularly preferably 500 parts by mass or less, relative to 100 parts by mass of the (A) colorant. If the content ratio of the (C) polymerizable compound is within the above range, sufficient curability as a coating film and sufficient alkali developability as a photosensitive coloring composition can be ensured, and the generation of stains, film residues, etc. on the substrate of the unexposed portion or on the light-shielding layer can be sufficiently suppressed.

[0112] <(D) Photopolymerization initiator>

[0113] (D) The photopolymerization initiator is a compound that generates an active species capable of initiating polymerization of the (C) polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. The first photosensitive coloring composition contains an oxime initiator as the (D) photopolymerization initiator. In the above case, free radicals can be sufficiently generated in the presence of the specific dye A, and film curing can be sufficiently performed. As the oxime initiator, an O-acyl oxime initiator can be preferably used.

[0114] Specific examples of O-acyl oxime initiators include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-, 1-(O -acetyl oxime), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), 1,2-propanedione, 3-cyclohexyl-1-[4-(phenylthio)phenyl]-, 1-(O-acetyl oxime) (a compound represented by the following formula (D-1)), a compound represented by the following formula (D-2), etc.

[0115] [Chemistry 7]

[0116]

[0117] As the O-acyl oxime initiator, commercially available products such as NCI-831, NCI-930 (produced by ADEKA Co., Ltd.) and PBG-3057 (produced by Changzhou Qiangli Electronic New Materials Co., Ltd.) can also be used.

[0118] As the O-acyl oxime initiator, compounds represented by the following formula (d-10), formula (d-11), and formula (d-12) can also be preferably used.

[0119] [Chemistry 8]

[0120]

[0121] (In formula (d-10), X 1 and X 2 Each of them is independently a single bond or -CO-. 1 and X 2 At least one of R is -CO-. 1 is an alkyl group having 2 to 6 carbon atoms, R 2 is an alkyl group having 4 to 10 carbon atoms. 4 is a monovalent organic group having a hydrocarbon ring or a heterocyclic ring. 3 and R 5 Each is independently an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

[0122] [Chemistry 9]

[0123]

[0124] (In formula (d-11) and formula (d-12), X 3 is a single bond or an alkanediyl group having 1 to 5 carbon atoms, X 4 -O-, -S- or -NR 10 -(where R 10 is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms). 5 and X 6 are independently a single bond or -CO-, R 6 and R 7 are independently a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group, R 8 and R 9 R is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms. 11 and R 12 are each independently a hydrogen atom or a monovalent substituent. )

[0125] In the formula (d-10), R 1 Preferably, it is ethyl or propyl. 2 It may be linear or branched, but is preferably linear. 4It is preferably a group in which a hydrocarbon ring or a heterocyclic ring is bonded to a carbon atom of an oxime ester group via a divalent linking group. The divalent linking group is preferably at least one selected from the group consisting of an alkanediyl group having 1 to 4 carbon atoms, -S-, -O- and -CO-, and more preferably a methylene group, an ethylene group, -S- or -O-. The hydrocarbon ring is preferably a cyclopentane ring or a cyclohexane ring, and the heterocyclic ring is preferably a dioxolane ring or a pyrimidine ring.

[0126] In the formula (d-11) and the formula (d-12), when R 6 , R 7 , R 8 or R 9 When there is a substituent, examples of the substituent include a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, and a cyano group. 11 and R 12 The substituents include: a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group and a cyano group, and a group in which at least one hydrogen atom of an alkyl group, a cycloalkyl group, a cycloalkylalkyl group or an alkylcycloalkyl group is substituted with a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group or a cyano group.

[0127] As the O-acyl oxime initiator, at least one selected from the group consisting of acyl oxime compounds having a diphenyl sulfide skeleton, acyl oxime compounds having a carbazole skeleton, and acyl oxime compounds having a fluorene skeleton can be preferably used in terms of making the contrast ratio of the cured film better. The O-acyl oxime initiator is more preferably at least one selected from the group consisting of acyl oxime compounds having a diphenyl sulfide skeleton and acyl oxime compounds having a fluorene skeleton.

[0128] As (D) photopolymerization initiator, an oxime initiator may be used alone or in combination with a photopolymerization initiator different from the oxime initiator (hereinafter, also referred to as "other initiators"). Other initiators are not particularly limited, and examples thereof include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, etc. Among these, the other initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, and triazine compounds.

[0129] Among these, acetophenone compounds are particularly preferred as other initiators used in combination with oxime initiators. The combined use of acetophenone compounds is suitable in that the solvent resistance of the obtained cured film can be further improved.

[0130] When other initiators are used in combination as the (D) photopolymerization initiator, the content of the oxime initiator is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more, relative to the total amount of the (D) photopolymerization initiator used (the total amount of the oxime initiator and other initiators), in order to further improve the heat resistance and solvent resistance of the obtained cured film.

[0131] The content ratio of (D) photopolymerization initiator is preferably 0.01 parts by mass or more, and more preferably 1 part by mass or more, relative to 100 parts by mass of (C) polymerizable compound. In addition, the content ratio of (D) photopolymerization initiator is preferably 120 parts by mass or less, and more preferably 100 parts by mass or less, relative to 100 parts by mass of (C) polymerizable compound. If the content of (D) photopolymerization initiator is within the range, sufficient curing of the coating film brought about by appropriate exposure and sufficient alkali developability as a photosensitive coloring composition can be ensured, and the generation of stains and film residues on the substrate or light-shielding layer of the unexposed part can be fully suppressed. In addition, the reduction in brightness of the coating film caused by yellowing of the polymerization initiator during post-baking can be fully suppressed. (D) Photopolymerization initiator can be used alone or in combination of two or more.

[0132] <(E) Solvent>

[0133] The photosensitive coloring composition is prepared as a liquid composition by mixing (E) a solvent. As the (E) solvent, a solvent that disperses or dissolves each component (A), component (C), component (D) or other components constituting the photosensitive coloring composition, does not react with these components, and has moderate volatility can be preferably used.

[0134] Specific examples of the (E) solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether;

[0135] Alkyl lactates such as methyl lactate and ethyl lactate; (cyclo)alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, and cyclohexanol; keto alcohols such as diacetone alcohol;

[0136] (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

[0137] Propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate and other diacetates;

[0138] Alkoxy carboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutyl propionate;

[0139] Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene;

[0140] N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amides or lactams, etc.

[0141] Among these, the (E) solvent is preferably at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, and ethyl pyruvate. In addition, (E) The solvent may be used alone or in combination of two or more.

[0142] When the photosensitive coloring composition contains the specific dye A, it is preferable that the (E) solvent contains the following first solvent and second solvent.

[0143] The first solvent is at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methoxybutyl acetate.

[0144] The second solvent is at least one selected from the group consisting of water and alcohols having 1 to 4 carbon atoms.

[0145] The specific dye A has low solubility in the first solvent and low solubility in the second solvent. More specifically, the solubility of the specific dye A at 25°C in the first solvent is 10 g / L or less, and the solubility at 25°C in the second solvent is 10 g / L or less. On the other hand, the specific dye A has good solubility in a mixed solvent of the first solvent and the second solvent, and its solubility at 25°C in the mixed solvent is sufficiently greater than 10 g / L. Therefore, it is preferred in terms of being able to suppress the presence of foreign matter in the coating film formed using the photosensitive coloring composition and improving productivity. In addition, the mixed solvent of the first solvent and the second solvent does not have such an odor, so it is excellent in terms of being able to make the working environment good and having good storage stability.

[0146] When a mixed solvent of a first solvent and a second solvent is used as the solvent (E), the content of the second solvent is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, relative to the total amount of solvent in the photosensitive coloring composition, from the viewpoint of sufficiently ensuring the solubility of the specific dye A in the solvent. In addition, with respect to the mixed solvent of the first solvent and the second solvent, the content of the second solvent is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and further preferably 1.5% by mass or less, relative to the total amount of solvent in the photosensitive coloring composition.

[0147] The content ratio of the (E) solvent in the first photosensitive coloring composition is not particularly limited, but is preferably an amount in which the total concentration of each component other than the solvent in the photosensitive coloring composition is 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass. By setting it as such a form, a colorant solution or colorant dispersion having good dispersibility and stability can be obtained. In addition, a coloring composition having good coating properties and stability can be obtained.

[0148] <(F) Additives>

[0149] In addition, the photosensitive coloring composition may contain various additives as needed. Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; adhesion promoters; antioxidants; ultraviolet absorbers, etc. The blending ratio of these additives can be appropriately set according to the type of each additive within the range that does not impair the effects of the present disclosure.

[0150] The photosensitive coloring composition of the present disclosure preferably contains a polyfunctional thiol compound. In this case, it is suitable in that the photosensitivity of the coloring composition is improved and the solvent resistance of the obtained cured film can be improved.

[0151] The polyfunctional thiol compound is not particularly limited as long as it is a compound having two or more thiol groups (-SH). Specific examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-bis(mercaptomethyl)benzene, butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyryloxy)butane. The present invention also includes condensates of trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, butanediol bis(3-mercaptoisobutyrate), and mercaptoalkyltrialkoxysilane (e.g., 3-mercaptopropyltrimethoxysilane). The polyfunctional thiol compound may be used alone or in combination of two or more.

[0152] The blending ratio of the polyfunctional thiol compound in the photosensitive coloring composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total amount of the solid content of the composition. In addition, the blending ratio of the polyfunctional thiol compound is preferably 10% by mass or less, and more preferably 3% by mass or less, relative to the total amount of the solid content of the coloring composition. If the content ratio of the polyfunctional thiol compound is within the above range, the coating film is sufficiently cured by an appropriate exposure amount, and the adhesion of the formed coloring layer to the substrate can be sufficiently improved, and the coloring layer is not easily detached from the substrate during development.

[0153] <Preparation of photosensitive coloring composition>

[0154] The photosensitive coloring composition of the present disclosure can be prepared by an appropriate method. As a preparation method thereof, for example, methods disclosed in Japanese Patent Laid-Open No. 2008-58642, Japanese Patent Laid-Open No. 2010-132874, etc. can be cited. In the case of using both a dye and a pigment as the (A) colorant, the following method can be adopted: as disclosed in Japanese Patent Laid-Open No. 2010-132874, after passing the dye solution through a first filter, the dye solution passed through the first filter is mixed with a separately prepared pigment dispersion, and the resulting coloring composition is passed through a second filter, thereby preparing. In addition, the following method can also be adopted: dissolving the dye, the (B) component, the (C) component, the (D) component, and other components used as needed in a solvent, passing the resulting solution through a first filter, mixing the solution passed through the first filter with a separately prepared pigment dispersion, and passing the resulting photosensitive coloring composition through a second filter, thereby preparing. Alternatively, the dye solution may be passed through a first filter, and then the dye solution passed through the first filter is mixed with the component (B), the component (C), the component (D), and other components used as necessary, and dissolved, and the resulting solution is passed through a second filter, and then the solution passed through the second filter is mixed with a separately prepared pigment dispersion, and the resulting photosensitive coloring composition is passed through a third filter to prepare the composition.

[0155] [Color filter and method for manufacturing the same]

[0156] The color filter of the present disclosure includes a colored layer formed using the photosensitive colored composition described above.

[0157] As a method for manufacturing a color filter, first, a light-shielding layer (black matrix) is formed on the surface of a substrate in a manner that divides the parts that form pixels as needed. Secondly, after applying a green photosensitive coloring composition (liquid composition) on this substrate, pre-baking is performed to evaporate the solvent to form a coating film. Secondly, after exposing the coating film through a photomask, an alkaline developer is used to develop the coating film, and the unexposed part of the coating film is dissolved and removed. Thereafter, a pixel array is formed by post-baking, and the pixel array is configured with a green pixel pattern in a prescribed arrangement.

[0158] Next, using each photosensitive coloring composition of red or blue, each photosensitive coloring composition is coated, pre-baked, exposed, developed and post-baked in the same manner as described above, and a red pixel array and a blue pixel array are sequentially formed on the same substrate. A color filter having a pixel array of the three primary colors of green, red and blue arranged on a substrate is thus obtained. However, the order in which pixels of each color are formed is not limited to the order described. The black matrix can be formed by setting a metal thin film of chromium or the like formed by sputtering or evaporation to a desired pattern using a photolithography method. In addition, a photosensitive coloring composition in which a black colorant is dispersed can be formed in the same manner as the formation of the pixels described above.

[0159] Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. If necessary, these substrates may be subjected to appropriate pretreatment such as chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum evaporation, etc.

[0160] When the photosensitive coloring composition is applied to the substrate, a suitable coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a rod coating method, etc. can be used, and spin coating and slit die coating methods are particularly preferred. Prebaking is performed at a temperature lower than the post-baking temperature, usually at 70°C to 110°C for about 1 minute to 10 minutes. The coating thickness is usually 0.6μm to 8μm, preferably 1.2μm to 5μm, based on the film thickness after drying.

[0161] As the light source of radiation used in exposure, for example, there can be listed: xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp and other lamp light sources or argon ion laser, yttrium aluminum garnet (Yttrium-Aluminum-Garnet, YAG) laser, XeCl excimer laser, nitrogen laser and other laser light sources. It is also possible to use ultraviolet light-emitting diode (LED) as the exposure light source. Preferably, the radiation has a wavelength in the range of 190nm to 450nm, and more preferably, the radiation has a wavelength in the range of 300nm to 450nm. The exposure amount of the radiation is generally preferably 10J / m 2 ~10,000J / m 2 The radiation exposure is more preferably 100 J / m 2 More than 200 J / m 2 In addition, the exposure amount of radiation is more preferably 5,000 J / m 2 Below, more preferably 2,000 J / m 2 the following.

[0162] As the alkaline developer, for example, aqueous solutions of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. are preferred. It is also possible to add an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the alkaline developer. Furthermore, water washing is usually performed after alkali development. As a development treatment method, the following can be applied: a shower development method, a spray development method, an immersion (dip) development method, a puddle development method, etc. The development conditions are preferably performed at room temperature for 5 seconds to 300 seconds. The post-baking conditions are usually performed at 180°C to 280°C for about 10 minutes to 60 minutes. The film thickness of the pixel formed in the above manner is usually 0.5μm to 5μm, preferably 1.0μm to 3μm.

[0163] After forming a protective film as needed on the pixel pattern obtained in the manner, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. A transparent photosensitive resin composition is usually used to form the spacer, but a spacer (black spacer) with light-shielding properties can also be made. In the case, a photosensitive coloring composition dispersed with a black colorant is used. The photosensitive coloring composition disclosed herein can also be suitably used to form the black spacer.

[0164] The photosensitive coloring composition disclosed herein can also be suitably used to form any color cured film such as each color pixel, black matrix, black spacer, etc. used in the color filter. The color filter formed in this manner has high brightness and color purity, so it is particularly useful for color liquid crystal display elements, solid-state imaging elements, color sensors, organic electroluminescence (EL) display elements, electronic paper, etc.

[0165] [Display components]

[0166] The display element of the present disclosure includes the color filter of the present disclosure. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

[0167] In addition to a cold cathode fluorescent lamp (CCFL), a color liquid crystal display element having a color filter disclosed herein may have a backlight unit using a white LED as a light source. Examples of white LEDs include: a white LED that combines a red LED, a green LED, and a blue LED and obtains white light by color mixing; a white LED that combines a blue LED, a red LED, and a green phosphor and obtains white light by color mixing; a white LED that combines a blue LED, a red light-emitting phosphor, and a green light-emitting phosphor and obtains white light by color mixing; a white LED that obtains white light by color mixing a blue LED and a YAG-based phosphor; a white LED that combines a blue LED, an orange light-emitting phosphor, and a green light-emitting phosphor and obtains white light by color mixing; a white LED that combines an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor and obtains white light by color mixing, etc.

[0168] The organic EL display element having the color filter of the present disclosure may adopt an appropriate structure, for example, the structure disclosed in Japanese Patent Laid-Open No. 11-307242. In addition, the electronic paper having the color filter of the present disclosure may adopt a structure disclosed in Japanese Patent Laid-Open No. 2007-41169.

[0169] Second Implementation Method

[0170] Next, the second embodiment will be described focusing on differences from the first embodiment.

[0171] The photosensitive coloring composition of the present embodiment (hereinafter referred to as the "second photosensitive coloring composition") contains (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, preferably (B) an alkali-soluble resin. Among the components, the components (B), (C) and (E) are basically the same as those in the first embodiment, so the description is cited and omitted.

[0172] The (A) colorant contained in the second photosensitive coloring composition includes a dye having a zinc phthalocyanine structure. As a dye having a zinc phthalocyanine structure, there is no particular limitation as long as it has a zinc phthalocyanine skeleton, and among these, a specific dye A can be preferably used. As the (A) colorant, only the specific dye A can be used, but in order to obtain the desired chromaticity, it is preferred to use the specific dye A and other colorants together. The description of the specific dye A and other colorants applies the description of the first embodiment. In terms of being able to fully display the desired color characteristics by the color change before and after heating (post-baking) of the coating film formed by using the photosensitive coloring composition, the (A) colorant (including other colorants) contained in the second photosensitive coloring composition is preferably a phthalocyanine dye.

[0173] The (D) photopolymerization initiator may not necessarily contain an oxime initiator, and any of the photopolymerization initiators exemplified in the description of the first embodiment may be used. In the second photosensitive coloring composition, the (D) photopolymerization initiator preferably contains an oxime initiator, and more preferably contains an O-acyl oxime initiator, in terms of being able to sufficiently promote film curing by an appropriate exposure amount. Regarding the type or content ratio of the O-acyl oxime initiator, the description of the first embodiment applies.

[0174] Regarding the second photosensitive coloring composition, the content ratio of (A) colorant (when containing two or more, the total amount of these) is set to 15% by mass to 45% by mass relative to the total solid content in the photosensitive coloring composition, and a coating film is formed on a substrate using this coloring composition. The color difference ΔEab before and after heating when the coating film is heated (post-baked) at 230°C for 20 minutes to form a cured film with a film thickness of 2.5 μm is calculated based on the CIE1976 standard. The value obtained is 5 to 30. By the color difference ΔEab before and after post-baking being within the range, the color change before and after post-baking is moderately small, and a color filter with high contrast, high brightness, and high heat resistance can be obtained. From the perspective of obtaining a color filter with high contrast, high brightness and high heat resistance, the color difference ΔEab before and after post-baking is preferably 6 or more, more preferably 7 or more, and more preferably 9 or more. In addition, the color difference ΔEab is preferably 25 or less, more preferably 20 or less, and more preferably 16 or less.

[0175] The color difference ΔEab before and after post-baking can be calculated as follows. First, a photosensitive coloring composition is applied to a substrate and pre-baked to form a coating film on the substrate. The "coating film" mentioned here is a film formed on a substrate by heating at a temperature lower than the post-baking temperature (i.e., pre-baking). The pre-baking conditions apply the description of the first embodiment. Next, exposure and development are performed using the conditions described in the first embodiment, and then post-baking is performed at 230°C for 20 minutes. The color difference ΔEab before and after the post-baking is calculated based on the CIE1976 standard. In order to make the film thickness after post-baking the desired value (2.5μm), it can be done by adjusting the coating conditions of the photosensitive coloring composition (for example, the rotation speed of the spin coater, etc.).

[0176] In order to achieve high color purity of the display element and suppress development failure, the content ratio of the (A) colorant in the photosensitive coloring composition (when containing two or more types, the total amount of these) is more preferably 15% by mass to 40% by mass, and further preferably 20% by mass to 40% by mass, relative to the total solid content in the photosensitive coloring composition.

[0177] Furthermore, the reason why the color difference ΔEab before and after post-baking can achieve high brightness and high heat resistance of the color filter is still uncertain, but as a hypothesis, it is believed that due to the structure of the pigment, certain chemical state changes such as the association of the pigment occur through heating during post-baking, which affects the color characteristics of the pigment. At this time, when the color difference ΔEab before and after post-baking is within the range, the color difference is controlled to a specific state, thereby controlling the color characteristics, and it is inferred that high brightness and high heat resistance of the color filter can be achieved. In order to make the color difference ΔEab before and after post-baking within the range, it can be done by adjusting the type of colorant or the color material concentration in the solid component, the concentration of the alkali-soluble resin, the concentration of the polymerizable compound, etc. More specifically, in order to make the color difference ΔEab before and after post-baking within the above range, the following method can be used: a photosensitive coloring composition is prepared using a coloring agent containing a dye having a zinc phthalocyanine structure, and the color difference ΔEab before and after post-baking is measured using this coloring composition by the above method. If the measured color difference ΔEab is to be within the range of 5 to 30, the concentration of the alkali-soluble resin, the concentration of the polymerizable compound, etc. are optimized by a conventional method for the coloring composition containing the coloring agent.

[0178] According to the second photosensitive coloring composition (the photosensitive coloring composition of [7]) shown above, a colored cured film with high brightness and excellent heat resistance can be obtained. In addition, by using the photosensitive coloring composition of this embodiment, a color filter and a display element with high brightness and high heat resistance can be obtained. The description of the color filter and the display element applies to the description of the first embodiment.

[0179] 《Third Implementation Mode》

[0180] Next, the third embodiment will be described focusing on differences from the first embodiment.

[0181] The photosensitive coloring composition of the present embodiment (hereinafter referred to as the "third photosensitive coloring composition") contains (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, preferably (B) an alkali-soluble resin. Of the components, component (B) and component (C) are basically the same as those in the first embodiment, so the description is cited and omitted.

[0182] In the third photosensitive coloring composition, the coloring agent (A) contains a dye (hereinafter referred to as “specific dye α”) satisfying the following requirements (i) and (ii).

[0183] (i) The solubility at 25° C. in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate or methoxybutyl acetate, or a mixed solvent of two or more thereof is 10 g / L or less.

[0184] (ii) The solubility at 25° C. in water or a primary alcohol having 1 to 4 carbon atoms, or a mixed solvent of two or more thereof is 10 g / L or less.

[0185] The specific dye α has good solubility in the mixed solvent of the first solvent and the second solvent, and its solubility at 25°C in the mixed solvent is greater than 10 g / L. The solubility of the specific dye α at 25°C in the mixed solvent of the first solvent and the second solvent is preferably 15 g / L or more, more preferably 20 g / L or more. The specific dye α is preferably a dye having a zinc phthalocyanine structure, and the specific dye A can be preferably used.

[0186] Furthermore, the third photosensitive coloring composition may contain only a dye satisfying the requirements of the formula (i) and the formula (ii) as the colorant (A), and may further contain a colorant different from the dye (preferably a yellow pigment). When a dye satisfying the requirements of the formula (i) and the formula (ii) and a colorant different from the dye are used in combination, the content ratio of the dye satisfying the requirements of the formula (i) and the formula (ii) is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 20% by mass or more. In addition, the content ratio of the dye satisfying the requirements of the formula (i) and the formula (ii) is preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less relative to the total amount of the colorant (A).

[0187] In the third photosensitive coloring composition, the (D) photopolymerization initiator may not necessarily contain an oxime initiator, and any of the photopolymerization initiators exemplified in the description of the first embodiment may be used. In terms of being able to sufficiently promote the curing of the coating film by an appropriate exposure amount, the (D) photopolymerization initiator preferably contains an oxime initiator, and more preferably contains an O-acyl oxime initiator. Regarding the type or content ratio of the O-acyl oxime initiator, the description of the first embodiment applies.

[0188] The third photosensitive coloring composition contains the first solvent and the second solvent as the (E) solvent. The content ratio of the second solvent is 0.2 mass % to 2.0 mass % relative to the total solvent amount in the photosensitive coloring composition. If the content ratio of the second solvent is less than 0.2 mass % or exceeds 2.0 mass %, the solubility of the dye in the solvent cannot be fully improved, and foreign matter is easily generated in the coating film, so it is not preferred. The content ratio of the second solvent is preferably 0.3 mass % or more relative to the total solvent amount in the photosensitive coloring composition. In addition, the content ratio of the second solvent is preferably 1.8 mass % or less, and more preferably 1.5 mass % or less relative to the total solvent amount in the photosensitive coloring composition.

[0189] As long as the effect brought about by using the first solvent and the second solvent is not impaired, the (E) solvent may contain other solvents different from the first solvent and the second solvent. From the viewpoint of sufficiently improving the solubility of the dye in the solvent, the (E) solvent in the third photosensitive coloring composition preferably contains the first solvent and the second solvent. The blending ratio of the (E) solvent in the third photosensitive coloring composition is applied to the description of the first embodiment.

[0190] Specific dye A has the characteristics of low solubility relative to the first solvent and low solubility relative to the second solvent, on the other hand, excellent solubility relative to the mixed solvent of the first solvent and the second solvent. Therefore, when comprising specific dye A as (A) colorant, and using the mixed solvent of the first solvent and the second solvent as (E) solvent, the solubility of the dye relative to the solvent can be improved, and the presence of foreign matter in the coating film can be suppressed. As other advantages of being set as a mixed solvent, even if each is a low solubility solvent of the dye alone, it can be used by mixing with other solvents, so the option of solvent is wide, and a general and stable quality safe solvent can be used. In addition, the mixed solvent of the first solvent and the second solvent is not so smelly, so it does not cause adverse effects on the working environment, and in addition, the storage stability is also excellent.

[0191] According to the third photosensitive coloring composition shown above (the photosensitive coloring composition of

[13] ), the generation of foreign matter in the coating film can be suppressed, and a colored cured film with less odor and excellent storage stability can be obtained. In addition, by using the third photosensitive coloring composition, the generation of foreign matter in the coating film can be suppressed, and the productivity of the color filter and the display element is excellent. The description of the color filter and the display element is applied to the description of the first embodiment.

[0192] 《Implementation Examples》

[0193] The present invention is specifically described below by way of examples, but the present invention is not limited to these examples. Furthermore, the "parts" and "%" in the examples and comparative examples are by mass unless otherwise specified. In the present examples, the weight average molecular weight (Mw) and acid value of the polymer are measured by the following method.

[0194] (Weight average molecular weight Mw)

[0195] This is a polystyrene-equivalent value measured by GPC (elution solvent: tetrahydrofuran).

[0196] (Acid value)

[0197] Weigh 0.5 g of the polymer solution to an accuracy of 1 mg and dispense into a glass container. Dilute to 50 mL with propylene glycol monomethyl ether acetate, add phenolphthalein, and titrate with 0.1 N ethanolic potassium hydroxide aqueous solution. The point colored pink is the end point. Perform a blank test in the same manner. Calculate the acid value (unit: mgKOH / g) based on the amount of 0.1 N ethanolic potassium hydroxide aqueous solution added to the polymer and the blank test.

[0198] [Example 1]

[0199] In this Example, a first photosensitive coloring composition was prepared and evaluated.

[0200] 1. Synthesis of compounds

[0201] 1-1. Synthesis of alkali-soluble resin (B-1)

[0202] A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. The mixture was heated to 80°C, and a mixed solution of 100 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 15 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-acryloyloxyethyl)succinate, and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise at the temperature for 1 hour, and the mixture was polymerized for 2 hours while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 100°C, and the polymerization was further performed for 1 hour, thereby obtaining an alkali-soluble resin solution (solid content concentration 33% by mass). The obtained alkali-soluble resin had an Mw of 12,200 and an acid value of 137 mgKOH / g. The alkali-soluble resin is referred to as “alkali-soluble resin (B-1)”.

[0203] 1-2. Synthesis of alkali-soluble resin (B-2)

[0204] A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and nitrogen substitution was performed. The mixture was heated to 80°C, and a mixed solution of 100 parts by mass of propylene glycol monomethyl ether acetate, 7 parts by mass of methacrylic acid, 15 parts by mass of styrene, 10 parts by mass of benzyl methacrylate, 20 parts by mass of 2-hydroxyethyl methacrylate, 28 parts by mass of 2-ethylhexyl methacrylate, 15 parts by mass of N-phenylmaleimide, 5 parts by mass of mono(2-acryloyloxyethyl)succinate, and 4 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise at the temperature for 1 hour, and the polymerization was performed for 2 hours while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 100°C, and the polymerization was further performed for 1 hour, thereby obtaining an alkali-soluble resin solution (solid content concentration 33% by mass). The Mw of the obtained alkali-soluble resin was 18,500, and the acid value was 59 mgKOH / g. The alkali-soluble resin is referred to as “alkali-soluble resin (B-2)”.

[0205] 1-3. Synthesis of alkali-soluble resin (B-3)

[0206] A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and 100 parts by mass of propylene glycol monomethyl ether, and nitrogen substitution was performed. The mixture was heated to 80° C., and a mixed solution of 100 parts by mass of propylene glycol monomethyl ether acetate, 25 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 18 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 20 parts by mass of mono(2-acryloyloxyethyl)succinate, and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise at the temperature for 1 hour, and polymerization was performed for 2 hours while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 100° C., and polymerization was performed for another 1 hour, thereby obtaining an alkali-soluble resin solution (solid content concentration 33% by mass). The obtained alkali-soluble resin had an Mw of 13,200 and an acid value of 214 mgKOH / g. The alkali-soluble resin was referred to as "alkali-soluble resin (B-3)".

[0207] 1-4. Synthesis of alkali-soluble resin (B-4)

[0208] In a flask equipped with a condenser and a stirrer, 200 parts by mass of propylene glycol monomethyl ether acetate and 72 parts by mass of propylene glycol monomethyl ether were placed and nitrogen purged. The mixture was heated to 80°C, and a mixed solution of 100 parts by mass of propylene glycol monomethyl ether acetate, 80 parts by mass of glycidyl methacrylate, 10 parts by mass of styrene, 10 parts by mass of dicyclopentanyl acrylate, and 4 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise at the temperature for 1 hour, and the polymerization was carried out for 2 hours while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 100°C, and after further 1 hour of superposition, the flask was replaced with air. Next, 41 parts by mass of acrylic acid, 0.4 g of triphenylphosphine as a catalyst, and 0.4 g of methylhydroquinone as a polymerization inhibitor were added, and the mixture was reacted at 110°C for 10 hours. Furthermore, 43 parts by mass of tetrahydrophthalic anhydride was added and reacted at 110°C for 3 hours to obtain an alkali-soluble resin solution (solid content concentration 33% by mass). The obtained alkali-soluble resin had an Mw of 15,300 and an acid value of 172 mgKOH / g. The alkali-soluble resin was referred to as "alkali-soluble resin (B-4)".

[0209] [Table 1]

[0210]

[0211] 1-5. Synthesis of polyfunctional thiol compound (F-1)

[0212] A multifunctional thiol compound (hereinafter referred to as compound (F-1)) which is a condensate of 3-mercaptopropyltrimethoxysilane was prepared according to the preparation example of the condensate (A-1) described in paragraph

[0054] of Japanese Patent Laid-Open No. 2007-291313. The thiol equivalent of compound (F-1) is 398 g / eq. The thiol equivalent is determined by oxidation with iodine and then measuring the excess iodine by titration with a standard sodium thiosulfate solution.

[0213] 2. Preparation of Colorant Dispersion

[0214] 2-1. Preparation of colorant dispersion (MB-Y-1)

[0215] 13 parts by mass of CI Pigment Yellow 138 (referred to as Y138) as the colorant (A), 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK-Chemie, solid content concentration 40.0% by mass) as a dispersant in terms of solution, 15.2 parts by mass of the alkali-soluble resin (B-1) synthesized in 1.1 above (solid content concentration 33% by mass) in terms of solution, and a mixed solution containing 53.4 parts by mass of propylene glycol monomethyl ether acetate and 5.9 parts by mass of propylene glycol monomethyl ether as a solvent were mixed and dispersed for 12 hours using a bead mill to prepare a colorant dispersion (MB-Y-1).

[0216] 2-2. Preparation of Colorant Dispersions (MB-G-1) to (MB-G-3) and Colorant Dispersions (MB-Y-2) to (MB-Y-3)

[0217] Colorant dispersions (MB-G-1) to (MB-G-3) and colorant dispersions (MB-Y-2) to (MB-Y-3) were prepared in the same manner as the colorant dispersion (MB-Y-1) except that the types and amounts of the constituent components were changed as shown in Table 2 below.

[0218] [Table 2]

[0219]

[0220] The abbreviations of the pigments, dispersants, and solvents in Table 2 are as follows.

[0221] G58: CI Pigment Green 58

[0222] G59: CI Pigment Green 59

[0223] G63: CI Pigment Green 63

[0224] Y138: CI Pigment Yellow 138

[0225] Y150: CI Pigment Yellow 150

[0226] Y231: CI Pigment Yellow 231

[0227] LPN21116: BYK-LPN21116 (manufactured by BYK-Chemie)

[0228] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0229] PGME: Propylene Glycol Monomethyl Ether

[0230] 3. Preparation of Dye Solution

[0231] 3-1. Preparation of dye solution (SG-1)

[0232] 10.0 parts by mass of the compound (G-dye-1) as the (A) coloring agent was dissolved in 90.0 parts by mass of cyclohexanone to prepare a dye solution (SG-1).

[0233] 3-2. Preparation of dye solutions (SG-2) to (SG-8) and dye solutions (SY-1) to (SY-3)

[0234] Dye solutions (SG-2) to (SG-8) and dye solutions (SY-1) to (SY-3) were prepared in the same manner as dye solution (SG-1) except that the types of constituent components were changed as shown in Table 3 below. In addition, in Table 3 below, "LPN21116" in the dispersant column is BYK-LPN21116 (manufactured by BYK-Chemie).

[0235] [Table 3]

[0236]

[0237] The dyes in Table 3 (G-dye-1 to G-dye-5, Y-dye-1 to Y-dye-3) are compounds represented by the following formulas, respectively.

[0238] [Chemistry 10]

[0239]

[0240] [Chemistry 11]

[0241]

[0242] [Chemistry 12]

[0243]

[0244] [Chemistry 13]

[0245]

[0246] The abbreviations of the solvents in Table 3 are as follows. PGMEA and PGME are the same as those in Table 2. CHN: cyclohexanone

[0247] NMP: N-methyl pyrrolidone

[0248] EEP: 3-ethoxy ethyl propionate

[0249] MBA: methoxy butyl acetate

[0250] IPA: isopropanol

[0251] 4. Preparation and evaluation of coloring compositions [1]

[0252] [Example 1]

[0253] (1) Preparation of coloring composition

[0254] The colorant dispersion (MB-Y-1) and the dye solution (SG-1) were mixed so that the chromaticity coordinate values ​​(x, y) in the CIE colorimetric system were x=0.275 and y=0.560 in the brightness evaluation described later, to prepare 100.0 parts by mass of a colorant mixed solution (MG-1). Next, 23.2 parts by mass of an alkali-soluble resin (B-1) (solid content concentration 33% by mass), 4.4 parts by mass of (C-1) a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 4.4 parts by mass of (C-2) a carboxylic acid-modified multifunctional acrylate (Aronix M-520, manufactured by Toagosei Co., Ltd.), and (D-1) an oxime-based initiator (Changzhou Qiangli) as a photopolymerization initiator were mixed. 0.7 mass parts of (D-2) oxime initiator (a compound represented by the following formula (D-2)) and 0.05 mass parts of (S-1) Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant were mixed, and methoxybutyl acetate in an amount equivalent to 10% of the total solvent amount was added so that the solid content concentration became 17.0%, and propylene glycol monomethyl ether acetate in an amount equivalent to the remaining solvent amount was further added to prepare a coloring composition (G-1).

[0255] (2) Evaluation

[0256] The colored composition (G-1) was evaluated according to the following (i) and (ii).

[0257] (i) Evaluation of brightness and contrast

[0258] The coloring composition (G-1) was applied to a soda glass substrate having a SiO2 film formed on the surface to prevent sodium ion dissolution using a spin coater, and then pre-baked for 100 seconds using a 90°C hot plate to form a coating. During coating, the rotation speed of the spin coater was adjusted so that the film thickness after baking was 2.5 μm. Next, after the substrate was cooled to room temperature, a high-pressure mercury lamp was used without a photomask at 400 J / m 2The coating film is exposed to radiation of wavelengths of 365 nm, 405 nm and 436 nm on a portion of the substrate. Thereafter, a developer containing a 0.04 mass % potassium hydroxide aqueous solution at 23°C is sprayed on the substrate under the conditions of a developing pressure of 110 kPa and a developer flow rate of 1.2 liters / minute for a time equivalent to 1.5 times the time until the film of the unexposed part disappears and the substrate surface is seen, thereby performing spray development. Thereafter, the substrate is washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 20 minutes to prepare an evaluation substrate having a colored cured film with a film thickness of 2.5 μm.

[0259] The spectrum of the obtained substrate was measured using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), and the chromaticity y (0.560 in Example 1) corresponding to the colorant mixed solution in the CIE color system was converted using a C light source and a 2-degree viewing field to calculate the brightness (Y). As a result, in Example 1, the brightness (Y) at a certain chromaticity was 64.7.

[0260] Furthermore, the substrate with the cured film formed thereon was sandwiched between two polarizing plates, and a fluorescent lamp (wavelength range 380nm to 780nm) was used to illuminate from the back side and the polarizing plate on the front surface side was rotated, and the maximum and minimum values ​​of the transmitted light intensity were measured using a brightness meter LS-100 (manufactured by Minolta). Then, the value obtained by dividing the maximum value by the minimum value was taken as the contrast ratio. As a result, in Example 1, the contrast ratio = 11000. Furthermore, the contrast ratio means that the larger the value, the better.

[0261] (ii) Evaluation of solvent resistance

[0262] The coloring composition (G-1) was applied to a sodium glass substrate having a SiO2 film formed on the surface to prevent sodium ion dissolution using a spin coater, and then pre-baked for 100 seconds using a 90°C hot plate to form a coating. Furthermore, during coating, the rotation speed of the spin coater was adjusted so that the film thickness after baking was 2.5 μm. Next, after the substrate was cooled to room temperature, a high-pressure mercury lamp was used with a photomask (slit width 90 μm / space width 210 μm) at 400 J / m 2The coating film is exposed to radiation having wavelengths of 365 nm, 405 nm and 436 nm at an exposure amount. Thereafter, a developer containing a 0.04 mass % potassium hydroxide aqueous solution at 23° C. is sprayed onto the substrate under the conditions of a development pressure of 110 kPa and a developer flow rate of 1.2 liters / minute for a period of time equivalent to 1.5 times the time until the film of the unexposed portion disappears and the substrate surface is seen, thereby performing spray development. Thereafter, the substrate is cleaned and air-dried with ultrapure water, and then further post-baked in a clean oven at 230° C. for 20 minutes to form a striped pattern (film thickness 2.5 μm) on the substrate. For the obtained substrate, the chromaticity (x, y) and brightness (Y) in the CIE colorimetric system are measured using the color analyzer with a C light source and a 2-degree field of view.

[0263] Next, the substrate was immersed in N-methyl-2-pyrrolidone (NMP) at 25°C for 15 minutes, and the chromaticity (x, y) and brightness (Y) were measured in the same manner using the color analyzer. The solvent resistance was evaluated based on the color change (ΔEab(1)) before and after NMP immersion. As a result, in Example 1, ΔEab(1)=1.2. Furthermore, the smaller the value of ΔEab(1), the better the solvent resistance of the colored cured film. ΔEab(1) is a value calculated based on the CIE1976 standard.

[0264] [Example 2 to Example 24 and Comparative Example 1 to Comparative Example 6]

[0265] The colorant dispersion, dye solution and dye were mixed in such a manner as to obtain the chromaticity (x, y) shown in Table 4 below, thereby preparing colorant mixed liquid (MG-2) to colorant mixed liquid (MG-21), respectively. However, when the colorant mixed liquid contains more than three color materials, the mixing ratio (mass ratio) of the color materials in the dye solution or colorant dispersion used is recorded in Table 4 (the same as Table 7). Furthermore, in Table 4, "-" indicates that the corresponding components are not formulated (the same as Table 7). In addition, except for changing the type and amount of each component of the coloring composition as shown in Table 5 below, coloring compositions (G-2) to coloring compositions (G-26) were prepared in the same manner as in Example 1. For the obtained coloring compositions (G-2) to coloring compositions (G-26), brightness, contrast and solvent resistance were evaluated in the same manner as in Example 1. These results are shown in Table 6 below.

[0266] [Table 4]

[0267]

[0268] [Table 5]

[0269]

[0270] The components other than the coloring agent mixed solution and the alkali-soluble resin solution used when preparing the coloring composition are shown in Table 5. The "additional solvent" in Table 5 indicates a solvent component other than PGMEA.

[0271] C-1: Trade name "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.

[0272] C-2: Aronix M-520 manufactured by Toagosei Co., Ltd.

[0273] C-3: Trade name "OT-1000" manufactured by Toagosei Co., Ltd.

[0274] D-1: Trade name "PBG-3057" manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd. (a compound represented by the following formula (D-1))

[0275] D-2: Compound represented by the following formula (D-2)

[0276] D-3: Omnirad 369, a trade name manufactured by IGM Resins BV (a compound represented by the following formula (D-3))

[0277] D-4: 4,4'-bis(diethylamino)benzophenone (a compound represented by the following formula (D-4))

[0278] D-5: Compound represented by the following formula (D-5)

[0279] D-6: Trade name "Irgacure OXE-02" manufactured by BASF (compound represented by the following formula (D-6))

[0280] D-7: Omnirad 907, a trade name manufactured by IGM Resins BV (a compound represented by the following formula (D-7))

[0281] F-1: Compound (F-1) (polyfunctional thiol compound obtained in Synthesis Example 1-5)

[0282] F-2: Pentaerythritol tetrakis (3-mercaptopropionate)

[0283] S-1: "Megafac F-554" manufactured by DIC Corporation

[0284] MBA: Methoxybutyl acetate

[0285] IPA: Isopropyl alcohol [Chemical 14]

[0286]

[0287] [Table 6]

[0288]

[0289] From the results of Table 6, it can be seen that according to the photosensitive coloring compositions of Examples 1 to 24 containing the specific dye A as the (A) colorant and the oxime initiator as the (D) photopolymerization initiator, a color filter having high brightness and high contrast and excellent solvent resistance can be obtained.

[0290] [Example 2]

[0291] In this example, a second photosensitive coloring composition was prepared and evaluated. The synthesis of the compound, the preparation of the colorant dispersion, and the preparation of the dye solution were as described above.

[0292] 5. Preparation and evaluation of coloring compositions [2]

[0293] [Example 25]

[0294] (1) Preparation of coloring composition

[0295] The colorant dispersion and the dye solution were prepared so that the chromaticity (x, y) shown in Table 7 below was obtained. The colorant mixed solution (MG-22) was prepared, and the type and amount of each component of the coloring composition were changed as shown in Table 8 below. A coloring composition (G-27) was prepared in the same manner as in Example 1.

[0296] (2) Evaluation

[0297] The colored composition (G-27) was evaluated according to the following (i) and (ii).

[0298] (i) Evaluation of color change before and after baking and heat resistance after additional baking

[0299] The coloring composition (G-27) was applied to a soda glass substrate having a SiO2 film formed on the surface to prevent sodium ion dissolution using a spin coater, and then pre-baked for 100 seconds using a 90°C hot plate to form a coating. During coating, the rotation speed of the spin coater was adjusted so that the film thickness after baking was 2.5 μm. Next, after the substrate was cooled to room temperature, a high-pressure mercury lamp was used without a photomask at 400 J / m 2The coating film was exposed to radiation having wavelengths of 365 nm, 405 nm and 436 nm at an exposure amount of 1.2 liters / minute. Then, a developer containing a 0.04 mass % potassium hydroxide aqueous solution at 23° C. was sprayed onto the substrate for a time corresponding to 1.5 times the time until the film of the unexposed part disappeared and the substrate surface was seen under the conditions of a development pressure of 110 kPa and a developer flow rate of 1.2 liters / minute, thereby performing spray development. Then, the substrate was washed with ultrapure water and air-dried to form an evaluation substrate.

[0300] For the obtained evaluation substrate, the chromaticity (x, y) and brightness (Y) were measured using the color analyzer, and then baked in a clean oven at 230°C for 20 minutes to form a colored cured film with a film thickness of 2.5 μm. The chromaticity (x, y) and brightness (Y) of the evaluation substrate were measured in the same manner, and the color change before and after baking (ΔEab(2)) was evaluated. Furthermore, the substrate was additionally baked in a clean oven at 230°C for 60 minutes, and the chromaticity (x, y) and brightness (Y) were measured in the same manner. The heat resistance was evaluated based on the color change before and after the additional baking (ΔEab(3)). These evaluation results are shown in Table 9 below. Furthermore, it can be said that if ΔEab(2) is within the range of 5 to 30, the required color characteristics are exhibited, so it is good, and the smaller the value of ΔEab(3), the less the color change caused by baking, and the better the heat resistance. It should be noted that ΔEab(2) and ΔEab(3) are values ​​calculated based on the CIE1976 standard.

[0301] (ii) Evaluation of brightness

[0302] The spectrum was measured using a color analyzer in the same manner as in Example 1, and the chromaticity y was converted to the chromaticity y shown in Table 7 below in the CIE color system using a C illuminant and a 2 degree viewing field, and the brightness (Y) was calculated. The results of brightness (Y) at a certain chromaticity are shown in Table 9 below.

[0303] [Example 26 to Example 28 and Comparative Example 7 to Comparative Example 9]

[0304] The colorant dispersion and the dye solution were mixed in such a manner as to obtain the chromaticity (x, y) shown in Table 7 below, thereby preparing colorant mixed solutions (MG-23) to colorant mixed solutions (MG-26), respectively. In addition, except for changing the type and amount of each component of the coloring composition as shown in Table 8 below, coloring compositions (G-28) to coloring compositions (G-33) were prepared in the same manner as in Example 1. For the obtained coloring compositions (G-28) to coloring compositions (G-33), color changes before and after baking, additional baking heat resistance, and brightness were evaluated in the same manner as in Example 27. These results are shown in Table 9 below. In addition, the "additional solvent" in Table 8 represents a solvent component other than PGMEA.

[0305] [Table 7]

[0306]

[0307]

[0308] [Table 9]

[0309]

[0310] From the results of Table 9, it can be seen that according to the photosensitive coloring compositions of Examples 25 to 28, a color filter having high brightness and excellent heat resistance can be obtained compared to Comparative Example 7 in which a dye having a copper phthalocyanine structure is used as a colorant and ΔEab(2) is 2.5. In addition, according to the photosensitive coloring compositions of Examples 25 to 28, a color filter having higher brightness can be obtained compared to Comparative Example 8 in which ΔEab(2) is 3.8, and a color filter having excellent heat resistance can be obtained compared to Comparative Example 9 in which the coloring composition was prepared in which the color material concentration in the solid content was 50.1% by mass.

[0311] [Example 3]

[0312] In this example, a third photosensitive coloring composition was prepared and evaluated. The synthesis of the compound, the preparation of the colorant dispersion, and the preparation of the dye solution were as described above.

[0313] 6. Preparation and evaluation of coloring compositions [3]

[0314] [Example 29]

[0315] (1) Preparation of coloring composition

[0316] 10.0 parts by mass of dye powder (G-dye-1), 80.0 parts by mass of colorant dispersion (MB-Y-1), 45.0 parts by mass of alkali-soluble resin (B-1) in terms of solution, 8.2 parts by mass of (C-1) a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, a trade name produced by Nippon Kayaku Co., Ltd.) and 8.2 parts by mass of (C-2) a carboxylic acid-modified multifunctional acrylate (Aronix M-520, a trade name produced by Toagosei Co., Ltd.) as (D) a photopolymerization initiator, and 8.2 parts by mass of (D-2) a polyfunctional acrylate (Aronix M-520, a trade name produced by Toagosei Co., Ltd.) as (D ... ) 3.0 parts by mass of an oxime initiator (trade name PBG-3057 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1.5 parts by mass of a compound (F-1) as a multifunctional thiol compound, and 0.05 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant were mixed, and methoxybutyl acetate in an amount equivalent to 10% of the total solvent and water in an amount equivalent to 0.4% of the total solvent were added in such a way that the solid content concentration became 17.0%, and propylene glycol monomethyl ether acetate in an amount equivalent to the remaining solvent was further added to prepare a coloring composition (G-34).

[0317] (2) Evaluation of foreign matter in coatings

[0318] The coloring composition (G-34) was applied on a soda glass substrate having a SiO2 film formed on the surface to prevent sodium ion elution using a spin coater, and then prebaked for 100 seconds using a 90°C hot plate to form a coating film.

[0319] The obtained coating film was observed at a magnification of 50 times using an optical microscope, and the number of foreign matters that could be confirmed in the field of view was counted. The above operation was performed at any five locations of the cured film for evaluation, and the total number of confirmed foreign matters was set as "good (○)" if less than 5, "acceptable (△)" if 5 or more and less than 20, and "poor (×)" if more than 20. As a result, Example 29 was evaluated as good (○).

[0320] (3) Evaluation of storage stability

[0321] The coloring composition (G-34) was placed in an oven at 40°C for 1 week, and the viscosity (%) before and after the temperature increase was measured. The viscosity change rate (%) was calculated based on the viscosity difference before and after the temperature increase, and the storage stability was evaluated. The case where the viscosity change rate was 5% or less was set to "good (○)", the case where it was more than 5% and less than 10% was set to "acceptable (△)", and the case where it was more than 10% was set to "poor (×)". As a result, in this Example 29, the storage stability was evaluated as good (○). In addition, the viscosity was measured at 25°C using an E-type viscometer (VISCONIC ELD.R, Toki Sangyo Co., Ltd.).

[0322] (4) Evaluation of odor

[0323] A total of 40 subjects, 10 each of males and females aged 20 to 34 and 35 to 50, were subjected to a sensory test related to odor by the following method.

[0324] Using a spin coater, 10 sheets of the coloring composition (G-34) were applied to a soda glass substrate having a SiO2 film formed on the surface to prevent sodium ion dissolution, and the number of people who felt the odor even with one sheet was counted. Regarding the evaluation, the case where less than 10 people out of 40 people answered that they felt the odor was rated as "good (○)", and the case where more than 10 people answered that they felt the odor was rated as "bad (×)". As a result, Example 29 was rated as good (○).

[0325] [Example 30, Example 31 and Comparative Example 10, Comparative Example 11]

[0326] In Example 29, except that the types and amounts of the constituent components were changed as shown in Table 10 below, coloring compositions (G-35) to (G-38) were prepared in the same manner as in Example 29 and evaluated. The evaluation results are shown in Table 11 below. In addition, regarding the coloring composition of Comparative Example 11, it was judged that there were many coating foreign matters in the initial stage, and the evaluation of storage stability was meaningless even if it was confirmed. Regarding the "solubility of the dye" in Table 11 below, the solubility at 25°C relative to the solvent used as the first solvent (a mixed solvent of PGMEA, PGME and MBA in Example 29) and the solubility relative to each of the solvent used as the second solvent (water in Example 29) is higher than 10 g / L, and the solubility at 25°C is represented as "○", and the solubility at 10 g / L or less is represented as "×". The "additional solvent" in Table 10 represents a solvent component other than PGMEA. The abbreviations of the solvents in Tables 10 and 11 are the same as those in Tables 2 and 3. "PGEE" stands for propylene glycol monoethyl ether.

[0327]

[0328] [Table 11]

[0329]

[0330] From the results of Table 11, it can be seen that the photosensitive coloring compositions of Examples 29 to 31 containing a mixed solvent of the first solvent and the second solvent have less coating film foreign matter, less odor, and excellent storage stability compared to Comparative Example 10 containing cyclohexanone without containing the second solvent. In addition, it can be seen that the photosensitive coloring compositions of Examples 29 to 31 have less coating film foreign matter and excellent storage stability compared to Comparative Example 11 containing no second solvent.

Claims

1. A photosensitive coloring composition comprising (A) a coloring agent, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and The colorant (A) comprises a dye represented by the following formula (1): The (D) photopolymerization initiator comprises an oxime initiator; In formula (1), R X1 ~R X16 Each independently represents a hydrogen atom, a halogen atom or -OR P1 , R P1 represents a monovalent organic group; wherein, R X1 ~R X16 At least one of them represents a halogen atom, and at least one represents -OR P1 . 2 . The photosensitive coloring composition according to claim 1 , wherein the coloring agent (A) further contains a yellow pigment. The photosensitive coloring composition according to claim 1 or 2, further comprising (B) an alkali-soluble resin. 4 . The photosensitive coloring composition according to claim 3 , wherein the acid value of the (B) alkali-soluble resin is 75 to 200 mgKOH / g. The photosensitive coloring composition according to claim 1 or 2, further comprising a polyfunctional thiol compound.

6. The photosensitive coloring composition according to claim 1 or 2, wherein the (E) solvent comprises: a first solvent which is at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate; and a second solvent which is at least one selected from the group consisting of water and an alcohol having 1 to 4 carbon atoms. The photosensitive coloring composition according to claim 1 or 2, further comprising a dispersant.

8. A photosensitive coloring composition comprising (A) a coloring agent, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and The photosensitive coloring composition contains 15% to 45% by mass of the coloring agent (A), based on the total solid content in the photosensitive coloring composition. The (A) colorant comprises a dye having a zinc phthalocyanine structure, A coating film is formed on a substrate using the photosensitive coloring composition, and the color difference ΔEab before and after heating when the coating film is heated at 230° C. for 20 minutes to a film thickness of 2.5 μm is calculated to be 5 to 30 based on the International Commission on Illumination 1976 standard.

9. A photosensitive coloring composition comprising (A) a coloring agent, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and The (E) solvent comprises: a first solvent selected from at least one of the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methoxybutyl acetate; and a second solvent selected from at least one of the group consisting of water and an alcohol having 1 to 4 carbon atoms, The second solvent is contained in an amount of 0.2% by mass to 2.0% by mass based on the total amount of solvents in the photosensitive coloring composition. The (A) colorant comprises a compound satisfying the following necessary conditions (i) and (ii); (i) a solubility at 25° C. of 10 g / L or less in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate or methoxybutyl acetate, or a mixed solvent of two or more thereof; (ii) The solubility at 25° C. in water or a primary alcohol having 1 to 4 carbon atoms, or a mixed solvent of two or more thereof is 10 g / L or less. 10 . A color filter formed using the photosensitive coloring composition according to claim 1 .

11. A display element comprising the color filter according to claim 10.

Images