CN119291994A

CN119291994A - Photosensitive coloring composition, color filter and display element

Info

Publication number: CN119291994A
Application number: CN202411516010.0A
Authority: CN
Inventors: 服部清太郎; 田中亮; 仓怜史; 铃木拓之
Original assignee: JSR Corp
Current assignee: Fuyang Xinyihua New Material Technology Co ltd
Priority date: 2018-09-14
Filing date: 2019-09-11
Publication date: 2025-01-10
Also published as: KR20200031514A; JP2020046655A; TW202011117A; JP7283300B2

Abstract

本发明提供一种可获得高亮度且高对比度、并且耐溶剂性优异的着色硬化膜的感光性着色组合物、彩色滤光片及显示元件。设为如下的感光性着色组合物，其含有(A)着色剂、(C)聚合性化合物、(D)光聚合引发剂、及(E)溶剂，且(A)着色剂包含下述式(1)所表示的染料，(D)光聚合引发剂包含肟系引发剂。(式(1)中，R^X1～R^X16分别独立地表示氢原子、卤素原子或‑OR^P1，R^P1表示一价有机基。其中，R^X1～R^X16中的至少一个表示卤素原子，至少一个表示‑OR^P1。) The present invention provides a photosensitive coloring composition, a color filter, and a display element that can obtain a colored cured film with high brightness and high contrast and excellent solvent resistance. The photosensitive coloring composition is set as follows, which contains (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and the (A) colorant includes a dye represented by the following formula (1), and the (D) photopolymerization initiator includes an oxime initiator. (In formula (1), R ^X1 to R ^X16 each independently represent a hydrogen atom, a halogen atom or -OR ^P1 , and R ^P1 represents a monovalent organic group. Among them, at least one of R ^X1 to R ^X16 represents a halogen atom, and at least one represents -OR ^P1 .)

Description

Photosensitive coloring composition, color filter and display element

The invention is a divisional application of patent application of application number 2019108593116 and invention name of photosensitive coloring composition, color filter and display element, which are proposed in 2019, 09 and 11.

Technical Field

The invention relates to a photosensitive coloring composition, a color filter and a display element.

Background

Colorants and dyes used for colored cured films such as color filters have been widely studied. The dye is excellent in improving the hue or brightness of a display image when an image is displayed, because of the color purity of the dye itself or the vividness of the hue. On the other hand, dyes generally have problems of poor heat resistance and solvent resistance, and low solubility in solvents, and are considered to be difficult to put into practical use. For this reason, various dyes have been proposed for use as colorants for display elements and the like (for example, see patent document 1 or patent document 2). Patent document 1 and patent document 2 disclose dyes having a phthalocyanine skeleton.

[ Prior Art literature ]

[ Patent literature ]

Patent document 1 japanese patent laid-open publication No. 2012-180519

[ Patent document 2] Japanese patent laid-open No. 05-345861

Disclosure of Invention

[ Problem to be solved by the invention ]

As for display elements such as liquid crystal displays, large-screen and high-definition liquid crystal televisions have been mainly used, and small display terminals such as smartphones and tablet personal computers (Personal Computer, PC) have been spread and used. Further, with the expansion of the use applications of display elements, further improvement in quality of display elements is demanded. In order to further improve the quality of display elements, it is desired to improve the quality of colored cured films such as color filters included in display elements.

For example, a color filter is required to achieve further higher brightness and higher contrast. In addition, in the color filter, after patterning, other layers may be formed in an overlapping manner, and resistance to a solvent contained in the other layers is required. Therefore, not only the color characteristics but also the solvent resistance need to be sufficiently high.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive coloring composition which can obtain a colored cured film having high brightness, high contrast and excellent solvent resistance.

[ Means of solving the problems ]

In order to solve the above problems, the present invention provides the following photosensitive coloring composition, color filter and display element.

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

[ Chemical 1]

( In the 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 at least one of R ^X1～R^X16 represents a halogen atom, and at least one represents-OR ^P1. )

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

[3] The photosensitive coloring composition according to the above [1] or [2], which further contains a polyfunctional thiol compound.

[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the (E) solvent contains 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 the second solvent is at least one selected from the group consisting of water and alcohols having 1 to 4 carbon atoms.

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

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

[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 comprises a dye having a zinc phthalocyanine structure, and a coating film is formed on a substrate using the photosensitive coloring composition, and a color difference [ delta ] Eab before and after heating is calculated based on International Commission on illumination (Commission Internationalede I' Eclairage, CIE) 1976, when the coating film is heated at 230 ℃ for 20 minutes to a film thickness of 2.5 [ mu ] m, and the color difference [ delta ] Eab before and after heating is 5 to 30, based on the total solid content in the photosensitive coloring composition.

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

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

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

[11] The photosensitive coloring composition according to any one of [7] to [10], which further contains a dispersant.

[12] The photosensitive coloring composition according to any one of [7] to [11], which further contains (B) an alkali-soluble resin. The acid value of the alkali-soluble resin (B) is preferably 75 mgKOH/g-200 mgKOH/g.

[13] A photosensitive coloring composition comprising (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, 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 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, and contains 0.2 to 2.0 mass% of the second solvent relative to the total solvent in the photosensitive coloring composition, and the (A) colorant comprises a compound satisfying the requirements of (i) and (ii) below.

(I) The solubility of the polymer is 10g/L or less at 25 ℃ relative to 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 of these.

(Ii) The solubility of the aqueous dispersion composition is 10g/L or less at 25 ℃ relative to water, primary alcohol with 1-4 carbon atoms or a mixed solvent of two or more of the above.

[14] The photosensitive coloring composition according to the [13], wherein the (A) colorant comprises the dye represented by the formula (1).

[15] The photosensitive coloring composition according to the item [14], wherein the (A) colorant further contains a yellow pigment.

[16] The photosensitive coloring composition according to any one of [13] to [15], which further contains a polyfunctional thiol compound.

[17] The photosensitive coloring composition according to any one of [13] to [16], which further contains a dispersant.

[18] The photosensitive coloring composition according to any one of [13] to [17], which further contains (B) an alkali-soluble resin. The acid value of the alkali-soluble resin (B) is preferably 75 mgKOH/g-200 mgKOH/g.

[19] A color filter formed using the photosensitive coloring composition according to any one of [1] to [18 ].

[20] A display element comprising the color filter according to [19 ].

[ Effect of the invention ]

According to the photosensitive coloring composition containing the zinc phthalocyanine dye represented by the formula (1) as the (A) colorant and the oxime-based initiator as the (D) photopolymerization initiator, a colored cured film with high brightness, high contrast and excellent solvent resistance can be obtained.

Detailed Description

The following describes matters related to the embodiment in detail. In the present specification, the numerical range described in "to" is used to include numerical values described before and after "to" as a lower limit value and an upper limit value.

First embodiment

[ Photosensitive coloring composition ]

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

Colorant (A)

The colorant (a) contained in the first photosensitive coloring composition contains a dye having a zinc phthalocyanine structure, specifically, a compound represented by the following formula (1) (hereinafter, also referred to as "specific dye a").

[ Chemical 2]

Examples of the halogen atom for R ^X1～R^X16 in the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the case where the formula (1) has 2 or more halogen atoms, the plurality of halogen atoms may be all of the same kind or may be different from each other. The halogen atom of R ^X1～R^X16 preferably contains at least a fluorine atom, and particularly preferably all fluorine atoms.

The number of halogen atoms in R ^X1～R^X16 is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and particularly preferably 8 or more, in terms of suitably achieving high luminance. The number of groups as halogen atoms in R ^X1～R^X16 is 15 or less, preferably 14 or less, and more preferably 12 or less.

R ^P1 in the group "-OR ^P1" is preferably 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 20 carbon atoms, a substituted OR unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, OR a substituted OR unsubstituted monovalent heterocyclic group having 6 to 20 carbon atoms.

In the present specification, the term "chain hydrocarbon group" means a linear hydrocarbon group and a branched hydrocarbon group which are composed only of a chain structure without a cyclic structure in the main chain. Wherein, the resin can be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group having a structure containing only alicyclic hydrocarbon as a ring structure, and not having an aromatic ring structure. The hydrocarbon group may be a hydrocarbon group having a chain structure in a part thereof, without being constituted of only alicyclic hydrocarbon. The term "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. The aromatic ring structure may be a chain structure or an alicyclic hydrocarbon structure. The "heterocyclic group" is a group obtained by removing n (n is an integer) hydrogen atoms from the ring portion of the heterocyclic ring.

In the case where the hydrocarbon group or the heterocyclic group of R ^P1 has a substituent, as the substituent, in addition to the halogen atom and the alkoxy group, examples include hydrocarbon groups or heterocyclic groups and-O-, -CO-; -COO-combined groups, etc. In the case where R ^P1 is a substituted or unsubstituted monovalent heterocyclic group, examples of the heterocyclic group-constituting heterocyclic ring include nitrogen-containing heterocyclic ring, sulfur-containing heterocyclic ring, oxygen-containing heterocyclic ring, and the like, and may be either an aromatic ring or a non-aromatic ring.

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

[ Chemical 3]

( In the formula (2), X ¹⁰ is a single bond or an oxygen atom, and R ²¹ 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. R 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. Wherein when k is 2 or 3, a plurality of X ¹⁰、R²¹ each independently have the definition, and when m is 2, a plurality of R ²⁰ each independently have the definition. "x" represents a bond to an aromatic ring in formula (1). )

In the formula (2), the substituent of the chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group includes an alkoxy group having 1 to 5 carbon atoms. R ²¹ is preferably a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 10 carbon atoms, 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, more preferably a linear alkyl group having 1 to 5 carbon atoms. When R ²¹ is a substituted alkyl group, a group having an alkoxy group having 1 to 5 carbon atoms as a substituent is preferable.

K is preferably 1 or 2, more preferably 1. When k=1, the group "-CO-X ¹⁰-R²¹" is preferably bonded at the 3-position or the 4-position, more preferably at the 4-position, relative to-O-. When k=2, 2 groups "-CO-X ¹⁰-R²¹" are preferably bonded to the 3, 5-or 2, 4-position, more preferably to the 3, 5-position, relative to-O-.

M is preferably 0 or 1, more preferably 0.

Preferable specific examples of the group represented by the above formula (2) include groups represented by the following formulae (2-1) to (2-15).

[ Chemical 4]

(Wherein "+" represents a bond.)

The number of "-OR ^P1" groups in R ^X1～R^X16 is preferably 2 OR more, more preferably 4 OR more, in terms of high improvement effect on solvent resistance and heat resistance. The number of "-OR ^P1" groups is 15 OR less, preferably 14 OR less, more preferably 12 OR less, and still more preferably 8 OR less.

In terms of solvent resistance and heat resistance, R ^X1～R^X16 is preferably at least 4 OR more of R ^X2、R^X3、R^X6、R^X7、R^X10、R^X11、R^X14 and R ^X15 are a group "-OR ^P1", particularly preferably R ^X2、R^X3、R^X6、R^X7、R^X10、R^X11、R^X14 and R ^X15 are all a group "-OR ^P1", and the remainder (R ^X1、R^X4、R^X5、R^X8、R^X9、R^X12、R^X13 and R ^X16) are halogen atoms.

Preferable specific examples of the specific dye A include compounds represented by the following formulas (1-1) to (1-6).

[ Chemical 5]

[ Chemical 6]

(Wherein Me represents methyl, et represents ethyl, and n-Bu represents n-butyl.)

(Other colorants)

In the first photosensitive coloring composition, the colorant (a) may contain the specific dye a alone or may contain the specific dye a together with a colorant (hereinafter, also referred to as "other colorant") different from the specific dye a. Further, by containing another colorant, a colored layer having a desired chromaticity can be obtained.

The other coloring agent is not particularly limited, and may be appropriately selected in color or kind according to the application. As other colorants, pigments, dyes other than the specific dye a, and natural pigments can be used, but in order to obtain a pixel having high brightness and color purity, at least one of an organic pigment and an organic dye is preferable.

As the organic pigment, a compound classified into pigment (pigment) in Color Index (c.i. (Color Index); issued by the institute of dyeing (The Society of Dyers and Colourists)) that is a compound to which the Color Index (c.i.) name as described below is attached, the following organic pigment can be preferably used.

C.i. pigment yellow 12, c.i. pigment yellow 13, c.i. pigment yellow 14, c.i. pigment yellow 17, c.i. pigment yellow 20, c.i. pigment yellow 24, c.i. pigment yellow 31, c.i. pigment yellow 55, c.i. pigment yellow 61, c.i. pigment yellow 61:1, c.i. pigment yellow 62, c.i. pigment yellow 83, c.i. pigment yellow 93, c.i. pigment yellow 100, c.i. pigment yellow 104, c.i. pigment yellow 109, c.i. pigment yellow 110, c.i. pigment yellow 129, c.i. pigment yellow 133, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 153, c.i. pigment yellow 154, c.i. pigment yellow 155, c.i. pigment yellow 166, c.i. pigment yellow 168, c.i. pigment yellow 180, c.i. pigment yellow 215, c.i. pigment yellow 209, c.i. pigment yellow 215, c.i. pigment yellow 191, c.i. pigment yellow 211, c.i. pigment yellow 1:191, c.i. pigment yellow;

Green pigments such as c.i. pigment green 1, c.i. pigment green 4, c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58, c.i. pigment green 59, c.i. pigment green 63, etc.;

blue pigments such as c.i. pigment blue 15:3, c.i. pigment blue 15:4, c.i. pigment blue 15:6, c.i. pigment blue 16, c.i. pigment blue 79, c.i. pigment blue 80, etc.;

Orange pigments such as c.i. pigment orange 38;

violet pigments such as c.i. pigment violet 19 and c.i. pigment violet 23.

In the case of using a pigment as another colorant, or in the case of not using a pigment, it is preferable to contain a dispersant in the photosensitive coloring composition. Further, a dispersant and a dispersing aid may be contained together. As the dispersant and the dispersing aid, known ones can be used. Specifically, examples of the dispersant include urethane dispersants, polyethylenimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, and acrylic dispersants, and examples of the dispersing aid include pigment derivatives.

As the organic dye, among the compounds to which the color index (c.i.) name is attached, the following organic dye may be preferably used.

Yellow dyes such as c.i. acid yellow 11, c.i. direct yellow 12, c.i. reactive yellow 2, c.i. mordant yellow 5, c.i. acid yellow 3, c.i. acid yellow 1, c.i. basic yellow 4, c.i. solvent yellow 33, c.i. disperse yellow 64, c.i. disperse yellow 42, c.i. solvent yellow 179, disperse yellow 201, etc.;

Green dyes such as c.i. direct green 59, c.i. direct green 28, c.i. acid green 25, etc.

Further, as the organic dye, a yellow dye described in Japanese patent application laid-open No. 2015-044982, japanese patent application laid-open No. 2017-207676, and Japanese patent application laid-open No. 2013-213208 can be used in addition to the above.

The specific dye a is generally green. Therefore, a photosensitive coloring composition containing a specific dye a is preferably used for forming green pixels. In this case, the (a) colorant preferably contains the specific dye a together with at least one selected from the group consisting of a green pigment, a green dye, a yellow pigment, and a yellow dye as the other colorant. The photosensitive coloring composition further preferably contains at least a yellow pigment as another coloring agent, and further preferably contains at least a yellow pigment.

When the colorant (a) contains another colorant, the content of the specific dye a in the colorant (a) may be appropriately adjusted so as to achieve a desired chromaticity, and is preferably 0.1 mass% or more, more preferably 1 mass% or more, still more preferably 5 mass% or more, and particularly preferably 20 mass% or more, based on the total amount of the colorant (a). The content of the specific dye a in the colorant (a) is preferably 80 mass% or less, more preferably 70 mass% or less, and particularly preferably 60 mass% or less, based on the total amount of the colorant (a). Furthermore, the specific dye A and the other coloring agent may be used singly or in combination of two or more.

The content ratio of the colorant (a) is usually 5 to 70% by mass based on the total solid content of the photosensitive coloring composition, from the viewpoint of forming a pixel having high brightness and excellent color purity, or from the viewpoint of forming a black matrix having excellent light shielding property. (A) The content ratio of the colorant is preferably 10% by mass or more, more preferably 12% by mass or more, and still more preferably 15% by mass or more, based on the total solid content of the photosensitive coloring composition. The content of the colorant (a) is preferably 60 mass% or less, more preferably 55 mass% or less, and still more preferably 45 mass% or less, based on the total solid content of the photosensitive coloring composition. In the present specification, the term "solid component" refers to a component other than the solvent (E) contained in the photosensitive coloring composition. Accordingly, the term "total solid content" refers to a composition obtained by combining (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and other components (including (B) an alkali-soluble resin) other than (A) and (C) to (E). For example, a photopolymerizable compound or an additive component (for example, a surfactant or the like) in a liquid state is contained in the solid component.

Alkali (B) can soluble resin ]

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. Of these, (B) the alkali-soluble resin is preferably a polymer having a carboxyl group (hereinafter, also referred to as "carboxyl group-containing polymer"). Examples of the carboxyl group-containing polymer include a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as "unsaturated monomer (b 1)") and an ethylenically unsaturated monomer copolymerizable with the unsaturated monomer (b 1) (hereinafter, also referred to as "unsaturated monomer (b 2)").

Examples of the unsaturated monomer (b 1) include (meth) acrylic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl ] ester, ω -carboxypolycaprolactone mono (meth) acrylate, and p-vinylbenzoic acid. In the present specification, the term "(meth) acrylic acid" means a concept including methacrylic acid and acrylic acid. (B) The alkali-soluble resin may have only one structural unit derived from the unsaturated monomer (b 1), or may have two or more kinds in combination.

Examples of the unsaturated monomer (b 2) include N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide;

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

Methyl (meth) acrylate, n-butyl (meth) acrylate, t-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 ] dec-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumylphenol, glycerol (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxy ] oxetane, (meth) acrylic esters such as 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, and 3- (vinyloxymethyl) -3-ethyloxetane;

And a macromer having a mono (meth) acryloyl group at a terminal of a polymer molecular chain, such as polystyrene, poly (meth) acrylic acid methyl ester, poly (meth) acrylic acid n-butyl ester, and polysiloxane. (B) The alkali-soluble resin may have only one structural unit derived from the unsaturated monomer (b 2), or may have two or more kinds in combination.

In the copolymer of the unsaturated monomer (b 1) and the unsaturated monomer (b 2), the copolymerization ratio of the unsaturated monomer (b 1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By having the unsaturated monomer (b 1) component in such a range, a photosensitive colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b 1) and the unsaturated monomer (b 2) include copolymers disclosed in Japanese patent application laid-open No. 7-140654, japanese patent application laid-open No. 8-259876, japanese patent application laid-open No. 10-31308, japanese patent application laid-open No. 10-300922, japanese patent application laid-open No. 11-174224, japanese patent application laid-open No. 11-258415, japanese patent application laid-open No. 2000-56118, japanese patent application laid-open No. 2004-101728, and the like. Further, as the alkali-soluble resin (B), for example, a carboxyl group-containing polymer having a polymerizable unsaturated bond (for example, a carbon-carbon double bond in a (meth) acryloyl group) in a side chain can be used as disclosed in JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, JP-A-2008-181095, and the like.

The alkali-soluble resin (B) generally has a weight average molecular weight (Mw) of 1,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) using tetrahydrofuran as a eluting solvent. Mw is preferably 3,000 or more. Further, mw is preferably 50,000 or less. When the Mw is within the above range, it is possible to ensure a film residue ratio, pattern shape, heat resistance, and electrical characteristics of a film suitable for a color filter while suppressing the generation of dry foreign matters or the reduction of resolution in coating by a slit nozzle method.

(B) The ratio (Mw/Mn) of Mw to number average molecular weight (Mn) of the alkali-soluble resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Further, mn is a polystyrene equivalent obtained by measuring the solvent for elution with tetrahydrofuran by GPC.

(B) The acid value of the alkali-soluble resin is preferably 75mgKOH/g to 200mgKOH/g. When the acid value of the alkali-soluble resin (B) is set to a value within the above range, the contrast of the colored layer obtained by using the photosensitive coloring composition of the present disclosure can be further improved. The acid value is more preferably 100mgKOH/g or more, and still more preferably 120mgKOH/g or more, from the viewpoint of providing a higher contrast of the colored layer. The acid value is more preferably 190mgKOH/g or less. Here, the term "acid value" as used herein means mg of KOH required for neutralizing 1g of the solid content of the alkali-soluble resin (B).

(B) The alkali-soluble resin can be produced by a known method. Further, for example, the structure, mw and Mw/Mn can be controlled by the methods disclosed in Japanese patent application laid-open No. 2003-222717, japanese patent application laid-open No. 2006-259680, international publication No. 07/029871 manual and the like. Further, the alkali-soluble resin (B) may be used singly or in combination of two or more.

In the photosensitive coloring composition, the content of the alkali-soluble resin (B) is usually 10 parts by mass to 1,000 parts by mass, preferably 20 parts by mass 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, an appropriate alkali developability in terms of a coating film formation process, a sufficient storage stability as a product of the obtained colored composition, and a sufficient color density as the obtained color filter for a desired film thickness can be ensured.

Polymerizable Compound (C)

(C) The polymerizable compound is a compound having preferably 2 or more polymerizable groups, and functions as a crosslinking agent. The polymerizable group is preferably a radical polymerizable group, and examples thereof include an ethylenically unsaturated group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, (C) polymerizable compounds are preferably compounds having 2 or more (meth) acryloyl groups or compounds having 2 or more N-alkoxymethylamino groups.

Specific examples of the compound having 2 or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting a trivalent or more aliphatic polyhydroxy compound with (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, a polyfunctional (meth) acrylate modified with alkylene oxide, a polyfunctional (meth) acrylic urethane obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Examples of the compound having 2 or more N-alkoxymethylaminos include compounds having a melamine structure, benzoguanamine structure, and urea structure. The melamine structure and benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are concepts that include melamine, benzoguanamine, or a condensate of these. Specific examples of the compound having 2 or more N-alkoxymethylaminos include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N' -tetra (alkoxymethyl) benzoguanamine, N, N, N ', N' -tetra (alkoxymethyl) glycoluril, and the like.

Among these, preferable (C) polymerizable compounds are polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional (meth) acrylic carbamates, polyfunctional (meth) acrylates having carboxyl groups, N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N' -tetra (alkoxymethyl) benzoguanamine, more preferably a multifunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having a valence of three or more with (meth) acrylic acid, a multifunctional (meth) acrylic urethane, a multifunctional (meth) acrylate having a carboxyl group. Among the polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, trimethylol propane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate are particularly preferred in terms of high strength of the colored layer, excellent surface smoothness of the colored layer, and less tendency to cause stains and film residue on the substrate of the unexposed portion and on the light shielding layer. For the same reason, among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferable. (C) The polymerizable compound may be used singly or in combination of two or more.

The content of the polymerizable compound (C) in the photosensitive coloring composition is preferably 10 parts by mass or more, particularly preferably 20 parts by mass or more, per 100 parts by mass of the colorant (a). The content of the polymerizable compound (C) is preferably 1,000 parts by mass or less, particularly preferably 500 parts by mass or less, per 100 parts by mass of the colorant (a). When the content ratio of the polymerizable compound (C) falls within the above range, it is possible to sufficiently suppress the occurrence of stains, film residues, and the like on the substrate of the unexposed portion or on the light shielding layer while securing sufficient hardenability as a coating film and sufficient alkali developability as a photosensitive coloring composition.

(D) photopolymerization initiator ]

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

Specific examples of the O-acyloxime initiator include 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), ethanone, 1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), ethanone, 1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxacyclopentyl) methoxybenzoyl } -9H-carbazol-3-yl ] -,1- (O-acetyloxime), 1, 2-propanedione, 3-cyclohexyl-1- [4- (phenylthio) phenyl ] -,1- (O-acetyloxime) (a compound represented by the following formula (D-1)), a compound represented by the following formula (D-2), and the like.

[ Chemical 7]

As the O-acyl oxime initiator, commercially available products such as NCI-831, NCI-930 (above, manufactured by Ai Dike (ADEKA) Co., ltd.) and PBG-3057 (above, manufactured by Hemsl electric materials Co., ltd.) can be used.

As the O-acyl oxime initiator, a compound represented by the following formula (d-10), formula (d-11) and formula (d-12) can be preferably used.

[ Chemical 8]

( In the formula (d-10), X ¹ and X ² are each independently a single bond or-CO-. Wherein at least one of X ¹ and X ² is-CO-. R ¹ is an alkyl group having 2 to 6 carbon atoms, and R ² is an alkyl group having 4 to 10 carbon atoms. R ⁴ is a monovalent organic group having a hydrocarbon ring or a heterocyclic ring. R ³ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group. )

[ Chemical 9]

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

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

In the above formula (d-11) and formula (d-12), when R ⁶、R⁷、R⁸ or R ⁹ has 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. Examples of the substituent for R ¹¹ and R ¹² include a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, 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.

As the O-acyl oxime initiator, at least one selected from the group consisting of an acyl oxime compound having a diphenyl sulfide skeleton, an acyl oxime compound having a carbazole skeleton, and an acyl oxime compound having a fluorene skeleton is preferably used in order to make the contrast ratio of the cured film better. The O-acyloxime initiator is more preferably at least one selected from the group consisting of an acyloxime compound having a diphenyl sulfide skeleton and an acyloxime compound having a fluorene skeleton.

The photopolymerization initiator (D) may be used alone or in combination with a photopolymerization initiator (hereinafter, also referred to as "other initiator") different from the oxime initiator. Examples of the other initiator include, but are not particularly limited to, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -diketone compounds, polynuclear quinone compounds, diazonium compounds, and imide sulfonate compounds. Of these, the other initiator is preferably at least one selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, and triazine-based compounds.

Among these, acetophenone compounds are particularly preferable as other initiators used in combination with the oxime-based initiator. The use of an acetophenone compound in combination is preferable in that the solvent resistance of the cured film obtained can be further improved.

When another initiator is used in combination as the (D) photopolymerization initiator, the content of the oxime-based initiator is preferably 20 mass% or more, more preferably 30 mass% or more, and even more preferably 40 mass% or more, based on the total amount of the (D) photopolymerization initiator used (the total amount of the oxime-based initiator and the other initiator), in terms of further improving the heat resistance and solvent resistance of the obtained cured film.

The content ratio of the photopolymerization initiator (D) is preferably 0.01 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the polymerizable compound (C). The content of the photopolymerization initiator (D) is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the polymerizable compound (C). When the content of the photopolymerization initiator (D) is within the above range, it is possible to sufficiently suppress the occurrence of stains and film residues on the substrate or the light shielding layer in the unexposed portion while ensuring sufficient hardening of the coating film due to an appropriate exposure amount and sufficient alkali developability as the photosensitive coloring composition. In addition, the decrease in the brightness of the coating film due to yellowing of the polymerization initiator at the time of post baking can be sufficiently suppressed. (D) The photopolymerization initiator may be used singly or in combination of two or more.

Solvent (E)

The photosensitive coloring composition is prepared by blending the solvent (E) to prepare a liquid composition. As the solvent (E), a solvent which disperses or dissolves the respective components (a), component (C), component (D) or other components constituting the photosensitive coloring composition, does not react with these components, and has a moderate volatility can be preferably used.

Specific examples of the solvent (E) 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, 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, tripropylene glycol monoethyl ether, and the like;

Alkyl lactate such as methyl lactate and ethyl lactate, and (cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, and cyclohexanol;

(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 methylether, diethylene glycol diethyl ether, tetrahydrofuran, ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like;

diacetates such as propylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;

Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;

other esters such as 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, and ethyl 2-oxobutyrate;

Amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and lactams.

Among these, the solvent (E) 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 monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methylethyl 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-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, and ethyl pyruvate in terms of solubility, pigment dispersibility, coatability, and the like. Further, the solvent (E) may be used singly or in combination of two or more.

When the photosensitive coloring composition contains the specific dye a, the solvent (E) preferably contains a first solvent and a second solvent described below.

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.

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

The solubility of the specific dye a with respect to the first solvent is low, and in addition, the solubility with respect to the second solvent is also low. More specifically, the solubility of the specific dye A at 25 ℃ with respect to the first solvent is 10g/L or less, and the solubility at 25 ℃ with respect to the second solvent is 10g/L or less. On the other hand, the solubility of the specific dye a with respect to the mixed solvent of the first solvent and the second solvent is good, and the solubility at 25 ℃ with respect to the mixed solvent is sufficiently more than 10g/L. Therefore, it is preferable to suppress the presence of foreign substances in the coating film formed by using the photosensitive coloring composition and to improve productivity. Further, since the mixed solvent of the first solvent and the second solvent is less odorous, the mixed solvent is excellent in that the working environment can be made good and the storage stability is good.

When a mixed solvent of the first solvent and the second solvent is used as the solvent (E), the content ratio of the second solvent is preferably 0.2 mass% or more, more preferably 0.3 mass% or more, relative to the total solvent amount in the photosensitive coloring composition, in terms of sufficiently securing the solubility of the specific dye a in the solvent. The content ratio of the second solvent in the mixed solvent of the first solvent and the second solvent is preferably 2.0 mass% or less, more preferably 1.8 mass% or less, and still more preferably 1.5 mass% or less, based on the total amount of the solvent in the photosensitive coloring composition.

The content ratio of the solvent (E) in the first photosensitive coloring composition is not particularly limited, and is preferably an amount such that the total concentration of the components of the photosensitive coloring composition excluding the solvent is 5 to 50% by mass, more preferably 10 to 40% by mass. By adopting such a form, a colorant solution or colorant dispersion having excellent dispersibility and stability can be obtained. In addition, a coloring composition having good coatability and stability can be obtained.

Additive (F)

In addition to the photosensitive coloring composition, various additives may be contained as necessary. Examples of the additives include fillers such as glass and alumina, high molecular compounds such as polyvinyl alcohol and poly (fluoroalkylacrylate), surfactants such as fluorine-based surfactants and silicon-based surfactants, adhesion promoters, antioxidants, and ultraviolet absorbers. The blending ratio of these additives may be appropriately set according to the kind of each additive within a range that does not impair the effects of the present disclosure.

The photosensitive coloring composition of the present disclosure preferably contains a polyfunctional thiol compound. In this case, it is preferable to improve the photosensitivity of the coloring composition and to improve the solvent resistance of the cured film obtained.

The polyfunctional thiol compound is not particularly limited as long as it is a compound having 2 or more thiol groups (-SH). Specific examples of the polyfunctional thiol compound include, for example, hexanedithiol, decanedithiol, 1, 4-bis (mercaptomethyl) benzene, butanedithiopropionate, butanedithioglycolate, ethyleneglycol dithioglycolate, trimethylol propane trithioglycolate, butanedithiopropionate, trimethylol propane tri (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylol propane tri (3-mercaptobutyrate), trimethylol ethane tri (3-mercaptobutyrate), trimethylol propane trithiopropionate, trimethylol propane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, bis (3-mercaptobutyryloxy) butane, and the like. Further, the polyfunctional thiol compound may be used singly or in combination of two or more.

The blending ratio of the polyfunctional thiol compound in the photosensitive coloring composition is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, based on the total amount of the solid components of the composition. The blending ratio of the polyfunctional thiol compound is preferably 10% by mass or less, more preferably 3% by mass or less, based on the total amount of the solid components of the coloring composition. When 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 colored layer to the substrate can be sufficiently improved, so that the colored layer is less likely to be detached from the substrate during development.

< Preparation of photosensitive coloring composition >

The photosensitive coloring composition of the present disclosure can be prepared by an appropriate method. Examples of the production method include those disclosed in japanese patent application laid-open publication No. 2008-58442 and japanese patent application laid-open publication No. 2010-132874. When both a dye and a pigment are used as the colorant (A), a method may be employed in which, as disclosed in Japanese patent application laid-open No. 2010-132874, a dye solution is passed through a first filter, the dye solution passed through the first filter is mixed with a pigment dispersion or the like which is separately prepared, and the resulting colored composition is passed through a second filter, thereby producing the colored composition. Alternatively, the photosensitive coloring composition may be prepared by dissolving the dye, the (B), the (C) and (D) components, and other components if necessary, in a solvent, passing the resulting solution through a first filter, mixing the solution passing through the first filter with a pigment dispersion prepared separately, and passing the resulting photosensitive coloring composition through a second filter. Alternatively, the photosensitive colored composition may be prepared by passing the dye solution through a first filter, then mixing and dissolving the dye solution having passed through the first filter with the above-mentioned component (B), component (C) and component (D) and other components optionally used, passing the resulting solution through a second filter, further mixing the solution having passed through the second filter with a pigment dispersion prepared separately, and passing the resulting photosensitive colored composition through a third filter.

[ Color Filter and method for producing the same ]

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

As a method of manufacturing a color filter, first, a light shielding layer (black matrix) is formed on the surface of a substrate in such a manner as to divide portions where pixels are formed as needed. Next, for example, a green photosensitive coloring composition (liquid composition) is applied to the substrate, and then a pre-baking is performed to evaporate the solvent, thereby forming a coating film. Then, the coating film is exposed through a photomask, and then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film. Thereafter, a post baking is performed to form a pixel array in which a green pixel pattern is arranged in a predetermined arrangement.

Next, each photosensitive coloring composition of red or blue is used, and the application, pre-baking, exposure, development, and post-baking of each photosensitive coloring composition are performed in the same manner as described above, so that a red pixel array and a blue pixel array are sequentially formed on the same substrate. Thus, a color filter having a pixel array of three primary colors, green, red, and blue, disposed on a substrate is obtained. However, the order in which the pixels of the respective colors are formed is not limited to the order. The black matrix can be formed by forming a metal thin film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography. Further, a photosensitive coloring composition in which a black coloring agent is dispersed can be used and formed in the same manner as in the case of forming the pixels.

Examples of the substrate used for forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, and the like. These substrates may be subjected to a suitable pretreatment such as a chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, a gas phase reaction method, and vacuum deposition, as necessary.

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), or a bar coating method can be used, and a spin coating method or a slit die coating method is particularly preferable. The pre-baking is performed at a temperature lower than the post-baking temperature, and is usually performed at 70 ℃ to 110 ℃ for about 1 minute to 10 minutes. The coating thickness is usually 0.6 μm to 8 μm, preferably 1.2 μm to 5 μm in terms of the film thickness after drying.

Examples of the light source of the radiation used for exposure include a light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, and a low-pressure mercury lamp, and a laser light source such as an argon ion laser, a Yttrium-Aluminum-Garnet (YAG) laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet Light Emitting Diode (LED) can also be used as an exposure light source. Radiation having a wavelength in the range of 190nm to 450nm is preferable, and radiation having a wavelength in the range of 300nm to 450nm is more preferable. The exposure amount of the radiation is preferably 10J/m ²～10,000J/m² in general. The exposure to radiation is more preferably 100J/m ² or more, and still more preferably 200J/m ² or more. The exposure to radiation is more preferably 5,000J/m ² or less, and still more preferably 2,000J/m ² or less.

As the alkali developer, for example, aqueous solutions of sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline (choline), 1, 8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene, and the like are preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer. Further, after alkali development, water washing is usually performed. As the development treatment method, a spray development method, a dip (dip) development method, a liquid coating (puddle) development method, or the like can be applied. The development condition is preferably carried out at normal temperature for 5 seconds to 300 seconds. The post-baking is usually carried out at 180 to 280 ℃ for about 10 to 60 minutes. The film thickness of the pixel formed in this manner is usually 0.5 μm to 5. Mu.m, preferably 1.0 μm to 3. Mu.m.

After a protective film is formed as needed on the pixel pattern obtained in the above manner, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer can be further formed to manufacture a color filter. The spacers are usually formed using a transparent photosensitive resin composition, but spacers having light shielding properties (black spacers) can also be produced. In this case, a photosensitive coloring composition in which a black colorant is dispersed is used. The photosensitive coloring composition of the present disclosure can also be suitably used to form the black spacer.

The photosensitive coloring composition of the present disclosure can also be suitably used for forming any colored cured film such as each color pixel, black matrix, black spacer, and the like used in a color filter. The color filter formed in this manner is particularly useful for color liquid crystal display devices, solid-state imaging devices, color sensors, organic Electroluminescence (EL) display devices, electronic papers, and the like, because of its high brightness and color purity.

[ Display element ]

The display element of the present disclosure is provided with 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.

The color liquid crystal display element provided with the color filter of the present disclosure may be provided with a backlight unit using a white LED as a light source, in addition to a cold cathode fluorescent lamp (CCFL: cold Cathode Fluorescent Lamp). Examples of the white LED include a white LED in which a red LED, a green LED, and a blue LED are combined and mixed to obtain white light, a white LED in which a blue LED, a red LED, and a green phosphor are combined and mixed to obtain white light, a white LED in which a blue LED, a red light emitting phosphor, and a green light emitting phosphor are combined and mixed to obtain white light, a white LED in which a blue LED and a YAG phosphor are mixed to obtain white light, a white LED in which a blue LED, an orange light emitting phosphor, and a green light emitting phosphor are combined and mixed to obtain white light, and a white LED in which an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor are combined and mixed to obtain white light.

An organic EL display element provided with the color filter of the present disclosure may be of an appropriate structure, and examples thereof include those disclosed in japanese patent application laid-open No. 11-307242. Examples of the electronic paper provided with the color filter of the present disclosure include the structure disclosed in japanese patent laid-open No. 2007-4169.

Second embodiment

Next, a second embodiment will be described focusing on differences from the first embodiment.

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

The colorant (a) contained in the second photosensitive coloring composition contains a dye having a zinc phthalocyanine structure. The dye having a zinc phthalocyanine structure is not particularly limited as long as it has a zinc phthalocyanine skeleton, and among these, a specific dye a can be preferably used. As the colorant (a), only the specific dye a may be used, but in order to obtain a desired chromaticity, it is preferable to use the specific dye a together with other colorants. The description of the specific dye a and other colorants applies to the description of the first embodiment. The colorant (a) contained in the second photosensitive coloring composition (including other colorants) is preferably a phthalocyanine-based dye in terms of sufficiently exhibiting desired color characteristics by color change before and after heating (post baking) of the coating film formed by using the photosensitive coloring composition.

(D) The photopolymerization initiator may not necessarily contain an oxime-based 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 photopolymerization initiator (D) preferably contains an oxime initiator, more preferably contains an O-acyl oxime initiator, in terms of sufficiently promoting film hardening by an appropriate exposure amount. The description of the first embodiment will be applied to the kind and content ratio of the O-acyl oxime initiator.

Regarding the second photosensitive coloring composition, the content ratio of the colorant (a) (when two or more types are contained, the total amount of these is set to 15 to 45 mass% with respect to the total solid content in the photosensitive coloring composition), a coating film is formed on a substrate using this coloring composition, and the value of the color difference Δeab before and after heating at 230 ℃ for 20 minutes to produce a cured film with a film thickness of 2.5 μm is calculated based on the CIE1976 standard and is 5 to 30. By setting the color difference Δeab before and after post baking within the above range, the color change before and after post baking is moderately small, and a color filter having high contrast, high brightness, and high heat resistance can be obtained. In view of obtaining a color filter having 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 still more preferably 9 or more. The color difference Δeab is preferably 25 or less, more preferably 20 or less, and further preferably 16 or less.

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 prebaked, thereby forming a coating film on the substrate. The "coating film" referred to herein is a film formed on a substrate by heating (i.e., pre-baking) at a temperature lower than the post-baking temperature. The prebaking conditions apply to the description of the first embodiment. Then, exposure and development were performed using the conditions described in the first embodiment, and then post-baking was performed at 230 ℃ for 20 minutes. The color difference ΔEab before and after the post bake was calculated based on the CIE1976 standard. In order to set the film thickness after post baking to a desired value (2.5 μm), the application conditions of the photosensitive coloring composition (for example, the rotation speed of a spin coater) can be adjusted.

In order to achieve high color purity of the display element and to suppress development failure, the content ratio of the colorant (a) in the photosensitive coloring composition (in the case of containing two or more kinds, the total amount of these) is more preferably 15 to 40 mass%, and still more preferably 20 to 40 mass%, with respect to the total solid content in the photosensitive coloring composition.

The reason why the color filter can achieve high brightness and high heat resistance by setting the color difference Δeab before and after post baking to the above range is not yet known, but it is assumed that some chemical state changes such as pigment association occur due to heating during post baking, which affects the color characteristics of the pigment, as a result of the structure of the pigment. At this time, when the color difference Δeab before and after post baking is within the above range, the color difference is controlled to be in a specific state, and as a result, the color characteristics are controlled, and as a result, it is estimated that the color filter can be made to have higher brightness and higher heat resistance. In order to bring the color difference Δeab before and after post baking into the above range, the type of the colorant, the color material concentration in the solid content, the concentration of the alkali-soluble resin, the concentration of the polymerizable compound, and the like may be adjusted. More specifically, the preparation of the photosensitive coloring composition using a colorant containing a dye having a zinc phthalocyanine structure is performed so that the color difference ΔEab before and after post baking is within the above range, and the concentration of the alkali-soluble resin, the concentration of the polymerizable compound, and the like are optimized for the coloring composition containing the colorant by a usual method when the color difference ΔEab before and after post baking is measured by the above method and the measured color difference ΔEab is within the range of 5 to 30.

According to the second photosensitive coloring composition (the photosensitive coloring composition of the above [7 ]) described above, a colored cured film having high brightness and excellent heat resistance can be obtained. In addition, by using the photosensitive coloring composition of the present embodiment, a color filter and a display element having 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.

Third embodiment

Next, a third embodiment will be described focusing on differences from the first embodiment.

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

In the third photosensitive coloring composition, the colorant (a) contains a dye (hereinafter referred to as "specific dye α") satisfying the following requirements (i) and (ii).

The solubility of the specific dye alpha is good relative to the mixed solvent of the first solvent and the second solvent, and the solubility of the specific dye alpha at 25 ℃ relative to the mixed solvent is more than 10g/L. The solubility of the specific dye α at 25 ℃ relative to the mixed solvent of the first solvent and the second solvent is preferably 15g/L or more, more preferably 20g/L or more. The specific dye α is preferably a dye having a zinc phthalocyanine structure, and the specific dye a may be preferably used.

The third photosensitive coloring composition may contain only a dye satisfying the requirements of the above-mentioned formulae (i) and (ii) as the colorant (a), or may further contain a colorant (preferably a yellow pigment) different from the dye. When the dye satisfying the requirements of the formulae (i) and (ii) and the colorant different from the dye are used in combination, the content ratio of the dye satisfying the requirements of the formulae (i) and (ii) is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and particularly preferably 20% by mass or more relative to the total amount of the colorant (a). The content ratio of the dye satisfying the requirements of the above-mentioned formulae (i) and (ii) is preferably 80 mass% or less, more preferably 70 mass% or less, and still more preferably 60 mass% or less, relative to the total amount of the colorant (a).

In the third photosensitive coloring composition, (D) the photopolymerization initiator may not necessarily contain an oxime-based initiator, and any of the photopolymerization initiators exemplified in the description of the first embodiment may be used. In terms of sufficiently promoting the hardening of the coating film by an appropriate exposure amount, the (D) photopolymerization initiator preferably contains an oxime-based initiator, more preferably contains an O-acyl oxime-based initiator. The description of the first embodiment will be applied to the kind and content ratio of the O-acyl oxime initiator.

The third photosensitive coloring composition contains the first solvent and the second solvent as (E) solvents. The content ratio of the second solvent is 0.2 to 2.0 mass% relative to the total solvent amount in the photosensitive coloring composition. If the content 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 sufficiently improved, and foreign matter is likely to be generated in the coating film, which is not preferable. The content ratio of the second solvent is preferably 0.3 mass% or more relative to the total amount of the solvent in the photosensitive coloring composition. The content ratio of the second solvent is preferably 1.8 mass% or less, more preferably 1.5 mass% or less, based on the total amount of the solvent in the photosensitive coloring composition.

The solvent (E) may contain a different solvent from the first solvent and the second solvent as long as the effect caused by the use of the first solvent and the second solvent is not impaired. From the viewpoint of sufficiently improving the solubility of the dye with respect to the solvent, the solvent (E) in the third photosensitive coloring composition preferably contains a first solvent and a second solvent. The explanation of the first embodiment is applied to the blending ratio of the solvent (E) in the third photosensitive coloring composition.

The specific dye a has a characteristic of low solubility in the first solvent and low solubility in the second solvent, and on the other hand, is excellent in solubility in a mixed solvent of the first solvent and the second solvent. Therefore, in the case where the specific dye a is contained as the (a) colorant and a mixed solvent of the first solvent and the second solvent is used as the (E) solvent, the solubility of the dye with respect to the solvent can be improved and the presence of foreign matter in the coating film can be suppressed. As another advantage of the mixed solvent, even if each solvent is a solvent having low solubility of the dye alone, the solvent can be used by mixing with other solvents, and therefore, the options of solvents are wide, and a safe solvent having general purpose and stable quality can be used. In addition, since the mixed solvent of the first solvent and the second solvent is not so odorous, the mixed solvent does not adversely affect the working environment, and is excellent in storage stability.

According to the third photosensitive coloring composition (the photosensitive coloring composition of [13 ]) described above, the occurrence of foreign matters in the coating film can be suppressed, and a colored cured film having less odor and excellent storage stability can be obtained. In addition, the use of the third photosensitive coloring composition can suppress the generation of foreign matters in the coating film, and can provide excellent productivity of the color filter and the display element. The description of the color filter and the display element applies to the description of the first embodiment.

Examples (examples)

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are mass-based unless otherwise specified. In this example, the weight average molecular weight (Mw) and the acid value of the polymer were measured by the following methods.

(Weight average molecular weight Mw)

The polystyrene equivalent was measured by GPC (solvent for elution: tetrahydrofuran).

(Acid value)

0.5G of the polymer solution was weighed in units of precision to 1mg and dispensed into glass containers. After 50mL of the solution was diluted with propylene glycol monomethyl ether acetate, phenolphthalein was added thereto, and titration was performed with a 0.1N aqueous alcoholic potassium hydroxide solution, whereby the pink-colored spot was used as an end point. Blank tests were performed in the same way. The acid value (unit: mgKOH/g) was calculated from the amount of the polymer added dropwise to a 0.1N aqueous ethanol potassium hydroxide solution for a blank test.

Example 1

In this example, a first photosensitive coloring composition was prepared and evaluated.

1. Synthesis of Compounds

1-1 Synthesis of alkali-soluble resin (B-1)

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 temperature was set to 80℃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 above temperature, and polymerization was carried out for 2 hours while maintaining the above temperature. Thereafter, the temperature of the reaction solution was raised to 100℃and polymerization was further carried out for 1 hour, whereby an alkali-soluble resin solution (solid content concentration 33 mass%) was obtained. The Mw of the resulting alkali-soluble resin was 12,200 and the acid value was 137mgKOH/g. The alkali-soluble resin was defined as "alkali-soluble resin (B-1)".

1-2 Synthesis of alkali-soluble resin (B-2)

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 temperature was set to 80℃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 above temperature, and polymerization was carried out for 2 hours while maintaining the above temperature. Thereafter, the temperature of the reaction solution was raised to 100℃and polymerization was further carried out for 1 hour, whereby an alkali-soluble resin solution (solid content concentration 33 mass%) was obtained. The Mw of the resulting alkali-soluble resin was 18,500 and the acid value was 59mgKOH/g. The alkali-soluble resin was set as "alkali-soluble resin (B-2)".

1-3 Synthesis of alkali-soluble resin (B-3)

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 was replaced with nitrogen. The temperature was set to 80℃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 above temperature, and polymerization was carried out for 2 hours while maintaining the above temperature. Thereafter, the temperature of the reaction solution was raised to 100℃and polymerization was further carried out for 1 hour, whereby an alkali-soluble resin solution (solid content concentration 33 mass%) was obtained. The Mw of the resulting alkali-soluble resin was 13,200 and the acid value was 214mgKOH/g. The alkali-soluble resin was set to "alkali-soluble resin (B-3)".

1-4 Synthesis of alkali-soluble resin (B-4)

200 Parts by mass of propylene glycol monomethyl ether acetate and 72 parts by mass of propylene glycol monomethyl ether were placed in a flask equipped with a condenser and a stirrer, and nitrogen gas was replaced. The mixture 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 at 80℃over 1 hour, and the polymerization was carried out while maintaining the temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100℃and the flask was further overlapped for 1 hour, followed by replacing the flask with air. Next, 41 parts by mass of acrylic acid, 0.4g of triphenylphosphine as a catalyst and 0.4g of methylhydroquinone as a polymerization inhibitor were charged, and reacted at 110℃for 10 hours. 43 parts by mass of tetrahydrophthalic anhydride was further added thereto and reacted at 110℃for 3 hours to obtain an alkali-soluble resin solution (solid content concentration: 33% by mass). The Mw of the resulting alkali-soluble resin was 15,300 and the acid value was 172mgKOH/g. The alkali-soluble resin was set to "alkali-soluble resin (B-4)".

TABLE 1

1-5 Synthesis of multifunctional thiol Compound (F-1)

A polyfunctional thiol compound (F-1)) which is a condensate of 3-mercaptopropyl trimethoxysilane was produced according to the production example of the condensate (A-1) described in paragraph [0054] of Japanese patent application laid-open No. 2007-29313. The thiol equivalent of the compound (F-1) was 398g/eq. The thiol equivalent is determined by oxidizing with iodine and then measuring excess iodine by titration with standard sodium thiosulfate solution.

2. Preparation of colorant dispersions

2-1 Preparation of colorant Dispersion (MB-Y-1)

13 Parts by mass of c.i. pigment yellow 138 (designated as Y138) as a colorant of (a) (BYK) -LPN21116 (manufactured by BYK-Chemie) as a dispersant, which was 12.5 parts by mass in terms of a solution, 15.2 parts by mass of the alkali-soluble resin (B-1) (solid content 33% by mass) synthesized in 1.1 as a 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, thereby preparing a colorant dispersion (MB-Y-1).

2-2 Preparation of colorant Dispersion (MB-G-1) to colorant Dispersion (MB-G-3), colorant Dispersion (MB-Y-2) to colorant Dispersion (MB-Y-3)

Colorant dispersions (MB-G-1) to (MB-G-3) and (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.

TABLE 2

The abbreviations of pigments, dispersants and solvents in table 2 are as follows.

G58:C.I. pigment Green 58

G59:C.I. pigment Green 59

G63:C.I. pigment Green 63

Y138 C.I. pigment yellow 138

Y150 C.I. pigment yellow 150

Y231 C.I. pigment yellow 231

LPN21116 Pick (BYK) -LPN21116 (manufactured by Pick chemical (BYK-Chemie)) Co., ltd

PGMEA propylene glycol monomethyl ether acetate (Propylene Glycol Monomethyl ETHER ACETATE)

PGME propylene glycol monomethyl ether (Propylene Glycol Monomethyl Ether)

3. Preparation of dye solutions

3-1 Preparation of dye solution (S-G-1)

10.0 Parts by mass of a compound (G-dye (dye) -1) as a colorant of (A) was dissolved in 90.0 parts by mass of cyclohexanone, thereby preparing a dye solution (S-G-1).

3-2 Preparation of dye solution (S-G-2) to dye solution (S-G-8), dye solution (S-Y-1) to dye solution (S-Y-3)

Dye solutions (S-G-2) to (S-G-8) and (S-Y-1) to (S-Y-3) were prepared in the same manner as the dye solution (S-G-1), except that the types of the constituent components were changed as shown in Table 3 below. In Table 3 below, "LPN21116" in the column of dispersants is Pick (BYK) -LPN21116 (manufactured by Pick chemical (BYK-Chemie)), which is a dispersant.

TABLE 3

The dyes (G-dye-1~G-dye, Y-dye-1~Y-dye-3) in Table 3 are compounds represented by the following formulas, respectively.

[ Chemical 10]

[ Chemical 11]

[ Chemical 12]

[ Chemical 13]

The abbreviations for the solvents in Table 3 are described below. PGMEA and PGME were the same as described in table 2. CHN cyclohexanone (cyclohexanone)

NMP N-methylpyrrolidone (N-methyl pyrrolidone)

EEP Ethyl 3-ethoxypropionate (3-ethoxy ethyl propionate)

MBA methoxybutyl acetate (methoxy butyl acetate)

IPA isopropyl alcohol (isopropanol)

4. Preparation and evaluation of coloring composition [1]

Example 1

(1) Preparation of coloring composition

100.0 Parts by mass of a colorant mixed solution (M-G-1) was prepared by mixing the colorant dispersion (MB-Y-1) and the dye solution (S-G-1) so that chromaticity coordinate values (x, Y) in the CIE color system became x=0.275 and y=0.560 at the time of luminance evaluation described later. Next, 23.2 parts by mass (solid content concentration 33% by mass) of an alkali-soluble resin (B-1), 4.4 parts by mass of a mixture of (C-1) dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD) DPHA manufactured by japan chemical Co., ltd.) and (C-2) carboxylic acid-modified multifunctional acrylate (trade name Luo Nisi (Aronix) M-520 manufactured by east asia chemical Co., ltd.), 0.7 part by mass of (D-1) oxime initiator (trade name PBG-3057 manufactured by new material manufactured by heavy electronic company, changzhou) and (D-2) oxime initiator (compound represented by the following formula (D-2), 0.7 part by mass of (S-1) mezzanine method (Megafac) F-554 (di methyl ether (DIC) manufactured by DIC) as a fluorine surfactant, and 0.05 part by mass of a mixture were added to prepare a mixture of 0.7 parts by mass of (D-1) oxime initiator (trade name PBG-3057) as a (D) photopolymerization initiator, and a solvent amount equivalent to a total amount of 1% of methyl acetate, and the mixture was added to a solution amount equivalent to the total amount of 1% of methoxy acetate.

(2) Evaluation

The coloring composition (G-1) was evaluated according to the following (i) and (ii).

(I) Evaluation of brightness and contrast

The coloring composition (G-1) was applied to a soda glass substrate having a SiO ₂ film formed on the surface thereof to prevent elution of sodium ions using a spin coater, and then, was prebaked for 100 seconds using a heating plate at 90 ℃. Further, at the time of coating, the rotation speed of the spin coater was adjusted so that the film thickness after post baking became 2.5. Mu.m. Then, after cooling the substrate to room temperature, the coating film was exposed to radiation having wavelengths of 365nm, 405nm and 436nm at a portion of the substrate with an exposure of 400J/m ² using a high-pressure mercury lamp without interposing a photomask. Thereafter, a developing solution containing 0.04 mass% potassium hydroxide aqueous solution at 23 ℃ was discharged to the substrate under a developing pressure of 110kPa and a developing solution flow rate of 1.2 liters/min for a time period corresponding to 1.5 times the time period until the film of the unexposed portion disappeared and the substrate surface was seen, whereby the shower development was performed. Thereafter, the substrate was rinsed with ultrapure water, air-dried, and then further baked in a clean oven (clean oven) at 230 ℃ for 20 minutes, thereby producing a substrate for evaluation having a colored cured film with a film thickness of 2.5 μm.

The spectrum of the obtained substrate was measured by a color analyzer (MCPD 2000 manufactured by tsukamurele electronics (r) (tsukamurella)), and the chromaticity Y (0.560 in example 1) corresponding to the colorant mixture in the CIE color system was converted into a C light source and a 2-degree field of view, and the luminance (Y) was calculated. As a result, in this example 1, the luminance (Y) at a certain chromaticity was 64.7.

Further, the substrate on which the cured film was formed was sandwiched between 2 polarizing plates, and the polarizing plates on the front surface side were rotated while being irradiated with a fluorescent lamp (wavelength range 380nm to 780 nm) from the back surface side, and the maximum and minimum values of transmitted light intensities were measured by a luminance meter LS-100 (manufactured by Minolta (r) (strand)). Then, the maximum value divided by the minimum value was used as the contrast ratio, and as a result, in example 1, the contrast ratio=11000. Further, the contrast ratio means that the larger the numerical value is, the better.

(Ii) Evaluation of solvent resistance

The coloring composition (G-1) was applied to a soda glass substrate having a SiO ₂ film formed on the surface thereof to prevent elution of sodium ions using a spin coater, and then, was prebaked for 100 seconds using a heating plate at 90 ℃. Further, at the time of coating, the rotation speed of the spin coater was adjusted so that the film thickness after post baking became 2.5. Mu.m. Then, after cooling the substrate to room temperature, the coating film was exposed to radiation having wavelengths of 365nm, 405nm and 436nm with an exposure dose of 400J/m ² through a photomask (slit width 90 μm/space width 210 μm) using a high-pressure mercury lamp. Thereafter, a developing solution containing 0.04 mass% potassium hydroxide aqueous solution at 23 ℃ was discharged to the substrate under a developing pressure of 110kPa and a developing solution flow rate of 1.2 liters/min for a time period corresponding to 1.5 times the time period until the film of the unexposed portion disappeared and the substrate surface was seen, whereby the shower development was performed. Thereafter, the substrate was rinsed with ultrapure water, air-dried, and further baked in a clean oven at 230 ℃ for 20 minutes, thereby forming a striped pattern (film thickness 2.5 μm) on the substrate. The chromaticity (x, Y) and the luminance (Y) in the CIE color system were measured with the color analyzer using a C light source and a 2-degree field of view.

Next, the substrate was immersed in N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP) at 25 ℃ for 15 minutes, and chromaticity (x, Y) and luminance (Y) were measured similarly by the color analyzer, and solvent resistance was evaluated based on color change (Δeab (1)) before and after NMP immersion. As a result, Δeab (1) =1.2 in this example 1. The smaller the value of Δeab (1), the better the solvent resistance of the colored cured film can be said to be. Δeab (1) is a value calculated based on the CIE1976 standard.

Example 2 to example 24, and comparative example 1 to comparative example 6

The colorant mixture (M-G-2) to the colorant mixture (M-G-21) were prepared by mixing the colorant dispersion, the dye solution, and the dye so as to have chromaticity (x, y) shown in Table 4. However, when 3 or more kinds of coloring materials are contained in the colorant mixture, the mixing ratio (mass ratio) of the coloring materials in the dye solution or the colorant dispersion to be used is shown in table 4 (the same applies to table 7). In table 4, "-" indicates that the components were not blended (the same applies to table 7). Coloring compositions (G-2) to (G-26) were prepared in the same manner as in example 1, except that the types and amounts of the respective components of the coloring compositions were changed as shown in table 5 below. The obtained coloring compositions (G-2) to (G-26) were evaluated for brightness, contrast and solvent resistance in the same manner as in example 1. These results are shown in table 6 below.

TABLE 4

TABLE 5

Table 5 shows the components other than the colorant mixture liquid and the alkali-soluble resin solution used in preparing the coloring composition. The "additional solvent" in table 5 indicates a solvent component other than PGMEA.

C-1 trade name "Kayara (KAYARAD) DPHA" manufactured by Japanese chemical Co., ltd "

C-2 trade name "ya Luo Nisi (Aronix) M-520" manufactured by Toyama Synthesis Co., ltd "

C-3 trade name "OT-1000" manufactured by Toyama Synthesis Co., ltd "

D-1 trade name "PBG-3057" manufactured by Changzhou powerful electronic New material company (Compound represented by the following formula (D-1))

D-2A Compound represented by the following formula (D-2)

D-3 IGM resin (Resins) B.V. trade name "Ounile (Omnirad) 369" (Compound represented by the following formula (D-3))

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

D-5A compound represented by the following formula (D-5)

D-6 trade name "Yanjia solid (Irgacure) OXE-02" (Compound represented by the following formula (D-6)) manufactured by Basf Co., ltd

D-7 IGM resin (Resins) B.V. trade name "Ounile (Omnirad) 907" (Compound represented by the following formula (D-7))

F-1 Compound (F-1) (multifunctional thiol Compound obtained in Synthesis examples 1-5)

F-2 pentaerythritol tetrakis (3-mercaptopropionate)

S-1 trade name "Meijia method (Megafac) F-554" manufactured by Dielsen (DIC) Co., ltd "

MBA methoxy butyl acetate

IPA isopropanol [ 14]

TABLE 6

From the results of table 6, it is found that the photosensitive coloring compositions of examples 1 to 24, which contain the specific dye a as the (a) colorant and the oxime-based initiator as the (D) photopolymerization initiator, can provide color filters having high brightness, high contrast, and excellent solvent resistance.

Example 2

In this example, a second photosensitive coloring composition was prepared and evaluated. Further, the synthesis of the compound, the preparation of the colorant dispersion, and the preparation of the dye solution are as described above.

5. Preparation and evaluation of coloring composition [2]

Example 25

(1) Preparation of coloring composition

A coloring composition (G-27) was prepared in the same manner as in example 1 except that the coloring composition (G-22) was prepared by preparing a coloring agent mixed solution (M-G-22) so that the coloring agent dispersion and the coloring agent solution became chromaticity (x, y) shown in table 7 below, and the types and amounts of the respective components of the coloring composition were changed as shown in table 8 below.

(2) Evaluation

The coloring composition (G-27) was evaluated according to the following (i) and (ii).

(I) Evaluation of color Change before and after baking and additional baking Heat resistance

The coloring composition (G-27) was coated on a soda glass substrate having a SiO ₂ film formed on the surface thereof to prevent elution of sodium ions using a spin coater, and then, was prebaked for 100 seconds using a heating plate at 90 ℃. Further, at the time of coating, the rotation speed of the spin coater was adjusted so that the film thickness after post baking became 2.5. Mu.m. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation having wavelengths of 365nm, 405nm and 436nm at an exposure dose of 400J/m ² using a high-pressure mercury lamp without interposing a photomask. Thereafter, a developing solution containing 0.04 mass% potassium hydroxide aqueous solution at 23 ℃ was discharged to the substrate under a developing pressure of 110kPa and a developing solution flow rate of 1.2 liters/min for a time period corresponding to 1.5 times the time period until the film of the unexposed portion disappeared and the substrate surface was seen, whereby the shower development was performed. Thereafter, the substrate was washed with ultrapure water and air-dried, thereby forming an evaluation substrate.

The chromaticity (x, Y) and the luminance (Y) of the obtained evaluation substrate were measured by the color analyzer, and then baked in a clean oven at 230 ℃ for 20 minutes to prepare a colored cured film having a film thickness of 2.5 μm. The chromaticity (x, Y) and the luminance (Y) were measured similarly for the evaluation substrate, and the color change (Δeab (2)) before and after baking was evaluated. Further, the substrate was additionally baked in a clean oven at 230 ℃ for 60 minutes, and chromaticity (x, Y) and luminance (Y) were measured similarly, and heat resistance was evaluated based on a color change (Δeab (3)) before and after the additional baking. The evaluation results are shown in table 9 below. Further, it can be said that when Δeab (2) is in the range of 5 to 30, the required color characteristics are exhibited, and therefore, the smaller the value of Δeab (3), the less the color change by baking, and the better the heat resistance. Δeab (2) and Δeab (3) are calculated based on the CIE1976 standard.

(Ii) Evaluation of brightness

The spectrum was measured by a color analyzer in the same manner as in example 1, and the chromaticity Y described in table 7 below in the CIE color system was converted into a C light source and a 2-degree field of view, and the luminance (Y) was calculated. The results of luminance (Y) at a constant chromaticity are shown in table 9 below.

[ Examples 26 to 28 and comparative examples 7 to 9]

The colorant mixture (M-G-23) to the colorant mixture (M-G-26) were prepared by mixing the colorant dispersion and the dye solution so as to have chromaticity (x, y) shown in Table 7. A coloring composition (G-28) to a coloring composition (G-33) were prepared in the same manner as in example 1, except that the types and amounts of the respective components of the coloring composition were changed as shown in Table 8 below. The color change before and after baking, additional baking heat resistance, and brightness were evaluated for the obtained colored compositions (G-28) to (G-33) in the same manner as in example 27. These results are shown in table 9 below. The "additional solvent" in table 8 indicates a solvent component other than PGMEA.

TABLE 7

TABLE 9

As is clear from the results of table 9, the photosensitive coloring compositions according to examples 25 to 28 can provide a color filter having high brightness and excellent heat resistance as compared with comparative example 7 in which a dye having a copper phthalocyanine structure was used as a colorant and Δeab (2) was 2.5. It was also found that the photosensitive coloring composition according to examples 25 to 28 gave a color filter having higher brightness than comparative example 8 in which Δeab (2) was 3.8, and a color filter having excellent heat resistance than comparative example 9 in which the coloring composition was prepared in which the concentration of the coloring material in the solid matter was 50.1 mass%.

Example 3

In this example, a third photosensitive coloring composition was prepared and evaluated. Further, the synthesis of the compound, the preparation of the colorant dispersion, and the preparation of the dye solution are as described above.

6. Preparation and evaluation of coloring composition [3]

Example 29

(1) Preparation of coloring composition

10.0 Parts by mass of a dye powder (G-dye-1), 80.0 parts by mass of a colorant dispersion (MB-Y-1), 45.0 parts by mass of an alkali-soluble resin (B-1) in terms of a solution, 3.0 parts by mass of a mixture of (C-1) dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as (C) polymerizable compounds (manufactured by Kayarad) DPHA, which is a trade name of Kayarad, and 8.2 parts by mass of a (C-2) carboxylic acid-modified multifunctional acrylate (manufactured by Toyama Synthesis Co., ltd.) which is a trade name of Luo Nisi (Aronix) M-520, which is a trade name of (D) photopolymerization initiator (D-1) which is a trade name of (D) new material Co., ltd.), 1.5 parts by mass of a compound (F-1) which is a multifunctional thiol compound, and (F-Megafac) F-554) which is a fluorine-based surfactant, which is a solvent, and a solvent which is a solvent of methyl ether, which is a solvent, are added to a mixture of 0.34% by mass, are equal to the total amount of a solvent, and the total amount of the mixture is equal to that is equal to 10.34% of the total amount of the solvent and the total amount of the aqueous solution to prepare the aqueous solution.

(2) Evaluation of foreign matter in coating film

The coloring composition (G-34) was coated on a soda glass substrate having a SiO ₂ film formed on the surface thereof to prevent elution of sodium ions using a spin coater, and then, was prebaked for 100 seconds using a heating plate at 90 ℃.

The obtained coating film was observed at a magnification of 50 times by using an optical microscope, and the number of foreign matters which could be confirmed in the field of view was counted. The above-described operation was performed at any five places of the cured film for evaluation, and the total number of the foreign matters confirmed was set to be less than 5 as "good (∈)", 5 or more and less than 20 as "acceptable (Δ)", and 20 or more as "poor (x)". As a result, in example 29, the evaluation was good (. Smallcircle.).

(3) Evaluation of storage stability

The coloring composition (G-34) was left in an oven at 40℃for 1 week, and the viscosity (%) before and after the heating was measured. The viscosity change rate (%) was obtained from 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 "good (o)", the case where it was more than 5% and 10% or less was "acceptable (Δ)", and the case where it was more than 10% was "poor (x)". As a result, in example 29, the storage stability was evaluated as good (good). Further, the viscosity was measured at 25℃using an E-type viscometer (Weisconsin (VISCONIC) ELD.R., east machine industry Co.).

(4) Evaluation of odor

The following method was used to conduct a functional test on malodor for 10 and 40 subjects, respectively, of men and women over 20 years old and under 34 years old, and over 35 years old and under 50 years old.

The coloring composition (G-34) was applied 10 sheets per person to a sodium glass substrate having a SiO ₂ film formed on the surface thereof for preventing elution of sodium ions by using a spin coater, and the number of people who felt odor was counted even 1 sheet. For the evaluation, the case where the answer to the odor was less than 10 out of 40 was "good (∈)", and the case where 10 or more were "bad (×)". As a result, in example 29, the evaluation was good (. Smallcircle.).

Example 30, example 31, comparative example 10, comparative example 11

In example 29, coloring compositions (G-35) to (G-38) were prepared and evaluated in the same manner as in example 29 except that the types and amounts of the constituent components were changed as shown in Table 10 below. The evaluation results are shown in table 11 below. Further, the coloring composition of comparative example 11 was found to have a large amount of foreign matters applied in the initial stage, and it was not significant to confirm the evaluation of the storage stability. Regarding "solubility of dye" in table 11 below, the solubility of the solvent used as the first solvent (in example 29, a mixed solvent of PGMEA, PGME, and MBA) and the solubility of the solvent used as the second solvent (in example 29, water) at 25 ℃ higher than 10g/L were indicated as "o", and those below 10g/L were indicated as "x". The "additional solvent" in table 10 indicates 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" means propylene glycol monoethyl ether (propylene glycol monoethyl ether).

TABLE 11

As is clear from the results in table 11, the photosensitive coloring compositions of examples 29 to 31, which are mixed solvents containing the first solvent and the second solvent, showed less foreign matters in the coating film, less odor, and excellent storage stability, as compared with comparative example 10, which does not contain the second solvent but contains cyclohexanone. It was also found that the photosensitive coloring compositions of examples 29 to 31 produced less foreign matters on the coating film and were excellent in storage stability as compared with comparative example 11 containing no second solvent.

Claims

1. A photosensitive coloring composition comprising (A) a colorant, (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-based initiator;

In the 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 at least one of R ^X1～R^X16 represents a halogen atom and at least one represents-OR ^P1.

2. The photosensitive coloring composition according to claim 1, wherein the (a) colorant further contains a yellow pigment.

3. 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 alkali-soluble resin (B) is 75mgKOH/g to 200mgKOH/g.

5. 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 contains 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 the second solvent contains at least one selected from the group consisting of water and an alcohol having 1 to 4 carbon atoms.

7. The photosensitive coloring composition according to claim 1 or 2, further comprising a dispersant.

8. A photosensitive coloring composition comprising (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and

The colorant (A) is contained in an amount of 15 to 45 mass% relative to 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 a value obtained by calculating a color difference DeltaEab before and after heating when the coating film is heated at 230 ℃ for 20 minutes to a film thickness of 2.5 [ mu ] m based on the International Commission on illumination 1976 standard is 5 to 30.

9. A photosensitive coloring composition comprising (A) a colorant, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and

The solvent (E) 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 methoxybutyl acetate, and a second solvent which is at least one selected from the group consisting of water and alcohols with 1-4 carbon atoms,

The second solvent is contained in an amount of 0.2 to 2.0 mass% relative to the total solvent in the photosensitive coloring composition,

The colorant (A) comprises a compound satisfying the requirements of the following (i) and (ii);

(i) The solubility of the polymer is 10g/L or less at 25 ℃ relative to 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 of these;

10. A color filter formed using the photosensitive coloring composition according to any one of claims 1 to 9.

11. A display element comprising the color filter of claim 10.