TW201533169A - Coloring composition, coloring cured film and display device - Google Patents

Abstract

The present invention provides a coloring composition which can form a coloring cured film having excellent heat resistance, excellent solvent resistance and can suppress pigment migration. The solution provided by the present invention is a coloring composition which comprises (A) colorant, and (B) polymerizable compound, in which the (A) colorant comprises a polymer of unsaturated monomer, wherein the unsaturated monomer includes the unsaturated monomer (a1) whose structure is represented by formula (1). In formula (1), R 1 to R 6 respectively represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a group comprising ethylenically unsaturated group; R 7 to R 8 respectively represents an alkyl group having 1 to 8 carbon atoms or a chlorine atom; R 9 to R 10 respectively represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom; l and m respectively represent an integer from 0 to 4. For R 1 to R 6, at least one is a group having ethylenically unsaturated group which is a CH2=CR11-COO-X group (R11 represents a hydrogen atom or a methyl group; X represents a divalent alkyl group having 5 to12 carbon atoms).

Description

Coloring composition, coloring cured film, and display element

The present invention relates to a coloring composition, a colored cured film, and a display element, and more particularly to a color hardening used for forming a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, or the like. A colored composition of a film, a colored cured film formed using the colored composition, and a display element including the colored cured film.

It is known that when a color filter is produced using a coloring sensitizing radiation composition, a pigment dispersion type sensitizing radiation linear composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter referred to as The method of "exposure" and development is carried out to obtain pixels of respective colors (for example, see Patent Documents 1 and 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see Patent Document 3). In addition, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed colored resin composition is known (for example, see Patent Document 4).

In order to achieve high luminance of the display element, high color purity, or high definition of the solid-state imaging element, it is known that it is effective to use a dye as a coloring agent. However, it is generally known that dyes have poor heat resistance and solvent resistance as compared with pigments, and it is strongly desired to develop a heat resistance and resistance. A dye excellent in solvent. For this reason, as a dye excellent in heat resistance and the like, for example, a triarylmethane compound has been proposed (for example, see Patent Documents 5 and 6).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-310706

[Patent Document 5] International Publication No. 2010/123071

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-017425

However, even if the triarylmethane compounds described in Patent Documents 5 to 6 are used, it cannot be said that the requirements for heat resistance and solvent resistance can be sufficiently satisfied. Further, the dye in the pixel of the colored pattern undergoes color transfer to a cured film containing no coloring agent such as a pixel of another color or a protective film (hereinafter also referred to as "transfer property"), so that a display element appears. The problem of low display characteristics is that, in view of this problem, the above triarylmethane compound may not be sufficiently satisfactory. Therefore, even when a triarylmethane compound is used as a coloring agent, there is a strong demand for a colored composition capable of forming a colored cured film which is excellent in heat resistance and solvent resistance and which has improved transferability.

Therefore, an object of the present invention is to provide a heat resistance capable of being formed. A colored composition of a colored cured film having excellent solvent resistance and suppressed transferability. Further, an object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the same.

The inventors of the present invention conducted intensive studies and found that the above problems can be solved by using a specific polymer as a colorant.

That is, the present invention provides a colored composition comprising (A) a colorant and (B) a polymerizable compound, wherein (A) a colorant contains a polymer of an unsaturated monomer (hereinafter also referred to as "the present colorant") The unsaturated single system contains an unsaturated monomer (a1) having a structure represented by the following formula (1).

In the formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated group, and Ar represents an aromatic hydrocarbon group, and R ⁷ ~R ⁸ independently represents an alkyl group or a chlorine atom having 1 to 8 carbon atoms, and R ⁹ to R ¹⁰ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and l and m are independently represented by each other. An integer from 0 to 4.

Wherein at least one of R ¹ to R ⁶ is a group having an ethylenically unsaturated group, and the group having an ethylenically unsaturated group is a CH ₂ =CR ¹¹ -COO-X- group (R ¹¹ It represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group having 5 to 12 carbon atoms. ]

Further, the present invention provides a colored cured film formed using the above colored composition and a display element comprising the colored cured film. Here, the "coloring cured film" means a display element, a pixel of each color used in the solid-state image sensor, a black matrix, a black spacer, and the like.

When the colored composition of the present invention is used, it is possible to form a colored cured film which is excellent in heat resistance and solvent resistance and which has improved transferability.

Therefore, the colored composition of the present invention can be used extremely well for producing a solid-state imaging element such as a color liquid crystal display element, an organic EL display element, a display element such as an electronic paper, or a CMOS image sensor.

[Formation of the Invention]

The invention is described in detail below.

Coloring composition

The constituent components of the colored composition of the present invention will be described in detail below.

- (A) colorant -

The colored composition of the present invention contains the present colorant.

First, the structure represented by the following formula (1) constituting the present colorant The unsaturated monomer (a1) (hereinafter also referred to as "unsaturated monomer (a1)") will be described. Further, the unsaturated monomer (a1) has various resonance structures, but in the present specification, these resonance structures are regarded as having the same structure as the unsaturated monomer having a structure represented by the following formula (1).

In the formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated group, and Ar represents an aromatic hydrocarbon group, and R ⁷ ~R ⁸ independently represents an alkyl group or a chlorine atom having 1 to 8 carbon atoms, and R ⁹ to R ¹⁰ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and l and m are independently represented by each other. An integer from 0 to 4.

Wherein at least one of R ¹ to R ⁶ is a group having an ethylenically unsaturated group, and the group having an ethylenically unsaturated group is a CH ₂ =CR ¹¹ -COO-X- group (R ¹¹ It represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group having 5 to 12 carbon atoms. ]

The alkyl group having 1 to 8 carbon atoms in R ¹ to R ¹⁰ in the above formula (1) may be a straight chain or a branched chain. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tert-butyl group, n-pentyl group, second pentyl group, and neopentyl group. Base, n-hexyl, n-heptyl, n-octyl and the like. Among them, the alkyl group having 1 to 8 carbon atoms in R ¹ to R ⁶ is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group. Further, the alkyl group having 1 to 8 carbon atoms in R ⁷ to R ¹⁰ is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group.

In the group having an ethylenically unsaturated group in R ¹ to R ⁶ , the number of ethylenically unsaturated groups may be one or two or more, but it is preferred to have one olefinicity. The state of the saturated group. Examples of the ethylenically unsaturated group include a group having a (meth)acryl fluorenyl group, a vinyl aryl group, a vinyloxy group, an allyl group and the like. Among them, from the viewpoint of reactivity, a (meth) acrylonitrile group is preferred.

The unsaturated monomer (a1) is a group having at least one of R ¹ to R ⁶ having an ethylenically unsaturated group, and the ethylenically unsaturated group is CH ₂ =CR ¹¹ -COO-X- group group.

Here, R ¹¹ is a hydrogen atom or a methyl group, and can be appropriately selected. Further, X represents a divalent hydrocarbon group having 5 to 12 carbon atoms.

Examples of the divalent hydrocarbon group having 5 to 12 carbon atoms represented by X include a divalent aliphatic hydrocarbon group having 5 to 12 carbon atoms, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group having 5 to 12 carbon atoms include an alkanediyl group having 5 to 12 carbon atoms, and may be a straight chain or a branched chain. Specific examples thereof include pentane-1,5-diyl, hexane-1,6-diyl, hexane-1,5-diyl, hexane-1,2-diyl, heptane- 1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, dodecane-1,12-diyl and the like. Among them, an alkanediyl group having a carbon number of 5 to 10 is preferred, and an alkanediyl group having a carbon number of 6 to 8 is more preferred, and particularly preferably a hexane. -1,6-diyl, octane-1,8-diyl.

Examples of the divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms include a cycloalkyl group having 5 to 12 carbon atoms. Specific examples thereof include a cyclopentyl group, a cyclohexylene group, and a cyclooctyl group. Among them, a cycloalkyl group having 5 to 8 carbon atoms is preferred, and a cycloalkyl group having 6 to 8 carbon atoms is more preferred, and a cyclohexyl group is particularly preferred. Further, the cyclohexylene group has a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,2-extended cyclohexyl group, and is preferably a 1,4-cyclohexylene group from the viewpoint of less steric hindrance.

Examples of the divalent aromatic hydrocarbon group having 5 to 12 carbon atoms include an extended aryl group having 6 to 12 carbon atoms. Specific examples thereof include a stretched phenyl group, an extended naphthyl group, and a stretched biphenyl group. Among them, a aryl group having 6 to 10 carbon atoms is preferred, and a phenyl group and a naphthyl group are more preferred. Further, the phenyl group has an ortho, a meta, and a para-position, and is preferably a para-oromer from the viewpoint of less steric hindrance. Among the anthranyl groups, a 1,4-naphthyl group is preferred.

Among such X, a divalent aliphatic hydrocarbon group having 5 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms are preferable. .

In any of the R ¹ ~ R ⁶ having an ethylenically unsaturated group in the case of the group, preferably the R ¹ ~ R ^{6 1} or 2 is CH ₂ = CR ¹¹ -COO-X The group, more preferably one of R ¹ to R ⁶ is a CH ₂ =CR ¹¹ -COO-X- group.

Further, the CH ₂ =CR ¹¹ -COO-X- group and the other group having an ethylenically unsaturated group which the unsaturated monomer (a1) has may be a total of two or more, more preferably one. CH ₂ =CR ¹¹ -COO-X- group.

The aromatic hydrocarbon group in Ar is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. As a concrete example For example, a group in which 2 to 4 hydrogen atoms are removed from benzene, naphthalene, biphenyl or anthracene can be mentioned. Among them, a group in which 2 to 4 hydrogen atoms are removed from benzene or naphthalene is preferred.

As l and m, it is preferably 0 or 1.

The unsaturated monomer (a1) can be used singly or in combination of two or more. Specific examples of the structure represented by the formula (1) are shown below.

The coloring agent is preferably a copolymer of an unsaturated monomer containing a copolymerizable ethylenically unsaturated monomer other than the unsaturated monomer (a1) (hereinafter also referred to as "unsaturated monomer (a2)"). Things. Examples of such an unsaturated monomer (a2) include an ethylenically unsaturated monomer having one or more carboxyl groups, an N-substituted maleimide, an aromatic vinyl compound, and a (meth) acrylate. A vinyl ether or a macromonomer having a mono(meth)acrylonitrile group at the end of a polymer molecular chain. The unsaturated monomer (a2) can be used singly or in combination of two or more.

Examples of the ethylenically unsaturated monomer having one or more carboxyl groups include (meth)acrylic acid, maleic acid, maleic anhydride, and mono[2-(methyl)acryloxyethyl ester of succinic acid. Ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

Further, examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

Further, examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and decene. .

Further, examples of the (meth) acrylate include (meth) acrylate methyl ester, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate (methyl group). Alkenyl acrylate, 2-hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 2-hydroxypropyl (meth) acrylate, vinyl (meth) acrylate, (A) (meth) acrylate of an unsaturated alcohol such as allylic acrylate, phenyl (meth) acrylate, aryl (meth) acrylate such as benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) single (A) (meth)acrylate of polyacrylate such as acrylate, polypropylene glycol (degree of polymerization 2~10) mono(meth)acrylic acid, glycerol mono(meth)acrylate, cyclohexyl (meth)acrylate , isobornyl (meth)acrylate, tricyclo[5.1.02 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, etc. Hydrocarbyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, A (meth) acrylate of an aromatic alcohol such as an ethylene oxide-modified (meth) acrylate of cumylphenol.

As the (meth) acrylate, a (meth) acrylate having an oxygen-containing saturated heterocyclic group can also be used. Here, the "oxygen-containing saturated heterocyclic group" means a saturated heterocyclic group having an oxygen atom as a hetero atom constituting a hetero ring, and preferably a cyclic ether group having 3 to 7 atoms in the ring. Examples of the cyclic ether group include an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, and a tetrahydrofuranyl group. Among them, from the viewpoint of reactivity, Preferred are oxiranyl, oxetanyl, 3,4-epoxycyclohexyl.

Examples of the (meth) acrylate having an oxygen-containing saturated heterocyclic group include glycidyl (meth)acrylate, 2-hydroxyethyl glycidyl (meth)acrylate, and (meth)acrylic acid-2. - Hydroxypropyl ester glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, (meth) acrylate 4-hydroxybutyl ester glycidyl ether, polyethylene glycol - polypropylene glycol (meth) acrylic acid a (meth) acrylate having an oxiranyl group such as an ester glycidyl ether, (Meth) acrylate having 3,4-epoxycyclohexyl group such as (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester, 3-[(meth)acryloxymethyl] (meth) acrylate having an oxetanyl group such as oxetane or 3-[(meth)acryloxymethyl]-3-ethyloxetane, methyl A (meth) acrylate having a tetrahydrofuran group such as tetrahydrofuran methyl acrylate or the like.

Further, examples of the vinyl ether include vinyl acetate, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, and pentacyclic ring. Pentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane, and the like.

Further, examples of the macromonomer having a mono(meth)acryl fluorenyl group at the terminal of the polymer molecular chain include polystyrene, poly(methyl) methacrylate, and poly(methyl) methacrylate. A macromonomer having a mono(meth)acrylinyl group at the end of the polymer molecular chain, such as a polyoxyalkylene.

Among them, the coloring agent preferably has (meth) acrylate as another copolymerizable ethylenically unsaturated monomer (a2) from the viewpoints of heat resistance, solvent resistance, transfer resistance, and dispersibility. More preferably, it contains at least one selected from the group consisting of a (meth) acrylate having an oxygen-containing saturated heterocyclic group and an aryl (meth) acrylate as another copolymerizable ethylenically unsaturated monomer ( A2). In this way, the heat resistance of the coloring agent can be improved, which is preferable. In the (meth) acrylate having an oxygen-containing saturated heterocyclic group, it is preferred to have at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, and a 3,4-epoxycyclohexyl group. A group of (meth) acrylate. Among the aryl (meth)acrylates, benzene (meth)acrylate is preferred. ester.

When the coloring agent has an unsaturated monomer (a2), the copolymerization ratio of the unsaturated monomer (a2) is preferably in the following state from the viewpoints of heat resistance, solvent resistance, transfer resistance, and dispersibility. kind.

That is, the ratio r of the ratio of the unsaturated monomer (a1) to the unsaturated monomer (a2) in all the structural units of the colorant is in terms of a molar ratio, preferably p/r = 1/99 to 30. /70, more preferably p/r=2/98~25/75, especially good for p/r=3/97~20/80.

Further, in the case where at least one selected from the group consisting of (meth) acrylate having an oxygen-containing saturated heterocyclic group and aryl (meth) acrylate is used as the unsaturated monomer (a2), The copolymerization ratio (s) of the (meth) acrylate having an oxygen-containing saturated heterocyclic group and the aryl (meth) acrylate in the unsaturated monomer (a2) is preferably from the viewpoint of heat resistance and solvent resistance. 5 to 45 mol%, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%.

The present colorant can have an anion as needed to be electrically neutral overall.

Examples of such anions include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a methide anion, and the like.

Examples of the halogen ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

Further, examples of the boron anion include inorganic boron anions such as BF ₄ ^- ; (CF ₃ ) ₄ B ^- , (CF ₃ ) ₃ BF ^- , (CF ₃ ) ₂ BF ₂ ^- , (CF ₃ ) BF ₃ ^- , (C ₂ F ₅ ) ₄ B ^- , (C ₂ F ₅ ) ₃ BF ^- , (C ₂ F ₅ )BF ₃ ^- , (C ₂ F ₅ ) ₂ BF ₂ ^- , (CF ₃ ) (C ₂ F _{5 2} BF ^- , (C ₆ F ₅ ) ₄ B ^- , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ^- , (CF ₃ C ₆ H ₄ ) ₄ B ^- , (C ₆ F ₅ ) ₂ BF ₂ ^- , (C ₆ F ₅ )BF ₃ ^- , (C ₆ H ₃ F ₂ ) ₄ B ^- , B(CN) ₄ ^- , B(CN)F ₃ ^- , B(CN) ₂ F ₂ ^- , B (CN) ₃ F ^- , (CF ₃ ) ₃ B(CN) ^- , (CF ₃ ) ₂ B(CN) ₂ ^- , (C ₂ F ₅ ) ₃ B(CN) ^- , (C ₂ F ₅ ) ₂ B(CN) ₂ ^- , (nC ₃ F ₇ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₂ B(CN) ₂ ^- , (nC ₆ F ₁₃ ) ₃ B(CN) ^- , (CHF ₂ ) ₃ B(CN) ^- , (CHF ₂ ) ₂ B(CN) ₂ ^- , (CH ₂ CF ₃ ) ₃ B(CN) ^- , (CH ₂ CF ₃ ) ₂ B(CN) ₂ ^- , (CH ₂ C ₂ F ₅ ) ₃ B(CN) ^- , (CH ₂ C ₂ F ₅ ) ₂ B(CN) ₂ ^- , (CH ₂ CH ₂ C ₃ F _{7 2} B(CN) ₂ ^- , (nC ₃ F ₇ CH ₂ ) ₂ B(CN) ₂ ^- , (C ₆ H ₅ ) ₃ B(CN) ^- , tetraphenylborate anion, tetra (monofluorobenzene) Borate anion, tetrakis(difluorophenyl)borate Root anion, tetrakis(trifluorophenyl)borate anion, tetrakis(tetrafluorophenyl)borate anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(tetrafluoromethylphenyl)borate anion, four (tolyl)borate anion, tetrakis(dimethylphenyl)borate anion, (triphenyl, pentafluorophenyl)borate anion, [tris(pentafluorophenyl),phenyl]borate anion, thirteen In addition to the organic boron anion such as tridecahydride-7 (8-dicarbaundecaborate anion), JP-A-10-195119 and JP-A-2010- A boron anion described in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei.

Further, examples of the phosphoric acid anion include inorganic phosphate anions such as HPO ₄ ^2- , PO ₄ ^3- , and PF ₆ ^- ; (C ₂ F ₅ ) ₂ PF ₄ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , [ (CF ₃ ) ₂ CF] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (nC ₃ F ₇ ) ₂ PF ₄ ^- , (nC ₃ F ₇ ) ₃ PF ₃ ^- , (nC ₄ F ₉ ) ₃ PF ₃ ^- , (C ₂ F ₅ )(CF ₃ ) ₂ PF ₃ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ^- , (nC ₄ F ₉ ) ₂ PF ₄ ^- , (nC ₄ F ₉ ) ₃ PF ₃ ^- , (C ₂ F ₄ H)(CF ₃ ) ₂ PF ₃ ^- , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ^- , (C ₂ F ₅ )(CF ₃ ) ₂ PF ₃ ^- , octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion, etc. .

In addition, examples of the carboxylic acid anion include, for example, CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ^{− ,} and the like, and JP-A-2009-265641 and JP-A JP-A-2009-265641 A carboxylic acid anion described in JP-A-2008-096680.

Further, examples of the sulfate anion include a sulfate anion and a sulfite anion.

Examples of the organic sulfonic acid anion include an alkylsulfonic acid anion such as a methanesulfonic acid anion, an ethanesulfonic acid anion, a trifluoromethanesulfonate anion, or a nonafluorobutanesulfonate anion; a benzenesulfonic acid anion; An arylsulfonate anion such as p-toluenesulfonic acid anion, p-trifluoromethanesulfonate anion, pentafluorobenzenesulfonate anion, naphthalenesulfonate anion, naphthalene disulfonate anion; 2-(meth)acryloxyloxy group- 1,1,2,2-tetrafluoroethanesulfonic acid anion, 2-(4-vinylphenoxy)-1,1,2,2-tetrafluoroethanesulfonic acid anion, in addition to The organic sulfonate anion described in the pamphlet of International Publication No. 2011/037195, Japanese Patent No. 3736221, and Japanese Patent Laid-Open No. 2011-070172.

Further, examples of the nitrogen anion include [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ ) N(CF ₃ SO ₂ )] ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ^- , [(FSO ₂ )N{CF ₃ CF ₂ (CF ₃ )CFSO ₂ }] ^- , [(FSO ₂ )N{(CF ₃ ) ₃ CSO ₂ }] ^- and the like, in addition to The nitrogen anions described in JP-A-2010-090341, JP-A-2011-116803, and JP-A-2010-090341.

Further, examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ^- , (CF ₃ CF). ₂ CF ₂ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ^- , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ^- , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ^- , (FSO ₂ ) ₃ C ^- and the like, in addition to Japanese Patent Laid-Open No. 2011-145540, and U.S. Patent No. 5,554,664 The methide anion described in Japanese Laid-Open Patent Publication No. Hei. No. 2004-085657, Japanese Patent Application Laid-Open No. Hei.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) (dissolving solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. In this way, heat resistance, solvent resistance, transfer property inhibition, film properties, electrical properties, pattern shape, and resolution can be improved.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the present colorant in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mn is a polystyrene-converted number average molecular weight measured by GPC (dissolving solvent: tetrahydrofuran).

The coloring composition of the present invention may be used by mixing other coloring agents other than the coloring agent. As other coloring agents, there are no particular restrictions, and colors and materials can be appropriately selected depending on the application. The other coloring agent may be a pigment or a dye other than the coloring agent, and other coloring agents may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining pixels having high luminance, contrast, and coloring power, an organic pigment is preferable as the pigment, and an organic dye is preferable as the dye.

As the organic pigment, for example, a compound classified as a pigment in a dye index (C.I.; issued by The Society of Dyers and Colourists), that is, a compound having the following dye index (C.I.) number can be cited.

Red pigments such as CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264; green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58 ; CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 80 and other blue pigments; CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215 and other yellow pigments; CI Pigment Orange 38 and other orange pigments; CI Pigment Violet 23 and other purple pigments.

In addition, Japanese Laid-Open Patent Publication No. 2001-081348, Japanese Patent Publication No. 2001-081348 The lakes described in JP-A-2010-237334, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, JP-A-2011-145346, and the like pigment.

Preferably, it contains at least one selected from the group consisting of a blue pigment and a violet pigment, and more preferably contains at least one selected from the group consisting of CI Pigment Blue 15:6 and CI Pigment Violet 23. . Thereby, it is possible to easily form a colored cured film which is excellent in heat resistance and solvent resistance and which has improved transferability, in particular, a blue pixel.

Further, as the dye, a triarylmethane dye, an anthraquinone dye, an azo dye or the like is preferable. More specifically, the publication of International Publication No. 2010/123071, Japanese Laid-Open Patent Publication No. 2011-116803, Japanese Laid-Open Patent Publication No. 2011-117995, Japanese Laid-Open Patent Publication No. 2011-133844, and Japanese Patent Laid-Open No. 2011-174987 An organic dye described in the publication No.

In the present invention, any other mixed pigment may be used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination of these methods. Further, these pigments may be used by modifying the surface of the particles with a resin as required. For example, a vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is used as the resin for modifying the surface of the pigment particles. For example, the method described in JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like can be used. Further, the organic pigment can be used by refining the primary particles by a so-called salt milling method. As a method of salt grinding, for example, it can be used in The method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179111.

Further, in the present invention, a well-known dispersing agent and dispersing aid may be added while using any other coloring agent to be mixed. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, and a polydispersant. An ethylene glycol diester dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, etc., and a dispersing adjuvant, a pigment derivative etc. are mentioned.

Such dispersants are commercially available, for example, as follows: Disperbyk-2000, Disperbyk-2001, BYK-LPN 6919, BYK-LPN 21116, BYK-LPN 22102 as an acrylic dispersant (the above is BYK Chemie ( BYK), etc.; Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 as a polyurethane dispersant (above BYK Chemie (BYK)) ), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) as a polyethylenimine dispersant, Ajisper PB821 and Ajisper-PB822 as a polyester dispersant Ajisper PB880, Ajisper PB881 (above is Ajinomoto Fine-Techno Co., Ltd.), and BYK-LPN21324 (BYK Chemie (BYK)).

Further, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

In the present invention, other coloring agents may be used singly or in combination of two or more.

The content ratio of the other colorant is preferably 70% by mass or less, and more preferably 50 parts by mass or less based on the total content of the colorant. The lower limit thereof is not particularly limited, and may be 0.01% by mass or more.

(A) colorant in the solid content of the coloring composition from the viewpoint of forming a black matrix or a black spacer having excellent heat resistance, solvent resistance, and transfer resistance, high brightness, excellent color purity, or excellent light-shielding property The content ratio is usually from 5 to 70% by mass, preferably from 10 to 60% by mass. Here, the solid content means a component other than the solvent described later.

- (B) Polymeric Compound -

In the present invention, the polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and modified by caprolactone. Polyfunctional (meth) acrylate, polyalkyl (meth) acrylate modified with alkylene oxide, polyfunctional amine group obtained by reacting (meth) acrylate having hydroxyl group with polyfunctional isocyanate An acid ester (meth) acrylate or a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic groups such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol. A polyvalent compound, a trivalent or higher aliphatic polyhydroxy compound such as glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and Pentaerythritol penta (meth) acrylate, glycerol dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include an acid anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic dianhydride. A tetrabasic dianhydride such as biphenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

In addition, the compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified as the polyfunctional (meth) acrylate which is modified by the caprolactone. Examples of the above-mentioned alkylene oxide-modified polyfunctional (meth)acrylate include at least one modified bisphenol A di(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide. And modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, tris(meth)acrylate, and at least one selected from the group consisting of ethylene oxide and propylene oxide. a trimethylolpropane tri(meth)acrylate, a pentaerythritol tri(meth)acrylate modified from at least one selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide And at least one modified pentaerythritol tetra(meth)acrylate of propylene oxide, at least one modified dipentaerythritol penta (meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, Modified by at least one selected from the group consisting of ethylene oxide and propylene oxide Dipentaerythritol hexa(meth) acrylate or the like.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Melamine structure, benzoguanamine structure means having more than one three Ring or phenyl substituted three The ring serves as the chemical structure of the basic skeleton, and the concept includes melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N', N', N", N"-hexa(alkoxymethyl) melamine, and N. , N, N', N'-tetrakis(alkoxymethyl)benzoguanamine, N, N, N', N'-tetrakis(alkoxymethyl) glycoluril, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having a trivalent or higher value with (meth)acrylic acid, or a polyfunctional (methyl) modified by caprolactone is preferable. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. The heat resistance, solvent resistance, and transfer property are preferably suppressed, and the strength of the colored layer is high, and the surface smoothness of the colored layer is excellent, and scumming, film residue, and the like are less likely to occur on the substrate and the light-shielding layer of the unexposed portion. In view of the polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate and pentaerythritol are particularly preferred. Acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, among polyfunctional (meth) acrylates having a carboxyl group, particularly preferably a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and dipentaerythritol Pentapropylene A compound obtained by reacting an acid ester with succinic anhydride.

In the present invention, the (B) polymerizable compound may be used singly or in combination of two or more.

The content of the (B) polymerizable compound in the present invention is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 700 parts by mass, even more preferably from 100 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. In this way, the heat resistance, the solvent resistance, and the transfer property are suppressed, and the curability and the alkali developability are further improved, and it is possible to suppress the occurrence of the unexposed portion on the substrate or the light shielding layer at a high level. Foam, film residue, etc.

-(C) Adhesive Resin -

The (C) binder resin in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferable, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (c1). )) a copolymer with other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as "unsaturated monomers (c2)").

Examples of the unsaturated monomer (c1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl)acryloxyethyl)ester, and ω-carboxypoly Lactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (c1) can be used individually or in mixture of 2 or more types.

In addition, examples of the unsaturated monomer (c2) include an ethylenically unsaturated monomer having one or more carboxyl groups exemplified in the unsaturated monomer (a2), N-substituted maleimide, and aromatic vinyl. Base compound An acrylate, a vinyl ether, a macromonomer having a mono(meth)acrylinyl group at the end of a polymer molecular chain, and the like. Specific examples are the same as described above.

The unsaturated monomer (c2) can be used singly or in combination of two or more.

In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably from 5 to 50% by mass, more preferably from 10%. 40% by mass. By copolymerizing the unsaturated monomer (c1) in this range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-10 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Revealed copolymers.

In a copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), as a preferred aspect, a (methyl group) having an oxygen-containing saturated heterocyclic group as an unsaturated monomer (c2) may be mentioned. A copolymer of acrylate (hereinafter also referred to as "specific copolymer").

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. It is also possible to use a (meth)acryl fluorenyl group in a side chain as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2008-181095. A carboxyl group-containing polymer such as a polymerizable unsaturated bond is used as a binder resin.

Specific examples of the carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain include a copolymer of a monomer containing an unsaturated carboxylic acid and having an epoxy group. A copolymer obtained by reacting a polymerizable unsaturated compound of an alkyl group, and a copolymer of a monomer containing an unsaturated carboxylic acid and a polymerizable unsaturated compound having an oxirane group is reacted with an unsaturated carboxylic acid to obtain a copolymer The copolymer is a polymer obtained by reacting a copolymer of a monomer containing an unsaturated carboxylic acid and a polymerizable unsaturated compound having a hydroxyl group with an unsaturated isocyanate compound.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) (dissolving solvent: tetrahydrofuran) of the binder resin of the present invention is usually 1,000 to 100,000, preferably 3,000. ~50,000,. According to this aspect, the residual film ratio, the pattern shape, the heat resistance, the electrical characteristics, and the resolution of the film are further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. The term "Mn" as used herein means a polystyrene-equivalent number average molecular weight measured by GPC (solution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, and can be disclosed, for example, in Japanese Laid-Open Patent Publication No. 2003-222717, JP-A-2006-259680, and International Publication No. 2007/029871. Method to control the structure of the binder resin, Mw, Mw / Mn.

In the present invention, the (C) binder resin may be used singly or in combination of two or more.

In the present invention, the content of the (C) binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. According to this aspect, the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics can be further improved.

-Photopolymerization initiator -

The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, it is possible to impart a radiation linearity to the coloring composition. The photopolymerization initiator used in the present invention is a compound which produces an active species capable of starting polymerization of (B) a polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, X-rays or the like. .

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. A compound, an O-indenyl hydrazine compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polynuclear hydrazine compound, a diazo compound, a quinone sulfinate compound, or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. As the photopolymerization initiator, it is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of the group of the compound and the O-mercaptopurine compound.

In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthiophene. Tons of ketone, 4-isopropylthioxanthone, 2,4- Dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Further, as a specific example of the acetophenone compound, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-N- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-N- Polinylphenyl)butan-1-one and the like.

Further, as a specific example of the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6- Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, in the case of using biimidazole as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine hydrogen donor such as a thiol hydrogen donor such as azole or 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more. However, from the viewpoint of further improving the light sensitivity, it is preferred to provide one or more kinds of thiol hydrogen donors and one or more amine hydrogens. The body is used in combination.

Also, as three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three with a halomethyl group Compound.

Further, as specific examples of the O-indenyl ruthenium compound, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoquinone), and B can be cited. Ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1-[ 9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-carbazole -3-yl]-, 1-(O-acetamidine) and the like. As a commercial item of the O-indenyl ruthenium compound, NCI-831, NCI-930 (above, ADEKA), DFI-020, DFI-091 (above, manufactured by Daito Chemix Co., Ltd.), or the like can be used.

In the present invention, in the case of using a photopolymerization initiator other than the biimidazole compound such as an acetophenone compound, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethyl Aminobenzyl acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 4-ethylhexyl 4-methylhexyl benzoate, 2,5- Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethyl Amino) chalcone and the like.

In the present invention, relative to (B) the quality of the polymerizable compound 100 The content of the photopolymerization initiator is preferably from 0.01 to 120 parts by mass, particularly preferably from 1 to 100 parts by mass. By such an aspect, the hardenability and the film properties can be further improved.

- solvent -

The colored composition of the present invention contains the above components (A) and (B) and other components added arbitrarily, but usually a solvent is added to prepare a liquid composition.

The solvent can be appropriately selected and used as long as it can disperse or dissolve the components (A) and (B) constituting the colored composition and other components, and does not react with these components and has moderate volatility.

Among such solvents, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol alone may be mentioned. Methyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, two (poly)alkylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, a (cyclo)alkyl alcohol such as propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol or cyclohexanol; a ketone alcohol such as diacetone alcohol; Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy (poly)alkylene glycol monoalkyl ether acetate such as butyl acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6- Diacetate such as hexanediol diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Alkoxycarboxylates such as ethyl ester, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate; ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid Butyl ester, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, pyruvate Ester, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-oxobutyric acid Other esters such as esters; aromatic hydrocarbons such as toluene and xylene; decylamine or decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone Classes, etc.

Among these solvents, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, and (poly)alkylene glycol monoalkyl ethers are preferred from the viewpoints of solubility, pigment dispersibility, coating properties and the like. Acetate, other ethers, ketones, diacetates, alkoxycarboxylates, other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butane Alcohol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ester, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyl Isopropyl acrylate, n-butyl butyrate, ethyl pyruvate, and the like.

In the present invention, the solvent may be used singly or in combination of two or more.

The content of the solvent is not particularly limited, but the total concentration of each component other than the solvent of the coloring composition is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. According to this aspect, a colorant dispersion having good dispersibility and stability, and a coloring composition excellent in coatability and stability can be obtained.

-additive-

The colored composition of the present invention may contain various additives as needed.

As the additive, for example, a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorosurfactant or an anthrone surfactant; and a vinyl group; Trimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane , adhesion promoters such as 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl) -6-tertiary butyl phenol), 2,6-di-tertiary butyl phenol, pentaerythritol tetrakis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate] ,3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]-2, 4,8,10-tetraoxaspiro[5.5]undecane, thiodiethylidene bis[3-(3,5-di-tri-tert-butyl-4-hydroxyphenyl)propionate] Antioxidant; UV absorbers such as 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone; sodium polyacrylate, etc. Anti-aggregating agent; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino group- Residue improver such as 1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2- (Meth) propylene oxiranyl ethyl ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, ω-carboxy polycaprolactone mono (methyl) A developability improver such as acrylate; a hardening accelerator such as 2-(0-[1'-methylpropyleneamino]carboxyamino)ethyl methacrylate; In addition, as the hardening accelerator, the hardening accelerator described in paragraphs [0162] to [0169] of JP-A-2012-088457 can be used.

The coloring composition of the present invention can be prepared by a suitable method, and the method disclosed in, for example, JP-A-2008-58642, JP-A-2010-132874, and the like can be used. In the case where both a dye and a pigment are used as the coloring agent, a method as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874 may be employed: after the dye solution is introduced into the first filter, the first filtration is passed. Device The dye solution is mixed with a separately prepared pigment dispersion or the like, and the obtained colored composition is passed through a second filter to prepare it. Further, a method of dissolving the dye, the above component (B), and other components used as needed in a solvent, and passing the resulting solution into the first filter, the solution passing through the first filter may be employed. The separately prepared pigment dispersion liquid was mixed, and the obtained coloring composition was passed through a second filter to prepare it. Further, after the dye solution is introduced into the first filter, the dye solution that has passed through the first filter is mixed with the component (B) and other components used as needed, and dissolved. The solution was passed through a second filter, and the solution passed through the second filter was mixed with a separately prepared pigment dispersion, and the obtained colored composition was passed through a third filter to prepare a solution.

Colored cured film and method of producing the same

The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically refers to each color pixel, black matrix, black spacer, or the like used in the color filter.

Next, a colored cured film used in a color filter and a method of forming the same will be described.

As a method of manufacturing a color filter, first, the following method can be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate as needed, and the portion where the pixels are formed is divided. Then, a liquid composition of, for example, a blue radiation sensitive coloring composition of the present invention is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, after post-baking A pixel array in which a blue pixel pattern (colored cured film) disposed in a predetermined arrangement is formed is baked.

Next, the composition is colored with each of the green or red radiation-sensitive resin, and the coating, prebaking, exposure, development, and post-baking of the respective radiation-sensitive coloring compositions are performed in the same manner as described above, and sequentially formed on the same substrate. Green pixel array and red pixel array. Thus, a color filter in which a pixel array of three primary colors of blue, green, and red is disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

Further, the black matrix may be formed by forming a desired pattern by a photolithography method using a metal thin film such as chromium formed by a sputtering method or a vapor deposition method, or a radiation-sensitive coloring composition in which a black pigment is dispersed may be used. It is formed in the same manner as the case of forming the above-described pixels.

Examples of the substrate used for forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, these substrates may be subjected to an appropriate pretreatment such as a drug treatment, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition using a decane coupling agent or the like as required.

When the radiation sensitive coloring composition is applied onto a substrate, suitable coating such as a spray coating 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 employed. The method is particularly preferably a spin coating method or a slit die coating method.

Prebaking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. In addition, dry and dry The drying conditions are usually carried out at 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

Examples of the radiation light source used when forming at least one selected from the group consisting of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium pressure mercury lamp. Light source such as low-pressure mercury lamp or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the exposure light source, an ultraviolet LED can also be used. The wavelength is preferably radiation in the range of 190 to 450 nm.

The exposure amount of the radiation is generally preferably from 10 to 10,000 J/m ² .

Further, as the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0] is preferable. An aqueous solution of -7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkali developer in an appropriate amount. Further, after alkali development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, a dipping type (liquid coating) development method, or the like can be used. The developing conditions are preferably carried out at room temperature for 5 to 300 seconds.

The post-baking conditions are usually carried out at 180 to 280 ° C for about 10 to 60 minutes.

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei 07-318723, No. 2000-310706, and the like can be employed. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Then, for example, a blue liquid composition of the thermosetting coloring composition of the present invention is sprayed with an inkjet device in the formed partition wall, and then prebaked to evaporate the solvent. Then, after exposing the coating film as needed, post-baking is performed to harden it to form a blue pixel pattern.

Then, using a green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thus, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

Further, since the partition walls not only have a light-shielding function but also function to prevent color mixing of the thermosetting coloring compositions of the respective colors sprayed into the divisions, the film thickness is thicker than that of the black matrix used in the first method. Therefore, the partition wall is usually formed of a black radiation linear composition.

The substrate used for forming the color filter, the light source of the radiation, and the method and conditions for prebaking and postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet method is the same as the height of the partition wall.

After the protective film is formed on the pixel pattern thus formed as needed, a transparent conductive film is formed by a sputtering method. It is also possible to further form a spacer after forming a transparent conductive film, thereby fabricating a color filter. interval The material is usually formed of a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) may also be used. In this case, a color-sensitive radiation composition in which a black colorant is dispersed is used, but the coloring composition of the present invention can be favorably used for the formation of the black spacer.

The colored composition of the present invention can be suitably used in forming any of the colored cured films such as the respective color pixels, the black matrix, and the black spacer used in the color filter.

The color filter containing the colored cured film of the present invention formed by this method has extremely high brightness and coloring power, and thus is applied to a color liquid crystal display element, a color image pickup element, a color sensor, an organic EL display element, and an electron. Paper and so on are extremely useful. Further, the display element to be described later may have at least one type of colored cured film formed using the colored composition of the present invention.

Display component

The display element of the present invention has the colored cured film of the present invention. 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 having the colored cured film of the present invention may be of a transmissive type or a reflective type, and a suitable structure may be employed. For example, a color filter may be formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may face each other with the liquid crystal layer interposed therebetween. Further, a structure in which a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be sandwiched between liquid crystals The layers face each other. The latter The structure has an advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. Further, in the case of employing the latter structure, the black matrix and the black spacer may be formed on either of the substrate side on which the color filter is formed and the substrate side on which the ITO electrode is formed.

The color liquid crystal display element including the colored cured film of the present invention may further include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED in which a red LED, a green LED, and a blue LED are combined and white light is obtained by color mixing; a white LED in which a blue LED, a red LED, and a green phosphor are combined and white light is obtained by color mixing is exemplified. a white LED that combines a blue LED, a red illuminating phosphor, and a green illuminating phosphor and obtains white light by color mixing; a white LED that obtains white light by color mixing of the blue LED and the YAG phosphor; LED, orange illuminating phosphor and green illuminating phosphor and white color white LED by color mixing; combining ultraviolet LED, red luminescent phosphor, green luminescent phosphor and blue luminescent phosphor and mixing colors A white LED or the like that obtains white light.

The color liquid crystal display element having the colored cured film of the present invention can be suitably TN (twisted nematic) type, STN (super twisted nematic) type, IPS (transverse electric field switching) type, VA (vertical alignment) type, OCB ( A suitable liquid crystal mode such as an optically compensated birefringence type.

In addition, the organic EL display device having the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242.

Further, the electronic paper having the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be cited.

[Examples]

The embodiments of the present invention will be further described in detail below by way of examples. However, the invention is not limited to the embodiments described below.

<Synthesis of the colorant>

Synthesis Example 1

(Synthesis of unsaturated monomer (a1) represented by formula (1))

To a 1 L three-necked flask equipped with a stirrer and previously subjected to nitrogen substitution, was added tris(dibenzylideneacetone)dipalladium (0) 3.36 g (3.67 mmol), (±)-2,2'-bis (two) Benzylphosphino)-1,1'-binaphthyl 4.58g (7.36mmol) and 450ml of 1,2-dimethoxyethane degassed by nitrogen bubbling in advance, stirred under a nitrogen stream at 80 ° C hour. Then, the mixture was cooled to below 40 ° C, and 25.0 g (0.260 mol) of sodium butoxide and 23.0 g (0.200 mol) of 4-aminocyclohexanol were sequentially added without introducing air into the system. - bromo naphthalene 38.0 g (0.184 mol), and stirred under reflux for 3 hours. After that, the reaction mixture was cooled to room temperature, filtered over Celite, and washed with ethyl acetate, and evaporated. The obtained residue was purified by hydrazine gel column chromatography to give 33.0 g (0.137 mol, yield: 74%) of a solid. This compound was designated as (A1).

To a 500 mL three-necked flask equipped with a stirrer and previously subjected to nitrogen substitution, 12.0 g (0.0497 mol) of the above compound (A1), 7.55 g (0.0746 mol) of triethylamine, and 6.07 g of 4-dimethylaminopyridine were added ( 0.0497 mol), ethyl acetate 250 mL, and cooled to an internal temperature of 5 °C. When the internal temperature did not exceed 10 ° C, 6.24 g (0.0259 mol) of methacrylium fluorene chloride was added dropwise to the mixture, and then the internal temperature was raised to room temperature, and the mixture was stirred at the same temperature for 4 hours under a nitrogen stream. Thereafter, the reaction mixture was washed with 300 mL of water and 300 mL of saturated brine, and the organic layer was dried over anhydrous sodium sulfate. Then, 200 g of toluene was added, and the mixture was concentrated to 40 g under reduced pressure on a rotary evaporator, and then, toluene was added. 40.5 g (0.0633 mol) of 4,4'-bis(diethylamino)benzophenone, 0.100 g of 4-methoxyphenol, and 8.05 g of phosphonium chloride were sequentially added to the obtained solution at room temperature. 0.0518 mol), stirred at 100 ° C for 2 hours under a nitrogen stream. Thereafter, the reaction mixture was cooled to room temperature, and most of the toluene was removed by distillation under reduced pressure using a rotary evaporator, and the obtained residue was dissolved in chloroform (500 mL) and washed with water (500 mL). The organic layer was concentrated under reduced pressure using a rotary evaporator, and acetone was added to the residue to give a total weight of 400 g. The solution obtained here was added dropwise to 3200 g of diisopropyl ether, and the obtained solid was collected by filtration. The solid was dried under reduced pressure at 50 ° C for 12 hours to obtain 18.0 g (0.0276 mol, yield 56%) of a colored solid. This compound was designated as (A2).

To a 100 mL Erlenmeyer flask equipped with a stirrer, 9.00 g (13.8 mmol) of the above compound (A2) and 5.94 g (20.7 mmol) of lithium bis(trifluoromethanesulfonyl)imide were added, and 90 mL of ethyl acetate was added thereto. 90 mL of ion-exchanged water was stirred at room temperature for about 2 hours. Then, the aqueous layer was separated and removed, and the organic layer was washed three times with 100 mL of ion-exchanged water. After concentrating the organic layer under reduced pressure, the residue was dried under reduced pressure at 50 ° C for 12 hours to obtain 11.4 g (12.7 mmol, yield: 92%) of the compound of the formula (A3). This compound was designated as (A3).

(Synthesis of Polymer (1))

A 100 mL three-necked flask equipped with a stirrer and equipped with a reflux cooling tube and a thermometer was sufficiently replaced with nitrogen, and 15.0 g of cyclohexanone was added thereto, under nitrogen. Heat down to an internal temperature of 80 ± 2 ° C. 4.50 g (5.02 mmol) of the compound (A3), 6.00 g (59.9 mmol) of methyl methacrylate, 4.50 g (52.3 mmol) of methacrylic acid, and a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 2.18 g (8.79 mmol) and 45.0 g of cyclohexanone were prepared into a solution, and the internal temperature was maintained at 80 ± 2 ° C, and the addition was carried out by a pump for 2 hours. After the completion of the dropwise addition, stirring was continued for another hour at the same temperature. Then, 0.728 g (2.93 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-65) was dissolved in cyclohexanone 1.13 g. The resulting solution was added to the reaction mixture in one portion, stirred at the same temperature for 30 minutes, and further stirred at 95 ° C for 30 minutes. The reaction liquid was cooled to room temperature, and added dropwise to a large amount of hexane to obtain a colored solid, and the colored solid was dried under reduced pressure at 50 ° C to obtain 13.9 g of a polymer represented by the following structural formula (yield 93) %). The Mw of the obtained polymer (1) was 5,100. This polymer was used as a coloring agent (A-1).

Synthesis Example 2

(Synthesis of polymer (2))

A 100 mL three-necked flask equipped with a stirrer and equipped with a reflux cooling tube and a thermometer was sufficiently nitrogen-substituted, and 15.0 g of cyclohexanone was added thereto, and the mixture was heated to an internal temperature of 70 ± 2 ° C under a nitrogen stream. 4.50 g (5.02 mmol) of the compound (A3), 3.00 g (30.0 mmol) of methyl methacrylate, 3.00 g (21.1 mmol) of glycidyl methacrylate, 4.50 g (52.3 mmol) of methacrylic acid, and polymerization. 2.02 g (8.13 mmol) of the initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) and 45.0 g of cyclohexanone were prepared to prepare a solution, and the internal temperature was maintained at 70 ± 2 ° C, and the mixture was dropped by a pump for 2 hours. After the completion of the dropwise addition, stirring was continued for another hour at the same temperature. Then, 0.728 g (2.71 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-65) was dissolved in cyclohexanone 1.16 g. The resulting solution was added to the reaction mixture in one portion and stirred at the same temperature for 3 hours. The reaction liquid was cooled to room temperature, and the mixture was added dropwise to a large amount of hexane to obtain a colored solid, and the colored solid was dried under reduced pressure at 50 ° C to obtain 14.1 g of a polymer represented by the following structural formula (yield 94). %). The Mw of the obtained polymer (2) was 5,300. This polymer was used as a coloring agent (A-2).

Synthesis Example 3~11

The polymer (3) to (11) were synthesized in the same manner as in Synthesis Example 2 except that the type and amount of the unsaturated monomer (a1) and the unsaturated monomer (a2) were changed to those shown in Table 1 in Synthesis Example 2. . The obtained polymers (3) to (11) were used as coloring agents (A-6) to (A-14), respectively. Further, in Table 2, the amounts of the unsaturated monomer (a1) and the unsaturated monomer (a2) used are described by the mass of the substance, and the copolymerization ratio of the unsaturated monomer (a1) in the coloring agent is used. p", the copolymerization ratio of the unsaturated monomer (a2) in the coloring agent is "r", and the (meth) acrylate having an oxygen-containing saturated heterocyclic group in the unsaturated monomer (a2) and (a) The copolymerization ratio of the aryl acrylate is represented by "s".

In Tables 1 and 2, each component is as follows.

(A3): the above compound (A3)

MMA: Methyl methacrylate

GMA: glycidyl methacrylate

OXMA: 3-(methacryloxymethyl)-3-ethyloxetane

M100: 3,4-epoxycyclohexyl methacrylate (trade name: CYCLOMER M100, manufactured by Daicel Chemical Co., Ltd.)

MAA: Methacrylic acid

EHMA: 2-ethylhexyl methacrylate

PhMA: phenyl methacrylate

PMI: N-phenyl maleimide

VA: vinyl acetate

Comparative Synthesis Example 1

Add 5.00 g (9.72 mmol) of CI Basic Blue 7, bis(trifluoromethanesulfonyl)imide lithium 4.19 g (14.6 mmol) to a 100 mL Erlenmeyer flask equipped with a stir bar, and add chloroform 50 mL, ion. Exchange 25 mL of water and stir at room temperature for about 2 hours. Then, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. After concentrating the organic layer under reduced pressure, the residue was dried under reduced pressure at 50 ° C for 12 hours to obtain 5.88 g (7.78 mmol, yield: 80%) of the compound of the formula. The obtained compound was used as a coloring agent (A-3).

Comparative Synthesis Example 2

The ClO ₄ ^- salt of the compound represented by the following formula (A4) was synthesized by the method described in the examples of Japanese Patent No. 3372221. Then, ClO ₄ except that the compounds of the above polymer (1) is synthesized by the following formula (A4) represented by ^- instead of the compound other than a salt (A3), polymer (1) is synthesized in the same manner to obtain a polymer. This polymer was used as a colorant (A-5).

<Synthesis of binder resin>

Synthesis Example 12

100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methyl group were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, mono(2-propenyloxyethyl) succinate A mixed solution of 15 parts by mass of an ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile), which was maintained at this temperature, and polymerized for 2 hours. Then, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The resulting binder resin had a Mw of 12,200 and an Mn of 6,500. This binder resin was referred to as "adhesive resin (C1)".

<Preparation of colorant solution>

Modulation example 1

10 parts by mass of the coloring agent (A-1) obtained above was dissolved in 90 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-1).

Modulation example 2

10 parts by mass of the coloring agent (A-2) obtained above was dissolved in 90 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-2).

Modulation example 3

5 parts by mass of the coloring agent (A-3) obtained above was dissolved in 95 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-3).

Modulation example 4

5 parts by mass of C.I. Basic Blue 7 was dissolved in 95 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-4).

Modulation example 5~14

A coloring agent solution (A-5) to (A-) was prepared in the same manner as in Preparation Example 1 except that the coloring agents (A-5) to (A-14) were used instead of the coloring agent (A-1) in Preparation Example 1. 14).

<Preparation of Pigment Dispersion>

Modulation example 15

15 parts by mass of CI Pigment Blue 15:6 as a coloring agent, BYK-LPN21116 (manufactured by BYK Chemie (BYK) Co., Ltd.) as a dispersing agent, 12.5 parts by mass (solid content concentration: 40% by mass), propylene glycol monomethyl as a solvent 72.5 parts by mass of the ether ether acetate was treated with a bead mill to prepare a pigment dispersion liquid (a-1).

Modulation example 16

15 parts by mass of CI Pigment Green 58 as a coloring agent, 8.3 parts by mass of BYK-LPN6919 (manufactured by BYK Chemie (BYK) Co., Ltd.) as a dispersing agent (solid content concentration: 60% by mass), propylene glycol monomethyl ether as a solvent 76.7 parts by mass of acetate, treated with a bead mill to prepare a pigment Dispersion (a-2).

Modulation example 17

15 parts by mass of CI Pigment Yellow 138 as a coloring agent, BYK-LPN21116 (manufactured by BYK Chemie (BYK) Co., Ltd.) as a dispersing agent, 12.5 parts by mass (solid content concentration: 40% by mass), propylene glycol monomethyl ether as a solvent 72.5 parts by mass of the acetate was treated with a bead mill to prepare a pigment dispersion liquid (a-3).

Example 1

30.5 parts by mass of the pigment dispersion liquid (a-1) as the coloring agent (A), 23.0 parts by mass of the colorant solution (A-1), and a binder resin (C1) solution (solid component) as the (C) binder resin In a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a photopolymerization, as a result of photopolymerization, a concentration of 33 mass%) of 26.3 parts by mass Starting agent 2-benzyl-2-dimethylamino-1-(4-N- 1.8 parts by mass of morphylphenyl)butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 parts by mass of NCI-930 (manufactured by ADEKA CORPORATION), and Megafac F as a fluorine-based surfactant 0.05 parts by mass of 554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a blue coloring composition (B-1) having a solid concentration of 20% by mass.

Heat resistance evaluation

After the blue coloring composition (B-1) was applied onto a soda glass substrate having a SiO ₂ film on the surface where sodium ions were eluted by a spin coater, it was prebaked by a hot plate at 90 ° C for 2 minutes to form a blue coloring composition (B-1). A coating film having a film thickness of 2.5 μm.

Then, after the substrate was cooled to room temperature, the coating film was irradiated with radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm through a reticle with a high pressure mercury lamp, and exposed at an exposure amount of 400 J/m ² . Thereafter, a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), and subjected to shower development for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a dot pattern on the substrate.

For the obtained dot pattern, the color coordinate value (x, y) and the stimulus value (Y) in the CIE color development system were measured with a C light source and a 2 degree field of view using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

Then, after the substrate was additionally baked at 230 ° C for 90 minutes, the chromaticity coordinate value (x, y) and the stimulating value (Y) were measured, and the color change before and after the additional baking, that is, ΔE ^* ab was evaluated. . As a result, the case where the ΔE ^* ab value was less than 3.0 was evaluated as “○”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “×”. The evaluation results are shown in Table 3. The smaller the ΔE ^* ab value, the better the heat resistance.

Solvent resistance evaluation

After the blue coloring composition (B-1) was applied onto a soda glass substrate having a SiO ₂ film on the surface where sodium ions were eluted by a spin coater, it was prebaked by a hot plate at 90 ° C for 2 minutes to form a blue coloring composition (B-1). A coating film having a film thickness of 2.5 μm.

Then, after the substrate was cooled to room temperature, the coating film was irradiated with radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm through a reticle with a high pressure mercury lamp, and exposed at an exposure amount of 400 J/m ² . Thereafter, a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), and subjected to shower development for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 230 ° C for 30 minutes to form a dot pattern on the substrate. Then, the above substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C for 40 minutes.

The chromaticity coordinate value (x, y) and the stimulating value (Y) before and after the immersion were measured, and the color change before and after immersion, ΔE ^* ab, was evaluated. As a result, the case where the ΔE ^* ab value was less than 3.0 was evaluated as “○”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “×”. The evaluation results are shown in Table 3. The smaller the ΔE ^* ab value, the better the solvent resistance.

Displacement evaluation

The green colored composition (G-1) prepared by the method described later was applied onto a soda glass substrate having a SiO ₂ film on which sodium ions were eluted by a spin coater, and then subjected to a hot plate at 90 ° C. The film was prebaked in minutes to form a coating film having a film thickness of 2.4 μm.

Then, after the substrate was cooled to room temperature, the coating film was irradiated with radiation including wavelengths of 365 nm, 405 nm, and 436 nm without using a high-pressure mercury lamp, and the exposure amount was 400 J/m ² . Face exposure. Thereafter, a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), and subjected to shower development for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 230 ° C for 30 minutes to form a green cured film (T-1) on the substrate.

After the blue coloring composition (B-1) was applied onto the green cured film (T-1) by a spin coater, it was prebaked in a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 2.5 μm. Then, after the substrate was cooled to room temperature, a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), and sprayed for 90 seconds. development. Then, the substrate was washed with ultrapure water and air-dried. The step from coating the blue colored composition (B-1) on the green cured film (T-1) to between air drying is referred to as (Step-1).

The stimulation value (Y) of the green cured film (T-1) was measured before and after (Step-1), and the change in the stimulation value before and after (Step-1), that is, ΔY was evaluated. As a result, the case where the ΔY value is less than 0.2 is evaluated as "○", the case where it is 0.2 or more and less than 0.7 is evaluated as "Δ", and the case where it is 0.7 or more is evaluated as "x". The evaluation results are shown in Table 3. The smaller the ΔY value, the more the transferability is suppressed.

The preparation method of the green coloring composition (G-1) used for the evaluation of the transfection property is as follows.

30.5 parts by mass of the pigment dispersion liquid (a-2) as the coloring agent (A), 25.0 parts by mass of the pigment dispersion liquid (a-3), and a binder resin (C1) solution (solid component) as the (C) binder resin 6.3 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a light (33% by mass) of 26.3 parts by mass, as light Polymerization initiator 2-benzyl-2dimethylamino-1-(4-N- 1.8 parts by mass of morphylphenyl)butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 parts by mass of NCI-930 (manufactured by Adeka Co., Ltd.), and Megafac F-554 as a fluorine-based surfactant (manufactured by DIC Corporation) 0.05 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a green colored composition (G-1) having a solid concentration of 20% by mass.

Examples 2 to 6 and Comparative Examples 1 to 3

A blue colored composition (B-2) was prepared in the same manner as in Example 1 except that the colorant solutions (A-2) to (A-9) were used instead of the colorant solution (A-1) in Example 1. ~(B-9). Further, heat resistance, solvent resistance, and transfer dyeing were carried out in the same manner as in Example 1 except that the blue colored composition (B-2) to (B-9) were used instead of the blue colored composition (B-1). Sexual evaluation. The evaluation results are shown in Table 3.

Example 7

50.0 parts by mass of the coloring agent solution (A-10) as the coloring agent (A), and 14.4 parts by mass of the binder resin (C1) solution (solid content concentration: 33% by mass) as (C) binder resin, as (B) 8.2 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) and NCI-930 (manufactured by Adeka Co., Ltd.) as a photopolymerization initiator Parts by mass, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole 0.2 parts by mass, 2,4-diethylthiophene 0.2 parts by mass of ketone and 0.1 parts by mass of 2-mercaptobenzothiazole, 0.04 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, and propylene glycol monomethyl ether acetate as a solvent were prepared. A blue coloring composition (B-10) having a solid content concentration of 20% by mass.

Then, heat resistance, solvent resistance, and transferability evaluation were performed in the same manner as in Example 1 except that the blue coloring composition (B-10) was used instead of the blue coloring composition (B-1) in Example 1. . The evaluation results are shown in Table 3.

Example 8~11

A blue color was prepared in the same manner as in Example 7 except that the colorant solutions (A-11) to (A-14) were used instead of the colorant solution (A-10) in Example 7. Color composition (B-11) ~ (B-14). Further, heat resistance, solvent resistance, and transferability were carried out in the same manner as in Example 7 except that the blue colored composition (B-11) to (B-14) were used instead of the blue colored composition (B-10). Evaluation. The evaluation results are shown in Table 3.

Claims (8)

A coloring composition comprising (A) a coloring agent and (B) a polymerizable compound, wherein (A) the coloring agent contains a polymer of an unsaturated monomer, and the unsaturated single system contains the following formula (1) Showing the unsaturated monomer (a1) of the structure, In the formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated group, and Ar represents an aromatic hydrocarbon group, and R ⁷ ~ R ⁸ independently of each other represents an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and R ⁹ to R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and l and m each independently represent 0. An integer of ～4, wherein at least one of R ¹ to R ⁶ is a group having an ethylenically unsaturated group, and the group having an ethylenically unsaturated group is CH ₂ =CR ¹¹ -COO-X- A group (R ¹¹ represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group having 5 to 12 carbon atoms). The colored composition of claim 1, wherein the polymer further comprises A copolymer of an unsaturated monomer which is a copolymerizable ethylenically unsaturated monomer (a2). The colored composition of claim 2, which contains at least one selected from the group consisting of (meth) acrylate having an oxygen-containing saturated heterocyclic group and aryl (meth) acrylate as another copolymerizable group Ethylenically unsaturated monomer (a2). The colored composition of claim 3, which comprises (methyl group) having at least one group selected from the group consisting of an oxiranyl group, an oxetane group, and a 3,4-epoxycyclohexyl group. Acrylate as a (meth) acrylate having an oxygen-containing saturated heterocyclic group. The colored composition according to any one of claims 1 to 4, further comprising at least one selected from the group consisting of a blue pigment and a purple pigment. The colored composition according to any one of claims 1 to 4, further comprising (C) a binder resin. A colored hardening film formed using the colored composition of any one of claims 1 to 6. A display element comprising the colored cured film of claim 7.