WO2019022051A1

WO2019022051A1 - Pigment composition for color filter, and color filter

Info

Publication number: WO2019022051A1
Application number: PCT/JP2018/027628
Authority: WO
Inventors: 省二船倉; 貴子田中; 悠介尾崎; 安井　健悟
Original assignee: Dic株式会社
Priority date: 2017-07-26
Filing date: 2018-07-24
Publication date: 2019-01-31
Also published as: JP6658963B2; TW201920496A; JPWO2019022051A1

Abstract

The present invention addresses the problem of providing: a pigment composition which exhibits excellent heat resistance and can attain excellent contrast and high reliability when used to produce a color filter; and a color filter having the pigment composition in pixels thereof. The present invention can solve this problem by providing a pigment composition for a color filter, the pigment composition containing a phthalocyanine-based pigment and an azomethine copper complex-based pigment and being characterized in that the mass ratio of the phthalocyanine-based pigment and the azomethine copper complex-based pigment is 99.9/0.1-96.5/3.5. By incorporating this pigment composition for a color filter into the pixels of a color filter, it is possible to obtain an excellent color filter that can solve the abovementioned problem.

Description

Pigment composition for color filter and color filter

The present invention relates to a pigment composition used to form a pixel portion of a color filter for display, and a color filter containing the pigment composition.

The color filter of the liquid crystal display device has a red pixel part (R), a green pixel part (G) and a blue pixel part (B). Each of these pixel parts has a structure in which a thin film of a synthetic resin in which an organic pigment is dispersed is provided on a substrate, and as the organic pigment, organic pigments of respective colors of red, green and blue are used.

Organic pigments used for color filter production have characteristics completely different from conventional general-purpose applications, specifically, to make the display screen of a liquid crystal display device clearer (higher contrast), or, similarly, the display screen is more There is a demand that the characteristics of the colored layer of the color filter do not adversely affect the liquid crystal alignment failure or the switching performance of the liquid crystal (reliability), etc., to be bright (high brightness).

In order to meet such requirements, various methods such as miniaturization of pigment particles and surface treatment have been proposed, but due to the recent increase in required performance, the characteristics of the color filter obtained by these methods can not be said to be sufficient. The case is happening. In addition, since color filters are generally fired at a high temperature of 230 ° C. or higher, the organic pigments used are required to have heat resistance of 230 ° C. or higher, and even after firing, brightness, contrast and reliability are required. There is a need for pigment compositions that do not degrade.

Among these, a method is disclosed in which a quinophthalone pigment and an azomethine pigment as a yellow pigment are contained at a constant ratio to a halogenated zinc phthalocyanine which is a green pigment (Patent Document 1). In addition, a method is also described in which a quinophthalone pigment and an azomethine pigment as a yellow pigment are contained at a constant ratio to an aluminum phthalocyanine pigment (Patent Document 2). However, in the methods described in Patent Documents 1 and 2, contrast and Heat resistance is not enough, and it can not be said that it has reached the demand specs of the market which has been increasing in recent years. There is also the issue of reliability.

JP, 2015-83664, A JP, 2010-72105, A

The problem to be solved by the present invention is a pigment composition which is excellent in heat resistance and can obtain excellent contrast and reliability when used in color filter production, and has the pigment composition in a pixel portion It is to provide a color filter.

MEANS TO SOLVE THE PROBLEM When the present inventors earnestly examined in order to solve the said subject, it finds out that the pigment composition which contains a phthalocyanine-type pigment and an azomethine copper complex type pigment by a specific ratio solves the said subject, and this invention It came to complete.

That is, the present invention is a pigment composition for color filters containing a phthalocyanine based pigment and an azomethine copper complex based pigment, wherein the mass ratio of the phthalocyanine based pigment to the azomethine copper complex based pigment is 99.9 / The present invention relates to a pigment composition for a color filter, which is characterized by 0.1 to 96.5 / 3.5. The present invention also relates to a color filter characterized by containing the composition.

The pigment composition for color filter of the present invention is remarkable that it can provide a highly reliable color filter having high contrast, little change in chromaticity x of post bake (230 ° C., 1 hour) and excellent heat resistance. Play an effect.

<Phthalocyanine pigment>
As the phthalocyanine pigment used in the present invention, any known phthalocyanine pigment can be used. The term "phthalocyanine pigment" as used herein includes those having and not having a central metal. In the case of having a central metal, mainly copper, zinc, aluminum and the like can be mentioned. For example, C.I. I. Pigment green 7, 36, 58, 59, 62, 63 and the like may be used. Also, for example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, blue or green pigments such as aluminum phthalocyanine derivatives can be used.
Here, examples of the above-mentioned aluminum phthalocyanine derivative include unsubstituted phthalocyanine aluminum (C.I. Pigment Blue 79), chlorinated phthalocyanine aluminum, and brominated phthalocyanine aluminum, and they are represented by, for example, the following general formula (3-1) Compounds and the like.

(In formula (3-1), R is a halogen atom, a hydroxy group, or a group represented by the following general formula (3-2). Also, X in formula (3-1) represents a halogen atom, m represents an integer of 0 to 16.)

(In the formula (3-2), X is a direct bond or an oxygen atom. Ar is a phenyl group or a naphthyl group. In the formula, an asterisk indicates a binding site.)

Examples of the halogen atom for R in the above-mentioned formula (3-1) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Among them, the halogen atom in R is preferably a chlorine atom or a bromine atom.

In formula (3-1), R is preferably a chlorine atom, a bromine atom, a hydroxy group or a group represented by the above general formula (3-2).

In formula (3-2), X is preferably an oxygen atom.

Among the compounds of formula (3-1), preferred are, for example, hydroxyaluminum phthalocyanine, chloroaluminum phthalocyanine (CI pigment blue 79), bromoaluminum phthalocyanine, and compounds represented by the following formula (3-1-1) And a compound represented by the following formula (3-1-2), a compound represented by the following formula (3-1-3), a compound represented by the following formula (3-1-4), and the like.

(N represents an integer of 1 to 16)

These phthalocyanine pigments may be used alone or in combination of two or more.
The phthalocyanine pigment used in the present invention may be composed of particles not coated with a pigment derivative and / or a polymer, but a pigment dispersion such as a paste for a color filter to be described later or a light curing such as a resist It is preferable that the pigment derivative and / or the polymer is coated in order to ensure a better affinity to the sex composition.

The polymer nonvolatile content is preferably 0.5 to 10 parts by mass with respect to 100 parts of the organic pigment. As the polymer at this time, any of known and commonly used polymers can be used, but an acrylic copolymer having a monomer A which strongly interacts with the phthalocyanine pigment and which is adsorbed on the pigment surface is preferable, a single amount As the body A, hydrocarbon cyclic compounds such as benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate Preferred are (meth) acrylic acid ester monomers. In addition to the monomer A, an acrylic copolymer having the monomer B that exerts a dispersion stabilizing effect after adsorption on the pigment surface is more preferable, and as the monomer B, (meth) acrylic acid alone is preferable. Preferred are monomers, and (meth) acrylic acid ester monomers such as glycidyl (meth) acrylate and acid phosphooxyethyl methacrylate. In addition, the acrylic copolymer may have a plurality of different monomers A, and further, an acrylic copolymer in which a plurality of different monomers A are copolymerized with a single monomer or a plurality of monomers B. It may be a polymer.
Furthermore, in addition to the monomer A and the monomer B, a polymer may be used in combination with other copolymerizable monomers.
In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid.
(Meth) acrylic acid ester is a compound containing an ester bond formed from (meth) acrylic acid and various other alcohols, and a carbon atom chain at the end of the ester bond COO derived from the above alcohol Say what contains. Typically, those in which the carbon chain is an alkyl group are referred to as (meth) acrylic acid alkyl esters. In the case of (meth) acrylic acid alkyl ester, the side chain means an alkyl group. In the industry, not only (meth) acrylic acid alkyl esters but also compounds in which the above carbon chain is other than an alkyl group are well known, so in the present invention, not only (meth) acrylic acid alkyl esters but also carbon chains , And compounds other than alkyl groups are referred to as (meth) acrylic acid esters.
As such (meth) acrylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, which is a (meth) acrylic acid alkyl ester n-Butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate [lauryl (meth) acrylate] (Meth) acrylic acid alkyl esters having an alkyl group such as octadecyl (meth) acrylate (stearyl (meth) acrylate); cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl ) (Meth) acrylic acid esters containing an alicyclic group such as acrylate and dicyclopentanyl (meth) acrylate; methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol # 400 (meth) acrylate, methoxy dipropylene glycol ( Meta) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate Meta) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonyl phenoxyethyl (meth) acrylate, p-nonyl pheno (Meth) acrylic acid esters containing an ether group such as polyethylene glycol (meth) acrylate; (meth) acrylic acid esters containing an aromatic ring such as benzyl (meth) acrylate; glycidyl (meth) acrylate, allyl glycidyl ether, (Meth) acrylic acid esters containing an epoxy group such as 4-hydroxybutyl (meth) acrylate glycidyl ether; acid phosphoxyoxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and acid phosphooxyoxyethyl methacrylate Polyoxypropylene glycol monomethacrylate, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, Ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate, and commercially available products such as Phosmer M, Phosmer CL, Phosmer PE, Phosmer MH (manufactured by Uni Chemical Co., Ltd.), Light Ester P-1 M (manufactured by Kyoeisha Chemical Co., Ltd.) And (meth) acrylic acid esters having a phosphoric acid group such as JAMP-514 (all, Johoku Chemical Industry Co., Ltd.), KAYAMER PM-2, KAYAMER PM-21 (all, Nippon Kayaku Co., Ltd.), etc. .
Other comonomers include, for example, vinyl esters such as vinyl acetate, vinyl propionate and vinyl tertiary carboxylate; heterocyclic vinyl compounds such as vinyl pyrrolidone; vinyl chloride, vinylidene chloride, vinylidene fluoride and the like Cyano group-containing monomers such as halogenated olefins, acrylonitrile and methacrylonitrile; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; vinyl ketones such as methyl vinyl ketone; α-olefins such as ethylene and propylene; butadiene and isoprene And dienes; styrene-based monomers such as styrene, vinyl toluene, α-methylstyrene, dimethylstyrene, and tert-butylstyrene.
Moreover, as copolymerizable unsaturated carboxylic acid, for example, crotonic acid, isocrotonic acid, 2- (meth) acroyloxyethyl succinic acid, 2- (meth) acroyloxy hexahydrophthalic acid, 2- ( Meta) acroyloxy ethyl glutarate; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and anhydrides thereof; monomethylmaleic acid, monoethylmaleic acid, monobutylmaleic acid, monooctylmaleic acid, monomethylfumaric acid, mono Monoalkyl esters of dicarboxylic acids such as ethyl fumaric acid, monobutyl fumaric acid, monooctyl fumaric acid, monomethyl itaconic acid, monoethyl itaconic acid, monobutyl itaconic acid, monooctyl itaconic acid and the like can be mentioned.

The phthalocyanine-based pigment and the azomethine copper complex-based pigment constituting the pigment composition of the present invention may be primary particles or secondary aggregates, but since they are used for preparation of color filter pixel portions, primary particle diameter is more than general purpose It is preferable that it is fine. From such a viewpoint, in the phthalocyanine pigment of the present invention and the azomethine copper complex pigment, the average particle diameter of primary particles is preferably 10 nm to 80 nm, and more preferably 10 nm to 40 nm. It is not preferable that the average particle diameter of the primary particles is 100 nm or more, because the luminance of the pixel portion is lowered. The average particle size of the primary particles is measured as follows. First, particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, for 50 primary particles constituting an aggregate on a two-dimensional image, the longest length (maximum length) and the shortest length (minimum length) of the inner diameter of each particle are determined. The average value of 1/2 of the sum of the maximum length and the minimum length of each particle is taken as the average particle size of the primary particles.

<Azomethine copper complex pigment>
Although any known azomethine copper complex pigment can be used as the azomethine copper complex pigment used in the present invention,
For example, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 129 and the like.

<Mass ratio of phthalocyanine pigment to azomethine copper complex pigment>
The composition for a color filter of the present invention is more preferably 99, when the mass ratio of the phthalocyanine based pigment to the azomethine copper complex based pigment is 99.9 / 0.1 to 96.5 / 3.5. In the case of 7 / 0.3 to 97.0 / 3.0, it is possible to obtain a highly reliable color filter which is excellent in heat resistance and has high contrast when used in color filter production.

Generally, in the case of blending for the purpose of toning with the green pigment in the green pixel part of the color filter, or in the method as described in Patent Document 1, the usage of the azomethine copper complex based pigment is different from the phthalocyanine based pigment and the azomethine copper complex. The weight ratio to the base pigment is at least about 96.3 / 3.7 to 60/40, and the constitution of the present invention is unexpectedly azomethine copper complex system for improving color filter characteristics also from the viewpoint of toning. Patent Documents 1 and 2, which have been suggested that it is necessary to contain a certain amount or more of the pigment, were studied from the opposite viewpoint.
As described above, the organic pigment used in the color filter is as fine as 10 nm to 80 nm in average particle diameter of primary particles, and easily crystal-grows at a high temperature of 230 ° C. or higher. In the pigment composition of the present invention, the mass ratio of the phthalocyanine based pigment to the azomethine copper complex based pigment is 99.7 / 0.3 to 96.5 / 3.5, at a high temperature of 230 ° C. or more Since a small amount of azomethine copper complex based pigment performs crystal growth suppression of the phthalocyanine based pigment in the baking treatment, the contrast reduction is suppressed, the change of the chromaticity x becomes small, and the color matching becomes easy and the dielectric loss tangent (tan δ) It is possible to improve the reliability of the color filter that it becomes smaller and there is no liquid crystal alignment defect and switching threshold deviation. Furthermore, a transparent resin containing an imide structure described in JP-A-2017-97181 deactivates phthalocyanine radicals generated by light irradiation to phthalocyanines in the ground state, thereby suppressing color change. It also occurs with system pigments and can also suppress color change due to light irradiation.

<Metal complex>
A metal complex can also be added to the pigment composition for color filters of the present invention. As metal complexes, the following metal complexes (complexes B1 to B6) can be used, or their hydrates can also be used.

As the complex B1, the following formula (4-1):

Formula (4-1)

(In the formula (4-1), n represents an integer of 1, 2, 3 or 4 and M represents
In the case of n = 1, one of Li (I), Na (I) and K (I) is shown,
When n = 2, Be (II), Mg (II), Ca (II), Ti (IV) = O, V (IV) = O, Mn (II), Fe (II), Co (II), Any one of Ni (II), Cu (II), Zn (II), Pd (II), Mo (VI) O ₂ , Sn (II), Sn (IV) Cl ₂ and Pt (II);
In the case of n = 3, Al (III), Sc (III), V (III), Cr (III), Mn (III), Fe (III), Co (III), Ga (III), Ru (III) , In (III), La (III) or Pr (III)
In the case of n = 4, either Ti (IV) or Zr (IV) is indicated,
And R ¹ and R ² each independently represent an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms.
Among them, Be (II), Mg (II), Ca (II), Ti (IV) = O, V (IV) = O, Mn (II), Fe (II), Co (II), Ni (II) ), Cu (II), Zn (II), Pd (II), Mo (VI) O2, Sn (II), Sn (IV) Cl2, Pt (II), Al (III), Sc (III), V) (III), Cr (III), Mn (III), Fe (III), Co (III), Ga (III), Ru (III), In (III), La (III), Pr (III) are preferred , Be (II), Mg (II), Ca (II), Ti (IV) = O, V (IV) = O, Mn (II), Fe (II), Co (II), Ni (II), Cu (II), Zn (II ), Pd (II), Mo (VI) O 2, Sn (II), Sn (I _{) Cl 2, Pt (II)} , Al (III), Fe (III) is more preferable.
Such a complex B1 can be appropriately synthesized and used, and may be a zinc such as Nasem zinc manufactured by Nippon Chemical Industrial Co., Ltd., or bis (2,4-pentanedionato) beryllium (II) manufactured by Tokyo Chemical Industry Co., Ltd. A commercial item can also be used.

As the complex B2, the following formula (4-2):

Formula (4-2)

(M in Formula (4-2) represents any one of Zn (II) (in the above case, m = 2), Al (III), Cr (III) (in the above case, m = 1), And each of R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an OH group).
Among them, Zn (II) and Al (III) are preferable, and Zn (II) is more preferable.
Such complex B2 may be appropriately synthesized and used, or may be a commercially available product such as zinc salicylate trihydrate manufactured by Wako Pure Chemical Industries, Ltd., or BONTRON E-304 manufactured by Orient Chemical Industries, Ltd. it can.

As complex B3, the following formula (4-3):

Formula (4-3)

And metal complexes represented by
Such complex B3 can be appropriately synthesized and used, or a commercial product such as (toluene-3,4-dithiolato) zinc (II) manufactured by Tokyo Chemical Industry Co., Ltd. can be used.

As complex B4, the following formula (4-4):

Formula (4-4)

And metal complexes represented by
Such complex B4 can be appropriately synthesized and used, or a commercial product such as dichloro (1,10-phenanthroline) copper (II) manufactured by Tokyo Chemical Industry Co., Ltd. can be used.

As the complex B5, the following formula (4-5):

Formula (4-5)

(M in Formula (4-5) represents any one of Zn (II), Fe (II), and Cu (II), and R represents any one of ethylene group, propylene group, and o-phenylene group. And n represents an integer of 1 or 2, and X represents a metal complex represented by chlorine atom, bromine atom, iodine atom, OH group or μ-O group.
Among them, R is preferably an ethylene group or a propylene group, more preferably a propylene group. Moreover, as M, Zn (II) and Cu (II) are preferable, and Cu (II) is more preferable.
Such complex B5 can be appropriately synthesized and used, or a commercially available product such as bis (1,3-propanediamine) copper (II) dichloride manufactured by Tokyo Chemical Industry Co., Ltd. can be used.

As the complex B6, the following formula (4-6):

Formula (4-6)

(R in Formula (4-6) represents a CH ₃ group or a CHO group,
A ¹ , A ² and A ³ each independently represent H, Na or K;
M represents a metal complex represented by Mg (II), Fe (II), Cu (II), Zn (II)),
Among them, M is preferably Fe (II), Cu (II) or Zn (II), and more preferably Fe (II) or Cu (II).
In addition, A ¹ to A ³ are preferably H or Na.
Such complex B6 can be appropriately synthesized and used, or a commercially available product such as sodium iron chlorophyllin manufactured by Wako Pure Chemical Industries, Ltd. can be used.

One of these metal complexes may be selected and used alone, and these metal complexes may be used for the phthalocyanine-based pigment, or a plurality of them may be used in combination.
For example, one or more of complex B1 can be selected and used, or one or more of complex B2 can be selected and used, or one of complex B5 can be used. Alternatively, two or more can be selected and used, or one or more can be selected and used from the group of complex B6.
Moreover, it can also be used together exceeding each complex group. For example, one or more selected from the group of complex B1 may be used in combination with the complex B3, or one or more selected from the group of complex B1 may be selected from the group of complex B2 One or more of them may be selected and used in combination.

<Mass ratio of phthalocyanine pigment to metal complex>
In the pigment composition for color filters of the present invention, the mass ratio of the phthalocyanine based pigment to the metal complex is preferably 99.999 / 0.001 to 60/40, more preferably 99.995 / 0.005. When it is ~ 75/25, and more preferably 99.99 / 0.01 ~ 85/15, when it uses for color filter preparation, it expresses high contrast and high light resistance, and more excellent color You can get a filter.

Bis (2,4-pentanedionato) zinc (II), tris (2,4-pentanedionato) aluminum (III), bis (2,4-pentanedionato) titanium (IV) oxide, tris (2, 4-Pentandionato) vanadium (III), zinc (II) salicylate trihydrate, zinc (II) 3,5-di-tert-butylsalicylic acid, chromium (III) 3,5-di-tert-butylsalicylic acid As for the above, when the mass ratio is 99.9 / 0.1 to 60/40, more preferably 99.5 / 0.5 to 75/25, still more preferably 99/1. In the case of ̃85 / 15, a better color filter can be obtained.

Tris (2,4-pentanedionato) iron (III), bis (2,4-pentanedionato) nickel (II), (toluene-3,4-dithiolato) zinc (II), dichloro (1,10-) As for phenanthroline) copper (II) and copper (II) chlorophyllin sodium, more preferably 99.99 / 0.01 to 80, when the above mass ratio is 99.995 / 0.005 to 75/25. When the ratio is / 20, more preferably 99.95 / 0.05 to 90/10, a better color filter can be obtained.

For bis (2,4-pentanedionato) copper (II), tris (2,4-pentanedionato) vanadium (IV) oxide, the above mass ratio is 99.999 / 0.001 to 85/15 More preferably in the range of 99.99 / 0.01 to 90/10, and more preferably in the range of 99.95 / 0.05 to 95/5. be able to.

The phthalocyanine pigment and the metal complex may be mixed in advance with the pigment, or may be mixed at the time of dispersion or preparation of the photocurable composition. When a plurality of metal complexes are used, those metal complexes may be mixed in advance, or may be mixed sequentially to the pigment, to the dispersion, or to the preparation of the photocurable composition.

<Pigment dispersed resin>
A pigment dispersion resin can also be added to the pigment composition for color filters of the present invention. The pigment dispersion resin is at least one selected from the group consisting of the following resins C1 to C2, and the difference between the basic functional group valence and the acidic functional group valence as the whole of the pigment dispersion resin (that is, the base valence-acid valence Resin or resin composition having a value of −45.8-90.8 mg KOH / g can be used.

One of the resins C1 is a resin (C1-1) having a basic functional group. Examples of the basic functional group include an amino group, an imino group, a pyridyl group and a quinoline group, and an amino group is more preferable. Examples of the resin skeleton include acrylic resins, polyester resins, urethane resins, and graft resins containing nitrogen atoms, and acrylic resins and graft resins containing nitrogen atoms are more preferable. In the case of an acrylic resin, it may be a block copolymer or a random copolymer, and a block copolymer is more preferable.

Another example of the resin C1 is a resin (C1-2) having an acidic functional group. As an acidic functional group, a carboxyl group, a sulfonic acid group, phenolic hydroxyl group, and a phosphoric acid group are mentioned, A carboxyl group and a sulfonic acid group are more preferable, and a carboxylic acid group is more preferable. Examples of the resin skeleton include acrylic resin, polyester resin, urethane resin, and graft resin, and acrylic resin is more preferable. In the case of an acrylic resin, it may be a block copolymer or a random copolymer.

As resin C2, resin which has both a basic functional group and an acidic functional group is mentioned. As a basic functional group and an acidic functional group, the various functional groups mentioned above are mentioned, An amino group, a carboxyl group, and a sulfonic acid group are more preferable. As a resin skeleton, acrylic resin, polyester resin, urethane resin, graft resin are mentioned, and acrylic resin and graft resin are more preferable. In the case of an acrylic resin, it may be a block copolymer or a random copolymer.

The above amino groups may be partially or completely quaternary ammonium. These resins can sufficiently exhibit the effects of the present invention when selected from C1 or C2 resins and used for phthalocyanine pigments, and, of course, a plurality of C1 and C2 resins can be used. You may use together and use it. In addition, one or more may be selected from the group of resin C1-1 and used, or one or more may be selected and used from the group of resin C1-2, and the group of resin C2 1 or 2 or more can be selected and used.
And it can also be used together more than each resin group. For example, 1 or 2 or more is selected from the group of resin C1-1, 1 or 2 or more selected from the group of resin C1-2, and 1 or 2 or more selected from the group of resin C-2 And may be used in combination.

When selecting the above resin, the balance between the base number and the acid number is important. Specifically, the difference between the base number and the acid number with respect to the entire resin, that is, the value of the base number-acid number is preferably a resin or a resin composition which is -45.8 to 90.8 mg KOH / g, -26. 3 to 90.8 mg KOH / g is more preferred, and -11.0 to 56.0 mg KOH / g is most preferred.

The values of the base number and the acid number can be determined from the following measurements, and these values can be used to calculate the value of the base number-acid number.
When a plurality of pigment dispersion resins are mixed, the base number-acid number value of the entire pigment dispersion resin can be calculated by weighting with the weight ratio of the individual resin values mixed, or It can also be calculated by measuring the resin in the mixed state.

The method shown below is an example of the method of measuring the base number and the acid number in a sample, and can be measured by other known methods. The amount of sample to be used, the type and amount of solvent, the type and concentration of titration reagent, the type of indicator and the like can be changed appropriately. The pigment dispersion resin to be measured may be 100% of the active ingredient or may be dissolved as a solution. In addition, the end point may be determined by coloration, or potentiometric titration may be used.

[Method of measuring base number]
The base number of the pigment dispersion resin is a value represented by mg of potassium hydroxide equivalent to the acid required to neutralize 1 g of the sample, and can be measured by the following method.
Approximately 5 g of a pigment dispersion resin is precisely weighed, dissolved in 100 mL of ethanol together with 1 mL of a bromophenol blue test solution as an indicator, titration is performed with 0.5 mol / L hydrochloric acid, and the point where the color of the solution turns green is the end point. Also, carry out a blank test in the same manner, and perform titration correction. Calculate the base number by the following formula.

Base number = 28.055 × (consumption of 0.5 mol / L hydrochloric acid / mL) / (solid content of pigment dispersion resin / g) (unit: mg KOH / g)

[Method of measuring acid number]
The acid value of the pigment dispersion resin is a value represented by mg of potassium hydroxide required to neutralize 1 g of the sample, and can be measured by the following method.
About 10 g of pigment dispersion resin is precisely weighed, dissolved in 100 mL of ethanol together with a few drops of phenolphthalein solution as an indicator, titration is performed with a 0.1 mol / L potassium hydroxide ethanol solution, and the color of the solution becomes pink. End point. Also, carry out a blank test in the same manner, and perform titration correction. The acid value is calculated by the following equation.

Acid value = 5.611 × (consumption of 0.1 mol / L potassium hydroxide ethanol solution / mL) / (pigment dispersion resin solid content / g) (unit: mg KOH / g)

The base number and acid number of the pigment dispersion resin can also be measured by the following methods. The pigment dispersion itself is titrated by a method such as that described above, and the dispersion solvent and the pigment obtained from the weight of the residue after volatilizing the solvent and the weight of the pigment recovered after centrifugation The base number and acid number of the pigment dispersion resin and the like can also be measured by combining with the weight ratio.

<Mass ratio of phthalocyanine pigment to pigment dispersion resin>
The pigment composition for color filters of the present invention is more preferably 1/0 when the mass ratio (pigment / resin) of the phthalocyanine pigment to the pigment dispersion resin is 1 / 0.1 to 1/1. When it is from 2 to 1 / 0.9, more preferably from 1 / 0.3 to 1 / 0.8, it exhibits high contrast and high light resistance when used in color filter production, Better color filters can be obtained.

The pigment composition of the present invention can be produced, for example, by mixing an organic pigment and, if necessary, other pigment derivatives and polymers in any order so as to achieve the above-mentioned mass ratio. In the pigment composition of the present invention, the organic pigment and the derivative may be sufficiently mixed in advance, and other pigment derivative and polymer may be added thereto. If necessary, the organic pigment and the other pigment derivative or polymer may be ground prior to mixing, while mixing, or after mixing, by any known conventional means such as ball milling or attritor, as described above. It can also be made to become a particle size ratio.

However, there is a simple method of producing a pigment composition that can exhibit a higher improvement effect. It is a method of solvent salt milling of an organic pigment.

In the present invention, solvent salt milling means kneading and grinding an organic pigment, an inorganic salt, and an organic solvent. When this treatment is performed, a crude pigment can also be used as the organic pigment.

This solvent salt milling process makes the organic pigment finer and dispersed. The pigment composition obtained by this treatment exhibits high brightness by being contained in a color filter.

The above-described pigment derivative and polymer can be contained in the system at any stage of producing the pigment composition of the present invention as described above, but from the viewpoint of uniformly dispersing each component, it is an organic compound in advance It is preferable to carry out solvent salt milling after being incorporated in the pigment.

Therefore, in the solvent salt milling process, it is preferable to knead and mill the organic pigment containing the pigment derivative and / or the polymer, the inorganic salt, and the organic solvent which does not dissolve it.

Typical methods for coating the organic pigment with a polymer include, for example, methods including, before, during or after the preparation of the pigment composition. Specifically, for example, a method of adding a polymer to a pigment composition of the present invention not coated with a polymer obtained in advance, depositing the polymer, a method of adding an emulsion of the polymer, a method of kneading and grinding with the polymer, etc. is there. In order to sufficiently control the crystal of the organic pigment in the solvent salt milling treatment, it is preferable to utilize the excellent crystal growth suppressing action of the pigment derivative, and the polymer does not inhibit the adsorption of the derivative to the organic pigment. It is preferable to After completion of the crystal control, these pigments, pigment derivatives and the like may be coated with a polymer.

The solvent salt milling treatment can be carried out by charging each of the above-described raw materials into a kneader and kneading and grinding in the kneader. As a kneading means at this time, for example, kneaders such as a kneader and mix miller can be mentioned.

As the inorganic salt for attrition, a water-soluble inorganic salt can be suitably used. For example, it is preferable to use an inorganic salt such as sodium chloride, potassium chloride or sodium sulfate. In addition, it is more preferable to use an inorganic salt having an average particle size of 0.3 to 70 μm. Such an inorganic salt can be easily obtained by pulverizing a usual inorganic salt for attrition.

In order to obtain a suitable pigment composition of the present invention, the amount of the inorganic salt used is 3 to 30 parts, in particular 7 to 30 parts, and particularly 15 to 30 parts, in terms of mass, per total of organic pigments. Is preferred.

Examples of the organic solvent include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- ( Hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene Using glycol monomethyl ether, dipropylene glycol monomethyl ether, etc. Come.

The amount of the organic solvent used is not particularly limited, but it is preferably 0.01 to 5 parts per mass of the total of the organic pigment in terms of mass.

In the method for producing a pigment composition of the present invention, an organic pigment or a pigment derivative can be further contained, if necessary, for the purpose of adjusting to the intended hue when performing the solvent salt milling treatment.

In the solvent salt milling treatment, the inorganic salt and the organic solvent as described above are charged in the necessary amount in the first charging step, and thereafter the mixture containing the organic pigment and the pigment derivative as the essential components is the necessary primary particles as described above. May be milled to an average particle size, or only a portion of the required amount may be charged to start milling, and the remaining amount of inorganic salt and / or organic solvent may be batchwise or divided along the way. Grinding may be carried out as prepared.

The temperature at the solvent salt milling treatment is preferably 150 ° C. or less, and more preferably 60 to 120 ° C. in particular. The solvent salt milling time is preferably 3 hours to 36 hours, and more preferably 5 hours to 24 hours.

Selecting conditions of solvent salt milling to obtain the pigment composition of the present invention having the required characteristics from time-lapse sampling during solvent salt milling, based on the average particle size value of particles in the pigment composition, etc. It can.

Thus, a mixture containing the pigment composition of the present invention, an inorganic salt, and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from this mixture, and the solid is washed, filtered, dried, ground, etc. The powder of the pigment composition of the present invention can be obtained by

In addition, as this cleaning method, any of water washing and hot water washing can be adopted. In the case of the mixture using a water-soluble inorganic salt and an organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water. It is preferable that the substance that is the source of the specific conductivity be removed as much as possible. In particular, the pigment composition of the present invention for preparing a color filter pixel portion is preferably washed to a specific conductivity of 50 μS / cm or less, preferably 20 μS / cm or less.

As a drying method after the above-mentioned washing and filtration, for example, dehydration and / or desolvation of the pigment composition of the present invention containing a liquid medium by heating at 80 to 120 ° C. by a heat source installed in a drier, etc. The method of drying by a batch system or continuous system, etc. are mentioned. Moreover, as a dryer used in that case, a box-type dryer, a band dryer, a spray dryer etc. are mentioned, for example.

The method of pulverization after drying is not to increase the specific surface area of the pigment composition or to reduce the average particle diameter of the primary particles, but to dry using a box dryer or a band dryer. The method is performed to dissolve and pigment the pigment composition having a lamp shape or the like, and examples thereof include a grinding method using a mortar, a hammer mill, a disc mill, a pin mill, a jet mill or the like.

The pigment composition of the present invention can be used in color filter pixel portions by a conventionally known method. In the production of a color filter pixel portion using the pigment composition of the present invention, a pigment dispersion method can be suitably employed.

A typical method in this method is a photolithography method, which applies a photocurable composition to be described later to the side of the transparent substrate for color filter on which the black matrix is provided, and heat drying (prebake) After that, pattern exposure is performed by irradiating ultraviolet rays through a photo mask to cure the photocurable compound of the portion corresponding to the pixel portion, and then the unexposed portion is developed with a developer, and the non-pixel portion is formed. And the pixel portion is fixed to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.

A photocurable composition to be described later is prepared for each color of red, green and blue, and the above operation is repeated to manufacture a color filter having red, green and blue colored pixel portions at predetermined positions. I can do it.

Examples of pigments for forming a red pixel portion include C.I. I. Pigment Red 254 and 177, and the like.
As a pigment for forming a blue pixel part, for example, C.I. I. Pigment Blue 15: 6 (ε-type copper phthalocyanine pigment) or C.I. I. Pigment Violet 23 (dioxazine violet pigment) and the like.
As a pigment for forming a green pixel part, for example, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, etc., and metal phthalocyanine pigments. In forming a green pixel portion, C.I. I. Pigment Yellow 138, 139, 150 and the like may be used in combination. Thereafter, if necessary, the entire color filter can be heat treated (post-baked) to thermally cure the unreacted photocurable compound.

As a method of apply | coating the photocurable composition mentioned later on transparent substrates, such as glass, a spin coat method, a slit coat method, a roll coat method, the inkjet method etc. are mentioned, for example.

The drying conditions of the coating film of the photocurable composition applied to the transparent substrate vary depending on the types of the respective components, the blending ratio, and the like, but are usually about 50 minutes to 150 ° C. for about 1 to 15 minutes. This heat treatment is generally called "pre-bake". As light used for photocuring of the photocurable composition, it is preferable to use ultraviolet light in the wavelength range of 200 to 500 nm or visible light. Various light sources emitting light in this wavelength range can be used.

Examples of the development method include a liquid deposition method, a dipping method, a spray method and the like. After exposure and development of the photocurable composition, the transparent substrate on which pixel parts of the necessary color are formed is washed with water and dried. The color filter thus obtained is subjected to heat treatment (post-baking) at a temperature of 100 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the colored coating film and at the same time light. The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.

The photocurable composition (also referred to as a pigment-dispersed photoresist) for forming the pixel portion of a color filter comprises the pigment composition of the present invention, a dispersant, a photocurable compound, and an organic solvent as essential components. It can be prepared by mixing them using a thermoplastic resin, if necessary. When the colored resin film forming the pixel portion is required to have toughness and the like that can withstand baking and the like performed in actual production of a color filter, only the photocurable compound is required to prepare the photocurable composition. It is not essential, however, to use this thermoplastic resin in combination. When a thermoplastic resin is used in combination, as the organic solvent, it is preferable to use one that dissolves it.

As a method for producing the photocurable composition, the pigment composition of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and dispersed by stirring so as to be uniform. After preparing a pigment dispersion (also called a colored paste) for forming the pixel part of the filter, add a photocurable compound and, if necessary, a thermoplastic resin, a photopolymerization initiator, etc. thereto. The method of using the photocurable composition is generally used.

Here, as the dispersant, for example, Disperbik 130, Disperbik 161, Disperbik 162, Disperbik 163, Disperbik 170 and the like manufactured by Big Chemie, Inc. may be mentioned. In addition, leveling agents, coupling agents, cationic surfactants and the like can also be used.

Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene, acetic acid ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, and ethoxyethyl propionate. Propionate solvents such as alcohol, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, hexane Aliphatic hydrocarbon solvents, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, Phosphorus, nitrogen compound-based solvent such as pyridine, .gamma.-lactone solvents butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid. The organic solvent is preferably a polar solvent such as propionate type, alcohol type, ether type, ketone type, nitrogen compound type and lactone type, and is water soluble. When a water-soluble organic solvent is used, water can also be used in combination therewith.

Examples of the thermoplastic resin used to prepare the photocurable composition include urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins and the like. Be

As the photocurable compound, for example, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol di Bifunctional monomers such as acrylate, etc., trimethylol propatone triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Relatively high molecular weight polyfunctional monomers such as monomers, polyester acrylates, polyurethane acrylates, polyether acrylates, etc. It is.

As the photopolymerization initiator, for example, acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4'-azidobenzal) -2-propane, 1,3-bis (4) '-Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazide stilbene-2,2'-disulfonic acid and the like.

Using each of the materials as described above, the pigment composition of the present invention uniformly converts 300 to 1,000 parts of the organic solvent and 0 to 100 parts of the dispersant per 100 parts by mass conversion. The pigment dispersion can be obtained by stirring and dispersing such that Then, 3 to 20 parts of the total of the thermoplastic resin and the photocurable compound and 0.05 to 3 parts of the photocurable compound per 1 part of the pigment dispersion of the present invention are added to the pigment dispersion. It is possible to obtain a photocurable composition for forming a color filter pixel portion by adding an agent and, if necessary, an organic solvent and stirring and dispersing so as to be uniform. Such a photocurable composition is usually prepared such that the average particle size of the dispersed particles is 100 nm or less.

The pigment dispersion and the photocurable composition prepared from the pigment composition of the present invention may be coarse particles of 5 .mu.m or more, preferably 1 .mu.m or more, by means of centrifugation, sintered filter, membrane filter, etc. Preferably, removal of coarse particles of 0.5 μm or more and mixed dust is performed.

As the developing solution, known and commonly used organic solvents and alkaline aqueous solutions can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, washing with an alkaline aqueous solution is a color filter. It is effective in forming a pixel portion.

Among the pigment dispersion methods, the method for producing a color filter pixel portion by photolithography has been described in detail, but the color filter pixel portion prepared using the pigment composition of the present invention is not limited to other electrodeposition methods and transfer methods. The color filter may be manufactured by forming the pixel portion by a method such as a micelle electrolysis method or a PVED (Photovoltaic Electrodeposition) method.

The color filter uses a photocurable composition of each color obtained using a blue pigment composition, a green pigment composition, and a red pigment composition, and encloses a liquid crystal material between a pair of parallel transparent electrodes and is transparent. The electrode is divided into discrete fine sections and any one of red (R), green (G) and blue (B) in each of the fine sections divided into grids by the black matrix on the transparent electrode It can be obtained by providing a color filter colored pixel portion selected from colors alternately in a pattern or forming a transparent electrode after forming a color filter colored pixel portion on a substrate.

The pigment composition for color filters of the present invention may be used in various known applications, such as paints, plastics (resin molded articles), printing inks, rubbers, leathers, toners for electrostatic image development, inks for inkjet recording, thermal transfer It can also be applied to coloring of ink and the like.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In the examples and comparative examples, unless otherwise noted, "parts" and "%" are on a mass basis.
Moreover, the measuring method used in the Example mentioned later is as follows.

[Evaluation of brightness]
The chromaticity x, y and the luminance at the C light source of the obtained color filter were measured with a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.) to calculate the luminance at a predetermined chromaticity. The higher the luminance, the better.

[Evaluation of contrast]
The contrast before and after firing at 230 ° C. of the obtained color filter was measured using a contrast tester (manufactured by Takasaka Electric Co., Ltd., device name: CT-1). In this device, there is a place where a color filter is installed between two polarizing plates, one of the polarizing plates is provided with a light source, and the other side is installed with a color luminance meter. The contrast is calculated from the ratio of the brightness (transmitted light intensity) between the time when the polarization axis is parallel and the time when it is vertical. In addition, it measured, after adjusting beforehand so that the contrast of the blank which is a state without a color filter may be set to 10,000. The higher the contrast, the better.

[Evaluation of heat resistance]
According to SEMI D29-1101 “Heat resistance test method of FPD color filter”, spin coated, dried at 90 ° C for 3 minutes, color filter substrate with spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.) The color filter substrate after firing at 230 ° C. for 1 hour was measured for chromaticity with a spectrophotometer U-3900, and then the color difference Δx was calculated from the chromaticity x before and after firing at 230 ° C. for 1 hour. The smaller Δx, the better.

[Dielectric loss tangent (tan δ)]
On a glass substrate on which gold was deposited for an electrode, a CF coating was formed so that the thickness of the coating after firing at 230 ° C. for 1 hour was 1 to 2 μm. Chromium for an electrode was vapor-deposited on the obtained coating film, and a capacitor cell sample was prepared, in which the coating film was sandwiched by gold electrodes. About the obtained sample, the real part and imaginary part of the impedance in 1 to 10000 Hz were measured with an impedance analyzer (Solartron SI1260 Toyoyo Technica company make), and dielectric loss tangent (tan-delta) was computed. The smaller the dielectric loss tangent, the better the reliability of the color filter, and for the dielectric loss tangent of 1 to 10000 Hz in Comparative Example 1, an overall lower one is ○, and the same overall is △, overall The thing which is high is taken as x.

[Evaluation of light resistance]
First, with respect to the obtained color filter (after firing at 230 ° C.), the chromaticity x, y and the luminance Y at the C light source were measured with a spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd., device name: U3900). The luminance at this time is assumed to be an initial luminance Ybefore.
Next, two drops of hexadecane were placed on the coating film of this color filter, and after sandwiching with a glass plate not coated with anything, a light resistance tester equipped with an optical filter for cutting a wavelength of 360 nm or less Xenon lamp light was irradiated using a Toyo Seiki Seisakusho Co., Ltd. device name: SUNTEST CPS +) (irradiation at a set temperature of 100 ° C. for 5 hours). The color filter after irradiation was washed with hexane to remove hexadecane and dried at normal temperature, and then the luminance Y was measured again with a spectral hardness meter. The luminance at this time is referred to as post-irradiation luminance Yafter.
The light resistance of each color filter was quantified as follows, focusing on the change in luminance before and after irradiation. First, for each color filter, the luminance decrease width ΔY = (Ybefore−Yafter) / Ybefore was calculated. Next, in order to eliminate the difference between the irradiation tests, the relative brightness reduction width which is a value normalized by ΔY (this is referred to as ΔYstd) of a standard sample (color filter described in Comparative Example 1 below) simultaneously measured in each irradiation experiment ΔYnorm = ΔY / ΔYstd × 100 [%] was determined. The light resistance was evaluated by this ΔYnorm. The smaller the ΔYnorm, the better the light resistance.

The comprehensive evaluation emphasizes the contrast after firing at 230 ° C. for 1 hour, and adds Δx, dielectric loss tangent and light resistance to this, and ◎ which is excellent as a color filter balance, ○ which is good and バランス which is poor △, and further inferior was regarded as x.

Example 1
97 parts of C.I. I. Pigment green 58 and 3 parts of C.I. I. Pigment Yellow 129 was dry blended to obtain a green pigment composition 1.
1.48 parts of BYK-LPN 6919 (60% solution of active ingredient, solid content amine value 120.0 mg KOH / g) by BK-Chemie 2.48 parts of green pigment composition 1; Unidic ZL-295 (effective by DIC Corporation) Component 40% solution, solid content acid value 75.0 mg KOH / g) 1.86 parts and propylene glycol monomethyl ether acetate 10.92 parts using 38 parts of 0.3-0.4 mm φ Sepul beads (manufactured by Saint-Gobain) It disperse | distributed for 2 hours with the Toyo Seiki Co., Ltd. product paint conditioner, and obtained the coloring composition (MG1). Add 4 parts of the coloring composition (MG1), 0.98 parts of Unidic ZL-295 manufactured by DIC Corporation, 0.22 parts of propylene glycol monomethyl ether acetate, and mix them with a paint shaker to obtain a green pixel part for a color filter. The composition for evaluation (CG1) for forming was obtained. The composition for evaluation (CG1) was spin-coated on soda glass so as to obtain a chromaticity y of 0.50, and spin-coated at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 7408 when the contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6517, and Δx was 0.0050.

Example 2
In Example 1, 97 parts of C.I. I. Pigment green 58 in 99 parts, and 3 parts of C.I. I. A green pigment composition 2 was obtained in the same manner as described above, except that 1 part of pigment yellow 129 was used. Next, a coloring composition (MG2) and a composition for evaluation (CG2) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 7291 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6477, and Δx was 0.0067.

[Example 3]
In Example 1, 97 parts of C.I. I. Pigment green 58 to 99.5 parts, and 3 parts of C.I. I. Pigment Yellow 129 was used in the same manner as described above except that 0.5 parts of Green Pigment Composition 3 was obtained. Next, a color composition (MG3) and a composition for evaluation (CG3) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 7129 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6500, and Δx was 0.0069.

Example 4
Example 1 3 part of C.I. I. Pigment yellow 129 as C.I. I. A green pigment composition 3 was obtained as Pigment Yellow 129 in the same manner as described above. Next, a color composition (MG4) and a composition for evaluation (CG4) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 6392 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6405 and Δx was 0.0059.

[Example 5]
In Example 1, 97 parts of C.I. I. Pigment green 58 in 99 parts, and 3 parts of C.I. I. Pigment yellow 129, C.I. in one part having an average primary particle diameter of 79 nm. I. A green pigment composition 2 was obtained as Pigment Yellow 129 in the same manner as described above. Next, a coloring composition (MG5) and a composition for evaluation (CG5) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 6848 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing, 6637, Δx was 0.0070.

[Example 6]
Green pigment composition 6 in the same manner as in Example 1 except that 2.04 parts of BYK-LPN6919 manufactured by BIC CHEMICAL CO., LTD. And 2.06 parts manufactured by DIC Corporation and 1.86 parts of UNIDIC ZL-295 manufactured by DIC Corporation are used. I got Next, a pigment composition (MG6) and a composition for evaluation (CG6) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 7397 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing, 6544, Δx was 0.0038. Moreover, when the light resistance test was done, the brightness | luminance fall relative width was 39%.

[Example 7]
1.24 parts of BYK-LPN6919 manufactured by BICK CHEMY of Example 1 and 1.64 parts manufactured by DIC Corporation and 1.86 parts of UNIDIC ZL-295 manufactured by DIC Corp. 1.26 parts in the same manner as described above. I got Next, a pigment composition (MG7) and a composition for evaluation (CG7) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 7242 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing, 6407, Δx was 0.0042. Moreover, when the light resistance test was done, the brightness | luminance fall relative width was 18%.

[Example 8]
A green pigment composition 8 in the same manner as in Example 1 except that 0.82 parts of BYK-LPN6919 manufactured by BIC CHEMICAL CO., LTD. And 0.82 parts of DIC Corporation and 1.86 parts of UNIDIC ZL-295 manufactured by DIC Corporation are used. I got Next, a pigment composition (MG8) and a composition for evaluation (CG8) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 7088 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing, 6271, Δx was 0.0038. Moreover, when the light resistance test was done, the brightness | luminance fall relative width was 11%.

[Example 9]
Green pigment composition 9 in the same manner as in Example 1 except that 0.40 parts of BYK-LPN6919 manufactured by BIC CHEMICAL CO., LTD. And 0.40 parts manufactured by DIC Corporation and 1.86 parts of UNIDIC ZL-295 manufactured by DIC Corporation are used. I got Next, a pigment composition (MG9) and a composition for evaluation (CG9) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 6886 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6092 and Δx was 0.0027. Moreover, when the light resistance test was done, the brightness | luminance fall relative width was 6%.

[Example 10]
In Example 1, 97 parts of C.I. I. Pigment green 58 in 94.5 parts, and 3 parts of C.I. I. Pigment yellow 129 to 0.5 parts of C.I. I. Pigment Yellow 129 and 5 parts of zinc (II) 3,5-di-tert-butyl salicylate (BONTRON E-304, manufactured by Orient Chemical Industry Co., Ltd.) were processed as described above to obtain a green pigment composition 10. Next, a pigment composition (MG10) and a composition for evaluation (CG10) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 6981 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6481, and Δx was 0.0027. Moreover, when the light resistance test was done, the brightness | luminance fall relative width was 34%.

[Example 11]
In Example 1, 97 parts of C.I. I. Pigment green 58 in 94.5 parts, and 3 parts of C.I. I. Pigment yellow 129 to 0.5 parts of C.I. I. Pigment Yellow 129 and 5 parts of bis (2,4-pentanedionato) zinc (II) in the same manner as described above to obtain a green pigment composition 11. Next, a pigment composition (MG11) and a composition for evaluation (CG11) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 6911 when the contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing, 6687, Δx was 0.0027. Moreover, when the light resistance test was done, the brightness | luminance fall relative width was 37%.

Comparative Example 1
In Example 1, 97 parts of C.I. I. Pigment green 58 to 100 parts and 3 parts of C.I. I. A green pigment composition 3 was obtained in the same manner as above, except that Pigment Yellow 129 was 0 part. Next, a coloring composition (MG6) and a composition for evaluation (CG6) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 7029 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6229, and Δx was 0.0072.

Comparative Example 2
In Example 1, 97 parts of C.I. I. Pigment green 58 in 95.0 parts, and 3 parts of C.I. I. Pigment yellow 129, 5.0 parts of C.I. I. A green pigment composition 3 was obtained as Pigment Yellow 129 in the same manner as described above. Next, a color composition (MG8) and a composition for evaluation (CG8) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 6049 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 6164 and Δx was 0.0053.

Comparative Example 3
In Example 1, 97 parts of C.I. I. Pigment green 58 in 95.0 parts, and 3 parts of C.I. I. Pigment yellow 129 to a C.I. I. A green pigment composition 3 was obtained as Pigment Yellow 129 in the same manner as described above. Next, a color composition (MG9) and a composition for evaluation (CG9) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 5376 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The contrast of the color filter substrate after firing was 5596, and Δx was 0.037.

Comparative Example 4
In Example 1, 97 parts of C.I. I. Pigment green 58 in 95.0 parts, and 3 parts of C.I. I. Pigment yellow 129, 30.0 parts of C.I. I. A green pigment composition 3 was obtained as Pigment Yellow 129 in the same manner as described above. Next, a color composition (MG10) and a composition for evaluation (CG10) for forming a green pixel portion for a color filter were prepared and dried at 90 ° C. for 3 minutes to obtain a color filter substrate for evaluation. It was 4058 when contrast of this glass substrate for evaluation was measured. Furthermore, baking was performed at 230 ° C. for 1 hour to obtain a color filter after baking. The brightness of the color filter substrate after firing, the contrast was 4826, Δx was 0.007, Δx was low, but the contrast was low, and the overall evaluation was x.

The evaluation results are shown in Tables 1, 2 and 3.
As can be seen from the comparison between Examples and Comparative Examples, according to the pigment composition of the present invention, the contrast after firing at 230 ° C. for 1 hour is high, the change in chromaticity x is small (Δx), and the heat resistance is excellent. It is possible to obtain a color filter excellent in balance that the dielectric loss tangent is low and the reliability is high.

In Examples 1 to 9, the contrast after firing for 1 hour at 230 ° C. is high, the change in chromaticity x (Δx) is small (high heat resistance), and the dielectric loss tangent is low, as compared with Comparative Examples 1 to 4. It can be seen that the balance of various required characteristics required for the color filter (high electrical reliability) is excellent. Furthermore, in Examples 10 to 11, it is understood that the performance is remarkably improved by adding a specific metal complex. In addition, Examples 6 to 11 also show a secondary effect of improving the light resistance.

Claims

What is claimed is: 1. A pigment composition for color filters comprising a phthalocyanine pigment and an azomethine copper complex pigment,
A pigment composition for a color filter, wherein the mass ratio of the phthalocyanine based pigment to the azomethine copper complex based pigment is 99.9 / 0.1 to 96.5 / 3.5.
The pigment composition for color filters according to claim 1, wherein the phthalocyanine pigment is a phthalocyanine pigment having zinc or aluminum as a central metal.
The pigment composition for color filters according to claim 1, wherein the phthalocyanine pigment is a halogenated zinc phthalocyanine pigment.
Azomethine copper complex pigments are C.I. I. Pigment Yellow 129. The pigment composition for a color filter according to any one of claims 1 to 3, which is characterized in that
A color filter comprising the pigment composition for a color filter according to any one of claims 1 to 4.