CN119286278A

CN119286278A - Colorant dispersion for color filter, colored resin composition for color filter, color filter, and display device

Info

Publication number: CN119286278A
Application number: CN202411411605.XA
Authority: CN
Inventors: 中村和彦; 井上渚; 田尻亘
Original assignee: DNP Fine Chemicals Co Ltd
Current assignee: DNP Fine Chemicals Co Ltd
Priority date: 2016-12-28
Filing date: 2017-12-26
Publication date: 2025-01-10
Also published as: WO2018124087A1; JPWO2018124087A1; JP7094891B2; TW201840740A; TWI748029B; CN110062900A

Abstract

The present invention provides a coloring resin composition for color filters that has excellent colorant dispersion stability and can form a coloring layer that reduces the phase difference value and improves the contrast. The coloring resin composition for color filters of the present invention contains a colorant, a dispersant, a binder component, and a solvent. The colorant contains a red colorant and a yellow colorant; the yellow colorant contains: at least one anion selected from the group consisting of mono-, di-, tri-, and tetra-anions of azo compounds with specific azo compounds and their tautomeric structures; ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and a melamine derivative; the dispersant is a polymer having a specific constituent unit.

Description

Colorant dispersion for color filter, colored resin composition for color filter, color filter and display device

The present application is a divisional application of application No. 201780076574.9, which is filed as "colorant dispersion for color filter, colored resin composition for color filter, color filter and display device", and which is filed as 2017, 12, 26, and 26.

Technical Field

The invention relates to a colorant dispersion liquid for a color filter, a coloring resin composition for a color filter, a color filter and a display device.

Background

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The popularity of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, an organic light-emitting display device such as an organic EL display having high visibility by self-luminescence has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvements in image quality and reduction in power consumption, such as improvements in contrast and color reproducibility, are strongly desired.

The conventional display device mostly depends on sRGB (IEC 61966-2-1), which is an international standard specification of color space. However, in order to make the expression closer to the actual object, there is a demand for display devices such as DCI (Digital CinemaInitiatives) and BT (Broadcasting Service Television).2020 which are capable of coping with AdobeRGB having a wider color reproduction range in the green direction than sRGB and also have a wider color reproduction range in the red and green directions, starting from the demand for further improvement of color reproducibility.

The color filter used in the liquid crystal display device generally includes a transparent substrate, a colored layer formed on the transparent substrate and including colored patterns of three primary colors of red, green, and blue, and a light shielding portion formed on the transparent substrate to divide the colored patterns.

As a method for forming such a colored layer, pigment dispersion method, dyeing method, electrodeposition method, printing method, and the like are known. Among them, pigment dispersion methods having average excellent characteristics are most widely used from the viewpoints of spectroscopic characteristics, durability, pattern shape, accuracy, and the like.

On the other hand, as a problem specific to the liquid crystal display device, there is a problem of viewing angle dependence due to refractive index anisotropy of the liquid crystal cell or the polarizing plate. The problem of this viewing angle dependence is that the hue or contrast of an image observed when the liquid crystal display device is viewed from the front side is changed from that when viewed from an oblique direction. The problem of such viewing angle characteristics has increased in severity with the recent increase in the size of liquid crystal display devices.

In order to improve such a problem of viewing angle dependence, a method of assembling a phase difference film into a liquid crystal display device has been widely used in the past. However, since color filters used in liquid crystal display devices have different phase differences depending on the color patterns of the respective colors of the color layers, there is a problem that the difference in phase differences of the color patterns of the respective colors cannot be compensated for when the phase difference film is used, and it is difficult to completely solve the problem of viewing angle dependence.

In particular, since the red colorant is likely to crystallize in its chemical structure, there is a problem that the retardation value in the thickness direction of the red colored layer tends to be larger than that of the colored layers of other colors.

In order to expand the color reproduction range using a conventionally used red colorant, there is a problem that, when a red pixel contained in a red chromaticity region having a high color density and exhibiting a yellow tone and a blue tone is produced, the contrast or brightness is lowered or platemaking property is deteriorated due to an increase in the pigment density.

Patent document 1 discloses a color filter in which c.i. pigment red 177 (hereinafter, abbreviated as PG177 in some cases) and at least one crystal selected from the group consisting of a 1:1 complex of azobarbituric acid and nickel, a tautomer thereof, and crystals in which other compounds are inserted into the crystal lattice of at least one of them are used in combination as a red pigment (c.i. pigment yellow 150 derivative (Ni complex)). However, when the pigment is used to express a dark red color, a very high concentration of the pigment must be used, and there are problems that the phase difference in the thickness direction becomes large, the contrast is lowered, and the platemaking property is deteriorated.

On the other hand, patent document 2 describes a novel metal azo pigment comprising an adduct of a metal azo compound composed of a dianion of a specific azo compound and at least 2 metal ions of Zn ²⁺ and Ni ²⁺ and melamine or a derivative thereof, which has a specific signal in an X-ray diffraction pattern and does not have a specific signal.

Prior art literature

Patent literature

Patent document 1 Japanese patent application laid-open No. 2010-144057

Patent document 2 Japanese patent application laid-open No. 2014-12838

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a colorant dispersion for a color filter, which is excellent in colorant dispersion stability and can form a coloring layer that reduces a phase difference value and improves a contrast, a coloring resin composition for a color filter, which is used for the color filter and can form a coloring layer that reduces a phase difference value and improves a contrast and has excellent color reproducibility, a color filter, which is used for the color filter and reduces a phase difference value and improves a contrast and has excellent color reproducibility, and a display device, which is used for the color filter and has reduced a phase difference value and improved contrast and excellent color reproducibility.

Technical unit for solving problems

The colorant dispersion for a color filter of the present invention is a colorant dispersion containing a colorant, a dispersant and a solvent, and is characterized in that,

The colorant contains a red colorant and a yellow colorant;

The yellow colorant comprises at least 1 kind of anions selected from the group consisting of monoazo compounds shown by the following general formula (A) and monoazo, dian, tri and tetraanions of azo compounds with tautomeric structures, ions of at least 2 kinds of metals selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, ni, cu and Mn, and compounds shown by the following general formula (B);

the dispersant is a polymer having a constituent unit represented by the following general formula (I).

The colored resin composition for a color filter of the present invention is a colored resin composition for a color filter comprising a colorant, a dispersant, a binder component and a solvent,

The colorant contains a red colorant and a yellow colorant;

[ Chemical 1]

General formula (A)

(In the general formula (A), R ^a is independently-OH, -NH ₂, -NH-CN, acylamino, alkylamino or arylamino, R ^b is independently-OH or-NH ₂.)

[ Chemical 2]

General formula (B)

(In the general formula (B), R ^c is each independently a hydrogen atom or an alkyl group.)

[ Chemical 3]

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a 2-valent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group optionally containing a hetero atom, and R ² and R ³ are optionally bonded to each other to form a ring structure.1

The color filter of the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least 1 of the colored layers is a colored layer which is a cured product of the colored resin composition for a color filter of the present invention.

The invention provides a display device characterized by comprising the color filter.

Effects of the invention

According to the present invention, a colorant dispersion for a color filter, which is excellent in colorant dispersion stability and can form a colored layer having a reduced phase difference and improved contrast, a colored resin composition for a color filter, which is used for the color filter and can form a colored layer having a reduced phase difference and improved contrast and excellent color reproducibility, a color filter, which is used for the color resin composition for a color filter and has a reduced phase difference and improved contrast and excellent color reproducibility, and a display device, which is provided with a reduced phase difference and improved contrast and excellent color reproducibility, by using the color filter, can be provided.

Drawings

Fig. 1 is a schematic diagram showing an example of a color filter according to the present invention.

Fig. 2 is a schematic diagram showing an example of the display device of the present invention.

Fig. 3 is a schematic diagram showing another example of the display device of the present invention.

Detailed Description

The colorant dispersion liquid for color filters, the colored resin composition for color filters, the color filters and the display device according to the present invention are described in detail below.

In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation including, for example, microwaves and electron beams. Specifically, electromagnetic waves and electron beams having a wavelength of 5 μm or less are referred to.

In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid, and (meth) acrylic acid ester means acrylic acid ester and methacrylic acid ester.

The c.i. pigment red is appropriately abbreviated as "PR", the c.i. pigment orange is appropriately abbreviated as "PO", and the c.i. pigment yellow is appropriately abbreviated as "PY".

[ Colorant Dispersion liquid ]

The colorant dispersion for color filters of the present invention contains a colorant, a dispersant and a solvent, and is characterized in that,

The colorant contains a red colorant and a yellow colorant;

[ Chemical 4]

General formula (A)

[ Chemical 5]

General formula (B)

[ Chemical 6]

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a 2-valent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group optionally containing a hetero atom, and R ² and R ³ are optionally bonded to each other to form a ring structure.)

The colorant dispersion of the present invention is excellent in colorant dispersion stability because the specific colorant is combined with the polymer having the constituent unit represented by the general formula (I) as a dispersant, and a colored layer having a reduced phase difference and improved contrast can be formed.

Since the red colorant generally has a ring-shaped planar structure, the red colorant is easily crystallized when a colored layer is formed as a colorant dispersion for a color filter, and thus the phase difference value in the thickness direction of the obtained colored layer is easily increased.

On the other hand, in the colorant dispersion of the present invention, it is presumed that the combination of the specific yellow colorant containing 2 or more metal ions and the specific dispersant belonging to the polymer having the structural unit represented by the general formula (I) causes an interaction between the red colorant and the specific yellow colorant containing 2 or more metal ions, and the crystal growth of the red colorant and the yellow colorant can be suppressed and micronized, and the combination of the dispersant and the specific yellow colorant can cause the red colorant and the yellow colorant to be micronized and dispersed, so that a colored layer having a reduced phase difference and improved contrast can be formed.

Conventionally, when 1 kind of colorant is used as a metal for forming a metal complex containing an azo compound represented by the general formula (a), the crystallinity is high, and it is difficult to make particles, and it is difficult to improve the contrast. In addition, the phase difference value of the colored layer obtained by combining with the red colorant tends to be high. In contrast, in the present invention, a specific yellow colorant containing 2 or more metal ions relative to the anion of the azo compound represented by the general formula (a) is used. The yellow colorant is expected to be micronized in the colorant dispersion by containing 2 or more kinds of metal ions, thereby suppressing not only the crystal growth of the yellow colorant but also the crystal growth of the red colorant.

In the present invention, by combining the specific yellow colorant with the red colorant, even if the P/V ratio ((mass of colorant component in the composition)/(mass of solid component other than colorant component in the composition)) is suppressed, a red pixel included in the red chromaticity region of the high color density can be produced.

By reducing the P/V ratio in the colored layer and suppressing the synergistic effect of the crystal growth of the red colorant, it is estimated that the phase difference value in the thickness direction of the colored layer is reduced.

Further, since the total content of the colorant components in the colored resin composition can be suppressed, the content of the binder component can be relatively increased, platemaking property can be improved, and a colored layer having more improved adhesion to the substrate can be formed.

The colorant dispersion of the present invention contains at least a colorant, a dispersant and a solvent, and may further contain other components within a range that does not impair the effects of the present invention.

The components of the colorant dispersion of the present invention will be described in detail below.

[ Colorant ]

The present invention is characterized in that the colorant contains a red colorant and a yellow colorant;

The yellow colorant contains at least 1 kind of anions selected from the group consisting of monoazo compounds represented by the following general formula (A) and monoazo, dian, triazo and tetraanions of the azo compounds of tautomeric structures thereof, ions of at least 2 kinds of metals selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, ni, cu and Mn, and compounds represented by the following general formula (B).

In the present invention, since the specific yellow colorant is used as the yellow colorant, the decrease in brightness can be suppressed when the specific yellow colorant is combined with the red colorant, crystallization can be suppressed to be micronized, and the dispersibility is excellent when the specific yellow colorant is combined with a specific dispersant described later, so that the contrast can be improved, and the phase difference value can be reduced.

[ Chemical 7]

General formula (A)

Examples of the acyl group in the acylamino group in the general formula (A) include an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, a carbamoyl group which may be substituted with an alkyl group, a phenyl group or a naphthyl group, a sulfamoyl group which may be substituted with an alkyl group, a phenyl group or a naphthyl group, a guanidino group which may be substituted with an alkyl group, a phenyl group or a naphthyl group, and the like. The alkyl group is preferably a carbon number of 1 to 6. The alkyl group may be substituted with, for example, halogen such as F, cl, br, -OH, -CN, -NH ₂, or an alkoxy group having 1 to 6 carbon atoms. The phenyl group and the naphthyl group may be substituted with, for example, halogen such as F, cl, br, -OH, -CN, -NH ₂、-NO₂, an alkyl group having 1 to 6 carbon atoms, and/or an alkoxy group having 1 to 6 carbon atoms.

The alkyl group in the alkylamino group in the general formula (a) is preferably a carbon number of 1 to 6. The alkyl group may be substituted with halogen such as F, cl, br, -OH, -CN, -NH ₂, and/or alkoxy having 1 to 6 carbon atoms.

Examples of the aryl group in the arylamino group in the general formula (A) include phenyl and naphthyl. These aryl groups may be substituted with, for example, halogen such as F, cl, br, -OH, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, -NH ₂、-NO₂, and-CN.

Among the azo compounds represented by the above general formula (a) and the azo compounds of tautomeric structures thereof, R ^a is preferably-OH, -NH ₂, -NH-CN or alkylamino, each independently, from the viewpoint of the hue (hue) which is a red hue (red taste). The 2R ^a groups may be the same or different, respectively.

In the above general formula (A), from the viewpoint of color tone, more preferably, both R ^a are-OH, both are-NH-CN or one is-OH and one is-NH-CN, even more preferably both are-OH.

In the azo compound represented by the general formula (a) and the azo compound having a tautomeric structure thereof, R ^b is preferably both-OH from the viewpoint of color tone.

Among these, at least 2 metals selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, ni, cu and Mn are preferably contained, and at least 1 metal that becomes a 2-valent or 3-valent cation is more preferably contained, and at least 1 selected from the group consisting of Ni, cu and Zn is more preferably contained, and at least Ni is further preferably contained.

Further, ni is preferably contained, and at least 1 metal selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, cu and Mn is preferably contained, and at least 1 metal selected from the group consisting of Zn, cu, al and Fe is more preferably contained, and among these, ni and Zn or Ni and Cu are preferable as the at least 2 metals.

The yellow colorant used in the present invention may be one in which the content ratio of at least 2 metals is appropriately adjusted.

From the viewpoint of the hue of red, the yellow colorant used in the present invention preferably contains Ni and at least 1 metal selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, cu and Mn in a molar ratio of 97:3 to 10:90, more preferably in a molar ratio of 90:10 to 10:90.

Among them, from the viewpoint of the red hue, ni and Zn are preferably contained in a molar ratio of Ni to Zn of 90:10 to 10:90, more preferably in a molar ratio of 80:20 to 20:80.

Or from the viewpoint of the red hue, ni and Cu are preferably contained in a molar ratio of 97:3 to 10:90, more preferably 96:4 to 20:80.

In the case where the yellow colorant is a red tone, even if the P/V ratio is suppressed, a red pixel included in the red chromaticity region of the high color density can be easily produced.

The yellow colorant used in the present invention may further contain a metal ion different from the specific metal ion. The yellow colorant used in the present invention may optionally contain at least 1 metal ion selected from the group consisting of Li, cs, mg, na, K, ca, sr, ba and La, for example.

Examples of the mode in which at least 2 metal ions are contained in the yellow colorant include a case in which at least 2 metal ions are contained in a common crystal lattice, and a case in which crystals each containing 1 metal ion are aggregated in different crystal lattices. Among them, the case where at least 2 kinds of metal ions are contained in a common crystal lattice is preferable from the viewpoint of further improving contrast. The method of containing at least 2 metal ions in a common crystal lattice or the method of agglomerating crystals each containing 1 metal ion in a different crystal lattice can be appropriately determined by an X-ray diffraction method, for example, by reference to japanese patent application laid-open No. 2014-12838.

The yellow colorant used in the present invention further contains a compound represented by the following general formula (B). The yellow colorant used in the present invention contains a complex molecule comprising a metal complex of an anion of an azo compound represented by the general formula (a) and an azo compound having a tautomeric structure thereof with a specific metal ion and a compound represented by the general formula (B) below. These intermolecular bonds may be formed, for example, by intermolecular interactions, or Lewis acid-base interactions, or coordination bonds. In addition, the guest molecule may be incorporated into a crystal lattice constituting the host molecule. Alternatively, 2 substances may be co-crystallized, and mixed substitution crystals may be formed in which atoms of the second component are located in regular lattice positions of the first component.

[ Chemical 8]

General formula (B)

The alkyl group in R ^c is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group is optionally substituted with an-OH group.

Among them, R ^c is preferably a hydrogen atom.

The content of the compound represented by the general formula (B) is generally 5 to 300 moles, preferably 10 to 250 moles, more preferably 100 to 200 moles, based on 1 mole of the azo compound represented by the general formula (a) and the azo compound of a tautomeric structure thereof.

The yellow colorant used in the present invention may further contain urea and substituted urea such as phenylurea, dodecylurea and the like, and polycondensates thereof with aldehydes, particularly formaldehyde, and heterocyclic rings such as barbituric acid, benzimidazolone-5-sulfonic acid, 2, 3-dihydroxyquinoxaline-6-sulfonic acid, carbazole-3, 6-disulfonic acid, 2-hydroxyquinoline, 2, 4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1, 3, 5-triazine-2, 4-diamine, 6-methyl-1, 3, 5-triazine-2, 4-diamine, cyanuric acid and the like.

The yellow colorant used in the present invention may further contain a water-soluble polymer such as an ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly (meth) acrylic acid, modified cellulose such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl and ethyl hydroxyethyl cellulose, and the like.

The yellow colorant used in the present invention can be prepared by referring to, for example, japanese patent application laid-open No. 2014-12838.

On the other hand, as the red colorant used in the present invention, a colorant having a transmittance at a wavelength of 520nm of 20% or less and a transmittance at a wavelength of 640nm of 70% or more, when the spectral transmittance spectrum of a coating film having a film thickness of 2.5 μm is measured, was used, with a P/V (mass of red colorant/mass of solid matter other than red colorant) ratio=0.2. The red colorant used in the present invention also contains a colorant expressed as c.i. pigment orange as a slightly yellowish red colorant (orange colorant having a strong red color).

In order to coat the red colorant alone for color measurement, a coating liquid may be prepared by blending an appropriate dispersant, binder component and solvent into the red colorant, and the resulting mixture may be applied to a transparent substrate, dried, and optionally cured. As the binder component, a non-curable thermoplastic resin composition may be used, or a photocurable (photosensitive) or thermosetting resin composition may be used, provided that a transparent coating film capable of color measurement can be formed. In addition, in the colored resin composition of the present invention described later, a coating film containing only a red colorant as a colorant may be formed by using a composition containing only a red colorant as a colorant, and color measurement may be performed. Specifically, for example, the solid component used in the resin composition of example 1 described below may be a solid component other than the red colorant.

The transparent coating film containing a dispersant and a binder, which can be measured in color, can be obtained by, for example, having a film thickness of 2.0 μm and a spectral transmittance spectrum at 380 to 780nm of 95% or more.

The spectral transmittance spectrum may be measured using a spectral measuring device (for example, an Olympus microscopic device OSP-SP 200). The measurement conditions were C light source.

The red colorant used in the present invention is not particularly limited, and examples thereof include diketopyrrolopyrrole-based pigments, naphthol-based azo pigments, other azo pigments, quinacridone-based pigments, dioxazine-based pigments, anthraquinone-based pigments, perinone (perinone-based) pigments, perylene-based pigments, thioindigo-based pigments, and the like. The red colorant used in the present invention preferably contains at least 1 selected from the group consisting of diketopyrrolopyrrole-based pigments, naphthol-based azo pigments, anthraquinone-based pigments, and perylene-based pigments in terms of suppression of the P/V ratio, and further preferably contains at least 1 selected from the group consisting of diketopyrrolopyrrole-based pigments and anthraquinone-based pigments in terms of easiness in formation of a high-color-density hue and high brightness.

Examples of the diketopyrrolopyrrole pigment include those represented by the following general formula (1).

[ Chemical 9]

General formula (1)

(In the general formula (1), A ³ and A ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, a phenyl group, an N, N-dimethylamino group, a trifluoromethyl group, or a cyano group, k and k 'each independently represent an integer of 0 to 5 inclusive, and when k and k' each represent an integer of 2 or more, a plurality of A ³ and A ⁴ may be the same or different, respectively.)

Specific examples of the diketopyrrolopyrrole pigments include c.i. pigment red 254, c.i. pigment red 255, c.i. pigment red 264, c.i. pigment red 270, c.i. pigment red 272, c.i. pigment orange 71, c.i. pigment orange 73, and diketopyrrolopyrrole pigment (BrDPP) represented by the following chemical formula (2).

[ Chemical 10]

Chemical formula (2)

Examples of the naphthol azo pigment include c.i. pigment red 144, c.i. pigment red 166, c.i. pigment red 214, c.i. pigment red 242, c.i. pigment red 21, c.i. pigment red 2, c.i. pigment red 112, c.i. pigment red 114, c.i. pigment red 5, c.i. pigment red 146, c.i. pigment red 170, c.i. pigment orange 38, c.i. pigment red 187, c.i. pigment red 150, and c.i. pigment red 185.

Examples of the other azo pigments include c.i. pigment red 38 and c.i. pigment red 41.

Examples of the anthraquinone pigments include c.i. pigment red 177, c.i. pigment red 168, and c.i. pigment orange 51.

Examples of the perylene pigments include c.i. pigment red 123, c.i. pigment red 149, c.i. pigment red 178, c.i. pigment red 179, c.i. pigment red 190, and c.i. pigment red 224.

From the viewpoint of easy achievement of the effect of the present invention, 1 or more red colorants selected from the group consisting of c.i. pigment red 254, c.i. pigment red 264, c.i. pigment red 272, diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2), c.i. pigment red 242, c.i. pigment orange 38, c.i. pigment red 177 and c.i. pigment red 179 are preferably used, and among these, a combination of c.i. pigment red 254 and diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) and c.i. pigment red 177 is suitably used as the red colorant.

The content ratio of the diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) to the c.i. pigment red 177 when the c.i. pigment red 254 and the diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) are combined is not particularly limited, and the content ratio is preferably 10 to 80 parts by mass, and the diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) is 10 to 70 parts by mass, and the content ratio of the c.i. pigment red 177 is 10 to 60 parts by mass, respectively, based on 100 parts by mass of the total amount of the red colorants. Within the above range, the effect of the above combination is excellent. The content ratio of the red colorant is a preferable ratio in the case of producing a colored resin composition to be described later, and 2 or more kinds of colorant dispersions can be appropriately mixed and used to produce a colored resin composition, so that the colorant dispersion itself can be appropriately used even if the content ratio is not the same as that of the colored resin composition to be described later.

In the colorant dispersion of the present invention, the red colorant and the specific yellow colorant are used in combination as the colorant, but other colorants exemplified by the colored resin composition described later may be used in combination. As the other colorant, for example, another yellow colorant, an orange colorant not contained in the above-mentioned red colorant, and the like are suitably used; among them, other yellow colorants exemplified by the coloring resin composition described later are suitably used from the viewpoint of color tone.

In the colorant dispersion of the present invention, the content ratio of each of the red colorant and the specific yellow colorant, and the content ratio when other colorants are used, are preferably the same as the content ratio of the colored resin composition described later. Among these, the colorant dispersion can be used by appropriately mixing 2 or more types of colorant to produce a colored resin composition, and therefore can be suitably used without having to have the same content ratio as the colored resin composition described later.

The average primary particle diameter of the colorant used in the present invention is not particularly limited as long as a desired color development can be performed in the case of a colored layer as a color filter, and is preferably in the range of 10nm to 100nm, more preferably 15nm to 60nm, depending on the type of the colorant used. When the average primary particle diameter of the colorant is within the above range, a display device including a color filter manufactured using the colorant dispersion liquid of the present invention can be provided with a high contrast and high quality.

The average dispersion particle diameter of the colorant in the colorant dispersion liquid is preferably in the range of 10nm or more and 100nm or more, more preferably in the range of 15nm or more and 60nm or less, depending on the type of colorant used.

The average dispersion particle diameter of the colorant in the colorant dispersion is the dispersion particle diameter of the colorant particles dispersed in the dispersion medium containing at least the solvent, as measured by a laser scattering particle size distribution meter. As particle diameter measurement by a laser scattering particle size distribution meter, the colorant dispersion is diluted appropriately to a concentration (for example, 1000 times or the like) that can be measured by the laser scattering particle size distribution meter by using a solvent used for the colorant dispersion, and measurement is performed at 23 ℃ by a dynamic light scattering method using a laser scattering particle size distribution meter (for example, a Nanotrac particle size distribution measuring apparatus UPA-EX 150 manufactured by daily nectar corporation). The average distribution particle diameter herein is a volume average particle diameter.

In the colorant dispersion liquid of the present invention, the colorant content is not particularly limited. The colorant content is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 8 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the total solid content in the colorant dispersion, from the viewpoints of dispersibility and dispersion stability.

Particularly, when a coating film or a colored layer having a high colorant concentration is formed, the composition is preferably formulated in a proportion of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, relative to 100 parts by mass of the total solid content in the colorant dispersion.

< Dispersant >

In the present invention, as the dispersant, a polymer having a constituent unit represented by the above general formula (I) is used. The constituent unit represented by the above general formula (I) has basicity and functions as an adsorption site for the colorant.

The colorant dispersion of the present invention is improved in the adsorption performance to the colorant, and in the dispersibility and dispersion stability of the colorant by using the polymer having the constituent unit represented by the above general formula (I).

In the general formula (I), A is a 2-valent linking group. Examples of the 2-valent linking group of A include an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-group, -COO-group, an ether group having 1 to 10 carbon atoms (-R '-OR "-: R' and R" are each independently an alkylene group), and a combination thereof.

Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a 2-valent linking group containing a-CONH-group or-COO-group.

The hydrocarbon group in the hydrocarbon group optionally containing a hetero atom in R ² and R ³ may be exemplified by an alkyl group, an aralkyl group, an aryl group, etc.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2-ethylhexyl, cyclopentyl and cyclohexyl, and the number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably methyl or ethyl.

Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, biphenylmethyl and the like. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.

Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

The heteroatom-containing hydrocarbon group has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom. Examples of the heteroatom optionally contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.

The hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, or a bromine atom.

The term "R ² and R ³ bond to each other to form a ring structure" means that R ² and R ³ form a ring structure via a nitrogen atom. The ring structure formed by R ² and R ³ optionally contains heteroatoms. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² is bonded to R ³ to form a pyrrolidine ring, a piperidine ring, or a morpholine ring, and more preferably at least one of R2 and R ³ is an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² is bonded to R ³ to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

Examples of the constituent unit represented by the above general formula (I) include alkyl-substituted amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, etc., and alkyl-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide, etc. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide are preferably used from the viewpoint of improving dispersibility and dispersion stability.

The constituent unit represented by the general formula (I) may contain 1 kind of constituent unit or may contain 2 or more kinds of constituent units.

The polymer having a constituent unit represented by the general formula (I) preferably further contains a site having affinity for a solvent from the viewpoint of improving dispersibility. The solvent affinity site is preferably selected from monomers having an ethylenically unsaturated bond which can be polymerized with a monomer from which the constituent unit represented by the general formula (I) is derived, and the solvent is suitably used in combination with the solvent so as to have solvent affinity. As a standard, the solvent affinity site is introduced so that the solubility of the polymer at 23 ℃ is 50 (g/100 g solvent) or more with respect to the solvent used in combination.

Among these, block copolymers or graft copolymers are preferable, and block copolymers are particularly preferable, from the viewpoints of improving dispersibility and dispersion stability of the colorant, heat resistance of the resin composition, and forming a colored layer having high brightness and high contrast. The block copolymers which are particularly preferred are described in detail below.

(Block copolymer)

When the block containing the constituent unit represented by the general formula (I) is an a block, the a block has an alkaline property and functions as an adsorption site for the colorant. On the other hand, the B block containing no constituent unit represented by the above general formula (I) has a function as a block having solvent affinity. In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and may be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like. Among them, from the viewpoint of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferable.

Examples of the constituent unit constituting the B block include a monomer having an unsaturated double bond, which is copolymerizable with a monomer from which the constituent unit represented by the general formula (I) is derived, and among these, the constituent unit represented by the following general formula (II) is preferable.

[ Chemical 11]

(In the general formula (II), A' is a direct bond or a 2-valent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, - [ CH (R ⁶)-CH(R⁷)-O]_x-R⁸ or a 1-valent group represented by- [ (CH ₂)_y-O]_z-R⁸; R ⁶ or R ⁷ are each independently a hydrogen atom or a methyl group; R ⁸ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or a 1-valent group represented by-CH ₂COOR⁹; R ⁹ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.)

The above-mentioned hydrocarbon group may optionally have a substituent.

X represents an integer of 1 to 30 inclusive, y represents an integer of 1 to 5 inclusive, and z represents an integer of 1 to 18 inclusive.

The 2-valent linking group A' of the general formula (II) may be the same as A in the general formula (I). Among them, from the viewpoint of solubility in an organic solvent, a 2-valent linking group having a-CONH-group or-COO-group is preferable as A'. From the standpoint of heat resistance of the resulting polymer or solubility to Propylene Glycol Monomethyl Ether Acetate (PGMEA) suitable for use as a solvent, or a cheaper material, a' is preferably-COO-group.

The hydrocarbon group in R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group.

Examples of the alkyl group having 1 to 18 carbon atoms include straight-chain, branched-chain and cyclic alkyl groups, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, ヅ praecox, adamantyl, and lower alkyl-substituted adamantyl groups.

The alkenyl group having 2 or more and 18 or less carbon atoms may be any of a straight chain, a branched chain, and a cyclic chain. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond of the alkenyl group is not limited, and from the viewpoint of reactivity of the obtained polymer, it is preferable that the alkenyl group has a double bond at the terminal.

Examples of the substituent of the aliphatic hydrocarbon such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.

Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or more, more preferably 7 or more and 14 or less.

Examples of the substituent of the aromatic ring such as an aryl group or an aralkyl group include an alkenyl group, a nitro group, a halogen atom, and the like, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In R ⁵, x is an integer of 1 to 30, preferably an integer of 1 to 26, more preferably an integer of 1 to 18, still more preferably an integer of 1 to 4, particularly preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3.z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

The hydrocarbon group in R ⁸ may be the same as the group shown in R ⁵. Among them, the hydrocarbon group in R ⁸ is preferably an alkyl group having 1 to 18 carbon atoms from the viewpoint of excellent developability.

R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be any of a straight chain, branched chain, or cyclic.

In addition, R ⁵ in the structural unit represented by the above general formula (II) may be the same or different from each other.

Among these, R ⁵ is preferably selected so as to be excellent in compatibility with a solvent to be described later, and specifically, for example, in the case where a glycol ether acetate-based solvent, an ether-based solvent, an ester-based solvent or the like which is generally used as a solvent of a color resin composition for a color filter is used as the solvent, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl or the like is preferable.

In addition, the constituent unit constituting the B block preferably contains- [ CH (R ⁶)-CH(R⁷)-O]_x-R⁸ or- [ (CH ₂)_y-O]_z-R⁸) as R ⁵ for excellent developability and excellent suppression of development residues.

In addition, R ⁵ may be a group substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group, in a range not to impair the dispersibility of the block copolymer, or the like, and the substituent may be added by reacting the block copolymer with a compound having the substituent after the synthesis of the block copolymer.

In the present invention, the glass transition temperature (Tg) of the solvent-compatible block portion of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-affinity block portion is preferably 80 ℃ or higher, more preferably 100 ℃ or higher.

The glass transition temperature (Tg) of the solvent-affinity block of the present invention can be calculated according to the following formula. In addition, the glass transition temperature of the colorant affinity block and the block copolymer can be calculated in the same manner.

1/Tg=∑(Xi/Tgi)

Here, the solvent affinity block is copolymerized from n monomer components i=1 to n. Xi is the weight percent of the ith monomer (Σxi=1), tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Wherein Σ adopts the sum of i=1 to n. The value of the glass transition temperature (Tgi) of the homopolymer of each monomer may be the value of Polymer Handbook (3 rdEdition) (J.Brandrup, E.H.Immergut (Wiley-Interscience, 1989)).

The number of constituent units constituting the block portion having affinity for the solvent may be appropriately adjusted within a range in which dispersibility of the colorant is improved. Among them, from the viewpoint of effectively acting the solvent affinity site and the colorant affinity site and improving the dispersibility of the colorant, the number of constituent units constituting the block portion of the solvent affinity is preferably 10 or more and 200 or less, more preferably 10 or more and 100 or less, still more preferably 10 or more and 70 or less.

The solvent affinity block may be selected so as to function as a solvent affinity site, and the repeating unit constituting the solvent affinity block may contain 1 kind or 2 or more kinds of repeating units.

Among these, the dispersant of the present invention preferably contains a polymer having a structure represented by the general formula (II) and an amine value of 40mgKOH/g or more and 120mgKOH/g or less, from the viewpoint of good dispersibility, no deposition of foreign matter at the time of forming a coating film, and improvement of brightness and contrast.

When the amine number is within the above range, the viscosity is excellent in stability with time and heat resistance, and alkali developability and solvent resolubility are also excellent. In the present invention, the amine value of the dispersant is preferably 80mgKOH/g or more, more preferably 90mgKOH1g or more, from the viewpoints of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 110mgKOH/g or less, more preferably 105mgKOH/g or less.

The amine number is the mg of potassium hydroxide equivalent to perchloric acid required for neutralizing the amine component contained in sample 1g, and can be measured by the method defined in JIS-K7237. In the case of the determination by this method, even if the amino group in the dispersant forms a salt with the organic acid compound, since the organic acid compound is usually dissociated, the amine value of the block copolymer itself used as the dispersant can be determined.

The acid value of the dispersant used in the present invention is preferably 1mgKOH/g or more in terms of the effect of suppressing the development residue. Among these, the acid value of the dispersant is more preferably 2mgKOH/g or more from the viewpoint of more excellent suppression effect of the development residue. On the other hand, the acid value of the dispersant is preferably 0mgKOH/g from the viewpoints of dispersibility and dispersion stability. In addition, the upper limit of the acid value of the dispersant used in the present invention is preferably 18mgKOH/g or less from the viewpoint of preventing deterioration of development adhesion and deterioration of solvent resolubility. Among them, the acid value of the dispersant is more preferably 12mgKOH/g or less, still more preferably 8mgKOH/g or less, from the viewpoint of improving the development adhesion and solvent resolubility.

In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1mgKOH/g or more, more preferably 2mgKOH/g or more. This is because the inhibition effect of the development residues is improved. On the other hand, the acid value of the block copolymer before salt formation is preferably 0mgKOH/g from the viewpoints of dispersibility and dispersion stability. The upper limit of the acid value of the block copolymer before salt formation is preferably 18mgKOH/g or less, more preferably 12mgKOH/g or less, and still more preferably 8mgKOH/g or less. This is because the development adhesion and the solvent resolubility are improved.

In the present invention, the glass transition temperature of the dispersant is preferably 30 ℃ or higher from the viewpoint of improving the development adhesion. That is, the dispersant is preferably 30 ℃ or higher in glass transition temperature, regardless of whether it is a block copolymer before salt formation or a salt-type block copolymer. If the glass transition temperature of the dispersant is low, particularly near the developer temperature (usually about 23 ℃), there is a possibility that the development adhesion will be reduced. This is presumably because, when the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, and as a result, the development adhesion is deteriorated. It is estimated that the reduction of development adhesion is suppressed because the molecular movement of the dispersant during development is suppressed by the glass transition temperature being 30 ℃ or higher.

The glass transition temperature of the dispersant is preferably 32 ℃ or higher, more preferably 35 ℃ or higher, from the viewpoint of development adhesion. On the other hand, from the viewpoint of ease of handling in use such as accurate weighing, it is preferably 200 ℃ or less.

The glass transition temperature of the dispersant of the present invention can be obtained by measurement by differential scanning calorimeter measurement (DSC) according to JIS K7121.

If the colorant concentration is increased and the dispersant content is increased, the binder amount is relatively reduced, so that the colored resin layer is easily peeled off from the base substrate during development. The dispersant contains a B block having a constituent unit derived from a carboxyl group-containing monomer, and has the above specific acid value and glass transition temperature, thereby improving development adhesion. If the acid value is too high, although the developability is excellent, it is estimated that peeling easily occurs when the polarity is too high but the development is performed.

From the above, in the present invention, the dispersant is preferably a polymer having a structure represented by the general formula (I) and an amine value of 40mgKOH/g or more and 120mgKOH/g or less, an acid value of 1mgKOH/g or more and 18mgKOH/g or less, and a glass transition temperature of 30 ℃ or more, because the dispersant is excellent in dispersion stability of the colorant and improves contrast, development residue is suppressed from occurring when a colored resin composition is produced, and the solvent resolubility is excellent and further the development adhesiveness is high.

The carboxyl group-containing monomer may be a monomer having an unsaturated double bond and a carboxyl group, which is copolymerizable with the monomer having a constituent unit represented by the general formula (I). Examples of such monomers include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimers. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω -carboxyl-polycaprolactone mono (meth) acrylate may be used. In addition, an anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as a precursor of the carboxyl group. Among them, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The content of the constituent units derived from the carboxyl group-containing monomer in the block copolymer before salt formation is not particularly limited as long as the acid value of the block copolymer is appropriately set within the above-mentioned specific acid value, and is preferably 0.05 mass% or more and 4.5 mass% or less, more preferably 0.07 mass% or more and 3.7 mass% or less, relative to the total mass of the total constituent units of the block copolymer.

When the content of the constituent units derived from the carboxyl group-containing monomer is not less than the above-mentioned lower limit, the effect of suppressing the development residue is exhibited, and when the content is not more than the above-mentioned upper limit, deterioration of development adhesion and deterioration of solvent resolubility can be prevented.

The constituent unit derived from the carboxyl group-containing monomer may be 1 or 2 or more constituent units, and may have the above specific acid value.

In addition, from the viewpoint of setting the glass transition temperature of the dispersant used in the present invention to a specific value or more and improving the development adhesion, it is preferable that the total of monomers in the B block is 75 mass% or more, more preferably 85 mass% or more, of the homopolymer of the monomers having a glass transition temperature (Tgi) of 10 ℃ or more.

In the block copolymer, the ratio m/n of the number m of the constituent units of the A block to the number n of the constituent units of the B block is preferably in the range of 0.05 to 1.5, and more preferably in the range of 0.1 to 1.0 from the viewpoints of dispersibility and dispersion stability of the colorant.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, more preferably 2000 to 15000, still more preferably 3000 to 12000, from the viewpoint of improving the dispersibility and dispersion stability of the colorant.

The weight average molecular weight (Mw) was determined by Gel Permeation Chromatography (GPC) based on standard polystyrene standards. The macromer or the salt-type block copolymer and the graft copolymer, which are the raw materials of the block copolymer, are also prepared under the above-mentioned conditions.

The method for producing the block copolymer is not particularly limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method. This is because chain transfer or deactivation is not easily caused, and a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and group transfer polymerization methods, living cationic polymerization methods, and the like. By sequentially polymerizing the monomers by these methods, a copolymer can be produced. For example, a block is produced first, and then the a block is polymerized with constituent units constituting the B block, whereby a block copolymer can be produced. In the above production method, the polymerization order of the a block and the B block may be reversed. Alternatively, the a block and the B block may be separately produced, and then the a block and the B block may be coupled.

Specific examples of such a block copolymer having a block containing a constituent unit represented by the above general formula (I) and a block having affinity for a solvent include the block copolymers described in Japanese patent No. 4911253.

In the present invention, from the viewpoint of dispersibility or dispersion stability of the colorant, a dispersant obtained by forming a salt with an organic acid compound or a halogenated hydrocarbon, which is at least a part of amino groups in a polymer containing a constituent unit represented by the above general formula (I), is also preferably used (hereinafter, such a polymer may be referred to as a salt-type polymer).

Among them, from the viewpoint of excellent dispersibility and dispersion stability of the colorant, it is preferable that the polymer containing a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. Specific examples of the organic acid compound used for such a dispersant include, for example, organic acid compounds described in japanese patent application laid-open No. 2012-236882 and the like, as preferable examples.

In addition, from the viewpoint of excellent dispersibility and dispersion stability of the colorant, at least 1 of allyl halide such as allyl bromide and benzyl chloride and aralkyl halide is preferable as the halogenated hydrocarbon.

In the colorant dispersion of the present invention, at least 1 kind of polymer having a constituent unit represented by the above general formula (I) is used as the dispersant, and the content thereof is appropriately selected in accordance with the kind of colorant used, the solid content concentration in a colored resin composition for color filters to be described later, and the like.

The content of the dispersant is preferably 3 parts by mass or more and 45 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of the total solid content in the colorant dispersion, from the viewpoints of dispersibility and dispersion stability.

In particular, when a coating film or a colored layer having a high colorant concentration is formed, the content of the dispersant is preferably 3 parts by mass or more and 25 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total solid content in the colorant dispersion.

In the present invention, the solid component includes all but the above-mentioned solvents, and includes monomers dissolved in the solvents.

< Solvent >

The solvent used in the present invention is not particularly limited, and may be an organic solvent which does not react with each component in the colorant dispersion and can dissolve or disperse these components. The solvent may be used alone or in combination of 2 or more.

Specific examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol, and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, N-butyl acetate, isobutyl acetate, N-butyl butyrate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and 2-heptanone, glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate, lactone solvents such as methoxyethoxyethyl acetate, ethoxyethyl acetate and Butyl Carbitol Acetate (BCA), carbitol acetate solvents such as propylene glycol diacetate and 1, 3-butanediol diacetate, glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether, aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, cyclic ether solvents such as tetrahydrofuran, unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene, saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane solvents, an organic solvent such as aromatic hydrocarbon such as xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of the solubility of other components. Among them, the solvent used in the present invention is preferably 1 or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl Carbitol Acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate, from the viewpoints of solubility of other components and coating suitability.

In addition, from the viewpoints of developability, solvent resolubility, and the like, a mixed solvent containing 2 or more solvents is also preferably used.

In the case of using a mixed solvent, the above glycol ether acetate-based solvent is preferably used as the first solvent because of high safety, moderate volatility, good dispersibility for proper solubility, and the like. Among them, 2-methoxyethyl acetate having a boiling point (referred to as a boiling point at atmospheric pressure, and the same applies hereinafter) of less than 150 ℃ or propylene glycol monomethyl ether acetate are more preferable, and Propylene Glycol Monomethyl Ether Acetate (PGMEA) is particularly preferable.

The second solvent (other than the first solvent) is preferably a solvent having an alcoholic hydroxyl group or a solvent having a boiling point of 150 ℃. The second solvent may be used alone or in combination of 1 or more than 2.

When a solvent having an alcoholic hydroxyl group is used as the second solvent, dispersibility becomes good and solvent resolubility becomes good.

Examples of the solvent having an alcoholic hydroxyl group include the above-mentioned alcohol-based solvent, the above-mentioned carbitol-based solvent, and the above-mentioned glycol ether-based solvent, and specific examples thereof include propylene glycol monomethyl ether (boiling point 121 ℃) and 3-methoxy-3-methyl-1-butanol (boiling point 174 ℃).

When a mixed solvent is used, the content of the solvent having an alcoholic hydroxyl group in the total solvent is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less. Further, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 1% by mass or more.

When the amount is within the above range, the solubility of the dispersant is easily improved, and the dissolution of the dispersant in the first solvent is not hindered, so that the dispersion stability is easily improved.

When the first solvent is a solvent having a boiling point of less than 150 ℃, uneven drying and foreign matter are less likely to occur and the solvent resolubility is also likely to be good if a solvent having a boiling point of 150 ℃ or more is used as the second solvent.

Examples of the solvent having a boiling point of 150 ℃ or higher include diethylene glycol ethyl methyl ether (boiling point 179 ℃), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188 ℃), diethylene glycol ethyl methyl ether (boiling point 179 ℃) and 3-methoxybutyl acetate (boiling point 172 ℃).

When a mixed solvent is used, the content of the solvent having a boiling point of 150 ℃ or higher is preferably 40 mass% or less, more preferably 30 mass% or less, based on the total solvent. Further, it is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more.

When the amount is within the above range, uneven drying is less likely to occur, and the drying time is not excessively long, so that the productivity is easily improved.

The boiling point of the "solvent having a boiling point of 150 ℃ or higher" is preferably 240 ℃ or less, particularly preferably 200 ℃ or less, from the viewpoint of not excessively long drying time and the like.

In the colorant dispersion of the present invention, the solvent is generally preferably in the range of 55 mass% to 95 mass%, more preferably in the range of 65 mass% to 90 mass%, and still more preferably in the range of 70 mass% to 88 mass%, with respect to the total amount of the colorant dispersion containing the solvent. If the solvent is too small, the viscosity tends to increase and the dispersibility tends to decrease. If the solvent is too much, the concentration of the colorant may be lowered, and it may be difficult to achieve the target chromaticity coordinates.

< Other ingredients >

The colorant dispersion of the present invention may further contain a dispersion auxiliary resin and other components as necessary without impairing the effect of the present invention.

Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by coloring resin compositions for color filters described later. Since the steric hindrance of the alkali-soluble resin makes the colorant particles less likely to contact with each other, there are cases where the effect of dispersing and stabilizing the colorant particles and reducing the dispersant by the dispersion stabilizing effect thereof is obtained.

Examples of the other components include a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, a shrinkage inhibitor, an antioxidant, an anticoagulant, and an ultraviolet absorber.

The colorant dispersion of the present invention is used as a preparation for preparing a colored resin composition for color filters described later. That is, the colorant dispersion liquid is a colorant dispersion liquid prepared at a stage before preparing a color resin composition for color filters described later, and having a relatively high P/V (mass of colorant component in the composition)/(mass of solid component other than the colorant component in the composition). Specifically, the ratio of (mass of the colorant component in the composition)/(mass of solid components other than the colorant component in the composition) is usually 1.0 or more. By mixing the colorant dispersion with each component described later, a colored resin composition for a color filter having excellent dispersibility can be prepared.

[ Method for producing colorant Dispersion ]

In the present invention, the method for producing the colorant dispersion is not particularly limited as long as the colorant is dispersed in a solvent by using the dispersant. Among them, from the viewpoint of excellent dispersibility and dispersion stability of the colorant, any of the following 2 production methods is preferable.

That is, the first method for producing a colorant dispersion of the present invention includes a step of preparing the dispersant, and a step of dispersing a colorant in a solvent in the presence of the dispersant. The colorant dispersion of the present invention can be obtained by co-dispersing 2 or more colorants in a solvent in the presence of the above-mentioned dispersing agent, or by dispersing or co-dispersing 1 or more colorants and then mixing 2 or more colorant dispersions.

The second method for producing a colorant dispersion of the present invention, when a dispersant which is a salt-type block copolymer is used, comprises the step of mixing a solvent, the block copolymer, the organic acid compound and a halogenated hydrocarbon with a colorant, and dispersing the colorant while forming a salt with at least a part of the terminal nitrogen portion of the constituent unit represented by the general formula (I) and the organic acid compound and the halogenated hydrocarbon. In the case of dispersing the colorant while forming the salt, 2 or more colorants may be co-dispersed, or 1 or more colorants may be dispersed or co-dispersed, and then 2 or more colorant dispersions may be mixed, whereby the colorant dispersion of the present invention can be obtained.

In the first and second manufacturing methods, the colorant may be dispersed using a conventional dispersing machine.

Specific examples of the dispersing machine include roll mills such as twin roll mill and triple roll mill, ball mills such as ball mill and vibration ball mill, and bead mills such as paint conditioner (pari コ n) continuous disc bead mill and continuous ring bead mill. Regarding preferable dispersion conditions of the bead mill, the diameter of the beads used is preferably 0.03mm or more and 3.0mm or less, more preferably 0.05 or more and 2.0mm or less.

[ Colored resin composition for color Filter ]

The colored resin composition for color filters of the present invention comprises a colorant, a dispersant, a binder component, and a solvent, and is characterized in that,

The colorant contains a red colorant and a yellow colorant;

The yellow colorant comprises at least 1 kind of anions selected from the group consisting of monoanions, dians, trisand tetrasnions of azo compounds shown by the general formula (A) and tautomeric structures thereof, ions of at least 2 kinds of metals selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, ni, cu and Mn, and compounds shown by the general formula (B);

the dispersant is a polymer having a constituent unit represented by the general formula (I).

The colored resin composition for a color filter of the present invention is excellent in the dispersion stability of a colorant as in the case of the colorant dispersion of the present invention, and can form a colored layer excellent in color reproducibility while reducing the phase difference value as in the case of the colorant dispersion of the present invention.

The colored resin composition for a color filter of the present invention contains at least a colorant, a dispersant, a binder component and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. The respective components contained in the colored resin composition for a color filter of the present invention are described below, but the red colorant, the specific yellow colorant, the dispersant and the solvent which are essential components among the colorants are the same as those described in the colorant dispersion of the present invention, and therefore, the description thereof is omitted here.

< Colorant >

The colorant in the colored resin composition for a color filter of the present invention contains a red colorant and the above-mentioned specific yellow colorant as essential components, but other colorants may be used in combination for adjusting the color tone.

The color filter may be formed by using, for example, a color filter having a color layer formed on a substrate, and a color filter having a color layer formed on a substrate. Among them, organic pigments are preferably used because of their high color development and high heat resistance. Examples of the organic Pigment include compounds classified as pigments (Pigment) in color index (c.i.; the Society ofDyers and Colourists company, issue), and specific examples thereof include the following color index (c.i.) numbering.

Examples of the dye that can be dispersed include dyes that can be dispersed by adding various substituents to the dye, or by insolubilizing a solvent by a known method of laking (salifying), or dyes that can be dispersed by using a solvent having a low solubility in combination. By using such a dye capable of being dispersed in combination with the above-mentioned dispersant, the dispersibility and dispersion stability of the dye can be improved.

The dye capable of being dispersed may be appropriately selected from conventionally known dyes. As such dyes, azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, and the like can be exemplified.

When the amount of the dye dissolved is 10mg or less per 10g of the solvent (or mixed solvent) as a standard, the dye can be judged to be dispersible in the solvent (or mixed solvent).

Among these, other yellow colorants and orange colorants not included in the above-mentioned red colorants are preferably used.

Examples of the other coloring agents include, but are not limited to, the following.

Examples of the other yellow colorant include c.i. pigment yellow 1、3、11、12、13、14、15、16、17、20、24、31、55、60、61、65、71、73、74、81、83、93、95、97、98、100、101、104、106、108、109、110、113、114、116、117、119、120、126、127、128、129、138、139、150、151、152、153、154、155、156、166、167、168、175、180 and 185.

In the colored resin composition for a color filter of the present invention, the content ratio of the red colorant to the entire colorant is not particularly limited, and may be appropriately adjusted in accordance with the desired chromaticity.

Among them, from the viewpoint of a decrease in the phase difference value and a widening in color reproducibility, and an improvement in contrast, the red colorant is preferably contained in an amount of 35 mass% or more and 99 mass% or less, more preferably 40 mass% or more and 98 mass% or less, still more preferably 45 mass% or more and 97 mass% or less, with respect to the total amount of the colorants.

Further, from the viewpoint of a reduction in the phase difference value and a widening in color reproducibility, and an improvement in contrast, the total content of the yellow colorants is preferably 1% by mass or more and 65% by mass or less, more preferably 2% by mass or more and 60% by mass or less, still more preferably 3% by mass or more and 55% by mass or less, with respect to the total amount of the colorants.

In the colored resin composition for a color filter of the present invention, the total content of at least 1 anion selected from the group consisting of monoazo compounds represented by the general formula (a) and monoazo, dian, triazo and tetraanions of azo compounds having a tautomeric structure thereof, and ions of at least 2 metals selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, ni, cu and Mn in the yellow colorant, and the compound represented by the general formula (B) (the specific yellow colorant) may be appropriately adjusted in accordance with a desired chromaticity, and is not particularly limited. From the standpoint of a reduction in the phase difference value and a widening in color reproducibility, and an improvement in contrast, the total content of the specific yellow colorants is preferably 10 mass% or more and 100 mass% or less, more preferably 15 mass% or more and 100 mass% or less, still more preferably 20 mass% or more and 100 mass% or less, and still more preferably 25 mass% or more and 100 mass% or less, with respect to the total amount of the yellow colorants.

In the colored resin composition for a color filter of the present invention, the coloring agent may further contain a red coloring agent and a coloring agent other than a yellow coloring agent within a range that does not impair the effects of the present invention, and the total content of the red coloring agent and the yellow coloring agent is preferably 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, still more preferably 80% by mass or more and 100% by mass or less, relative to the total amount of the coloring agents.

< Binder component >

The colored resin composition for color filters of the present invention contains a binder component for imparting adhesion to a surface to be coated for film forming property. In order to impart sufficient hardness to the coating film, a curable binder component is preferably contained. The curable binder component is not particularly limited, and any conventionally known curable binder component used for forming a colored layer of a color filter can be suitably used.

As the curable binder component, for example, a material containing a photocurable binder component containing a photocurable resin which is polymerizable and curable by visible light, ultraviolet light, electron beam, or the like, and a thermosetting binder component containing a thermosetting resin which is polymerizable and curable by heating can be used.

When a photolithography step is used in forming the colored layer, a photosensitive binder component having alkali developability is suitably used. In addition, a thermosetting adhesive component may be further used as the photosensitive adhesive component.

Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinone diazide group-containing compound (o-ki ヅ a ヅ a) as a photosensitive imparting component.

On the other hand, as the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is suitably used.

In the colored resin composition for a color filter of the present invention, a negative photosensitive binder component is preferable in terms of ease of patterning by photolithography using a conventional process.

Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described.

(Alkali-soluble resin)

The alkali-soluble resin of the present invention has an acidic group, can function as a binder resin, and can be suitably selected from resins that are soluble in an alkali developer used in patterning.

In the present invention, the alkali-soluble resin may be aimed at an acid value of 40mgKOH/g or more.

The alkali-soluble resin preferred in the present invention is a resin having an acidic group and usually having a carboxyl group, and specifically includes an acrylic resin such as an acrylic copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group, an epoxy (meth) acrylate resin having a carboxyl group, and the like. Among them, those having a carboxyl group in a side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain are particularly preferable. This is because the film strength of the formed cured film can be improved by containing the photopolymerizable functional group. In addition, 2 or more types of acrylic resins such as acrylic copolymers and styrene-acrylic copolymers and epoxy acrylate resins may be used in combination.

Acrylic resins such as acrylic copolymers having a carboxyl group and styrene-acrylic copolymers having a carboxyl group are (co) polymers obtained by (co) polymerizing a carboxyl group-containing ethylenically unsaturated monomer, and optionally, another copolymerizable monomer, by a known method.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω -carboxyl-polycaprolactone mono (meth) acrylate may be used. In addition, an anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as a precursor of the carboxyl group. Among them, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. The alkali-soluble resin has a hydrocarbon ring as a bulky group, so that shrinkage during curing is suppressed, peeling between the resin and the substrate is alleviated, and adhesion of the substrate is improved. In addition, the present inventors have found that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the resulting colored layer, particularly the swelling of the colored layer, can be suppressed. The effect thereof has not been elucidated, but it is presumed that the inclusion of a bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, and as a result, the strength of the coating film increases and the swelling due to the solvent is suppressed.

Examples of the hydrocarbon ring include an aliphatic hydrocarbon ring optionally having a substituent, an aromatic hydrocarbon ring optionally having a substituent, and a combination thereof, and the hydrocarbon ring optionally has a substituent such as an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amido group, a hydroxyl group, a nitro group, an amino group, a halogen atom, and the like.

The hydrocarbon ring may be contained as a 1-valent group or may be contained as a 2-valent or more group.

Specific examples of the hydrocarbon ring include aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2, 6) ] decane (dicyclopentane) and adamantane, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene and fluorene, chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane and stilbene, and a kadol structure (9, 9-diaryl fluorene).

The hydrocarbon ring is preferably an aliphatic hydrocarbon ring from the viewpoint of improving heat resistance and adhesion of the colored layer and improving brightness of the resulting colored layer.

In addition, the aforementioned kadol structure is particularly preferably contained in view of improving the curability of the colored layer and improving the solvent resistance ((NMP swelling inhibition).

The alkali-soluble resin is also preferably a crosslinked cyclic hydrocarbon ring which is an aliphatic hydrocarbon ring having a structure in which 2 or more rings share 2 or more atoms.

Specific examples of the crosslinked cyclic hydrocarbon ring include norbornane, isobornane, adamantane, tricyclo [5.2.1.0 (2, 6) ] decane, tricyclo [5.2.1.0 (2, 6) ] decene, tricyclopentene, tricyclopentane, tricyclopentadiene and dicyclopentadiene, and groups in which some of these groups are substituted with a substituent.

Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.

The lower limit of the carbon number of the crosslinked hydrocarbon ring is preferably 5 or more, particularly preferably 7 or more from the viewpoints of compatibility with other materials and solubility in an alkali developer. The upper limit is preferably 12 or less, particularly preferably 10 or less.

The alkali-soluble resin preferably has a maleimide structure represented by the following general formula (III).

[ Chemical 12]

General formula (III)

In general formula (III), R ^M is an optionally substituted hydrocarbon ring. ]

In the case where the alkali-soluble resin has a maleimide structure represented by the general formula (III), since the hydrocarbon ring has a nitrogen atom, the alkali-soluble resin has excellent compatibility with an alkali dispersant which is a polymer having a constituent unit represented by the general formula (I), and has a high development speed, thereby improving the effect of suppressing development residues.

Specific examples of the optionally substituted hydrocarbon ring in R ^M of the general formula (III) include the same as those described above.

Examples thereof include aliphatic hydrocarbon rings such as cyclopentyl, cyclohexyl and cyclooctyl, aromatic hydrocarbon rings such as phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, methoxyphenyl, benzyl, hydroxyphenyl and naphthyl, and groups in which some of these groups are substituted with substituents.

Among the alkali-soluble resins used in the present invention, an acrylic copolymer having a constituent unit having a hydrocarbon ring is preferably used in terms of easy adjustment of the amount of each constituent unit and easy improvement of the function of the constituent unit by increasing the amount of the constituent unit having a hydrocarbon ring, in addition to the constituent unit having a carboxyl group.

The acrylic copolymer having a constituent unit having a carboxyl group and the hydrocarbon ring can be produced by using an ethylenically unsaturated monomer having a hydrocarbon ring as the "copolymerizable other monomer".

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and styrene, and from the viewpoint that the effect of maintaining the cross-sectional shape of the colored layer after development during the heating treatment is large, at least 1 selected from the group consisting of cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, and styrene is preferably used.

In addition, the alkali-soluble resin used in the present invention preferably has an olefinic double bond in a side chain. In the case of having an olefinic double bond, the alkali-soluble resins or the alkali-soluble resins and the polyfunctional monomer can form a cross-linking bond in the curing step of the resin composition at the time of manufacturing the color filter. The cured film has improved film strength and development resistance, and the cured film is suppressed from thermal shrinkage, so that the cured film has excellent adhesion to the substrate.

The method for introducing an olefinic double bond into the alkali-soluble resin can be appropriately selected by a conventionally known method. Examples of the method include a method of introducing an olefinic double bond into a side chain by adding a compound having both an epoxy group and an olefinic double bond in the molecule, for example, glycidyl (meth) acrylate, to a carboxyl group of an alkali-soluble resin, a method of introducing an olefinic double bond into a side chain by introducing a constituent unit having a hydroxyl group into a copolymer in advance, and a method of introducing an olefinic double bond into a side chain by adding an isocyanate group to a compound having an olefinic double bond in the molecule.

The alkali-soluble resin of the present invention may further contain other constituent units such as methyl (meth) acrylate, ethyl (meth) acrylate, and the like, and constituent units having an ester group. The constituent unit having an ester group functions not only as a component that inhibits alkali solubility of the colored resin composition for a color filter, but also as a component that enhances solubility in a solvent and further solvent resolubility.

The alkali-soluble resin of the present invention is preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a constituent unit having a carboxyl group and a constituent unit having a hydrocarbon ring, and more preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a constituent unit having a carboxyl group, a constituent unit having a hydrocarbon ring, and a constituent unit having an olefinic double bond.

The alkali-soluble resin can be produced to have desired properties by appropriately adjusting the charge amounts of the respective constituent units.

The amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughening on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 50 mass% or less, more preferably 40 mass% or less, relative to the total amount of the monomers.

If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is not less than the above-mentioned lower limit, the solubility of the resulting coating film in an alkali developer is sufficient, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is not more than the above-mentioned upper limit, the formed pattern tends to be less likely to come off from the substrate and the film on the pattern surface tends to be rough during development in the alkali developer.

In addition, in the acrylic resin such as the acrylic copolymer and the styrene-acrylic copolymer having a constituent unit having an olefinic double bond, which can be more preferably used as the alkali-soluble resin, the compound having both an epoxy group and an olefinic double bond is preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less, relative to the amount of the carboxyl group-containing ethylenically unsaturated monomer charged.

The weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When the amount of the binder is less than 1,000, the function of the cured binder is significantly reduced, and when the amount exceeds 50,000, the formation of a pattern is difficult in the development of an alkali developer.

The weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by Shodex GPC SYSTEM-21H using polystyrene as a standard and THF as an eluent.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and an epoxy (meth) acrylate compound obtained by reacting an acid anhydride with a reactant of an unsaturated group-containing monocarboxylic acid is suitable.

The epoxy compound, unsaturated group-containing monocarboxylic acid and acid anhydride may be appropriately selected from known ones. The epoxy (meth) acrylate resin having a carboxyl group may be used alone in an amount of 1 kind or in an amount of 2 or more kinds.

From the viewpoint of the developability (solubility) of the aqueous alkali solution used in the developer, the alkali-soluble resin is preferably a resin having an acid value of 50mgKOH/g or more. From the viewpoint of the developability (solubility) of the aqueous alkali solution used in the developer and the adhesion to the substrate, the acid value of the alkali-soluble resin is preferably 70mgKOH/g or more and 300mgKOH/g or less, and among these, 80mgKOH/g or more and 280mgKOH/g or less.

In the present invention, the acid value may be measured in accordance with JIS K0070.

The equivalent amount of the ethylenic unsaturated bond in the case where the side chain of the alkali-soluble resin has an ethylenic unsaturated group is preferably in the range of 100 to 2000, particularly preferably in the range of 140 to 1500, from the viewpoint of obtaining the effect of improving the film strength of the cured film, improving the development resistance, and being excellent in the adhesion to the substrate. When the equivalent of the ethylenic unsaturated bond is 2000 or less, the development resistance and the adhesion are excellent. Further, when the ratio is 100 or more, the ratio of the other constituent units such as the constituent unit having a carboxyl group and the constituent unit having a hydrocarbon ring can be relatively increased, and therefore the developing property and the heat resistance are excellent.

The ethylenically unsaturated bond equivalent here means a weight average molecular weight per 1 mol of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Mathematics (1)

Equivalent of ethylenically unsaturated bond (g/mol) =w (g)/M (M0 l)

(In the formula (1), W represents the mass (g) of the alkali-soluble resin, M represents the number of moles (M0 l) of the olefinic double bond contained in the alkali-soluble resin W (g))

The above-mentioned ethylenically unsaturated bond equivalent can be calculated by measuring the number of ethylenically double bonds contained in 1g of the alkali-soluble resin, for example, according to the iodine number test method described in JIS K0070:1992.

The alkali-soluble resin used in the color filter colored resin composition may be used alone or in combination of 1 or more than 2, and the content thereof is not particularly limited, but is preferably in the range of 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 40 mass% or less, relative to the total solid content of the color filter colored resin composition. When the content of the alkali-soluble resin is not less than the above-mentioned lower limit, sufficient alkali developability is easily obtained, and when the content of the alkali-soluble resin is not more than the above-mentioned upper limit, film roughness and pattern peeling are easily suppressed at the time of development.

(Multifunctional monomer)

The polyfunctional monomer used in the colored resin composition for a color filter is not particularly limited as long as it is polymerizable by the photoinitiator, and a compound having 2 or more ethylenically unsaturated double bonds is usually suitably used, and a polyfunctional (meth) acrylate having 2 or more acryl groups or methacryl groups is particularly preferable.

The polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in Japanese patent application laid-open No. 2013-029832.

These polyfunctional (meth) acrylates may be used singly or in combination of 1 or more than 2. In addition, when excellent photocurability (high sensitivity) is required for the colored resin composition for color filters of the present invention, the polyfunctional monomer preferably has 3 or more (trifunctional) polymerizable double bonds, preferably poly (meth) acrylates of 3-or more polyols, dicarboxylic acid modifications thereof, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid modifications of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modifications of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The content of the above-mentioned polyfunctional monomer used in the colored resin composition for a color filter is not particularly limited, but is preferably in a range of 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 40 mass% or less, relative to the total solid content of the colored resin composition for a color filter. When the content of the polyfunctional monomer is not less than the above-mentioned lower limit, the photocuring is sufficiently advanced, and elution of the exposed portion during development can be suppressed, and when the content of the polyfunctional monomer is not more than the above-mentioned upper limit, the alkali developability is sufficient.

(Photoinitiator)

The initiator used in the colored resin composition for a color filter of the present invention is not particularly limited, and 1 or 2 or more initiators may be used in combination from among the conventional various initiators.

Examples of the initiator include aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α -aminoketones, bisimidazoles, N-dimethylaminobenzophenone, halomethyl-s-triazine compounds, and thioxanthones. Specific examples of the initiator include aromatic ketones such as benzophenone, 4' -bis-diethylaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, benzoins such as ethylbenzoin, bisimidazoles such as 2- (o-chlorophenyl) -4, 5-phenylimidazole dimer, halomethyl oxadiazole compounds such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole, halomethyl-s-triazine compounds such as 2- (4-butoxy-naphthalen-1-yl) -4, 6-bis-trichloromethyl-s-triazine, halomethyl-s-triazine compounds such as 2, 2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinylacetone, 1, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 1-hydroxy-cyclohexyl-phenylketone, biphenyl acyl, benzoyl benzoic acid, benzoyl benzoate, 4-methyl-4 ' -thiomethyl-thioketone, 2-dimethyl thioketone, 2-thiomethyl-4-thioketone, 2-thiomethyl-thioketone and other than-thiomethyl-4-thioketone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, α -dimethoxy- α -phenylacetophenone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylsulfanyl) phenyl ] -2- (4-morpholinyl) -1-propanone, and the like.

Among them, 2-methyl-1- [4- (methylsulfanyl) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 4' -bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. From the viewpoints of sensitivity adjustment, inhibition of water penetration (water staining), and improvement of development resistance, it is more preferable to combine an α -aminoacetophenone initiator such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one with a thioxanthone initiator such as diethylthioxanthone.

When the α -aminoacetophenone initiator and the thioxanthone initiator are used, the total content thereof is preferably 5% by mass or more and 15% by mass or less relative to the total solid content of the colored resin composition. If the amount of the initiator is 15 mass% or less, sublimates in the production process are reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water penetration is improved.

In the present invention, from the viewpoint of improving sensitivity, the initiator preferably contains an oxime ester photoinitiator. By using the oxime ester photoinitiator, in forming a thin line pattern, variation in line width in the plane is easily suppressed. Furthermore, the use of an oxime ester photoinitiator tends to improve the developability and suppress the occurrence of water-bleeding. The water-bleeding means a phenomenon in which, when a component that improves alkali developability is used, marks such as water-bleeding occur after alkali development and after washing with pure water. Such water-bleeding is not problematic for the product because it disappears after post-baking, but is detected as uneven abnormality in the appearance inspection of the pattern surface after development, resulting in a problem that normal products cannot be distinguished from abnormal products. Therefore, if the inspection sensitivity of the inspection device is lowered during the appearance inspection, the yield of the final color filter product is lowered, which is a problem.

Among them, the oxime ester photoinitiator is preferably an aromatic ring, more preferably a condensed ring containing an aromatic ring, and even more preferably a condensed ring containing a benzene ring and a heterocycle, from the viewpoint of reducing contamination of a colored resin composition for color filters and contamination of devices due to decomposition products.

The oxime ester photoinitiator may be appropriately selected from oxime ester photoinitiators such as those described in 1, 2-octanedione-1- [4- (phenylthio) -, 2- (o-benzoyl oxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime), japanese patent application laid-open No. 2000-80068, japanese patent application laid-open No. 2001-233836, japanese patent application laid-open No. 2010-527339, japanese patent application laid-open No. 2010-527338, and Japanese patent application laid-open No. 2013-04153. As the commercial products, irgacure OXE-02 (manufactured by BASF), ADEKA ARKLS NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by ADEKA), ADEKA ARKLS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou power electronic new material), irgacure OXE-01 (manufactured by BASF), TR-PBG-365 (manufactured by Changzhou power electronic new material) having a fluorene skeleton, and the like can be used. From the viewpoint of brightness, it is particularly preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton. In addition, from the viewpoint of high sensitivity, an oxime ester photoinitiator having a carbazole skeleton is preferably used.

In addition, 2 or more oxime ester photoinitiators are preferably used in combination, from the viewpoints of easy improvement of brightness and development resistance and high effect of inhibiting the occurrence of water penetration. From the viewpoints of high brightness and high heat resistance, it is particularly preferable to use 2 kinds of oxime ester photoinitiators having a diphenyl sulfide skeleton in combination, or to use an oxime ester photoinitiator having a diphenyl sulfide skeleton in combination with an oxime ester photoinitiator having a fluorene skeleton. In addition, from the viewpoint of excellent sensitivity and an effect of suppressing the occurrence of water penetration, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton in combination with an oxime ester photoinitiator having a fluorene skeleton or an oxime ester photoinitiator having diphenyl sulfide.

In addition, from the viewpoint of suppressing water penetration and improving sensitivity, it is preferable to use an oxime ester photoinitiator in combination with a photoinitiator having a tertiary amine structure. This is because a photoinitiator having a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, so that radicals generated by the initiator are less likely to be deactivated by oxygen, and sensitivity can be improved. Examples of the commercially available photoinitiator having a tertiary amine structure include 2-methyl-1- (4-methylsulfanyl-phenyl) -2-morpholinopropan-1-one (for example, irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, irgacure 369, manufactured by BASF), and 4,4' -bis (diethylamino) benzophenone (for example, hicure ABP, manufactured by Sichuan).

In addition, it is preferable to combine a thioxanthone-based initiator with an oxime ester-based photoinitiator from the viewpoints of sensitivity adjustment, inhibition of water penetration, and improvement of development resistance, and it is preferable to combine 2 or more oxime ester-based photoinitiators with a thioxanthone-based initiator from the viewpoints of improvement of brightness and development resistance, easiness in adjustment of sensitivity, inhibition of water penetration, and improvement of development resistance.

The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually 0.01 to 100 parts by mass, preferably 5 to 60 parts by mass, based on 100 parts by mass of the polyfunctional monomer. If the content is not less than the above-mentioned lower limit, the photocuring is sufficiently advanced to suppress dissolution of the exposed portion upon development, whereas if it is not more than the above-mentioned upper limit, yellowing of the resulting colored layer becomes weak to suppress a decrease in brightness.

In addition, as the photoinitiator used in the colored resin composition for a color filter of the present invention, the total content of 2 or more oxime ester photoinitiators is preferably in the range of 0.1 to 12.0 mass%, more preferably 1.0 to 8.0 mass%, based on the total solid content of the colored resin composition for a color filter, from the viewpoint of sufficiently exhibiting the effect of the use of these photoinitiators.

The binder component used in the colored resin composition for a color filter of the present invention is preferably blended in a proportion of 35 mass% or more and 97 mass% or less, more preferably 40 mass% or more and 96 mass% or less, relative to the total solid content of the colored resin composition for a color filter. When the lower limit is not less than the above, a colored layer excellent in hardness and adhesion to a substrate can be obtained. In addition, when the amount is equal to or less than the upper limit value, the developing property is excellent, and the occurrence of micro wrinkles due to heat shrinkage can be suppressed.

< Optional additional Components >

The colored resin composition for color filters may optionally contain various additives.

Examples of the additives include mercapto compounds, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like, in addition to antioxidants.

The colored resin composition for a color filter of the present invention preferably further contains an antioxidant from the viewpoints of improving heat resistance, suppressing discoloration of the colorant, and improving brightness. In addition, from the viewpoint of improving the adhesion of the SiN substrate, the colored resin composition for a color filter of the present invention preferably further contains an antioxidant.

The antioxidant may be appropriately selected from known substances. Specific examples of the antioxidant include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like, and from the viewpoint of heat resistance, hindered phenol antioxidants are preferably used.

The hindered phenol antioxidant is an antioxidant which has at least 1 phenol structure and has a structure in which at least one of the 2-and 6-positions of a hydroxyl group having a carbon number of 4 or more is substituted by the phenol structure.

Specific examples of the hindered phenol antioxidant include dibutylhydroxytoluene (BHT), pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: irganox 1010, manufactured by BASF), 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate (trade name: irganox3114, manufactured by BASF), 2,4, 6-tris (4-hydroxy-3, 5-di-t-butylbenzyl) mesitylene (trade name: irganox 1330, manufactured by BASF), 6- (4-hydroxy-3, 5-di-t-butylphenylamino) -2, 4-bis (octylthio) -1,3, 5-triazine (trade name: irganox 565, manufactured by BASF), and the like, 2,2' -Thiodiethyl bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: irganox 1035, manufactured by BASF), 1, 2-bis [3- (4-hydroxy-3, 5-di-t-butylphenyl) propionyl ] hydrazine (trade name: irganox MD1024 manufactured by BASF), octyl 3- (4-hydroxy-3, 5-diisopropylphenyl) propionate (trade name: irganox 1135, manufactured by BASF), 4, 6-bis (octylthiomethyl) -o-cresol (trade name: irganox 1520L manufactured by BASF), a process for producing the same, and a process for producing the same, N, N' -hexamethylenebis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide ] (trade name: irganox1098, manufactured by BASF), 1, 6-hexanediol bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: irganox 259, manufactured by BASF), 1-dimethyl-2- [ (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ]2,4,8, 10-tetraoxaspiro [5.5] undecane (trade name: ADK STABAO-80, manufactured by ADEKA), bis (3-t-butyl-4-hydroxy-5-methylbenzoic acid) ethylenebis (oxyethylene) (trade name: irganox 245, manufactured by BASF), 1,3, 5-tris [ [4- (1, 1-dimethylethyl) -3-hydroxy-2, 6-dimethylphenyl ] methyl ] -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione (trade name: irganox 1790, manufactured by BASF), 2 '-methylenebis (6-tert-butyl-4-methylphenol) (trade name: SUMILIZER MDP-S, manufactured by Sumitomo chemical Co., ltd.), 6' -thiobis (2-tert-butyl-4-methylphenol) (trade name: irganox 1081, manufactured by BASF), 3, 5-di-tert-butyl-4-hydroxybenzenesulfonic acid diester (trade name: irgamod, manufactured by BASF), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate (trade name: SUMILIZER GM, manufactured by Sumitomo chemical Co., ltd.), 4' -thiobis (6-tert-butyl-m-cresol) (trade name: SUMILIZER WX-R, manufactured by Sumitomo chemical Co., ltd.), 6' -di-tert-butyl-4, 4' -butylidenedimethylene phenol (trade name: ADEKASTAB AO-40, manufactured by ADEKA), and the like. other oligomeric and polymeric compounds having hindered phenol structures may also be used.

Among them, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX 1010, manufactured by BASF corporation) is preferable from the viewpoints of heat resistance and light resistance.

Further, from the viewpoint of being able to form a colored layer which reduces the phase difference and improves the brightness and contrast, a hindered phenol antioxidant having a molecular weight of 1000 or less and a molecular weight of 280 equivalents or less per 1 phenolic hydroxyl group is preferable, and a hindered phenol antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per 1 phenolic hydroxyl group is more preferable. It is presumed that such an antioxidant has high fluidity and many active sites per weight unit, and therefore, the above-described effects can be easily obtained by suppressing aggregation of a colorant due to rapid curing shrinkage at the time of exposure or post baking or suppressing yellowing of a resin or the like by radical trapping. Examples of such antioxidants include 6,6 '-di-t-butyl-4, 4' -butylene-m-cresol (trade name: ADEKASTAB AO-40, manufactured by ADEKA), and the like.

In the present invention, it is preferable to use a latent antioxidant as the antioxidant from the viewpoint of being able to form a colored layer that reduces the phase difference value and improves the contrast. If a latent antioxidant is used, it is presumed that the radical trapping effect is high particularly in post-baking, and therefore, aggregation of the colorant due to rapid curing shrinkage in post-baking is suppressed, and the above effect is easily obtained. The latent antioxidant in the present invention is a compound having a protecting group that can be released by heating and exhibiting an antioxidant function by the release of the protecting group. Among them, a substance which can easily detach a protecting group by heating at 150 ℃ or higher is preferable. Examples of potential antioxidants are described in International patent publication No. 2014/021023.

The latent antioxidant suitably used in the present invention includes a latent hindered phenol antioxidant in which the phenolic hydroxyl group of the hindered phenol antioxidant is protected with a protecting group that can be detached by heating. Examples of the latent hindered phenol-based antioxidant include a reaction product of a phenolic hydroxyl group of the hindered phenol-based antioxidant with an acid anhydride, an acid chloride, a Boc-based reagent, an alkyl halide, a silyl chloride, an allyl ether compound, or the like. Among them, a structure in which hydrogen of a phenol group of the hindered phenol antioxidant is substituted with a urethane-based protecting group such as t-butoxycarbonyl group is suitably used, and specific examples thereof include the following chemical formulas (a) to (c), but are not limited thereto.

[ Chemical 13]

Chemical formula (a)

Chemical formula (b)

Chemistry (c)

The method for producing the latent antioxidant is not particularly limited, and the latent antioxidant can be obtained by reacting a phenol compound produced by the method described in Japanese patent application laid-open No. 57-111375, japanese patent application laid-open No. 3-173843, japanese patent application laid-open No. 6-128195, japanese patent application laid-open No. 7-206771, japanese patent application laid-open No. 7-252191, japanese patent application laid-open No. 2004-501128, with an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide, a silyl chloride, an allyl ether compound, or the like. In addition, commercial products can also be used.

In the colored resin composition for a color filter of the present invention, it is preferable that the oxime ester photoinitiator and the antioxidant are contained in combination as the colored resin composition, from the viewpoint of improving the brightness by a synergistic effect.

The content of the antioxidant is preferably 0.05 parts by mass or more and 10.00 parts by mass or less, more preferably 0.10 parts by mass or more and 5.00 parts by mass or less, relative to 100 parts by mass of the total solid content in the colored resin composition. When the lower limit is not less than the above-mentioned lower limit, heat resistance and light resistance are excellent. On the other hand, if the upper limit is less than or equal to the above, the colored resin composition of the present invention can be made into a photosensitive resin composition having high sensitivity.

When the antioxidant is used in combination with the oxime ester photoinitiator, the content of the antioxidant is preferably 1 part by mass or more and 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, still more preferably 5 parts by mass or more and 45 parts by mass or less, relative to 100 parts by mass of the total amount of the oxime ester photoinitiators. If the amount is within the above range, the effect of the combination is excellent.

The colored resin composition for a color filter of the present invention preferably further contains a mercapto compound from the viewpoint of enhancing the effect of suppressing the occurrence of water penetration.

In addition, in the colored resin composition for a color filter of the present invention, when the oxime ester photoinitiator and the mercapto compound are contained in combination as the photosensitive colored resin composition, it is preferable from the viewpoint of improving development resistance, further improving the effect of suppressing the occurrence of water bleeding, further improving linearity when forming a fine line pattern, or improving the ability to form a fine line pattern according to the design of a mask line width. The term "linearity improvement" means that the end portion of the colored layer formed in the development step after the application of the colored composition has little unevenness, and is formed in a straight line or a nearly straight line.

The mercapto compound functions as a chain transfer agent, and has a property of accelerating the reaction by receiving radicals from the slowly reacting radicals and improving curability.

Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyloxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and tetraethyleneglycol bis (3-mercaptopropionate).

The thiol compound may be used alone or in combination of 2 or more, and among them, 1 or more selected from the group consisting of polyfunctional thiol compounds having 2 or more thiol groups in 1 molecule are preferably used from the viewpoint of increasing the crosslinking density and improving the water-penetration inhibition effect.

Further, from the viewpoint of easily maintaining a good water penetration inhibiting effect even when stored for a long period of time, a Zhongji compound having Zhongji carbon atoms to which mercapto groups are bonded is preferable, and a multifunctional Zhongji compound having 2 or more of these Zhongji atoms in 1 molecule is more preferable.

The content of the mercapto compound used in the colored resin composition for a color filter is not particularly limited, and from the viewpoint of sufficiently exerting the above-described effects, the mercapto compound is preferably in the range of 0.2% by mass or more and 7% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, relative to the total solid content of the colored resin composition for a color filter.

In addition, the colored resin composition for a color filter of the present invention preferably further contains an ultraviolet absorber from the viewpoint of being able to form a colored layer that reduces the phase difference value and improves the contrast. The effect of improving these characteristics is presumably due to the aggregation of the colorant caused by the rapid curing shrinkage in the exposure step. The ultraviolet absorber may be appropriately selected from known ones. Specific examples of the ultraviolet absorber include benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds. Among them, benzotriazole compounds are preferably used in view of the ability to form a colored layer which reduces the phase difference and improves the contrast.

Examples of the benzotriazole-based compound include a mixture of 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate and 2-ethylhexyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethylacetate and 95% of phenylpropionic acid, 3- (2-H-benzotriazol-2-hydroxy-5 ' -hydroxy-phenyl) -5-chlorophenyl ] -2H-benzotriazole, and a linear side chain compound of 3- (2-H-benzyl) -1, 7-hydroxy-ethyl-7-2-phenyl ] propionate, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1, 3-tetramethylbutyl) phenol and the like, but are not limited thereto.

As a commercial product, "TINUVIN P"、"TINUVIN PS"、"TINUVIN 109"、"TINUVIN 234"、"TINUVIN 326"、"TINUVIN 328"、"TINUVIN 329"、"TINUVIN 384-2"、"TINUVIN 900"、"TINUVIN 928"、"TINUVIN 99-2"、"TINUVIN 1130" manufactured by BASF and the like can be exemplified.

The benzotriazole-based compound represented by the following general formula (IV) is preferable from the viewpoint of being capable of forming a colored layer which reduces the phase difference value and improves the contrast.

[ Chemical 14]

General formula (IV)

(In the general formula (IV), R ¹¹ and R ¹² each independently represent a hydrogen atom or an optionally phenyl-substituted alkyl group having 1 to 20 carbon atoms, and X represents a hydrogen atom or a chlorine atom.)

In the general formula (IV), R ¹² is preferably methyl, tert-butyl, tert-amyl, tert-octyl or alpha, alpha-dimethylbenzyl, and R ¹¹ is preferably hydrogen atom, tert-butyl, tert-amyl or alpha, alpha-dimethylbenzyl.

The content of the ultraviolet absorber used in the colored resin composition for a color filter is not particularly limited, but is preferably 0.05 parts by mass or more and 10.00 parts by mass or less, more preferably 0.10 parts by mass or more and 5.00 parts by mass or less, relative to 100 parts by mass of the total solid content in the colored resin composition. When the lower limit is not less than the above-mentioned lower limit, heat resistance and light resistance are excellent. On the other hand, if the upper limit is less than or equal to the above, the colored resin composition of the present invention can be made into a photosensitive resin composition having high sensitivity.

In the colored resin composition for a color filter of the present invention, it is preferable from the viewpoint of improving the brightness by a synergistic effect if the above oxime ester photoinitiator and the ultraviolet absorber are contained in combination as the colored resin composition.

When the ultraviolet absorber is used in combination with the oxime ester photoinitiator, the content of the ultraviolet absorber is preferably 1 to 250 parts by mass, more preferably 3 to 80 parts by mass, still more preferably 5 to 45 parts by mass, based on 100 parts by mass of the total amount of the oxime ester photoinitiators. If the amount is within the above range, the effect of the combination is excellent.

Further, specific examples of the surfactant and the plasticizer include those described in Japanese patent application laid-open No. 2013-029832.

Examples of the silane coupling agent include KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、KBM-903、KBE-903、KBM573、KBM-403、KBE-402、KBE-403、KBM-303、KBM-802、KBM-803、KBE-9007、X-12-967C( SILICONE Co., ltd.). Among them, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacrylic group and an acrylic group are preferable from the viewpoint of adhesion of SiN substrates.

The content of the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the total solid content in the colored resin composition. When the lower limit value is not less than the upper limit value, siN adhesion is excellent.

< Blending ratio of each component in colored resin composition for color Filter >

The total content of the colorants is preferably 3 mass% or more and 65 mass% or less, more preferably 4 mass% or more and 60 mass% or less, based on the total solid content of the color resin composition for color filters. When the lower limit is not less than the above, the colored layer has a sufficient concentration when the colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 μm or more and 5.0 μm or less). When the upper limit is less than or equal to the above, the storage stability is excellent, and a colored layer having sufficient hardness and adhesion to a substrate can be obtained. In particular, when a colored layer having a high colorant concentration is formed, the content of the colorant is preferably 15% by mass or more and 65% by mass or less, more preferably 25% by mass or more and 60% by mass or less, relative to the total solid content of the colored resin composition for a color filter.

The content of the dispersant is not particularly limited as long as the colorant can be uniformly dispersed, and for example, 1 mass% or more and 40 mass% or less relative to the total solid content of the colored resin composition for color filters can be used. The solid content of the colored resin composition for color filters is preferably 2 to 30 mass%, particularly preferably 3 to 25 mass%. When the content is not less than the above lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the colored resin composition for a color filter is excellent. In addition, if the upper limit value is less than or equal to the above, the development property becomes good. In particular, when a colored layer having a high colorant concentration is formed, the content of the dispersant is preferably 2% by mass or more and 25% by mass or less, more preferably 3% by mass or more and 20% by mass or less, relative to the total solid content of the colored resin composition for a color filter.

The solvent content may be appropriately set in a range in which a colored layer can be formed with high accuracy. The total amount of the colored resin composition for color filters containing the solvent is usually preferably in the range of 55 mass% or more and 95 mass% or less, and more preferably in the range of 65 mass% or more and 88 mass% or less. When the content of the solvent is within the above range, a composition excellent in coatability can be obtained.

In the colored resin composition for a color filter of the present invention, the P/V ratio ((mass of the colorant component in the composition)/(mass of solid components other than the colorant component in the composition)) is preferably 0.1 or more, more preferably 0.2 or more from the viewpoint of degassing or heat shrinkage, while the P/V ratio is preferably 0.8 or less, more preferably 0.7 or less from the viewpoint of suppression of occurrence of phase differences and excellent in manufacturing convenience, that is, excellent in solvent resolubility, development residue, development adhesion, development resistance, effect of suppressing occurrence of water-bleeding, and the like, and more preferably 0.6 or less from the viewpoint of development residue and development adhesion.

< Cured film of colored resin composition for color Filter >

The color resin composition for color filters is preferably formed as a cured film having chromaticity coordinates in the range of x=0.550 to 0.700 and y=0.290 to 0.450 in the XYZ color system of JISZ8701 measured using a C light source.

Among them, from the viewpoint of improving color reproducibility, a cured film having chromaticity coordinates in the range of x=0.570 to 0.693 and y=0.300 to 0.426 in the XYZ color system of JIS Z8701 measured using a C light source is preferably formed, a cured film having chromaticity coordinates in the range of x=0.600 to 0.690 and y=0.300 to 0.348 is more preferably formed, and a cured film having chromaticity coordinates in the range of x=0.630 to 0.690 and y=0.300 to 0.329 is even more preferably formed.

In the cured film of the colored resin composition for a color filter, a color space in which x=0.570 to 0.693, y=0.300 to 0.426, and a stimulus value Y is 9.0.ltoreq.y, and a color space in which x=0.600 to 0.690, y=0.300 to 0.348, and a stimulus value Y is 9.5.ltoreq.y are exhibited in chromaticity coordinates in an XYZ color system of JIS Z8701, which is measured by using a C light source in a single pixel, and a film thickness of 2.8 μm or less is preferable. The film thickness of the cured film herein refers to a film thickness obtained by applying and drying a color resin composition for color filters, then exposing the cured polyfunctional monomer, and then post-baking the cured polyfunctional monomer for 30 minutes in a clean oven at 230 ℃.

The preferred blending ratio or combination of the color spaces in the range of x=0.570 to 0.693, y=0.300 to 0.426, and the stimulus value Y is 9.0.0.ltoreq.y in the chromaticity coordinates of the XYZ color system of JIS Z8701 measured using a C light source with a film thickness of 2.8 μm or less, the preferred red colorant is 45.0 mass% or more and 98.0 mass% or less, the preferred red colorant is 2.0 mass% or more and 55.0 mass% or less, the preferred red colorant is 50.0 mass% or more and 95.0 mass% or less, the preferred red colorant is 5.0 mass% or more and 50.0 mass% or less, and the preferred red colorant is 55.0 mass% or more and 90.0 mass% or less, and the preferred red colorant is 10.0 mass% or more and 45.0 mass% or less, respectively, in the chromaticity coordinates of the XYZ color system of JIS Z8701 measured by using a C light source with a single pixel.

< Method for producing colored resin composition for color Filter >

The method for producing the colored resin composition for color filters of the present invention is not particularly limited, and can be obtained, for example, by adding an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and other components as necessary to the colorant dispersion of the present invention and mixing the resulting mixture using a known mixing unit. Alternatively, a colorant dispersion liquid of each colorant is prepared by using the above-mentioned dispersant, and each colorant dispersion liquid, binder component, and other components as needed are mixed by using a known mixing unit, thereby obtaining the colorant.

[ Color Filter ]

The color filter of the present invention comprises at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers has a colored layer which is a cured product of the colored resin composition for a color filter of the present invention.

The color filter according to the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention. According to fig. 1, a color filter 10 of the present invention includes a substrate 1, a light shielding portion 2, and a coloring layer 3.

(Colored layer)

At least one of the colored layers used in the color filter of the present invention is a cured product of the colored resin composition for a color filter of the present invention, or a colored layer formed by curing the colored resin composition.

The colored layer is usually formed in an opening of a light shielding portion on a substrate described later, and is usually composed of a colored pattern of 3 colors or more.

The arrangement of the coloring layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a delta type, or a 4-pixel arrangement type. The width, area, etc. of the colored layer can be arbitrarily set.

The thickness of the colored layer is suitably controlled by a coating method, by adjusting the solid content concentration, viscosity, and the like of the colored resin composition for a color filter, and is generally preferably in the range of 1 μm to 5 μm.

The colored layer can be formed by the following method, for example.

First, the colored resin composition for a color filter of the present invention is applied to a substrate described below using a coating unit such as a spray coating method, dip coating method, bar coating method, roll coating method, spin coating method, or die coating method, to form a wet coating film. Among them, spin coating and die coating can be preferably used.

Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, whereby an alkali-soluble resin and a polyfunctional monomer are subjected to photopolymerization reaction to form a cured coating film. Examples of the light source used for exposure include ultraviolet rays and electron beams such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, and the like.

In addition, a heat treatment may be performed after the exposure to promote the polymerization reaction. The heating conditions are appropriately selected in accordance with the blending ratio of each component in the colored resin composition for color filters to be used, the thickness of the coating film, and the like.

Next, a developing treatment is performed using a developing solution, and the unexposed portions are dissolved and removed to form a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. To the alkali solution, a surfactant or the like may be added in an appropriate amount. In addition, the development method may employ a general method.

After the development treatment, the cured coating film of the colored resin composition for color filters is usually dried to form a colored layer by washing with a developer. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected depending on the application of the coating film.

(Light shielding section)

The light shielding portion in the color filter of the present invention is a light shielding portion formed in a pattern on a substrate described later, and may be the same as a light shielding portion used as a light shielding portion in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape, a matrix shape, or the like. The light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light shielding portion may be a resin layer containing light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in the resin binder. In the case of the resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.

The film thickness of the light shielding portion is set to be about 0.2 μm or more and about 0.4 μm or less in the case of a metal thin film, and is set to be about 0.5 μm or more and about 2 μm or less in the case of dispersing or dissolving the black pigment in the binder resin.

(Substrate)

As the substrate, a transparent substrate, a silicon substrate, a substrate on which aluminum, silver/copper/palladium alloy thin films, or the like is formed, or the like is used. On these substrates, other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, the transparent rigid material such as quartz glass, alkali-free glass, and synthetic quartz plate, and the transparent flexible material such as transparent resin film, optical resin plate, and flexible glass, which are not flexible, are mentioned.

The thickness of the transparent substrate is not particularly limited, and a substrate of, for example, 100 μm or more and 1mm or less can be used in combination with the use of the color filter of the present invention.

In addition to the substrate, the light shielding portion, and the colored layer, the color filter of the present invention may be formed with, for example, a top coat layer, a transparent electrode layer, and further an alignment film, alignment protrusions, columnar spacers, and the like.

[ Display device ]

The display device of the present invention is characterized by comprising the color filter of the present invention. The constitution of the display device in the present invention is not particularly limited, and may be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device. Even in a liquid crystal display device of a transverse electric field type, various display defects such as disturbance of alignment of liquid crystal due to electric characteristics of green pixels and aging due to threshold variation of switching can be suppressed, and thus the liquid crystal display device of the present invention is suitably selected.

< Liquid Crystal display device >

The liquid crystal display device of the present invention is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The liquid crystal display device according to the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of a display device according to the present invention, and is a schematic diagram showing an example of a liquid crystal display device. As illustrated in fig. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 including a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and a known configuration can be made as a liquid crystal display device generally using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be used. Examples of such driving methods include a TN method, an IPS method, an OCB method, and an MVA method. Any of these modes may be suitably used in the present invention.

The counter substrate may be appropriately selected in accordance with the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

< Organic light-emitting display device >

The organic light-emitting display device of the present invention is characterized by comprising the color filter of the present invention and an organic light-emitting body.

The organic light emitting display device according to the present invention will be described with reference to the drawings. Fig. 3 is a schematic diagram showing another example of the display device of the present invention, and is a schematic diagram showing an example of the organic light emitting display device. As shown in fig. 3, the organic light emitting display device 100 of the present invention has a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

Examples of the lamination method of the organic light-emitting body 80 include a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 on the upper surface of the color filter, and a method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60. In the organic light-emitting element 80, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, the cathode 76, and other components can be appropriately used. The organic light emitting display device 100 thus fabricated may be applied to, for example, an organic EL display of a passive driving type or an organic EL display of an active driving type.

The organic light-emitting display device of the present invention is not limited to the configuration shown in fig. 3, and may be configured as a known organic light-emitting display device generally using a color filter.

Examples (example)

The following examples are presented to illustrate the invention in detail. The present invention is not limited to these descriptions.

The acid value of the block copolymer before salt formation was obtained by a method according to the method described in JIS K0070.

The amine value of the block copolymer before salt formation was determined by a method according to the method described in JIS K7237.

The weight average molecular weight (Mw) of the block copolymer before salt formation was determined by GPC (gel permeation chromatography) as a standard polystyrene equivalent according to the measurement method of the present invention described above.

The glass transition temperatures (Tg) of the block copolymers before and after salt formation were measured by a method according to the method described in JIS K7121 using Differential Scanning Calorimeter (DSC) (manufactured by SII NANOTECHNOLOGY, EXSTAR DSC 7020).

Preparation example 1 preparation of Azo derivative 1

To 550g of distilled water, 23.1g of barbituric acid and 19.2g of barbituric acid were introduced. Next, an aqueous potassium hydroxide solution was used to prepare azobarbituric acid (0.3 mol), and 750g of distilled water was mixed. 5g of 30% hydrochloric acid was added dropwise. Thereafter, 38.7g of melamine was introduced. Then, 0.57 mol of nickel chloride solution was mixed with 0.03 mol of copper chloride solution and added thereto, followed by stirring at a temperature of 80 ℃ for 8 hours. The pigment was separated by filtration, washed, dried at 120 ℃ and ground with a mortar to give the Azo derivative 1 (Ni: cu=95:5 (molar ratio) Azo pigment).

Preparation example 2 preparation of Azo derivative 2

In production example 1, azo pigment of Azo derivative 2 (Ni: zn=65:35 (molar ratio)) was obtained in the same manner as in production example 1 except that 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution were used instead of 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution.

Preparation example 3 preparation of Azo derivative 3

In production example 1, azo pigment of Azo derivative 3 (Ni: cu=70:30 (molar ratio)) was obtained in the same manner as in production example 1, except that 0.42 mol of nickel chloride solution and 0.18 mol of copper chloride solution were used instead of 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution.

Preparation example 4 preparation of Azo derivative 4

In production example 1, azo pigment of Azo derivative 4 (Ni: zn=35:65 (molar ratio)) was obtained in the same manner as in production example 1, except that 0.21 mol of nickel chloride solution and 0.39 mol of zinc chloride solution were used instead of 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution.

Synthesis example 1 preparation of dispersant a

Into a 500mL round bottom four-necked separation flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 part by mass of lithium chloride were charged, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to-60 ℃, 4.9 parts by mass of butyllithium (15% by mass of hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. 3.3 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.2 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 4.2 parts by mass of 2-ethylhexyl methacrylate (EHMA), 7.0 parts by mass of n-Butyl Methacrylate (BMA), 24.7 parts by mass of benzyl methacrylate (BzMA), and 13.3 parts by mass of Methyl Methacrylate (MMA) were added dropwise using an addition funnel over a period of 60 minutes. After 30 minutes, 30.8 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After allowing to react for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was purified by reprecipitation in hexane, filtration, and vacuum drying, and diluted with PGMEA to prepare a 30 mass% solid content solution. 32.5 parts by mass of water was added thereto, and the temperature was raised to 100℃and the reaction was carried out for 7 hours, whereby the constituent units derived from EEMA were deprotected to prepare constituent units derived from methacrylic acid (MAA). The resulting block copolymer PGMEA solution was purified by reprecipitation in hexane, filtration and vacuum drying, to obtain a block copolymer a-1 (acid value 12mgKOH/g, tg44 ℃) comprising an a block containing a constituent unit represented by the general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer and having solphilicity. The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography) to give a weight average molecular weight Mw of 8100. The amine value was 110mgKOH/g.

In a 100mL round-bottomed flask, 29.35 parts by mass of block copolymer A-1 was dissolved in 29.35 parts by mass of PGMEA, and 1.59 parts by mass (0.1 mol of phenylphosphonic acid relative to 1 mol of DMMA unit of block copolymer A-1) of phenylphosphonic acid (Tokyo) was added, followed by stirring at a reaction temperature of 30℃for 20 hours, to thereby obtain a salt type block copolymer A-1 (dispersant a) solution. The amine number after salt formation was calculated specifically as follows.

To the NMR sample tube, 9 parts by mass of the salt type block copolymer A-1 (solid matter after reprecipitation) and 1g of a solution obtained by mixing 91 parts by mass of chloroform-D1 NMR were added, and the 1 ³ C-NMR spectrum was measured at room temperature under the condition of 10000 times of accumulation by using a nuclear magnetic resonance apparatus (FT NMR, JNM-AL400, japan). From the ratio of the peak value of the carbon atoms adjacent to the nitrogen atoms not forming a salt and the peak value of the carbon atoms adjacent to the nitrogen atoms forming a salt in the terminal nitrogen site (amino group) in the obtained spectral data, the ratio of the number of amino groups forming a salt to the total number of amino groups was calculated, and it was confirmed that the ratio was not different from the theoretical salt forming ratio (all 2 acid groups of phenylphosphonic acid formed a salt with the terminal nitrogen site of DMMA of the block copolymer a-1).

The amine number after salt formation was calculated to be 88mgKOH/g by subtracting 0.20 molar parts of the amine number of the DMMA unit (22 mgKOH/g) from 110mgKOH/g before salt formation. The acid value of the block copolymer A-1 after salt formation is the same as that of the block copolymer A-1 before salt formation. The acid value, amine value and Tg of the block copolymer A-1 before and after salt formation are shown in Table 1.

(Synthesis examples 2 to 4: production of dispersants b to d)

In Synthesis example 1, a solution of a block copolymer A-2~A-4 before salt and a solution of a block copolymer A-2 (dispersant b) to A-4 (dispersant d) were synthesized in the same manner as in Synthesis example 1 except that the contents shown in Table 1 were changed. 2.8 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used in Synthesis example 2, 2.2 parts by mass in Synthesis example 3, and 1.1 parts by mass in Synthesis example 4. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

Synthesis example 5 preparation of dispersant e

After drying a 500mL four-necked separation flask under reduced pressure, ar (argon) substitution was performed.

Under Ar flow, 100g of dehydrated THF, 2.0g of methyltrimethylsilyl dimethyl ketene acetal, 0.15ml of a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2g of mesitylene were added. 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-Butyl Methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA) and 35.7 parts by mass of Methyl Methacrylate (MMA) were added dropwise thereto using a dropping funnel over 45 minutes. Since heat is generated as the reaction proceeds, the temperature is kept at less than 40 ℃ by ice cooling. After 1 hour, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After 1 hour of reaction, 5g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give block copolymer A-5. The weight average molecular weight was 8,350 as determined by GPC measurement (NMP LiBr10 mM), and the amine number was 95mgKOH/g.

In a 100mL round-bottomed flask, 29.35 parts by mass of block copolymer A-5 was dissolved in 29.35 parts by mass of PGMEA, 3.17 parts by mass (0.20 mol of phenylphosphonic acid per 1 mol of DMMA unit of block copolymer A-5, manufactured by Tokyo formation) was added, and the mixture was stirred at a reaction temperature of 30℃for 20 hours, thereby obtaining a salt type block copolymer A-5 (dispersant e) solution. The amine value after salt formation was calculated in the same manner as in Synthesis example 1. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

Synthesis example 6 preparation of dispersant f

In Synthesis example 5, a solution of a salt-type block copolymer A-6 (dispersant f) was synthesized in the same manner as in Synthesis example 5, except that 3.80 parts by mass (0.3 mol of benzyl chloride per 1mol of DMMA unit of block copolymer A-5) of benzyl chloride (Tokyo formation) was used instead of phenylphosphonic acid. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

Synthesis example 7 preparation of dispersant g

In Synthesis example 5, a block copolymer A-7 before salt formation and a solution of a salt block copolymer A-7 (dispersant g) were obtained in the same manner as in Synthesis example 5 except that 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-Butyl Methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA) and 35.7 parts by mass of Methyl Methacrylate (MMA), 7.6 parts by mass of n-Butyl Methacrylate (BMA), 32.9 parts by mass of Methyl Methacrylate (MMA) and PME-1000 (methoxypolyethylene glycol monomethacrylate (number of repetition of polyethylene glycol chains n.apprxeq.23), trade name BLEMMERPME-1000, manufactured by day oil) were used in place of 13.4 parts by mass of n-Butyl Methacrylate (BMA), 14.9 parts by mass of dimethylaminoethyl methacrylate (DMMA) and 26.6 parts by mass of methyl methacrylate were used. The ammonia valence after salt formation was calculated in the same manner as in Synthesis example 1. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

TABLE 1

Table i

Synthesis example 8 preparation of alkali-soluble resin A solution

A mixture of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA and 3 parts by mass of AIBN was introduced into a polymerization vessel charged with 150 parts by mass of PGMEA, and the mixture was dropwise added under a nitrogen stream at 100℃over 3 hours. After the completion of the dropwise addition, the mixture was heated at 100℃for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.

Subsequently, 20 parts by mass of Glycidyl Methacrylate (GMA), 0.2 parts by mass of triethylamine and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ℃ for 10 hours to bubble air into the reaction solution. The alkali-soluble resin A obtained was a resin in which a side chain having an olefinic double bond was introduced into a main chain formed by copolymerization of BzMA, MMA and MAA using GMA, and had a solid content of 42.6% by mass, an acid value of 74mgKOH/g and a weight average molecular weight of 12000. The weight average molecular weight was determined using Shodex GPCSystem-21H with polystyrene as standard and THF as eluent. The method for measuring the acid value was measured based on JIS K0070.

Synthesis example 9 preparation of alkali-soluble resin B solution

An alkali-soluble resin B solution was obtained in the same manner as in synthesis example 8, except that 20 parts by mass of styrene and 20 parts by mass of N-phenylmaleimide (tokyo chemical industry co., ltd.) were used instead of 40 parts by mass of BzMA as a comonomer species in polymerization in synthesis example 8. The solid content was 42.6% by mass, the acid value was 74mgKOH/g, and the weight-average molecular weight was 12000.

Synthesis example 10 Synthesis of latent antioxidant (Compound a)

0.01Mol of a phenol compound represented by the following formula (3), 0.05mol of di-t-butyl dicarbonate and 30g of pyridine were mixed, and 0.025mol of 4-dimethylaminopyridine was added thereto at room temperature under nitrogen atmosphere, followed by stirring at 60℃for 3 hours. After cooling to room temperature, the reaction solution was poured into 150g of ion-exchanged water, and 200g of chloroform was added to separate oil from water. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100g of methanol was added to the residue to crystallize the residue. The white powdery crystals were dried under reduced pressure at 60℃for 3 hours to obtain a latent antioxidant (compound a) represented by the above chemical formula (a). The structure of the obtained latent antioxidant was confirmed by IR and NMR.

[ 15]

[ Chemical formula 3]

Example 1

(1) Production of colorant Dispersion R1

6.23 Parts by mass of a dispersant a solution of Synthesis example 1 as a dispersant, 2.57 parts by mass of a diketopyrrolopyrrole pigment (BrDPP, trade name IrgaphorRED S3621 CF, manufactured by BASF corporation) represented by the following chemical formula (2) as a Red colorant, 3.86 parts by mass of C.I. pigment Red 254 (trade name Hostaperm Red D2B-COF LV3781 manufactured by CLARIANT), 2.08 parts by mass of C.I. pigment Red 177 (trade name Cromophtal Red A2B manufactured by BASF), 24.49 parts by mass of an Azo derivative obtained in preparation example 2 as a yellow colorant, 100 parts by mass of an alkali-soluble resin A solution obtained in Synthesis example 8, 66.12 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0mm were placed in a mayonnaise bottle, and the same manner as a pigment shaker (manufactured by light Tian Tiegong Co., ltd.) was used for pre-pulverization, and the dispersion was carried out by adding the zirconia beads having a particle size of 2.0mm and a pigment shaker (200 mm) and the same as a pigment dispersion was used as a pigment dispersion liquid of a final particle size of 1R.

[ 16]

[ Chemical formula 2]

(2) Production of colored resin composition R1 for color Filter

1.90 Parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 8, 0.60 parts by mass of a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.) and 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907 (IRG 907), manufactured by BASF) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1 (photo initiator: irgacure369 (manufactured by BASF)) 0.04 parts by mass, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime) (photo initiator: trade name ADEKA ARCSNCI-831 (NCI 831), manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (trade name MEGAFEC F559, manufactured by DIC (manufactured by Siro) 0.07 parts by silane coupling agent (trade name KBM-503, manufactured by Sione)), 0.05 parts by mercapto compound (pentaerythritol tetrakis (3-mercaptobutyrate)), PGMEA 5.85 parts by mass, 3-methoxy-3-methyl-1-butyl acetate 3.92 parts by mass, and color filter resin composition R1 was obtained.

(3) Formation of colored layer

The colored resin composition R1 obtained in the above (2) was applied onto a GLASS substrate (NH TECHNO GLASS Co., ltd. "NA 35") having a thickness of 0.7mm and a thickness of 100mm, and then dried at 80℃for 3 minutes by using a hot plate, irradiated with ultraviolet light of 60mJ/cm ² by using an ultra-high pressure mercury lamp, and further post-baked at 230℃in a clean oven for 30 minutes, whereby the film thickness was adjusted so that the film thickness after curing became 2.10. Mu.m, thereby forming a colored layer R1.

(Example 2. About.11, comparative example 1)

(1) Production of colorant dispersions R2 to R9, RC1

In examples 2 to 6 and comparative example 1, colorant dispersions R2 to R6 were obtained in the same manner as in (1) of example 1, except that the dispersant a solution was replaced as shown in table 2, the types and amounts of the dispersants were changed to the same mass parts as the solid content, and the PGMEA amount was adjusted so that the total was 100 mass parts.

In examples 7 to 9, colorant dispersions R7 to R9 were obtained in the same manner as in example 3 (1), except that the types and the amounts of the colorants used in example 3 (1) were changed as shown in table 2.

In comparative example 1, a colorant dispersion RC1 was obtained in the same manner as in example 1 (1), except that the dispersant a solution was replaced as shown in table 2, the types and the amounts of the dispersants were changed to the same mass parts as the solid content, the PGMEA amount was adjusted so that the total was 100 mass parts, and the types and the amounts of the colorants were changed, respectively, in example 1 (1).

(2) Production of colored resin compositions R2 to R11 and RC1 for color filters

In examples 2 to 9 and comparative example 1, the same procedure as in (2) of example 1 was repeated except that the colorant dispersions R2 to R9 and RC1 were used as shown in Table 2 instead of the colorant dispersion R1 of example 1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios became the values shown in Table 2 so that the film thicknesses became 2.10. Mu.m, respectively, to obtain colored resin compositions R2 to R9 and RC1 for color filters.

In example 10, a color filter resin composition R10 was obtained in the same manner as in (2) of example 3, except that the alkali-soluble resin B solution obtained in synthesis example 9 was used instead of the alkali-soluble resin a solution in example 3, and 0.03 parts by mass of an antioxidant (trade name IRGANOX 1010 (1010, manufactured by BASF) was further added.

In example 11, a colored resin composition R11 for a color filter was obtained in the same manner as in (2) of example 10, except that 0.04 parts by mass of an oxime ester-based photoinitiator (trade name TR-PBG-365 (PBG 365, manufactured by the company of new powerful electronics) was used instead of the IRG3690.04 parts by mass of the photoinitiator and 0.02 parts by mass of an oxime ester-based photoinitiator (trade name TR-PBG-3057 (PBG 3057), manufactured by the company of new powerful electronics) was used instead of the NCI8310.02 parts by mass of the photoinitiator, as shown in table 2.

(3) Formation of colored layer

In the same manner as in (3) of example 1, except that the colored resin compositions R2 to R11 and RC1 were used in place of the colored resin composition R1, colored layers R2 to R11 and RC1 were obtained in the same manner as in (3) of example 1.

TABLE 2

The table is shown below for short.

Y150 derivative C.I. pigment yellow 150 derivative (Ni complex) (trade name: LEVASCREEN YELLOW G, manufactured by LANXESS Co., ltd.);

Byk-161 trade name Disperbyk-161 (urethane dispersant, 30% by mass of solid content, manufactured by BYK Chemie);

Solvent A, propylene Glycol Monomethyl Ether Acetate (PGMEA);

Solvent B3-methoxy-3-methyl-1-butyl acetate.

(Example 12 to 23)

(1) Preparation of colorant dispersions R12 to R23

In examples 12 to 23, colorant dispersions R12 to R23 were obtained in the same manner as in (1) of example 3, except that the types and blending amounts of the colorants were changed as shown in table 3 in (1) of example 3, and the PGMEA amounts were adjusted so that the total amounts became 100 parts by mass.

(2) Production of colored resin compositions R12 to R23 for color filters

The same procedure as in (2) of example 11 was repeated except that the colorant dispersions R12 to R23 were used in place of the colorant dispersion R3 of (2) of example 11, and the alkali-soluble resin amounts were adjusted so that the P/V ratios became values shown in Table 3 so that the film thicknesses became 2.50. Mu.m, respectively, to obtain colored resin compositions R12 to R23 for color filters.

(3) Formation of colored layer

In example 11 (3), colored layers R12 to R23 were obtained in the same manner as in example 11 (3) except that the colored resin compositions R12 to R23 were used instead of the colored resin composition R11.

(Comparative example 2 to 7)

(1) Production of colorant dispersions RC 2-RC 7

In comparative examples 2 to 7, colorant dispersions RC2 to RC7 were obtained in the same manner as in (1) of example 1, except that the dispersant a solution was replaced as shown in table 3, the types and amounts of the dispersants were changed to the same mass parts as the solid components, the types and amounts of the colorants were changed as shown in table 3, and the PGMEA amounts were adjusted so that the total amounts became 100 mass parts.

(2) Production of colored resin compositions RC2 to RC7 for color filters

The same procedure as in (2) of example 11 was repeated except that the colorant dispersions RC2 to RC7 were used in place of the colorant dispersion R3 of (2) of example 11, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios became values shown in Table 3 so that the film thicknesses became 2.50. Mu.m, respectively, to obtain colored resin compositions RC2 to RC7 for color filters.

(3) Formation of colored layer

In example 11 (3), colored layers RC2 to RC7 were obtained in the same manner as in example 11 (3) except that the colored resin compositions RC2 to RC7 were used instead of the colored resin composition R11.

TABLE 3

R264: C.I. pigment Red 264 (trade name: irgazin Red L4010 HD, manufactured by BASF);

R242 C.I. pigment Red 242 (trade name: novoperm Scarlet 4RF, manufactured by CLARIANT);

The transmittance at a wavelength of 520nm is 20% or less and the transmittance at a wavelength of 640nm is 70% or more when the spectral transmittance spectrum of a 2.5 μm coating film is measured, with the ratio of P/V (mass of Red colorant/mass of solid matter other than Red colorant) of C.I. pigment orange 38 = 0.2.

R177: C.I. pigment Red 177 (trade name: cromophtal RedA B, manufactured by BASF);

r179 C.I. pigment Red 179 (trade name: paliogen Maroon L3980,BASFDispersions&Pigments Asia Pacific);

r272, C.I. pigment Red 272 (trade name: irgazin FLAME RED K3800, manufactured by BASF);

byk-161 trade name Disperbyk 161 (urethane dispersant, 30% by mass solids, BYK Chemie);

6919 Disperbyk-LPN6919 (Polymer having a constituent unit represented by the general formula (I), amine value 120mgKOH/g, solid content 60% by mass, BYK Chemie).

(Production of example 24 to 41)

(1) Preparation of colorant dispersions R24 to R41

In examples 24 to 41, colorant dispersions R24 to R41 were obtained in the same manner as in (1) of example 3, except that the types and blending amounts of the colorants were changed as shown in table 4 in (1) of example 3, and the PGMEA amounts were adjusted so that the total amounts became 100 parts by mass.

(2) Production of colored resin compositions R24 to R41 for color filters

The same procedure as in (2) of example 11 was repeated except that the colorant dispersions R24 to R41 were used in place of the colorant dispersion R3 of (2) of example 11, and the amounts of the alkali-soluble resins were adjusted so that the film thicknesses became 2.80. Mu.m and the P/V ratios became the values shown in Table 4, respectively, to obtain colored resin compositions R24 to R41 for color filters.

(3) Formation of colored layer

In the same manner as in (3) of example 11 except that the colored resin compositions R24 to R41 were used in place of the colored resin composition R11, colored layers R24 to R41 were obtained in the same manner as in (3) of example 11.

TABLE 4

Example 42

(1) Production of colorant Dispersion

6.23 Parts by mass of a dispersant c solution of Synthesis example 3 as a dispersant, 13.0 parts by mass of a diketopyrrolopyrrole pigment (BrDPP, trade name Irgaphor RED S3621CF, manufactured by BASF corporation) represented by the above chemical formula (2) as a colorant, 14.59 parts by mass of an alkali-soluble resin A solution obtained in Synthesis example 8, 100 parts by mass of PGMEA 66.20 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, and oscillated for 1 hour by a paint shaker (manufactured by light Tian Tiegong Co., ltd.) to obtain a pre-pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and the dispersion was carried out by a paint shaker for 4 hours to obtain a RED colorant dispersion r1.

The same procedure as for the Red colorant dispersion r1 was repeated except that 13.0 parts by mass of c.i. pigment Red 254 (trade name: hostaperm Red D2B-COF LV3781, manufactured by CLARIANT) was used as a colorant instead of 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the above formula (2) as a colorant in the Red colorant dispersion r1, to obtain a Red colorant dispersion r2.

The Red colorant dispersion r3 was obtained in the same manner as the Red colorant dispersion r1 except that 13.0 parts by mass of c.i. pigment Red 177 (trade name: paliogen Red L4045, manufactured by basf) was used as a colorant instead of 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2) as a colorant.

The red colorant dispersion r1 was prepared in the same manner as the red colorant dispersion r1 except that 13.0 parts by mass of the Azo derivative 213.0 parts by mass of the colorant was used instead of the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) as a colorant, thereby obtaining a yellow colorant dispersion y.

(2) Production of colored resin composition R42 for color Filter

11.65 Parts by mass of the red colorant dispersion liquid r obtained in the above (1), 23.57 parts by mass of the red colorant dispersion liquid r, 31.92 parts by mass of the red colorant dispersion liquid r, 4.15 parts by mass of the yellow colorant dispersion liquid y, 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 8, 0.60 part by mass of a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyaku Synthesis Co., ltd.), 0.60 part by mass of 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropane-1-one (photo initiator: trade name Irgacure907, manufactured by BASF) 0.09 part by mass, 0.04 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiator: irgacure369, manufactured by BASF) 0.04 part by mass of ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] -,1- (o-acetyl oxime) (trade name ADEKAARCS NCI-A, trade name) 0.02-fluoro-3-yl) -3-butanone (trade name) 0.07 part by BASF), 0.05 part by mass of a surface active butyl methacrylate (3.03 part by weight of butyl methacrylate (3.03) 0.07 part by weight of butyl methacrylate (3.55 part by weight of butyl methacrylate) 0.55 part by weight of butyl methacrylate (3-3), a colored resin composition R42 for a color filter was obtained.

(3) Formation of colored layer

In the same manner as in (3) of example 1 except that the colored resin composition R42 was used instead of the colored resin composition R1, a colored layer R42 was obtained.

The obtained colored resin composition R42 for a color filter had the same composition as the colored resin composition R3 for a color filter of example 3, and the evaluation results of the colored resin composition R42 for a color filter and the colored layer R42 were the same as the evaluation results of the colored resin composition R3 for a color filter and the colored layer R3.

(Example 43 to 48)

(1) Production of colorant Dispersion R47

In example 47, a colorant dispersion R47 was obtained in the same manner as in (1) of example 1, except that the dispersant a solution was replaced with the dispersant g solution and the solid content was changed to the same mass parts as shown in table 5, and the PGMEA amount was adjusted so that the total was 100 mass parts in (1).

(2) Production of colored resin compositions R43 to R48 for color filters

In example 43, a color resin composition R43 for a color filter was obtained in the same manner as in (2) of example 3 except that the alkali-soluble resin B solution obtained in synthesis example 9 was used instead of the alkali-soluble resin a solution in example 3, 0.02 parts by mass of an oxime ester-based photoinitiator (trade name IrgacureOXE 01 (OXE 01, manufactured by BASF) was used instead of the IRG3690.04 parts by mass, and 0.04 parts by mass of an oxime ester-based photoinitiator (trade name Irgacure OXE02 (OXE 02), manufactured by BASF) was used instead of the NCI8310.02 parts by mass, as shown in table 5.

In example 44, a colored resin composition R44 for a color filter was obtained in the same manner as in (2) of example 11, except that 0.03 parts by mass of an antioxidant (trade name, ADEKA starb AO-40 (AO-40, manufactured by ADEKA)) was used instead of 0.03 parts by mass of the antioxidant (trade name, IRGANOX 1010 (manufactured by BASF)) of example 11.

In example 45, a colored resin composition R45 for a color filter was obtained in the same manner as in (2) of example 11, except that 0.03 parts by mass of the latent antioxidant (compound a) of synthesis example 10 was used instead of 0.03 parts by mass of the antioxidant (trade name IRGANOX 1010 (1010, manufactured by BASF corporation) of example 11.

In example 46, a colored resin composition R46 for a color filter was obtained in the same manner as in (2) of example 11, except that 0.03 parts by mass of an ultraviolet absorber (benzotriazole-based compound, manufactured by BASF corporation) was added in place of 0.03 parts by mass of the antioxidant (manufactured by IRGANOX 1010 (1010), manufactured by BASF corporation).

In example 47, a colored resin composition R47 for a color filter was obtained in the same manner as in (2) of example 3, except that the colorant dispersion R47 was used instead of the colorant dispersion R3 of example 3.

In example 48, a colored resin composition R48 for a color filter was obtained in the same manner as in (2) of example 43, except that in example 43, a colorant dispersion R47 was used instead of the colorant dispersion R3, and 0.03 parts by mass of an antioxidant (trade name ADEKA starb AO-40 (AO-40, manufactured by ADEKA) and 0.03 parts by mass of an ultraviolet absorber (benzotriazole-based compound, trade name TINUVIN 329, manufactured by basf) were added.

(3) Formation of colored layer

In the same manner as in (3) of example 1, except that the colored resin compositions R43 to R48 were used in place of the colored resin composition R1, colored layers R43 to R48 were obtained in the same manner as in (3) of example 1.

TABLE 5

[ Evaluation method ]

< Evaluation of dispersibility of colorant Dispersion >

The viscosity immediately after the preparation and after the storage at 25℃for 30 days were measured for the colorant dispersions obtained in examples and comparative examples, and the viscosity change rate was calculated from the viscosities before and after the storage, to evaluate the viscosity stability. In the viscosity measurement, a vibration viscometer was used to measure the viscosity at 25.0±0.5 ℃. The results are shown in tables 2 to 5.

(Viscosity stability evaluation criterion)

A, the viscosity change rate before and after preservation is less than 10%;

The viscosity change rate before and after preservation is more than 10% and less than 15%;

the viscosity change rate before and after preservation is more than 15% and less than 25%;

and D, the viscosity change rate before and after preservation is more than 25%.

The value of the colorant is 13 mass% based on the total mass of the solvent in the colorant dispersion.

The colorant dispersion liquid was practically usable when the evaluation result was C, but the colorant dispersion liquid was more excellent when the evaluation result was B, and the dispersion stability of the colorant dispersion liquid was excellent when the evaluation result was a.

< Evaluation of optical Property, evaluation of contrast >

The contrast, chromaticity (x, Y) and luminance (Y) of the colored layers obtained in examples and comparative examples were measured using a tsukamu electron beam-splitting characteristic measuring apparatus LCF-1500M and a pot electric contrast measuring apparatus CT-1B.

(Contrast evaluation reference)

X is set to a value of 0.570-0.600 under a C light source

AA exceeding 10000;

A:8000~10000;

B:6000~7999;

c is less than 6000.

X is set to a value of 0.607 to 0.630 under a C light source

AA exceeding 9000;

A:7000~9000;

B:5000~6999;

c is less than 5000.

X is set to a value of 0.650 to 0.693 under a C light source

AA exceeding 8000;

A:6000~8000;

B:4000~5999:

c is less than 4000.

< Evaluation of phase Difference >

The retardation of the colored layer is indicated by a retardation in the thickness direction (Rth) calculated by the following formula. The retardation (Rth) was measured by using a retardation measuring device (AxoscanTM MuellerMatrix Polarimeter manufactured by axome corporation). The measurement wavelength of the red-colored layer was measured at 620nm and 665 nm.

Rth=((Nx+Ny)/2-Nz)d

Nx is the refractive index of the in-plane slow axis direction;

Ny is the refractive index of the in-plane fast axis direction;

Nz, refractive index in the thickness direction;

d film thickness (nm).

< Evaluation of solvent resolubility >

The front end of a glass substrate having a width of 0.5cm and a length of 10cm was immersed in the colored resin compositions for color filters obtained in examples and comparative examples, and the composition was applied to a portion of 1cm in length of the glass substrate. The pulled-up glass substrate was placed in a constant temperature and humidity machine with the glass surface level, and dried at a temperature of 23 ℃ and a humidity of 80% rh for 10 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. The re-dissolved state of the dried coating film at this time was visually determined and evaluated.

(Solvent resolubility evaluation criterion)

The AA is dried and the film is completely dissolved in less than 8 seconds;

A, completely dissolving a dried coating film;

b, generating a thin sheet of a dry coating film in a solvent, and coloring the solution;

And C, a sheet of a dry coating film is not generated in the solvent, and the solution is not colored.

The evaluation criteria of AA, a or B are evaluated as good in solvent resolubility and can be practically used without any problem, and the evaluation results of a and AA are more excellent in effect.

< Evaluation of development residue >

The colored resin compositions for color filters obtained in examples and comparative examples were applied on GLASS substrates (NH TECHNO GLASS Co., ltd., "NA 35") having a thickness of 0.7mm and 100mm X100 mm, respectively, using a spin coater, and then dried at 60℃for 3 minutes using a hot plate, thereby forming colored layers having a thickness of 2.5. Mu.m. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developer. After the unexposed portion (50 mm. Times.50 mm) of the glass substrate on which the colored layer was formed was visually observed, the glass substrate was sufficiently wiped with a lens cleaning cloth (trade name TORAYSEE MK cleaning cloth manufactured by Toli Co., ltd.) containing ethanol to visually observe the degree of coloration of the lens cleaning cloth.

(Development residue evaluation reference)

AA, even if the same evaluation was performed using a colored layer having a thickness of 3.5 μm, the development residue was not visually confirmed, and the lens cleaning cloth was completely colorless;

a, the development residues are not confirmed visually, and the lens cleaning cloth is completely free from coloring;

B, confirming slight coloring of the lens cleaning cloth by visual observation without confirming development residues;

c, visually confirming slight development residues and confirming the coloration of the lens cleaning cloth;

the development residue was visually confirmed, and the staining of the lens cleaning cloth was confirmed.

If the evaluation criterion is AA, a, B or C, the practical use is possible, but if the evaluation result is B, and further is a, and further is AA, the effect is more excellent.

< Evaluation of development resistance >

The colored resin compositions for color filters obtained in examples and comparative examples were applied on GLASS substrates (NH TECHNO GLASS Co., ltd., "NA 35") having a thickness of 0.7mm, respectively, using a spin coater. After drying by heating on a hot plate at 80℃for 3 minutes, ultraviolet rays of 40mJ/cm ² were irradiated using an ultra-high pressure mercury lamp. The film thickness at this time was measured and set to T1 (. Mu.m). Thereafter, shower development was performed using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developer. The film thickness after development was measured and set to T2 (. Mu.m). T2/T1X 100 (%) was calculated.

(Development resistance evaluation reference)

AA more than 98%;

more than 95% and less than 98%;

More than 90% and less than 95%;

c is less than 90%.

The evaluation criteria AA, a, and B make practical use possible, but the results of the evaluation are a and AA, which are more excellent.

< Evaluation of Water penetration >

The colored resin compositions for color filters obtained in examples and comparative examples were applied to a glass substrate (manufactured by NHTECHNO GLASS Co., ltd., "NA 35") using a spin coater and then baked to a film thickness of a colored layer having a thickness of 1.6 μm, and then dried at 60℃for 3 minutes using a hot plate, and ultraviolet rays of 60mJ/cm ² were irradiated on the entire surface of the glass substrate without using a photomask using an ultra-high pressure mercury lamp, thereby forming a colored layer on the glass substrate. Then, spin development was performed using 0.05wt% potassium (KOH) as a developer, and after 60 seconds of contact with the developer, the substrate was rinsed with pure water to perform development treatment, and after spinning the rinsed substrate for 10 seconds and centrifuging to remove water, the contact angle of pure water was measured immediately as follows to evaluate water penetration.

For the contact angle measurement of pure water, 1.0. Mu.L of a droplet of pure water was dropped onto the surface of the colored layer immediately after the water was removed by centrifugation, and the static contact angle after the droplet was landed for 10 seconds was measured by the θ/2 method. The measurement device used a contact angle meter DM 500 manufactured by Kyowa interface science Co.

(Water penetration evaluation criterion)

AA, contact angle is more than 80 degrees;

A, the contact angle is more than 75 degrees and less than 80 degrees;

the contact angle is more than 65 degrees and less than 75 degrees;

the contact angle is more than 50 degrees and less than 65 degrees;

and D, the contact angle is less than 50 degrees.

If the water penetration evaluation criterion is AA, a or B, practical use is possible, but if the evaluation result is a, further AA, the effect is more excellent.

< SiN adhesion evaluation >

The colored resin compositions for color filters obtained in examples and comparative examples were applied to SiN substrates (Foresight, manufactured by the company corporation) using a spin coater, and then dried at 80 ℃ for 3 minutes using a hot plate, irradiated with ultraviolet light of 60mJ/cm ² using an ultra-high pressure mercury lamp, and further post-baked in a clean oven at 230 ℃ for 30 minutes, whereby the film thickness was adjusted so that the film thickness after curing became 2.10 μm, thereby forming a colored layer.

The resulting colored layer was subjected to a cross-cut adhesion test according to JIS K5600-5-6, and after repeating a peeling operation using a tape 5 times, the presence or absence of peeling of the coating film was observed and evaluated on the basis of the following evaluation.

(SiN adhesion evaluation criterion)

No peeling of eyes of any grids;

a, although there is small stripping of the coating film at the cross point of the cross section, the occupied area of stripping is less than 5%;

And B, peeling the coating along the scribing line and at the crossing point. The occupied area of stripping is more than 5% and less than 15%;

And C, peeling off the coating film locally and wholly along the scribing line. The occupied area of peeling is 15% or more and less than 35%.

[ Summary of results ]

As is clear from the results of the tables, the colorant dispersions of examples 1 to 41 and 47, in which the above-mentioned specific yellow colorant was combined with the red colorant and further the dispersants belonging to the polymer having the constituent unit represented by the general formula (I) were combined, were excellent in viscosity stability. On the other hand, it was found that the colorant dispersion of comparative example 1, in which a conventional yellow colorant and a urethane-based dispersant were combined with a red colorant, had poor viscosity stability. Further, it was revealed that the colorant dispersion of comparative example 2, in which the urethane-based dispersant was combined, had poor viscosity stability even when the specific yellow colorant was combined with the red colorant.

The colorant dispersions of comparative examples 3 to 7, in which the conventional yellow colorant was combined with the red colorant, exhibited poor viscosity stability even when the dispersant belonging to the polymer having the constituent unit represented by the general formula (I) was used.

It was found that the color resin compositions for color filters of examples 1 to 48, in which the specific yellow colorant was combined with the red colorant and the dispersant which was a polymer having a constituent unit represented by the general formula (I), were further combined, were excellent in the dispersion stability of the colorant, and the phase difference value of the colored layer using the color resin composition was reduced, and the contrast was excellent. It is apparent that the colored layers of the colored resin compositions of examples 1 to 48, which have excellent adhesion to SiN, were used, and that the colored layers of the colored resin compositions of examples 11, 44, 45, 46, and 48, which have excellent adhesion to SiN, were used. In addition, the adhesion to SiN of example 10 was a close to AA, and was good.

On the other hand, comparative examples 1 and 3 to 7, in which colorants different from those of the examples were combined, had a difference in average contrast and a difference in phase, as compared with the examples having the same chromaticity coordinates (x, y).

Even when the specific yellow colorant is combined with the red colorant, the comparative example 2 in which the urethane-based dispersant is combined has a larger contrast difference and a larger phase difference than the example in which the same chromaticity coordinates (x, y) are used.

In comparative examples 1, 3 to 7, the P/V ratio of the colored resin composition tends to be larger than that of the examples having the same chromaticity coordinates (x, y), and the adhesion to SiN is also poor.

In comparative example 1, the solvent resolubility, the inhibition of development residues, the development resistance, and the water bleeding were also inferior to those of the examples having the same chromaticity coordinates (x, y).

In the examples where the alkali-soluble resin contains both a maleimide structure having a hydrocarbon ring and a styrene structure and an antioxidant is added, it is clear that a colored layer is formed which suppresses development residues and improves brightness.

Further, it was found that when 2 kinds of oxime ester photoinitiators are used in combination with an antioxidant, a colored layer having improved development resistance and brightness is formed. Among them, from the viewpoint of excellent brightness, it is preferable to use an oxime ester photoinitiator having a fluorene skeleton in combination with an oxime ester photoinitiator having diphenyl sulfide, and from the viewpoint of an improved water penetration inhibition effect, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton in combination with an oxime ester photoinitiator having diphenyl sulfide.

In example 44 in which a hindered phenol antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per 1 phenolic hydroxyl group was used, a colored layer having a reduced phase difference and improved brightness was formed. In example 44, a colored layer with a contrast close to AA and improved contrast was obtained.

In example 45 using a latent antioxidant, a colored layer having a reduced phase difference value, a contrast similar to that of AA, and an improved contrast was obtained.

In example 46 using an ultraviolet absorber, a colored layer having a reduced phase difference value, a contrast similar to that of AA, and an improved contrast was obtained.

In example 48 in which an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having diphenyl sulfide were used in combination, and a hindered phenol antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per 1 phenolic hydroxyl group and an ultraviolet absorber were used in combination, a colored layer having a reduced phase difference, improved brightness, and improved water penetration inhibition effect was formed. In example 48, a colored layer with a contrast also close to AA and a contrast also improved was obtained.

Symbol description

1, A substrate;

2, a shading part;

3a coloring layer;

A color filter 10;

20 a counter substrate;

30 liquid crystal layer;

40 a liquid crystal display device;

50 an organic protective layer;

60 inorganic oxide film;

71 a transparent anode;

72 a hole injection layer;

73 hole transport layer;

74 a light emitting layer;

75 electron injection layer;

76 cathode;

An 80 organic light emitter;

100 organic light emitting display device.

Claims

1. A colored resin composition for color filters, which contains a colorant, a dispersant, a binder component and a solvent, wherein,

The colorant comprises a red colorant and a yellow colorant;

the dispersant is a polymer having a constituent unit represented by the following general formula (I);

the colored resin composition for a color filter further contains an antioxidant;

General formula (A)

In the general formula (A), R ^a is independently-OH, -NH ₂, -NH-CN, acylamino, alkylamino or arylamino, R ^b are each independently-OH or-NH ₂;

General formula (B)

In the general formula (B), R ^c is independently a hydrogen atom or an alkyl group;

In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a 2-valent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group optionally containing a hetero atom, and R ² and R ³ are optionally bonded to each other to form a ring structure.

2. The colored resin composition for a color filter according to claim 1, wherein,

The red colorant contains at least 1 selected from the group consisting of diketopyrrolopyrrole pigments, naphthol azo pigments, anthraquinone pigments, and perylene pigments.

3. The colored resin composition for a color filter according to claim 1 or 2, wherein,

At least 2 metals in the yellow colorant contain Ni and at least 1 metal selected from the group consisting of Cd, co, al, cr, sn, pb, zn, fe, cu and Mn.

4. The colored resin composition for a color filter according to claim 1 or 2, wherein,

At least 2 metals in the yellow colorant are Ni and Zn, or Ni and Cu.

5. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The binder component comprises an alkali-soluble resin, a multifunctional monomer and a photoinitiator,

The photoinitiator is an oxime initiator.

6. The colored resin composition for color filters according to claim 1 or 2, which is capable of forming a cured film having chromaticity coordinates in the XYZ color system of JIS Z8701, which is measured by using a C light source, in the range of x=0.550 to 0.700 and y=0.290 to 0.450.

7. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The antioxidant contains at least one of a hindered phenol-based antioxidant and a latent hindered phenol-based antioxidant.

8. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The antioxidant contains a hindered phenol antioxidant having a molecular weight of 1000 or less and a molecular weight of 280 equivalents or less per 1 phenolic hydroxyl group.

9. The colored resin composition for a color filter according to claim 1 or 2, further comprising an ultraviolet absorber.

10. The colored resin composition for a color filter according to claim 1 or 2, further comprising an ultraviolet absorber which is a benzotriazole-based compound, a benzophenone-based compound, or a triazine-based compound.

11. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The photoinitiator contains 2 oxime initiators.

12. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The solvent contains a glycol ether acetate solvent as a first solvent and a solvent having an alcoholic hydroxyl group as a second solvent.

13. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The crystal growth of the red colorant and the yellow colorant is inhibited by the interaction between the red colorant and the yellow colorant.

14. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The red colorant is contained in an amount of 40 to 98 mass% and the yellow colorant is contained in an amount of 2 to 60 mass% relative to the total amount of the colorants.

15. The colored resin composition for a color filter according to claim 1 or 2, wherein,

The red colorant is more than 1 selected from the group consisting of C.I. pigment red 254, C.I. pigment red 264, C.I. pigment red 272, diketopyrrolopyrrole pigment represented by the following chemical formula (2), C.I. pigment red 242, C.I. pigment orange 38, C.I. pigment red 177 and C.I. pigment red 179,

Chemical formula (2)

16. The colored resin composition for a color filter according to claim 15, wherein,

The red colorant is a combination of c.i. pigment red 254 and diketopyrrolopyrrole pigment represented by the above chemical formula (2), brDPP and c.i. pigment red 177.

17. A color filter comprising at least a substrate and a coloring layer provided on the substrate,

At least 1 of the colored layers is a cured product of the colored resin composition for a color filter according to any one of claims 1 to 16.

18. A display device characterized by having the color filter according to claim 17.