JP2012078409A - Blue pigment dispersion liquid for color filter, blue photosensitive resin composition for color filter, color filter, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue pigment dispersion liquid for a color filter capable of having a desired chromaticity by improving visibility in an oblique direction of a blue coloring layer, to provide a blue photosensitive resin composition for a color filter capable of having the desired chromaticity by improving the visibility in the oblique direction of the blue coloring layer, to provide a color filter formed by using the photosensitive resin composition, and to provide a liquid crystal display device having this color filter.SOLUTION: The blue pigment dispersion liquid for the color filter is a pigment dispersion liquid containing at least a pigment, a pigment dispersant and a solvent. The pigment contains at least C.I. Pigment Blue 15:6 and C.I. Pigment Violet 19. The blue photosensitive resin composition for the color filter contains a binder component in a component of the pigment dispersion furthermore.

Description

  The present invention relates to a blue pigment dispersion for a color filter, a blue photosensitive resin composition for a color filter, a color filter, and a liquid crystal display device.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. In recent years, the penetration rate of home-use liquid crystal televisions has been increasing, and the market for liquid crystal displays is expanding. Furthermore, with regard to the performance of the liquid crystal display, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Under such circumstances, there is an increasing demand for higher brightness, higher contrast, and improved color reproducibility even in a color filter having a function of displaying liquid crystal displays in color.

A liquid crystal display device has a problem of viewing angle dependency due to refractive index anisotropy of a liquid crystal cell or a polarizing plate as a specific problem. This problem of viewing angle dependency is a problem that the color and contrast of an image that is visually recognized change when the liquid crystal display device is viewed from the front and when viewed from an oblique direction. Such a problem of viewing angle characteristics has become more serious as the liquid crystal display device has recently been enlarged.
In order to improve such a viewing angle dependency problem, a method of incorporating a retardation film into a liquid crystal display device has been widely used. However, since the color filter used in the liquid crystal display device has a different phase difference depending on the color pattern of each color of the colored layer, when the above-described retardation film is used, the difference in the phase difference of the color pattern of each color is compensated. It is difficult to completely solve the problem of viewing angle dependency.

In order to compensate for the difference in retardation of the colored patterns of the respective colors, Patent Document 1 discloses a method of forming a retardation layer having an optimal retardation by an ink jet method using the colored patterns of the colored layers of the color filter. It is disclosed. In Patent Document 2, the overcoat layer formed to cover the colored layer is made of a material having retardation in the thickness direction, and the thickness of the colored pattern of each color of the colored layer and the laminated portion of the overcoat layer A technique is disclosed in which the thickness of each overcoat layer is different so that the retardation in the direction is uniform. However, these methods have a problem that the process becomes complicated because it is necessary to form a retardation layer or an overcoat layer having a different thickness on the colored pattern of each color.
Therefore, recently, in order to improve the problem of the viewing angle dependency of the liquid crystal display, it is required to make the phase difference value of each colored layer itself close to zero also in the color filter.

Patent Document 3 discloses a coloring composition for a color filter that can improve visibility in an oblique direction. In Patent Document 3, as a retardation adjusting agent, an organic compound selected from one or more selected from an organic compound having a planar structure group having one or more crosslinkable groups, a melamine compound, a porphyrin compound, and a polymerizable liquid crystal compound Is used to reduce the retardation difference for each color.
However, in Patent Document 3, the retardation can be controlled in the positive direction by the retardation adjusting agent, but cannot be controlled in the negative direction. I. It was difficult to bring the retardation value close to zero for pigments having a positive birefringence such as CI Pigment Blue 15: 6.
In Patent Document 4, the color filter colored layer has an average refractive index in a specific range, and an absolute value of the birefringence is 0.01 or less, so that display characteristics are excellent. It is described that a liquid crystal display device can be obtained. In Patent Document 4, attention is paid to a polymer that is a film forming component of the colored layer, and a polymer having a planar structure group such as a fluorene group in the side chain is contained, or a birefringence index that is positive and negative with respect to the polymer. The birefringence-reducing particles having a low birefringence are included.

JP 2007-279448 A JP 2010-160345 A JP 2008-185984 A JP 2000-136253 A

  The present invention has been made under such circumstances, and a blue pigment dispersion for a color filter capable of improving visibility in an oblique direction while suppressing a change in chromaticity of a blue colored layer, and blue coloring Blue photosensitive resin composition for color filter capable of improving visibility in oblique direction while suppressing change in chromaticity of layer, color filter formed using the photosensitive resin composition, and this color filter An object of the present invention is to provide a liquid crystal display device having

As a result of intensive studies to achieve the above object, the present inventors have found that C.I. I. Pigment blue 15: 6 and C.I. I. It was found that by combining the pigment violet 19, a pigment dispersion and a photosensitive resin composition capable of improving visibility in an oblique direction while suppressing a change in chromaticity were obtained.
The present invention has been completed based on such findings.

  That is, the blue pigment dispersion for a color filter according to the present invention is a pigment dispersant containing at least a pigment, a pigment dispersant, and a solvent, and the pigment contains at least C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Violet 19 is included.

  The blue photosensitive resin composition for a color filter according to the present invention is a photosensitive resin composition containing at least a pigment, a pigment dispersant, a photosensitive binder component, and a solvent. , At least C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Violet 19 and the like.

  In the blue pigment dispersion for color filter according to the present invention and the blue photosensitive resin composition for color filter according to the present invention, the pigment further contains C.I. I. It is preferable that the pigment violet 23 is included from the viewpoint of achieving the above object and further achieving a high luminance requirement.

  In the blue pigment dispersion for a color filter according to the present invention and the blue photosensitive resin composition for a color filter according to the present invention, the pigment dispersant includes a repeating unit (1) represented by the following general formula (I) and the following: It is a block copolymer having a repeating unit (2) represented by the general formula (II) and in which at least a part of the amino group of the repeating unit (1) and an organic acid compound form a salt. However, the pigment dispersibility and dispersion stability are improved, high brightness and high contrast can be achieved, and excellent alkali developability can be obtained.

[In Formula (I) and Formula (II), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 4} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R 6)} -CH It is a monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, It is a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]

  In the blue pigment dispersion for a color filter according to the present invention and the blue photosensitive resin composition for a color filter according to the present invention, the organic acid compound in the pigment dispersant is represented by the following general formula (III) and the following general formula: Being at least one selected from the group consisting of organic acids represented by the formula (IV) can further improve pigment dispersibility and dispersion stability, achieve high brightness and high contrast, and From the viewpoint that excellent alkali developability can be obtained.

[In Formula (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, 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. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]

  In the blue pigment dispersion for a color filter according to the present invention and the blue photosensitive resin composition for a color filter according to the present invention, the inclusion of an alkali-soluble resin improves pigment dispersibility and dispersion stability, It is preferable in terms of brightness, high contrast, and excellent alkali developability.

Further, the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers comprises the blue photosensitive resin composition for a color filter of the present invention. Provided is a color filter having a colored layer formed by curing.
Furthermore, the present invention provides a liquid crystal display device comprising the color filter, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

ADVANTAGE OF THE INVENTION According to this invention, the blue pigment dispersion liquid for color filters which can improve the visibility of a diagonal direction can be provided, suppressing the change of chromaticity of a blue colored layer.
ADVANTAGE OF THE INVENTION According to this invention, the blue photosensitive resin composition for color filters which can improve the visibility of a diagonal direction can be provided, suppressing the change of chromaticity of a blue colored layer.
By using the photosensitive resin composition of the present invention, visibility in an oblique direction is improved, and a color filter including a blue colored layer having a desired chromaticity can be provided.
Furthermore, according to this invention, the liquid crystal display device by which the visibility of the diagonal direction was improved can be provided by using the said color filter provided with the blue colored layer.

It is the schematic which shows an example of the color filter of this invention. It is the schematic which shows an example of the liquid crystal display device of this invention.

Hereinafter, the blue pigment dispersion for color filters, the blue photosensitive resin composition for color filters, the color filter, and the liquid crystal display device of the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.
In the present invention, as the retardation of the colored layer, retardation in the thickness direction (Rth) calculated by the following formula was used as an index.
Rth = ((Nx + Ny) / 2−Nz) d
nx: Refractive index in the in-plane slow axis direction ny: Refractive index in the in-plane fast axis direction nz: Refractive index in the thickness direction d: Film thickness (nm)
In addition, C.I. I. Pigment Blue “PB” and C.I. I. Pigment Violet may be abbreviated as “PV”.

1. Blue pigment dispersion for color filter The blue pigment dispersion for a color filter according to the present invention is a pigment dispersant containing at least a pigment, a pigment dispersant, and a solvent, and the pigment contains at least C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Violet 19 is included.

  The color filter manufactured using the pigment dispersant of the present invention contains PB15: 6 and PV19 in the pigment to reduce the phase difference in the film thickness direction of the color filter or to a desired value. Can be adjusted.

The action of exerting the above-described effects by containing the specific pigment is estimated as follows.
The polymer film generally has a phase difference in the film thickness direction. The same applies to a color filter manufactured by curing a pigment dispersant, but the phase difference in the film thickness direction increases or decreases depending on the type and concentration of the pigment contained.
The inventors of the present invention have proposed that the value of the retardation (Rth) when the colored layer is formed is the Rth when the colored layer is formed by combining the main pigment that realizes chromaticity and a pigment that is positive and negative as a sub-pigment. It was conceived that the absolute value of the colored layer was brought close to zero or made negative by offsetting.
According to the present invention, PV19 whose Rth value shifts to the negative side when the colored layer is formed is selected and combined with PB15: 6, and the content of PV19 is adjusted to reduce the Rth of the colored layer to zero. Or it can be brought close to a desired value.

The blue pigment dispersion for color filters of the present invention contains at least C.I. I. Pigment blue 15: 6 and C.I. I. It contains a pigment containing Pigment Violet 19, a pigment dispersant, and a solvent as essential components, and may contain other components as necessary.
Hereinafter, each component of the blue pigment dispersion of the present invention will be described in detail in order.

1.1. C. Pigment used in the present invention I. Pigment Blue 15: 6 is ε-type copper phthalocyanine having a structure represented by the following chemical formula.

  In addition, C.I. I. Pigment Violet 19 is a β-type unsubstituted quinacridone having a structure represented by the following chemical formula.

  In the present invention, the content ratio of PB15: 6 and PV19 is appropriately adjusted within a range in which Rth when the colored layer is formed is a desired value, and is not particularly limited. For example, 100 parts by weight of PB15: 6 is used. When used, PV19 can be used in an amount of 1 to 30 parts by weight. Furthermore, with respect to PB15: 6, 100 parts by weight, PV19 is preferably used in a proportion of 3 to 25 parts by weight, particularly preferably in a proportion of 5 to 20 parts by weight. This is because, within this range, Rth can be adjusted to a desired value without greatly reducing the luminance.

C. used in the present invention. I. The average primary particle size of pigments such as CI Pigment Red 15: 6 is not particularly limited as long as it can produce a desired color when used as a colored layer of a color filter, and varies depending on the type of pigment used. Is preferably in the range of 10 to 70 nm, and more preferably in the range of 10 to 50 nm. When the average primary particle size of the pigment is in the above range, the blue pigment dispersion for color filter of the present invention and a liquid crystal display device produced using the photosensitive resin composition have high contrast and high quality. can do.
In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

The average dispersed particle size of the pigment in the pigment dispersion varies depending on the type of pigment used, but is preferably in the range of 10 to 70 nm, and more preferably in the range of 10 to 50 nm.
The average dispersed particle size of the pigment in the pigment dispersion is a dispersed particle size of pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. For particle size measurement with a laser light scattering particle size distribution meter, the pigment dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times, etc.) It can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.

  C. used in the present invention. I. Pigment blue 15: 6 and C.I. I. Pigment violet 19 can be produced by a known method such as a recrystallization method or a solvent salt milling method. In addition, commercially available C.I. I. Pigment Blue 15: 6 (for example, Chromofine Blue5201A, manufactured by Dainichi Seika Kogyo Co., Ltd.) and commercially available C.I. I. Pigment Violet 19 (for example, trade name: Hostaperm Red Violet ERX, manufactured by Clariant, etc.) may be used after milling.

In the blue pigment dispersion for color filter of the present invention, other pigments may be used as long as the chromaticity required for the specification can be achieved and the effects of the present invention are not impaired. Examples of other pigments include other blue pigments and purple pigments.
The content ratio of other pigments is appropriately adjusted and is not particularly limited. However, when PB15: 6 is 100 parts by weight, the total of other pigments (including other pigments and pigment derivatives described later) The total) can usually be used at 30 parts by weight or less, preferably 20 parts by weight or less.

  Examples of other blue pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Blue 80.

  Examples of other purple pigments include C.I. I. Pigment violet 1, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;

  Among them, C.I. I. It is preferable that the pigment violet 23 is contained in that the Rth value is brought close to zero and the high luminance requirement is satisfied.

  Note that C.I. used in the present invention. I. Pigment Violet 23 has a structure represented by the following chemical formula.

  In the present invention, the content ratio of PB15: 6 and PV23 is not particularly limited as long as sufficient luminance can be secured when the colored layer is formed. For example, when PB15: 6 is 100 parts by weight, PV23 is 1 -10 parts by weight can be used. Furthermore, it is preferable to use PV19 in a ratio of 1 to 30 parts by weight, particularly preferably in a ratio of 5 to 15 parts by weight with respect to PB15: 6, 100 parts by weight. This is because a high luminance requirement can be satisfied within this range.

  In the blue pigment dispersion for color filter of the present invention, C.I. I. Pigment blue 15: 6 and C.I. I. The content of the pigment violet 19 may be adjusted as appropriate, and is not particularly limited. Usually, C.I. I. Pigment blue 15: 6 and C.I. I. The content of the pigment containing Pigment Violet 19 is preferably in the range of 5 to 40% by weight, more preferably 10 to 20% by weight, based on the total amount of the blue pigment dispersion for color filters.

1.2. Pigment Dispersant The pigment dispersant used in the present invention is blended in the pigment dispersion in order to disperse the above pigments satisfactorily.
The pigment dispersant is not particularly limited, and for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.
The content of the pigment dispersant is not particularly limited as long as the pigment can be uniformly dispersed. For example, 10 to 150 parts by weight can be used with respect to 100 parts by weight of the pigment. Furthermore, it is preferable to mix | blend in the ratio of 15-80 weight part with respect to 100 weight part of pigments, and it is preferable to mix | blend especially in the ratio of 15-50 weight part.
In addition, in this invention, the pigment derivative at the time of prescribing | regulating content contains the pigment derivative which may be contained besides a pigment.

  Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diaminoethane, 1 , 4-bis (2-hydroxyethyl) piperazine and amines having a hydroxy group such as 1- (2-hydroxyethyl) piperazine, and the like, and other compounds such as nipecotamide, isonipecotamide, and nicotinamide are listed. be able to.

  Further, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Acid salts; amides obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyester, salts thereof, and the like can be mentioned.

  Among them, as the pigment dispersant used in the present invention, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (parts) of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid Amine salts, (partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides Polysiloxanes; long-chain polyaminoamide phosphates; amides obtained by the reaction of poly (lower alkylene imines) and free carboxyl group-containing polyesters and salts thereof can be dispersed in non-aqueous systems (solvent systems). It is preferable because it is a dispersant that can utilize effective steric hindrance and acid-base adsorption.

  Among these, the pigment dispersant used in the present invention has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), The block copolymer in which at least a part of the amino group of the repeating unit (1) and an organic acid compound form a salt improves the pigment dispersibility and dispersion stability of the pigment dispersion, and increases the brightness. And high contrast can be achieved, and excellent alkali developability can be achieved.

[In Formula (I) and Formula (II), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 4} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R 6)} -CH It is a monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, It is a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]
The block copolymer that is preferably used as the pigment dispersant of the present invention will be described below.

1.2.1. Block copolymer The block copolymer, which is preferably used as a pigment dispersant, is a salt-type block copolymer in which at least a part of an amino group and an organic acid compound form a salt. The structural unit (1) to be formed has a high adsorptivity to a pigment which is a component insoluble in the solvent due to a decrease in solubility in the solvent due to salt formation, while the structural unit (2) is By having solubility in the solvent, the pigment can be stabilized in the solvent, and as a result, the dispersibility and stability of the pigment can be improved.
Moreover, since the salt formation site | part formed with an organic acid compound has high solubility with respect to the aqueous alkali solution at the time of alkali image development, it can be made excellent in alkali developability. Therefore, when a color filter is produced using the blue photosensitive resin composition for a color filter containing the block copolymer, the alkali development time can be shortened and the productivity is excellent. be able to. Moreover, the high quality color filter with few residues of the blue photosensitive resin composition for color filters in an unexposed location can be obtained by being excellent in alkali developability.

The block copolymer has a repeating unit (1) represented by the general formula (I) and a repeating unit (2) represented by the general formula (II).
In the said general formula (I), R < ¹ > shows a hydrogen atom or a methyl group, R < ² > and R < ³ > show a hydrogen atom or a C1-C8 alkyl group each independently. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
R ² and R ³ may be the same as or different from each other.

A is an alkylene group having 1 to 8 carbon atoms, * — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — **, or * — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — ** is a divalent group. Here, * represents a linking site on the ester bond side, and ** represents a linking site on the amino group side. The alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various kinds. Hexylene group and various octylene groups.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more 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. is there. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2. In the present invention, when x, y, and z are within the above ranges, the blue pigment dispersion for color filter of the present invention has excellent pigment dispersibility.
As said A, a C1-C8 alkylene group is preferable and a methylene group and ethylene group are more preferable. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

In the general formula (II), R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (R ⁷ ) —. O] _x -R ⁸ or - indicates a _{[(CH 2) y -O]} z -R 8.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, cyclohexane Examples include an octyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, various butenyl, various hexenyl, various octenyl, various decenyl, various dodecenyl, various tetradecenyl, various hexadecenyl, various octadecenyl, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that there is a double bond at the terminal of the alkenyl group.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

R ⁶ and R ⁷ are the same as described above, and R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aralkyl group. , An aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , wherein R ⁹ is a hydrogen atom or a linear, branched, or cyclic group having 1 to 5 carbon atoms. It is an alkyl group.
In the monovalent group represented by R ⁸ , the substituent that may be included is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a halogen atom such as F, Cl, or Br. And so on.
The alkyl group having 1 to 18 carbon atoms of ^{R 8,} and alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the ^{R 4.}
In the above R ⁴ , x, y and z are as described in A above.
Moreover, R ⁴ in the repeating unit (2) represented by the general formula (II) may be the same as or different from each other.

As the R ⁴ , it is preferable to use one having excellent solubility with a solvent described later, and specifically, although it varies depending on the repeating unit constituting the block copolymer, the solvent is In the case of using ether alcohol acetate type, ether type and ester type solvents generally used as color filter solvents, methyl group, ethyl group, n-butyl group, 2-ethylhexyl group, benzyl Groups and the like are preferred.

Here, the reason for setting R ⁴ in this way is that the repeating unit (2) containing R ⁴ has high solubility in the solvent, and the amino group of the repeating unit (1) The dispersibility and stability of the pigment should be particularly excellent when the salt forming site formed by the organic acid compound and / or halogenated hydrocarbon described later has high adsorptivity to the pigment. Because you can.

Further, R ⁴ is substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group as long as it does not interfere with the dispersion performance of the block copolymer. Alternatively, after the synthesis of the block copolymer, the substituent may be added by reacting with the compound having the substituent. Moreover, after synthesizing a block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting a block copolymer having a carboxyl group with glycidyl (meth) acrylate, or reacting a block copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can do.

  The ratio m / n of the unit number m of the structural unit (1) and the unit number n of the structural unit (2) in the block copolymer is preferably in the range of 0.01 to 1, More preferably, it is in the range of 05 to 0.5. When the ratio m / n is within the above range, the adsorptivity to the pigment is good, the solubility with the solvent by the structural unit (2) is not lowered, and the dispersibility and stability of the pigment are lowered. There is nothing to do.

Regarding the molecular size of the block copolymer, the number m of the repeating unit (1) is an integer of 3 to 200, preferably an integer of 3 to 50. The number n of the repeating units (2) is an integer of 10 to 200, preferably an integer of 20 to 100, more preferably an integer of 20 to 70. In the present invention, when m and n are within the above ranges, the solvent-soluble part and the solvent-insoluble part effectively act, and the blue pigment dispersion for color filter of the present invention is made dispersible in pigment. It can be excellent.
Further, the weight average molecular weight Mw of the block copolymer is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 15000, and further preferably in the range of 3000 to 12000. preferable. By being within the above range, it becomes possible to achieve both wettability and dispersion stability with respect to a pigment in the initial stage of dispersion in which the pigment is uniformly dispersed.

  The weight average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

  The binding order of the block copolymer is not particularly limited as long as it has the repeating unit (1) and the repeating unit (2) and can stably disperse the pigment. The unit (1) is preferably bonded to only one end of the block copolymer. That is, the repeating unit (1) and the repeating unit (2) may be bonded in the order of repeating unit (1) -repeating unit (2), or repeating unit (1) -repeating unit. (2) -repeated unit (1) may be bonded in this order, or repeating unit (1) -repeating unit (2) may be bonded repeatedly, but in the present invention, However, those bonded in the order of repeating unit (1) -repeating unit (2) are preferred. The reason is that it is excellent in the adsorptivity with respect to a pigment, and also the aggregation of pigment dispersants using such a block copolymer can be effectively suppressed.

  In the case where two or more structural units (1) and structural units (2) are included, a block copolymer in which the structural units (1), the structural units (2 ′), and the structural units (2 ″) are combined in this order, A block copolymer bonded in the order of structural unit (1 ')-structural unit (1 ")-structural unit (2), or structural unit (1')-structural unit (1")-structural unit (2 ') -The block copolymer etc. which couple | bonded in order of the structural unit (2 ") may be sufficient.

1.2.2. Organic Acid Compound As the organic acid compound that forms a salt with the amino group of the structural unit (1) constituting the block copolymer, an organic phosphoric acid compound having a structure represented by the following chemical formula (III) and And / or an organic sulfonic acid compound having a structure represented by the following general formula (IV).

[In Formula (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, 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. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]

  In the block copolymer, by using the organic acid compound, the pigment dispersant can be made excellent in pigment dispersibility and stability. Furthermore, when an organic acid compound is used, the salt-forming site has high solubility in an alkaline aqueous solution at the time of alkali development, so that a photosensitive resin composition excellent in alkali developability can be obtained. .

In the general formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, or — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} , R ^a and R ^a Any of ^' includes carbon atoms.

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aryl group, and the aralkyl group are as described for R ⁴ . The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that the alkenyl group has a double bond at the terminal.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, nitro groups, and the like.
In addition, examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include alkenyl groups, nitro groups, and halogen atoms in addition to linear or branched alkyl groups having 1 to 4 carbon atoms. .

R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, 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. , —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^f , and R ^f is a hydrogen atom or It is a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.

In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, linear 1 to 4 carbon atoms, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
Alkyl group having 1 to 18 carbon atoms of the above ^{R e} is as shown by ^{R 4} above, an alkenyl group, an aralkyl group having 2 to 18 carbon atoms, an aryl group, said ^{R a} and R ^{a '} It is as shown in.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. R ^a ″ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R. ^e is a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above ^{R a} and R ^{a '.} In addition, when R ^{a ″} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.

In R ^a , R ^{a ′} and R ^{a ″} , s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. s is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

In the general formula (IV), R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —. _O] s ^-R _e, - shows a _{[(CH 2) t -O]} u -R e, or -O-R ^{b '.}
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above ^{R a} and R ^{a '.}

When R ^b is —O—R ^b ′, it becomes an acidic sulfate. R ^b ′ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
In R ^b and R ^b ′, each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R c)} -CH (R d) -O] s -R e, - [(CH ₂ ) _t— O] _u —R ^e is as described above for R ^a , R ^a and R ^{a ″} .
R ^c , R ^d, and R ^e are as described for R ^a , R ^{a ′,} and R ^{a ″} .
In said ^Rb and ^Rb ', s is an integer of 1-18, t is an integer of 1-5, u is an integer of 1-18. Preferred s, t, and u are the same as R ^a , R ^{a ′,} and R ^{a ″} described above.

As the organic acid compound represented by the general formula (III), R ^a and R ^{a ′} in the general formula (III) each independently have a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or a substituent. Aryl group or aralkyl group, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{a ″} , one of R ^a and R ^{a ′} contains a carbon atom, and R ^{a ″} is a methyl group, ethyl Group, aryl group or aralkyl group which may have a substituent, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) and _{^{t -O] u -R e, R}} c and ^{R d} are each independently a hydrogen atom or a methyl group Ri, from the viewpoint of can be made of those ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) a = CH ₂ is excellent in pigment dispersibility.

Moreover, as an organic acid compound represented by general formula (IV), ^Rb in general formula (IV) is a methyl group, an ethyl group, the aryl group which may have a substituent, an aralkyl group, a vinyl group. , An allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{b ′} R ^{b ′} is a methyl group, an ethyl group, an aryl group or an aralkyl group optionally having a substituent, a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , wherein R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e In which —CO—CH═CH ₂ or —CO—C (CH ₃ ) ═CH ₂ has excellent pigment dispersibility It is preferable from the point which can be made.

Of these, organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' From the viewpoint of pigment dispersibility, an aromatic ring is preferred. At least one of R ^a , R ^{a ′} and R ^{a ″} , or R ^b or R ^{b ′} , an aryl group or aralkyl group which may have a substituent, more specifically, a benzyl group, A phenyl group, a tolyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of pigment dispersibility. In the general formula (III), when one of R ^a and R ^{a ′} has an aromatic ring, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

From the viewpoint of heat resistance and chemical resistance, the organic acid compound represented by the above general formula (III) and general formula (IV) has a carbon atom directly bonded to phosphorus (P) or sulfur (S). R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , a monovalent group represented by R ^a and R ^{a ′} Either preferably contains a carbon atom. R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. , — [(CH ₂ ) _t —O] _u —R ^e is preferably a monovalent group.

The organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' Has a polymerizable group, that is, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u. It is preferable that -R ^e and R ^e is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , especially R ^a , R ^{a ′} and / or R ^{a ′. '} And / or R ^b and / or R ^b' are preferably vinyl, allyl, 2-methacryloyloxyethyl, or 2-acryloyloxyethyl.
In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the color filter of the present invention are exposed during exposure when forming a colored layer using the photosensitive resin composition for a color filter of the present invention. Can be easily polymerized with an alkali-soluble resin, a polyfunctional monomer, and the like contained in the photosensitive resin composition, and the pigment dispersant can be stably present in the colored layer of the color filter. To do. When a liquid crystal display device is manufactured using such a color filter, the pigment dispersant can be prevented from bleeding out to the liquid crystal layer or the like.

  In addition, since the organic acid compound contains a polymerizable group, the polymerizable groups of the organic acid compound can be polymerized before being used for forming the colored layer, and as a result, the pigment dispersant has a high molecular weight. Therefore, the photosensitive resin composition for a color filter at an unexposed portion can be made particularly excellent in alkali developability during development for forming a colored layer.

  In addition, the organic acid compound represented by the said general formula (III) and general formula (IV) can be used individually by 1 type or in combination of 2 or more types.

  The content of the organic acid compound in the block copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited, and is generally represented by the general formula (I). 0.05-1.0 molar equivalent is preferable with respect to a tertiary amino group. Furthermore, the content of the organic acid compound is 0.2 to 0.8 mol with respect to the tertiary amino group from the viewpoint of excellent pigment adsorbing power, solubility in a solvent, pigment dispersibility and pigment dispersion stability. It is preferable that it is equivalent. In addition, when using 2 or more types of the said organic acid compound and / or halogenated hydrocarbon together, content which added these should just be in the said range.

1.2.3. Production method of the block copolymer In the present invention, the production method of the block copolymer preferably used as a pigment dispersant has the above repeating unit (1) and the repeating unit (2), and the above repeating unit. There is no particular limitation as long as it is a method that can produce a salt formed by the amino group of the unit (1) and the organic acid compound. In the present invention, for example, the repeating unit (1) and the repeating unit (2) are polymerized using a known polymerization means, and then dissolved or dispersed in a solvent described later, and then the organic acid is dissolved in the solvent. The pigment dispersant can be produced by adding the compound and stirring.

  The polymerization means is not particularly limited as long as it is a means capable of polymerizing the above repeating unit (1) and repeating unit (2) in a desired number to obtain a desired molecular weight, and has a vinyl group. A method generally used for polymerization of a compound can be employed, and for example, anionic polymerization, living radical polymerization, or the like can be used. In the present invention, among them, a method in which polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), is used. preferable. According to this method, the molecular weight, the molecular weight distribution, etc. can be easily set in a desired range, so that the dispersibility of the pigment dispersant can be made uniform.

  In the blue pigment dispersion for a color filter of the present invention, when the block copolymer is used as a pigment dispersant, one type of the block copolymer may be used, or two or more types may be used in combination.

1.3. Solvent The blue pigment dispersion for color filter according to the present invention contains a solvent for dispersing the pigment. The solvent used in the pigment dispersion is not particularly limited as long as it is an organic solvent that does not react with each component in the pigment dispersion and can dissolve or disperse them.
Examples of the solvent used in the pigment dispersion of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol, Carbitol solvents such as ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; methoxyethyl acetate , Propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxy Cellosolve acetate solvents such as til acetate and ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Ether solvents such as monomethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; benzene, toluene and xylene , Unsaturated hydrocarbon solvents such as naphthalene; saturated hydrocarbons such as N-heptane, N-hexane and N-octane Organic solvents such as system solvents can be mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; methyl methoxypropionate, ethoxypropionic acid Ester solvents such as ethyl and ethyl lactate; ketone solvents such as cyclohexanone are preferred Used. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, 3-methoxybutyl acetate and cyclohexanone is preferable from the viewpoints of solubility of other components and coating suitability.

These solvents may be used alone or in combination of two or more.
The pigment dispersion of the present invention is prepared by using the solvent as described above usually at a ratio of 60 to 85% by weight with respect to the total amount of the pigment dispersion containing the solvent. When the amount of the solvent is too small, the viscosity increases and the pigment dispersibility tends to decrease. Moreover, when there are too many solvents, a pigment density | concentration will fall and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

1.4. Other Components The pigment dispersion of the present invention may further contain a pigment derivative, a pigment dispersion auxiliary resin, and other components as necessary.
The pigment derivative is a compound having a role of imparting a functional group to the pigment skeleton and adding various functions to the pigment. When a pigment derivative is added to the pigment at the time of pigment dispersion, the pigment-like skeleton of the pigment derivative is adsorbed or bonded to the surface of the pigment, whereby the surface of the pigment becomes polar, so that the affinity between the dispersant and the pigment is increased. It is considered that the dispersibility and dispersion stability can be secured. When the pigment derivative is used in further combination, by combining the pigment derivatives within a range that does not impair the effect of the present invention, it is possible to cancel Rth when the colored layer is formed while achieving desired chromaticity. They are used in combination as appropriate.
As pigment dispersion auxiliary resin, the alkali-soluble resin illustrated with the photosensitive resin composition mentioned later is mentioned, for example. In some cases, the steric hindrance of the alkali-soluble resin makes it difficult for the pigment particles to come into contact with each other.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

1.5. Method for Producing Pigment Dispersion The pigment dispersion of the present invention is prepared by the above-described C.I. Pigment Blue 15: 6 and C.I. I. A step of dispersing a pigment containing pigment violet 19;
In the dispersion process, as a disperser for performing dispersion treatment, a roll mill such as a two-roll or a three-roll, a ball mill such as a ball mill or a vibration ball mill, a paint conditioner, a continuous disk type bead mill, a bead mill such as a continuous annular type bead mill, or the like. Can be mentioned. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.05 to 1.0 mm.

  Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of 0.5 to 5.0 μm after dispersion.

In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. For example, when a paint shaker is used so that the average dispersed particle diameter of the pigment is about 15 to 50 nm. Is preferably 5 to 50 hours from the viewpoint of realizing high contrast by refining the pigment.
In this way, a pigment dispersion having excellent pigment particle dispersibility is obtained. The pigment dispersion is used as a preliminary preparation for preparing a blue photosensitive resin composition for a color filter having excellent pigment dispersibility.

2. Blue photosensitive resin composition for color filter The blue photosensitive resin composition for a color filter according to the present invention comprises at least the blue pigment dispersion for a color filter according to the present invention and a photosensitive binder component. And

Since the blue photosensitive resin composition for a color filter according to the present invention contains the pigment dispersion according to the present invention, it is possible to improve the visibility of the blue colored layer in an oblique direction, and there is also a demand for high contrast. Achieved and excellent in alkali developability.
Hereinafter, components used in the blue photosensitive resin composition for a color filter of the present invention will be described.
In addition, about the component which can be contained in the blue pigment dispersion liquid for color filters which concerns on the said invention, since the thing similar to what was demonstrated in the location of the said pigment dispersion liquid can be used, description here is abbreviate | omitted. .

2.1. Photosensitive binder component In the present invention, from the viewpoint of imparting sufficient strength, durability, and adhesion to the coating film, after forming a pattern on the substrate by coating or transfer, the coating film is cured by a polymerization reaction. A binder component can be used. In addition to the photosensitive binder component described below, a thermosetting binder component that can be polymerized and cured by heating such as an epoxy resin may be further used. In preparing the resin composition according to the present invention using the pigment dispersion according to the present invention having excellent pigment dispersibility, it is necessary to appropriately select a binder component so as not to inhibit the excellent pigment dispersibility. is there.

The photosensitive binder component contains a photo-curable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, and the exposed portion is cured and the unexposed portion is dissolved and removed to dissolve and remove the uncoated portion. Negative-type photosensitive binder components that can be prepared.
In the blue photosensitive resin composition for a color filter according to the present invention, a negative photosensitive binder component is preferable because a pattern can be easily formed by an existing process by a photolithography method.

  A negative photosensitive binder component containing a photo-curable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams is composed of an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, a sensitizer, and the like. Configured.

2.1.1. Alkali-soluble resin The alkali-soluble resin in the present invention has a carboxyl group in the side chain, acts as a binder resin, and is used when forming a pattern, particularly preferably as long as it is soluble in an alkali developer. It can be appropriately selected and used.
A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the photosensitive resin composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photosensitive resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Examples of the acrylic copolymer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) Acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, disi Lopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2- Selected from hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, etc. 1 type or more and (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and dimer of acrylic acid (for example, Toagosei Chemical Co., Ltd. M -5600), itaconic acid, crotonic acid Maleic acid, fumaric acid, vinyl acetate, a copolymer consisting of one or more selected from these anhydrides can be exemplified. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by weight, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
Although it does not specifically limit as an epoxy compound, A bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, an aliphatic epoxy compound, or Examples thereof include epoxy compounds such as bisphenolfluorene type epoxy compounds. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

Acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendo Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polycarboxylic anhydrides such as ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, endobicyclo- [2 , 2,1] -Hept-5-ene-2,3-dica Polycarboxylic anhydride derivatives such as carbon anhydride, and the like. These may be used alone or in combination of two or more.
The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, but is preferably 1000 to 40000, more preferably 2000 to 5000.

2.1.2. Polyfunctional monomer Examples of the polyfunctional monomer in the present invention include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol ; Poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid modified products; polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins , Oligo (meth) acrylates such as spirane resin; both terminal hydrides such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone Examples include di (meth) acrylates of roxylated polymers; tris (2- (meth) acryloyloxyethyl) phosphate, and the like.

  Of these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. Succinic acid modified product of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) ) Succinic acid modified products of acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable. The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of alkali-soluble resin, Preferably it is 20-300 weight part. If the content of the polyfunctional monomer is less than the above range, the photocuring may not sufficiently proceed and the exposed part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability is lowered. there's a possibility that.

2.1.3. Photopolymerization initiator and sensitizer The negative photosensitive binder component usually contains a photopolymerization initiator having activity with respect to the wavelength of the light source used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction format of the polymer having photopolymerization and the photopolymerization monomer (for example, radical polymerization and cationic polymerization) and the kind of each material, and is not particularly limited.

The photopolymerization initiator is a compound that generates free radicals by the energy of ultraviolet rays, and is a biimidazole compound, benzoin compound, acetophenone compound, benzophenone compound, α-diketone compound, polynuclear quinone compound, xanthone Compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, oxime ester compounds, etc. Is mentioned.
For example, aromatic ketones such as benzophenone, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ethers, methylbenzoin, benzoin such as ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) ) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5- 2 amount of triarylimidazole 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Halomethyloxadiazole compounds such as styryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) ) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyrene Ryl-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphe Rusulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone , Isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 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- (methylthio) phenyl]- 2- (4-morpholinyl) -1-propanone and the like can be mentioned. These can be used alone or in combination.

  The content of the photoinitiator used in the blue photosensitive resin composition for a color filter of the present invention is usually about 0.01 to 100 parts by weight, preferably 5 to 60 parts per 100 parts by weight of the polyfunctional monomer. Parts by weight. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the colored layer may not have sufficient hardness. In some cases, the content of the pigment or the like in the solid content of the conductive resin composition is relatively reduced, and a sufficient coloring density cannot be obtained.

  Moreover, in this invention, 1 or more types chosen from the group of a sensitizer and a hardening accelerator can also be further used together with the said photoinitiator as needed. Specific examples of the sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4- Dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Etc. Specific examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4, Examples include chain transfer agents such as 6-dimethylaminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, and 3-mercapto-4-methyl-4H-1,2,4-triazole.

2.1.4. Optional Additive Component The blue photosensitive resin composition for a color filter of the present invention may contain various additives as necessary within a range that does not impair the object of the present invention. Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Among these, surfactants that can be used include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Examples include glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. In addition, a fluorosurfactant can also be used.
Furthermore, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

2.2. Mixing ratio of each component in the photosensitive resin composition The total pigment content is 10 to 50% by weight, more preferably 15 to 40% by weight, based on the total solid content of the photosensitive resin composition. It is preferable to do. If the amount of the pigment is too small, the transmission density when the photosensitive resin composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm) may not be sufficient. If the amount of the pigment is too large, the photosensitive property may be insufficient. There is a possibility that the properties as a coating film such as adhesion to the substrate when the resin composition is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness may be insufficient, and its photosensitivity. Since the ratio of the amount of the dispersant used for dispersing the pigment in the resin composition increases, characteristics such as developability and heat resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Further, the total content of the pigment dispersant is preferably in the range of 1 to 60% by weight, more preferably in the range of 5 to 50% by weight, based on the total solid content of the photosensitive resin composition. Preferably there is. If the content is less than 1% by weight relative to the total solid content of the photosensitive resin composition, it may be difficult to uniformly disperse the pigment. If the content exceeds 60% by weight, , There is a risk of lowering curability and developability.
The total amount of the alkali-soluble resin, polyfunctional monomer, and photoinitiator is blended in a proportion of 15 to 89% by weight, preferably 25 to 80% by weight, based on the total solid content of the photosensitive resin composition. Is preferred.
Further, the content of the solvent is not particularly limited as long as the colored layer can be accurately formed. Usually, it is preferably in the range of 65 to 95% by weight, more preferably in the range of 75 to 88% by weight, based on the total amount of the photosensitive resin composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

2.3. Production of Blue Photosensitive Resin Composition for Color Filter As a method for producing the photosensitive resin composition of the present invention, the pigment dispersion according to the present invention, other pigment dispersions, a photosensitive binder component, and if necessary Furthermore, the method of adding and mixing a solvent and various additive components can be mentioned.
As the pigment dispersion, a PB15: 6 pigment dispersion, a PV19 pigment dispersion, and, if necessary, a pigment dispersion of a different color are prepared as different pigment dispersions, respectively, and a photosensitive resin composition is prepared. You may mix at the time of preparation of a thing.
The blue photosensitive resin composition for a color filter of the present invention is preferable in that a pigment dispersion is produced and used in advance, so that aggregation of the pigment can be effectively prevented and dispersed uniformly.

Next, the color filter of the present invention will be described.
3. Color filter The color filter of the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is the blue light-sensitive for color filter of the present invention described above. It has a colored layer formed by curing a functional resin composition. By using the photosensitive resin composition of the present invention, the color filter of the present invention has improved visibility in the oblique direction, high brightness and high contrast, and the residue of the photosensitive resin composition in the unexposed areas. It is possible to provide a low-quality, high-productivity blue colored layer.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

3.1. Colored layer The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed by curing the above-described blue photosensitive resin composition for a color filter of the present invention. Depending on the type of pigment formed in the opening of the light-shielding part on the transparent substrate and contained in the blue photosensitive resin composition for color filters, it is composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
Although the thickness of the said colored layer is suitably controlled by adjusting the coating method, the solid content density | concentration of a photosensitive resin composition for color filters, a viscosity, etc., it is preferable normally that it is the range of 1-5 micrometers.

The colored layer can be formed, for example, by the following method.
First, the blue photosensitive resin composition for a color filter of the present invention described above is applied onto a transparent substrate described later using a coating means such as a spray coating method, a dip coating method, a bar coating method, a call coating method, or a spin coating method. Apply to form a wet coating.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. And a coating film of a blue photosensitive resin composition for a color filter. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the blue photosensitive resin composition for the color filter to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the photosensitive resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

3.2. Light-shielding part The light-shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light-shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y film (y is an arbitrary number) and three layers of Cr film may be laminated.
When the light-shielding part is a material in which a black colorant is dispersed or dissolved in a binder resin, the light-shielding part can be formed by any method that can pattern the light-shielding part, and is not particularly limited. For example, the photolithographic method using the photosensitive resin composition for light shielding parts, the printing method, the inkjet method etc. can be mentioned.

  In the above case, when a printing method or an inkjet method is used as a method for forming the light shielding portion, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxy Examples thereof include ethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin and the like.

  In the above case, when a photolithography method is used as a method for forming the light shielding portion, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the photosensitive resin composition for a light-shielding part containing a black pigment such as carbon black or titanium black as a pigment and a photosensitive resin. Sensitizers, coatability improvers, development improvers, crosslinking agents, polymerization inhibitors, plasticizers, flame retardants and the like may be added.

  On the other hand, when the light shielding part is a metal thin film, the method for forming the light shielding part is not particularly limited as long as the light shielding part can be patterned, and for example, photolithography, vapor deposition using a mask. Method, printing method and the like.

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.

3.3. Transparent substrate The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

Next, the liquid crystal display device of the present invention will be described.
4). Liquid crystal display device The liquid crystal display device of the present invention includes the above-described color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device 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 generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to 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.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Production Example 1 Synthesis of Binder Resin A)
A polymerization tank was charged with 130 parts by weight of diethylene glycol ethyl methyl ether (EMDG) as a solvent, heated to 110 ° C. in a nitrogen atmosphere, then 32 parts by weight of methyl methacrylate (MMA), 22 parts by weight of cyclohexyl methacrylate (CHMA). , 24 parts by weight of methacrylic acid (MAA), 2 parts by weight of azoisobutyronitrile (AIBN) as an initiator and 4.5 parts by weight of n-dodecyl mercaptan as a chain transfer agent, It was dripped continuously.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by weight of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, while blowing air, 22 parts by weight of glycidyl methacrylate (GMA) was added, the temperature was raised to 110 ° C., 0.2 parts by weight of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours to obtain a binder. Resin A (44 wt% solid content) was obtained.
The obtained binder resin A had a weight average molecular weight of 8,500 and an acid value of 85 mgKOH / g. The weight average molecular weight was calculated by gel permeation chromatography (GPC) using polystyrene as a standard substance and THF as an eluent, and the acid value was measured according to JIS-K0070.

(Production Example 2 Preparation of Dispersant Solution A)
In a 100 mL round-bottomed flask, 22.38 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), a repeating unit (1) represented by the above general formula (I) and a repeating unit represented by the above general formula (II) Block copolymer having a unit (2) (trade name: BYK-LPN6919, manufactured by Big Chemie) (weight average molecular weight 7800, amine number 130, solid content 60% by weight) 10.00 parts by weight, phenylphosphonic acid (product) Name: PPA (manufactured by Nissan Chemical Co., Ltd.) 0.59 parts by weight (0.3 molar equivalents relative to the amino group) is added, and the mixture is treated with ultrasonic waves for 15 minutes to form a partial salt having a solid content of 20%. Dispersant solution A, which is a copolymer-type dispersant, was used.
At this time, the amino group of the block copolymer (BYK-LPN6919) is partially salted by an acid / base reaction with the phosphonic acid group of PPA. The acid value of the resulting dispersant solution A was 71 mgKOH / g.

(Production Example 3 Preparation of Dispersant Solution B)
In a 100 mL round bottom flask, 21.94 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) is added with the repeating unit (1) represented by the general formula (I) and the repeating unit represented by the general formula (II). 10.00 parts by weight of a block copolymer having a unit (2) (trade name: BYK-LPN6919, manufactured by Big Chemie), 0.49 parts by weight of benzyl chloride (manufactured by Kanto Chemical Co., Ltd.) 3 mol equivalents) was added, and the mixture was stirred at 110 ° C. for 3 hours to form a dispersant solution B which is a block copolymer type dispersant in which a partial salt having a solid content of 20% was formed.
At this time, the amino group of the block copolymer (BYK-LPN6919) is partially salted by a quaternization reaction with benzyl chloride. The acid value of the obtained dispersant solution B was 0 mgKOH / g.

(Production Example 4 Preparation of PB15: 6 pigment dispersion A)
CI Pigment Blue 15: 6 refined PB15: 6: average primary particle size 20 to 40 nm) 3.90 parts by weight as a colorant component, Dispersant Solution A7.80 prepared in Production Example 2 as a pigment dispersant Part by weight, 3.54% by weight of the binder resin A prepared in Production Example 1 and 14.76 parts by weight of propylene glycol monomethyl ether acetate were mixed, and the mixture was shaken with a 2 mm zirconia bead for 1 hour and further with a 0.1 mm zirconia bead 6 Dispersion was carried out over time to obtain PB15: 6 pigment dispersion A having a pigment concentration of 13%. The bead filling rate in the vessel at the time of dispersion was 50%.

(Production Example 5 Preparation of PB15: 6 pigment dispersion B)
A PB15: 6 pigment dispersion B having a pigment concentration of 13% was obtained in the same manner as in Production Example 4, except that the dispersant solution A was changed to 7.80 parts by weight of the dispersant solution B prepared in Production Example 3. .

(Production Example 6 Preparation of PV19 Pigment Dispersion A)
CI Pigment Violet 19 (trade name: Hostaperm Red Violet ERX, manufactured by Clariant) as a coloring material component, and 5.25 parts by weight of the dispersant solution A prepared in Production Example 2 as a pigment dispersant. 1.43% by weight of binder resin A prepared in Example 1 and 21.22 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed in a paint shaker for 1 hour with 2 mm zirconia beads, and further for 12 hours with 0.1 mm zirconia beads. A PV19 pigment dispersion A having a pigment concentration of 7% was obtained. The bead filling rate in the vessel at the time of dispersion was 50%.

(Production Example 7 Preparation of PV19 pigment dispersion B)
A PV19 pigment dispersion B having a pigment concentration of 7% was obtained in the same manner as in Production Example 6 except that the dispersion solution A was changed to 5.25 parts by weight of the dispersion solution B prepared in Production Example 3 in Production Example 6.

(Production Example 8 Preparation of PV23 Pigment Dispersion A)
As in Production Example 6, the pigment concentration was 7% as in Production Example 6 except that the coloring material component was CI Pigment Violet 23 (trade name: Hostaper Violet RL-NF, manufactured by Clariant) 2.10 parts by weight. Of PV23 pigment dispersion A was obtained.

(Production Example 9 Preparation of PR209 Pigment Dispersion A)
As in Production Example 6, the pigment concentration was 7% as in Production Example 6 except that the colorant component was 2.10 parts by weight of CI Pigment Red 209 pigment (trade name: Hostaperm Red EG TRANSp, manufactured by Clariant). PR209 pigment dispersion A was obtained.

(Production Example 10 Preparation of PR202 Pigment Dispersion A)
In Production Example 6, the pigment concentration was 7 as in Production Example 6 except that the colorant component was CI Pigment Red 202 Pigment (trade name: Quindo Magenta 202 RV6853, manufactured by Sun Chemicals Co., Ltd.) 2.10 parts by weight. % PR202 pigment dispersion A was obtained.

(Production Example 11 Preparation of PR122 Pigment Dispersion A)
In Production Example 6, the pigment concentration was 7% as in Production Example 6 except that the colorant component was CI Pigment Red 122 Pigment (trade name: PV Fast Pink E, manufactured by Clariant) 2.10 parts by weight. PR122 pigment dispersion A was obtained.

(Production Example 12 Preparation of transparent photosensitive resin composition)
37.3 parts by weight of binder resin A of Production Example 1 (solid content 44% by weight) as an alkali-soluble resin, and 5-6 functional acrylate monomer as a monomer component (trade name: Aronix M403, manufactured by Toagosei Co., Ltd.): 16.4 weights Part, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 5.4 weight Part, 2,4-diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) 1.8 parts by weight, propylene glycol monomethyl ether acetate 39.13 parts by weight, transparent with a solid content of 40% by weight A photosensitive resin composition was obtained.

(Reference Example 1 Preparation of Blue Photosensitive Resin Composition A-0 for Color Filter)
PB15: 6 pigment dispersion A prepared in Production Example 4 8.88 parts by weight, transparent photosensitive resin composition prepared in Production Example 12 7.31 parts by weight, propylene glycol monomethyl ether acetate 8.62 parts by weight, as additives Silane coupling agent (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 parts by weight and fluorine leveling agent (trade name: R08MH, manufactured by DIC) 0.05 parts by weight are mixed and pressure filtered. To obtain a blue photosensitive resin composition A-0 for a color filter (solid content concentration: 20 wt%, pigment concentration in solid content: 23.0 wt%, pigment composition: PB15: 6 only).

(Example 1 Preparation of blue photosensitive resin composition A-1 for color filter)
8.17 parts by weight of PB15: 6 pigment dispersion A prepared in Production Example 4, 1.32 parts by weight of PV19 pigment dispersion A prepared in Production Example 6, 7.31 parts by weight of the transparent photosensitive resin composition prepared in Production Example 12 Parts, propylene glycol monomethyl ether acetate 8.01 parts, additive silane coupling agent (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 part by weight, fluorine leveling agent (trade name: R08MH, DIC) 0.05 parts by weight were mixed, and pressure filtration was performed, and blue photosensitive resin composition A-1 for color filters (solid content concentration: 20% by weight, pigment concentration in solid content: 23. 0 wt%, pigment composition: PR15: 6 / PV19 = 92/8).

(Example 2 Preparation of blue photosensitive resin composition A-2 for color filter)
In Example 1, except that PB15: 6 pigment dispersion A was 7.59 parts by weight, PV19 pigment dispersion A was 2.39 parts by weight, and propylene glycol monomethyl ether acetate 7.51 parts by weight, Blue photosensitive resin composition A-2 for filter (solid content concentration: 20 wt%, pigment concentration in solid content: 23.0%, pigment composition: PR15: 6 / PV19 = 85.5 / 14.5) Obtained.

(Example 3 Preparation of blue photosensitive resin composition A-3 for color filter)
In Example 1, except that PB15: 6 pigment dispersion A was 6.83 parts by weight, PV19 pigment dispersion A was 3.79 parts by weight, and propylene glycol monomethyl ether acetate was 6.87 parts by weight. Blue photosensitive resin composition A-3 for filters (solid content concentration: 20% by weight, pigment concentration in the solid content: 23.0% by weight, pigment composition: PR15: 6 / PV19 = 77/23) was obtained.

(Comparative Example 1 Preparation of Blue Photosensitive Resin Composition B-1 for Color Filter)
In Example 1, PB15: 6 pigment dispersion A 7.50 parts by weight, PV23 pigment dispersion A prepared in Production Example 8 instead of PV19 pigment dispersion A 0.36 parts by weight, transparent photosensitive resin composition 8 Blue photosensitive resin composition B-1 for color filters (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that 0.000 part by weight and 8.94 parts by weight of propylene glycol monomethyl ether acetate Pigment concentration: 20.0% by weight, pigment composition: PR15: 6 / PV23 = 97.5 / 2.5).

(Comparative Example 2 Preparation of Blue Photosensitive Resin Composition B-2 for Color Filter)
In Example 1, 7.35 parts by weight of PB15: 6 pigment dispersion A, 0.64 parts by weight of PV23 pigment dispersion A prepared in Production Example 8 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 8 A blue photosensitive resin composition for color filter B-2 (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that 0.000 part by weight and 8.81 parts by weight of propylene glycol monomethyl ether acetate were used. Pigment concentration: 20.0% by weight, pigment composition: PR15: 6 / PV23 = 95.5 / 4.5).

(Comparative Example 3 Preparation of Blue Photosensitive Resin Composition B-3 for Color Filter)
In Example 1, 7.19 parts by weight of PB15: 6 pigment dispersion A, 0.93 parts by weight of PV23 pigment dispersion A prepared in Production Example 8 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 8 A blue photosensitive resin composition for color filter B-3 (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that 0.000 part by weight and propylene glycol monomethyl ether acetate 8.68 parts by weight Pigment concentration: 20.0% by weight, pigment composition: PR15: 6 / PV23 = 93.5 / 6.5).

(Comparative Example 4 Preparation of Blue Photosensitive Resin Composition C-1 for Color Filter)
In Example 1, 8.61 parts by weight of PB15: 6 pigment dispersion A, 0.49 parts by weight of PR209 pigment dispersion A prepared in Production Example 9 instead of PV19 pigment dispersion A, transparent photosensitive resin composition 7 Blue photosensitive resin composition C-1 for a color filter (solid content concentration: 20% by weight, solid content) Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR209 = 97.0 / 3.0).

(Comparative Example 5 Preparation of blue photosensitive resin composition C-2 for color filter)
In Example 1, 8.25 parts by weight of PB15: 6 pigment dispersion A, 1.15 parts by weight of PR209 pigment dispersion A prepared in Production Example 9 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 7 Blue photosensitive resin composition for color filter C-2 (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that .31 parts by weight and propylene glycol monomethyl ether acetate 8.08 parts by weight Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR209 = 93.0 / 7.0).

(Comparative Example 6 Preparation of blue photosensitive resin composition C-3 for color filter)
In Example 1, 7.86 parts by weight of PB15: 6 pigment dispersion A, 1.90 parts by weight of PR209 pigment dispersion A prepared in Production Example 9 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 7 Blue photosensitive resin composition for color filter C-3 (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that .31 parts by weight and 7.74 parts by weight of propylene glycol monomethyl ether acetate were used. Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR209 = 88.5 / 11.5).
(Comparative Example 7 Preparation of Blue Photosensitive Resin Composition D-1 for Color Filter)
In Example 1, 8.17 parts by weight of PB15: 6 pigment dispersion A, 1.32 parts by weight of PR202 pigment dispersion A prepared in Production Example 10 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 7 A blue photosensitive resin composition for color filter D-1 (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1, except that the amount was .31 parts by weight and propylene glycol monomethyl ether acetate was 8.01 parts by weight. Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR202 = 92.0 / 8.0).

(Comparative Example 8 Preparation of blue photosensitive resin composition D-2 for color filter)
In Example 1, 7.63 parts by weight of PB15: 6 pigment dispersion A, 2.31 parts by weight of PR202 pigment dispersion A prepared in Production Example 10 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 7 Blue photosensitive resin composition D-2 for color filters (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that the amount was 31 parts by weight and 7.55 parts by weight of propylene glycol monomethyl ether acetate. Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR202 = 86.0 / 14.0).

(Comparative Example 9 Preparation of blue photosensitive resin composition D-3 for color filter)
In Example 1, 7.10 parts by weight of PB15: 6 pigment dispersion A, 3.30 parts by weight of PR202 pigment dispersion A prepared in Production Example 10 instead of PV19 pigment dispersion A, transparent photosensitive resin composition 7 Blue photosensitive resin composition for color filter D-3 (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that the amount was .31 parts by weight and 7.10 parts by weight of propylene glycol monomethyl ether acetate. Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR202 = 80.0 / 20.0).

(Comparative Example 10 Preparation of blue photosensitive resin composition E-1 for color filter)
In Example 1, 8.17 parts by weight of PB15: 6 pigment dispersion A, 1.32 parts by weight of PR122 pigment dispersion A prepared in Production Example 11 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 7 Blue photosensitive resin composition E-1 for color filter (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that the amount was .31 parts by weight and propylene glycol monomethyl ether acetate was 8.01 parts by weight. Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR122 = 92.0 / 8.0).

(Comparative Example 11 Preparation of Blue Photosensitive Resin Composition E-2 for Color Filter)
In Example 1, 7.63 parts by weight of PB15: 6 pigment dispersion A, 2.31 parts by weight of PR122 pigment dispersion A prepared in Production Example 11 instead of PV19 pigment dispersion A, and transparent photosensitive resin composition 7 Blue photosensitive resin composition E-2 for color filter (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that the amount was .31 parts by weight and 7.55 parts by weight of propylene glycol monomethyl ether acetate. Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR122 = 86.0 / 14.0).

(Comparative Example 12 Preparation of blue photosensitive resin composition E-3 for color filter)
In Example 1, 7.10 parts by weight of PB15: 6 pigment dispersion A, 3.30 parts by weight of PR122 pigment dispersion A prepared in Production Example 11 instead of PV19 pigment dispersion A, transparent photosensitive resin composition 7 Blue photosensitive resin composition E-3 for color filter (solid content concentration: 20% by weight, solid content) in the same manner as in Example 1 except that the content was .31 parts by weight and 7.10 parts by weight of propylene glycol monomethyl ether acetate. Pigment concentration: 23.0% by weight, pigment composition: PR15: 6 / PR122 = 80.0 / 20.0).

(Example 4 Preparation of blue photosensitive resin composition F-1 for color filter)
In Example 1, 7.59 parts by weight of PB15: 6 pigment dispersion B prepared in Production Example 5 instead of PB15: 6 pigment dispersion A was prepared in Production Example 7 instead of PV19 Pigment Dispersion A. Blue photosensitive resin composition F-1 for color filter (solid content concentration) in the same manner as in Example 1 except that PV19 pigment dispersion B was 2.39 parts by weight and propylene glycol monomethyl ether acetate 7.51 parts by weight : 20% by weight, pigment concentration in the solid content: 23.0%, pigment composition: PR15: 6 / PV19 = 85.5 / 14.5).

Example 5 Preparation of Blue Photosensitive Resin Composition F-2 for Color Filter
In Example 1, 6.83 parts by weight of PB15: 6 pigment dispersion B prepared in Production Example 5 instead of PB15: 6 pigment dispersion A was prepared in Production Example 7 instead of PV19 Pigment Dispersion A. Blue photosensitive resin composition F-2 for color filter (solid content concentration) in the same manner as in Example 1 except that the PV19 pigment dispersion B was 3.79 parts by weight and 6.87 parts by weight of propylene glycol monomethyl ether acetate. : 20% by weight, pigment concentration in solid content: 23.0% by weight, pigment composition: PR15: 6 / PV19 = 77/23).

(Example 6 Preparation of blue photosensitive resin composition G-1 for color filter)
In Example 1, 7.51 parts by weight of PB15: 6 pigment dispersion A, 1.15 parts by weight of PV19 pigment dispersion A, and 0.31 part by weight of PV23 pigment dispersion A prepared in Production Example 8, transparent photosensitive resin Blue photosensitive resin composition G-1 for color filters (solid content concentration: 20% by weight) in the same manner as in Example 1 except that 7.65 parts by weight of the composition and 8.18 parts by weight of propylene glycol monomethyl ether acetate were used. Pigment concentration: 4.3 wt%, pigment composition: PR15: 6 / PV19 / V23 = 90.5 / 7.5 / 2.0).

(Example 7 Preparation of blue photosensitive resin composition G-2 for color filter)
In Example 1, 7.05 parts by weight of PB15: 6 pigment dispersion A, 1.77 parts by weight of PV19 pigment dispersion A, 0.54 parts by weight of PV23 pigment dispersion A prepared in Production Example 8, and a transparent photosensitive resin Blue photosensitive resin composition G-2 for color filters (solid content concentration: 20% by weight) in the same manner as in Example 1 except that 7.65 parts by weight of the composition and 7.79 parts by weight of propylene glycol monomethyl ether acetate were used. Pigment concentration: 4.3 wt%, pigment composition: PR15: 6 / PV19 / V23 = 85.0 / 11.5 / 3.5).

(Evaluation)
<Optical performance and retardation evaluation>
The blue photosensitive resin composition for a color filter obtained in each Example and Comparative Example was applied on a 0.7 mm thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. did. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (blue colored layer) was obtained by irradiating 60 mJ / cm ² of ultraviolet rays using an ultra-high pressure mercury lamp and post-baking in a clean oven at 230 ° C. for 30 minutes. The thickness of the colored layer after curing was adjusted so that the target chromaticity y = 0.120.
The contrast, chromaticity (x, y), luminance (Y), and retardation (Rth) of the obtained red colored substrate were measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectral light measuring device OSP-SP200” manufactured by Olympus Corporation.
Retardation (Rth) was measured using a retardation layer measuring apparatus (Axoscan ^™ Mueller Matrix Polarimeter manufactured by AXOMETRICS), the measurement wavelength of the blue colored layer was 450 nm, and retardation (Rth) was calculated by the following equation.
Rth = ((Nx + Ny) / 2−Nz) d
nx: Refractive index in the in-plane slow axis direction ny: Refractive index in the in-plane fast axis direction nz: Refractive index in the thickness direction d: Film thickness (nm)
The results are shown in Table 1.

<Alkali developability evaluation>
The blue photosensitive resin composition for a color filter obtained in each example and comparative example was applied on a glass substrate having a thickness of 0.7 mm using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer has been formed is shower-developed using an aqueous 0.05 wt% potassium hydroxide solution as an alkaline developer, and the time until the glass surface where the colored layer is formed is developed. Measured as time.
The results are shown in Table 1.

From the results in Table 1, the following was clarified.
From the results of Examples 1 to 3, the blue photosensitive resin composition of the present invention has a retardation value (Rth) at a desired chromaticity of zero or zero by increasing the content of PV19 relative to PB15: 6. It could be a negative value.

  Similarly, in Examples 4 and 5 in which the pigment dispersant was changed, the retardation value at the desired chromaticity could be made zero or negative by increasing the content of PV19.

  From the results of Examples 6 to 7, even when PB15: 6, PV19 and PV23 are contained, the value of the phase difference value at the desired chromaticity can be reduced by increasing the content of PV19 in the same manner. And by adding PV23, the fall of the brightness | luminance was able to be suppressed.

  From the results of Comparative Examples 1 to 3, although the phase value can be lowered even if only PV23 is used without using PV19, it is difficult to control the phase value to zero or less at a desired chromaticity, not a sufficient amount of change. It is.

  From the results of Comparative Examples 4 to 6, although the phase value can be lowered even if PR209 is used without using PV19, it is not a sufficient change amount, and it is difficult to control to zero or less at a desired chromaticity. is there.

  From the results of Comparative Examples 7 to 9, although the phase value can be lowered even if PR202 is used without using PV19, it is difficult to control to zero or less at a desired chromaticity, not a sufficient amount of change. is there.

  From the results of Comparative Examples 10 to 12, when PR122 was used without using PV19, the phase difference value increased conversely.

  The pigments used in Comparative Examples 1 to 12, PV23, PR209, PR202, and PR122 are all the same quinacridone pigments as PV19. From this, it can be seen that even if the pigment has a similar skeleton, the difference in the influence of the pigment on the retardation value is large, and an appropriate pigment must be selected.

  It can be seen that by combining PB15: 6 and PV19 with the pigment, it is easy to make the phase difference value close to zero or to have a negative value.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device

Claims (11)

  A pigment dispersion containing at least a pigment, a pigment dispersant, and a solvent, wherein the pigment contains at least C.I. I. Pigment blue 15: 6 and C.I. I. A blue pigment dispersion for a color filter containing CI Pigment Violet 19.   The pigment further contains C.I. I. The blue pigment dispersion for color filters according to claim 1, comprising Pigment Violet 23. The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further has the repeating unit (1). The blue pigment dispersion for a color filter according to claim 1 or 2, which is a block copolymer in which at least a part of an amino group and an organic acid compound form a salt.

[In Formula (I) and Formula (II), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 4} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R 6)} -CH It is a monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, It is a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ] The organic acid compound in the pigment dispersant is at least one selected from the group consisting of organic acids represented by the following general formula (III) and the following general formula (IV). The blue pigment dispersion for color filters according to item 1.

[In Formula (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, 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. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]   Furthermore, the blue pigment dispersion liquid for color filters of any one of Claims 1 thru | or 4 containing alkali-soluble resin.   A photosensitive resin composition containing at least a pigment, a pigment dispersant, a photosensitive binder component, and a solvent, wherein the pigment is at least C.I. I. Pigment blue 15: 6 and C.I. I. A blue photosensitive resin composition for a color filter, comprising Pigment Violet 19.   Furthermore, C.I. I. The blue photosensitive resin composition for a color filter according to claim 6, comprising Pigment Violet 23. The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further has the repeating unit (1). The blue photosensitive resin composition for a color filter according to claim 6 or 7, which is a block copolymer in which at least a part of an amino group and an organic acid compound form a salt.

[In Formula (I) and Formula (II), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 4} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R 6)} -CH It is a monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, It is a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ] The organic acid compound in the pigment dispersant is at least one selected from the group consisting of organic acids represented by the following general formula (III) and the following general formula (IV). 2. A blue photosensitive resin composition for a color filter according to item 1.

[In Formula (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, 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. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]   A blue filter for a color filter according to any one of claims 6 to 9, wherein the color filter comprises at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a color filter. A color filter comprising a colored layer formed by curing a resin composition.   11. A liquid crystal display device comprising: the color filter according to claim 10; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.

Images