KR20160071375A - Red-pigment-dispersion resist composition for color filter - Google Patents

Abstract

An object of the present invention is to provide a red pigment-dispersed resist composition for a color filter which is excellent in dispersion stability, has a high coloring power and a high luminance, and does not cause a build up in heating.
In order to solve the above problems, the red pigment-dispersed resist composition for a color filter of the present invention comprises: a. A pigment dispersion of a specific CI Pigment Red 264, b. At least one pigment dispersion of a specific CI Pigment Red 254, a pigment dispersion of a specific CI Pigment Red 177, and a Pigment dispersion of a specific CI Pigment Red 179; c. Alkali-soluble resin, d. Photopolymerizable compounds, e. Photopolymerization initiator, f. And the content of CI Pigment Red 264 relative to the total mass of the pigment is 50% by mass or more and less than 100% by mass.

Description

Disclosed is a red-pigment-dispersion resist composition for color filter.

The present invention relates to a red pigment-dispersed resist composition for a color filter which enables the production of a color filter for use in a color liquid crystal display device, an image pickup device and the like.

A color filter used in a color liquid crystal display or the like is formed by arranging fine stripes of two or more different colors in parallel on a surface of a transparent substrate such as glass or arranging fine pixels in a matrix . The pixel size has a fine size of several tens to several hundreds of micrometers and is regularly arranged in a predetermined order on a color basis.

In a color liquid crystal display device, white light from a backlight is transmitted through a color filter as described above to display a color image on a screen. Therefore, high transparency is required as a basic performance of a color filter. So-called dyeing method in which a dye excellent in color characteristics is dispersed in a resin in a molecular state and is dyed is used. In recent years, however, with the diversification of applications, it has become necessary to improve reliability such as heat resistance and light resistance, and organic pigments have been used instead of those dyes having limited performance. Various methods such as a printing method, an ink-jet method, and a photolithography method have been proposed for the production of color filters.

In recent years, in particular, in order to cope with the demand for social power saving in a liquid crystal display device of a portable device, in particular, in order to obtain a bright display screen more efficiently among limited power consumption, transparency of visible light is high, There is a demand for a color filter having pixels that enable contrast enhancement.

The transmittance and contrast performance of the visible light greatly depends on the performance of the pigment dispersed in each color pixel of the color filter. In the case of the red pixel, it is difficult to realize the performance required by one kind of pigment, Color) pigments have been proposed.

For example, a system (see, for example, Patent Document 1) for using Pigment Red 177, which is a main red pigment, in combination with a coloring red pigment has been proposed. In this example, red color pigments Pigment Red 5, 9, 10, 17, 48: 1, 48: 2, 48: 3, 48: 4, 52 : 2, 119, 166, 216, 224, 226 are examples. However, in the case of a combination system of these red pigments, improvement in the transmittance and contrast performance is limited.

Further, a system (see, for example, Patent Document 2) in which Pigment Red 242, which is a main red pigment, is used in combination with Pigment Red 177 or 254 as a coloring red pigment has been proposed. Also, a system (for example, Patent Document 3 and Patent Document 4) in which a red pigment such as Pigment Red 177, 207, 209, 224, 242 or the like as a coloring red pigment is used in combination with Pigment Red 254 as a main red pigment have.

However, when Pigment Red 242 is used as the main pigment, there arises a problem that the color tone is shifted to yellow. On the other hand, when Pigment Red 254 is used, the transmittance is high, but the film thickness of the colored film becomes thick and the contrast decreases. In addition, there arises a problem that the heat resistance is deteriorated due to the characteristics of the pigment (the vaporization occurs).

In recent years, a backlight using an LED as a light source has also appeared, and an effect that the color reproduction area of the color filter is expanded by the device improvement of various backlights is also obtained. However, since the wavelengths of light to be irradiated are different from each other, the available coloring pigments are also selective. For example, in the case of a backlight in which an LED is used as a light source, the combination of the above-described pigments has to increase the pigment concentration of a pixel from the relationship of the absorption wavelength of light. Therefore, the red pigment-dispersed resist composition requires a high concentration, and there is a problem in that it is difficult to manufacture the composition itself or to preserve stable stability over time. On the other hand, when the pigment concentration is set at a conventional concentration, the thickness of the pixel coating for obtaining the required color density becomes too thick, which makes it difficult to manufacture a color filter.

In order to solve this problem, when Pigment Red 179 or Pigment Red 208 suitable for the wavelength of the light emitted from the LED is used, the color density is obtained without increasing the pigment concentration of the pixel and the film thickness is in a controllable range , This system has a problem that brightness is inherently lowered.

It is also conceivable to use a red pigment such as Pigment Red 264 and Pigment Red 177 as a method of maintaining a high tinting power with respect to the wavelength of light emitted from the LED and increasing the luminance (for example, Patent Document 5 Reference).

Pigment Red 264, however, was very difficult to make the pigment into fine particles, so that the system using Pigment Red 264 did not sufficiently proceed to fine particles by the known method, and high coloring power and adequate fluidity could not be obtained. In particular, if the fine particles are not sufficiently formed, the viscosity of the composition for a color filter becomes low, and therefore, a great deal of attention has been required to obtain a necessary thickness for use.

Japanese Patent Application Laid-Open No. 10-148712 Japanese Patent Application Laid-Open No. 11-014824 Japanese Patent Application Laid-Open No. 2002-372618 Japanese Patent Application Laid-Open No. 2003-248115 Japanese Patent Application Laid-Open No. 10-300920

Disclosure of the Invention [0008] It is an object of the present invention to provide a red pigment-dispersed resist composition for a color filter which is excellent in dispersion stability, has a high coloring power and a high luminance,

The main pigment was changed to C.I. Pigment Red 264 and C.I. Pigment Red 177 or C.I. Pigment Red 179 or C.I. Pigment Red 254, it is possible to obtain a red pixel which can be highly colored at a high luminance even when various backlight devices are used. For this purpose, it is necessary to disperse these pigments into fine particles and stably disperse them in a red pigment-dispersed resist composition for a color filter. The dispersion stability of the fine particles of Pigment Red 264 can not be sufficiently obtained.

As a result of intensive investigations on techniques for improving the dispersion stability of the fine particles of these four pigments, the applicant has found that the fine particles obtained by microparticulating each pigment in the presence of the sulfonated compound of the compound having the same skeleton A pigment dispersing aid, a basic group-containing polymeric pigment dispersant, an alkali-soluble resin and an organic solvent specified in the present invention are added to and dispersed in the cargo to obtain individual pigment dispersions, and then the pigment dispersions are mixed to prepare a red pigment dispersion Thereby forming a resist composition. In the case of the red pigment-dispersed resist composition for a color filter obtained from this method, Pigment Red 264 and the like are remarkably improved even when compared with the prior art, so that the problems of the present invention can be solved completely, and the present invention has been completed.

That is,

(1) a. The following pigment dispersion of C. I. Pigment Red 264,

b. One or more pigments selected from the following pigment dispersions of C. I. Pigment Red 254, the following pigment dispersions of C. I. Pigment Red 177 and the following C. I. Pigment Red 179 pigment dispersions,

c. Alkali-soluble resin,

d. Photopolymerizable compound,

e. A photopolymerization initiator,

f. Organic solvent

Of a to f,

And a content of CI Pigment Red 264 relative to the total mass of the pigment is 50 mass% or more and less than 100 mass%.

Pigment Dispersion of CI Pigment Red 264: CI Pigment Red 264 was finely pulverized to give a pigment dispersion auxiliary agent, a basic pigment-containing polymer pigment dispersant, an alkali-soluble resin and an organic solvent represented by Chemical Formulas 1 and / The pigment dispersion obtained by adding and dispersing

Pigment Dispersion of CI Pigment Red 254: CI Pigment Red 254 was made into fine particles, to which a pigment dispersion auxiliary represented by Chemical Formulas 1 and / or 2, a polymer pigment dispersing agent containing a basic group, an alkali soluble resin and an organic solvent The pigment dispersion obtained by adding and dispersing

Pigment Dispersion of CI Pigment Red 177: CI Pigment Red 177 was made into fine particles, to which a pigment dispersion auxiliary agent represented by Chemical Formula 1 and / or 2, a polymer pigment dispersing agent containing a basic group, an alkali-soluble resin and an organic solvent The pigment dispersion obtained by adding and dispersing

C. I. Pigment Dispersion of Pigment Red 179: C.I. A pigment dispersion obtained by adding and dispersing a pigment dispersion auxiliary agent, a basic group-containing polymer pigment dispersant, an alkali-soluble resin and an organic solvent represented by the general formulas (1) and / or (2) to a fine particle product obtained by making I. Pigment Red 179 into fine particles.

Wherein X and Y are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, NO ₂ , CH ₃ or OCH ₃ . M is H, Na, K, NH ₄ or NR ¹ R ² R ³ R ⁴ (wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and are a saturated group having 1 to 10 carbon atoms Or an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group of 6 to 10 carbon atoms which may be substituted with another substituent). and m represents an integer of 1 or more.

(2) The red pigment-dispersed resist composition for a color filter described in (1) above, wherein the basic group-containing polymeric pigment dispersant is an acrylic block copolymer having tertiary and / or quaternary amino groups.

(3) The pigment dispersion of the CI Pigment Red 264, the pigment dispersion of the CI Pigment Red 254, the Pigment dispersion of the CI Pigment Red 177, the Pigment dispersion of the CI Pigment Red 179, (1) or (2), wherein the red pigment dispersion is a dispersion.

Pigment Dispersion of CI Pigment Red 264: CI Pigment Red 264 in the presence of a sulfonate of a compound having the same backbone as the CI Pigment Red 264. A pigment dispersion auxiliary agent, a pigment dispersant containing a basic group, an alkali-soluble resin, and an organic solvent,

Pigment Dispersion of CI Pigment Red 254: CI Pigment Red 254 in the presence of a sulfonate of a compound having the same skeleton, to a fine particle product obtained by micropelling CI Pigment Red 254, A pigment dispersion auxiliary agent, a pigment dispersant containing a basic group, an alkali-soluble resin, and an organic solvent,

Pigment Dispersion of CI Pigment Red 177: CI Pigment Red 177 in the presence of a sulfonate of a compound having the same skeleton as the CI Pigment Red 177, A pigment dispersion auxiliary agent, a pigment dispersant containing a basic group, an alkali-soluble resin, and an organic solvent,

C. I. Pigment Dispersion of Pigment Red 179: C.I. I. Pigment Red 179 in the presence of a sulfonated compound of a compound having the same skeleton, the pigment dispersion auxiliary represented by the general formula (1) and / or (2), the basic pigment containing a basic pigment A pigment dispersion obtained by adding and dispersing a dispersant, an alkali-soluble resin and an organic solvent.

(4) the sulfonated compound of the compound having the same skeleton as the CI Pigment Red 264 is the sulfonated compound of CI Pigment Orange 71, and the sulfonated compound of the same skeleton as the CI Pigment Red 254 is CI Pigment Orange 71 Wherein the sulfonated compound of the compound having the same skeleton as the CI Pigment Red 177 is a sulfonated product of the CI Pigment Red 177 and the sulfonated product of the compound having the same skeleton as the CI Pigment Red 179 is the CI Pigment (3), wherein the pigment dispersion auxiliary agents represented by the above-mentioned formulas (1) and / or (2) are (Formula 3 and 4) and / or (Formula 5 and 6) The present invention relates to a red pigment dispersion resist composition for a color filter.

(5) The photographic material as described in any one of (1) to (4) above, wherein barium sulfate having a primary particle size of 5 to 20 nm is contained in an amount of 5 to 15 mass parts per 100 mass parts of the total mass of the pigment To a red pigment-dispersed resist composition for a color filter.

According to the present invention, when used as a pigment-dispersed resist composition for a color filter, a bright display can be obtained with higher chromaticity values x and y as a red filter and higher brightness Y.

In addition, the viscosity of the pigment-dispersed resist composition can be set in a suitable range, and the film thickness can be made thinner, so that it is not difficult to manufacture a color filter.

Hereinafter, the red pigment-dispersed resist composition for a color filter of the present invention (hereinafter, simply referred to as "pigment-dispersed resist composition") will be described in more detail.

The pigment-dispersed resist composition of the present invention contains a pigment.

As the pigment, a. C. I. To pigment dispersion of Pigment Red 264, b. At least one pigment dispersion selected from the three specific pigment dispersions of C. I. Pigment Red 254, C. I. Pigment Red 177, C. I. Pigment Red 179 is contained.

By using such a composition of the pigment dispersion, high contrast, high brightness, high heat resistance and high solvent resistance are imparted to a color filter.

The content of C. I. Pigment Red 264 is from 50 mass% to less than 100 mass% with respect to the total mass of the pigment. If the content of C.I. Pigment Red 264 is less than 50% by mass, the luminance tends to decrease.

It is preferable that the C. I. Pigment Red 264, C. I. Pigment Red 254, C. I. Pigment Red 177 and C. I. Pigment Red 179 each have an average particle diameter of 0.02 to 0.07 μm. By having an average particle size in the above range, a high contrast property is imparted.

In the present invention, the average particle diameter refers to a volume average particle diameter measured by a laser diffraction particle size measurement method, a measuring device: Nano Track (UPA-EX150, manufactured by Nikkiso Co., Ltd.).

In the present invention, other pigments may be added and mixed in addition to the above-mentioned colored pigments within the range not impairing the effect of the present invention. Examples of other pigments include yellow pigments and orange pigments.

The total amount of the pigment to be used in the present invention is preferably 5 to 80% by mass, more preferably 20 to 50% by mass, based on the total mass of the solid content of the pigment dispersion resist composition.

The pigment dispersion resist composition of the present invention may contain a pigment dispersion auxiliary agent.

The pigment dispersion auxiliary (A) (hereinafter simply referred to as " pigment dispersion auxiliary agent (A) ") which is a sulfonation product of a compound having the same skeleton as each pigment to be used in the microparticulation of each pigment (Hereinafter also simply referred to as " pigment dispersion auxiliary agent (B) ") which is a compound represented by the above formula (1) and / or (2) Or two kinds of pigment dispersion auxiliary agents.

The pigment dispersion auxiliary (A) used in the present invention is CI Pigment Red 264, in the case of CI Pigment Red 254, a sulfonated product of a pigment having diketopyrrolopyrrole skeleton, preferably CI Pigment Red 254, 255, 264, 272, the sulfonated compounds of CI Pigment Orange 71, 73, particularly preferably the sulfonated compounds of CI Pigment Orange 71, 73, in the case of Pigment Red 177, the sulfonated compounds of pigments having an anthraquinone skeleton, Is preferably a sulfonated product of CI Pigment Red 177, an anthraquinone derivative described in JP-A No. 2002-22922, particularly preferably a sulfonated product of CI Pigment Red 177, or a pigment of Pigment Red 179, , Preferably the sulfonated CI Pigment Red 179 can be used.

As the pigment dispersion auxiliary (B) used in the present invention, the compounds represented by the above-mentioned formulas (1) and / or (2) are used.

X and Y in the general formulas (1) and (2) are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, NO ₂ , CH ₃ or OCH ₃ . M represents H, Na, K, NH ₄ or NR ¹ R ² R ³ R ⁴ .

R ¹ , R ² , R ³ and R ⁴ are the same or different from each other and represent an alkyl group having 1 to 10 carbon atoms which may be substituted with another substituent, with respect to the "NR ¹ R ² R ³ R ⁴ " (M) A saturated or unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group of 6 to 10 carbon atoms which may be substituted with another substituent.

Examples of the saturated or unsaturated aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, An alkenyl group such as a vinyl group, an allyl group and a 1-butenyl group, an alkynyl group such as an ethynyl group and a propynyl group, and the like. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

Examples of the substituent other than the above include a hydroxyl group, a halogen, a carboxyl group, an amino group, and a lower alkyl group (having 1 to 5 carbon atoms). In addition, ^{one of} R ¹ R ² R ³ and R ⁴ may be substituted with another substituent, or two or more thereof may be substituted with another substituent. In the above formulas (1) and (2), " m "

In the pigment dispersion auxiliary agent (B), the compound represented by Formula (1) is enol type, and the compound represented by Formula (2) is a keto tautomer, and both compounds are included in the present invention. That is, the pigment dispersion auxiliary agent (B) of the present invention includes both the compound represented by the above formula (1) or (2) and the compound represented by the above formula (1)

Preferable examples of the pigment dispersion auxiliary agent (B) are those having a good fluidity and dispersion stability even in a finely dispersed state of the organic pigment, and at the same time, a pigment dispersion having a higher level of transparency and coloring power can be obtained. Preferred are sulfonates of Pigment Red 2 (Formula 3 and / or Formula 4) and / or sulfones of C.I. Pigment Red 17 (Formula 5 and / or Formula 6).

The amount of the pigment dispersion auxiliary (A) to be used is 0.5 to 30 parts by mass, preferably 5 to 15 parts by mass, per 100 parts by mass of the total amount of each pigment, and the amount of the pigment dispersion auxiliary (B) Preferably 0.5 to 30 parts by mass, and more preferably 5 to 15 parts by mass.

The pigment-dispersed resist composition of the present invention contains a polymeric pigment dispersant containing a basic group.

Examples of the basic group-containing polymeric pigment dispersant in the present invention include the following.

(1) a polyester having a free carboxyl group and an amino group and / or an imino group of a polyamine compound (for example, polyallyl amine, polyvinylamine, poly (lower alkylene amine) such as polyethylene polyimine) Amide and polyester amide (Japanese Patent Application Laid-Open No. 2001-59906), a reaction product with at least one compound selected from the group consisting of amide and polyester amide

(2) a carbodiimide compound having at least one side chain and at least one basic nitrogen-containing group selected from the group consisting of a polyester side chain, a polyether side chain and a polyacrylic side chain in the molecule (WO04 / 000950)

(3) a reaction product of a low molecular weight amino compound such as poly (lower) alkyleneimine, methyliminobispropylamine and the like and a polyester having a free carboxyl group (JP-A-54-37082, JP- 311177),

(4) The polyisocyanate compound is produced by reacting an isocyanate group of a polyisocyanate compound with a polyester having one hydroxyl group such as an alcohol such as methoxypolyethylene glycol or caprolactone polyester, a compound having two or three isocyanate group-reactive functional groups, A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a tertiary amino group (JP-A No. 02-612)

(5) a reaction product in which a polyisocyanate compound and a hydrocarbon compound having an amino group are reacted with a polymer of an acrylate having an alcoholic hydroxyl group,

(6) a reaction product obtained by adding a polyether chain to a low molecular weight amino compound,

(7) a reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group (JP 04-210220 A),

(8) a reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group (JP-A-09-87537)

(9) a reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group and a polyamine compound at one end (Japanese Patent Application Laid-Open No. 09-194585)

(10) A photopolymerizable composition comprising at least one compound selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, Methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, an amino group and a polycaprolactone such as acrylamide, methacrylamide, N-methylolamide, vinylpyridine, At least one kind of basic group-containing polymerizable monomers such as monomers having a skeleton, and at least one copolymer of styrene, styrene derivatives and other polymerizable monomers (JP-A-01-164429)

(11) an acrylic block copolymer having a basic group such as a tertiary amino group or a quaternary ammonium salt group and a basic group comprising a block having no basic functional group (JP-A-2005-55814 Acrylic block copolymer)),

(12) A pigment dispersant obtained by Michael addition reaction of a polycarbonate compound with polyallylamine (Japanese Patent Application Laid-Open No. 09-194585)

(13) carbodiimide compounds each having at least one polybutadiene chain and a basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-257243),

(14) Carbodiimide compounds each having at least one side chain having an amide group in the molecule and a basic nitrogen-containing group (Japanese Patent Laid-Open Publication No. 2006-176657)

(15) a polyurethane compound having a constituent unit having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized by a quaternizing agent (JP-A-2009-175613),

(16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in a molecule with an active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton, A compound having an isocyanate group derived from an isocyanate compound having an isocyanurate ring and a carbazole ring and an azobenzene skeleton in total of urethane bond and urea bond produced by the reaction between an isocyanate group and an active hydrogen group Japanese Patent Application Laid-Open No. 2010-107965).

Among them, an acrylic block copolymer having tertiary and / or quaternary amino groups in terms of dispersibility is preferable.

In the pigment-dispersed resist composition of the present invention, the content of the pigment dispersant is preferably 1 to 200 parts by mass, more preferably 1 to 60 parts by mass, per 100 parts by mass of the total organic pigment to be used. When the content of the pigment dispersant is less than 1 part by mass, the pigment dispersibility may be lowered. On the other hand, when the content is more than 200 parts by mass, there is a concern that the developability is lowered.

The pigment-dispersed resist composition of the present invention comprises: c. And contains an alkali-soluble resin.

The alkali-soluble resin is not particularly limited as long as it is soluble in a developing solution used in the developing process, particularly preferably in an alkali developing solution, when a color filter is produced. Among these, an alkali-soluble resin having a carboxyl group is preferable as the alkali-soluble resin, and a copolymer of an ethylenically unsaturated monomer having at least one carboxyl group and another copolymerizable ethylenically unsaturated monomer is preferable.

Specific examples of the copolymer of the ethylenically unsaturated monomer having at least one carboxyl group and another copolymerizable ethylenically unsaturated monomer include an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid and an ethylenically unsaturated monomer having a carboxyl group Acrylate copolymerizable with styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , And at least one ethylenically unsaturated monomer selected from the group consisting of glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer.

The acid value of the copolymer is preferably 50 to 300 mg KOH / g. In this case, when the acid value is less than 50 mgKOH / g, the solubility of the resist composition in the alkaline developer may be lowered, while when it exceeds 300 mgKOH / g, the solubility in the alkaline developer becomes excessive, There is a tendency that the coloring layer is easily removed from the substrate and the surface of the colored layer is roughened.

In the present invention, the acid value is a value calculated arithmetically based on the content of the ethylenically unsaturated monomer having a carboxyl group and the theoretical acid number and the content thereof.

In the pigment-dispersed resist composition of the present invention, an alkali-soluble resin is contained, and the content thereof is preferably small in view of the dispersibility and the dispersion stability at the time of pigment dispersion described below.

The mass average molecular weight of the alkali-soluble resin in the present invention is usually preferably from 1,000 to 100,000. When the mass average molecular weight of the alkali-soluble resin is less than 1,000, the solubility in an alkali developing solution is increased, and development characteristics are sometimes deteriorated. On the other hand, if it exceeds 10,000, the solubility in an organic solvent decreases and the viscosity of the resist composition may increase.

In the present invention, the mass average molecular weight of the alkali-soluble resin is a mass average molecular weight in terms of polystyrene obtained based on GPC. In the present invention, Water 2690 (manufactured by Waters Corporation) and PLgel 5 μm MIXED-D (manufactured by Polymer Laboratories) are used as the apparatus.

In the pigment-dispersed resist composition of the present invention, the content of the alkali-soluble resin is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, relative to 100 parts by mass of the total organic pigments contained.

When the content of the alkali-soluble resin is less than 10 parts by mass, for example, alkali developability may be lowered, or scumming or film residue may occur on the substrate or the light-shielding layer of the unexposed portion. On the other hand, if it is more than 1,000 parts by mass, the concentration of the organic pigment is relatively decreased, so that it may be difficult to achieve the intended color density when the film is formed into a thin film.

In the pigment-dispersed resist composition of the present invention, d. It contains a photopolymerizable compound.

Examples of the photopolymerizable compound in the present invention include monomers and oligomers having at least one photopolymerizable unsaturated bond in the molecule. The photopolymerizable unsaturated bond is an unsaturated bond that can be polymerized by the action of radicals or cations generated when the photopolymerization initiator described below is decomposed by an active energy ray such as ultraviolet rays or electron beams.

Examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate Alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; alkoxylalkyl methacrylates such as N, N < RTI ID = 0.0 > Aminoalkyl methacrylates or acrylates such as dimethylaminoethyl methacrylate and N, N-dimethylaminoethyl acrylate; polyalkylenes such as diethylene glycol ethyl ether, triethylene glycol butyl ether and dipropylene glycol methyl ether; Methacrylic acid esters or acrylic acid esters of glycol alkyl ethers; Methacrylic acid esters or acrylic acid esters of polyalkylene glycol aryl ethers such as tylene glycol phenyl ether, etc., isobonyl methacrylate or acrylate, glycerol methacrylate or acrylate, 2-hydroxyethyl methacrylate or acrylate Can be exemplified.

Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate Polyglycol dimethacrylate, polyglycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, Methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol penta methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, But are not limited to, acrylonitrile, acrylonitrile, acrylonitrile, acrylonitrile, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, , Dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like. These monomers may be used alone or in combination of two or more.

In the present invention, the content of the photopolymerizable compound is preferably in the range of 3 to 50 mass% relative to the total solid content in the pigment dispersion resist composition.

The pigment-dispersed resist composition of the present invention comprises: e. And contains a photopolymerization initiator.

The photopolymerization initiator in the present invention is not particularly limited as long as it is capable of generating radicals and cations by being irradiated with active energy rays such as ultraviolet rays or electron beams, and examples thereof include benzophenone, N, N'-tetraethyl- 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, hydroxy anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-dichloroanthraquinone, 3- Chloro-2-methyl anthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethyl anthraquinone, 4- (methylthio) phenyl] -2-morpholinopropane-1-one, and triazine-based photopolymerization initiators. These photopolymerization initiators may be used alone or in combination of two or more.

In the present invention, the content of the photopolymerization initiator is preferably in the range of 1 to 20% by mass relative to the total solid content in the pigment dispersion resist composition.

The pigment-dispersed resist composition of the present invention comprises: Contains organic solvents.

Examples of the organic solvent in the present invention include inks, paints, liquid crystal color filter resists, and organic solvents suitably used in the ink jet field. Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Ether organic solvents such as monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; ether solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ether type organic solvents such as ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ketones such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, system Organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxybutyl propionate, methyl 3-methoxypropionate, 3- Ester organic solvents such as ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethylhydroxyacetate, and formic acid-n-amyl; organic solvents such as methanol, ethanol, isopropyl alcohol, , And nitrogen-containing organic solvents such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These may be used alone or in combination of two or more.

Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexane monomethyl ether acetate and the like are preferable from the viewpoints of solubility, dispersibility, Hexane, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and n-amyl formate are preferable And propylene glycol monomethyl ether acetate is more preferable.

These organic solvents are preferably contained in the red pigment-dispersed resist composition in an amount of 50% by mass or more, more preferably 70% by mass or more in terms of solubility of the alkali-soluble resin, pigment dispersibility, Do.

The pigment-dispersed resist composition of the present invention preferably further contains barium sulfate for the purpose of improving heat resistance and brightness. In the present invention, the content of barium sulfate is 0 to 15 parts by mass, preferably 5 to 12 parts by mass, based on 100 parts by mass of each pigment. If the amount of the barium sulfate exceeds 15 parts by mass, the coloring ability is greatly lowered. The barium sulfate preferably has a primary particle diameter of 5 to 20 nm. If the primary particle size of the barium sulfate exceeds 20 nm, contrast tends to be lowered and foreign matter tends to be generated. The above-mentioned barium sulfate is used after dispersing or dispersing the pigment obtained by the microparticulation treatment.

In addition, the pigment-dispersed resist composition of the present invention may be suitably used with various additives such as a thermo-alloy paper, an ultraviolet absorber, and an antioxidant, if necessary.

From the above-described constituent materials, the pigment-dispersed resist composition of the present invention can be produced, for example, by the following production method.

First, each untreated pigment is subjected to a microparticulation treatment (salt milling treatment) to obtain a pigment which has been subjected to microparticulation. More preferably, a pigment dispersion auxiliary agent (A), which is a sulfonated compound of a compound having the same skeleton as that of each pigment, is mixed with the pigment dispersion auxiliary agent (A) to obtain a mixture with the pigment dispersion auxiliary agent (A). It is possible to finely homogenize the pigment while suppressing the crystallization of the pigment by performing the microparticulation treatment in the presence of the pigment dispersion auxiliary agent (A) which is the sulfonated product of the compound having the same skeleton as each pigment. The particle size of the dispersion comprising the micronized pigment is about 50 to 70 nm.

The amount of the pigment dispersion auxiliary (A) to be used is 0.5 to 30 parts by mass, preferably 3 to 10 parts by mass, per 100 parts by mass of the pigment.

As the above microparticulation treatment, a pigment is ground with an inorganic salt in the presence of a sulfonated compound of a compound having the same skeleton as the pigment, using a kneading apparatus or the like which rotates the kneader or three stirring blades while rotating them, And a salt milling treatment in which the primary particle diameter of the pigment is further finely grained. The pigment obtained by the salt milling treatment in the presence of the sulfone compound of the compound having the same skeleton as the pigment becomes finely particulate so that the primary particle diameter is further finely and uniformly formed. In addition, the salt milling process using a kneading apparatus in which the three stirring blades are revolved while rotating each other is also referred to as a trimming process.

The tri-mix processing will be described in more detail below.

The above-mentioned trimmixing treatment is carried out by mixing a mixture containing a pigment, a water-soluble inorganic salt (hereinafter simply referred to as "inorganic salt") and an aqueous dispersion medium (hereinafter simply referred to as "dispersion medium" Kneading with a kneading device in which three stirring blades are revolved while rotating, and then the inorganic salt and the dispersion medium are removed.

In this process, three stirring blades are used as a kneading device, which is a planetary motion, that is, an orbital motion while rotating. As a result, the dead spaces between the agitating blades and between the agitating blades and the inner surface of the apparatus become very small, and a stronger and more uniform shearing force is obtained. The particle diameter of the pigment subjected to the grinding treatment by the inorganic salt under the shearing force becomes finer and more uniform than the primary particle diameter, and a color filter having transparency and contrast ratio higher than that of the conventional one can be obtained.

Here, " idle motion " refers to movement in which the stirring blade circulates in the tank. The " kneading apparatus for pivotally moving stirring blades " means a kneading apparatus for rotating the stirring blade itself by moving the stirring blade itself. However, in the present specification, if the relative movement of the tank and the stirring blade is the same (for example, the tank is rotated), the kneading apparatus is also included in the " kneading apparatus for idly moving the stirring blade ".

Further, as the structure of the kneading apparatus, it is preferable to satisfy the following conditions (1) and (2).

(1) The triangle obtained by using the point where the three rotation axes intersect with the plane orthogonal to the rotation axis of the three stirring blades is an equilateral triangle.

(2) The pivotal axis intersects the center of the equilateral triangle.

It is also preferable that the stirring blade has a length extending from the bottom of the tank to the liquid level and a width from the inner wall of the tank to the center thereof. Examples of such a kneading apparatus include a tri-mix (manufactured by Inoue Manufacturing Co., Ltd.) and the like.

Also, in this treatment, a wet treatment method in which a pigment, an inorganic salt, and a dispersion medium are put into a tank and kneaded is available.

The inorganic salt is not particularly limited as long as it is water-soluble, but salt (sodium chloride) is preferably used from the viewpoint of cost.

The particle size of the inorganic salt is preferably 200 占 퐉 or less, and more preferably 50 占 퐉 or less. Thereby, the particle diameter of the colored pigment can be finer and more uniform than the primary particle diameter.

In the present invention, the particle size of the inorganic salt means a volume average particle size measured by a laser diffraction particle size measurement method, a measuring device: Nanotrak (UPA-EX150, manufactured by Nikkiso Co., Ltd.).

The dispersion medium is not particularly limited as long as it is a water-soluble dispersion medium having both water-soluble and inorganic salt-free conditions. Among them, a high boiling point solvent having a boiling point of 120 占 폚 or higher is preferable from the viewpoint of stability since the temperature rises at the time of salt milling and the solvent is liable to evaporate.

Examples of such a water-soluble dispersion medium include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, Ethoxy-2-propanol and the like; glycols such as diethylene glycol, triethylene glycol, liquid polyethylene glycol, dipropylene glycol and low molecular weight polypropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and the like.

Examples of the method of performing the tri-mix process using the above materials and apparatuses include the following methods.

The pigment dispersion auxiliary (A), the inorganic salt, and the dispersion medium, which are the sulfonated compounds of the compound having the same skeleton as the pigment, are put into the tank. Then, the three agitating blades of the kneading apparatus are revolved to perform idle motion to polish the pigment with an inorganic salt. Thereafter, hot water is added to form a slurry, which is filtered, and the remaining inorganic salt and dispersing medium are removed by washing with water. In the grinding treatment of this pigment, it is preferable to appropriately adjust the addition amount (viscosity) of the material, the inner diameter of the tank, and the like so that the stress for kneading can be sufficiently applied. For example, when processing using the above-mentioned tri-mix, it is preferable that the load amperage is processed in a combination of 50% to 85% of the rated current value of the motor.

Subsequently, each mixture containing each of the above-mentioned particulate materials, the pigment dispersant, the pigment dispersion auxiliary (B), the alkali-soluble resin, the organic solvent and, if necessary, barium sulfate is obtained. Each of the obtained mixtures is kneaded using various dispersing machines such as a roll mill, a kneader, a high-speed stirrer, a bead mill, a ball mill, a sand mill, an ultrasonic dispersing machine and a high pressure dispersing machine and subjected to dispersion treatment to obtain respective pigment dispersions. It is also possible to add a photopolymerizable compound in advance to the pigment dispersion.

A method of obtaining the pigment-dispersed resist composition of the present invention from each pigment dispersion will be described.

A method of obtaining the pigment-dispersed resist composition of the present invention from each pigment dispersion can be obtained, for example, by the following (1) and (2).

(1) at least one selected from CI Pigment Red 264 Pigment Dispersion and CI Pigment Red 254 Pigment Dispersion, CI Pigment Red 177 Pigment Dispersion and CI Pigment Red 179 Pigment Dispersion, And then a photopolymerizable compound, a photopolymerization initiator, a remaining alkali-soluble resin, an organic solvent and, if necessary, barium sulfate are added to obtain a pigment-dispersed resist composition.

(2) To each pigment dispersion, a photopolymerizable compound, a photopolymerization initiator, a residual alkali-soluble resin, an organic solvent and, if necessary, barium sulfate were added to obtain each pigment-dispersed resist composition. Then, a CI Pigment Red 264 pigment- At least one selected from CI Pigment Red 254 pigment dispersion resist composition, CI Pigment Red 177 pigment dispersion resist composition and CI Pigment Red 179 pigment dispersion resist composition is mixed so as to have a predetermined pigment ratio to obtain a pigment dispersion resist composition .

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "%" means "% by mass" and "part" means "part by mass". In the present specification, "Trimix" is a trademark of Inoue KK, and "Irgacure" is a registered trademark of Ciba Specialty Chemicals.

<Pigment Dispersion Adjuster>

(Pigment Dispersion Adjuster A-1)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask and stirred with a magnetic stirrer. Pigment Orange 71 (10 g) was added, and the mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was put in a 1 L beaker, the reaction mixture was poured into the ice water and stirred for 30 minutes by a magnetic stirrer. This was filtrated and washed with water under reduced pressure, and the obtained solid was dried to obtain 12 g of pigment dispersion auxiliary agent A-1.

(Pigment Dispersion Adjuster A-2)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask and stirred with a magnetic stirrer. Pigment Red 177 (10 g) was added thereto, followed by stirring at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was put in a 1 L beaker, the reaction mixture was poured into the ice water and stirred for 30 minutes by a magnetic stirrer. This was filtrated / washed under reduced pressure, and the resulting solid was dried to obtain 12 g of pigment dispersion auxiliary agent A-2.

(Pigment Dispersion Adjuster A-3)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask and stirred with a magnetic stirrer. 10 g of Pigment Red 179 was added, and the mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was put in a 1 L beaker, the reaction mixture was poured into the ice water and stirred for 30 minutes by a magnetic stirrer. This was filtrated and washed with water under reduced pressure, and the obtained solid was dried to obtain 12 g of pigment dispersion auxiliary agent A-3.

(Pigment Dispersion Adjuster B-1)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask and stirred with a magnetic stirrer. Pigment Red 2 (10 g) was added thereto, and the mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was put in a 1 L beaker, the reaction mixture was poured into the ice water and stirred for 30 minutes by a magnetic stirrer. This was filtrated and washed with water under reduced pressure, and the obtained solid was dried to obtain 12 g of pigment dispersion auxiliary agent B-1.

(Pigment Dispersion Adjuster B-2)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask and stirred with a magnetic stirrer. Pigment Red 17 (10 g) was added thereto, followed by stirring at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was put in a 1 L beaker, the reaction mixture was poured into the ice water and stirred for 30 minutes by a magnetic stirrer. This was filtrated and washed with water under reduced pressure, and the obtained solid was dried to obtain 12 g of pigment dispersion auxiliary agent B-2.

&Lt; Fine Particleization Treatment &gt;

Preparation Example 1 (Fine-grained PR264 (Pigment Red 264) (for dispersions 3 and 4))

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 800 parts of Pigment Red 264, 40 parts of pigment dispersion auxiliary A-1, 8,000 parts of sodium chloride having a particle diameter of 20 占 퐉 and 1,920 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. After filtration and washing were repeated to remove sodium chloride and diethylene glycol, the mixture was dried at 40 DEG C per day to obtain 95 parts of microparticulated PR264.

Preparation Example 2 (Fine particleization treatment PR254 (Pigment Red 254) (for dispersions 7 and 8))

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 800 parts of Pigment Red 254, 40 parts of pigment dispersion auxiliary A-1, 8,000 parts of sodium chloride having a particle diameter of 20 占 퐉 and 1,920 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, and the mixture was dried at 40 DEG C per day to obtain 95 parts by weight of ultrafiltered PR254.

Preparation Example 3 (Fine particleization treatment PR177 (Pigment Red 177) (for dispersion 10))

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 800 parts of Pigment Red 177, 40 parts of pigment dispersion auxiliary A-1, 8,000 parts of sodium chloride of 20 占 퐉 in particle diameter and 1,920 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, and the mixture was dried at 40 DEG C per day to obtain 95 parts of microparticulated PR177.

Preparation Example 4 (Fine particleization treatment PR179 (Pigment Red 179) (for dispersion liquid 12))

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 800 parts of Pigment Red 179, 40 parts of pigment dispersion auxiliary A-1, 8,000 parts of sodium chloride of 20 占 퐉 in particle diameter and 1,920 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. The filtration and washing were repeated to remove sodium chloride and diethylene glycol, and the mixture was dried at 40 DEG C per day to obtain 95 parts of fine particle treatment PR179.

Preparation Example 5 ((Pigment Red Pigment Red 264 without Pigment Dispersion Adjuster Addition) (for Dispersions 1 and 2))

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 750 parts of Pigment Red 264, 7,500 parts of sodium chloride having a particle diameter of 20 mu m, and 1,800 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 40 DEG C per day to obtain 95 parts of PR264.

Preparation Example 6 (Pigment Reduction Pigment Red 254 (for Dispersions 5 and 6) without Addition of Pigment Dispersion Adjuster A-1)

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 750 parts of Pigment Red 254, 7,500 parts of sodium chloride having a particle diameter of 20 占 퐉 and 1,800 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. After filtration and washing were repeated to remove sodium chloride and diethylene glycol, the mixture was dried at 40 DEG C per day to obtain 95 parts of the finely divided product 6.

Preparation Example 7 (Pigment Red Pigment Red 177 (for dispersion 9) without addition of Pigment Dispersion Adjuster A-2)

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 750 parts of Pigment Red 177, 7,500 parts of sodium chloride having a particle diameter of 20 占 퐉 and 1,800 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. After filtration and washing were repeated to remove sodium chloride and diethylene glycol, the mixture was dried at 40 DEG C per day to obtain 95 parts of finely pulverized product 7.

Preparation Example 8 (Pigment Red Pigment Red 179 (for dispersion 11) without addition of Pigment Dispersion Adjuster A-3)

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 750 parts of Pigment Red 179, 7,500 parts of sodium chloride having a particle diameter of 20 mu m, and 1,800 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, and then dried at 40 DEG C per day to obtain 95 parts of fine particulate material 8.

Preparation Example 9 (Pigment Red Pigment Red 170 (for dispersion liquid 13) without addition of pigment dispersion auxiliary)

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 750 parts of Pigment Red 170, 7,500 parts of sodium chloride having a particle diameter of 20 占 퐉, and 1,800 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. After filtration and washing were repeated to remove sodium chloride and diethylene glycol, the mixture was dried at 40 DEG C per day to obtain 95 parts of fine particulate product 9.

Preparation Example 10 (Pigment Red Pigment Red 178 (for dispersion liquid 14) without addition of a pigment dispersion auxiliary)

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 750 parts of Pigment Red 178, 7,500 parts of sodium chloride having a particle diameter of 20 占 퐉 and 1,800 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. The filtration and washing were repeated to remove sodium chloride and diethylene glycol, and then dried at 40 DEG C per day to obtain 95 parts of fine particulate material 10.

Preparation Example 11 (Pigment Red Pigment Red 187 (for dispersion 15) without addition of a pigment dispersion auxiliary)

Trim Mix TX-15 (trade name, manufactured by INOUE MFG. 750 parts of Pigment Red 187, 7,500 parts of sodium chloride having a particle diameter of 20 占 퐉 and 1,800 parts of diethylene glycol. Which was in the range of 70% of the rated current value of 9.3 A and further kneaded at 45 캜 for 3 hours to perform salt milling. Next, 1,300 parts of the kneaded product obtained was charged into 3 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, and the mixture was dried at 40 DEG C per day to obtain 95 parts of fine particle product 11. [

<Pigment dispersant>

Acrylic block copolymer having quaternary amino group

<Alkali-soluble resin>

BzMA / MAA copolymer (benzyl methacrylate / methacrylic acid copolymer, theoretical acid value: 120 mgKOH / g, mass average molecular weight: 25,000)

&Lt; Photopolymerizable compound &gt;

DPEHA (dipentaerythritol hexaacrylate)

<Photopolymerization initiator>

2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one manufactured by Ciba Specialty Chemicals,

<Organic solvents>

PGMEA (propylene glycol monomethyl ether acetate)

(Preparation of dispersion and resist composition)

<Red pigment dispersion>

Each of the particulate materials for each dispersion and the other components were mixed with each other to obtain the composition shown in Table 1 and kneaded at a temperature of 40 to 50 캜 for 3 hours by a bead mill to obtain respective red pigment dispersions.

&Lt; Pigment-dispersed resist composition for color filter &

(BzMA / MAA copolymer, DPEHA, Irgacure, PGMEA) different from the respective pigment dispersion compositions obtained in the above process were homogeneously mixed using a high-speed stirrer so as to have the composition shown in Table 1, Followed by filtration to obtain a red pigment-dispersed resist composition for each color filter.

&Lt; Red pigment-dispersed resist composition for color filter of Examples and Comparative Examples &gt;

The red pigment-dispersed resist compositions for the respective color filters were combined so as to be the compositions shown in Table 2 to obtain the red pigment-dispersed resist compositions for color filters of Examples 1 to 6 and Comparative Examples 1 to 7.

Assessment Methods

The following evaluation was carried out, and the evaluation results are shown in Tables 1 and 2.

<Viscosity>

Each of the pigment-dispersed resist compositions for color filter of the examples and comparative examples was taken in a glass bottle and the stopper was closed and stored at room temperature for 1 day. Then, 25 parts of a 25 &Lt; / RTI &gt; The lower the viscosity, the better the fluidity and the better the pigment dispersion.

<Dispersion stability>

The pigment-dispersed resist compositions for color filters in Examples and Comparative Examples were each taken in a glass bottle, the stopper was closed, and the state after being stored at room temperature for 7 days was evaluated according to the following evaluation criteria.

○: Thickening and sediment are not confirmed.

△: Strongly shaken, the thickening or sediment to the extent of returning to the original state is confirmed.

X: Thickening or sediment to the extent that it does not return to its original state even when shaken strongly is confirmed.

<Evaluation of Color Characteristics of Pigment-Dispersed Resist Composition for Color Filter>

The color characteristics (x, y, and Y) of each resist of Example and Comparative Example in which the film thickness was 1.0 占 퐉 were measured by a spectrophotometer (UV-2500PC manufactured by Shimadzu Corporation, 2 ° view angle of C light source). Here, in Examples 1 to 5 and Comparative Examples 1 to 6, the film thickness for setting the chromaticity x = 0.670 and the lightness Y at y = 0.312 was used. In Examples 5 to 6 and Comparative Example 7, chromaticity x = 0.670 and y = The film thickness for obtaining the lightness Y in the film thickness was obtained.

According to the examples of Examples 1 to 6, the film thickness required to obtain the chromaticity x = 0.670 and y = 0.312 required for the color filter was as thin as 2.11 to 2.60 占 퐉, and the brightness at this time was as bright as 13.2 to 14.5. In addition, the contrast was high for Bare 10,000 and 1,000.

On the other hand, according to Comparative Example 1 using the PR264 material without using the particulate PR264, the lightness and the film thickness were good, but the process for obtaining the necessary film thickness was complicated because the viscosity was low.

According to Comparative Example 2 in which PR177 was used in place of PR264, it was difficult to use it for a color filter because the film thickness required for chromaticity was thick and the viscosity was low.

According to Comparative Example 3 using PR170 instead of PR264 and Comparative Example 4 using PR178, the brightness was low and the contrast was low.

According to Comparative Example 5 using PR179 instead of PR264 in Example 1, the luminance was lowered.

According to Comparative Example 6 using PR187 instead of PR264 and Comparative Example 7 using PR177, the film thickness required for obtaining the required chromaticity became thick, and it was difficult to use it for a color filter. Further, according to Comparative Example 7, viscosity was low and handling was difficult.

As apparent from these results, remarkable effects can be obtained by adopting PR264 which has been subjected to fine particle treatment, rather than using PR170, PR179, PR187 and PR177 which have been subjected to the microparticulation treatment. In addition, to obtain such an effect, it is necessary not to use PR264 simply but to make it into fine particles.

Claims (5)

a. The following pigment dispersion of CI Pigment Red 264,
b. One or more pigments selected from the following pigment dispersions of CI Pigment Red 254, the following pigment dispersions of CI Pigment Red 177 and the following pigment dispersions of CI Pigment Red 179,
c. Alkali-soluble resin,
d. Photopolymerizable compound,
e. A photopolymerization initiator,
f. Organic solvent
Of a to f,
And the content of CI Pigment Red 264 relative to the total mass of the pigment is 50 mass% or more and less than 100 mass%.

Pigment Dispersion of CI Pigment Red 264: CI Pigment Red 264 was finely pulverized to give a pigment dispersion auxiliary agent, a basic pigment-containing polymer pigment dispersant, an alkali-soluble resin and an organic solvent represented by Chemical Formulas 1 and / The pigment dispersion obtained by adding and dispersing

Pigment Dispersion of CI Pigment Red 254: CI Pigment Red 254 was made into fine particles, to which a pigment dispersion auxiliary represented by Chemical Formulas 1 and / or 2, a polymer pigment dispersing agent containing a basic group, an alkali soluble resin and an organic solvent The pigment dispersion obtained by adding and dispersing

Pigment Dispersion of CI Pigment Red 177: CI Pigment Red 177 was made into fine particles, to which a pigment dispersion auxiliary agent represented by Chemical Formula 1 and / or 2, a polymer pigment dispersing agent containing a basic group, an alkali-soluble resin and an organic solvent The pigment dispersion obtained by adding and dispersing

Pigment Dispersion of CI Pigment Red 179: CI Pigment Red 179 was finely pulverized to obtain a pigment dispersion auxiliary agent, a basic pigment-containing polymer pigment dispersant, an alkali-soluble resin and an organic solvent represented by Chemical Formulas 1 and / A pigment dispersion obtained by adding and dispersing.

Wherein X and Y are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, NO ₂ , CH ₃ or OCH ₃ . M is H, Na, K, NH ₄ or NR ¹ R ² R ³ R ⁴ (wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and are a saturated group having 1 to 10 carbon atoms Or an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group of 6 to 10 carbon atoms which may be substituted with another substituent). and m represents an integer of 1 or more. The method according to claim 1,
Wherein the basic group-containing polymeric pigment dispersant is an acrylic block copolymer having tertiary and / or quaternary amino groups. 3. The method according to claim 1 or 2,
The pigment dispersion of Pigment Red 264, the pigment dispersion of CI Pigment Red 254, the pigment dispersion of CI Pigment Red 177 and the pigment dispersion of CI Pigment Red 179 are the following pigment dispersions By weight based on the total weight of the color filter.

Pigment Dispersion of CI Pigment Red 264: CI Pigment Red 264 in the presence of a sulfonate of a compound having the same backbone as the CI Pigment Red 264. A pigment dispersion auxiliary agent, a pigment dispersant containing a basic group, an alkali-soluble resin, and an organic solvent,

Pigment Dispersion of CI Pigment Red 254: CI Pigment Red 254 in the presence of a sulfonate of a compound having the same skeleton, to a fine particle product obtained by micropelling CI Pigment Red 254, A pigment dispersion auxiliary agent, a pigment dispersant containing a basic group, an alkali-soluble resin, and an organic solvent,

Pigment Dispersion of CI Pigment Red 177: CI Pigment Red 177 in the presence of a sulfonate of a compound having the same skeleton as the CI Pigment Red 177, A pigment dispersion auxiliary agent, a pigment dispersant containing a basic group, an alkali-soluble resin, and an organic solvent,

Pigment Dispersion of CI Pigment Red 179: CI Pigment Red 179 in the presence of a sulfonated compound of a compound having the same skeleton, to a fine particle product obtained by micropelling CI Pigment Red 179, A pigment dispersion obtained by adding and dispersing a pigment dispersing aid, a polymeric pigment dispersant containing a basic group, an alkali-soluble resin and an organic solvent. The method of claim 3,
Wherein the sulfonated compound of the compound having the same skeleton as the CI Pigment Red 264 is the sulfonated compound of CI Pigment Orange 71 and the sulfonated compound of the compound having the same skeleton as the CI Pigment Red 254 is the sulfonated product of CI Pigment Orange 71 Wherein the sulfonated compound of the compound having the same skeleton as the CI Pigment Red 177 is the sulfonated compound of the CI Pigment Red 177 and the sulfonated compound of the compound having the same skeleton as the CI Pigment Red 179 is the CI Pigment Red 179 Wherein the pigment dispersion adjuvant represented by the general formula (1) and / or the general formula (2) is (Formula 3 and 4) and / or (Formula 5 and 6).

5. The method according to any one of claims 1 to 4,
And further contains 5 to 15 parts by mass of barium sulfate having a primary particle diameter of 5 to 20 nm based on 100 parts by mass of the total mass of the pigment.