JP2002194244A - Pigment dispersion composition, coloring photosensitive composition obtained by using the same and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersion composition excellent in dispersion stability and color tones, and, in particular, capable of giving a color filter having a high light transmittance when used for preparing a color filter. SOLUTION: The pigment dispersion composition comprises a pigment, a dispersant having a rising wavelength of 400-550 nm in the transmitted spectrum and an average particle size of at most 100 nm and a resin, all dispersed in an organic solvent. Preferably, the resin in the pigment dispersion composition is a polymer bearing an acidic group having an acid value of 60-130.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pigment dispersion composition,
The present invention relates to a colored photosensitive composition and a color filter using the same.

[0002]

2. Description of the Related Art Conventionally, pigments have been widely used in many fields such as paints, printing inks, color display boards, etc., because they exhibit a vivid color tone and high coloring power. Further, since the photosensitive composition containing a pigment can form an image having a clear color tone by light irradiation, for example, formation of a multicolor image on a substrate such as a color proof, and color formation of a liquid crystal color display or the like Widely used as a filter material. In such various uses, the pigment is usually used as a pigment dispersion composition dispersed in a medium such as an organic solvent.

[0003] In the above-mentioned pigment dispersion composition, if the dispersion stability of the pigment is insufficient, the pigment may agglomerate and the fluidity as a paint may not be obtained. Further, there is a problem that a uniform coating film cannot be formed when a colored coating film is formed, for example, when used for producing a color filter. Furthermore, the desired color tone and light transmittance may not be obtained due to aggregation of the pigment, which may adversely affect the display characteristics and the like of the color filter. For the purpose of improving the dispersion stability of the pigment in the pigment dispersion composition, a dispersant is often added to the pigment dispersion composition. The dispersants can be broadly classified into polymer dispersants and low molecular compound dispersants. Examples of the polymer dispersants include polyacrylates, sodium maleate olefin copolymers, and polyesters having a terminal carboxyl group (Japanese Patent Publication No. 54-34
009), a polyester having an acidic group and / or a basic group starting from tetrakis (2-hydroxyalkyl) ethylenediamine (JP-A-2-2452).
No. 31), a macromonomer (an oligomer having an ethylenically unsaturated group at a terminal), a monomer having a hydroxyl group,
Copolymers comprising four kinds of carboxy group-containing monomers and monomers other than these (JP-A-8-259876) and the like are known. As the low molecular compound dispersant, sorbitan fatty acid esters, polyoxyethylene alkylamines, alkyldiamines, alkanolamine derivatives (US Pat. No. 3,536,510) and the like are known. An example is Tokuhei 5
-72943 and JP-A-8-48890.

[0004]

When a conventional dispersant is used, the dispersion stability of the pigment is improved to some extent. However, for example, when used in the production of color filters, color proofs, and the like, an extremely thin colored coating film is formed, and the coating film is required to have sharp coloring properties. There is. When the pigment is refined, the viscosity of the pigment dispersion composition is increased, and as a result, the quality of the color filter and the color proof to be produced may be reduced. On the other hand, by adding a pigment derivative having the same skeleton as the pigment, a pigment dispersion composition having improved dispersion stability of the pigment, for example, US Pat. No. 4,664,714,
U.S. Pat. No. 4,310,359, U.S. Pat.
973, 981) and JP-A-59-96175. Further, a pigment dispersion composition in which a pigment derivative having the same skeleton as the pigment to be dispersed and a urethane-based pigment dispersant are used in combination to improve the dispersibility of the pigment is described in JP-A-62-295966. . When a dispersant having the same skeleton as the pigment is used, the dispersion stability of the pigment is improved. However, since the dispersant is colored, the color tone originally possessed by the pigment may be impaired. As a result, it may be difficult to adjust the pigment dispersion composition to a desired color.

The present invention has been made in view of the above-mentioned problems, and has excellent dispersion stability and color tone. In particular, a pigment capable of stably producing a color filter having high contrast when used for producing a color filter. It is an object to provide a dispersion composition. Further, the present invention provides a colored photosensitive composition capable of forming an image having a clear color tone and high light transmittance, and particularly capable of stably producing a color filter having a high contrast when used for producing a color filter. The task is to provide Another object of the present invention is to provide a color filter having a clear color tone and a high light transmittance and having a high contrast.

[0006]

Means for solving the above problems are as follows. <1> Pigment and transmission wavelength rising wavelength of 4
A pigment dispersion composition comprising a dispersant having an average particle size of 100 to 550 nm and an average particle diameter of 100 nm or less, and a resin dispersed in an organic solvent. <2> The pigment dispersion composition according to <1>, wherein the resin is a polymer having an acidic group. <3> The acid value of the polymer having an acidic group is from 60 to 1.
30. The pigment dispersion composition according to <2>, wherein the composition is 30. <4> The pigment dispersion composition according to any one of <1> to <3>, wherein the dispersant and the pigment have an azo dye skeleton.

<5> The dispersant is a compound represented by the following general formula (I): <1> to <4>
The pigment dispersion composition according to any one of <1> to <3>.

[0008]

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In the general formula (I), A represents a component capable of forming an azo dye together with XY. X represents a single bond or a group selected from divalent linking groups represented by the following structural formulas. Y represents a group represented by the following general formula (II).

[0010]

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[0011]

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In the general formula (II), Z represents a lower alkylene group. -NR ₂ represents a 5- or 6-membered saturated heterocyclic ring containing lower alkylamino group, or a nitrogen atom. a represents 1 or 2.

<6> The pigment dispersion composition according to any one of <1> to <5>, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. It is a colored photosensitive composition characterized by the following. <7> A color filter having two or more patterned colored layers having different hues on a substrate, wherein the colored layer is made of the colored photosensitive composition according to claim 6. It is a color filter.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. <Pigment dispersion composition> The pigment dispersion composition of the present invention has a pigment and a rising wavelength of a transmission spectrum of 400 to 550.
and a dispersant having an average particle diameter of 100 nm or less and a resin are dispersed in an organic solvent. Here, the rising wavelength of the transmission spectrum refers to the wavelength indicated by the arrow in the graph of FIG. 1, and refers to the wavelength at which the transmittance begins to rapidly rise in the transmission spectrum curve. More specifically, it refers to the wavelength at the intersection of the tangent at the bottom of the transmission spectrum curve and the tangent at the rise. In the present invention, the transmission spectrum of the dispersant is a composition composed of a dispersant (concentration 10%), an acrylic resin (concentration 20%), and a solvent (concentration 70%) and having a thickness of 3 μm. Refers to the transmission spectrum of the coating film.

Conventionally, when a dispersant having a pigment skeleton is used, the dispersion stability of the pigment can be improved, but the dispersant has a considerable effect on the color tone of the pigment, and the original color tone of the pigment cannot be sufficiently exhibited. There was a case. In the present invention, by using a compound having a transmission spectrum rising in the above range as a dispersant, while improving the dispersion stability of the pigment, the effect of the dispersant on the color tone of the pigment dispersion composition is suppressed, and the pigment originally has Fully exhibit the color tone possessed by. In particular, when used for the production of a color filter that needs to be finely divided, the viscosity of the color filter is small, and the color filter has a clear color tone and high light transmission, and has a high contrast. Can be manufactured stably.

The rising wavelength of the transmission spectrum of the dispersant used in the present invention is preferably from 400 nm to 550 nm, and more preferably from 410 nm to 500 nm. Further, the dispersant has a rising wavelength of the transmission spectrum within the above range and a peak of the transmission spectrum from a visible part to a near-infrared part, specifically, 450 nm to
It is preferably a compound having a pigment skeleton existing at 700 nm.

FIG. 2 shows a blue pigment (B) having a peak at a wavelength of 450 nm, a green pigment (G) having a peak at a wavelength of 550 nm, a red pigment (R) having a peak at a wavelength of 650 nm, and a dispersant having a rising wavelength of 475 nm. (D)
Is schematically shown.

In FIG. 2, paying attention to the transmission spectrum of the green pigment and the transmission spectrum of the dispersant, it can be seen that the color tone and the transmittance of the green pigment are particularly affected by the position of the rising wavelength of the dispersant. When the rising wavelength of the dispersant exceeds 550 nm, the transmittance is significantly reduced. When the rising wavelength of the dispersant is less than 400 nm, the desired chromaticity cannot be obtained, and the amount of other pigment (for example, yellow pigment) used as a complementary color increases. FIG. 3 shows an example of the transmission spectrum (G) of the green pigment and an example of the transmission spectrum (G + D) of the green pigment when the dispersant is added. As shown in FIG. 3, when a dispersant having a rise in the wavelength range is used, a green pigment dispersion composition can be prepared without impairing the color tone of the original green pigment.

Looking at the transmission spectrum of the red pigment and the spectrum of the dispersant in FIG. 2, it can be seen that the effect of the transmission spectrum on the red pigment is small when the dispersant is added. The dispersant exhibiting a rising wavelength in the above range exhibits a transmission spectrum peak at the same position as the yellow pigment, but generally, the yellow pigment is often added for adjusting the color tone of the red pigment, so the effect is Few. Another advantage is that the amount of the yellow pigment added for adjusting the color tone can be reduced.

When the transmission spectrum of the blue pigment in FIG. 2 is added to the transmission spectrum of the dispersant, the transmittance of the transmission spectrum of the blue pigment tends to decrease. Is preferably reduced as compared with the pigment dispersion compositions of other colors.

The dispersant used in the present invention has an average particle size of 10
0 nm or less. Preferably it is 80 nm or less, more preferably 60 nm or less. When the particle size of the dispersant is in the above range, the light transmittance can be further increased, particularly,
When used for manufacturing a color filter, a color filter having high light transmittance can be manufactured.

As the dispersant used in the present invention, a compound having a pigment skeleton is preferable, and a compound having an azo dye skeleton is preferable. Particularly, a compound represented by the following general formula (I) is preferable. When the dispersant is used, the dispersant is adsorbed on the surface of the pigment particles by the nitrogen atom of the dispersant, the surface of the pigment particles is covered with the dispersant, and the adsorption of the pigment particles to each other is suppressed. However, the pigments hardly aggregate. As a result, the pigment particles are uniformly dispersed in a finely divided state, and the dispersibility of the pigment is particularly improved.

[0023]

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In the general formula (I), A represents a component capable of forming an azo dye together with XY. A can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazonium compound. Hereinafter, specific examples of the above A are shown, but the present invention is not limited to these specific examples.

[0025]

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[0026]

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In the general formula (I), X is a single bond (Y is-
It means that it is directly connected to N = N-. ) Or a group selected from divalent linking groups represented by the following structural formulas.

[0028]

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In the above general formula (I), Y is the following general formula (II)
Represents a group represented by

[0030]

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In the general formula (II), Z represents a lower alkylene group. Z is represented by — (CH ₂ ) _b —, where b is 1 to
Represents an integer of 5, preferably 2 or 3. General formula (I
During I), -NR ₂ represents a 5- or 6-membered saturated heterocyclic ring containing lower alkylamino group, or a nitrogen atom. The -NR
_{When 2} represents a lower alkylamino group, -N (C _n H
_{2n + 1} ) ₂ , wherein n represents an integer of 1 to 4, and preferably represents 1 or 2. On the other hand, when -NR ₂ represents a 5- or 6-membered saturated hetero ring containing a nitrogen atom, a hetero ring represented by the following structural formula is preferable.

[0032]

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In the general formula (II), Z and —NR ₂
May each have a lower alkyl group or an alkoxy group as a substituent. In the general formula (II), a represents 1
Or 2 and preferably 2.

Hereinafter, specific examples of the compound represented by the general formula (I) will be shown, but the present invention is not limited to these specific examples.

[0035]

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[0036]

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[0037]

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[0038]

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Along with the compound represented by the general formula (I), JP-A No. 2000-239554 describes
It is preferable to use in combination the amine compound represented by the general formula (III) and / or the amine compound represented by the general formula (IV) described in Columns to 0043. The compound represented by the general formula (I) can be synthesized according to the method described in columns 0033 to 0035 of JP-A-2000-239554. In addition, as the compound represented by the general formula (I), a commercially available product may be used, and for example, “Solsperse 22000” manufactured by Abina may be mentioned.

The preferable range of the content of the dispersant in the pigment dispersion composition of the present invention also varies depending on the type of the dispersant used. 0.1 to parts by mass
The amount is preferably 100 parts by mass, more preferably 1 to 30 parts by mass. In the preparation of the blue pigment dispersion composition, generally, it is preferably 10 parts by mass, more preferably 2 to 5 parts by mass, per 100 parts by mass of the pigment. It is preferable that the content be in the above range, since it is easy to adjust the chromaticity when producing a color filter or the like while preventing the viscosity of the pigment dispersion composition from excessively increasing.

As the pigment usable in the pigment dispersion composition of the present invention, an organic pigment can be used. Examples of the organic pigment include a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, a black pigment, and the like. When the dispersant is a compound having an azo pigment skeleton (for example, the compound represented by the general formula (I)), the pigment used in combination is preferably a pigment having an azo dye skeleton.

Examples of the yellow pigment include C.I. I.
Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 12, C.I. Pigment Yellow 17, C.I. I. Pigment Yellow 83,
C. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 109,
C. I. Pigment yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 12
5, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 1
39, C.I. I. Pigment Yellow 185, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. I. Pigment yellow,
C. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 16
8, C.I. I. Pigment Yellow 185 and the like.

Examples of the orange pigment include C.I.
I. Pigment Orange 36, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I.
Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 71, and the like.

Examples of the red pigment include C.I. I.
Pigment Red 9, C.I. I. Pigment Red 97,
C. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I.
I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I.
Pigment Red 192, C.I. I. Pigment Red 2
15, C.I. I. Pigment Red 216, C.I. I. Pigment Red 217, C.I. I. Pigment Red 22
0, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226,
C. I. Pigment Red 227, C.I. I. Pigment Red 228, C.I. I. Pigment Red 240, C.I.
I. Pigment Red 242, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 209, C.I.
I. Pigment Red 146, C.I. I. Pigment Red 11, C.I. I. Pigment Red 81, C.I. I. Pigment Red 213, C.I. I. Pigment Red 27
2, C.I. I. Pigment Red 270, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264,
C. I. Pigment Red 254, and the like.

As the violet pigment, for example,
C. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 30, C.I.
I. Pigment Violet 37, C.I. I. Pigmented Violet 40, C.I. I. Pigment Violet 5
0 and the like.

Examples of the blue pigment include C.I. I.
Pigment Blue 15, C.I. I. Pigment Blue 1
5: 6, C.I. I. Pigment Blue 22, C, I.P. Pigment Blue 60, C.I. I. Pigment Blue 64, and the like.

Examples of the green pigment include C.I. I.
Pigment Green 7, C.I. I. Pigment Green 3
6, etc. Examples of the brown pigment include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26,
And the like. Examples of the black pigment include C.I.
I. Pigment Black 7, and the like.

These pigments may be used alone or in combination of two or more. In the present invention, among these, pigments having an acidic group such as Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 185, and Pigment Yellow 83 are preferable,
Pigment Yellow 138, Pigment Yellow 13
9, Pigment Yellow 185, Pigment Red 25
4, Pigment Green 36, Pigment Blue 15 and the like are particularly preferred.

The preferred range of the pigment content in the pigment dispersion composition of the present invention varies depending on the type used, but is generally preferably 5 to 80% by mass, and more preferably 10 to 80% by mass.
70 mass% is more preferable. It is preferable that the content is within the above range, since it is possible to prevent the viscosity from excessively increasing while maintaining a high coloring power.

[0050]

As a resin usable in the pigment dispersion composition of the present invention, a polymer having an acidic group is preferable. When a polymer having an acidic group is used as the resin, steric repulsion can be imparted, the dispersion stability of the pigment is improved, and alkali developability when used as a colored photosensitive composition is improved. . Examples of the polymer having an acidic group include a copolymer of (meth) acrylic acid and a (meth) acrylate, a styrene / maleic anhydride copolymer, and a styrene / maleic anhydride copolymer and an alcohol. And the like. These may be used alone or in combination of two or more. Among them, pigment dispersibility is excellent, when used as a colored photosensitive composition, polyfunctional monomer, excellent compatibility with photopolymerization initiator, alkali developer solubility, organic solvent solubility, strength, softening Those having an appropriate temperature and the like are preferable, and specifically, a copolymer of (meth) acrylic acid and a (meth) acrylic acid ester (for example, methacrylic acid / benzyl methacrylate today's polymer) is preferable.

The acid value of the polymer having an acidic group is 60
It is preferably from 130 to 130. When the acid value is in the above range, the dispersion stability is good and the viscosity can be kept low, which is preferable. The unit of the acid value is represented by milligrams of potassium hydroxide required to neutralize 1 g of the polymer. Further, the acid value of the polymer can be adjusted by the molar ratio of the monomers constituting the polymer.

The weight average molecular weight of the polymer having an acidic group is preferably 5,000 to 200,000. When the weight average molecular weight is less than 5,000, when used as a colored photosensitive composition, there may be a problem in forming a coating film, and when it exceeds 200,000, the viscosity of the colored photosensitive composition increases. Sometimes.

Although the preferred range of the content of the resin in the pigment dispersion composition of the present invention varies depending on the kind used, it is generally 10 to 200 parts by mass relative to 100 parts by mass of the pigment. Is preferably 20 to 15
0 parts by mass is more preferred. It is preferable that the content be in the above-mentioned range, since a steric repulsion effect can be obtained and the viscosity of the dispersion can be prevented from excessively increasing.

The pigment dispersion composition of the present invention may optionally contain other components such as a surfactant. It is preferable to include a surfactant because the dispersion stability of the pigment is further improved. Examples of the surfactant include an alkyl naphthalene sulfonate, an anionic surfactant represented by a phosphoric acid ester salt, a cationic surfactant represented by an amine salt, an aminocarboxylic acid, and a betaine type. Examples include an amphoteric surfactant.

The pigment dispersion composition of the present invention is obtained by dispersing a pigment (for example, red, green, and blue pigments), a dispersant, and a resin together with a solvent using a dispersing machine such as a sand mill. Can be. At this time, after the pigment and the dispersant are preliminarily mixed and refined, the mixture may be dispersed in an organic solvent (or vehicle), or the pigment and the dispersant may be separately refined beforehand. It may be dispersed or dissolved in an organic solvent (or vehicle) and the resulting dispersion or solution may be mixed, or the pigment and dispersant which have been subjected to micronization may be separately added and dispersed in an organic solvent (or vehicle). You may. In particular, it is preferable that the pigment and the dispersant are previously subjected to a fine treatment simultaneously or individually. Here, the vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state. In addition to the organic solvent, a component that is liquid and binds to the pigment to solidify the coating film (binder resin) ) Is also included.

The disperser used for dispersing the pigment and the dispersant which have been subjected to the micronization treatment in the organic solvent is not particularly limited, and examples thereof include a kneader, a roll mill, an attritor,
Known dispersing machines such as a super mill, a dissolver, a homomixer, and a sand mill are exemplified.

In the pigment dispersion composition of the present invention, the organic solvent in which the dispersant, the pigment and the resin are dispersed is not particularly limited, and can be appropriately selected from known organic solvents. For example, ethylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, and ethylene glycol monoethyl ether, and their acetic esters; ethyl acetate, n-acetic acid Propyl, i-propyl acetate, n-butyl acetate, i-acetate
Acetates such as butyl; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol; And alcohols such as glycerin. These may be used alone or in combination of two or more. Among these,
Alkylene glycol monoalkyl ethers and their acetates, acetates, methyl ethyl ketone and the like are preferred.

The content of the organic solvent in the pigment dispersion composition is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the pigment. When the content is within the above range, the viscosity of the pigment dispersion composition can be prevented from excessively increasing, and it is not difficult to secure a space during storage, which is preferable.

In the present invention, the dispersant has an average particle size of 100 nm or less. In order to keep the average particle size of the dispersant within the above range, it is possible to disperse the dispersant and the pigment at the same time as the primary particles by dispersing the dispersant and the pigment for a long time using a high-speed sand mill or the like. Requires a great deal of energy, and the fine pigment particles and dispersant obtained by such a method are liable to cause weak agglomeration generally called flocculation, and the dispersion tends to have high viscosity and thixotropic There is a problem that it is difficult to obtain a uniform color filter coating film. Therefore, it is preferable to disperse both the pigment and the dispersant after the primary particles are refined.

The fine treatment of the dispersant and the pigment is performed by
It may be performed simultaneously or individually. Simultaneous refining in the state where the pigment and dispersant coexist,
This is preferable because of good productivity. As the miniaturization process,
A method of mechanically pulverizing a pigment and a dispersant to reduce the particle size (referred to as a grinding method), and a method of dissolving a pigment and a dispersant in a good solvent to deposit a pigment and a dispersant having a small particle size by adding the solution to a poor solvent ( (Referred to as a precipitation method), and a method of producing fine particles having a small particle size during synthesis (referred to as a synthetic precipitation method). Depending on the synthesis method and chemical properties of the pigment and dispersant used,
It can be performed by selecting an appropriate method. The miniaturization process may be performed by combining two or more methods. Also,
When the pigment and the dispersant are individually subjected to the fine treatment, the fine treatments may be different from each other.

In the above-mentioned grinding method, after the pigment and / or dispersant is ground with a grinding agent such as salt using a ball mill, a sand mill or a kneader, the grinding agent is removed.
By a method of making the primary particles fine, relatively uniform pigment particles and / or dispersed particles can be obtained.

In the above-mentioned precipitation method, a pigment and / or a dispersant are dissolved in an appropriate good solvent, and then mixed with a poor solvent.
In the method of precipitating fine crystal particles, the type and amount of the solvent,
The size of the primary particles can be controlled by the deposition temperature, the deposition rate, and the like. Solvents used include concentrated sulfuric acid, polyphosphoric acid,
Strongly acidic solvents such as chlorosulfonic acid or basic solvents such as liquid ammonia and sodium methylate in dimethylformamide.

Among the above-mentioned precipitation methods, there is a leuco method as a special precipitation method. Vat dye pigments such as flavantron-based, perinone-based, perylene-based, and indanthrone-based pigments are reduced to alkaline hydrosulfite, and the quinone group becomes a hydroquinone sodium salt (leuco compound) and becomes water-soluble. By adding an appropriate oxidizing agent to this aqueous solution and oxidizing it, fine pigments and dispersants can be precipitated.

The synthetic precipitation method is a method of synthesizing a pigment and / or a dispersing agent and simultaneously depositing them as fine crystal particles. However, when removing the produced fine pigment and / or fine dispersant from the solvent, filtration, which is a general separation method, becomes difficult unless the particles are aggregated into large secondary particles. It is applied to azo-based pigments and the like that are synthesized in aqueous systems where secondary aggregation is likely to occur.

For the fine treatment, any of the above-mentioned methods may be used, but among these methods, the grinding method is preferable because the material is not relatively limited. The pulverization method is described in detail below. In this method, a pigment and a dispersant are mechanically kneaded with a water-soluble inorganic salt such as salt and a water-soluble organic solvent not dissolving the same (hereinafter, this step is called salt milling), and then the inorganic salt and the organic salt are mixed. This is a method of obtaining a pigment and a dispersant having fine primary particles by removing the solvent, washing with water, and drying. However, since the salt milling treatment may cause the pigment and the dispersant to grow in crystal, a method of preventing the crystal growth by adding a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment is effective. is there.

As for the ratio of the pigment and the dispersant to the inorganic salt, the higher the ratio of the inorganic salt, the higher the efficiency of the fineness of the pigment and the dispersant, but the lower the throughput of the pigment and the dispersant, the lower the productivity. . In general, 1 to 20 parts by weight of an inorganic salt is added to 1 part by weight of a pigment and a dispersant, and preferably 2 to 10 parts by weight.
It is recommended to use parts by weight. Further, the wetting agent is added so that the pigment and the dispersant and the inorganic salt become a uniform mass, depending on the mixing ratio of the pigment and the dispersant and the inorganic salt,
Usually, amounts of 50% to 300% by weight of the pigment are used.

More specifically, the salt milling is performed by adding a small amount of a water-soluble organic solvent as a wetting agent to a mixture of a pigment and a dispersant and a water-soluble inorganic salt, kneading the mixture with a kneader or the like, and then kneading the mixture. Into water and stirred with a high-speed mixer or the like to form a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment and / or a dispersant in which the primary particles are fined.

The pigment dispersion composition of the present invention can be used as a paint, a printing ink and the like. Further, for example, a coating solution containing the pigment dispersion composition is applied on a support and dried to form a layer of the pigment dispersion composition, or a layer of the pigment dispersion composition formed on a temporary support. Is transferred onto a support, a layer of a known positive or negative photosensitive resin composition is formed thereon, exposed and developed, and then exposed in the same region with the photosensitive resin composition layer. An image can be formed by a method of removing the layer of the pigment dispersion composition described above. Further, by mixing with the photosensitive composition, it can be used for image formation as a colored photosensitive composition capable of forming an image by light irradiation. This will be described later.

<Colored Photosensitive Composition> The colored photosensitive composition of the present invention comprises a pigment dispersion composition of the present invention, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. And is characterized by containing. Since the colored photosensitive composition of the present invention contains the pigment dispersion composition, the composition has excellent color tone and excellent dispersion stability of the pigment. In particular, when used for the production of color filters,
A color filter having a clear color tone and high light transmittance and having high contrast can be stably manufactured.

Examples of the polyfunctional monomer having two or more ethylenically unsaturated double bonds include, for example, those described in
Known (meth) acrylic acid esters, urethane (meth) acrylates, (meth) acrylic acid amides, allyl compounds, vinyl esters, and the like as described in JP-A-258538. These may be used alone or in combination of two or more. Among these, (meth) acrylates are preferred.

The content of the polyfunctional monomer having an ethylenically unsaturated double bond in the colored photosensitive composition is preferably from 10 to 60% by mass based on the total solid content. When the content is in the above range, it is preferable because the curing ability at the time of exposure is sufficiently maintained and the performance of other materials is not suppressed.

The photopolymerization initiator has a wavelength of about 30
It is preferred to use at least one compound having a molecular extinction coefficient of at least about 50 at 0 to 500 nm, such as, for example, JP-A-2-4866.
No. 4, JP-A-1-152449, and JP-A-2-153353, aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens, and the like. No. These may be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl)-
A combination of 4,5-diphenylimidazole dimers,
And 4- [p-N, N-di (ethoxycarbonylmethyl) -2,6-di (trichloromethyl) -s-triazine].

The content of the photopolymerization initiator in the colored photosensitive composition is preferably from 0.2 to 10% by mass based on the total solid content of the colored photosensitive composition. It is preferable that the content is within the above range, because it is possible to prevent the exposure sensitivity from becoming too high and difficult to control while maintaining the exposure sensitivity at a high level.

The colored photosensitive composition of the present invention is prepared by mixing the pigment dispersion composition of the present invention, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. can do. In addition, at the time of preparation,
A resin may be further added. As the resin, a polymer having the acidic group which can be used in a pigment dispersion composition is preferable. It is preferable to use the same resin as the resin used when preparing the pigment dispersion composition. In the colored photosensitive composition of the present invention, the content of the resin (particularly, polymer having an acidic group) is preferably about 20 to 80% by mass based on the total solid content. When the content is within the above range, it is preferable because it is possible to maintain the strength of the coating film at a high level and to prevent the ability of another material from being hardly exhibited.

The colored photosensitive composition of the present invention can be used for image formation by light irradiation. Formation of a colored image using the colored photosensitive composition is basically performed in the following (1) to
It can be performed by the step (3). (1) After preparing the pigment dispersion composition, using the same to prepare the colored photosensitive composition (2) coating the obtained colored photosensitive composition on a substrate and drying, or Step of transferring a layer formed by coating and drying on another temporary support onto a substrate to form a layer of a colored photosensitive composition (3) Layer of a colored photosensitive composition formed on a substrate For exposing and developing a pattern to form a pattern

As the substrate, a transparent material such as a glass plate or a transparent plastic plate is generally used. In order to improve the adhesion between the substrate and the colored photosensitive composition, various commercially available silane coupling agents or the like are added to the colored photosensitive composition, or the substrate is subjected to a coupling treatment in advance. May be.

The application of the coating solution of the colored photosensitive composition to the substrate can be performed by using a known coating means such as a spin coater, a roll coater, a bar coater, and a curtain coater.

As a method for transferring the layer of the colored photosensitive composition formed on the temporary support onto the substrate, a method using a heat roll laminator under normal pressure or reduced pressure is preferable.

Examples of the developing solution used in the development include hydroxides or carbonates of alkali metals or alkaline earth metals, hydrogencarbonates, asymonia water, and aqueous solutions of quaternary ammonium salts. Can be These may be used alone or in combination of two or more. Among these, an aqueous solution of sodium carbonate is particularly preferred.

<Color Filter> The color filter of the present invention is a color filter having two or more patterned colored layers having different hues on a substrate, wherein the colored layer is a colored photosensitive composition of the present invention. It is characterized by consisting of things. Since the colored layer of the color filter of the present invention is formed of the colored photosensitive composition of the present invention, the color filter has a clear color tone, high light transmittance, and high contrast. .

The color filter of the present invention is obtained by repeating the steps (2) and (3) to obtain a plurality of colors (usually R,
G, B). The color filter of the present invention can also be manufactured using a transfer method. For example, Japanese Patent Application Laid-Open Nos. 4-208940, 5-72724, 5-80503, and 5-1733 disclose a method of manufacturing a color filter using a transfer method.
The details are described in Japanese Patent Publication No. 20 and the like, and can be applied to the present invention.

The color filter of the present invention has a mode in which the colored layer is formed directly on a transparent substrate such as glass,
An embodiment in which the colored layer is formed on a substrate on which an active element such as an FT is formed (color filter on array: COA) is included.

The color filter of the present invention can be widely used for display devices such as personal computers, word processors, engineering workstations, navigation systems, televisions and videos.

[0085]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 A red pigment dispersion composition having the following composition was prepared. C. I. Pigment Red 254 6.4 g Pigment Dispersant 1 shown below 0.6 g Methacrylic acid / benzyl methacrylate 15.8 g (molar ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution, acid value 105) 1-methoxy-2-propyl acetate・ ・ ・ ・ ・ ・ ・ ・ 57.2g

The maximum absorption wavelength λmax of the following pigment dispersion composition
(In CHCl ₃ ) 391 nm, and the rising wavelength of the transmission spectrum was 445 nm. In addition, the pigment dispersant 1 is prepared by the following salt milling treatment (refinement treatment).
And used for preparation. 500 g of sodium chloride,
5 g of hydrogenated rosin ester (trade name: Ester Gum HP, manufactured by Arakawa Chemical Co., Ltd.), 150 g of the following pigment dispersant, and 300 g of polyethylene glycol were kneaded in an oven kneader (trade name: S1-1, manufactured by Moriyama Seisakusho) for 5 hours. The kneaded material was put into 2 liters of warm water and vigorously stirred at about 70 ° C. for 2 hours with a dissolver. Thereafter, the obtained dispersion was filtered, the residue on the filter was washed with water to remove sodium chloride and polyethylene glycol, and dried in a dry oven at about 40 ° C. for 2 days. The average particle size of the powder particles of the obtained pigment dispersant was 80 nm.

[0088]

Embedded image

The red pigment composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 9 hours.
A red pigment dispersion composition was prepared.

Example 2 A red pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment dispersant 1 was replaced with the following pigment dispersant 2.

[0091]

Embedded image

Example 3 A red pigment dispersion composition was prepared in the same manner as in Example 1, except that Pigment Dispersant 1 was replaced with "Solsperse 22000".

[Embodiment 4] In Embodiment 1, C.I. I.
Pigment Red 254, C.I. I. Pigment Red 177, except that Pigment Red 177 was used, to prepare a red pigment dispersion composition.

Fifth Embodiment In the first embodiment, the C.I. I.
Pigment Red 254, C.I. I. Pigment Yellow 139, except that Pigment Yellow 139 was used, to thereby prepare a yellow pigment dispersion composition.

[Sixth Embodiment] In the first embodiment, C.I. I.
Pigment Red 254, C.I. I. Pigment Yellow 138, except that Pigment Yellow 138 was used, to prepare a yellow pigment dispersion composition.

[Embodiment 7] In Embodiment 1, C.I. I.
Pigment Red 254, C.I. I. Pigment Green 36, except that Pigment Green 36 was used, to prepare a green pigment dispersion composition.

[Embodiment 8] In the embodiment 1, the C.I.
Pigment Red 254, C.I. I. A blue pigment dispersion composition was prepared in the same manner as in Example 1, except that the content of the pigment dispersant 1 was changed to 0.3 g instead of Pigment Blue 15: 6.

Comparative Example 1 A red pigment dispersion composition was prepared in the same manner as in Example 1, except that the pigment dispersant 1 was not added at all.

Comparative Example 2 A commercially available dispersant “EFKA-745” was used in Example 7 in place of the pigment dispersant 1.
A green pigment dispersion composition was prepared in the same manner as in Example 7, except that (the rising wavelength of the transmission spectrum was 400 nm or less, manufactured by Efka Chemicals).

Comparative Example 3 A red pigment dispersion composition was prepared in the same manner as in Example 1, except that the pigment dispersant 1 (average particle size: 120 nm) which had not been subjected to the salting treatment was used. Was prepared.

The obtained pigment dispersion compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated as follows. Also,
The chromaticity of the pigment dispersion compositions of Examples 1 and 7 and Comparative Examples 2 and 3 was measured. Table 1 shows the evaluation results and the chromaticity measurement results. (1) Viscosity measurement: For the obtained pigment dispersion composition,
The viscosity was measured using a type viscometer, and the degree of thickening was evaluated.

(2) Contrast measurement: The obtained pigment dispersion composition was applied on a glass substrate so as to have a thickness of 6 μm to prepare a sample. This sample was placed between two polarizing plates, the amount of transmitted light when the polarization axis was parallel and when the polarization axis was perpendicular was measured, and the ratio was defined as the contrast (“19”).
1990 7th Color Optics Conference, 512 color display 1
0.4 "size color filter for TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka").

[0103]

[Table 1]

From the results shown in Table 1, it was found that the pigment dispersion compositions of the examples had low viscosity, excellent dispersion stability and high contrast. On the other hand, in the case of the pigment dispersion composition of the comparative example, the viscosity was high and the pigment could not be dispersed.

In Example 7, a copolymer having an acid value of 50 (molar ratio of methacrylic acid / benzyl methacrylate copolymer: 14/86) was used as the methacrylic acid / benzyl methacrylate copolymer. When a pigment dispersion composition was prepared in the same manner, the viscosity was slightly higher than that of Example 7 and the dispersibility was poor. Similarly, in Example 7, except that a copolymer having an acid value of 145 (the molar ratio of methacrylic acid / benzyl methacrylate copolymer was 37/63) was used as the methacrylic acid / benzyl methacrylate copolymer. When a pigment dispersion composition was prepared in the same manner, the viscosity was slightly higher than in Example 7, and the dispersibility was poor.

Example 9 The following composition was mixed to prepare a colored photosensitive composition for producing a color filter. Red pigment dispersion composition of Example 1 32.4 g Methacrylic acid / benzyl methacrylate copolymer 9.0 g (Mole ratio 28/72, weight Average molecular weight 30,000, 30% 1-methoxy-2-propyl acetate solution) pentaerythritol tetraacrylate 5.2 g 4- [p-N, N-di (ethoxycarbonylmethyl)]- 2,6-di (trichloromethyl) -5-triazine 0.2 g hydroquinone monomethyl ether 0.01 g 1-methoxy-2-propyl acetate ... 62g

The mixing was performed for 9 hours at a peripheral speed of 9 m / s using a zirconia bead having a diameter of 0.65 mm with a motor mill M50 (manufactured by Eiger). About the obtained colored photosensitive composition for producing a color filter, Example 1 was used.
The viscosity was measured in the same manner as described above, a color filter was prepared as described below, and the contrast was measured in the same manner as in Example 1. Table 2 shows the results.

That is, the colored photosensitive composition for producing a color filter was applied on a glass substrate using a spin coater and dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. Next, after exposure with an ultrahigh pressure mercury lamp under a nitrogen stream, development was performed with a 1% aqueous sodium carbonate solution. The contrast of the obtained color filter was measured in the same manner as in Example 1.

Example 10 The procedure of Example 9 was repeated, except that the red pigment dispersion composition of Example 1 was replaced by the red pigment dispersion composition of Example 2. A water-soluble composition was prepared and evaluated in the same manner as in Example 9.

Example 11 The procedure of Example 9 was repeated, except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Example 3. A water-soluble composition was prepared and evaluated in the same manner as in Example 9.

Example 12 In Example 9, 32.4 g of the red pigment dispersion composition of Example 1 was used, 25.9 g of the red pigment dispersion composition of Example 4 was used, and the yellow pigment of Example 5 was used. A colored photosensitive composition was prepared in the same manner as in Example 9 except that the dispersion composition was changed to 6.5 g, and evaluated in the same manner as in Example 9.

Example 13 In Example 9, 32.4 g of the red pigment dispersion composition of Example 1 was replaced with 13.0 g of the yellow pigment dispersion composition of Example 6, and the green pigment of Example 7 was used. A colored photosensitive composition was prepared in the same manner as in Example 9 except that the dispersion composition was replaced with 19.4 g, and evaluated in the same manner as in Example 9.

Example 14 The procedure of Example 9 was repeated, except that the red pigment dispersion composition of Example 1 was replaced with the blue pigment dispersion composition of Example 8 to obtain a colored photosensitive composition. A water-soluble composition was prepared and evaluated in the same manner as in Example 9.

[0114]

[Table 2]

[0115]

According to the present invention, there is provided a pigment dispersion composition which is excellent in dispersion stability and color tone, and in particular, can stably produce a color filter having a high contrast when used for producing a color filter. Can be. Further, according to the present invention, it is possible to form an image having a clear color tone and high light transmittance, and in particular, it is possible to stably produce a color filter having high contrast when used for producing a color filter. A composition can be provided. Furthermore, according to the present invention, it is possible to provide a color filter having a clear color tone and a high light transmittance and having a high contrast.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram used for explaining a rising wavelength of a transmission spectrum according to the present invention.

FIG. 2 is a diagram schematically showing a transmission spectrum of a pigment and a transmission spectrum of a dispersant according to the pigment dispersion composition of the present invention.

FIG. 3 is a diagram schematically showing a transmission spectrum of a green pigment and a transmission spectrum of a green pigment containing a dispersant according to the pigment dispersion composition of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 505 505 F term (Reference) 2H025 AA02 AA03 AB13 AC01 AD01 BC13 BC42 CA00 CB42 CC12 CC20 FA17 2H048 BA02 BA45 BA48 BB02 BB14 BB22 BB42 4J037 AA30 CB28 CC13 CC16 CC17 DD23 DD24 EE08 EE28 EE43 FF02 FF15

Claims (7)

[Claims] 1. A pigment, wherein the rising wavelength of a transmission spectrum is 400 to 550 nm and the average particle size is 100 nm.
A pigment dispersion composition comprising the following dispersant and a resin dispersed in an organic solvent. 2. The pigment dispersion composition according to claim 1, wherein the resin is a polymer having an acidic group. 3. The polymer having an acidic group having an acid value of 6
The pigment dispersion composition according to claim 2, wherein the number is from 0 to 130. 4. The pigment dispersion composition according to claim 1, wherein the dispersant and the pigment have an azo dye skeleton. 5. The pigment dispersion composition according to claim 1, wherein the dispersant is a compound represented by the following general formula (I). Embedded image (In the general formula (I), A represents a component capable of forming an azo dye together with XY. X represents a single bond or a group selected from a divalent linking group represented by the following structural formula. Y represents
It represents a group represented by the following general formula (II). ) Embedded image (In the general formula (II), Z represents a lower alkylene group.
R ₂ is a lower alkylamino group or 5 containing a nitrogen atom;
Represents a 6 to 6 membered saturated heterocycle. a represents 1 or 2. ) 6. The pigment dispersion composition according to claim 1, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. A colored photosensitive composition comprising: 7. A color filter having two or more patterned colored layers having different hues on a substrate, wherein the colored layer is made of the colored photosensitive composition according to claim 6. Description: Color filter.