JP2008038061A - Fuchsine-colored composition for color filter, and color filter to be set on color image pickup tube device using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuchsine-colored composition for color filter, with high dispersion stability, high storage stability in particular. <P>SOLUTION: The fuchsine-colored composition for color filter comprises a pigment vehicle consisting of a transparent resin, its precursor or their mixture, a quinacridone-based fuchsine-colored pigment, and a quinacridone-based pigment dispersant represented by the general formula(1)[ wherein, X is SO<SB>2</SB>, CO or CH<SB>2</SB>; m and n are each an integer of 1-4; R<SB>1</SB>and R<SB>2</SB>are each a (substituted) alkyl or combined together to form a heterocyclic ring that may also contain nitrogen, oxygen or sulfur atom(s) ]. The color filter to be set on a color image pickup tube device using the composition is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a color filter mounted on a color imaging device typified by C-MOS, CCD, and the like, and a magenta coloring composition used for manufacturing the same.

A color image pickup device such as a CCD generally performs color separation by disposing a color filter including a filter segment of an additive mixture of magenta, cyan, and yellow on the light receiving device.
In recent years, a color filter mounted on a color image sensor such as a CCD has been required to have a high density in order to reduce the thickness of the image sensor due to a reduction in area per pixel due to downsizing of the image sensor and an increase in the number of pixels. In order to carry out this, a color filter is generally produced using a colored composition having an increased pigment content. However, since the dispersibility becomes worse as the concentration is increased, the storage stability of the colored composition is unstable. In particular, due to thixo origin, the coating surface does not have a uniform film thickness. Even if two or more kinds of pigments are mixed to improve thixotropy, there is a problem that spectral characteristics are not satisfied.

In the situation where the demand for color characteristics for color filters is increasing, such as high density thinning of color filters, improvement of color separation, and uniformity of coating when forming pixels, the simpleness of pigments used in the past Such a high concentration makes it difficult to cope with it.
JP 09-046716 A JP 2006-098684 A

An object of the present invention is to provide a magenta coloring composition for a color filter that is mounted on a color imaging tube element, which has excellent dispersion stability and particularly high storage stability.
Another object of the present invention is to provide a color filter which is mounted on a color image pickup tube element and includes a magenta color filter segment having a uniform film thickness and a high density.

（式中、Ｘは、ＳＯ₂、ＣＯまたはＣＨ₂を表す。ｍおよびｎは、それぞれ独立に１〜４の整数を表す。Ｒ₁およびＲ₂は、それぞれ独立に置換もしくは無置換のアルキル基、もしくはＲ₁とＲ₂とで一体となって、更に窒素、酸素またはイオウ原子を含んでもよいヘテロ環を表す。） The magenta coloring composition for a color filter mounted on the color image pickup tube element of the present invention comprises a pigment carrier made of a transparent resin, a precursor thereof, or a mixture thereof, a quinacridone-based magenta color pigment, and a general formula (1). It contains the quinacridone pigment dispersant represented.

(In the formula, X represents SO ₂ , CO or CH _2. M and n each independently represents an integer of 1 to 4. R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group. Or R ₁ and R ₂ together represent a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom.)

In the magenta coloring composition of the present invention, the quinacridone-based magenta pigment is at least selected from CI Pigment Red 122, CI Pigment Red 192, CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 209, and CI Pigment Violet 19. It is preferable to use one kind of pigment.
The color filter attached to the color image pickup tube element of the present invention is a color filter including at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment, The magenta color filter segment is formed using the magenta color coloring composition.

The quinacridone pigment dispersant contained in the magenta coloring composition of the present invention is excellent in dispersion stability, and the magenta coloring composition containing the pigment dispersant has particularly high coating uniformity, storage stability, and the like. .
Therefore, by using the magenta color coloring composition of the present invention, it is possible to produce a color filter mounted on a color image pickup tube element having a uniform magenta color filter segment.

First, the magenta coloring composition of the present invention will be described.
The magenta coloring composition of the present invention comprises a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a quinacridone magenta color pigment, and a quinacridone pigment dispersant represented by the above general formula (1). It contains.
As the quinacridone-based magenta color pigment, commercially available quinacridone-based magenta organic pigments can be used alone or in admixture of two or more kinds, and dyes, natural pigments, and inorganic pigments can be used in combination. The quinacridone-based magenta color pigment may be refined by salt milling, acid pasting, or the like.

  Quinacridone-based magenta color pigments have better resistance to heat, light, solvents, etc. than magenta-colored pigments other than quinacridone-based pigments, and there are almost no changes in color or structure due to differences in the environment in which the pigment is placed. However, it is excellent in all of the points that it can be produced at low cost and that the process of producing pigments is stable. In particular, the pigments with the color index numbers CI Pigment Red 122, CI Pigment Red 192, CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 209, and CI Pigment Violet 19 have a wavelength range of light transmitted through the pigment. The wavelength range of light absorbed by the pigment is optimal as a color filter to be mounted on a color image sensor consisting of magenta, cyan, and yellow filter segments. Use at least one of these pigments. Is preferred.

  The quinacridone pigment dispersant represented by the general formula (1) is a compound in which a specific basic substituent is introduced into the quinacridone pigment. By using the pigment dispersant, a quinacridone magenta pigment is obtained. It becomes possible to satisfactorily disperse in the pigment carrier, and it becomes possible to produce a magenta colored composition having excellent coating uniformity and storage stability. There are two main reasons. The first is that the quinacridone pigment dispersant represented by the general formula (1) has good compatibility with the quinacridone magenta color pigment. The second is the general formula (1). The quinacridone pigment dispersant represented by the formula is that the pigment dispersants do not aggregate when the quinacridone magenta pigment is dispersed in the pigment carrier.

When the compatibility with the first quinacridone-based magenta pigment is described in detail, the base of the pigment and the pigment dispersant used in the present invention is the same as that of quinacridone, and the base of the pigment and the pigment dispersant is the same. In the same case, the pigment dispersant is efficiently adsorbed on the pigment, and a dispersion excellent in dispersion stability can be produced. When the matrix of the pigment and the pigment dispersant is not the same, the pigment dispersant does not adsorb efficiently to the pigment, and the pigment and the pigment dispersant exist individually, so that the dispersion does not have excellent dispersion stability. .
When the second pigment is dispersed in the pigment carrier, it will be described in detail that the pigment dispersants do not aggregate with each other. The pigment dispersants may aggregate depending on the type of substituents the pigment dispersant has. The quinacridone pigment dispersant represented by the general formula (1) is an excellent dispersant because the substituent contained in the structure does not cause aggregation of the pigment dispersants.

In the magenta coloring composition of the present invention, the quinacridone-based magenta pigment and the quinacridone-based pigment dispersant represented by the general formula (1) are usually in a weight ratio of 50:50 to 99: 1, preferably 60:40. To 95: 5, more preferably 70:30 to 95: 5, and still more preferably 85:15 to 95: 5. If the amount of the quinacridone pigment dispersant represented by the general formula (1) is less than the above range, the effect of stabilizing the dispersion of the pigment is not sufficiently exhibited. May be undesirably changed, and the manufacturing cost is also a problem.
In the magenta colored composition of the present invention, the quinacridone-based magenta pigment and the quinacridone-based pigment dispersant represented by the general formula (1) are based on the weight (100% by weight) of the nonvolatile content of the colored composition. In total, it can be used in an amount of 7 to 10% by weight, preferably 8 to 9% by weight.

  The magenta colored composition of the present invention preferably further contains a resin-type dispersant. The resin-type dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and functions to adsorb to the pigment and stabilize the dispersion of the pigment on the pigment carrier. To do. Resin-type dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes Long chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly lower alkylene imines and polyesters having a free carboxyl group, salts thereof, and the like are used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are also used. These can be used alone or in admixture of two or more. The resin dispersant can be used in an amount of 1 to 30% by weight, preferably 5 to 15% by weight, based on the non-volatile content of the colored composition (100% by weight).

  As described above, the pigment carrier is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Alternatively, two or more kinds can be mixed and used. The pigment carrier can be used in an amount of 20 to 70% by weight, preferably 30 to 55% by weight, based on the non-volatile content of the coloring composition (100% by weight).

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Photosensitive resins include (meth) acrylic compounds and cinnamic acid having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. And a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  As monomers and oligomers, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa Various acrylic esters and methacrylic esters such as (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, (meth) acrylic acid, styrene, vinyl acetate, (meth) Examples include acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the magenta colored composition of the present invention.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4'-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used. . The photopolymerization initiator can be used in an amount of 5 to 30% by weight, preferably 5 to 15% by weight, based on the nonvolatile content weight of the coloring composition (100% by weight).

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together. The sensitizer can be used in an amount of 0.1 to 30% by weight based on the weight of the photopolymerization initiator (100% by weight).

The magenta coloring composition of the present invention is prepared by dispersing a quinacridone-based magenta color pigment in a pigment carrier solution, or after preparing a pigment dispersion by dispersing a quinacridone-based magenta color pigment in water or an organic solvent. It is manufactured by a method of mixing with a solution. The method for dispersing the pigment is not particularly limited, but a method using a bead mill, a sand mill, a ball mill, a three roll mill, a two roll mill or the like is preferable. The magenta pigment and the quinacridone pigment dispersant represented by the general formula (1) can be separately dispersed in the pigment carrier solution and then mixed, but in order to improve the dispersibility of the magenta pigment When dispersing the magenta color pigment, it is preferable to add a quinacridone pigment dispersant represented by the general formula (1).
When dispersing the magenta color pigment in the pigment carrier, a dispersion aid such as a surfactant and other dye derivatives can be appropriately used.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines. These can be used alone or in admixture of two or more.

Another pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. You can use what you have. In particular, a pigment derivative having a basic group and a triazine derivative having a basic group are preferably used because they have a large pigment dispersion effect.
Specific examples of the basic group possessed by the dye derivative include substituents represented by the following general formulas (2), (3), (4) and (5).
General formula (2)

一般式（３）

General formula (3)

一般式（４）

General formula (4)

一般式（５）

General formula (5)

[Wherein, X represents SO ₂ , CO, CH ₂ NHCOCH ₂ , CH ₂ or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, Alternatively, R ₁ and R ₂ together represent an optionally substituted heterocyclic ring further containing a nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or Represents an optionally substituted phenyl group.

Y represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or optionally substituted. Represents a phenyl group.
Z represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.
P represents a substituent represented by the general formula (6) or a substituent represented by the general formula (7).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (6) or a substituent represented by the general formula (7). In the equation (6) and (7), R ₁ to R ₇ and n are the same as R ₁ to R ₇ and n in the formula (2) to (4).
General formula (6)

一般式（７）

General formula (7)

  Examples of the organic dye constituting the dye derivative having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metals Complex dyes may be mentioned. Moreover, the organic pigment illustrated previously may be sufficient.

  A pigment derivative having a basic group can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formulas (8) to (11) into an organic dye, it reacts with the substituent to form a substituent represented by the general formulas (2) to (5). Amine components such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine- It can be obtained by reacting 2-ylamino] aniline or the like.

When the organic dye is an azo dye, the basic group is introduced by introducing a substituent represented by the general formulas (2) to (5) into the diazo component or the coupling component in advance and then performing a coupling reaction. An azo pigment derivative having the same can also be produced.
Equation (8) -SO ₂ Cl
Formula (9) -COCl
Equation (10) -CH ₂ NHCOCH ₂ Cl
Formula (11) -CH ₂ Cl

  Examples of the amine component used for forming the substituents represented by the general formulas (2) to (5) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine. N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, di Butylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, N N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylamino Amylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N , N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylamino The Pyramine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Ethyl isonipecotate, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, N-amino Examples thereof include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  As other pigment derivatives, those shown in Tables 1 to 9 can be used, but are not limited thereto. The pigment derivatives can be used alone or in admixture of two or more.

  In order to make it easy to form a filter segment by applying a magenta colored composition on a transparent substrate such as a glass substrate so that the dry film thickness is 1 to 2.5 μm, a solvent is included. Can do. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

The magenta coloring composition can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The colored resist material is a composition containing a thermosetting resin, a thermoplastic resin or a photosensitive resin, a monomer, and a photopolymerization initiator, a quinacridone-based magenta color pigment, and a quinacridone-based compound represented by the general formula (1). A pigment dispersant is dispersed.
The magenta colored composition is formed by a method such as centrifugal separation, sintering filter, membrane filter, etc. for coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and mixed dust. Removal is preferably performed.

  The dispersion stability of the magenta colored composition can be evaluated by measuring the thixo index. The thixo index is a numerical value obtained by measuring the viscosity of a magenta colored composition at different shear rates and dividing the viscosity result at a low shear rate by the viscosity result at a high shear rate. The thixo index value is ideally 1, and it is estimated that there is no degree of pigment aggregation. Since the pigment is preferably not aggregated as much as possible, the value of the thixo index is preferably closer to 1. Therefore, the thixo index of the magenta colored composition is preferably 1.0 or more and 1.4 or less, and more preferably 1.0 or more and 1.2 or less.

Next, the color filter will be described.
The color filter attached to the color image pickup tube element of the present invention is formed by forming filter segments of at least three colors of Y (yellow), M (magenta), and C (cyan) on a transparent substrate or a reflective substrate. is there. The magenta color filter segment is formed using the magenta color coloring composition of the present invention by a printing method or a photolithography method. Further, the cyan filter segment and the yellow filter segment contain a pigment carrier made of a transparent resin, a precursor thereof, or a mixture thereof, and a pigment, and if necessary, a pigment dispersant, a photopolymerization initiator, a solvent, and the like. It is formed by a printing method or a photolithography method using a known coloring composition.

The coloring composition forming the yellow filter segment includes CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, It can be used yellow pigments such 75,176,177,179,180,181,182,185,187,188,193,194,199,198,213,214.
For the coloring composition forming the cyan filter segment, pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 80, and the like can be used.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above-mentioned various printing inks. Therefore, the color filter manufacturing method is low cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted with a dispersant or extender pigment.

  When each color filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is spray coated, spin coated, slit coated, roll coated, die coated on a transparent substrate. By a coating method such as the above, coating is performed so that the dry film thickness becomes 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the examples, “part” represents “part by weight”. First, a method for preparing a quinacridone pigment dispersant and an acrylic resin solution used in Examples and Comparative Examples will be described.
(Preparation of quinacridone pigment dispersant A)
To 100 parts of chlorosulfonic acid, 10 parts of unsubstituted quinacridone is added at 10 to 20 ° C., stirred at 40 to 50 ° C. for 3 hours, poured into 1000 parts of ice water, filtered, washed with water, and quinacridone monosulfonate. Of water cake. The water cake of this chlorosulfonated product was added to 300 parts of ice water and reslurried, 20 parts of N, N-diethylaminopropylamine was added, and the mixture was stirred at 10 ° C. or lower for 4 hours, filtered and washed with water. Next, this water cake was added to 300 parts of 0.5% aqueous sodium carbonate solution, stirred for 1 hour, filtered, washed with water until neutral and dried, and 16 parts of quinacridone pigment having the structure of the following general formula (12) Dispersant A was obtained.

(Preparation of quinacridone pigment dispersant B)
10 parts of quinacridone-2,9-dicarboxylic acid obtained by hydrolyzing 2,9-dicarboxylic acid methyl ester of quinacridone in concentrated sulfuric acid is added to 50 parts of chlorosulfonic acid and stirred at 10 to 20 ° C. for 3 hours. The solution was poured into 1000 parts of ice water, filtered and washed with water to obtain a dicarboxylic acid chloride water cake. This water cake was added to a mixed solvent consisting of 200 parts of water and 100 parts of dioxane, reslurried, 20 parts of N, N-diethylaminoethylamine and 5 parts of sodium carbonate were added, and the mixture was stirred at 10 to 20 ° C. for 3 hours. Next, the mixture was stirred at 70 to 80 ° C. for 1 hour, filtered, washed with water, and dried to obtain 18 parts of quinacridone pigment dispersant B having the structure of the following general formula (13).

(Preparation of acrylic resin solution)
A separable four-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, charged with 70.0 parts of cyclohexanone, heated to 80 ° C. and purged with nitrogen in the reaction vessel. 13.3 parts of butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2, 2 A mixture of 0.4 parts of '-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

[Example 1]
A mixture having the following composition was uniformly stirred and mixed, then dispersed with an Eiger mill for 4 hours using zirconia beads having a diameter of 0.8 mm, and then filtered with a 5 μm filter to prepare a pigment dispersion.
Quinacridone magenta color pigment CI Pigment Red 122
("Hosta Palm Pink E" manufactured by Clariant) 9.0 parts Quinacridone pigment dispersant A 1.0 part Acrylic resin solution 50.0 parts Cyclohexanone 40.0 parts

Next, the mixture having the composition shown below including the obtained pigment dispersion was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an alkali developing resist material.
Pigment dispersion 60.0 parts Photopolymerization initiator 1.2 parts (“Irgacure 907” manufactured by Ciba Specialty Chemicals)
4.2 parts of trimethylolpropane triacrylate (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part Acrylic resin solution 11.0 part Cyclohexanone 23.2 parts

[Example 2]
An alkali developing resist material was obtained in the same manner as in Example 1 except that the quinacridone pigment dispersant A was changed to the quinacridone pigment dispersant B.
[Comparative Example 1]
An alkali developing resist material was obtained in the same manner as in Example 1 except that the quinacridone pigment dispersant A was changed to the quinacridone pigment derivative A-40 shown in Table 6.
[Comparative Example 2]
An alkali developing resist material was obtained in the same manner as in Example 1 except that the quinacridone-based magenta color pigment was changed to a xanthene-based magenta color pigment CI Pigment Red 81: 1 ("Fanal Pink D 4830" manufactured by BASF). .

The viscosity and the thixo index at 6 rpm and 60 rpm of the obtained alkali developing resist material were measured using an E type viscometer (“R110” manufactured by Toki Sangyo Co., Ltd.).
Further, the viscosity of the obtained alkali development resist material at 60 rpm before and after standing at 40 ° C. for 7 days was measured using an E-type viscometer (“R110” manufactured by Toki Sangyo Co., Ltd.). The amount of change in viscosity before and after standing at 40 ° C for 7 days is less than 10% ◎ 10% to less than 20% ○, 20% to less than 50% △, 50% or more is evaluated as storage stability did.

Further, the obtained alkali developing resist material was spin-coated on a 360 mm × 465 mm substrate having a thickness of 0.7 mm so that the average film thickness was 1.8 μm, dried at 70 ° C. for 30 minutes, The film thickness (referred to as A) and the average value (referred to as B) of the film thickness of 4 points in the 200 mm portion from the center on the diagonal line were measured, and the coating uniformity was evaluated by the following formula.
(A−B) × 100 / {(A + B) / 2} [%]
The coating uniformity was evaluated with the above% being less than 1%, ◎, 1% to less than 2%, ◯, 2% to less than 5%, and 5% or more.
Table 10 shows the evaluation results.

表１０の結果より、実施例１、２で得られたレジスト材は、比較例１、２で得られたレジスト材に比べ、保存安定性、塗布均一性、すなわち分散安定性が非常に優れていた。
さらに、実施例１のレジスト材は、チキソインデックスの結果から、キナクリドン系分散剤がより凝集を引き起こし難い置換基を有していたと考えられ、実施例２よりもさらに優れていたといえる。
ついで、マゼンタ色フィルタセグメント、シアン色フィルタセグメント、およびエロー色フィルタセグメントを具備するカラーフィルタを作成するため、エロー色レジスト材およびシアン色レジスト材を下記の方法で作製した。

From the results of Table 10, the resist materials obtained in Examples 1 and 2 are very excellent in storage stability, coating uniformity, that is, dispersion stability, compared to the resist materials obtained in Comparative Examples 1 and 2. It was.
Furthermore, it can be said that the resist material of Example 1 was superior to Example 2 because it was considered that the quinacridone-based dispersant had a substituent that hardly caused aggregation from the result of the thixo index.
Subsequently, in order to create a color filter having a magenta color filter segment, a cyan color filter segment, and an yellow color filter segment, an yellow color resist material and a cyan color resist material were produced by the following method.

(Elow color resist material)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare an yellow pigment dispersion.
Using the obtained yellow color pigment dispersion, an alkali development type yellow color resist material was obtained in the same manner as the alkali development type resist material of Example 1.
Yellow pigment CI Pigment Yellow 150 9.0 parts ("Epi Pigment 4GN-GT" manufactured by LANXESS)
Dye derivative A-33 shown in Table 5 1.0 part Acrylic resin solution 50.0 parts Cyclohexanone 40.0 parts

(Cyan resist material)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a cyan dispersion.
An alkali-developable cyan resist material was obtained in the same manner as the alkali-developable resist material of Example 1.
Cyan pigment CI Pigment Blue 15: 3 9.0 parts ("Rionol Blue FG7531" manufactured by Toyo Ink Manufacturing Co., Ltd.)
Dye derivative A-48 shown in Table 8 1.0 part Acrylic resin solution 50.0 parts Cyclohexanone 40.0 parts

The magenta color resist material obtained in Example 1 or Comparative Example 1 was applied to a glass substrate by spin coating so that the chromaticity was x = 0.348 and y = 0.196 with a C light source. After drying, striped pattern exposure was performed with an exposure machine, and development was performed with an alkaline developer for 90 seconds to form a stripe-shaped magenta filter segment. The alkali developer is 1.5% by weight of sodium carbonate, 0.5% by weight of sodium bicarbonate, 8.0% by weight of an anionic surfactant (“PERILEX NBL” manufactured by Kao Corporation) and 90% by weight of water. What was used.
Next, the yellow color resist material was applied with a film thickness such that x = 0.388 and y = 0.594 chromaticity with a C light source. After drying, a stripe pattern adjacent to the magenta filter segment was exposed with an exposure machine to form a striped yellow filter segment.

Further, a striped cyan filter segment is applied adjacent to the magenta and yellow filter segments by coating with a C light source so as to have a chromaticity of x = 0.172 and y = 0.246. Formed.
The shape of each color filter segment was good, and the resolution was also good. Finally, the obtained color filter is heated in an oven at 230 ° C. for 30 minutes to completely react the remaining polymerizable functional groups, and the magenta, yellow, and cyan colors on the transparent substrate. A color filter having a stripe-shaped filter segment was obtained.

  The color filter produced using the magenta color resist material obtained in Example 1 did not vary in chromaticity in the surface of the magenta color filter segment, and was excellent for a color imaging device. On the other hand, the color filter produced using the magenta color resist material obtained in the comparative example has a poor imaging sensitivity due to the chromaticity variation in the surface of the magenta color filter segment.

Claims (3)

A color imaging tube element comprising: a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof; a quinacridone-based magenta color pigment; and a quinacridone-based pigment dispersant represented by the general formula (1). A magenta colored coloring composition for a color filter to be mounted on a surface.

(In the formula, X represents SO ₂ , CO or CH _2. M and n each independently represents an integer of 1 to 4. R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group. Or R ₁ and R ₂ together represent a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom.)   It contains at least one pigment selected from CI Pigment Red 122, CI Pigment Red 192, CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 209, and CI Pigment Violet 19, as a quinacridone-based magenta color pigment. A magenta colored composition for a color filter to be mounted on the color image pickup tube element according to claim 1. 3. A color filter comprising at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment, wherein the magenta color filter segment is magenta coloration according to claim 1 or 2. A color filter mounted on a color imaging tube element, characterized by being formed using a composition.