JP5612178B2 - Coloring composition for color filter, color filter, and method for producing color filter - Google Patents

Description

The present invention, colored composition for a color filter, a color filter formed by using the color filter for coloring composition, and relates to the production how of the color filter.

  The color filter is a colored photosensitive composition obtained by mixing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components, In general, it is produced by forming a colored pattern by using a photolithography method or the like.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

  It is effective to use a pigment whose primary particle diameter is miniaturized to meet the above requirements. As a method for reducing the primary particle diameter of the pigment, for example, the pigment is combined with a water-soluble inorganic salt such as a synthetic resin that is solid and water-insoluble at room temperature, sodium chloride, and a water-soluble organic solvent that at least partially dissolves the synthetic resin. After kneading mechanically with a kneader or the like (hereinafter, kneading a mixture containing a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is called salt milling), and then washing with water, the water-soluble inorganic salt and the water-soluble organic There is a method for removing the solvent (see, for example, Patent Document 1). In this method, the primary particle pulverization and crystal growth occur in parallel with each other, so that a pigment with a small surface area is obtained in the end although the particle size distribution is narrow and the average particle size is small. This method is suitable for applications where a pigment having a large diameter needs to be dispersed at high concentration.

However, the pigments thus produced often cause severe aggregation in the drying process after desalting, and thus the dispersibility and dispersion stability are often not good. When the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the formed coloring pattern, and the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is low. There is a problem that it deteriorates remarkably. In addition, when the dispersion stability of the pigment is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the colored photosensitive composition is reduced, or in the exposure process. There is a tendency that the sensitivity is lowered and the alkali solubility in the developing process is lowered. Further, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened.
In order to solve such a problem, a method of adding rosin or a rosin derivative or a synthetic polymer compound during salt milling has been proposed (for example, see Patent Document 2).

In recent years, color filters having high brightness as well as contrast have been demanded. As a method for obtaining a color filter with high luminance and high contrast, a conventional C.I. I. Pigment Green 36 and C.I. I. Instead of Pigment Green 7, a method using polyhalogenated zinc phthalocyanine has been proposed. (For example, see Patent Documents 3 and 4)
Japanese Patent Laid-Open No. 7-13016 JP-A-8-179111 JP 2004-70342 A JP 2008-19383 A

  Although the use of polyhalogenated zinc phthalocyanine as described above has improved the contrast and brightness to some extent, the technology can improve the contrast and brightness and further improve the voltage holding ratio. Is not established yet.

Then, this invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, a first object of the present invention is to provide a colored composition for a color filter that can form a colored film that is excellent in contrast and brightness, and also excellent in voltage holding ratio.
The second object of the present invention is to provide a color filter using a color filter coloring composition that can form a colored film having excellent contrast and brightness and also excellent voltage holding ratio, and a method for producing the color filter. It is to provide.

Means for solving the above-mentioned problems are as follows.
That is, the coloring composition for a color filter of the present invention comprises (a) a pigment containing a polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm, and (b) an N-substituted maleimide, styrene, benzyl (meth) acrylate. , and referred to as (meth) viewed it contains acrylic acid as a copolymerization component, the (meth) alkali-soluble resin copolymerization ratio of acrylic acid is 20 mass% to 45 mass% (hereinafter, appropriately specific alkali-soluble resin. ), (C) a dispersant, (d) a polyfunctional monomer, (e) a photopolymerization initiator, and (f) an organic solvent.

In the coloring composition for color filter of the present invention, polybrominated zinc phthalocyanine is preferably used as the polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm.
The color filter coloring composition of the present invention further includes C.I. I. It is a preferable aspect to contain CI Pigment Yellow 150.
The color filter coloring composition is a copolymer component of the alkali-soluble resin contained N- position-substituted maleimide of the present invention, Ru is preferably embodiment der using N- phenylmaleimide.
In the coloring composition for a color filter of the present invention, it is preferable that the alkali-soluble resin has a weight average molecular weight of 5,000 to 20,000.
In the coloring composition for a color filter of the present invention, the number average molecular weight of the alkali-soluble resin is preferably 5,000 to 15,000.

The color filter of the present invention has a colored region formed on the substrate using the colored composition for a color filter of the present invention.
The method for producing a color filter of the present invention comprises a step of coating a colored composition for color filter of the present invention on a substrate to form a film, a step of exposing the formed film, and a film after exposure. forming a developing the colored pattern, you comprising a.
The coloring composition for a color filter of the present invention comprises a step of obtaining a pigment containing polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm by refining polyhalogenated zinc phthalocyanine by solvent salt milling, and an average primary particle size A pigment containing 10 to 40 nm of polyhalogenated zinc phthalocyanine, an alkali-soluble resin containing N-substituted maleimide, styrene, benzyl (meth) acrylate, and (meth) acrylic acid as a copolymerization component, a dispersant, According to a manufacturing method comprising: a step of preparing a pigment dispersion by dispersing in an organic solvent; and a step of mixing the pigment dispersion, a polyfunctional monomer, and a photopolymerization initiator. Preferably it is manufactured.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the coloring composition for color filters which can form the colored film excellent in the contrast and the brightness | luminance, and also excellent in the voltage retention , and the manufacturing method of the coloring composition for color filters can be provided.
According to the present invention, there are provided a color filter using a coloring composition for a color filter that can form a colored film having excellent contrast and brightness and also excellent voltage holding ratio, and a method for producing the color filter. Can do.

A coloring composition using polyhalogenated zinc phthalocyanine as a coloring composition for a color filter as described in Patent Documents has high luminance and high contrast, but does not have excellent voltage holding ratio. Since polyhalogenated zinc phthalocyanine has a low voltage holding ratio, it is difficult to achieve high contrast, high brightness, and high voltage holding ratio with these colored compositions using polyhalogenated zinc phthalocyanine.

In the present invention, a specific alkali-soluble resin (b) containing polyhalogenated zinc phthalocyanine as a pigment and N-substituted maleimide, styrene, benzyl (meth) acrylate and (meth) acrylic acid as a copolymerization component is used. By using it, the coloring composition for color filters excellent in contrast, brightness | luminance, and voltage holding ratio was able to be obtained.
The reason is not clear, but (b) by using a specific alkali-soluble resin, a dense and excellent coating film is formed, and a liquid crystal such as a low molecular weight component or an ionic component involved in a decrease in voltage holding ratio. This is considered to prevent elution into the layer.
For the reasons described above, the color filter produced using the coloring composition for a color filter of the present invention is considered to have high luminance, high contrast, and excellent voltage holding ratio.

  Hereinafter, the coloring composition for color filter of the present invention, the color filter, and the production method thereof will be described in detail.

<Coloring composition for color filter>
The colored composition for a color filter of the present invention comprises (a) a pigment containing a polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm, and (b) an N-position substituted maleimide, styrene, benzyl ( meth) acrylate and, (meth) viewed contains acrylic acid, the (meth) an alkali-soluble resin copolymerization ratio of acrylic acid is 20 mass% to 45 mass%, and (c) dispersing agent, (d) It contains a polyfunctional monomer, (e) a photopolymerization initiator, and (f) an organic solvent.
Hereinafter, each component contained in the coloring composition for a color filter of the present invention will be described in detail.

[(A) Polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm]
As a pigment contained in the coloring composition for a color filter of the present invention, polyhalogenated zinc phthalocyanine can be used alone, or polyhalogenated zinc phthalocyanine and a conventionally known organic pigment can be used in combination.

  Since zinc phthalocyanine generally has 16 hydrogen atoms in the phthalocyanine ring, up to 16 of these hydrogen atoms can be substituted with halogen atoms. Examples of the halogen atom include bromine, chlorine, fluorine, and iodine. Bromine and chlorine are more preferable, and bromine is still more preferable. When the number of substituents is fixed, for example, zinc phthalocyanine substituted with a bromine atom is darker than zinc phthalocyanine substituted with a chlorine atom.

These halogen atoms as substituents may all be the same or different.
For example, when a hydrogen atom in a phthalocyanine ring is substituted with a bromine atom or a chlorine atom, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, and the number of hydrogen atoms (unsubstituted) is 0 to 16 In addition, the total number of bromine atoms and chlorine atoms is 1 or more, and theoretically 136 types of substitution products can be produced in total.
Of the 16 substitutable hydrogen atoms in the phthalocyanine ring, 8 to 16 are preferably substituted, and more preferably 12 to 16 are substituted.

  Such a polyhalogenated zinc phthalocyanine is preferably a compound represented by the following general formula 1.

In General Formula 1, X _{1 to} X ₁₆ each independently represent a chlorine atom, a bromine atom, or a hydrogen atom. However, at least eight of X _{1 to} X ₁₆ are chlorine atoms or bromine atoms.

  Here, it is preferable that the polyhalogenated zinc phthalocyanine contains 8 or more bromine atoms because it develops a yellowish and light green color and is optimal for use in a green pixel portion pattern of a color filter. . In the present invention, polyhalogenated zinc phthalocyanine containing 8 or more bromine atoms is referred to as polybrominated zinc phthalocyanine. The polybrominated zinc phthalocyanine preferably has 8 to 16 bromine atoms, and more preferably 12 to 16 bromine atoms. As the polyhalogenated zinc phthalocyanine of the present invention, polybrominated zinc phthalocyanine is preferably used for the reasons described above.

  The average composition of the polyhalogenated zinc phthalocyanine can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.

  The polyhalogenated zinc phthalocyanine can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. More specific production methods are described in detail in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like.

  The polyhalogenated zinc phthalocyanine used in the present invention has an average primary particle size of 10 nm to 40 nm, more preferably 10 nm to 35 nm, and still more preferably 15 nm to 35 nm. By using a polyhalogenated zinc phthalocyanine having an average primary particle diameter in this range, a colored composition for a color filter having excellent dispersibility stability and coloring power, high luminance and high contrast can be obtained.

  The average primary particle diameter in the present invention is a long one of 100 polyhalogenated zinc phthalocyanine primary particles constituting an aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. The average value of the diameter (major axis) and the shorter diameter (minor axis) is obtained and averaged.

  In obtaining a polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm, it may be finely divided by any method, but it can easily suppress crystal growth and has a relatively small average particle size. It is preferable to employ a solvent salt milling treatment in terms of obtaining particles.

  The solvent salt milling means kneading and grinding polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent. The polyhalogenated zinc phthalocyanine having a large particle size may be subjected to solvent salt milling after dry grinding. Specifically, polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  In obtaining a polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm, it is preferable to increase the amount of inorganic salt used relative to the amount of polyhalogenated zinc phthalocyanine used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts by mass and more preferably 7 to 15 parts by mass with respect to 1 part by mass of the polyhalogenated zinc phthalocyanine.

  As the organic solvent, an organic solvent capable of suppressing crystal growth is preferably used, and as such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene group Call, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol.

  Although the usage-amount of a water-soluble organic solvent is not specifically limited, 0.01-5 mass parts and 0.8-2 mass parts are preferable with respect to 1 mass part of polyhalogenated zinc phthalocyanines in conversion of mass.

  30-150 degreeC is preferable and the temperature at the time of solvent salt milling has more preferable 80-100 degreeC. The solvent salt milling time is preferably 5 to 20 hours, and more preferably 8 to 18 hours.

  In this way, a mixture containing polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from the mixture, and if necessary, a solid mainly composed of polyhalogenated zinc phthalocyanine is obtained. Fine polyhalogenated zinc phthalocyanine powder can be obtained by washing, filtering, drying, grinding, etc.

  As washing, either water washing or hot water washing can be employed. The number of washings can be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

  Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles. For example, as in the case of drying using a box-type dryer or a band dryer, When it becomes a shape or the like, it is performed in order to break the pigment into powder, and examples thereof include mortar, hammer mill, disc mill, pin mill, jet mill and the like.

  In this way, fine particles of polyhalogenated zinc phthalocyanine are obtained. The polyhalogenated zinc phthalocyanine used in the present invention is a pigment, but has a property that the cohesion of the primary particles is weaker than that of the conventional copper halide phthalocyanine, and it is easier to unravel.

  When the primary and horizontal aspect ratios of the polyhalogenated zinc phthalocyanine of the present invention are 1 to 3, the viscosity characteristics are improved in each application field and the fluidity is further increased. In order to obtain the aspect ratio, as in the case of obtaining the average particle diameter of the primary particles as described above, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, an average value of the longer diameter (major diameter) and the shorter diameter (minor diameter) is obtained for 100 primary particles constituting the aggregate on the two-dimensional image, and the average value is calculated using these values. .

  The polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm used in the present invention can be obtained by, for example, the above-mentioned method, but as a commercial product, it can be purchased from DIC Corporation as the FASTGEN GREEN series. .

  In the coloring composition for a color filter of the present invention, polyhalogenated zinc phthalocyanine can be used alone, or polyhalogenated zinc phthalocyanine and a conventionally known organic pigment can be used in combination. The average primary particle diameter of conventionally known organic pigments used in combination is preferably 10 nm to 40 nm.

  A conventionally known organic pigment used in combination is preferably a yellow pigment or a green pigment, and particularly preferably used in combination from the viewpoint of obtaining a preferable hue as a color filter.

  Examples of yellow pigments used in combination include C.I. I. Pigment Yellow 83, 110, 138, 139, 150, 180, 185, and the like. I. Pigment Yellow 150. In the present invention, the combined proportion of the polyhalogenated zinc phthalocyanine and the yellow pigment is preferably 10 to 100 parts by mass of the yellow pigment with respect to 100 parts by mass of the polyhalogenated zinc phthalocyanine.

  Examples of the green pigment used in combination include C.I. I. Pigment Green 36, 7 and the like, but the amount used is preferably 50 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass of the polyhalogenated zinc phthalocyanine because color characteristics may be impaired. It is as follows.

  In the coloring composition for a color filter of the present invention, polyhalogenated zinc phthalocyanine and C.I. I. It is most preferable to use Pigment Yellow 150 in combination from the viewpoint of obtaining a preferable hue and high brightness as a color filter.

  In the coloring composition for color filter of the present invention, the total amount of the pigment containing polyhalogenated zinc phthalocyanine is 5 to 60% with respect to the total amount excluding the solvent in the coloring composition for color filter of the present invention. Preferably, it is 10 to 50%, more preferably 15 to 45%. By using the addition amount in this range, a color filter having excellent color characteristics, high contrast, and high luminance can be obtained.

[(B) Specific alkali-soluble resin]
The colored composition for a color filter of the present invention contains (b) a specific alkali-soluble resin containing N-substituted maleimide, styrene, benzyl (meth) acrylate and (meth) acrylic acid as copolymerization components.
The specific alkali-soluble resin (b) of the present invention comprises at least the above four types of copolymerization components, and can also contain other copolymerization components.
The above four types of copolymer components will be described below.

  Examples of N-substituted maleimides include N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, and N-succinimidyl. -3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, or N- (acridinyl) maleimide is more preferred. N-phenylmaleimide or N-cyclohexylmaleimide is preferred. More preferred is N-phenylmaleimide from the viewpoint of the dispersibility of the pigment in the color filter coloring composition and the voltage holding ratio.

These N-position substituted maleimides can be used alone or in admixture of two or more.
The copolymerization ratio of N-substituted maleimide is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. By setting it as the said range, the fall of a voltage holding rate is suppressed and the adhesiveness of a pixel and a board | substrate improves.

Moreover, the copolymerization ratio of styrene is preferably 5 to 40% by mass, more preferably 5 to 30% by mass.
The copolymerization ratio of benzyl (meth) acrylate is preferably 10 to 60% by mass, more preferably 10 to 50% by mass.
By setting the copolymerization ratio of styrene and benzyl (meth) acrylate within the above range, the dispersibility of the pigment in the color filter coloring composition is improved.

  The copolymerization ratio of (meth) acrylic acid is preferably 15 to 50% by mass, more preferably 20 to 45% by mass. By setting it as the said range, the alkali developability of the coloring composition obtained becomes favorable, and the drop-off | omission of the pixel from the board | substrate at the time of image development and the film | membrane roughness of the pixel surface can be suppressed.

  The (b) specific alkali-soluble resin in the colored composition for a color filter of the present invention may use other copolymer components in addition to the above essential copolymer components.

As other copolymerization components that can be used, as carboxyl group-containing unsaturated monomers, for example,
Unsaturated monocarboxylic acids such as crotonic acid, α-chloroacrylic acid, cinnamic acid; unsaturated such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid Dicarboxylic acid or its anhydride; Trivalent or higher unsaturated polycarboxylic acid or its anhydride; Succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as ω-carboxypolycaprolactone mono (meth) acrylate, and polymers having a carboxy group and a hydroxyl group at both ends ( And (meth) acrylate.

Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name.
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

  Examples of copolymerizable unsaturated monomers as other copolymerization components include α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o-methoxystyrene. , M-methoxystyrene, p-methoxystyrene, p-hydroxy-α-methylstyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m- Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; indenes such as indene and 1-methylindene;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [ 5.2.1.02,6] Unsaturated carboxylic acid esters such as decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl An unsaturated carboxylic acid aminoalkyl ester such as aminopropyl (meth) acrylate; an unsaturated carboxylic acid glycidyl ester such as glycidyl (meth) acrylate; a carboxylic acid vinyl ester such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; Unsaturated amides such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n -A macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as butyl (meth) acrylate and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  The copolymerization ratio of the other copolymerization component that can be used is usually 0 to 50% by mass, preferably 0 to 30% by mass.

  In the present invention, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the specific alkali-soluble resin in the present invention is preferably 3,000 to 50,000, more preferably 4, 000 to 30,000, more preferably 5,000 to 20,000.

Moreover, the number average molecular weight (Mn) measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of (b) specific alkali-soluble resin in this invention becomes like this. Preferably it is 3,000-30,000, More preferably It is 4,000 to 20,000, more preferably 5,000 to 15,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of (b) specific alkali-soluble resin in this invention becomes like this. Preferably it is 1-4, More preferably, it is 1-3.

In the present invention, by using such a specific alkali-soluble resin (b) having Mw and Mn, a color filter coloring composition having excellent developability can be obtained, thereby having a sharp pattern edge. A pixel pattern can be formed, and residues, background stains, film residues, and the like are less likely to occur on the unexposed substrate and the light shielding layer during development.
In this invention, (b) specific alkali-soluble resin can be used individually or in mixture of 2 or more types.

  The amount of the (b) specific alkali-soluble resin used in the present invention is preferably 10 to 300 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the (a) pigment. By making it within this range, the voltage holding characteristics and alkali developability are good, and it is possible to suppress the occurrence of background stains and film residue on the unexposed portion of the substrate and the light shielding layer, and to obtain a better color density. it can.

  In this invention, in the range which does not impair the effect of this invention, well-known alkali-soluble resin other than said (b) specific alkali-soluble resin can be used together.

  Examples of such alkali-soluble resins that can be used in combination include alkali-soluble resins containing acidic functional groups such as carboxyl groups and phenolic hydroxyl groups. The alkali-soluble resin containing a carboxyl group is preferably a copolymer of a carboxyl group-containing unsaturated monomer and another unsaturated monomer, more preferably acrylic acid and / or methacrylic acid and methyl methacrylate, 2 -Copolymer with at least one selected from the group of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as "alkali-soluble resin (II ) ").

  Specific examples of the alkali-soluble resin (II) include acrylic acid / benzyl acrylate copolymer, methacrylic acid / benzyl acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / styrene copolymer. Polymer, acrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, Acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl acrylate Relate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer Polymer, acrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, acrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / styrene copolymer Polymer, methacrylic acid / methyl methacrylate / styrene copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylate Acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl methacrylate / polystyrene macro Monomer copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2 -Hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl An acrylic acid copolymer of a methacrylate macromonomer copolymer can be exemplified.

These alkali-soluble resins (II) can be used alone or in admixture of two or more.
The amount of the alkali-soluble resin that can be used in combination is usually 100 parts by mass or less, preferably 60 parts by mass or less, with respect to 100 parts by mass of the specific alkali-soluble resin (b) of the present invention. By setting it in this range, the voltage holding ratio of the obtained pixel becomes good.
In addition, the preferable molecular weight of the alkali-soluble resin that can be used in combination and the distribution thereof are the same as in the case of the (b) specific alkali-soluble resin of the present invention.

[(C) Dispersant]
The coloring composition for a color filter of the present invention contains (c) a dispersant. Any known dispersant can be used. For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl Ether, polyoxyethylene alkylphenyl ether such as polyoxyethylene n-nonylphenyl ether; polyethylene glycol diester such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid ester; fatty acid modified polyester; tertiary amine modified polyurethane; polyethyleneimine In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (TOKE) Products), Megafuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Disperbyk-101, 103, -107, -110, -111, -115, -130, -160, -160, -161, -162, -163, -164, -165, -166, -170, -180, -182, -2000, -2001 (above, manufactured by Big Chemie Japan Co., Ltd.), Solsperse S5000, 12000, 13240, 13940, 17000, 17000, 20000, 22000, 24000, 24000GR, 26000, 27000, 28000 (above, manufactured by Avicia Co., Ltd.), EFKA46, 47, 48, 745, 4540, 4550, 6750, EFKA LP4008, 4009, 4010, 4015, 4050, 4055, 4560, 4800, EFKA Polymer400, 401, 402, 403, 450, 451, 453 (above, manufactured by Fuka Chemicals Co., Ltd.); Ajispa-PB-821, 822 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.
These dispersants can be used alone or in admixture of two or more.

  It is preferable that the dispersing agent contained in the coloring composition for color filters of this invention contains at least 1 sort (s) of a primary amine, a secondary amine, a tertiary amine, or carboxylic acid. Moreover, as a form of a dispersing agent, it is preferable that they are any of a comb type dispersing agent, a block type dispersing agent, and a terminal adsorption type dispersing agent.

  Here, the block type dispersant refers to a block type polymer compound composed of a pigment adsorbing block and a block not adsorbing to the pigment. Although it does not restrict | limit especially as a monomer which comprises a pigment adsorption block, For example, the monomer which has a functional group which can adsorb | suck to a pigment is mentioned. Specific examples include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic nitrogen atom.

As a method for obtaining the block polymer compound in the present invention, a conventionally known method can be used.
For example, living polymerization, iniferter method and the like are known. Furthermore, as another method, when radically polymerizing a monomer having a pigment adsorbing group or a monomer having no pigment adsorbing group, thiolcarboxylic acid, 2-acetylthioethyl ether, 10-acetylthiodecanethiol A polymer obtained by polymerizing a compound containing a thioester and a thiol group in the molecule such as sodium hydroxide or an alkali such as ammonia to obtain a polymer having a thiol group at one end. Also known is a method of radical polymerization of the monomer component of the other block in the presence of the obtained polymer having a thiol group at one end. Among these, living polymerization is preferable.

  The weight average molecular weight of the block type polymer compound is not particularly limited, but is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, a dispersion stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersion. Can demonstrate its sexuality.

  Commercially available products can also be used as the block polymer compound. Specific examples include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.

The graft polymer compound used as the comb-type dispersant is not particularly limited, but the polyalkyleneimine described in JP-A-54-37082, JP-A-61-174939, etc. is reacted with a polyester compound. Preferable examples include compounds in which the side chain amino group of polyallylamine described in JP-A-9-169821 is modified with polyester, polyester polyol-added polyurethane described in JP-A-60-166318, and the like. Further, as described in JP-A-9-171253 and Macromonomer Chemistry and Industry (IPC Publishing Department, 1989), a graft containing a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component. A suitable type of polymer compound can also be mentioned.

  The weight average molecular weight of the graft polymer compound is not particularly limited, but is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, a dispersion stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersion. Can demonstrate its sexuality.

  Commercially available products of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.

  Examples of the terminal-modified polymer compound used as the terminal adsorption type dispersant include a polymer having a functional group at the terminal of the polymer described in JP-A-9-77994 and JP-A-2002-273191. Mention may be made of molecular compounds.

  The molecular weight of the terminal-modified polymer compound is preferably a weight average molecular weight of 1,000 to 50,000. When the number average molecular weight is 1,000 or more, the steric repulsion effect as a dispersant can be more effectively obtained, and when it is 50,000 or less, the steric repulsion effect is more effectively suppressed, and the pigment The adsorption time can be shortened.

  Examples of commercially available terminal-modified polymer compounds include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol.

  The amount of (c) dispersant used in the present invention (in terms of solid content) is preferably 1 to 60 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 10 parts per 100 parts by mass of the pigment (a). -40 mass parts. By setting it as the said range, the storage stability of a coloring composition is favorable and generation | occurrence | production of the residue on a board | substrate is suppressed.

[(D) polyfunctional monomer]
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
Examples of the polyfunctional monomer include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin, trimethylolpropane, Poly (meth) acrylates of polyhydric alcohols such as pentaerythritol and dipentaerythritol and their dicarboxylic acid modified products; oligo (meth) such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin Acrylate; di (meth) acrylate of a hydroxylated polymer at both ends such as hydroxypoly-1,3-butadiene at both ends, hydroxypolyisoprene at both ends, and hydroxypolycaprolactone at both ends Chromatography with or include a tris [2- (meth) acryloyloxyethyl] phosphate and the like.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are preferred, and trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexa Acrylates are particularly preferred because they are excellent in pixel strength and surface smoothness, and are less likely to cause background contamination and film residue on the unexposed substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types. In the case of using a mixture of two or more, it is preferable from the viewpoint of developability to use a combination of a compound having a small number of functional groups and a compound having a large number of functional groups.

  The amount of the polyfunctional monomer used in the present invention is preferably 5 to 500 with respect to 100 parts by mass of the alkali-soluble resin [(b) specific alkali-soluble resin + total amount of other alkali-soluble resins that can be used in combination]. It is 20 mass parts, More preferably, it is 20-300 mass parts. By setting it in this range, the strength, surface smoothness, and alkali developability of the pixel are good, and the occurrence of background contamination and film residue on the unexposed portion of the substrate and the light shielding layer is suppressed.

Moreover, in this invention, the monofunctional monomer which has one polymerizable unsaturated bond can also be used together with (d) polyfunctional monomer.
Examples of the monofunctional monomer include monomers similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified as the alkali-soluble resin that can be used in combination, and N- (meta ) In addition to acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl-ε-caprolactam, trade names include M-5600 (manufactured by Toagosei Co., Ltd.) and the like.
These monofunctional monomers can be used alone or in admixture of two or more.

  The total amount of (d) polyfunctional monomer and monofunctional monomer used in the present invention is the alkali-soluble resin [(b) specific alkali-soluble resin + total amount of other alkali-soluble resins that can be used in combination] Preferably it is 5-500 mass parts with respect to 100 mass parts, More preferably, it is 20-300 mass parts. By setting it in this range, the strength, surface smoothness, and alkali developability of the pixel are good, and the occurrence of background contamination and film residue on the unexposed portion of the substrate and the light shielding layer is suppressed.

  The proportion of the monofunctional monomer used in the present invention is preferably 90% by mass or less, more preferably 50% by mass with respect to the total amount of (d) the polyfunctional monomer and the monofunctional monomer. % Or less. By setting it as the said range, the intensity | strength and surface smoothness of a pixel become favorable.

[(E) Photopolymerization initiator]
In the present invention, (e) the photopolymerization initiator is obtained by exposing the above-mentioned (d) polyfunctional monomer and optionally monofunctional by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that can generate an active species capable of initiating polymerization of a functional monomer.

  Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds. Examples include compounds and oxime ester compounds.

  In the present invention, the (e) photopolymerization initiator can be used alone or in admixture of two or more. As the (e) photopolymerization initiator in the present invention, acetophenone compounds, oxime ester compounds can be used. At least one selected from the group of compounds, biimidazole compounds and triazine compounds is preferred.

Among the preferable photopolymerization initiators (e) in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropanone-1, 2-methyl-1- (4-methylthiophenyl). ) -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2- And diphenylethanone-1.
Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone -1 is preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used when (e) an acetophenone-based compound is used as the photopolymerization initiator is based on (d) a total of 100 parts by mass of the polyfunctional monomer and the monofunctional monomer. Preferably it is 0.01-100 mass parts, More preferably, it is 1-80 mass parts, More preferably, it is 5-60 mass parts. By setting it in this range, sufficient curing by exposure can be obtained, and a colored layer in which pixel patterns are arranged according to a predetermined arrangement can be obtained. In addition, dropping of the formed pixels from the substrate during development can be suppressed.

Among the preferable photopolymerization initiators (e) in the present invention, specific examples of oxime ester compounds include oxime ester compounds described in JP-A No. 2000-66385, 1-phenyl-1,2-propanedione-2. -(O-ethoxycarbonyl) oxime, O-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime and the like can be mentioned.
The said oxime ester type compound can be used individually or in mixture of 2 or more types.

  In this invention, the usage-amount in the case of using (e) an oxime ester type compound as a photoinitiator is (d) with respect to a total of 100 mass parts of a polyfunctional monomer and a monofunctional monomer. Preferably, it is 0.01-100 mass parts, More preferably, it is 1-80 mass parts, More preferably, it is 5-60 mass parts. By setting it in this range, sufficient curing by exposure can be obtained, and a colored layer in which pixel patterns are arranged according to a predetermined arrangement can be obtained. In addition, dropping of the formed pixels from the substrate during development can be suppressed.

  Among the preferable photopolymerization initiators (e) in the present invention, specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4 -Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2' -Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetra Examples include phenyl-1,2'-biimidazole.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferred, and among these, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1 2,2'-biimidazole is more preferred.

The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved matter and precipitates, has high sensitivity, and sufficiently proceeds with a curing reaction by exposure with a small amount of energy, and is not exposed. Therefore, the exposed coating is clearly divided into a hardened portion that is insoluble in the developer and an uncured portion that has a high solubility in the developer. A high-definition colored layer in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In this invention, the usage-amount in the case of using a biimidazole type compound as (e) photoinitiator is (d) with respect to 100 mass parts in total of a polyfunctional monomer and a monofunctional monomer. Preferably, it is 0.01-50 mass parts, More preferably, it is 1-40 mass parts, More preferably, it is 1-30 mass parts. By setting it in this range, sufficient curing by exposure can be obtained, and a colored layer in which pixel patterns are arranged according to a predetermined arrangement can be obtained. In addition, dropping of the formed pixels from the substrate during development can be suppressed.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as the (e) photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, these hydrogen donors will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and the like are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Of these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than a biimidazole compound.

  In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed pixels are difficult to drop off from the substrate during development, and that the pixels have high strength and sensitivity.

Specific examples of a preferred combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like are further preferable combinations. Are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the particularly preferred combination is 2-mercaptobenzothi Is a tetrazole / 4,4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is preferably 1: 1 to 1: 4, more preferably 1: 1 to 1. : 3.

  In the present invention, the amount used when the hydrogen donor is used in combination with the biimidazole compound is preferably 0 with respect to 100 parts by mass of the total of (e) the polyfunctional monomer and the monofunctional monomer. 0.01 to 50 parts by mass, more preferably 1 to 40 parts by mass, and still more preferably 1 to 30 parts by mass. By setting it in this range, good sensitivity can be obtained, and the formed pixels can be prevented from falling off the substrate during development.

Among the preferable photopolymerization initiators (e) in the present invention, specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis ( Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2- Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trick (Romethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) The triazine type compound which has halomethyl groups, such as -s-triazine, can be mentioned.
Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used when (e) a triazine-based compound is used as a photopolymerization initiator is based on (d) a total of 100 parts by mass of the polyfunctional monomer and the monofunctional monomer. Preferably it is 0.01-60 mass parts, More preferably, it is 1-50 mass parts, More preferably, it is 1-40 mass parts. By setting it in this range, sufficient curing by exposure can be obtained, and a colored layer in which pixel patterns are arranged according to a predetermined arrangement can be obtained. In addition, dropping of the formed pixels from the substrate during development can be suppressed.

[(F) Organic solvent]
As the organic solvent (f) in the present invention, the above-described components (a) to (e) constituting the colored composition and additive components described later are dispersed or dissolved, and do not react with these components, and are moderate. As long as it has the volatility of, it can select and use suitably.
Examples of such solvents include alcohols such as methanol, ethanol, and benzyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, such as tripropylene glycol monoethyl ether (poly) alkylene glycol monoalkyl ether;

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methyl-3-methoxybutyl acetate, n-butyl propionate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, 2 -Methyl hydroxy-3-methylbutyrate, ethyl 2-oxobutyrate Can other esters;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these (f) organic solvents, from the viewpoints of solubility, pigment dispersibility, coatability and the like, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether Acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, N-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl -3-Methoxybutylpropionate, ethyl pyruvate and the like are preferable.
Said (d) organic solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ- A high boiling point solvent such as butyrolactone, ethylene carbonate, propylene carbonate, or ethylene glycol monophenyl ether acetate can be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  (F) Although the usage-amount of an organic solvent is not specifically limited, From viewpoints, such as the applicability | paintability of the coloring composition obtained, and storage stability, the total density | concentration of each component except the solvent of the said composition is. Preferably, it is desirable to use suitably so that it may become 5-50 mass%, More preferably, it will be 10-40 mass%.

-Additive component-
The colored composition for a color filter in the present invention can contain various additive components as necessary in addition to the components (a) to (f) described above.
As the additive component, an organic acid or an organic amino compound (provided that the action of further improving the dissolution characteristics of the colored composition in an alkaline developer and further suppressing the remaining of the undissolved product after development) The hydrogen donor is excluded).
The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.

  Examples of the aliphatic carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid; oxalic acid and malonic acid , Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, Examples thereof include aliphatic dicarboxylic acids such as itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid; and aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoric acid.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and compounds in which a carboxyl group is bonded to a phenyl group via a divalent carbon chain.
Examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; trimellitic acid Trivalent or higher aromatic polycarboxylic acids such as trimesic acid, merophanic acid, pyromellitic acid; phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, Examples thereof include coumaric acid and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in the above-described solvent, prevention of soiling and film residue on the unexposed portion of the substrate and the light shielding layer, and the like. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, an aromatic dicarboxylic acid is preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.

  The amount of the organic acid used is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass in total of the components (a) to (e) and the additive component. By setting it as the said range, the adhesiveness of the formed pixel and a board | substrate becomes favorable.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include mono (cyclo) such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, and n-hexylamine. Alkylamines;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec- Di (cyclo) alkylamines such as butylamine, di-t-butylamine;

Dimethyl ethylamine, methyl diethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, tri-n-propylamine, tri -Tri (cyclo) alkylamines such as i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine;
Mono (cyclo) alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol;

Di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine;
Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Amino (cyclo) alkanediols such as 2, 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Examples thereof include aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, and 3-aminoisobutyric acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a divalent carbon chain.
Examples of the phenyl group-containing amine include aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N- Aromatic amines such as diethylaniline, p-methyl-N, N-dimethylaniline;

aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples thereof include aminobenzoic acid such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, and the like.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in the above-described solvent, prevention of soiling and film residue on the unexposed portion of the substrate and the light shielding layer, and the like. And amino (cyclo) alkanediol are preferred, among which 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1 3-propanediol, 4-amino-1,2-butanediol and the like are particularly preferable. As the phenyl group-containing amine, aminophenol is preferable, and o-aminophenol, m-aminophenol, p-aminophenol and the like are particularly preferable.
The organic amino compounds can be used alone or in admixture of two or more.

  The amount of the organic amino compound used is preferably 15 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass in total of the components (a) to (e) and the additive component described above. By setting it as the said range, the adhesiveness of the formed pixel and a board | substrate becomes favorable.

Examples of additive components other than those described above include dispersion aids such as yellow pigment derivatives such as quinophthalone derivatives;
Fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether and poly (fluoroalkyl acrylate); nonionic, cationic and anionic surfactants;

  Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl-methyl-dimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Adhesion promoters such as 3-chloropropyl methyl dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;

  Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) UV absorbers such as -5-chlorobenzotriazole and alkoxybenzophenone; anti-aggregation agents such as sodium polyacrylate; 1,1'-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy-2, A thermal radical generator such as 4-dimethylvaleronitrile; an epoxy resin such as a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound;

  Megafuck F171, F172, F173, F173, F177, F141, F142, F143, F144, R30, F437 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383 , S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.);

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (Eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine), phthalocyanines (eg phthalocyanine, metal phthalocyanine), porphyrins (Eg, tetraphenylporphyrin, central metal substituted porphyrin), chlorophylls (eg, chlorophyll, chlorophyllin, central metal substituted chlorophyll), metal complexes, anthra Non include (e.g., anthraquinone), squaryliums (e.g., squarylium) can be exemplified such as sensitizing dyes of.

<Color filter>
[Method for preparing coloring composition for color filter]
The method for preparing the coloring composition for a color filter of the present invention is not particularly limited, but in advance (a) a pigment, (c) a dispersant, (b) an alkali-soluble resin and (f) an organic solvent. It is preferable to prepare a pigment dispersion by dispersing in a medium.

  The amount of the solvent used in preparing the pigment dispersion is preferably 300 to 1,200 parts by mass, more preferably 400 to 1000 parts by mass with respect to 100 parts by mass of the pigment.

When preparing a pigment dispersion using a bead mill, for example, glass beads having a diameter of about 0.01 to 1 mm, titania beads or zirconia beads are used, and the pigment mixture is preferably cooled with cooling water or the like. However, it can be carried out by mixing and dispersing.
In this case, the filling rate of beads is preferably 50 to 90% of the mill capacity. The treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

Moreover, when preparing a pigment dispersion using a roll mill, for example, a three-roll mill or a two-roll mill is used, and the pigment mixture is preferably treated while being cooled with cooling water or the like. be able to.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is preferably about 108 dyn / second. The treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

  When preparing the pigment dispersion, the amount of (b) alkali-soluble resin used is preferably 5 to 100% by mass, more preferably, based on the total amount of (b) alkali-soluble resin used in the color filter coloring composition. Is 10 to 90% by weight. (B) By making the usage-amount of alkali-soluble resin into 5 mass% or more, the storage stability of the composition obtained becomes favorable and the residue which generate | occur | produces on a board | substrate can be suppressed.

  The prepared pigment dispersion is mixed in a conventional manner with (d) a polyfunctional monomer and (e) a photopolymerization initiator and optionally (b) an alkali-soluble resin and (f) the remainder of the organic solvent. Thereby, the coloring composition for color filters of this invention can be obtained.

[Method of forming color filter]
Next, a method for forming the color filter of the present invention using the color filter coloring composition of the present invention (hereinafter also simply referred to as “colored composition”) will be described.
The method for forming a color filter of the present invention includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the coloring composition of this invention on a board | substrate.
(2) A step of exposing radiation to at least a part of the coating.
(3) A step of developing the coated film after exposure.
(4) A step of post-baking the coating after development.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, on the surface of the substrate, if necessary, a light-shielding layer is formed so as to partition a portion for forming a pixel, and after applying the coloring composition of the present invention on this substrate, pre-baking is performed to obtain a solvent. Is evaporated to form a film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. it can.
In addition, these substrates may be subjected to known pretreatments such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. You can also.

When the coloring composition is applied to the substrate, a known application method such as spin coating, cast coating, roll coating, or the like can be employed. A coating method using a spin coater or a slit die coater is preferred.
The prebaking conditions are preferably about 70 to 110 ° C. and about 2 to 4 minutes.
The coating thickness is preferably 0.1 to 8.0 [mu] m, more preferably 0.2 to 6.0 [mu] m, still more preferably 0.2 to 4.0 [mu] m, as the film thickness after drying.

-(2) Process-
Next, radiation is exposed to at least a part of the formed film. When exposing a part of the film in this step, it is preferably exposed through a photomask having a predetermined pattern.
As radiation used for exposure, for example, radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray can be appropriately selected and used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.
Exposure of radiation is preferably 10~10,000J / ^{m 2} approximately.

-(3) Process-
Next, the exposed film is developed using a developer, preferably an alkali developer, and the unexposed portion of the film is dissolved and removed to form a predetermined pattern.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of diazabicyclo- [4.3.0] -5-nonene is preferred.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is preferable to wash with water after alkali development.
As the development processing method, for example, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The development conditions are preferably about 5 to 300 seconds at room temperature.

-(4) Process-
Subsequently, the substrate on which the pixel pattern is arranged in a predetermined arrangement can be obtained by post-baking the developed film.
As post-baking treatment conditions, for example, a temperature of 180 to 240 ° C. for about 15 to 90 minutes is preferable.
The film thickness of the pixel thus formed is preferably 0.1 to 6.0 μm, more preferably 0.5 to 3.0 μm.

By repeating the steps (1) to (4) using each colored composition in which a red, green or blue pigment is dispersed, red, green and blue pixel patterns are formed on the same substrate. A colored layer in which pixel patterns of three primary colors of red, green and blue are arranged in a predetermined arrangement can be formed on the substrate.
In the present invention, the order of forming the pixel patterns of the respective colors can be arbitrarily selected.

The color filter of the present invention is formed using the color composition for color filter of the present invention.
The color filter of the present invention is extremely useful for a color imaging device, a color sensor and the like in addition to a transmissive or reflective color liquid crystal display device.

The color filter of the present invention can be suitably used for a color liquid crystal display device having the color filter.
The color liquid crystal display device can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other through the liquid crystal layer. Furthermore, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed include a liquid crystal layer. It is also possible to adopt a structure facing each other. The latter structure has the advantage that the aperture ratio can be remarkably improved and a bright and high-definition liquid crystal display device can be obtained.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In addition, the following Example 2 shall be read as Reference Example 2.

(Synthesis Example 1)
A flask equipped with a condenser and a stirrer was charged with 2.7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol monomethyl ether acetate, followed by 25 parts by mass of methacrylic acid, N— Charge 25 parts by mass of phenylmaleimide, 30 parts by mass of benzyl methacrylate, 5 parts by mass of n-butyl methacrylate, 15 parts by mass of styrene and 5 parts by mass of α-methylstyrene dimer (chain transfer agent), and after substituting with nitrogen, gently stir. However, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was continued for another hour, whereby a resin solution ( Solid content concentration = 33.0 mass%) was obtained. The obtained resin was Mw = 15,000 and Mn = 7,500. This resin is referred to as “resin (B-1)”.

(Synthesis Example 2)
A flask equipped with a condenser and a stirrer was charged with 2.7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol monomethyl ether acetate, followed by 18 parts by mass of methacrylic acid, N— Charge 8 parts by weight of phenylmaleimide, 40 parts by weight of benzyl methacrylate, 12 parts by weight of n-butyl methacrylate, 22 parts by weight of styrene, and 5 parts by weight of α-methylstyrene dimer (chain transfer agent). However, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was continued for another hour, whereby a resin solution ( Solid content concentration = 33.0 wt%) was obtained. The obtained resin was Mw = 14,000 and Mn = 7,200. This resin is referred to as “resin (B-2)”.

(Synthesis Example 3)
A flask equipped with a condenser and a stirrer was charged with 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monomethyl ether acetate, followed by 25 parts by weight of methacrylic acid and benzyl methacrylate. 75 parts by mass and 5 parts by mass of α-methylstyrene dimer (chain transfer agent) were charged, and after purging with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring, and this temperature was maintained for 3 hours. Polymerized. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.3 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was continued for another hour, whereby a resin solution ( Solid content concentration = 33.2% by weight) was obtained. The obtained resin was Mw = 17,000 and Mn = 8,600. This resin is referred to as “resin (B-3)”.

Example 1
(A) Polybrominated zinc phthalocyanine (average primary particle diameter 25 nm) and C.I. I. 30 parts by weight of a 100/50 (mass ratio) mixture with CI Pigment Yellow 150 (average primary particle size 25 nm), (c) 10 parts by weight of Ajisper PB821 (solid content concentration 100.0% by weight) as a dispersant, (b) alkali A mixed liquid comprising 15 parts by mass of the resin (B-1) obtained in Synthesis Example 1 as a soluble resin, and (f) 50 parts by mass of ethyl 3-ethoxypropionate and 100 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent. Was pre-dispersed for 30 minutes using a bead disperser disperse mat (manufactured by GETZMANN) using 0.8 mmφ zirconia beads (manufactured by Nikkato Co., Ltd.).
Then, this dispersion was performed for 3 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.05 mmφ zirconia beads (manufactured by Nikkato Co., Ltd.) to obtain a green pigment dispersion composition. .
Next, 547 parts by mass of this pigment dispersion composition, (b) 50 parts by mass of resin (B-1) as an alkali-soluble resin, (d) 50 parts by mass of dipentaerythritol hexaacrylate as a polyfunctional monomer, (e) 10 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, 5 parts of mercaptobenzthiazole, 5 parts of 4,4′-bis (diethylamino) benzophenone and 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole 10 parts by mass, and (f) 600 parts by mass of propylene glycol monomethyl ether acetate as the organic solvent Parts were mixed to prepare a colored composition (G1).

  After applying two colored compositions (G1) on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) using a spin coater so that the y value as an index of color density is 0.595. And prebaking for 2 minutes in a clean oven at 90 ° C. to form a coating film.

Next, after this substrate was cooled to room temperature, one of the two coated substrates was irradiated with radiation containing each wavelength of 365 nm, 405 nm, and 436 nm through a photomask using a high-pressure mercury lamp. The exposure was performed at an exposure amount of 1,000 J / m ² . Thereafter, the substrate is immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. To form a green stripe pixel pattern on the substrate. This substrate is a substrate for evaluating foreign matter and chromaticity.
Furthermore, another coating film substrate was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 1,000 J / m ² without using a photomask using a high-pressure mercury lamp. . Thereafter, post-baking was performed at 230 ° C. for 30 minutes to form a solid green film on the substrate. This substrate is used as a contrast ratio evaluation substrate.

<Evaluation of foreign matter and chromaticity>
When the formed pixel pattern was observed with an optical microscope, no foreign matter was observed on the pixel.
Further, when the chromaticity of the pixel was evaluated with a color analyzer MCPD2000 (manufactured by Otsuka Electronics Co., Ltd.), it was (x, y, Y) = (0.298, 0.595, 59.6).

<Evaluation of contrast ratio>
The obtained substrate is sandwiched between two polarizing plates, and the polarizing plate on the front side is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the transmitted light intensity is measured with a luminance meter LS-100 (MINOLTA). The maximum value and the minimum value were measured by the company), and the contrast ratio was evaluated as a value obtained by dividing the maximum value by the minimum value. It can be said that the contrast value is good if it exceeds 10,000.

<Evaluation of voltage holding ratio>
The aforementioned colored composition (G1) was applied to a glass substrate with an ITO electrode (trade name: 1737 manufactured by Corning) so as to have a film thickness of 2.0 μm, and dried (prebaked) in an oven at 90 ° C. for 2 minutes. . Thereafter, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 1,000 J / m ² without using a photomask. Thereafter, post-baking was performed at 230 ° C. for 30 minutes to obtain a cured film. After bonding the substrate on which this cured film was formed and the substrate on which ITO electrodes were simply deposited in a predetermined shape with a sealing agent mixed with 5 μm glass beads, Merck liquid crystal MJ971189 (trade name) was injected, A liquid crystal cell was produced.

Next, after putting the liquid crystal cell in a constant temperature layer at 70 ° C. for 48 hours, the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica.
The voltage holding ratio is a value of a voltage applied at a liquid crystal cell potential difference after 16.7 milliseconds / 0 milliseconds.
The conditions for measuring this voltage holding ratio are as follows.

-Measurement conditions-
・ Distance between electrodes: 5 to 15 μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
-Applied voltage pulse width: 16.67 msec

The evaluation index is as follows. Here, it can be seen that the larger the index number, the higher the voltage holding ratio and the better the electrical characteristics.
-Evaluation index-
5: 90% or more 4: 85% or more and less than 90% 3: 80% or more and less than 85% 2: 75% or more and less than 80% 1: less than 75%

The voltage holding ratio of the colored cured film formed from the colored composition in Example 1 measured by the above method was “4”. A voltage holding ratio of “3” or higher can be said to be good.
Accordingly, the color filter formed by the colored cured film also has a good voltage holding ratio.

(Example 2)
As (b) alkali-soluble resin in Example 1, resin (B-2) was used instead of resin (B-1), and colored composition (G2) was prepared. Evaluation was performed.
No foreign matter was found on the pixels. The chromaticity of the pixel was (x, y, Y) = (0.298, 0.595, 59.6), and the contrast ratio was 10,900. Further, the voltage holding ratio of the colored cured film formed of the colored composition in Example 2 was “3”.
Accordingly, the color filter formed by the colored cured film also has a good voltage holding ratio.

(Comparative Example 1)
As (b) alkali-soluble resin in Example 1, resin (B-3) was used instead of resin (B-1), and a colored composition (G3) was prepared. Evaluation was performed.
No foreign matter was found on the pixels. The chromaticity of the pixel was (x, y, Y) = (0.299, 0.595, 59.5), and the contrast ratio was 10,500. Moreover, the voltage holding ratio of the colored cured film formed of the colored composition in Comparative Example 1 was “2”.

Claims (8)

(A) Copolymerization component of pigment containing polyhalogenated zinc phthalocyanine having an average primary particle size of 10 nm to 40 nm, (b) N-position substituted maleimide, styrene, benzyl (meth) acrylate, and (meth) acrylic acid an alkali-soluble resin viewed contains a copolymerization ratio of the (meth) acrylic acid is 20 mass% to 45 mass% as a (c) dispersing agent, and (d) a polyfunctional monomer, (e) A coloring composition for a color filter comprising a photopolymerization initiator and (f) an organic solvent.   The coloring composition for a color filter according to claim 1, wherein the polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm is polybrominated zinc phthalocyanine.   Furthermore, C.I. I. The coloring composition for a color filter according to claim 1 or 2, which contains CI Pigment Yellow 150.   The colored composition for a color filter according to any one of claims 1 to 3, wherein the N-substituted maleimide is N-phenylmaleimide. The colored composition for a color filter according to any one of claims 1 to 4 , wherein the alkali-soluble resin has a weight average molecular weight of 5,000 to 20,000. The colored composition for a color filter according to any one of claims 1 to 5 , wherein the alkali-soluble resin has a number average molecular weight of 5,000 to 15,000. The color filter which has a colored area | region formed on the board | substrate using the coloring composition for color filters of any one of Claims 1-6 . A step of applying a colored composition for color filter according to any one of claims 1 to 6 to form a film on a substrate, a step of exposing the formed film, and a film after exposure And developing a colored pattern to form a colored pattern.