JP6155809B2 - Photosensitive coloring composition and color filter using the same - Google Patents

Description

  The present invention relates to a photosensitive coloring composition, and in particular, a photosensitive coloring composition used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., particularly a thin film transistor (TFT) type color. A photosensitive coloring composition for use in a color filter of a color filter on array system (hereinafter sometimes abbreviated as COA system), comprising a filter segment having a colored layer formed on a driving substrate of a liquid crystal display device, and The present invention relates to a colored film for a color filter formed using a photosensitive coloring composition, and a color filter formed using the colored film for a color filter.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display. By providing a color filter between these two polarizing plates, color display is possible, and in recent years it has come to be used in televisions, personal computer monitors, etc., so there is a demand for higher brightness and higher contrast for color filters. Is growing.

  As a method for producing the color filter, after forming a pattern with a photoresist, a dyeing method for dyeing the pattern, or by forming a transparent electrode of a predetermined pattern in advance, and using a pigment-containing resin dissolved and dispersed in a solvent by voltage application Electrodeposition method for ionization and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material Recently, the pigment dispersion method has become mainstream. However, a color filter using a pigment as a colorant disturbs the degree of polarization controlled by the liquid crystal due to light scattering by the pigment particles, resulting in a decrease in brightness and contrast of the color liquid crystal display device. There is a problem that it is easy.

  As a technique for solving this problem, the practical application of a dye-based curable composition using a dye that can exist in a dissolved state in a medium of the curable composition as a colorant has been studied and proposed (for example, patents). Reference 1). However, a color filter using a dye as a colorant has the following problems. That is, the dye used for the color resist agent is required to have heat resistance, light resistance and solubility in the resin and the organic solvent used for the resin.

Therefore, in order to increase solubility and improve heat resistance and light resistance, color filters using a salt of an anionic dye and a cationic surfactant as a colorant have been proposed (for example, Patent Documents 2 and 3). reference). Generally, it is known that the solubility of an anionic dye in an organic solvent is increased by changing the sodium sulfonate group (—SO ₃ Na) of the anionic dye into an organic amine salt. In the above colorants, by changing the sodium sulfonate group of the anionic dye to the base salt of the cationic surfactant, the solubility of the anionic dye in the organic solvent is increased and the molecular weight is increased to increase the heat resistance. , Improve light resistance. However, in these methods, sufficient solubility with respect to the solvent used in the preparation of the color filter cannot be obtained, and since the compatibility with the resin is poor, the long-term storage stability of the color filter coloring composition, It has been difficult to provide strong adhesion between the coating film and a transparent substrate such as glass.

  In addition, as a salt-forming compound of an anionic dye, those using a cationic resin as a counter have been studied as crystalline aqueous coloring materials (see, for example, Patent Document 4). In color filter applications that require use in a dissolved state, detailed studies have not been made.

  The color filter is formed by forming a colored layer directly or through a passivation film such as a silicon nitride film on a transparent substrate such as glass or a driving substrate on which a thin film transistor (TFT) is disposed. It consists of fine band (striped) filter segments of different colors or more arranged in parallel or intersecting, or fine filter segments arranged in a fixed arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  The liquid crystal used in such a liquid crystal display device is easily affected by the electrical characteristics of members such as a color filter inherent in the liquid crystal display device, and adversely affects liquid crystal orientation disorder and switching performance due to liquid crystal contamination. Display defects may become a problem. In order to solve such a problem, the color layer of the color filter is required to have insulation, and it is necessary to increase the insulation by increasing the film thickness or to form a color film having a low dielectric constant. In order to solve such a problem, a method of selecting a dielectric loss tangent of two layers obtained by laminating an overcoat layer in a color layer of a green (green) pixel within a specific range has been studied (see Patent Document 5). .

  In particular, a colored layer is formed directly or via a passivation film such as a silicon nitride film on a driving substrate on which a thin film transistor (TFT), which has recently been attracting attention, and a substrate on which the colored layer is formed. In the COA method (see Patent Document 6) in which a transparent electrode for driving a liquid crystal is bonded to a substrate formed by vapor deposition or sputtering (see Patent Document 6), coloring is directly performed on a driving substrate on which a thin film transistor (TFT) is arranged. In order to form a layer, the pixel aperture ratio (aperture ratio) can be greatly increased, so that it is possible to achieve high brightness and low power consumption. There is a problem that it is easily affected by characteristics.

In order to solve such a problem, the color filter segment is usually formed with a thickness of about 1.6 to 2 μm, whereas in the COA method, it is formed with a thickness of about 3 μm or a film with a higher crosslinking density. In many cases, this is achieved by a method of reducing the influence of the electrical characteristics of the color filter. In the COA method, since the thickness of the film in the baking process is increased by designing it to be a thick film, when the conventional photosensitive coloring composition is used in the COA method, the remaining film ratio is greatly reduced.
Furthermore, it is necessary to provide a contact hole for connecting the transparent electrode and the thin film transistor (TFT) in the color filter segment because the thick color filter segment is formed on the thin film transistor (TFT) instead of the insulating layer. For this reason, the photosensitive coloring composition forming the pixel needs to have a resolution superior to that of a normal photosensitive coloring composition. The resolution of the photosensitive coloring composition is generally adjusted by the type and amount of the photopolymerization initiator and monomer, and the photopolymerization initiator and monomer with low sensitivity are selected or the amount is selected. In some cases, it can be improved by adjusting, but on the other hand, the adhesiveness between the photosensitive coloring composition and the glass substrate is lowered due to a decrease in sensitivity, and pattern peeling tends to occur. In addition, a photopolymerization initiator with high sensitivity tends to have a thicker pattern than a mask, and it is difficult to open a minute contact hole. Further, in the COA system, required characteristics with respect to the profile angle (= an angle formed by the pattern cross section with the substrate) are strict, and it is difficult to control the profile angle with the conventional photosensitive coloring composition. That is, it is difficult to satisfy all of the pattern adhesion, contact hole opening, and profile angle.

In recent years, color filters have been required to have higher transparency and higher density. In order to produce a high-concentration color filter, it is necessary to increase the colorant concentration in the color composition to be used. By increasing the colorant concentration of the color composition, exposure sensitivity and solubility during development, etc. Characteristics that contribute to image formation are relatively lowered. As a result, the solubility of the non-exposed area in the development process deteriorates, and the colored composition in the non-exposed area remains undissolved during development, or the resist remains undissolved on the substrate as a peeled piece. May cause color misregistration. As a result, the quality of the color filter and the yield during production are reduced. Furthermore, liquid crystal is a material with extremely high insulating properties, and when the polar compound remaining in the color filter composition is eluted into the liquid crystal cell, the voltage between the electrodes decreases, leading to a decrease in voltage holding ratio, resulting in display unevenness. Generation | occurrence | production, orientation failure, etc. arise and it becomes the cause of reducing the performance as a liquid crystal display element. Therefore, the coloring composition is required to have insolubility in liquid crystals (this resistance is referred to as voltage holding characteristic, which is an index of electric characteristics representing the display performance of a liquid crystal display element (LCD)).
When the blue pigment [A1] and the xanthene dye [A3] are used as the colorant (A), the transparency is high due to the high solubility of the dye compared to the case of using only the pigment. On the other hand, there was a problem that fluorescence was generated from the dye itself, and the contrast ratio was lowered. This is mainly due to the presence of fluorescence in the leakage light at the time of contrast measurement, and the luminance on the cross side increases.

In the case of a blue coloring composition for a color filter using only a pigment, a copper phthalocyanine compound having an acidic substituent or a copper phthalocyanine compound having a basic substituent is added for the purpose of improving contrast by improving the dispersibility of the blue pigment. Has been known for some time.
Moreover, since the copper phthalocyanine compound which has the said substituent has transparency in a 400-450 nm wavelength range, it is suitable as a component added to a blue coloring composition. However, when a xanthene dye capable of higher brightness is used together with a blue pigment, a problem arises in that the contrast ratio decreases due to the fluorescence emission of the xanthene dye. When a copper phthalocyanine compound having a group (for example, a sulfonic acid compound of copper phthalocyanine) was used, no effect was observed.

JP-A-6-75375 JP-A-5-333207 JP 2004-307391 A JP-A-2005-350648 JP 2004-117537 A JP 2004-94263 A

  The object of the present invention is a thick film, high resolution, high residual film ratio, good adhesion to a glass substrate, excellent solubility in an alkaline developer, voltage holding characteristics and developability, and An object of the present invention is to provide a photosensitive coloring composition having high transmittance, high contrast ratio and excellent heat resistance, a colored film for color filter using the same, and a color filter using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a colorant (A) containing a blue pigment [A1], an amine compound [A2] of copper phthalocyanine and a xanthene dye [A3]. The weight ratio of blue pigment [A1] to copper phthalocyanine amine compound [A2] ([A2] / ([A1] + [A2])) is 0.05 to 0.4, and The amount of the colorant (A) is 5 to 15 when the solid content of the ionic coloring composition is 100, and the photopolymerization initiator (D) is composed of an acetophenone compound, an acylphosphine oxide compound, and an oxime compound. A photosensitive coloring composition comprising at least one compound selected from the group consisting of a thick film, high resolution, a high residual film ratio, good adhesion to a glass substrate, and an alkaline developer. Solubility and electricity Excellent retention characteristics and developability, yet high transmittance, found to be excellent even in a high contrast ratio and heat resistance is obtained without the present invention based on this finding. The photosensitive coloring composition of the present invention can be suitably used for a COA system that requires thick film formation.

That is, the present invention provides a colorant (A) comprising a blue pigment [A1], a copper phthalocyanine amine compound [A2] having a structure represented by the following general formula (1), and a xanthene dye [A3], and a resin. A photosensitive coloring composition comprising (B), a monomer (C), and a photopolymerization initiator (D), wherein the weight ratio of blue pigment [A1] and copper phthalocyanine amine compound [A2] ([[ A2] / ([A1] + [A2])) is 0.05 to 0.40, and the amount of the colorant (A) when the solid content of the photosensitive coloring composition is 100 parts by weight is 5 to 5. 15 parts by weight, and the photopolymerization initiator (D) includes at least one compound selected from the group consisting of acetophenone compounds, acylphosphine oxide compounds, and oxime compounds. .
General formula (1):
P-Lm
[In General Formula (1), P is an m-valent copper phthalocyanine pigment residue,
m is an integer of 1 to 4,
L is a substituent independently selected from the group represented by general formula (2), general formula (3), and general formula (4). ]
General formula (2):
General formula (3):
General formula (4):

  The present invention also relates to the photosensitive coloring composition, wherein the resin (B) contains an alkali-soluble photosensitive resin and / or a thermosetting resin.

  The present invention also relates to the photosensitive coloring composition, wherein the thermosetting resin contains at least an epoxy compound.

  In the present invention, the blue pigment [A1] is C.I. I. Pigment Blue 15: 6. The photosensitive coloring composition as described above.

  Moreover, this invention relates to the colored film for color filters formed using the said photosensitive coloring composition.

Further, the present invention is to expose the unexposed portion after exposure with an integrated light quantity of 50 mJ / cm ² using ultraviolet light with an illuminance of 30 mW / cm ² using an ultrahigh pressure mercury lamp through a photomask having a 30 μm through-hole pattern, and then developing the unexposed portion. When the thickness of a coating film is 3.0 micrometers, the through-hole pattern of 20-35 micrometers is formed, It is related with the said colored film for color filters characterized by the above-mentioned.

  The present invention also relates to a color filter comprising a filter segment formed using the colored film for a color filter.

  The present invention also relates to a color filter comprising a filter segment having a colored layer which is a colored film for the color filter on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device.

  In the present invention, the weight ratio of the blue pigment [A1] and the copper phthalocyanine amine compound [A2] ([A2] / ([A1] + [A2])) is 0.05 to 0.40, The amount of the colorant (A) when the solid content of the photosensitive coloring composition is 100 is 5 to 15, and the photopolymerization initiator (D) is composed of an acetophenone compound, an acylphosphine oxide compound, and an oxime compound. By using a photosensitive coloring composition characterized by containing at least one compound selected from the group, it has a high resolution and a high residual film ratio while being a thick film, and has good adhesion with a glass substrate, It is possible to obtain a color filter that is excellent in solubility in an alkaline developer, voltage holding ratio characteristics and developability, and further has high transmittance, high contrast ratio, and excellent heat resistance. In particular, the present invention is useful for a COA type color filter including a filter segment in which a colored layer is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device.

Hereinafter, the present invention will be described in detail.
The photosensitive coloring composition of the present invention comprises a colorant (A) comprising a blue pigment [A1], an amine compound [A2] of copper phthalocyanine and a xanthene dye [A3], a resin (B), a monomer (C ) And a photopolymerization initiator (D).

<Colorant (A)>
The colorant (A) of the photosensitive coloring composition of the present invention contains a blue pigment [A1], an amine compound [A2] of copper phthalocyanine, and a xanthene dye [A3]. Furthermore, a pigment or dye other than [A1] to [A3] may be included as a colorant.

<< Blue Pigment [A1] >>
As the blue pigment, a phthalocyanine pigment, a triarylmethane lake pigment, or the like is used. As the phthalocyanine pigment, it is preferable to use a copper phthalocyanine blue pigment.
Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigments having ε-type and α-type structures are preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1.
Examples of triarylmethane lake pigments include C.I. I. Pigment blue 1, 1: 2, 1: 3, C.I. I. Pigment Blue 2, 2: 1, 2: 2, C.I. I. Pigment blue 3, C.I. I. Pigment Blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10, 10: 1, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, 56: 1, C.I. I. Pigment blue 57, C.I. I. Pigment blue 58, C.I. I. Pigment blue 59, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62 and the like.
Among these, C.I. I. It is particularly preferable to use CI Pigment Blue 15: 6.

(Miniaturization of pigment)
The blue pigment [A1] used in the blue coloring composition of the present invention or other pigments that can be used in combination can be refined by a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. Therefore, it is preferable to have the range of 20-100 nm. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, for 100 or more pigment particles, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. At this time, the pigment particles were sampled on a grid mesh to prepare a sample for TEM observation.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

<< Amine compound of copper phthalocyanine [A2] >>
When the blue pigment [A1] and the xanthene dye [A3] are used as the colorant (A), the transparency is high due to the high solubility of the dye compared to the case of using only the pigment. On the other hand, there was a problem that fluorescence was generated from the dye itself, and the contrast ratio was lowered. This is mainly due to the presence of fluorescence in the leakage light at the time of contrast measurement, and the luminance on the cross side increases.

In the case of a blue coloring composition for a color filter using only a pigment, a copper phthalocyanine compound having an acidic substituent or a copper phthalocyanine compound having a basic substituent is added for the purpose of improving contrast by improving the dispersibility of the blue pigment. Has been known for some time.
Moreover, since the copper phthalocyanine compound which has the said substituent has transparency in a 400-450 nm wavelength range, it is suitable as a component added to a blue coloring composition. However, when a xanthene dye capable of higher brightness is used together with a blue pigment, a problem arises in that the contrast ratio decreases due to the fluorescence emission of the xanthene dye. When a copper phthalocyanine compound having a group (for example, a sulfonic acid compound of copper phthalocyanine) was used, no effect was observed.
As a result of studies conducted by the present inventors to solve the problem of reduction in contrast due to the fluorescence emission, in addition to the colorant (A) containing the blue pigment [A1] and the xanthene dye [A3], a detailed description will be given later. By using the amine compound [A2] of copper phthalocyanine, it was possible to realize high contrast by eliminating the generation of fluorescence from the xanthene dye and lowering the cross-side luminance.
The reason why the fluorescence quenching effect becomes remarkable when these substances are used is not clear, but when the amine compound [A2] of copper phthalocyanine is used, it is highly compatible with xanthene dyes and copper phthalocyanine pigments. High efficiency of fluorescence quenching, especially when copper phthalocyanine sulfonic acid amide compound is used among the amine compounds of copper phthalocyanine, in addition to the above action, it is easy to form a charge transfer complex with xanthene dyes, so fluorescence emission itself is remarkably suppressed And the fluorescence is considered to be significantly quenched. In addition to the above-described fluorescence quenching effect, the high compatibility between the dye and the copper phthalocyanine blue pigment when using the copper phthalocyanine sulfonic acid amide compound is due to the light scattering due to the uneven distribution of the copper phthalocyanine particles and the dye in the resist. As a result, it is considered that the cross luminance becomes extremely low and the contrast ratio is particularly excellent.

  Examples of the amine compound [A2] of copper phthalocyanine include a basic compound having a basic substituent on a copper phthalocyanine pigment (copper phthalocyanine sulfonic acid amide compound), and a salt-forming compound of an acidic substituent and a quaternary ammonium salt (copper phthalocyanine). Sulfonic acid ammonium salt) or a compound into which a phthalimidomethyl group which may have a substituent is introduced. This will be specifically described below.

As the amine compound [A2] of copper phthalocyanine used in the present invention, among the above, basic compounds having a basic substituent on the copper phthalocyanine pigment, particularly copper phthalocyanine sulfonate ammonium salt, copper phthalocyanine tertiary amine compound, copper phthalocyanine Sulphonic acid amide compounds are preferred.
Specifically, the copper phthalocyanine amine compound [A2] represented by the following general formula (1) having a basic group represented by the following general formulas (2) to (4) Can be preferably used.

General formula (1):
P-Lm
[In General Formula (1), P is an m-valent copper phthalocyanine pigment residue, m is an integer of 1 to 4, and L is independently General Formula (2) and General Formula (3). And a substituent selected from the group represented by formula (4). ]
General formula (2):
General formula (3):
General formula (4):
[In the general formula (2) ~ (4), X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond Y ⁰ is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10, Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z is an alkylene group having 1 to 20 carbon atoms. Or an arylene group having 1 to 20 carbon atoms.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² with further nitrogen, oxygen Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and R ⁸ is a substituent represented by the general formula (2) or the general formula (3). Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ]

Examples of the amine component used for forming the substituents represented by the general formulas (2) to (4) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonicopetic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Is mentioned.

  The amine compound [A2] of copper phthalocyanine having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the following general formulas (5) to (8) into copper phthalocyanine, the above reacts with the above substituents to form the substituents represented by the general formulas (2) to (4). Amine components such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine- It can be obtained by reacting 2-ylamino] aniline or the like.

General formula (5): -SO ₂ Cl
General formula (6): -COCl
Formula _{(7): -CH 2 NHCOCH 2} Cl
Formula (8): —CH ₂ Cl

  In the reaction of the substituents of the general formulas (5) to (8) with the amine component, a part of the substituents of the general formulas (5) to (8) are hydrolyzed so that chlorine is substituted with a hydroxyl group. It may be mixed. In that case, the general formula (5) and the general formula (6) are a sulfonic acid group and a carboxylic acid group, respectively. Or a salt with a monoamine.

  Of the amine compound [A2] of copper phthalocyanine of the present invention, the substituent represented by the general formula (4) can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by the general formulas (2) and (3) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

Among the amine compounds of copper phthalocyanine used in the present invention, the most preferable form is a copper phthalocyanine sulfonic acid amide compound which is a copper phthalocyanine basic compound. The copper phthalocyanine sulfonic acid amide compound refers to the general formulas (2) to (4) among the copper phthalocyanine compounds having the above basic substituent, wherein X in the general formulas (2) to (4) is —SO ₂ —, —CH ₂ NHSO ₂ CH ₂ —, Y ⁰ is —NH—, or a direct bond, n is an integer of 1 to 10, and Y ¹ is —NH—, —NR ⁹ —Z—NR ^10. It is a compound which is-. (Here, R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z is a group having 1 to 20 alkylene groups, preferably an alkylene group having 1 to 10 carbon atoms, or an arylene group having 1 to 20 carbon atoms, preferably an arylene group having 1 to 10 carbon atoms. Examples include a methylene group, an ethylene group, and propylene. Group and phenylene group.)

The amine compound [A2] of copper phthalocyanine used in the present invention can be used alone, but two or more kinds may be used in combination.
In the colorant composition of the present invention, the compounding amount of the copper phthalocyanine amine compound [A2] is the weight ratio of the blue pigment [A1] and the copper phthalocyanine amine compound [A2] ([A2] / ([A1] + [A2])) is preferably 0.05 to 0.40. If it is less than 0.05, the contrast is lowered due to insufficient suppression of fluorescence and the dispersibility of the amine compound [A2] of copper phthalocyanine, and if it exceeds 0.40, the color characteristics are affected, resulting in low brightness. A more preferred weight ratio ([A2] / ([A1] + [A2])) is 0.20 to 0.30.

<< Xanthene dye [A3] >>
The xanthene dye [A3] that can be preferably used in the present invention is red or purple, and has any form of an oil-soluble dye, an acid dye, a direct dye, and a basic dye.
A red or purple color means C.I. I. Solvent Red, C.I. Oil soluble dyes such as I. solvent violet, C.I. I. Basic Red, C.I. Basic dyes such as I. basic violet, C.I. I. Acid Red, C.I. Acid dyes such as I. Acid Violet, C.I. I. Direct Red, C.I. I. Direct belongs to direct dyes such as violet.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as an acid dye.

  The xanthene dye [A3] used in the present invention has a transmittance of 90% or more in the region of 650 nm in the transmission spectrum, a transmittance of 75% or more in the region of 600 nm, and a transmittance of 5% in the region of 500 to 550 nm. Hereinafter, those having a transmittance of 70% or more in the 400 nm region are preferable. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

  Xanthene-based basic dyes also have spectral characteristics with high transmittance at 400 to 450 nm, but display images using color filters that are further poor in light resistance and heat resistance and require high reliability. Its properties are not sufficient for use in devices. Therefore, in order to improve the disadvantages of these dyes, it is preferable to salt the xanthene-based basic dye using an organic acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used.

  Further, xanthene acid dyes have spectral characteristics having high transmittance at 400 to 450 nm. However, in spite of having good spectral characteristics, light resistance and heat resistance are poor as in general dyes, and the characteristics are as follows for use in image display devices using color filters that require high reliability. Not enough. Therefore, in order to improve the drawbacks of these dyes, xanthene acid dyes can be chlorinated or sulfonamidated using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc. It is preferably used as a sulfonic acid amide compound.

  Among these, as the xanthene dye [A3] that can be preferably used in the present invention, it is preferable to use a xanthene acid dye or a xanthene oil-soluble dye, and in particular, a counter component that functions as a counter ion. It is preferable to use a compound prepared by chlorination using a quaternary ammonium salt compound, or a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Among the xanthene dyes [A3], rhodamine dyes are preferable because they are excellent in color developability and resistance.

  Hereinafter, the form of the xanthene dye [A3] used in the present invention will be specifically described in detail.

[Xanthene oil-soluble dye]
The oil-soluble dye of the xanthene dye will be described. Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like.
Among them, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, CI Solvent, which are rhodamine-based oil-soluble dyes having high coloring properties. Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

[Xanthene basic dye]
The basic dye of the xanthene dye will be described. Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like.
Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.

[Xanthene acid dyes]
The acidic dye of the xanthene dye will be described. Examples of acidic dyes of xanthene dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (Edible Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (edible red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388, or C.I. which is a rhodamine acid dye. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

  Further, the xanthene-based acid dye can have both high heat resistance, light resistance and solvent resistance by chlorination and sulfonamidation as a quaternary ammonium salt.

(Salt-forming compound consisting of xanthene acid dye and quaternary ammonium salt compound)
The xanthene dye [A3] used in the present invention is preferably used as a salt-forming compound comprising the xanthene acid dye and the quaternary ammonium salt compound described above.

-Quaternary ammonium salt compound A quaternary ammonium salt compound becomes a counter of a xanthene type acid dye by having an amino group.

  A preferred form of the quaternary ammonium salt compound which is a counter component of the salt-forming compound is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state where the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

It is preferable that the molecular weight of the counter part which is a cation component of a quaternary ammonium salt compound is in the range of 190-900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) + moiety in the following general formula (9). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and further, solubility in a solvent is lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the color developing component in the molecule is lowered, the color developability is lowered, and the lightness is also lowered. More preferably, the molecular weight of the counter portion is in the range of 240-850. Particularly preferred is a counter portion with a molecular weight in the range of 350-800.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

Moreover, what is represented by following General formula (9) is used as a quaternary ammonium salt compound.

General formula (9)
(In General Formula (9), R _{1 to} R ₄ each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , and R ₄ And C has 5 to 20. Y represents an inorganic or organic anion.)

R ₁ to R ₄ in by the a 5 to 20 the number of at least two and C, solubility in solvents is improved. When the number of alkyl groups having a C number of less than 5 is 3 or more, solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if there is an alkyl group in which the number of C exceeds 20, the color forming property of the salt-forming compound is impaired.

Specifically, tetramethylammonium chloride (molecular weight of the cation moiety is 74), tetraethylammonium chloride (molecular weight of the cation moiety is 122), monostearyltrimethylammonium chloride (molecular weight of the cation moiety is 312), distearyldimethylammonium chloride ( Cation portion molecular weight 550), tristearyl monomethylammonium chloride (cation portion molecular weight 788), cetyltrimethylammonium chloride (cation portion molecular weight 284), trioctylmethylammonium chloride (cation portion molecular weight 368), dioctyl Dimethylammonium chloride (cation part molecular weight 270), monolauryltrimethylammonium chloride (cation part molecule) 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium Chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearyl ammonium chloride (cation part molecular weight 388) ), and benzyl dimethyl octyl ammonium chloride (molecular weight of the cationic portion 248), dialkyl (alkyl C ₁₄ -C ₁₈₎ di It is preferable to use methylammonium chloride (cured beef tallow) (the molecular weight of the cation moiety is 438 to 550).

  The Y-component constituting the anion may be an inorganic or organic anion, but is preferably a halogen, usually chlorine.

Specific examples of the quaternary ammonium salt compound products include Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Lion Corp. , 2C-75,2HT-75,2HT flakes, 2O-75I, 2HP-75,2HP flakes and the like, among others QUARTAMIN D86P (distearyldimethylammonium chloride), Arquad 2HT-75 (di (alkyl C ₁₄ ~ _C18 ) dimethylammonium chloride) is preferred.

The quaternary ammonium salt compound may be in the form of a resin having a cationic group, particularly an amino group or an ammonium group in the side chain, and capable of forming a quaternary ammonium salt structure by reacting and salting with a xanthene acid dye. . (See Reference 1)
(Reference 1) Japanese Patent Application No. 2011-150752

Resin having a cationic group in the side chain The resin having a cationic group in the side chain is an alkali resin containing a structural unit represented by the following general formula (10), and the cationic group in the general formula (10) However, a salt-forming compound can be obtained by forming a salt with the anionic group of the xanthene acid dye.

General formula (10)

[In General Formula (10), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₆ to R ₈ are each independently a hydrogen atom, an optionally substituted alkyl group, an alkenyl group which may be substituted or an optionally substituted aryl group, the R ₆ to R ₈ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₉ —, —COO—R ₉ —, and R ₉ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

In general formula (10), examples of the alkyl group for R ₅ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. It is done. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable. When the alkyl group represented by R ₅ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.
Among the above, R ₅ is most preferably a hydrogen atom or a methyl group.

In general formula (10), examples of the alkyl group in R _{6 to} R ₈ include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n -Dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1 , 3,3-tetramethylbutyl), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.
Examples of the alkenyl group in R _{6 to} R ₈ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R _{6 to} R ₈ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group, or aryl group represented by R _{6 to} R ₈ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.
R _{6 to} R ₈ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

Two of R _{6 to} R ₈ may be bonded to each other to form a ring.

In the general formula (10), the Q component linking the acrylic moiety and the ammonium base represents an alkylene group, an arylene group, -CONH-R5-, -COO-R5-, and R5 represents an alkylene group. From the viewpoint of availability and availability, —CONH—R ₉ — and —COO—R ₉ — are preferable. R ₉ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

  The Y − component in the general formula (10) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  In order to obtain an acrylic resin containing the structural unit represented by the general formula (10), not only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component but also having an amino group After obtaining an acrylic resin having an amino group copolymerized with an ethylenically unsaturated monomer as a monomer component, it may be obtained by reacting an onium chlorinating agent and ammonium chloride.

  Specific examples of the ethylenically unsaturated monomer having an ammonium base, the ethylenically unsaturated monomer having an amino group, and an onium chlorinating agent are shown below. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth) acryloyl. Alkyl (meth) acrylate quaternary ammonium salts such as oxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloylamide quaternary ammonium salts such as dimethyl Allyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

  Alternatively, an alkoxycarbonylalkyl halide can also be used as the onium chlorinating agent. The alkoxycarbonylalkyl halide is represented by the following general formula (11).

Formula (11)
Z-R ₆₀ -COOR ₇₀

(In the general formula (11), Z is a halogen such as chlorine or bromine, preferably bromine, and R ₆₀ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. R ₇₀ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.)

Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ₇₀ It is obtained by hydrolysis and conversion to carboxylate ions (—COO—). Thereby, the ethylenically unsaturated monomer which has a carboxybetaine structure and has an ammonium base can be obtained.

-Manufacturing method of salt-forming compound The salt-forming compound of a xanthene acid dye and a quaternary ammonium salt compound can be manufactured by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, after the xanthene acid dye is dissolved in water, the quaternary ammonium salt compound is added and the chlorination treatment may be performed while stirring. Here, the sulfonic acid group (—SO ₃ H), sodium sulfonate group (—SO ₃ Na) part in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

  In addition, the salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (10) and a xanthene acid dye are dissolved. It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain represented by the formula (10) and an aqueous solution of a xanthene acid dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the xanthene acid dye are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the xanthene-based acidic dye is water-soluble and can be removed by washing with water. The resin having a cationic group in the side chain to be used and the xanthene acid dye may be used alone or in a plurality of types having different structures.

Examples of the salt-forming compound include C.I. I. Acid Red 289 and C.I. I. By using a salt-forming compound of Acid Red 52 and a quaternary ammonium salt compound having a molecular weight of the counter cation moiety of 350 to 800, it has excellent solvent solubility and is more heat resistant when used in combination with a pigment described later. Excellent in light resistance, light resistance and solvent resistance. In addition, it is presumed that the salt formation compound that is favorable when used in combination with the pigment is adsorbed on the pigment while being dissolved and dispersed in the solvent. At this time, the primary particle diameter of the pigment is preferably 20 to 100 nm.
Although the coloring composition of this invention is mentioned later, the form of the blue coloring composition used together with a blue pigment and the red coloring composition used together with a red pigment is preferable.

(Sulphonic acid amide compound of xanthene acid dye)
The xanthene-based acid dye in the present invention is preferably sulfonated to give a sulfonic acid amide compound because high heat resistance, light resistance, and solvent resistance can be imparted.
A sulfonic acid amide compound of a xanthene acid dye that can be preferably used for the xanthene dye [A1] of the present invention is obtained by chlorinating a xanthene acid dye having —SO ₃ H and —SO ₃ Na by a conventional method, This compound can be prepared by reacting SO ₃ H with —SO ₂ Cl and reacting with an amine having an —NH ₂ group.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
For example, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.

    The amount of the colorant (A) when the solid content of the photosensitive coloring composition is 100 parts by weight is preferably 5 to 15 parts by weight.

<Resin (B)>
The resin is for dispersing a colorant, and is preferably a thermoplastic resin, a thermosetting resin, or the like.
The resin (B) is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  The weight average molecular weight (hereinafter also referred to as Mw) of the resin (B) is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80 in order to disperse the colorant (A) preferably. , 000. The number average molecular weight (hereinafter also referred to as Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  Further, from the viewpoint of pigment dispersibility, developability, and heat resistance, a carboxyl group that functions as a pigment adsorbing group and an alkali-soluble group during development, an aliphatic group and an aromatic group that function as an affinity group for a pigment carrier and a solvent. The balance is important for pigment dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is deteriorated, and it may be difficult to form a fine pattern. On the other hand, if it exceeds 300 mgKOH / g, the fine pattern may not remain.

  The resin (B) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the colorant (A) from the viewpoint of film formability and various resistances, and has a high colorant concentration and good color characteristics. Since it can be expressed, it is preferably used in an amount of 500 parts by weight or less, more preferably 40 parts by weight or more and 300 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the energy ray-curable resin having an ethylenically unsaturated active double bond include a resin into which an unsaturated ethylenic double bond is introduced by the following methods (a) and (b).

<Method (a)>
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of an unsaturated monobasic acid having an unsaturated elenic double bond is added, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to give an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

<Method (b)>
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
In the present invention, it is preferable to further include a thermosetting compound in combination with the thermoplastic resin which is a binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by including a thermosetting compound, it reacts at the time of firing the filter segment to increase the crosslinking density of the coating film, so that the heat resistance of the filter segment is increased. This improves the effect of suppressing pigment aggregation during firing of the filter segment and improving the contrast ratio.

  Examples of thermosetting compounds include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, and phenol compounds and / or resins, but the present invention is not limited thereto. In the coloring composition for a color filter of the present invention, an epoxy compound and / or a resin are preferably used.

The epoxy compound may be a low molecular compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Polyphenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimene) Methanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, alcohols Etc. glycidylated Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine-based epoxy resin, glycidyl ester type epoxy resins, but are not limited to these would normally epoxy compound used. These may be used alone or in combination of two or more.

  As a commercial item, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more) Is a trade name; manufactured by Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name) ; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (Product Name; Japan Epoxy Resin Co., Ltd.), EPPN-201 (Product Name; Nippon Kayaku Co., Ltd.), JER152, JER154 Name: Japan Epoxy Resin Co., Ltd. , EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (above are trade names: manufactured by Daicel Chemical Industries, Ltd.) , Denacol EX-810, EX-830, EX-851, EX-512, EX-421, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation) However, it is not limited to these.

  The compounding amount of the epoxy compound is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 0.5 part by weight, the effect of improving the contrast ratio and the heat resistance is small. If the amount is more than 300 parts by weight, problems may occur when forming a filter segment by photolithography.

  Moreover, in order to assist hardening of a thermosetting compound, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited, and can react with thermosetting compounds. Any curing agent may be used as long as it is. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting compounds.

<Monomer (C)>
It is important that the monomer (C) of the present invention contains at least a polyfunctional monomer (C1) having an acidic group. Use of the polyfunctional monomer (C1) having an acidic group is important because it can achieve both adhesion to a glass substrate, excellent solubility in an alkali developer, and high voltage retention characteristics. In the present invention, the monomer (C) further contains an oligomer in addition to a monomer capable of reacting with ultraviolet rays or heat, and is preferably a polyfunctional monomer / oligomer. It is also preferable to use a monomer / oligomer having no acidic group in combination.

  The blending amount of the monomer (C) is preferably 20 to 50% by weight in 100% by weight of the nonvolatile content of the coloring composition, and is 30 to 45% by weight from the viewpoints of photocurability, resolution and fringe shape. It is more preferable.

(Polyfunctional monomer having an acid group (C1))
As the polyfunctional monomer (C1) having an acid group, for example, an esterified product of a poly (meth) acrylate containing a free hydroxyl group of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polycarboxylic acid; Esterified products with monohydroxyalkyl (meth) acrylates are preferred. Specific examples include monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. Monoesterified products of carboxylic acids with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2, Tricalic acid such as 4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid Free carboxyl group-containing oligoesterified products of boric acids and monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. Can be mentioned.

Moreover, as the polyfunctional monomer (C1) having an acid group, a compound represented by the following general formula (12) is also preferable. By using the compound of the general formula (12), the solubility of the photosensitive coloring composition of the present invention in an alkaline developer is improved, and the generation of insoluble matter with the developer is prevented in the development process on the production line. This can prevent clogging of the filter.
Formula (12):
_{(H 2 C = C (R} 11) COO) m1 -X1- (OCOCH (R 11) CH 2 S (R 12) COOH) n1
(Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydrocarbon group having 1 to 12 carbon atoms, and X1 is an (m1 + n1) -valent carbon number of 3 to 60). Organic group, m1 represents an integer of 2 to 18, and n1 represents an integer of 1 to 3. )
Here, the compound represented by the general formula (12) can be easily obtained by, for example, the following method.

(1) A method in which a compound giving an organic group represented by X1 is esterified with acrylic acid to acrylate, and then a mercapto compound is added to the obtained compound.
(2) After modifying the compound giving an organic group represented by X1 with a polyisocyanate compound, the obtained compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. Method.
(3) A method in which a compound giving an organic group represented by X1 is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

  Examples of the compound that gives an organic group represented by X1 include pentaerythritol, pentaerythritol caprolactone-modified product, pentaerythritol polyisocyanate-modified product, dipentaerythritol, dipentaerythritol caprolactone-modified product, and dipentaerythritol polyisocyanate. Denatured products can be mentioned.

  Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

  The said polyfunctional monomer (C1) which has an acid group can be used individually or in mixture of 2 or more types. The usage-amount of the polyfunctional monomer (C1) which has an acid group in this invention is 20 to 50 weight% in the non volatile matter of 100 weight% of a photosensitive coloring composition, Preferably it is 30 to 45%. In this case, if the amount of the polyfunctional monomer having an acid group is less than 5 parts by weight, the pixel strength or the smoothness of the pixel surface tends to decrease. There is a tendency for the background to be lowered or to become soiled or film remaining in areas other than the area where the pixels are formed.

  The monomer (C) in the present invention includes the polyfunctional monomer (C1) having the acidic group, and may further include a polyfunctional monomer or a monofunctional monomer having no acidic group.

(Polyfunctional monomer)
Examples of the polyfunctional monomer include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, capro Lactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate, tris - (2-acryloxyethyl) can be given isocyanurate.

(Monofunctional monomer)
Examples of monofunctional monomers include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid, 2 -Methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene Glico Acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and commercially available products such as 2-acryloyloxyethyl succinic acid (trade name M-5300) Can be mentioned.

  When the polyfunctional monomer (C1) having an acid group is used in combination with another monomer, these other monomers can be used alone or in combination of two or more. . In that case, the usage-amount of another monomer is 0-90 weight part normally with respect to a total of 100 weight part with the polyfunctional monomer (C1) which has an acid group which is the total monomer amount, Preferably it is 0-50. Parts by weight.

  In the present invention, it is preferable to use a monomer that does not use laprolactone as a raw material from the viewpoint of voltage holding ratio.

  In the present invention, a monomer having an isocyanuric acid skeleton is preferably used as a raw material from the viewpoint of lightness.

<Photopolymerization initiator (D)>
The colored composition for a color filter of the present invention is prepared in the form of an alkali developing type colored resist material by adding a photopolymerization initiator to cure the composition by ultraviolet irradiation and form a filter segment by a photolithographic method. .
The photopolymerization initiator (D) of the present invention includes at least one compound selected from the group consisting of acetophenone compounds, acylphosphine oxide compounds, and oxime compounds.

  As the acetophenone compound, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, and the like.

  Examples of the acyl phosphine oxide compound include bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  As the oxime compound, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- And 9H-carbazol-3-yl]-, 1- (o-acetyloxime). In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester compound.

  From the viewpoint of the remaining film ratio, an oxime compound that is a highly sensitive initiator is preferred, and an oxime compound containing a carbazole group is more preferred. Further, from the viewpoint of lightness, keto-type carbazole group-containing oxime compounds are most preferable.

The oxime compound in the present invention is preferably a compound represented by the following general formula (13). In general formula (13), R ₁ represents a substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl. Group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted Substituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group Substituted or unsubstituted acyl group, substituted or unsubstituted Acyloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphinoyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group,.
Formula (13)

Examples of the substituted or unsubstituted alkenyl group for R ₁ include straight-chain, branched-chain, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. Specific examples include a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2- Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3- Examples thereof include butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

As the substituted or unsubstituted alkyl group for R _{1, a} linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally one or more Examples thereof include a linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by -O-. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. Examples thereof include, but are not limited to, CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _{2 and the} like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The substituted or unsubstituted alkyloxy group in R ₁ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1 Examples include a linear, branched, monocyclic or condensed polycyclic alkyloxy group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the substituted or unsubstituted aryl group in R ₁ include monocyclic or condensed polycyclic aryl groups having 6 to 24 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 1 -Anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2 -Fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group P-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromopheny Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, and the like, but are not limited thereto. It is not a thing.

Examples of the substituted or unsubstituted aryloxy group in R ₁ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9- Although a fluorenyloxy group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted heterocyclic group for R ₁ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl Group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2- Indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, - quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ₁ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted alkylsulfanyl group in R ₁ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group and an ethylthio group. Propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylsulfanyl group in R ₁ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, Examples thereof include, but are not limited to, a 9-anthrylthio group and a 9-phenanthrylthio group.

The substituted or unsubstituted alkylsulfinyl group in R ₁ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and a butylsulfinyl group. Group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. However, it is not limited to these.

  As the substituted or unsubstituted arylsulfinyl group, an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and specific examples include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group Group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfinyl group § sulfonyl phenylsulfinyl group, 4-dimethylaminophenyl sulfinyl but Le group and the like, but is not limited thereto.

The substituted or unsubstituted alkylsulfonyl group for R ₁ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a butylsulfonyl group. Hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group and the like. It is not limited to these.

The substituted or unsubstituted arylsulfonyl group for R ₁ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and 2-chlorophenyl. Sulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3- Nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfo Group, 4-but-dimethylaminophenyl sulfonyl group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted acyl group for R ₁ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or 2 to 20 carbon atoms. A carbonyl group substituted with an alkyloxy group, a carbonyl group bonded with a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, or a carbonyl group substituted with a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms A carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include a formyl group, an acetyl group Group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxy Carbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthryl Carbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, Although an isonicotinoyl group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted acyloxy group in R ₁ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, A fluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group, and the like can be given.

Examples of the substituted or unsubstituted amino group in R ₁ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the substituted or unsubstituted phosphinoyl group in R ₁ include phosphinoyl groups having 2 to 50 carbon atoms. Specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenyl. Examples include, but are not limited to, phosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group. is not.

Examples of the substituted or unsubstituted carbamoyl group in R ₁ include a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N- Butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N 2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3 -Cyanoff Nylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

Examples of the substituted or unsubstituted sulfamoyl group in R ₁ include sulfamoyl groups having 0 to 30 carbon atoms, and specific examples thereof include sulfamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, N N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group A substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.

R ₂ is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, Examples of the substituted or unsubstituted alkylsulfonyl group, the substituted or unsubstituted arylsulfonyl group, the substituted or unsubstituted acyloxy group, and the substituted or unsubstituted amino group include the substituted or unsubstituted alkenyl group in R ¹ described above. Substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or Unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl It is synonymous with a group, a substituted or unsubstituted acyloxy group, and a substituted or unsubstituted amino group.

R _{3 to} R ₅ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl A group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

As a halogen atom in R < ₃ > -R < ₅ >, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted in R _{3 to} R ₅ Unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted acyl group, and substituted or unsubstituted The amino group is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group in R ¹ described above. Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic group It is synonymous with a Si group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted amino group.

R _{6 to} R ₉ are each independently a hydrogen atom, halogen atom, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, or It is a substituent represented by Formula (14).

General formula (14)

(In formula (14), R _{1 ′} and R _{2 ′} have the same meanings as R ₁ and R _2. )
The halogen atom in R < ₆ > -R < ₉ > is synonymous with the halogen atom in R < ³ > -R < ⁵ >.

Examples of the haloalkyl group in R _{6 to} R ₉ include an alkyl group having 1 to 15 carbon atoms in which all the hydrogen atoms are substituted with the halogen atoms described above, and specific examples include a trifluoromethyl group and a trichloromethyl group. , Tribromomethyl group, triiodomethyl group, pentafluoroethyl group, pentachloroethyl group, pentabromoethyl group, pentaiodoethyl group, trifluorodibromoethyl group, tribromodiiodoethyl group, heptafluoropropyl group, hepta Chloropropyl group, heptabromopropyl group, nonafluorobutyl group, nonachlorobutyl group, nonabromobutyl group, undecafluoropentyl group, undecachloropentyl group, undecabromopentyl group, tridecafluorohexyl group, tridecachlorohexyl Group, pentadecafluoro Examples thereof include, but are not limited to, a ptyl group, a heptadecafluorooctyl group, a nonadecafluorononyl group, a henicosafluorodecyl group, a tricosafluoroundecyl group, and a pentacosafluorododecyl group. .

  The haloalkyl group is more preferably a trifluoromethyl group or a pentafluoroethyl group from the viewpoint of the synthesis surface and the characteristics as a colored composition.

A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, or a substituted group in R _{6 to} R ₉ Or an unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted aryl The sulfinyl group, the substituted or unsubstituted alkylsulfonyl group, the substituted or unsubstituted arylsulfonyl group, and the substituted or unsubstituted amino group are the substituted or unsubstituted alkyl group, substituted or unsubstituted in R ¹ described above. Alkyloxy group, substituted or unsubstituted A reel group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, substituted or Unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, and substituted or unsubstituted Synonymous with amino group.

Examples of the substituent position of the substituent in R ₆ to R _9, from the characteristic surface of the synthetic surface and coloration composition, if substituted at the R ₇ is preferred.

R _{10 to} R ₁₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl Although they are a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group, all of R _{10 to} R ₁₄ do not become hydrogen atoms at the same time.

The haloalkyl group in R _{10 to} R ₁₄ has the same meaning as the haloalkyl group in R _{6 to} R ₉ described above, and is a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl. group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfinyl group for R ¹ described above, a substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted It is synonymous with an alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted acyl group.

At least one of R _{10 to} R ₁₄ is preferably a nitro group or a substituted or unsubstituted acyl group from the viewpoint of the synthesis surface and the characteristics as a colored composition, and is a nitro group or the following general formula (15) Is more preferable.

General formula (15)

(In the formula (15), R _{15 to} R ₁₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl A sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.)

The haloalkyl group in R _{15 to} R ₁₉ has the same meaning as the haloalkyl group in R _{6 to} R ₉ described above, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted An arylsulfanyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted amino group are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group in R ¹ , Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group Substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted acyl group, and substituted or unsubstituted It is synonymous with the amino group.

Here, the substitution position of the nitro group in R _{10 to} R ₁₄ or the substituent represented by the formula (13) is more preferably substituted with R ₁₂ in view of the characteristics as a synthetic surface or a coloring composition. preferable.

The hydrogen atom of the substituent in R _{1 to} R ₁₉ described above may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and other heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups Group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, Trimethylammonium, dimethylsulfonium, trif Cycloalkenyl phenacyl phosphonium Niu mill group, and the like.

The oxime compound in the present invention is characterized in that an electron-withdrawing substituent is substituted on the phenyl group of the N-phenylcarbazole skeleton. Oxime ester-based photopolymerization initiators are believed to decompose the oxime ester moiety by absorbing ultraviolet rays to produce iminyl radicals and alkyloxy radicals, and the radicals of the active species produced by further decomposition cause the reaction. However, since the oxime compound contained in the photosensitive coloring composition of the present invention has a structure represented by the general formula (13), the decomposition efficiency by ultraviolet irradiation is very high, and the exposure amount is small. A pattern can be formed.
The reason why the oxime compound of the present invention can function with higher sensitivity than the conventional initiator is considered as the following three reasons, but details are not clear.

  The first reason is that the oxime compound of the present invention absorbs energy by a given energy beam very well because the structure represented by the general formula (13) has a good ultraviolet absorption performance. Be able to. Furthermore, it is conceivable that the obtained energy is efficiently used for the decomposition of the oxime ester moiety, so that the decomposition by the energy beam irradiation is fast and a large amount of radicals can be generated instantaneously.

The second reason is that the oxime compound of the present invention is derived from the structure represented by the general formula (13) because the decomposition of the imineyl radical generated by absorbing ultraviolet rays into the radical of the active species. It can be very fast. If the iminyl radical to be produced is metastable, the decomposition is slowed down and the amount of active radicals produced is reduced, but this is greatly affected by the chemical structure of the UV-absorbing moiety. When the oxime compound of the present invention has the structure represented by the general formula (11), the decomposition of the iminyl radical generated by the light irradiation decomposition is very fast, resulting in the generation of a large amount of radicals. Conceivable.
Further, as described above, it is considered that the recombination is suppressed in the oxime compound of the present invention because the decomposition of the iminyl radical is very fast. When the number of recombination is large, the active species generated by the decomposition is reduced, so that the function as a radical polymerization initiator is lowered.

  The third reason is the synergistic effect of the effect of the carbazole substituted with the above-described electron-withdrawing substituent that can function as a good ultraviolet absorption performance and the effect of the keto oxime ester.

Examples of the photopolymerization initiator that can be used in combination include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, Benzophenone compounds such as hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone Thioxanthone compounds such as 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, , 4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) ) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-tri Triazine compounds such as gin, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (o-methoxy) Phenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, Imidazole compounds such as 9,10-phenanthrenequinone, quinone compounds such as camphorquinone and ethylanthraquinone, borate compounds, carbazole compounds, titanocene compounds and the like.
These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerization initiator (D) is preferably 0.5 to 20% by weight in a total of 100% by weight of the solid content of the photosensitive coloring composition. If it is less than 0.5% by weight, the adhesion to the substrate is poor, and if it exceeds 20% by weight, there will be a problem in resolution. From these viewpoints, 1 to 15% by weight is more preferable, and further preferably 1.5 to 10% by weight.

As characteristics when the photosensitive coloring composition is used for COA, the profile angle is preferably 35 to 65 °, more preferably 40 to 60 °, and the taper length is preferably 7 μm or less. Therefore, when the monomer amount and the initiator amount are within the above ranges, the profile angle and the taper length can be controlled to the required values, and a color filter suitable for the COA method can be manufactured.

<Solvent>
The photosensitive coloring composition of the present invention can contain a solvent. Thus, the colorant is sufficiently dispersed and permeated in the photosensitive coloring composition, and is applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.5 to 5.0 μm to form a filter segment. Can be made easier.

  Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2 -Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m- Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate , O-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol Methyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether Dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Acetate Amyl, isobutyl acetate, propyl acetate, and a dibasic acid ester and the like.

Among them, from the viewpoint of storage stability of the colored composition of the present invention, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol acetates such as ethylene glycol monoethyl ether acetate, benzyl alcohol, etc. It is preferable to use ketones such as aromatic alcohols and cyclohexanone.
A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since a solvent can adjust a coloring composition to appropriate viscosity and can form the filter segment of the target uniform film thickness, it is used in the quantity of 800-4000 weight part with respect to 100 weight part of coloring agents (A). It is preferable.

<Dispersion>
The photosensitive coloring composition of the present invention comprises a colorant carrier comprising a resin (B) as a colorant, an amine compound (C) of copper phthalocyanine, and a solvent as necessary. It can be produced by finely dispersing using various dispersing means such as a roll mill, a sand mill, a kneader, or an attritor. The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other colorants and the like separately dispersed in a colorant carrier.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the salt-forming compound is also expected to play a role as a pigment dispersion aid.

(Resin type dispersant)
The resin-type dispersant has a pigment-affinity part that has the property of adsorbing to the additive pigment and a part that is compatible with the colorant carrier, and adsorbs to the additive pigment to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The amount of the resin-type dispersant and surfactant added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the added pigment (100% by weight). It is. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Leveling agent>
In order to improve the leveling property of the photosensitive coloring composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent is preferably used in an amount of 0.003 to 0.5% by weight in 100% by weight of the photosensitive coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the photosensitive coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant (A).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant (A).

<Removal of coarse particles>
The photosensitive coloring composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, a colored layer that is a colored film using the photosensitive coloring composition of the present invention, a color filter, and a method for producing the color filter will be described.

  The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. The said filter segment is formed on a base material by apply | coating the photosensitive coloring composition of this invention by a spin coat system or a die coat system.

  As the base material of the color filter, glass plates such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc. with high transmittance for visible light, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A transparent substrate such as a resin plate or a reflective substrate can be used. These substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after forming the panel.

  If a black matrix is formed in advance before forming the filter segments on these transparent or reflective substrates, the contrast of the liquid crystal display panel can be further increased. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed. Alternatively, a thin film transistor (TFT) formed in advance on the transparent substrate or the reflective substrate may be used as a driving substrate for a thin film transistor (TFT) type color liquid crystal display device, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  Here, a method for forming a colored layer on the TFT substrate will be described. First, on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate, a light shielding layer is formed so as to divide the pixel forming portion as necessary. After forming and applying the photosensitive coloring composition on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked, whereby the pixel pattern has a predetermined arrangement. An arranged pixel array is formed. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer.

  As a development processing method, 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. Of these, the shower development method or the spray development method is preferable from the viewpoint of achieving both a good profile angle, contact and hole opening.

  In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. However, it is not preferable to apply a resin or the like on the coating film of the colored composition because it is difficult to open contact holes if the sensitivity is too high because polymerization inhibition is prevented. .

The coating thickness (thickness of the colored film) when forming the filter segment on the transparent substrate or the reflective substrate is preferably a dry film thickness of 0.1 to 5 μm, more preferably 0.5 to 3 μm. .
In particular, when the colored composition of the present invention is used in a COA system, insulation is required to prevent crosstalk occurring between the gate electrode and the transparent electrode, and a thick film is preferable. It is preferable to use a film thickness of 0.1 to 10 μm, more preferably 0.5 to 5 μm.
The colored film using the photosensitive coloring composition of the present invention is exposed with an integrated light quantity of 50 mJ / cm ² with ultraviolet light having an illuminance of 30 mW / cm ² using an ultrahigh pressure mercury lamp through a photomask having a 30 μm through-hole pattern. Then, after developing the unexposed portion, a through-hole pattern of 20 to 35 μm can be formed when the thickness of the coating film is 3.0 μm when post-baked at 230 ° C. for 20 minutes in an oven.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “part” represents “part by weight”, and “%” represents “% by weight”.
Moreover, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.
The degree of fineness of the pigment was evaluated by the specific surface area of pigment particles and the average primary particle size. The specific surface area was measured with an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the BET method of nitrogen adsorption.

<Measurement method>
(Resin polymerization average molecular weight (Mw))
The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Ammonium salt value of a resin having a cationic group in the side chain)
The ammonium salt value of the resin having a cationic group in the side chain represented by the general formula (10) was determined by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then hydroxylated. It is the value converted into the equivalent of potassium, and shows the ammonium salt value of solid content.

  First, photopolymerization initiator 6, acrylic resin solution, fine pigment, resin having a cationic group in the side chain, salt-forming compound, xanthene dye-containing solution, copper phthalocyanine amine compound, resin type used in Examples and Comparative Examples The manufacturing method of a dispersing agent solution and a pigment dispersion is demonstrated.

<Method for producing photopolymerization initiator>
[Synthesis of Photopolymerization Initiator 6]
Dissolve 100.0 g of N-benzophenoylcarbazole in 1000 ml of chloroform, add 85.0 g of aluminum chloride, and stir at 0 ° C., and then add a solution of 32.0 g of propionyl chloride in 500 ml of chloroform over 2 hours. It was dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 113.0 g of the intermediate compound (a1). Next, 38.4 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a1), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to give precursor compound (b1) 99. .8 g was obtained. Next, 6.3 g of acetic anhydride and 10.6 g of sodium acetate were added to 30.0 g of compound (b1) in 300 ml of ethyl acetate, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.4 g of photopolymerization initiator 6.

Photopolymerization initiator 6
Formula (16)

[Synthesis of Photopolymerization Initiator (7)]
Dissolve 100.0 g of N-benzophenoylcarbazole in 1000 ml of chloroform, add 84.0 g of aluminum chloride and stir at 0 ° C., and then add a solution of 36.8 g of butanoyl chloride in 500 ml of chloroform over 2 hours. And dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 109.3 g of the intermediate compound (a2). Next, 40.0 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a2), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b2) 89 .3 g was obtained. Next, when 30.0 g of compound (b2) was stirred in 300 ml of ethyl acetate, 6.1 g of acetic anhydride and 10.3 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 30.0 g of a photopolymerization initiator (7).

Photopolymerization initiator (7)
Formula (17)

[Synthesis of Photopolymerization Initiator (8)]
A solution in which 100.0 g of N- (p-nitrophenyl) carbazole was dissolved in 1000 ml of chloroform, 101.8 g of aluminum chloride was further added, and 44.3 g of butanoyl chloride was dissolved in 500 ml of chloroform was stirred at 0 ° C. It was dripped over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 113.6 g of an intermediate compound (a3). Next, 40.0 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a3), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1500 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b3) 107. 0.2 g was obtained. Next, when 50.0 g of compound (b3) was stirred in 500 ml of ethyl acetate, 19.9 g of acetic anhydride and 11.7 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 57.6 g of a photopolymerization initiator (8).

Photopolymerization initiator (8)
General formula (18)

[Synthesis of Photopolymerization Initiator (9)]
Dissolve 100.0 g of N-benzophenoyl-1,3-dimethyl-carbazole in 1000 ml of chloroform, add 78.6 g of aluminum chloride and dissolve 29.6 g of propionyl chloride in 500 ml of chloroform with stirring at 0 ° C. The solution was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 111.8 g of intermediate compound (a4). Next, 35.7 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a4), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b4) 98. .3 g was obtained. Next, when 30.0 g of compound (b4) was stirred in 300 ml of ethyl acetate, 5.9 g of acetic anhydride and 10.0 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.2 g of a photopolymerization initiator (9).

Photopolymerization initiator (9)
General formula (19)

<Method for producing acrylic resin solution>
(Acrylic resin solution 1)
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Thereafter, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 7 A mixture of 0.4 part and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 40% by weight. Acrylic resin solution 1 was prepared by adding ether acetate.

(Acrylic resin solution 2)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed. Next, the inside of the flask was purged with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. Tetrahydrophthalic anhydride was further added. 30.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 8000 and an acid value of 71 mgKOH / g. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 2.

(Acrylic resin solution 3)
Put 182 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirring device in a separable four-necked flask, and heat to 100 ° C. while injecting nitrogen gas into the vessel. Mixture of 70.5 parts of benzyl methacrylate, 22.0 parts of dicyclopentanyl methacrylate, 43.0 parts of methacrylic acid, 136 parts of propylene glycol monomethyl ether acetate, and 3.6 parts of azobisisobutyronitrile from a dropping tube at a temperature. Was added dropwise over 2 hours and further stirred at 100 ° C. for 5 hours to conduct a polymerization reaction. Next, the inside of the flask was purged with air, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were added to 35.5 parts of glycidyl methacrylate, the reaction was continued at 110 ° C. for 6 hours, and the weight average molecular weight 25000, An acrylic resin solution having an acid value of 88 mgKOH / g was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 3.

(Acrylic resin solution 4)
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Thereafter, a mixture of 69.5 parts of benzyl methacrylate, 15.5 parts of methacrylic acid, 15.0 parts of dicyclopentanyl methacrylate, and 0.4 part of 2,2′-azobisisobutyronitrile was added from the dropping tube over 2 hours. The solution was added dropwise to carry out a polymerization reaction. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 17100 and an acid value of 99 mgKOH / g. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 4.

(Acrylic resin solution 5)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 14 parts of methacrylic acid, 26 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution having a weight average molecular weight of 18000 and an acid value of 50 KOH-mg / g. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 40% by mass. Thus, a resin solution 5 was prepared.

(Acrylic resin solution 6)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 23.0 parts of n-butyl methacrylate, 25.0 parts of benzyl methacrylate, 13.0 parts of methacrylic acid, 14.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd.) “Aronix M110”) 25.0 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 32000 and an acid value of 78 KOH-mg / g. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 40% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 6.

(Measurement method of acid value)
To 0.5 to 1 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L aqueous KOH solution is used as a titrant, and an automatic titrator (“COM-555” Hiranuma Sangyo) The acid value of the resin solution was measured. Then, the acid value per non-volatile content of the resin was calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

<Method for producing blue pigment [A1]>
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a blue pigment [A1] were obtained. The specific surface area of the blue pigment [A1] was 80 m ² / g.

<Method for Producing Amine Compound [A2] of Copper Phthalocyanine>
After adding 30 parts of copper phthalocyanine to 300 parts of chlorosulfonic acid and completely dissolving it, 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, then 15 parts of N, N-dimethylaminopropylamine was added, and the mixture was stirred at room temperature for 3 hours, then at 60 ° C. for 2 hours, filtered, washed with water and dried. And 36 parts of a copper phthalocyanine sulfonic acid amide compound (E-3) were obtained. The obtained copper phthalocyanine sulfonic acid amide compound was subjected to composition analysis using a liquid chromatograph / mass spectrometer platform LCZ manufactured by Waters, and those having 3 or more substituents were not included. SO ₂ NH (CH ₂ ) Copper phthalocyanine sulfonic acid amide compound (C-3-D1) having one ₃ N (CH ₃ ) ₂ and copper phthalocyanine sulfonic acid amide compound having _two SO ₂ NH (CH ₂ ) ₃ N (CH ₃ ) ₂ ( C-3-D2), and each weight ratio was 85:15.

General formula (20)

<Method for Preparing Resin Having Cationic Group in Side Chain Represented by General Formula (10)>
74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, and 15.6 parts of methyl ethyl ketone were homogenized. Then, it was charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 33 mgKOH / g.

<Production Method of Xanthene Dye [A3]>
<Method for producing salt-forming compound>

(Salt making compound)
In the following procedure, C.I. I. A salt-forming compound comprising Acid Red 52 and a resin having a cationic group in the side chain was produced.
A resin having a cationic group in the side chain of 51 parts was added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, the reaction solution was dropped onto the filter paper, and it was judged that the salt-forming compound was obtained with the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound of Acid Red 52 and a resin having a cationic group in the side chain was obtained. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

<Method for producing xanthene dye-containing solution>
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a xanthene dye-containing solution.
Salt-forming compound (A-1): 20.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 80.0 parts

<Preparation Method of Resin Type Dispersant Solution>
A commercially available resin-type dispersant, “EFKA4300” manufactured by BASF, and ethylene glycol monomethyl ether acetate were used to prepare a solution having a nonvolatile content of 40% by weight and used as a resin-type dispersant solution.

<Method for producing pigment dispersion>
(Preparation of blue pigment dispersion)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a blue pigment dispersion was obtained.
Blue fine pigment [A1] (CI Pigment Blue 15: 6): 9.6 parts Copper Phthalocyanine Amine Compound [A2]: 2.4 parts Resin Type Dispersant (“EFKA4300” manufactured by BASF): 16. 0 part propylene glycol monomethyl ether acetate (PGMAC): 72.0 parts

[Example 1]
<Preparation of coloring composition>
The colored composition of Example 1 was stirred and mixed so that the following mixture was uniform, and then filtered and mixed with a 5.0 μm filter to prepare a blue photosensitive colored composition (R-1).

Blue pigment dispersion: 14.51 parts by weight Salt-forming compound solution: 9.82 parts by weight Acrylic resin solution 1: 7.65 parts by weight Epoxy compound solution 1: 5.39 parts by weight Monomer 2 (dipentaerythritol hexaacrylate): 3.60 parts by weight of monomer 3 (succinic anhydride adduct of a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate): 3.60 parts by weight of photopolymerization initiator 1 (2- (dimethylamino) -2-[( 4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone): 0.97 parts by weight Photopolymerization initiator 2 (2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one)
: 0.65 parts by weight Propylene glycol monomethyl ether acetate: 53.81 parts by weight

[Examples 2 to 69 and Comparative Examples 1 to 7]
The photosensitive coloring compositions (R-2 to 76 ) of Examples 2 to 69 and Comparative Examples 1 to 7 are shown in Tables 1 to 7.
Obtained in the same manner as in Example 1 according to the composition of
However, Examples 1-21, 29-32, 55, 56 are reference examples.

Abbreviations in Tables 1 to 7 are shown below.
Epoxy compound 1: EHPE3150 (poly [(2-oxiranyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propanediol ether (manufactured by Daicel Chemical Industries))
Epoxy compound 2: EX-611 (sorbitol tetraglycidyl ether (manufactured by Nagase ChemteX Corporation))
Epoxy compound 3: EX-201 (resorcinol diglycidyl ether (manufactured by Nagase ChemteX Corporation))
Epoxy compound solutions 1 to 3 were prepared by adding propylene glycol monomethyl ether acetate to the epoxy compounds 1 to 3 so that the nonvolatile content was 20% by weight.

Monomer 1: caprolactone-modified dipentaerythritol hexaacrylate (“KAYARAD DPCA-30” manufactured by Nippon Kayaku Co., Ltd.)
Monomer 2: Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Monomer 3: Carboxyl group-containing polyfunctional monomer (C1-1): Succinic anhydride adduct of a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate (“Aronix M-520” manufactured by Toagosei Co., Ltd.) Acid value: 30 mg KOH / g)
Monomer 4: carboxyl group-containing polyfunctional monomer (C1-2): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd.) TO-1382 ”acid value: 29 mg KOH / g)
Monomer 5: carboxyl group-containing polyfunctional monomer (C1-3): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd.) TO-2349 ”acid value: 68 mg KOH / g)
Monomer 6: Tris- (2-acryloxyethyl) isocyanurate (“A-9300” manufactured by Shin-Nakamura Chemical Co., Ltd.)

Photopolymerization initiator 1: acetophenone series: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by BASF “ IRGACURE 379 ")
Photopolymerization initiator 2: Acetophenone series: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF)
Photopolymerization initiator 3: Acylphosphine oxide type: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE 819” manufactured by BASF)
Photopolymerization initiator 4: Oxime ester type: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“IRGACURE OXE-01” manufactured by BASF)
Photopolymerization initiator 5: ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoy-9H-carbazol-3-yl], 1- (O-acetyloxime) (“IRGACURE” manufactured by BASF OXE-02 ")
Photopolymerization initiator 10: 2,2′-bis (O-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (“Biimidazole” manufactured by Kurokin Kasei)
Photopolymerization initiator 11: 9H-carbazole-9-acetic acid-3- [4,6-bis (trichloromethyl) -1,3,5-triazin-2-yl] -2-methoxy-1-methyl Ethyl ester

<Contrast ratio and brightness evaluation>
Using a spin coater, the blue photosensitive coloring compositions (R-1 to R-67) obtained in Examples 1 to 60 and Comparative Examples 1 to 7 were placed on a 100 mm × 100 mm, 0.7 mm thick glass substrate. Then, each blue coloring composition was applied to a film thickness such that y = 0.09 with a C light source, and this substrate was baked at 230 ° C. for 20 minutes. Thereafter, Tables 8 and 9 show the evaluation results of the contrast ratio and brightness of the obtained substrate.

<Adhesion, resolution, profile angle, fringe linearity>
Using the spin coater, the color filter coloring compositions obtained in the examples and comparative examples were formed on a substrate in which a silicon nitride film was formed on the surface of a TFT liquid crystal driving substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm. The film thickness after drying is applied at a rotational speed of 3.0 μm, dried under reduced pressure, and then irradiated with ultraviolet light at an illuminance of 30 mW / cm ² and an integrated light amount of 50 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Exposure was performed. Thereafter, a 0.2 wt% sodium carbonate aqueous solution was used as a developer, and an uncured portion of the coating film was removed by a shower development method at a developer pressure of 0.1 mPa to remove a regular octagonal through hole with a diameter of 30 μm and a line width of 50 μm. A pattern containing fine lines was formed. Thereafter, an evaluation substrate was produced by baking at 230 ° C. for 20 minutes in an oven. Using the prepared substrate, adhesion, resolution, and cross-sectional shape were evaluated according to the following criteria. Moreover, about the thing with bad adhesiveness, resolution and cross-sectional shape evaluation were not performed.

(Adhesion)
Visual evaluation was performed in three stages according to the following criteria. △ ○ is a practical level.
○: No pattern peeling is observed Δ: Pattern peeling is slightly recognized ×: Pattern peeling is recognized

(Resolution)
The hole diameter was measured with analysis software (Image-Pro, manufactured by Planetron Co., Ltd.) using an optical microscope, and evaluated according to the following criteria. △ ○ is a practical level.
○: A hole of 25 to 35 μm can be formed with respect to the mask hole diameter of 30 μm. Δ: A hole of 15 μm or more to less than 25 μm can be formed with respect to the mask hole diameter of 30 μm. ×: A hole of 15 μm or more cannot be formed with respect to the mask hole diameter of 30 μm. Alternatively, a hole exceeding 35 μm is formed.

(Profile angle)
As a characteristic when the photosensitive coloring composition is used for COA, the profile angle is preferably 35 to 65 °, and more preferably 40 to 60 °. Cut the fine line portion of the pattern together with the substrate, and use a scanning electron microscope (SEM) to take a pattern cross-section photograph from the direction of the substrate cut surface at a magnification of 10,000 times. The formed angle (θ) was evaluated in three stages according to the following criteria (when the pattern cross section is curved, the angle formed by the straight line connecting the outer contact and the substrate contact and the substrate). Δ to ○ are practical levels.
○: Profile angle is 40 to 60 ° Δ: Profile angle is 35 to 40 °, or 60 to 65 ° ×: Profile angle is 35 ° or less, or 65 ° or more

(Fringe linearity)
The fringe of the pattern was observed using an optical microscope and evaluated in two stages according to the following criteria.
○: Tapered fringe portion maintains linearity ×: Tapered fringe portion is extraordinary and lacks linearity

<Developer solubility>
Using the spin coater, the color filter coloring compositions obtained in the examples and comparative examples were formed on a substrate in which a silicon nitride film was formed on the surface of a TFT liquid crystal driving substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm. Four coated substrates were prepared so that the film thickness after drying was 3.0 μm, and the substrate dried under reduced pressure was dissolved in 50 g of a developer composed of a 0.2 wt% sodium carbonate aqueous solution. The solution was allowed to stand and the presence or absence of a precipitate after one day was confirmed.
○: No sediment even after standing for 1 day △: No sediment when left for 1 day, but turbidity x: 1 day standing, with sediment

<Voltage holding ratio (VHR)>
Using the spin coater, the color filter coloring compositions obtained in the examples and comparative examples were formed on a substrate in which a silicon nitride film was formed on the surface of a TFT liquid crystal driving substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm. The film thickness after drying is applied at a rotational speed of 3.0 μm, dried under reduced pressure, and then irradiated with ultraviolet light at an illuminance of 30 mW / cm ² and an integrated light amount of 50 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Exposure was performed. Thereafter, a 0.2 wt% aqueous sodium carbonate solution is used as a developer, developed by a shower development method at a developer pressure of 0.1 mPa, and baked at 230 ° C. for 20 minutes in an oven to obtain a coated substrate of a resist material. It was. After removing 0.05 parts of the resist coating film from the obtained coated substrate, it was immersed in 1.5 parts of liquid crystal (MLC-2041 manufactured by Merck Co., Ltd.), aged in a 120 ° C. oven for 60 minutes, and 4000 rpm. After centrifuging for 15 minutes, a supernatant liquid was collected to prepare a resist extraction liquid crystal sample liquid.
On the other hand, two glass substrates having an ITO transparent electrode with an effective electrode size of 10 mm × 10 mm are arranged facing each other so that the ITO transparent electrode surfaces face each other, and a small cell is produced using a sealing agent so that the cell gap becomes 9 μm. did. A resist-extracted liquid crystal sample solution is injected into the small cell between the cell gaps, a voltage of 5 V is applied at 60 ° C. for 60 μsec, and the cell voltage [V ₁ ] after 16.67 msec has elapsed after the voltage release, Measured with Toyo Technica VHR-1S. The measurement was repeated 5 times, and the measured cell voltages were averaged. And the voltage holding rate (%) was calculated | required from the following formula using the obtained cell voltage.

Voltage holding ratio (%) = ([V ₁ ] / 5) × 100
The evaluation criteria for the voltage holding ratio (%) are as follows. Δ to ◎ are practical levels.
◎: 95% or more ○: 90% or more and less than 95% △: 85% or more and less than 90% ×: less than 85%

<Residual film ratio>
Using the spin coater, the color filter coloring compositions obtained in the examples and comparative examples were formed on a substrate in which a silicon nitride film was formed on the surface of a TFT liquid crystal driving substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm. The film thickness after drying was applied at a rotation speed of 3.0 μm, and after drying under reduced pressure, the film thickness T1 of the colored film was measured. Then, exposure was performed with an integrated light quantity of 50 mJ / cm 2 with ultraviolet rays having an illuminance of 30 mW / cm 2 using a super high pressure mercury lamp through a photomask. Thereafter, using a 0.2 wt% aqueous sodium carbonate solution as a developer, the film was developed by a shower development method at a developer pressure of 0.1 mPa, and baked in an oven at 230 ° C. for 20 minutes to obtain a film thickness of the colored film. T2 was measured.

  In addition, as a film thickness meter, a surface shape measuring device DEKTAK150 (manufactured by ULVAC-ES) was used.

Using the film thicknesses T1 and T2 of the obtained colored film, the remaining film ratio (%) was calculated from the following formula, and four-stage evaluation was performed based on the following criteria. Δ to ◎ are practical levels.
Remaining film ratio (%) = T2 / T1 × 100

A: 80% or more B: 70 to less than 80% B: 60 to less than 70% X: Less than 60% Evaluation results are shown in Tables 8 and 9.

  As shown in Tables 8 and 9, the weight ratio ([A2] / ([A1] + [A2])) of the blue pigment [A1] and the amine compound [A2] of copper phthalocyanine is 0.05-0. 40, the amount of the colorant (A) when the solid content of the photosensitive coloring composition is 100 parts by weight is 5 to 15 parts by weight, and the photopolymerization initiator (D) is an acetophenone compound, acylphosphine. The photosensitive coloring composition containing at least one compound selected from the group consisting of an oxide compound and an oxime compound is evaluated more than Comparative Examples 1 to 7 with respect to contrast, brightness, and adhesion to a substrate. Was good, and each characteristic was compatible.

  Moreover, when Examples 18-43 are compared, by using an oxime compound for a photoinitiator (D), a remaining film rate is high at the same resolution compared with other photoinitiators, and a favorable result is obtained. Obtained. Further, when Examples 44 and 51 to 53 were compared, Example 44 having a keto-type oxime ester compound having a carbazole skeleton among the oxime compounds had the best adhesion, and both characteristics could be achieved.

  Further, when Examples 44 and 57 were compared, Example 57 using a monomer having an isocyanuric acid skeleton had the highest lightness and was balanced with other photolithography characteristics, and better results were obtained.

  Although it is a thick film, it has high resolution, high residual film ratio, good adhesion to the glass substrate, excellent solubility in alkaline developer, voltage holding characteristics and developability, and high transmittance and high contrast. A photosensitive coloring composition excellent in heat resistance and a color filter suitable for the COA system was obtained.

Claims (8)

A colorant (A) comprising a blue pigment [A1], an amine compound [A2] of copper phthalocyanine having a structure represented by the following general formula (1), and a xanthene dye [A3];
Resin (B);
Monomer (C);
A photosensitive coloring composition containing a photopolymerization initiator (D),
The weight ratio ([A2] / ([A1] + [A2])) of the blue pigment [A1] and the copper phthalocyanine amine compound [A2] is 0.05 to 0.40,
The amount of the colorant (A) when the solid content of the photosensitive coloring composition is 100 parts by weight is 5 to 15 parts by weight,
The photopolymerization initiator (D) includes an oxime compound containing a carbazole group,
The photosensitive coloring composition, wherein the amount of the photopolymerization initiator (D) when the solid content of the photosensitive coloring composition is 100 parts by weight is 0.5 to 10.0 parts by weight.
General formula (1):
P-Lm
[In general formula (1),
P is an m-valent copper phthalocyanine pigment residue,
m is an integer of 1 to 4,
L is a substituent independently selected from the group represented by general formula (2), general formula (3), and general formula (4). ]
General formula (2):

General formula (3):


General formula (4):

[In general formula (2)-general formula (4),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z is an alkylene group having 1 to 20 carbon atoms. Or an arylene group having 1 to 20 carbon atoms.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² with further nitrogen, oxygen Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and R ⁸ is a substituent represented by the general formula (2) or the general formula (3). The substituents shown,
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ] The photosensitive coloring composition according to claim 1, wherein the resin (B) contains an alkali-soluble photosensitive resin and / or a thermosetting resin. The photosensitive coloring composition according to claim 2, wherein the thermosetting resin contains at least an epoxy compound. Blue pigment [A1] is C.I. I. The photosensitive coloring composition according to claim 1, which is CI Pigment Blue 15: 6. It is applied so that the film thickness after drying becomes 3.0 μm, and the integrated light quantity is 50 mJ / with ultraviolet light having an illuminance of 30 mW / cm ² using a super high pressure mercury lamp through a photomask having a 30 μm through-hole pattern. When exposed at cm ² and then developed using a 0.2 wt% sodium carbonate aqueous solution as a developer, the uncured portion of the coating film was removed by a shower development method at a developer pressure of 0.1 mPa and developed to 20 to 35 μm. The through-hole pattern of this is formed, The photosensitive coloring composition for color filters in any one of Claims 1-4 characterized by the above-mentioned. A colored film for a color filter formed by forming a coating film using the photosensitive coloring composition according to claim 1, developing after exposure, and patterning. A color filter comprising a filter segment formed using the colored film for a color filter according to claim 6. A color filter comprising a filter segment having a colored layer which is a colored film for a color filter according to claim 6 on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device.