JP2011099975A - Colored photosensitive composition, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a colored photosensitive composition which is used to form a green colored pattern in a color filter, has excellent curability and a large development latitude in the formation, reduces pattern defects in development, and forms a green colored pattern having excellent chemical resistance. <P>SOLUTION: The colored photosensitive composition comprises (A) a halogenated zinc phthalocyanine pigment, (B) a polymerizable compound, (C) a binder resin, (D) an acyl phosphine type photopolymerization initiator, and (E) a compound containing an epoxy ring. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colored photosensitive composition, a color filter produced using the same, and a liquid crystal display device including the color filter.

Conventionally, in a small liquid crystal display device such as a mobile phone, a mobile game machine, and a PDA, it is essential to use a backlight light source with a limited electric capacity such as a secondary battery or a dry battery. As the color material of the filter, a color material that is highly transparent and can display a color by transmitting the bright line of the backlight well has been advantageously used.
In recent years, the increase in size of liquid crystal display devices has progressed in applications such as liquid crystal display monitors for personal computers and liquid crystal televisions. In these liquid crystal display devices, there is no restriction on the power supply of the backlight, and the RGB color reproduction of display devices is emphasized. ing. Therefore, in addition to the conventional transparency, the color material of the color filter is required to have higher image quality, that is, improvement in contrast and color purity.

In response to the above requirements, a pigment composition in which the particle diameter of the pigment is made finer, and further an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other components are used as a colorable composition, which is used for photolithography. For example, a color filter in which a three-color pattern of red, green, and blue is formed on a transparent substrate such as glass has been developed and put to practical use.
In the green coloring pattern, chlorinated copper phthalocyanine pigment (CI PIGMENT Green 7), chlorinated brominated copper phthalocyanine pigment (CI PIGMENT Green 36), etc. are generally used from the viewpoint of color tone and fastness. Green pigment is used. In recent years, for the purpose of increasing the color saturation (color purity and color density) of pigments, polyhalogenated metal phthalocyanine pigments such as aluminum, titanium, cobalt, nickel, zinc, tin, and lead have been studied instead of copper. In particular, various pigments have been proposed for polyhalogenated zinc phthalocyanine pigments having high chroma (see, for example, Patent Documents 1 to 3). For example, detailed studies on the degree of substitution of Br and Cl, a pigment treatment method using a betaine-type surfactant, various crystal forms, etc. have progressed, and in the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) is a polyhalogenated copper phthalocyanine having a maximum diffraction peak at 26.4 ° or 25.5 °, and has high chroma (color purity and color density) and is excellent in stability over time and useful. It has been reported.

In addition, each of the above patent documents suggests that a color filter having high transparency and high color purity can be obtained using these pigments, but the dispersibility of the pigment, the latitude during development, etc. are insufficient. As a result, it is difficult to produce a pattern with a desired shape stably, resulting in problems such as chipping of the pattern, loss of pattern size stability, or development residue. Was demanded. In addition, since the curability is inferior, a large amount of exposure is required, and there is a problem of deteriorating productivity.
In order to solve the above problems, many attempts have been made to improve the sensitivity by improving the photopolymerization initiator used in the colored photosensitive composition for a color filter. (For example, refer patent documents 4-6.).
However, these technologies do not provide sufficient sensitivity, and further enhancement of sensitivity is required.
In addition, C.I. I. When using a copper halide phthalocyanine such as CI Pigment Green 36, it is necessary to increase the pigment concentration in order to improve the saturation. As a result, when the green coloring pattern is formed, the deep part of the film is in a low exposure state. For this reason, there is a problem that the colored pattern shape after development becomes a reverse taper.

JP 2003-161823 A JP 2007-284592 A JP 2008-24743 A JP-A-6-289611 Japanese Patent Laid-Open No. 9-80225 International Publication No. 2009/088786 Pamphlet

This invention makes it a subject to achieve the following objectives.
That is, the first object of the present invention is used for the formation of a green colored pattern in a color filter. In forming the green color pattern, the curability is excellent, the development latitude is large, and the pattern chipping during development is suppressed. And it is obtaining the colored photosensitive composition which can form the green coloring pattern excellent in chemical resistance.
In addition, a second object of the present invention is to obtain a color filter having high color purity and high color characteristics by using the colored photosensitive composition, and further using this color filter. An object of the present invention is to obtain a liquid crystal display device with high brightness and clear images.

Means for solving the above problems are as follows.
The colored photosensitive composition of the present invention comprises (A) a halogenated zinc phthalocyanine pigment, (B) a polymerizable compound, (C) a binder resin, (D) an acylphosphine photopolymerization initiator, and (E) an epoxy ring. It is characterized by containing the containing compound.
In the present invention, the (A) halogenated zinc phthalocyanine pigment is preferably a compound represented by the following general formula (1) and containing 9 to 13 bromine atoms on average in the molecule.

In the general formula (1), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom, a chlorine atom, or a bromine atom.

  In the present invention, the (D) acylphosphine-type photopolymerization initiator is preferably a compound represented by the following general formula (2).

In the general formula (2), R ¹ and R ² each independently represent a monovalent substituent, Q ¹ represents a monovalent substituent, and n represents an integer of 0 to 5.

Further, in the present invention, in the general formula (2), both R ¹ and R ² represents an aryl group, Q ¹ represents an alkyl group, compounds wherein n is 3 is preferred.
Furthermore, it is also a preferable embodiment that the compound represented by the general formula (2) is a compound represented by the following general formula (3).

In the general formula (3), R ¹ represents a monovalent substituent, Q ¹ and Q ² each independently represent a monovalent substituent, and n and m each independently represents an integer of 0 to 5. .

In the general formula (3), a compound in which R ¹ represents a (branched) alkyl group, Q ¹ and Q ² both represent an alkoxy group, and n and m are both 2 is preferable.

In the colored photosensitive composition of the present invention, (E) the compound containing an epoxy ring is preferably an alicyclic epoxy compound.
Moreover, it is also preferable that (E) the compound containing an epoxy ring is a compound which satisfy | fills the following conditions.
(Molecular weight) / (Number of epoxy rings) ≧ 100

  Moreover, it is a preferable aspect that the colored photosensitive composition of this invention is for color filters.

The color filter of this invention is a color filter which has a coloring pattern which uses the colored photosensitive composition of this invention on a board | substrate.
The liquid crystal display device of the present invention is a liquid crystal display device provided with the color filter of the present invention.

According to the present invention, it is used for forming a green colored pattern in a color filter. In forming the green color pattern, it is excellent in curability, has a large development latitude, further suppresses pattern chipping during development, and is resistant to chemicals. A colored photosensitive composition capable of forming a green coloring pattern having excellent properties can be obtained.
In addition, by using the colored photosensitive composition, a color filter having high color purity and high contrast and good color characteristics can be obtained, and further, using this color filter, a liquid crystal of a clear image with high luminance can be obtained. A display device can be obtained.

  Hereinafter, the colored photosensitive composition of the present invention, a color filter using the colored photosensitive composition, and a liquid crystal display device including the color filter will be described in detail.

≪Colored photosensitive composition≫
The colored photosensitive composition of the present invention comprises (A) a halogenated zinc phthalocyanine pigment, (B) a polymerizable compound, (C) a binder resin, (D) an acylphosphine photopolymerization initiator, and (E) an epoxy ring. It is characterized by containing the containing compound.
Hereinafter, the essential components (A) to (E) constituting the colored photosensitive composition of the present invention and other optional components will be described in detail.

<(A) Halogenated zinc phthalocyanine pigment>
Generally, since the halogenated zinc phthalocyanine pigment has 16 hydrogen atoms in the phthalocyanine ring, up to 16 of these hydrogen atoms can be substituted with bromine atoms and / or chlorine atoms. These halogen atoms may all be the same or different. When the number of substituents is constant, green becomes darker in the order of bromine atom> chlorine atom. When these hydrogen atoms are substituted with bromine atoms, for example, chlorine atoms, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, and the number of hydrogen atoms is 0 to 16, in theory. A total of 136 types of substitution products can be produced. However, at this time, at least one of the 16 is a halogen atom. The number of halogen atom substitutions is preferably 8 or more and 16 or less, more preferably 12 or more and 16 or less, from the viewpoint of obtaining a green color with high luminance.

In the present invention, the (A) halogenated zinc phthalocyanine pigment is a generic term for compounds represented by the following general formula (1).
In the following general formula (1), X ^{1 to} X ¹⁶ are each independently a hydrogen atom, a chlorine atom, or a bromine atom, and at least one of these is a chlorine atom or a bromine atom.
In the present invention, the halogenated zinc phthalocyanine pigment at least 8 or more is a bromine atom in X ¹ to X ¹⁶ in formula (1) are preferred.

In the general formula (1), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom, a chlorine atom, or a bromine atom, and at least one of these is a chlorine atom or a bromine atom.

In the compound represented by the general formula (1), when eight or more of X ^{1 to} X ¹⁶ are substituted with a bromine atom, a yellowish and light green color is obtained, and the green coloring pattern of the color filter is obtained. Ideal for use. In the present invention, a zinc halide phthalocyanine pigment substituted with 8 or more bromine atoms is most preferred. The number of bromine atoms substituted is more preferably 9 to 13 on average.

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

The halogenated zinc phthalocyanine pigment can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. More specific production methods are described in detail in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like.
Among these, a zinc halide phthalocyanine pigment disclosed in Japanese Patent Application Laid-Open No. 2004-70342, which has a simple process, is preferable from the viewpoint of cost. In addition, in terms of stability, although depending on other additives and the way of assembling the post-process, the crystal-converted zinc halide phthalocyanine pigment disclosed in JP-A-2008-19383 is preferable. In particular, a resin-coated zinc halide phthalocyanine pigment disclosed in JP-A-2007-320986 is a preferred embodiment for improving dispersibility.

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

  In the present invention, the average primary particle diameter is obtained by photographing particles in a field of view with a transmission electron microscope and measuring 100 primary particles of a zinc halide phthalocyanine pigment constituting an aggregate on a two-dimensional image. The weighted arithmetic mean values of the longer diameter (major axis) and the shorter diameter (minor axis) are obtained and averaged.

  In obtaining a halogenated zinc phthalocyanine pigment having an average primary particle size in the range of 10 nm to 40 nm, it may be finely divided by any method, but it can easily suppress crystal growth and has an average primary particle size of Solvent salt milling is preferably employed in that relatively small pigment particles can be obtained.

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

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

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

  As the organic solvent, an organic solvent capable of suppressing crystal growth is preferably used, and a water-soluble organic solvent is suitable as such an organic solvent. Specifically, for example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (Hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol , Dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol It can be used.

  The amount of the water-soluble organic solvent used in this case is not particularly limited, but is preferably 0.01 part to 5 parts, and 0.8 part to 2 parts per 1 part of the halogenated zinc phthalocyanine pigment in terms of mass. Part is more preferred.

The temperature during solvent salt milling is preferably 30 ° C to 150 ° C, and more preferably 80 ° C to 100 ° C.
Further, the solvent salt milling time is preferably 5 hours to 20 hours, more preferably 8 hours to 18 hours.

  Thus, a mixture containing a halogenated zinc phthalocyanine pigment, an inorganic salt, and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from the mixture, and the halogenated zinc phthalocyanine pigment is mainly used as necessary. A fine powder of zinc halide phthalocyanine pigment can be obtained by washing, filtering, drying, pulverizing, etc. the solid.

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

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

Thus, fine zinc halide phthalocyanine pigment powder is obtained.
The (A) halogenated zinc phthalocyanine pigment used in the present invention has weaker primary particle agglomeration force than conventional copper halide phthalocyanine pigments, and has a property that is easier to unravel. Therefore, it becomes possible to form a high-contrast film by using the colored photosensitive composition of the present invention.

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

  The zinc halide phthalocyanine pigment of the present invention having an average primary particle size in the range of 10 nm to 40 nm can be obtained by, for example, the above-described method, but can also be purchased from DIC Corporation.

<Yellow pigment>
In the colored photosensitive composition of the present invention, the hue of the colored photosensitive composition can be adjusted and the transmittance can be increased by using (B) the yellow pigment in combination with (A) the halogenated zinc phthalocyanine pigment. it can.
A conventionally known yellow pigment can be used as such a yellow pigment.
Examples of yellow pigments include disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments, benzimidazolone yellow pigments, nickel azo yellow pigments, diketopyrrolopyrrole orange pigments, Orange pigments such as perinone-based orange pigments can also be used as needed.

As a specific example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, and C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, Etc.

Of these, C.I. I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, etc. And more preferably C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139.
In particular, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 138, C.I. I. It is preferable to use Pigment Yellow 139 because of high transmittance and high contrast.

  The average primary particle diameter of these pigments is preferably in the range of 10 nm to 40 nm because of high transmittance and high contrast. More preferably, it is the range of 10 nm-30 nm. Solvent salt milling is effective for reducing the average primary particle size and making it finer, as with zinc halide phthalocyanine, and may be used together with zinc halide phthalocyanine pigment for solvent salt milling or separately. You may use for salt milling.

(A) The use ratio of the halogenated zinc phthalocyanine pigment and the yellow pigment is preferably 10 parts to 200 parts, and 20 parts to 100 parts, in terms of mass, with respect to 100 parts of the halogenated zinc phthalocyanine pigment. More preferably.
If the said mass ratio is this range, the light transmittance will be large and color purity can be made high.

  In the colored photosensitive composition of the present invention, the total amount of the pigment containing (A) the zinc halide phthalocyanine pigment is 5% to 60 in terms of mass with respect to the total amount excluding the solvent in the colored photosensitive composition of the present invention. %, More preferably 10% to 50%, and most preferably 15% to 45%. By using the colored photosensitive composition of the present invention having an addition amount in this range, a color filter having excellent color characteristics, high contrast, and high luminance can be obtained.

<Pigment dispersion composition>
The colored photosensitive composition of the present invention is prepared by previously dispersing (A) a halogenated zinc phthalocyanine pigment and, if necessary, a yellow pigment together or separately to prepare a pigment dispersion composition. It is a preferable aspect to prepare using.
The pigment dispersion composition is obtained by dispersing a pigment in a solvent. At this time, a dispersant, a resin, or the like may be added as necessary. Furthermore, it can comprise using other components as needed, such as a pigment derivative.

-Preparation of pigment dispersion composition-
The preparation mode of the pigment dispersion composition used in the present invention is not particularly limited. For example, a pigment, a pigment dispersant, and a solvent are mixed with a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. And can be obtained by carrying out a fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

  Before bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

-Pigment concentration-
As content in the pigment dispersion composition of a pigment, 10 mass%-60 mass% are preferable with respect to the total solid of this composition, and 15 mass%-50 mass% are more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

-Dispersant-
The pigment dispersion composition preferably contains at least one dispersant. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L12 , P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 , 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  As content in the pigment dispersion composition of a dispersing agent, 1 mass%-100 mass% are preferable with respect to the total mass of a pigment, and 3 mass%-70 mass% are more preferable.

-Pigment derivative-
A pigment derivative is added to the pigment dispersion composition as necessary. The pigment is dispersed in the colored photosensitive composition as fine particles by adsorbing to the pigment surface a part having affinity with the dispersant or a pigment derivative having a polar group introduced and using this as the adsorption point of the dispersant. And re-aggregation can be prevented. As a result, such a pigment dispersion composition can be suitably used for forming a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Here, the organic pigments specifically include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzimidazo And Ron pigments. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of a pigment derivative, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is within the above range, the dispersion can be favorably performed while the viscosity is kept low, the dispersion stability after dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  Furthermore, a polymer compound such as an alkali-soluble resin described later can be added to the pigment dispersion composition. Polar groups such as acid groups contained in the alkali-soluble resin are considered to be effective for the dispersion of the pigment, and are often effective for the dispersion stability of the pigment dispersion.

-Solvent-
Examples of the solvent in the pigment dispersion composition include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone, Mention may be made of solvents such as methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene and xylene.

  The content of the solvent in the pigment dispersion composition can be contained so that the solid content concentration including the pigment and the pigment dispersant is 5% by mass to 50% by mass from the viewpoint of handleability.

  The content of the pigment dispersion composition in the colored photosensitive composition of the present invention is such that the pigment content is in the range of 5% by mass to 70% by mass with respect to the total solid content of the colored photosensitive composition. Is preferable, and an amount in the range of 15% by mass to 60% by mass is more preferable. When the content of the pigment dispersion composition is within the above range, the color density is sufficient and effective in securing excellent color characteristics.

<(B) Polymerizable compound>
The polymerizable compound used in the present invention is not particularly limited as long as it can be polymerized, and is a low molecular compound having at least one ethylenic double bond, a dimer, a trimer, an oligomer or the like capable of addition polymerization. Can be preferably used.
Examples of the polymerizable compound include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an aromatic polyhydroxy compound and an unsaturated carboxylic acid, Esters, unsaturated isocyanates and polycarboxylic acids, and esters obtained by esterification with polyhydric hydroxy compounds such as fatty acid polyhydroxy compounds and aromatic polyhydroxy compounds, polyisocyanate compounds and (meth) Examples thereof include a compound having a urethane skeleton obtained by reacting an acryloyl-containing hydroxy compound.

  Specific polymerizable compounds used in the present invention are classified according to the number of polymerizable groups (ethylenic double bonds) in one molecule as shown below, but the present invention is not limited thereto. It is not something.

[Compound having one polymerizable group in one molecule]
Examples of the compound having one polymerizable group in one molecule include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) ) Acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexylglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, cyanoethyl (meth) ) Acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H perf Orodecyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxy Butyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (Meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO Examples thereof include modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, and EO-modified-2-ethylhexyl (meth) acrylate.

[Compound having two polymerizable groups in one molecule]
As the compound having two polymerizable groups in one molecule, a compound having a (meth) acryloyl group as the polymerizable group is suitable. Specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meta) ) Acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) a Relate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, Bisphenol A bis (acryloyloxyethyl) ether, bisphenol A epoxy resin modified with (meth) acrylic acid, 3-methylpentanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol -Tricyclodecane di (meth) acrylate and the like, preferably dimethylol-tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, bisphenol A type epoxy (Meth) acrylic acid modified product of fat, and the like.

[Compound having three polymerizable groups in one molecule]
Examples of the compound having three polymerizable groups in one molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) Acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri Meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

[Compound having four or more polymerizable groups in one molecule]
Examples of the compound having four or more polymerizable groups in one molecule include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetrapropionate ( (Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide Modified hexa (meth) acrylate, captolactone-modified dipentaerythritol hexa (meth) acrylate, UA-30 manufactured by Kyoeisha Chemical Co., Ltd. H, UA-306T, a urethane acrylate, such as UA-306I.

Among these, a compound having two or more polymerizable groups in one molecule is preferable from the viewpoint of forming a film that suitably maintains solvent resistance and ITO sputtering suitability, and has three or more polymerizable groups. Compounds are more preferred. In particular, compounds having 4 or more polymerizable groups are advantageous. For example, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable from the viewpoint of solvent resistance and suitability for ITO sputtering, and mixtures thereof (in terms of mass) As the mixing ratio, a mixture of dipentaerythritol pentaacrylate: dipentaerythritol hexaacrylate = 2-4: 8-6) is preferably used.
On the other hand, from the viewpoint of development latitude, a compound having 1 to 3 polymerizable groups in one molecule is advantageous, and a compound having a hydroxyl group or a carboxyl group in the molecule greatly contributes to improvement in developability.
In addition, in order to achieve both solvent resistance, ITO sputtering suitability and development latitude, a compound having 1 to 2 polymerizable groups in one molecule and a compound having 3 or more polymerizable groups are used in combination. It is also possible to do. When used in combination, the compound having 1 to 2 polymerizable groups per molecule is preferably used in the range of 1% by mass to 50% by mass with respect to the total amount of the polymerizable compound. It is more preferably used in the range of 40% by mass to 40% by mass, and still more preferably in the range of 5% by mass to 20% by mass.

  In the present invention, the compounding amount of the polymerizable compound is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 60% by mass, and still more preferably based on the total mass of the colored photosensitive composition of the present invention. Is in the range of 15% to 50% by weight.

<(C) Binder resin>
As the binder resin (C) contained in the colored photosensitive composition of the present invention, any polymer compound that is soluble in a solvent can be used, but as a preferred binder resin, alkali developability by photolithography is considered. Alkali-soluble resins are preferred.
The alkali-soluble resin can be contained at the stage of preparing the pigment dispersion composition, and it can be added separately in both the steps of preparing the pigment dispersion composition and the colored photosensitive composition. Is possible.

  The alkali-soluble resin is a linear organic polymer, and is a polymer compound having at least one alkali-soluble group (for example, carboxyl group, phosphate group, sulfonate group, etc.) therein. Those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution are more preferable.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable. In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.
The polymer can be used by mixing in an arbitrary amount.

In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.
Other alkali-soluble binder resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224. Known polymer compounds described in JP-A No. 2000-56118, JP-A No. 2003-233179, JP-A No. 2009-52020, and the like can be used.

  As the alkali-soluble resin, in particular, a copolymer containing (meth) acrylic acid and other monomers copolymerizable therewith as a structural unit can be easily obtained and adjusted for alkali solubility and the like. Since it is easy, it is used suitably.

  Examples of the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

  Specific examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl. (Meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like.

Examples of vinyl compounds include styrene, α-methylstyrene, vinyl toluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer. , _CH 2 ^{= CR} 31 ^{R 32 [wherein, R 31} represents a hydrogen atom or an alkyl group of 1 to 5 carbon ^{atoms, R 32} represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. ^{_{], CH 2 = C (R 31}} ) (COOR 33) ^{[wherein, R 31} represents a hydrogen atom or an alkyl group of 1 to 5 carbon ^{atoms, R 33} is several alkyl group or C 1 to 8 carbon atoms 6 Represents -12 aralkyl groups. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Other preferred copolymerizable monomers are selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably, CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ). These R ³¹ , R ³² and R ³³ have the same meanings as described above.

  As content of binder resin, such as alkali-soluble resin, in the colored photosensitive composition of this invention, 1 mass%-20 mass% are preferable with respect to the total solid of this composition, More preferably, 2 mass% It is -15 mass%, Most preferably, it is 3 mass%-12 mass%.

<(D) Acylphosphine-type photopolymerization initiator>
The (D) acylphosphine type photopolymerization initiator in the present invention is not particularly limited as long as it is a photopolymerization initiator having an acylphosphine structure in the molecule, and a conventionally known compound can be used.
Among these, from the viewpoint of exposure sensitivity, a compound represented by the following general formula (2) is particularly preferably used.

In the general formula (2), R ¹ and R ² each independently represent a monovalent substituent, Q ¹ represents a monovalent substituent, and represents an integer of n0 to 5.

  In terms of exposure sensitivity, the compound represented by the general formula (2) is particularly preferably a compound represented by the following general formula (3).

上記一般式（３）中、Ｒ^１は１価の置換基を表し、Ｑ^１及びＱ^２はそれぞれ独立に１価の置換基を表し、ｎ及びｍはそれぞれ独立に０〜５の整数を表す。

In the general formula (3), R ¹ represents a monovalent substituent, Q ¹ and Q ² each independently represent a monovalent substituent, and n and m each independently represents an integer of 0 to 5. .

Specific examples of the monovalent substituent in R ¹ , R ² , Q ¹ , and Q ² include an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic group, and an aromatic group. Group carbonyl group and the like.
That is, when R ² in the general formula (2) is an aromatic carbonyl group, the compound is represented by the general formula (3).

Examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. Among them, an alkyl group and a substituted alkyl group are exemplified. , An alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable.
The aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

Examples of the alkyl group include linear, branched and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. The preferred range of the number of carbon atoms in the alkyl part of the substituted alkyl group is the same as in the case of the alkyl group.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group, cyclopentyl group, neopentyl group. Group, isopropyl group, isobutyl group and the like.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, carbon number 30 The following alkoxy groups (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio groups having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methylthioethylthioethyl group, etc.) An aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryloxy A carbonyloxy group, an acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, Carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group) Etc.), an aryl group having 30 or less carbon atoms For example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group) Etc.), substituted ureido groups, substituted phosphono groups, heterocyclic groups and the like.
Here, the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in a salt state. In that case, as a cation which forms a salt, an alkali metal ion, an alkaline-earth metal ion, etc. are mentioned.

  Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups. The number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20. The alkenyl group may be a substituted alkenyl group having a substituent or an unsubstituted alkenyl group, and the preferred range of the number of carbon atoms in the alkenyl part of the substituted alkenyl group is the same as that of the alkenyl group. . Moreover, as a substituent of a substituted alkenyl group, the same substituent as the case of a substituted alkyl group is mentioned.

  Examples of the alkynyl group include linear, branched, and cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2 to 30, and more preferably 2 to 20. The alkynyl group may be a substituted alkynyl group having a substituent or an unsubstituted alkynyl group, and the preferred range of the number of carbon atoms in the alkynyl part of the substituted alkynyl group is the same as in the case of the alkynyl group. . Moreover, as a substituent of a substituted alkynyl group, the same substituent as the case of a substituted alkyl group is mentioned.

  Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 35, and more preferably 7 to 25. The aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group, and the preferred range of the number of carbon atoms in the aralkyl part of the substituted aralkyl group is the same as in the case of the aralkyl group. . Moreover, as a substituent of a substituted aralkyl group, the same substituent as the case of a substituted alkyl group is mentioned.

Examples of the aromatic group include an aryl group and a substituted aryl group. As a carbon atom number of an aryl group, 6-30 are preferable and 6-20 are more preferable. The preferable range of the number of carbon atoms in the aryl part of the substituted aryl group is the same as that of the aryl group.
Examples of the aryl group include a phenyl group, an α-naphthyl group, and a β-naphthyl group.
Moreover, as a substituent of a substituted aryl group, the same substituent as the case of a substituted alkyl group is mentioned.

  As said aliphatic oxy group, a C1-C30 alkoxy group is preferable, for example, a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, a phenoxyethoxy group etc. are mentioned. However, it is not limited to these.

  The aromatic oxy group is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenoxy group, a methylphenyloxy group, a chlorophenyloxy group, a methoxyphenyloxy group, and an octyloxyphenyloxy group. However, it is not limited to these.

  The heterocyclic group is preferably a heterocyclic group containing an N, O or S atom, and examples thereof include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, and a pyrrolyl group.

  As said aromatic carbonyl group, what has a phenyl group, a naphthyl group, etc. is mentioned as an aromatic group.

  In addition, from the viewpoint of thermal stability, the acylphosphine-type photopolymerization initiator in the present invention has a bulky substituent (for example, a methyl group, an ethyl group, a propyl group, or a butyl group) at the ortho position of the phenyl group to which the carbonyl is linked. And an alkyloxy group such as a methoxy group and an ethoxy group, and a substituent such as a halogen atom such as chlorine and bromine. Examples of such compounds include P-1 to P-14, P-16 to P-18, P-28 to P-30, and P-32 to P-36 in the exemplary compounds described below. Are preferably used.

In the general formula (2), a compound in which R ¹ and R ² both represent an aryl group, Q ¹ represents an alkyl group, and n is 3 has excellent thermal stability and high sensitivity. To preferred. As such a compound, P-2 in the exemplary compounds described later corresponds.
In the general formula (3), a compound in which R ¹ represents a (branched) alkyl group, Q ¹ and Q ² both represent an alkoxy group, and n and m are both 2, is also thermally stable. It is preferable from the viewpoint of excellent properties and high sensitivity. Such a compound corresponds to P-34 in the exemplified compounds described later.

  Specific examples of the acylphosphine-type photopolymerization initiator represented by the general formula (2) or the general formula (3) include, for example, Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Examples thereof include compounds described in JP-A-10-95788 and JP-A-10-29997.

  Specific examples of the acylphosphine-type photopolymerization initiator include the following compounds (Exemplary Compounds P-1 to P-38), but the present invention is not limited to these. .

  Among the exemplified compounds, for example, (P-2) [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide] is available under the trade name of Darocur TPO (manufactured by Ciba Specialty Chemicals), (P-29) [Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide] is available under the trade name Irgacure 819 (manufactured by Ciba Specialty Chemicals).

  The content of the acylphosphine type photopolymerization initiator in the colored photosensitive composition of the present invention is used in the range of 0.1% by mass to 30% by mass, preferably 0.2% by mass to 25% in terms of solid content. It is used in the range of mass%, more preferably in the range of 0.5 mass% to 20 mass%.

  One of the characteristics of the colored photosensitive composition of the present invention is that an acylphosphine-type photopolymerization initiator is used as a photopolymerization initiator, and as a result, the development latitude in pattern formation is widened and formed. It is possible to form a rectangular shape or a good shape with a forward taper with few defects such as chips. The reason why such an effect occurs is not clear, but the acylphosphine type photopolymerization initiator has a better photobleaching property due to exposure than other photopolymerization initiators. It is presumed that the polymerization reaction in the deep part advances, and the difference in developability between the surface of the pattern and the deep part in the alkaline aqueous solution becomes small and occurs.

<Sensitizing dye>
In the present invention, a sensitizing dye corresponding to the image exposure wavelength can be used in combination with the above-mentioned (D) acylphosphine-type photopolymerization initiator as necessary for the purpose of increasing the sensitivity.
As the sensitizing dye used, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, JP-A-5-210240, JP-A-4-288818 Examples thereof include dyes having a dialkylaminobenzene structure, xanthone compounds, thioxanthone compounds, anthraquinone compounds, anthrones, and benzophenones.

The content of the sensitizing dye in the present invention is preferably about 0.05% by mass to 30% by mass and more preferably 0.1% by mass to 20% by mass with respect to the colored photosensitive composition as a solid content. Preferably, it is 0.2 mass%-10 mass%.
Moreover, if it describes in relation to an acylphosphine type photoinitiator about content, 200: 1 to 1: 200 are preferable by mass ratio of an acylphosphine type photoinitiator: sensitizing dye, 50: 1 to 1 : 50 is more preferable, and 20: 1 to 1: 5 is still more preferable.

<Other photopolymerization initiators>
The colored photosensitive composition of the present invention is required to contain at least the aforementioned acylphosphine-type photopolymerization initiator as a photopolymerization initiator, but other photopolymerization initiators may be used as long as the effects of the present invention are not impaired. You may use together.
Known photopolymerization initiators that can be used in combination include, for example, camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, such as α-hydroxycycloalkylphenyl ketones or 2-hydroxy-2-methyl-1-phenyl- Propanone, dialkoxyacetophenones, α-hydroxy- or 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzyl ketals such as benzyl dimethyl ketal, phenyl glyoxalate and its derivatives, dimeric glyoxalic acid Phenyl, peresters such as benzophenone tetracarboxylic acid peresters (eg as described in EP 1126,541), halomethyltriazines such as 2- [2- (4-methoxy -Phenyl) -vinyl] -4,6-bis-trichloromethyl [1,3,5] triazine, 2- (4-methoxy-phenyl) -4,6-bis-trichloromethyl [1,3,5] triazine 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl [1,3,5] triazine Hexaarylbisimidazole / co-initiator systems such as ortho-chlorohexaphenyl-bisimidazole in combination with 2-mercaptobenzothiazole; ferrocenium compounds or titanocenes such as dicyclopentadienyl-bis (2 , 6-difluoro-3-pyrrolo-phenyl) titanium; described, for example, in GB 2,339,571 It is also possible to use mixtures of such O- acyloxime ester compound. A boric acid compound can also be used as a co-initiator.

  The content of the other polymerization initiator in the colored photosensitive composition of the present invention is preferably 0.01 parts by weight to 20 parts by weight, more preferably 0.1 parts by weight with respect to 100 parts by weight of the polymerizable compound. Part to 10 parts by weight, more preferably 0.5 part to 5 parts by weight.

<Co-sensitizer>
The colored photosensitive composition of the present invention preferably contains a co-sensitizer.
In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation, or suppressing polymerization inhibition of the polymerizable compound by oxygen.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Further examples of co-sensitizers include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B-55. -34414, a hydrogen donor described in JP-A-6-308727, and a sulfur compound (eg, trithiane).

  The content of the co-sensitizer is 0.1% by mass to 30% by mass with respect to the mass of the total solid content of the colored photosensitive composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. The range is preferable, the range of 1% by mass to 25% by mass is more preferable, and the range of 0.5% by mass to 20% by mass is still more preferable.

<(E) Compound having epoxy ring>
The colored photosensitive composition of the present invention uses (E) a compound having an epoxy ring as a thermal polymerization component in order to increase the strength of the formed coating film.
Use of a compound having an epoxy ring is preferable because solvent resistance is improved and ITO sputtering suitability of the formed film is improved.

(E) As a compound which has an epoxy ring, it is a compound which has two or more epoxy rings in a molecule | numerator, such as a bisphenol A type, a cresol novolak type, a biphenyl type, and an alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) Similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above made by Tohto Kasei), Denacol EM-125, etc. (above made by Nagase Kasei), biphenyl type 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl, etc.
Examples of the alicyclic epoxy compounds include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST. -4000, ST-5080, ST-5100 and the like (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S and 4032 (manufactured by Dainippon Ink and Co., Ltd.).
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid In addition to diglycidyl ester, amine-type epoxy resins such as Epototo YH-434 and YH-434L, glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resin, and the like can also be used.

Among these, as a compound having an epoxy ring, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage during curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is poor.
In addition, when the compound which has an epoxy ring is a high molecular compound, said molecular weight means a weight average molecular weight.

  Examples of the compound having an epoxy ring include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701 (manufactured by Tohto Kasei), Plaxel GL-61, GL-62 (manufactured by Daicel Chemical). 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Epicron N-680, N-695, HP-7200H (manufactured by DIC), on-coat EX-1010, 1011, 1012, 1020, 1030, 1040, 1050, 1051 (against Nagase Sangyo) and the like are preferable.

  As content of the compound which has an (E) epoxy ring in the colored photosensitive composition of this invention, 0.1 mass%-10 mass% are preferable with respect to the total solid of a colored photosensitive composition, 0 0.5 mass% to 5.0 mass% is more preferable, and 1.0 mass% to 3.0 mass% is still more preferable.

<Solvent>
In general, the colored photosensitive composition of the present invention can be suitably prepared using a solvent together with the above components.
Examples of the solvent used include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and 3-oxypropionate 3-oxypropionic acid alkyl esters such as ethyl acid (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxy 2-oxypropionic acid alkyl esters such as methyl lopionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid) Propyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2 -Ethyl ethoxy-2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, propylene glycol methyl ether acetate, etc. Is preferred.
A solvent may be used independently and may be used in combination of 2 or more type.

<Other ingredients>
In the colored photosensitive composition of the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, a polymer compound other than an alkali-soluble resin, and a surfactant. Further, various additives such as an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

[Fluorine organic compounds]
By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved.
That is, the interfacial tension between the solid surface of the substrate and the coating liquid is lowered, the wettability to the substrate is improved, and the coating property to the substrate is improved, so a thin film of about several μm is formed with a small amount of liquid. Even in this case, it is effective in that it is possible to form a uniform film with small thickness unevenness.

  The fluorine content of the fluorine-based organic compound is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

The fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when, for example, a coating film to be formed is thinned. It is also effective in slit coating that easily causes liquid breakage.
The addition amount of the fluorine-based organic compound is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1% with respect to the total mass of the pigment dispersion composition or the colored photosensitive composition. 0.0% by mass.

(Thermal polymerization initiator)
It is also effective to contain a thermal polymerization initiator in the colored photosensitive composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

[Surfactant]
The colored photosensitive composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability, and various nonionic, cationic, and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

(Thermal polymerization inhibitor)
It is preferable to add a thermal polymerization inhibitor to the colored photosensitive composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, Benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

  In addition to the above, in the colored photosensitive composition, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid Copolymers, acidic cellulose derivatives, polymers having hydroxyl groups, acid anhydrides added, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; , Anionic surfactants, specifically phthalocyanine derivatives (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.);

  Other examples of additives include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Sorbitan fatty acid esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF; W004, W005, W017 ( Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Polymer dispersing agents such as FKA Polymer 401, EFKA Polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000 , 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Zeneca); P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2- Hydroxyphenyl) -5-chlorobenzo Examples thereof include ultraviolet absorbers such as triazole and alkoxybenzophenone; and aggregation preventing agents such as sodium polyacrylate.

In addition, when the alkali solubility of the uncured part is promoted and the developability of the colored photosensitive composition is further improved, the colored photosensitive composition of the present invention is added with an organic carboxylic acid, preferably a molecular weight of 1000 or less. Of low molecular weight organic carboxylic acids can be added.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid; oxalic acid and malonic acid Fats such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid Aliphatic dicarboxylic acids; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid , Aromatic resins such as trimellitic acid, trimesic acid, merophanic acid and pyromellitic acid Acids; other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid Examples include acids.

  The colored photosensitive composition of the present invention contains a binder resin such as an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition described above, and is necessary for this. Accordingly, it can be prepared by mixing an additive such as a surfactant.

≪Color filter and manufacturing method≫
The color filter of the present invention is produced by forming a colored film (colored pattern) on a substrate such as glass using the above-described colored photosensitive composition of the present invention.
More specifically, for example, the colored photosensitive composition of the present invention is applied to the substrate directly or via another layer (preferably by a coating method such as spin coating, slit coating, cast coating, roll coating, etc. A photosensitive film is formed by coating), and the formed photosensitive film is exposed through a predetermined mask pattern, and after exposure, the uncured portion is developed and removed with a developing solution (for example, three colors or four colors). A color filter can be most preferably manufactured by forming a color pattern (for example, colored pixels).
Thereby, the color filter used for a liquid crystal display device or a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method.

  First, when forming the photosensitive film | membrane by providing the coloring photosensitive composition of this invention on a board | substrate, the thickness of the photosensitive film | membrane is generally 0.3 micrometer-5.0 micrometers as thickness after drying, Preferably it is 0.5 micrometer-3.5 micrometers, Most desirably, it is 1.0 micrometer-2.5 micrometers.

  Examples of the substrate to which the colored photosensitive composition of the present invention is applied include, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and transparent conductive films used in liquid crystal display devices and the like. And a photoelectric conversion element substrate used for a solid-state imaging device, such as a silicon substrate, and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.

The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
Examples of other layers in the case where the colored photosensitive composition is applied to the substrate via another layer include a gas barrier layer and a solvent resistant layer.

  Drying (pre-baking) of the photosensitive film with the colored photosensitive composition of the present invention applied (preferably applied) on the substrate is carried out for 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate, oven or the like. Can be performed under the following conditions.

Next, as the radiation used for exposure to the above-described photosensitive film, ultraviolet rays such as g-line, h-line, i-line, and j-line are particularly preferable.
In addition, an exposure method using a laser light source is applied to the exposure, and an ultraviolet laser can be used as the light source. Here, laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  In the present invention, it is preferable to use an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm for exposure of the photosensitive film, and to use an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm. It is preferable in that it matches the photosensitive wavelength of the photosensitive film.

Specifically, as the ultraviolet light laser, the third harmonic (355 nm) of an Nd: YAG laser, which is a solid laser that has a large output and is relatively inexpensive, and the XeCl (308 nm) and XeF (353 nm) of an excimer laser are preferable. Can be used.
The exposure amount to the photosensitive ^film, is preferably from ^{1mJ / cm 2 ~100mJ / cm 2} , 1mJ / cm 2 ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  There are no particular restrictions on the exposure apparatus capable of such exposure, but commercially available devices include Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen). A company-made product can be used, and devices other than those described above are also preferably used.

  In the exposure of the photosensitive film, a light emitting diode (LED) and a laser diode (LD) can be used. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength of 340 nm to 370 nm.

  Since the parallelism of the ultraviolet laser is good, pattern exposure can be performed without using a mask at the time of exposure. However, it is more preferable to expose the pattern using a mask because the linearity of the pattern is further enhanced.

After the exposure as described above is performed, the photosensitive film is developed.
In this development, the uncured portion of the photosensitive film after exposure is eluted into the developer, leaving only the cured portion. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Any developer can be used as long as it dissolves the photosensitive film made of the colored photosensitive composition in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  Examples of the organic solvent used for development include those listed as the above-mentioned solvents that can be used when preparing the pigment dispersion composition or the colored photosensitive composition of the present invention.

Examples of the alkaline aqueous solution used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium. Concentrations of alkaline compounds such as hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, 0.001% by mass to 10% by mass, preferably Is an alkaline aqueous solution dissolved so as to be 0.01% by mass to 1% by mass.
In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans (rinse) with water after image development.

After the development, excess developer is washed away, dried, and then generally subjected to a heat treatment (post-bake) at a temperature of 100 ° C to 250 ° C.
Post-baking is heating after development for complete curing, and is usually performed at about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above condition. be able to.

By repeating the above operations in accordance with the desired number of hues for each color in sequence, a color filter in which a plurality of colored cured films (colored patterns) are formed can be produced.
Since the color filter of the present invention has a color pattern formed using the colored photosensitive composition of the present invention, the color filter has a high color purity and a high contrast and a good color characteristic.

≪Liquid crystal display device≫
The liquid crystal display device of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter of the present invention, is opposed to the electrode substrate, and the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display device of the present invention. It is done.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

-Synthesis of zinc halide phthalocyanine pigments-
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride.
Halogenation was performed by mixing 3.1 parts of sulfuryl chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride and 1 part of zinc phthalocyanine at 40 ° C., and dropping 2.2 parts of bromine. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts of a purified partially brominated zinc phthalocyanine crude pigment.

1 part of this partially brominated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol and 0.09 part of xylene were charged into a double arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts of water at 80 ° C. and stirred for 1 hour, followed by filtration, washing with hot water, drying and grinding to obtain a partially brominated zinc phthalocyanine pigment (hereinafter referred to as PG58 as appropriate).
The obtained partially brominated zinc phthalocyanine pigment has an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) and contains an average of 10 bromines in one molecule, based on a halogen content analysis by mass spectrometry. there were.
The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

(Synthesis Example 1) Synthesis of Resin (i-1) 6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature. A polyester resin (i-1) was obtained.
The scheme is shown below.

(Synthesis Example 2) Synthesis of Resin (J-1) 10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) and 100 g of polyester resin (i-1) are mixed, and 120 ° C. for 3 hours. The intermediate (J-1B) was obtained by heating. Thereafter, the mixture was allowed to cool to 65 ° C., 200 g of propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as PGMEA) containing 3.8 g of succinic anhydride was slowly added and stirred for 2 hours. Thereafter, PGMEA was added to obtain a 10 mass% PGMEA solution of the resin (J-1). The resin (J-1) has a side chain derived from the polyester resin (i-1) and a carboxy group derived from succinic anhydride.
A synthesis scheme is shown below.

-Preparation of Green Pigment (PG58) Dispersion Composition-
In a high-speed disperser “TSC-6H” manufactured by Igarashi Machinery Manufacturing Co., Ltd. charged with 0.5 mm diameter zirconia beads, 14.9 parts of a partially brominated zinc phthalocyanine pigment obtained by the above method and an acrylic dispersant manufactured by BYK Chemie A dispersion of a partially brominated zinc halide phthalocyanine pigment (green pigment (PG58) dispersion composition) prepared by charging 7.2 parts of “BYK-2001” and 78 parts of PGMEA and stirring at 2000 rpm for 8 hours. ) Was prepared.

-Preparation of yellow pigment (PY150) dispersion composition-
C. as a pigment I. A mixture of 40 parts of Pigment Yellow 150 (average particle size 60 nm, hereinafter referred to as PY150) and 223 parts of PGMEA 10% by mass of the resin (J-1) (22.3 parts in terms of solid content) The mixture was dispersed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm) to prepare a yellow pigment (PY150) dispersion composition.

-Preparation of yellow pigment (PY138) dispersion composition-
C. as a pigment I. A mixture of 40 parts of Pigment Yellow 138 (average particle size 60 nm, hereinafter referred to as PY138) and 223 parts of PGMEA 10% by mass of the resin (J-1) (22.3 parts in terms of solid content), A yellow pigment (PY138) dispersion composition was prepared by mixing and dispersing with a bead mill (zirconia beads 0.3 mm) for 3 hours.

-Preparation of green pigment (PG36) dispersion composition-
C. as a pigment I. Pigment Green 36 (average particle size 60 nm, hereinafter referred to as PG36) and a mixture of 40 parts of PGMEA 10% by mass of the resin (i-1) (20 parts in terms of solid content) were mixed with a bead mill. (Zirconia beads 0.3 mm) was mixed and dispersed for 3 hours to prepare a green pigment (PG36) dispersion composition. With respect to this pigment dispersion composition, the average primary particle diameter of the pigment was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 25 nm.

Example 1
A colored photosensitive composition having the following composition 1 was prepared.
(Composition 1)
Green pigment (PG58) dispersion composition 26.1 parts Yellow pigment (PY150) dispersion composition 14.3 parts Binder resin (benzyl methacrylate-acrylic acid (= copolymerization molar ratio 6: 4) copolymer, (Weight average molecular weight 9000) 2.8 parts · pentaerythritol triacrylate 3.58 parts · acylphosphine type photopolymerization initiator (Exemplary Compound P-2) 1.02 parts · compound having an epoxy ring (2,2-bis ( 1,2-epoxy-4- (2-oxolanyl) cyclohexane adduct of hydroxymethyl-1-butanol, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd. 0.480 parts, polymerization inhibitor (p-methoxyphenol) 0.0018 parts・ Surfactant (Fluorosurfactant, DIC's trade name MegaFuck F781-F)
0.0334 parts-Silane coupling agent (3-methacryloyloxy-trimethoxysilylpropane) 0.320 parts-Solvent (PGMEA) 51.42 parts

(Examples 2 to 20, Comparative Examples 1 to 11)
In (Composition 1), the pigment dispersion composition, the polymerizable compound, and the photopolymerization initiator are changed as shown in Table 1 below, and the contents of the polymerizable compound and the photopolymerization initiator are shown in Table 1 below. Each of Examples 2 to 20 and Comparative Examples 1 to 10 was changed in the same manner as in Example 1 except that the compounds having an epoxy ring were appropriately changed to those described in Table 1 below. A colored photosensitive composition was prepared.
Moreover, the coloring photosensitive composition of the comparative example 11 was prepared like Example 1 except not having added the compound which has an epoxy ring in (composition 1).

In addition, “DPHA”, “A-BPE-20”, “A-BPE-10”, “UA-306H”, “Epiclon N-695”, and “Oncoat EX-1020” in the following Table 1 are: It is a commercial product as shown below.
-DPHA: 7: 3 mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
A-BPE-20: 2,2-bis [4- (acryloyloxy-polyethoxy) phenyl] propane (trade name: A-PPE-20 manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-BPE-10: 2,2-bis [4- (acryloyloxy-polyethoxy) phenyl] propane (trade name: A-PPE-10 manufactured by Shin-Nakamura Chemical Co., Ltd.)
UA-306H: Urethane polyfunctional acrylic monomer (trade name: UA-306H, manufactured by Kyoei Chemical Co., Ltd.)
・ Epicron N-695: a compound having a cresol novolak type epoxy ring manufactured by DIC ・ Oncoat EX-1020: a compound having a fluorene type epoxy ring

Further, “Comparative Compound R-1” and “Comparative Compound R-2” in Table 1 below are the compounds shown below.
Compound R-1 for comparison: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholpropan-1-oneComparison compound R-2: 2- (methoxyphenyl) -4,6 -Bis (chloromethyl) -s-triazine

-Formation of photosensitive film-
The obtained colored photosensitive composition was applied to a glass substrate (Corning Millennium 0.7 mm thick). Specifically, the coloring photosensitive composition is applied at a coating speed of 120 mm / second by adjusting the distance between the slit nozzle and the substrate and the discharge amount so that the film thickness of the photosensitive layer after post-baking is about 2.4 μm. The product was applied.

-Pre-baking and exposure-
Next, the coated photosensitive film was dried with a vacuum dryer until the degree of vacuum reached 66 Pa, and then heated (prebaked) at 100 ° C. for 120 seconds using a hot plate.
Then, it exposed at 60 mJ / cm < ² > with respect to the photosensitive film | membrane using the proximity exposure machine (The Hitachi High-Tech make, LE5565A). The pattern shape at the time of exposure was a stripe shape having a width of 90 μm.

-Development and post-baking-
The exposed photosensitive film is developed with a 1.0% developer (CDK) of potassium hydroxide developer CDK-1 (Fuji Film Electronics Materials) using a developing device (manufactured by Hitachi High-Technologies Corporation). -1 is 1 part by weight, pure water is 99 parts by weight diluted solution (25 ° C.) and the shower pressure is set to 0.2 MPa, and the development time is 10 seconds to 110 seconds in 10 second increments. And washed with pure water.

The substrate for each development time of 10 seconds was observed with an optical microscope, the development status was evaluated, and the results are summarized in Table 2 below. In Table 2, the lower limit of the development time is a lower limit of usable development time in seconds, and means that the non-pixel portion cannot be removed in a time shorter than this time. The upper limit of the development time is the upper limit number of seconds of usable development time, and means that pixels are missing or dropped in a time longer than this time. Since the development time is preferably 80 seconds or less because of the limitation of the process (tact time), it was evaluated up to 80 seconds. The development latitude indicates a difference in the number of seconds between the upper limit of the development time and the lower limit of the development time.
After the development was completed, it was baked (post-baked) in an oven at 220 ° C. for 30 minutes.

-Evaluation of pattern linearity-
Using an optical microscope, the edge portion of the pixel pattern was photographed and evaluated at 200 times reflection. Observe the pixel edge part in a 5cm x 5cm photo, and "good" if the pixel edge part looks straight, part of the pixel edge part (within 1/3 of the total length) Non-linear but not jagged “slightly good”, pixel edge part exceeding 1/3 of the total length, or part (1/1 of the total length) (4 or less) was defined as “slightly bad”, and “bad” when the pixel edge portion was more than ¼ of the entire length. The results are shown in Table 2.
The edge portion of the pixel pattern is preferably linear. If the edge portion of the pixel pattern becomes jagged due to a residual film, undercut, or the like, it is necessary to make a large overlap with the black matrix, which widens the width of the black matrix and lowers the aperture ratio. If the overlap with the black matrix is not large, there is a possibility that a portion that does not have a colored layer and is white is formed near the edge of the black matrix. Further, when the edge portion of the pixel pattern is jagged, there is a problem that the transparent electrode formed thereon is disconnected and the resistance value is increased.

-Evaluation of pattern shape and chip-
Using an optical microscope, the edge portion of the pixel pattern was photographed at 200 times reflection, and its shape and chip were evaluated. The edge of a pixel is observed in a 5cm x 5cm photo, and the edge (usually the shape of the edge disappears in a half-moon shape. If even one of the lines is discontinuously narrowed and is recognized as missing, it is evaluated that there is a chip. The results are shown in Table 2.
When chipping occurs, the portion is white and light is lost, which is not preferable.

-Evaluation of chemical resistance-
The post-baked coating film (development time was 60 seconds) produced by the above-described method was immersed in an NMP (N-methyl-2-pyrrolidone) solution at 40 ° C. for 30 minutes. The change in color before and after immersion was determined by ΔE * ab and evaluated according to the following criteria.
(Judgment criteria)
Good: ΔE * ab is less than 2.0 Slightly good: ΔE * ab is 2.0 or more and less than 3.0 Bad: ΔE * ab is 3.0 or more

The criteria for the determination in Table 2 are shown below.
○: Wide development latitude (50 seconds or more), pattern linearity is slightly better or better, pattern shape is forward taper or rectangular, chemical resistance is good or slightly good, and brightness is excellent The thing was made into "(circle)".
X: The case where any one or more of the above “◯” does not correspond was defined as “x”.

From Table 2, in the present invention, Examples 1 to 20 using (D) an acylphosphine-type photopolymerization initiator and (E) a compound having an epoxy ring have a large development latitude, and the pattern linearity is also high. It was good. On the other hand, Comparative Examples 2 to 5 and Comparative Examples 7 to 10 using other polymerization initiators each had a small development latitude, and the pattern linearity and shape were poor. In Comparative Examples 1, 4, 5, 6, 9, and 10 using Pigment Green 36, which has been widely used as a green pigment, outside the scope of the present invention, the Y value, which is a luminance index, is as low as 58.5. (Y value = 60.5 in the examples). Further, in the system using the conventional pigment Pigment Green 36, the development latitude was rather narrow because the chipping occurred earlier.
Here, the Y value was calculated as a result of measuring the substrate after baking with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100) and having a C light source field of 2 degrees.
In Comparative Example 11 where (D) an acylphosphine-type photopolymerization initiator was used but (E) a compound having an epoxy ring was not used, the pattern linearity was good, but the development latitude was small, Further, chipping occurred, the pattern shape was poor, and the chemical resistance was poor.

(Example 21)
Using the colored photosensitive composition of Example 14, the linearity, shape, and chip of the same pattern as in Example 1 were evaluated except that the exposure process was changed to the following. However, good results similar to those of Example 14 were obtained. From this result, it was found that the excellent effect of the present invention can be obtained by pattern exposure using a laser exposure machine as well as exposure using a high-pressure mercury lamp.
-Exposure-
Using EGIS (buoy technology Co., Ltd., YAG laser third harmonic wavelength 355 nm, pulse width 6 nsec) as a laser exposure device, photomask with 20 times pulse irradiation of about 1 mJ / cm ^{2 on} the photosensitive film surface Went through.

Claims (11)

  A colored photosensitive composition containing (A) a halogenated zinc phthalocyanine pigment, (B) a polymerizable compound, (C) a binder resin, (D) an acylphosphine-type photopolymerization initiator, and (E) a compound containing an epoxy ring. . 2. The colored photosensitive composition according to claim 1, wherein the (A) halogenated zinc phthalocyanine pigment is a compound represented by the following general formula (1) and containing 9 to 13 bromine atoms on average in the molecule. .

(In General Formula (1), X ^{1 to} X ¹⁶ each independently represents a hydrogen atom, a chlorine atom, or a bromine atom.) The colored photosensitive composition according to claim 1 or 2, wherein the (D) acylphosphine-type photopolymerization initiator is a compound represented by the following general formula (2).

(In General Formula (2), R ¹ and R ² each independently represent a monovalent substituent, Q ¹ represents a monovalent substituent, and n represents an integer of 0 to 5.) 4. The colored photosensitive composition according to claim 3, wherein in the general formula (2), R ¹ and R ² both represent an aryl group, Q ¹ represents an alkyl group, and n is 3. 5. The colored photosensitive composition according to claim 3, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(In General Formula (3), R ¹ represents a monovalent substituent, Q ¹ and Q ² each independently represent a monovalent substituent, and n and m each independently represents an integer of 0 to 5. .) The coloring according to claim 5, wherein in the general formula (3), R ¹ represents a (branched) alkyl group, Q ¹ and Q ² both represent an alkoxy group, and n and m both represent 2. Photosensitive composition.   The colored photosensitive composition according to any one of claims 1 to 6, wherein the compound (E) containing an epoxy ring is an alicyclic epoxy compound. The colored photosensitive composition according to any one of claims 1 to 7, wherein the compound containing the (E) epoxy ring is a compound satisfying the following condition.
(Molecular weight) / (Number of epoxy rings) ≧ 100   It is an object for color filters, The colored photosensitive composition of any one of Claims 1-8.   The color filter which has a coloring pattern which uses the colored photosensitive composition of any one of Claims 1-9 on a board | substrate.   A liquid crystal display device comprising the color filter according to claim 10.