KR20120080123A - Colored photosensitive composition, method for manufacturing color filter, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PURPOSE: A colored photo-sensitive composition, a method for manufacturing a color filter using the same, the color filter, a liquid crystal display device, and an organic electroluminescence display device are provided to secure the superior color characteristic of the color filter and to keep superior pattern forming characteristic. CONSTITUTION: A colored photo-sensitive composition includes a coloring material with a phthalocyanine structure, a solvent, polymeric monomer, a binder resin, a photopolymerization initiator, and a compound represented by chemical formula 1. In chemical formula 1, R1 and R2 are respectively divalent to tetravalent coupling groups; Y1 and Y2 are respectively single bonds, oxygen elements, ester groups, C2 to C30 alkylene groups, C6 to C30 divalent aromatic groups, polyethylene glycol groups, and the divalent coupling groups of the same; P1 and P2 are respectively polymerizable groups; and m and n are respectively the integer of 1 to 3.

Description

Colored photosensitive composition, manufacturing method of color filter, color filter, liquid crystal display device, and organic EL display device {COLORED PHOTOSENSITIVE COMPOSITION, METHOD FOR MANUFACTURING COLOR FILTER, COLOR FILTER, LIQUID CRYSTAL DISPLAY DEVICE, AND ORGANIC EL DISPLAY DEVICE}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a colored photosensitive composition, and relates to a method for producing a color filter using the colored photosensitive composition, a color filter, a liquid crystal display device including the color filter, and an organic EL display device.

Conventionally, in small liquid crystal display devices such as mobile phones, mobile game machines, PDAs, and organic EL displays, the use of a backlight light source having a limited capacitance such as a secondary battery or a battery is essential, and thus the color material of the color filter used in these display devices. As a colorant, a color material having high luminance and capable of displaying color brightly through the bright lines of the backlight has been advantageously used.

In recent years, the enlargement of a liquid crystal display device and an organic electroluminescent display device is advanced for the use of display monitors, televisions, etc. of a personal computer, and RGB color reproduction is emphasized in these display devices. Therefore, in addition to the conventional luminance improvement, the color material of the color filter is required to have higher image quality, namely contrast and color purity.

In response to the above requirements, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other components are added to the pigment composition in which the particle diameter of the pigment is further refined as a coloring photosensitive composition, and the transparent substrates, such as glass, are formed by a photolithography method. The color filter in which the coloring pattern of red, green, blue, etc. was formed on was developed and put into practical use.

Green pigments, such as a chlorinated copper phthalocyanine pigment (C. I. pigment green 7) and a chlorinated copper phthalocyanine pigment (C. I. pigment green 36), are generally used for the green coloring pattern from a viewpoint of color tone and fastness. have. Recently, polyhalogenated metal phthalocyanine pigments such as aluminum, titanium, cobalt, nickel, zinc, tin, and lead have been studied for the purpose of improving the saturation (color purity and color concentration) of the pigment, and the center metal is copper. Various pigments are proposed about this high polyhalogenated zinc phthalocyanine pigment (C. I. pigment green 58 etc.). For example, detailed studies such as substitution degree of Br and Cl (for example, refer to Japanese Patent Documents 1 and 2), pigment treatment method using betaine-type surfactant, various crystal forms, etc. are carried out, and in the X-ray diffraction spectrum It has been reported that polyhalogenated copper phthalocyanine having a Bragg angle (2θ ± 0.2 °) with a maximum diffraction peak at 26.4 ° or 25.5 ° for Cu-Kα rays has high saturation (color purity and color density) and is excellent in stability over time. (See, for example, Japanese Patent Document 3). Moreover, using these pigments, it is proposed to obtain a color filter having high transparency and high color purity.

In addition, the color filter needs to have various reliability so as not to be discolored or discolored by the light of the backlight or the heat of irradiation. In order to improve the reliability, the coloring photosensitive composition which improved the coloring material itself (for example, refer patent document 4-6) and the coloring photosensitive composition which added the compound, such as a quencher and a light stabilizer, have been reported (for example, See Japanese Patent Document 7, 8). And in order to reduce the loss of the matting agent and the light stabilizer in a process, the polymeric monomer and polymer which have a function of reliability improvement are also reported (for example, refer patent document 9, 10).

Japanese Patent Publication No. 2003-161823 Japanese Patent Publication No. 2007-284592 Japanese Patent Publication No. 2008-24743 Japanese Patent Publication No. 2008-138037 Japanese Patent Publication No. 2009-149779 Japanese Patent Publication No. 2009-215380 Japanese Patent Laid-Open No. 2000-214580 Japanese Patent Publication No. 2004-139050 Japanese Patent Publication No. 2004-155812 Japanese Patent Publication No. 2010-54808

Generally, since dyes deteriorate heat resistance and light resistance compared to pigments, the improvement of the reliability has been especially actively performed regarding dyes. However, also in pigments, it is known that reliability is deteriorated when it is miniaturized for the improvement of brightness, and it was necessary to improve reliability while maintaining the characteristic of high transparency and high color purity with respect to such pigments.

This invention is made | formed in view of the said problem, Comprising: It is a subject of this invention to provide the coloring photosensitive composition from which the outstanding light resistance and heat resistance are obtained, maintaining favorable pattern formation property. Moreover, it is providing the manufacturing method of a color filter with a good color characteristic using the said coloring photosensitive composition, a color filter, a liquid crystal display device provided with the said color filter, and an organic electroluminescence display.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said subject was remarkably improved by the following means, and reached this invention.

<1> (A) Color material which has phthalocyanine frame | skeleton, (B) solvent, (C) polymerizable monomer, (D) binder resin, (E) photoinitiator, and (F) compound represented by following General formula (1) Colored photosensitive composition containing these.

[In General Formula (1), R <^1> and R <^2> represents a divalent tetravalent coupling group each independently, and Y <^1> and Y <^2> respectively independently represent a single bond, an oxygen atom, an ester group, 2 or more carbon atoms, and 30 The following alkylene group, a C6 or more, 30 or less divalent aromatic group, a polyethyleneglycol group, or a bivalent coupling group formed by combining two or more types is shown. P ¹ and P ² each independently represent a polymerizable group. m and n each independently represent an integer of 1 or more and 3 or less]

<2> Colored photosensitive composition as described in <1> whose content of the compound represented by said (F) general formula (1) is 0.1 mass% or more and 5.0 mass% or less with respect to the total solid of a composition.

<3> The colored photosensitive composition as described in <1>, wherein at least one of the polymerizable groups represented by P ¹ and P ² in General Formula (1) is a polymerizable group selected from acryloyl group and methacryloyl group.

<4> The coloring photosensitive composition as described in <1>, wherein the color material having the (A) phthalocyanine skeleton contains a color material containing a metal in a molecule thereof.

<5> The colored photosensitive composition as described in <1>, wherein the color material having the (A) phthalocyanine skeleton contains a green pigment.

<6> The color material according to any one of <1>? <5>, wherein the colorant having the (A) phthalocyanine skeleton is C. I. pigment green 7, C. I. pigment green 36, or C. I. pig The coloring photosensitive composition containing garment green 58.

<7> Process of providing the coloring photosensitive composition in any one of <1>? <6> on a board | substrate, and forming a colored layer; And exposing the colored layer in a pattern, and then developing and removing the uncured portion with a developer to form a colored pattern.

<8> Color filter manufactured by the manufacturing method of the color filter as described in <7>.

<9> A liquid crystal display device comprising the color filter according to <8>.

<10> The organic electroluminescence display provided with the color filter as described in <8>.

According to this invention, the coloring photosensitive composition from which the outstanding light resistance and heat resistance can be obtained can be provided, maintaining favorable pattern formation property. In addition, a method for producing a color filter having good color characteristics, a color filter, a liquid crystal display device including the color filter, and an organic EL display device can be provided using the colored photosensitive composition.

Hereinafter, the coloring photosensitive composition of this invention, the color filter using the said coloring photosensitive composition, and the liquid crystal display device using the said color filter are demonstrated in detail.

<Coloring Photosensitive Composition>

The coloring photosensitive composition of this invention is a coloring material which has at least (A) phthalocyanine frame | skeleton, (B) solvent, (C) polymerizable monomer, (D) binder resin, (E) photoinitiator, (F) with general formula (1) It is characterized by containing the compound represented.

Hereinafter, each component contained in the coloring photosensitive composition of this invention is described.

<(A) Color material having a phthalocyanine skeleton>

In the coloring photosensitive composition of this invention, since the coloring material which has a phthalocyanine frame | skeleton is used as a coloring material, the color filter with high color purity and contrast is obtained.

Since the color material having a phthalocyanine skeleton has 16 hydrogen atoms in the phthalocyanine ring, these hydrogen atoms can be replaced with up to 16 bromine atoms and / or chlorine atoms. All of these halogen atoms may be the same or different.

As substitution number of a halogen atom, it is preferable that they are 8 or more and 16 or less, More preferably, it is the range of 10 or more and 16 or less.

The green pigment having a phthalocyanine skeleton as a colorant having a phthalocyanine skeleton in the present invention exhibits a high gloss-bright green color by being substituted with eight or more bromine atoms, and is suitable for use in the green pixel portion pattern of the color filter. In particular, the bromine atom having 10 to 16 substitutions is more suitably used in the present invention because of its higher brightness.

Moreover, in this invention, the blue pigment which has a phthalocyanine skeleton as a color material which has a phthalocyanine skeleton is also a preferable form.

In the present invention, it is particularly preferable to use a phthalocyanine pigment containing a metal in the molecule from the viewpoint of obtaining a color having high luminance.

The metal is not particularly limited as long as it can maintain the stability of the colorant, but copper, aluminum, titanium, cobalt, nickel, zinc, tin, lead, and the like are preferable, and zinc is preferably contained in terms of color.

The phthalocyanine pigment can be produced by a known production method such as, for example, chlorosulfonic acid method, halogenated phthalonitrile method, melting method and the like. More specific manufacturing methods are described in detail in Japanese Patent Application Laid-Open No. 2008-19383, Japanese Patent Application Laid-Open No. 2007-320986, Japanese Patent Application Laid-Open No. 2004-70342, and the like.

Among them, zinc halide phthalocyanine pigments disclosed in Japanese Patent Application Laid-open No. 2004-70342, which have a simple manufacturing process, are preferable in view of cost. In addition, from the viewpoint of stability, the crystal-converted zinc phthalocyanine pigment disclosed in Japanese Patent Laid-Open No. 2008-19383 is preferable, although it is also based on a method of combining other additives and a later step. Moreover, especially for the improvement of dispersibility, the resin-coated zinc halide phthalocyanine pigment disclosed by Unexamined-Japanese-Patent No. 2007-320986 is a preferable form.

As a color pigment which has a phthalocyanine frame | skeleton of this invention, C. I. pigment green 7, C. I. pigment green 36, C. I. pigment green 58, etc. are mentioned. I. Pigment Blue 15, C. I. Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 6. The color material which has a phthalocyanine skeleton may use 2 or more types together.

Among these, it is preferable that the color material which has a phthalocyanine skeleton contains C. I. pigment green 7, C. I. pigment green 36, or C. I. pigment green 58.

The range of 10 nm-100 nm is preferable, and, as for the average primary particle diameter of the phthalocyanine pigment of this invention, the range of 10 nm-70 nm is more preferable. By using the phthalocyanine type pigment of the average primary particle diameter of this range, the coloring photosensitive composition for color filters which is excellent in dispersibility stability and coloring power, and has high brightness and high contrast can be obtained.

In addition, the average primary particle diameter in this invention is a long diameter (long diameter) with respect to 100 primary particles of the phthalocyanine pigment which image | photographs the particle | grains in a visual field with a transmission electron microscope, and comprises the aggregate on a two-dimensional image. The average value of the diameter (short diameter) and the shorter side is calculated | required, respectively, and is the average value.

If the primary particle of the phthalocyanine pigment of this invention has a further aspect ratio of 1-3, the viscosity characteristic will improve in each application field, and fluidity will become higher. In order to determine the aspect ratio, the particles in the field of view are photographed using a transmission electron microscope or a scanning electron microscope as in the case of obtaining the average particle diameter of the primary particles as described above. And the average value of the diameter (long diameter) of a long side and the diameter (short diameter) of a short side is calculated | required about 100 of the primary particles which comprise the aggregate on a two-dimensional image, and it calculates using these values.

In order to obtain a phthalocyanine pigment whose average primary particle diameter is in the range of 10 nm to 100 nm, it may be finely granulated by any method, but pigment particles which can easily suppress crystal growth and have relatively small average primary particle diameters are obtained. In view of the above, it is preferable to employ a solvent salt milling treatment.

This solvent salt milling means kneading and grinding phthalocyanine pigment, an inorganic salt, and an organic solvent. The phthalocyanine pigment having a large particle diameter may be subjected to solvent salt milling after dry grinding. Specifically, a phthalocyanine pigment, an inorganic salt and an organic solvent which does not dissolve it are put into a kneading machine, and kneading grinding is performed therein. As the kneader at this time, for example, a kneader, a mixed muller or the like can be used.

As said inorganic salt, a water-soluble inorganic salt can be used suitably, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, sodium sulfate. Moreover, it is more preferable to use the inorganic salt of average particle diameters 0.5-50 micrometers. Such inorganic salts are easily obtained by pulverizing ordinary inorganic salts.

In obtaining the phthalocyanine pigment which has an average primary particle diameter of 10 nm-100 nm, it is preferable to make ratio of the inorganic salt use amount with respect to the usage-amount of the phthalocyanine pigment in solvent salt milling high. That is, the amount of the inorganic salt used is preferably 5 to 20 parts, more preferably 7 to 15 parts based on 1 part of the phthalocyanine pigment in terms of mass.

As the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth. As such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene. Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol 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 and the like can be used.

Although the usage-amount of the water-soluble organic solvent at this time is not specifically limited, 0.01-5 parts and 0.8-2 parts are preferable with respect to 1 part of phthalocyanine pigments by mass conversion.

30-150 degreeC is preferable and, as for the temperature at the time of solvent salt milling, 80-100 degreeC is more preferable. 5-20 hours are preferable and, as for solvent salt milling time, 8-18 hours are more preferable.

In this way, a mixture containing a phthalocyanine pigment, an inorganic salt, and an organic solvent as a main component is obtained, but the organic solvent and the inorganic salt are removed from this mixture, and, if necessary, washing, filtration and drying of the solid mainly composed of the phthalocyanine pigment. The fine powder of phthalocyanine pigment can be obtained by performing pulverization or the like.

As washing | cleaning, both water washing and hot water can be employ | adopted. The number of washings may be repeated in a 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.

As said filtration collection and drying after washing | cleaning, the batch-type or continuous drying etc. which dehydrate and / or a solvent of a pigment by 80-120 degreeC heating etc. by the heating source provided in the dryer are mentioned, for example, As a drier, there are generally a box drier, a band drier and a spray drier. In addition, the grinding | pulverization after drying is not operation which enlarges a specific surface area or makes the average particle diameter of a primary particle small, For example, as for the case of drying using a box type drier or a band drier, a pigment may become a lamp shape. It is performed in order to disintegrate and grind | pulverize a pigment at the time, For example, grinding | pulverization with a mortar, a hammer mill, a disk mill, a pin mill, a jet mill, etc. are mentioned.

Although the coloring agent which has the (A) phthalocyanine frame | skeleton of this invention can be obtained, for example by the method mentioned above, it is also possible to use the pigment or pigment dispersion liquid circulating generally.

The colorant having the (A) phthalocyanine skeleton thus obtained has a weak cohesive force of the primary particles and more easily disintegrates, so that the covering power is increased to facilitate the production of a high contrast colored film.

In this invention, although these phthalocyanine pigments may be used independently, you may use multiple types together. In addition, when used together, it can be used in mixture with other halogenated phthalocyanine pigments from which a bromination rate or a chlorination rate differs, or brominated phthalocyanine etc. in which a center metal differs. By changing the bromination rate and the chlorination rate, or by changing the center metal, it is expected that the color tone as the pigment changes to increase the change in color that can be reproduced.

In the coloring photosensitive composition of this invention, the transmittance | permeability can be enlarged by adjusting the color of a coloring photosensitive composition by combining another color material with the color material which has (A) phthalocyanine frame | skeleton.

For example, in order to form a green pixel, you may use together a yellow pigment and a orange pigment with respect to a phthalocyanine green pigment. Examples of the yellow pigments include diketopyrrolopyrrole orange pigments, in addition to yellow pigments such as disazo yellow pigments, isoindolin yellow pigments, quinophthalone yellow pigments, benzimazolone yellow pigments and nickel azo yellow pigments; Tangerine pigments, such as a perinone series orange pigment, can also be used as needed.

For example, C. I. Pigment Yellow 1, 1: 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, 174, 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 and the like.

Among these, C. 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, and more preferably C. I. Pigment Yellow 150, C. I. Pigment Yellow 185, C. I. Pigment Yellow 138, C. I. Pigment Yellow 139.

In particular, the use of C. I. Pigment Yellow 150, C. I. Pigment Yellow 138, and C. I. Pigment Yellow 139 is preferable because the transmittance is high and the contrast is high.

In addition, in order to form a blue pixel, you may use together a purple pigment with respect to a phthalocyanine blue pigment. Examples of the purple pigment include a quinacridone purple pigment, an oxazine purple pigment, an anthraquinone purple pigment, an indigoide purple pigment, and a xanthene purple pigment.

As a specific example, there are C. I. pigment violet 1, 19, 23, 29, 32, 36, 38. Especially, C. I. pigment violet 23 is preferable because of its 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. In order to make the average primary particle diameter small and fine, the salt milling method is effective similarly to phthalocyanine, and may be salt milled with a phthalocyanine pigment, or salt milling separately.

The average primary particle diameter is obtained by observing with SEM or TEM and measuring 100 particle sizes in the part where the particles do not aggregate and calculating the average value.

In the coloring photosensitive composition of this invention, the total amount of the color material which has a phthalocyanine frame | skeleton is the total amount except the (B) solvent in the coloring photosensitive composition of this invention (hereinafter, "the total amount except this (B) solvent in a coloring photosensitive composition"). Total solid content ”is preferably 5 to 60%, more preferably 10 to 50%, and most preferably 15 to 45%. By using the added amount in this range, it is possible to obtain a color filter having excellent color characteristics, high contrast and high luminance.

Pigment Dispersion Composition

In adjustment of the coloring photosensitive composition of this invention, it is a preferable aspect to disperse | distribute the color material which has (A) phthalocyanine frame | skeleton, and another color material together or separately previously, and to leave it as a pigment dispersion composition.

Although the pigment dispersion composition disperse | distributed the said pigment and a solvent, a dispersing agent, resin, etc. are added and used as needed. Moreover, other components, such as a pigment derivative, can be further used as needed.

Preparation of Pigment Dispersion Composition

Although the preparation form of the pigment dispersion composition of this invention is not specifically limited, For example, a pigment of 0.01-1 mm is used for a pigment, a pigment dispersant, and a solvent using a longitudinal or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, etc. It can obtain by performing a microdispersion process with the beads which consist of a zirconia and the like.

Before kneading, kneading and dispersing with strong shearing force using two rolls, three rolls, ball mill, trom mill, disper, kneader, cornider, homogenizer, blender, single screw or twin screw extruder It is also possible to do this.

Further details on kneading and dispersion are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964).

Pigment concentration

As content in the pigment dispersion composition of a pigment, 10-60 mass% is preferable with respect to the total solid (mass) of the said composition, and 15-50 mass% is more preferable. When content of a pigment is in the said range, color concentration is enough and it is effective in ensuring the outstanding color characteristic.

Dispersant

It is preferable that a pigment dispersion composition contains at least 1 sort (s) of a dispersing agent. By containing this dispersing agent, the dispersibility of a pigment can be improved.

As a dispersing agent, a well-known pigment dispersing agent and surfactant can be selected suitably, for example.

Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer POLYFLOW No. 75, No. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusu Co., Ltd.); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by Yusu Co., Ltd.); Amphoteric surfactants having a carboxybetaine structure, an amidebetaine structure, a sulfobetaine structure, a hydroxybetaine structure, and the like; Fluorine-based surfactants such as MEGAFACE F171, F172, and F173 (manufactured by DIC Corporation); EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (all manufactured by Ciba Specialty Chemicals Inc.), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE Polymeric dispersants such as AID 9100 (all manufactured by San Nopco Limited); Various SOLSPERSE dispersants (manufactured by Lubrizol Japan Limited) such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Adeka Corporation) and ISONET S-20 ( Sanyo Chemical Industries, 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 (manufactured by Byk Chemie). In addition, an acrylic copolymer, an oligomer or polymer having a N, N-disubstituted amino group or an acid group-based polar group at a molecular terminal or side chain, a polyurethane resin modified by a tertiary amine, described in Japanese Unexamined Patent Publication No. 2009-52010 AB type, ABA type block copolymer, etc. are mentioned.

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

Pigment Derivatives

A pigment derivative is added to a pigment dispersion composition as needed. By adsorbing a pigment derivative having affinity to the dispersant or a polar group introduced thereon onto the surface of the pigment, and using this as the adsorption point of the dispersant, the pigment can be dispersed as fine particles in the colored photosensitive composition to prevent re-agglomeration. It is effective for constructing a high and excellent color filter.

The pigment derivative is a compound in which an organic pigment is used as a mother skeleton, and an acidic group, a basic group and an aromatic group are introduced into the side chain as a substituent. The organic pigments specifically include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin type pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments and benzimidazolone. Pigments; and the like. Generally, pale yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine, and quinoline, which are not called dyes, are also included. As a pigment derivative, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Unexamined-Japanese-Patent No. 8-295810 What is described in Unexamined-Japanese-Patent No. 11-199796, Unexamined-Japanese-Patent No. 2005-234478, Unexamined-Japanese-Patent No. 2003-240938, Unexamined-Japanese-Patent No. 2001-356210, etc. can be used.

As content in the pigment dispersion composition of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content of the pigment derivative is within this range, the dispersion can be performed satisfactorily while keeping the viscosity of the pigment dispersion composition low, and the dispersion stability after dispersion can be improved.

As a result, a colored photosensitive composition having a high transmittance and excellent color characteristics can be obtained. When the colored photosensitive composition is applied to, for example, a color filter manufacturing application, a color filter having good color characteristics and high contrast. Can be obtained.

Moreover, it is also possible to further add high molecular compounds, such as alkali-soluble resin mentioned later, to a pigment dispersion composition. Polar groups such as acid groups contained in alkali-soluble resins are considered to be effective for dispersion of pigments, and are often effective for dispersion stability of pigment dispersions.

-solvent-

It will not specifically limit, if it is an organic solvent used for a general pigment dispersible composition as a solvent in a pigment dispersion composition. For example, 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 And solvents such as methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene and the like. Moreover, the solvent listed to the (B) solvent mentioned later can also be used. In order to adjust boiling point, a viscosity, and the dispersibility of a pigment, it is also possible to use multiple together.

Content of the solvent in a pigment dispersion composition is suitably selected according to the use of a pigment dispersion composition, etc. When a pigment dispersion composition is used for preparation of the coloring photosensitive composition mentioned later, 5-50 mass% of solid content concentration (total amount except a solvent in a pigment dispersion composition is called solid content) containing a pigment and a pigment dispersant from a handleability viewpoint is It may contain as much as possible.

As content of the pigment dispersion composition in the coloring photosensitive composition of this invention, the total content of the pigment containing the color material which has (A) phthalocyanine frame | skeleton with respect to the total solid (mass) of a coloring photosensitive composition has a range of 5-70 mass% The amount which becomes, and the amount which becomes the range of 15-60 mass% is more preferable. When content of a pigment dispersion composition is in the said range, color concentration is enough and it is effective in ensuring the outstanding color characteristic.

<(B) solvent>

The coloring photosensitive composition of this invention can be suitably prepared using a solvent with each component contained in a coloring photosensitive composition.

Examples of the solvent 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 methyl lactate Ethyl lactate, methyl oxyacetic acid, ethyl oxyacetic acid, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, 3-oxypropionate methyl and 3-oxy 3-oxypropionic acid alkyl esters such as ethyl propionate (for example, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropionic acid 2-oxypropionic acid alkyls such as methyl, 2-oxypropionate, and 2-oxypropionic acid propyl Leu (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate) , 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, acetoacetic acid Ethyl, 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Aromatic hydrocarbons such as toluene, xylene; And the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, and cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like are bonded.

A solvent may be used independently and may be used in combination of 2 or more type.

<(C) Polymerizable Monomer>

In this invention, a polymeric monomer is used as a hardening component of a coloring photosensitive composition.

The polymerizable monomer of the present invention is not particularly limited as long as it is polymerizable, and compounds capable of addition polymerization such as low molecular compounds, dimers, trimers, and oligomers having at least one ethylenic double bond can be suitably used.

Examples of the compound having at least one of these ethylenic double bonds include esters of unsaturated carboxylic acids, unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatic polyhydroxy compounds. Esters obtained by esterification of polyunsaturated hydroxy compounds such as esters of unsaturated carboxylic acids, unsaturated carboxylic acids and polyhydric carboxylic acids and fatty acid polyhydroxy compounds, aromatic polyhydroxy compounds and the like, and polyisocyanate compounds ( Ethylenic compounds etc. which have a urethane skeleton which made the meta) acryloyl containing hydroxy compound react are mentioned.

Although a specific polymerizable monomer can be classified and classified into the number of polymerizable groups in 1 molecule as shown below, it is not limited to this.

In addition, in this specification, an acrylate and a methacrylate are named generically (meth) acrylate.

[Compound having one polymerizable group in one molecule]

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-ethylhexyl diglycol (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-perfluorodecyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) Acrylate, phenoxymethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl ( Ta) 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 modified nonylphenol (meth) acrylate, PO modified nonylphenol (meth) acrylate, EO modified-2-ethylhexyl (meth) acrylate, etc. are mentioned.

[Compound having two polymerizable groups in one molecule]

Examples of the compound having two (meth) acryloyl groups in the same molecule as the polymerizable group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di ( Meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1 , 3-diacryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, bis (acrylic of bisphenol A Loyloxyethyl) ether, bisphenol A epoxide (Meth) acrylic acid modified compound, 3-methylpentanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol- tricyclodecane di (meth) acrylate of a resin And dimethylol-tricyclodecane di (meth) acrylate, neopentylglycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, and bisphenol A type epoxy resins. And meta) acrylic acid modified substances.

[Compound having three polymerizable groups in one molecule]

For example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, alkylene oxide modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionic acid dipentaerythritol tri (meth) acrylic Rate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth ) Acrylate, ethoxylated glycerin triacrylate, etc. are mentioned.

[Compound having 4 or more polymerizable groups in 1 molecule]

As a compound which has four or more polymerizable groups in 1 molecule, for example, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, and propionic acid dipentaerythritol tetra ( Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylic Alkylene oxide modified hexa (meth) acrylate of phosphate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Kyoeisha Chemical Co., Ltd. And urethane acrylates such as UA-306H, UA-306T, and UA-306I of the product.

A preferable compounding quantity of a polymerizable monomer is 5-80 mass% with respect to the total solid (mass) of the coloring photosensitive composition of this invention, Preferably it is 10-60 mass%, More preferably, it is the range of 15-50 mass%.

Among these, from the viewpoint of suitably maintaining solvent resistance and ITO sputterability in a later step, a (meth) acrylate monomer having two or more (meth) acryloyl groups in the same molecule is preferable, and three or more polymerizable groups It is more preferable to have It is particularly advantageous to have four or more polymerizable groups, for example dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof (mixing ratio in terms of mass is dipentaerythritol pentaacrylate: dipentaerythritol hexa). Acrylate = 2-4: 8-6) is used suitably from a solvent tolerance or an ITO sputtering suitability.

From the viewpoint of developing latitude, it is advantageous to have one to three hydrophilic groups in the same molecule, and in particular, a compound having a hydroxyl group and a carboxyl group in the molecule contributes to the improvement of developability. From this viewpoint, the compound which has acidic groups, such as a carboxyl group, in the terminal of an acrylate monomer is preferable. Specifically, an acid-modified compound (for example, Toagosei Co., Ltd., ARONIX manufactured by unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid) or an acid group such as a carboxyl group introduced into the terminal of the polyfunctional acrylate compound M-510, ARONIX M-520, ARONIX TO-2349, etc. are mentioned, Especially, ARONIX M-520 and ARONIX TO-2349 are used suitably.

In order to make solvent resistance, ITO sputter aptitude and development latitude compatible, in addition to using a compound containing three or more polymerizable groups and an acid group in the same molecule, a compound having an acid group and a compound having three or more polymerizable groups in one molecule It can also be used in combination. When using together, it is used in the range of 1-50 mass%, when the polymerizable monomer is 100 mass parts, the range of 1-40 mass% is preferable, and the range of 5-20 mass% is more preferable.

<(D) Binder Resin>

As the (D) binder resin of the present invention, any of the polymer compounds soluble in the solvent can be used, but as the preferred binder resin, alkali-soluble resins are preferable in consideration of alkali developability by the photolithography method.

Alkali-soluble resin can also be contained in the adjustment step of a pigment dispersion composition, and can also be added separately at the stage of both adjustment of a pigment dispersion composition and adjustment of a coloring photosensitive composition.

As alkali-soluble resin, it is a linear organic polymer polymer, It is alkali-soluble polymer which has at least 1 alkali-soluble group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.), More preferably, it is soluble in an organic solvent, It is preferable that it is developable by.

For the production of alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. The polymerization conditions such as the temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be determined experimentally. .

As said linear organic polymer, the polymer which has a carboxylic acid in a side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-25957, Japanese Patent Publication No. 59-53836, Japan Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like as described in the respective publications of Japanese Patent Application Publication No. 59-71048; and The acid cellulose derivative which has a carboxylic acid in a side chain, what added an acid anhydride to the polymer which has a hydroxyl group, etc. are mentioned, The high molecular polymer which has a (meth) acryloyl group in a side chain is also mentioned as a preferable thing.

Among these, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a benzyl (meth) acrylate / (meth) acrylic acid / other monomer composed of other monomers is suitable. In addition, what copolymerized methacrylic acid 2-hydroxyethyl etc. can also be mentioned as a useful thing. The said polymer can be mixed and used in arbitrary quantity.

In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropyl described in JP-A-7-140654 Acrylate / polymethylmethacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methylmethacrylate / methacrylic acid copolymer, 2-hydroxy Ethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer; and the like.

As other alkali-soluble binder resins, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, and Japanese Patent Publication The well-known high molecular compound of Unexamined-Japanese-Patent No. 11-174224, Unexamined-Japanese-Patent No. 2000-56118, Unexamined-Japanese-Patent No. 2003-233179, Unexamined-Japanese-Patent No. 2009-52020, etc. can be used.

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is easily available, and since it is easy to adjust alkali solubility, it is used suitably.

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

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, etc. Can be mentioned.

As said vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, for example , Polystyrene macromonomer, polymethylmethacrylate macromonomer, CH ₂ = CR ³¹ R ³² [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and 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 having 1 to 5 carbon atoms, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or 6 to 12 carbon atoms Aralkyl group].

These copolymerizable other monomers can be used individually by 1 type or in combination of 2 or more types. Preferred copolymerizable other monomers are at least one selected from CH ₂ = CR ³¹ R ³² , CH ₂ = C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene, Especially preferred are CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ). Of these, R ³¹ , R ³² and R ³³ have the same meanings as described above.

In the present invention, the (D) binder resin may be used as a single compound or a plurality of compounds may be used in combination. As content of binder resin, such as alkali-soluble resin in a coloring photosensitive composition, 1-20 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 2-15 mass%, Especially preferably, it is 3-12. Mass%.

Moreover, the range of 0.1-10 is preferable at mass ratio, as for the mix | blending of (C) polymeric monomer / (D) binder resin, the range of 0.4-8 is more preferable, The range of 0.5-5 is still more preferable.

<(E) Photoinitiator>

The (E) photoinitiator in this invention can be used widely without limitation as long as it is a well-known compound which has the ability to start superposition | polymerization by light irradiation.

As a well-known photoinitiator used generally, a camphor quinone, a benzophenone, a benzophenone derivative, an acyl phosphine, an acyl phosphine derivative, an acetophenone, an acetophenone derivative, for example (alpha)-hydroxycycloalkylphenyl ketones Or 2-hydroxy-2-methyl-1-phenyl-propane, dialkoxyacetophenones, α-hydroxy- or 4-alloyl-1,3-dioxolanes, benzoinalkyl ethers and benzylke Dehydration, for example benzyldimethylketal, phenyl glyoxalate and derivatives thereof, dimer phenyl oxalate, peresters, for example benzophenonetetracarboxylic acid peresters (for example those described in EP 1126,541) ), Halomethyltriazines, for example 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] Azine, 2-methyl-4,6-bis-trichloromethyl [1,3,5] triazine, oximes, such as O-benzoyl-4'-benzmercapto) benzoyl-hexyl-ketoxime, O -Acetyl-1- [9-ethyl-6- (2-methylbenzoyl) -9-carbazol-3-yl] -ethane-1-onoxime, hexaarylbisimidazole / co-initiator system, for example 2 Ortho-chlorohexaphenyl-bisimidazole in combination with mercaptobenzothiazole; Ferrocenium compounds or titanocenes such as dicyclopentadienyl-bis (2,6-difluoro-3-pyrrolo-phenyl) titanium; For example, a mixture with an O-acyl oxime ester compound as described in GB 2,339,571 may be used. Boric acid compounds can also be used as co-initiators.

As for content of the photoinitiator in the coloring photosensitive composition of this invention, about 0.05-30 mass% of all solid content is preferable, It is more preferable that it is 0.1-20 mass%, It is more preferable that it is 0.2-10 mass%.

It is also preferable that the coloring photosensitive composition of this invention contains a co-sensitizer. In the present invention, the sensitizer has an effect of further improving the sensitivity of the sensitizing dye and the initiator to actinic radiation, or inhibiting the polymerization inhibition of the photopolymerizable compound by oxygen.

Examples of such a desensitizer include, for example, MR Sander, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, Research Disclosure 33825 The compound described in the arc is mentioned, Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthio dimethylaniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides, for example, thiol compounds described in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, N-phenyl mercaptobenzo Imidazole, 2-mercapto-4 (3H) -quinazolin, β-mercaptonaphthalene, butanediolbis (3-mercaptobutyrate), butanediolbis (3-mercaptopropionate), ethylene glycolbis (3- Mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), and the like.

Other examples include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyltin acetate, etc.) described in JP-A-48-42965, and JP-A-55-34414. Hydrogen donors described, Sulfur compounds described in Japanese Patent Application Laid-open No. Hei 6-308727 (e.g., trithiane, etc.), Thioxanthone compounds (2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 1 -Chloro-4-propoxy thioxanthone, etc.) etc. are mentioned.

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

<(F) Compound represented by General Formula (1)>

The coloring photosensitive composition of this invention contains (F) the compound represented by following General formula (1) (henceforth "specific additive" suitably).

When the coloring photosensitive composition of this invention is used for a color filter as mentioned later, heat processing (post baking) is performed at the temperature of 100-250 degreeC in the formation process of a coloring pattern. Therefore, when the additive is used for the purpose of improving the reliability, it is required that the effect is not lost after the heat treatment. Since a specific additive is hard to volatilize or decompose | disassemble by heat, it is especially excellent in heat resistance and exhibits a remarkable effect in the form of this invention.

By using the compound represented by the following general formula (1), the coloring photosensitive composition of this invention does not impair the brightness | luminance and color purity inherent to a color material, and is excellent in heat resistance and light resistance after heat processing, and developability? It becomes possible to make solvent resistance compatible.

[In General Formula (1), R <^1> and R <^2> represents a divalent tetravalent coupling group each independently, and Y <^1> and Y <^2> respectively independently represent a single bond, an oxygen atom, an ester group, 2 or more carbon atoms, and 30 The following alkylene group, a C6-C30 aromatic group, a polyethyleneglycol group, or the bivalent coupling group formed by combining two or more types is shown. P ¹ and P ² each independently represent a polymerizable group. m and n each independently represent an integer of 1 or more and 3 or less]

As a 2-4 tetravalent coupling group in R <^1> , R <^2> in General formula (1), a C2-C10 hydrocarbon group and a C6-C10 aromatic group are mentioned.

Examples of the hydrocarbon group having 2 to 4 carbon atoms of 2 to 4 carbon atoms in R ¹ and R ² include alkyl such as ethylene group, propylene group, propane-1,3-diyl group and propane-2,2-diyl group. A lene group and a substituted alkylene group are mentioned, Preferably it is an ethylene group and a propylene group.

Examples of the aromatic group having 6 to 10 carbon atoms in R ¹ and R ² include arylene groups such as phenylene group, naphthylene group, toluylene group, and xylylene group and substituted arylene groups. And a phenylene group and a toluylene group.

Examples of the ester groups in Y ¹ and Y ² in the general formula (1) include carboxylic acid esters, phosphoric acid esters and sulfonic acid esters, and are preferably carboxylic acid esters.

Examples of the aliphatic alkylene group having 2 to 30 carbon atoms in Y ¹ and Y ² include alkylene groups such as ethylene group, propylene group, propane-1,3-diyl group, propane-2,2-diyl group, and the like. A substituted alkylene group is mentioned, Preferably it is an ethylene group and a propylene group, As an aromatic group of 6 to 30 carbon atoms, Arylene groups, such as a phenylene group, a naphthylene group, toluylene group, and a xylylene group, and substituted aryl A ethylene group is mentioned, Preferably it is a phenylene group and toluylene group.

Moreover, as a C2 or more and 30 or less polyethyleneglycol group in Y <^1> , Y <^2> , it is 1-15 as a repeating number of an ethylene glycol residue, and 1-10 are more preferable.

Formula (1) of P ^1, acryloyloxy group as a monovalent polymerizable group polymerizable by heat or light irradiation of the P ² (meth) acryloyl, (meth) acrylate, (meth) acrylamide group, a vinyl A group, a vinyloxy group, a maleimide group, an epoxy group, glycidyl group, etc. are mentioned, Preferably it is a (meth) acryloyl group and a (meth) acryloyloxy group, and a (meth) acryloyl group is especially preferable. .

In addition, as m and n, they are each independently an integer of 1 or more and 3 or less.

Although the mechanism of improving light resistance by addition of the azoxy compound which is a specific additive represented by General formula (1) is not elucidated correctly, it is estimated as follows. It is estimated that discoloration at the time of light resistance test is suppressed because the radical which produces | generates when the color material which has a phthalocyanine frame | skeleton is excited by light irradiation is captured by the azoxy compound represented by General formula (1).

In particular, the azoxy compound having a polymerizable group is less volatilized and decomposed by heating than other nonpolymerizable azoxy compounds, and thus has excellent heat resistance. Therefore, it is estimated that the azoxy compound captures radicals most effectively in light irradiation after postbaking.

The specific additive of the present invention consists of azoxy moiety (a moiety containing a subarachnoid group and a chemical structure linked thereto, hereinafter referred to as azoxy moiety) and a polymerizable moiety, and the azoxy moiety and the polymerizable moiety are directly bonded to each other. There may be a connection site which couple | bonds both.

In addition, you may use together 2 or more types of specific additives for the coloring photosensitive composition of this invention.

Next, each site | part which a specific additive of this invention has is demonstrated.

The axoxy moiety is composed of a chemical structure in which the subfamily group and the subfamily group (-N = NO-) in the central portion are connected to improve the light resistance of the colored photosensitive composition. The chemical structure connected to the subfamily is not particularly limited as long as the compound represented by the general formula (1) is constituted. Examples thereof include various hydrocarbon groups and various aromatic groups. Among these, an aromatic group is preferable from a viewpoint of the activity of a subgroup time, and a benzene ring is especially preferable.

The polymerizable site is responsible for preventing the volatilization and decomposition of the azoxy compound exhibiting the effect of suppressing deterioration due to light irradiation and improving the heat resistance. As a polymerizable site | part of the specific additive of this invention, if it is a structure in which a polymerization reaction advances by heat or light irradiation, generally known polymerizable groups can be used without a restriction | limiting in particular. As a specific polymeric group, a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, a vinyl group, a vinyloxy group, a maleimide group, an epoxy group, glycidyl group, etc. are mentioned. Some of these polymerizable groups may be further substituted. Among these, a (meth) acryloyl group and a (meth) acryloyloxy group are preferable at the point of the simplicity of synthesis.

Although the connection site | part can be used widely without a restriction | limiting especially if it is a general organic group, a cyclic aliphatic group, a linear aliphatic group, an aromatic group, Especially an alkylene chain and a polyethyleneglycol chain are preferable. The said organic group may have a branch, and when it has a branch, may have a some polymeric site | part or azoxy site | part in each terminal.

As said alkylene chain, an ethylene group, a propylene group, a propane-1, 3-diyl group, a propane-2, 2-diyl group is mentioned.

As carbon number of the said alkylene chain, 1-30 are preferable and 1-10 are more preferable. The range of preferable carbon number regarding a polyethyleneglycol chain is the same as that of an alkylene chain.

As for content of the compound represented by (F) General formula (1) in this invention, about 0.1-5.0 mass% is preferable with respect to the total solid of a coloring photosensitive composition, It is more preferable that it is 0.2-4.0 mass%, 0.5 It is more preferable that it is 2.0 mass%.

By setting it as this range, the effect of the apex part is fully exhibited, the sensitivity with respect to exposure is high, and since it can form a desired pattern at the time of using as a color filter, the problem that a surface roughness and a deletion generate | occur | produce does not arise.

(F) Among the compounds represented by the general formula (1), compounds having the structure of the following general formula (2) are preferable from the viewpoints of the stability of the compound, the activity of the subfamily and the ease of handling.

Formula (2) ^{of, Y 1, Y 2, P} 1, P 2, m, and n are each Y in the formula ^{(1) 1, Y 2,} P 1, P 2, m, and n and It is the same meaning.

It is preferable that P <^1> and P <^2> in General formula (2) are a (meth) acryloyl group and a (meth) acryloyloxy group. It is preferable that Y <^1> and Y <^2> in General formula (2) are a single bond or the linking group shown below. M and n in General formula (2) are respectively independently 1 and 3 integers.

In the following linking group, * represents a linking position with an aromatic ring or a polymerizable site | link | linked to the axoxy site | part. p each independently represents an integer of 30 or less, preferably an integer of 3 or more and 15 or less, and more preferably an integer of 3 or more and 10 or less.

Although the specific example of a compound represented by General formula (1) and (2) is shown below, the specific additive in this invention is not limited to these compounds.

Among the compounds represented by the general formula (1), particularly, 4,4'-azoxystyrene, 4,4'-azoxycinnamic acid alkyl ester compounds (for example, the following compounds a and b) and the like are suitably used.

<Other additives>

The coloring photosensitive composition of this invention can contain various additives, such as a ultraviolet absorber, a thermal-polymerization initiator, surfactant, a development accelerator, a thermal polymerization inhibitor, a filler, a dispersing agent, and an aggregation inhibitor, as needed.

<Ultraviolet absorber>

You may add the normal ultraviolet absorber which does not contain a polymeric group in the range which does not harm to the compound represented by said (F) General formula (1). In this case, it is preferable to use an organic ultraviolet absorbent having good compatibility with the compound represented by the formula (F) (1) because a synergistic effect can be expected. In particular, a derivative of a compound whose main skeleton is a hydroxybenzophenone series, a benzotriazole series, a cyanoacrylate series, a triazine series, or a dienoate series is preferable. It may be a polymer such as a vinyl polymer further containing residues of these ultraviolet absorbers in the side chain.

Specifically 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy Benzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4 '-Dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2 , 2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2- (2-hydroxy-5-t-methylphenyl) benzotriazole , 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano- 3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2- (2-hydroxy-4-hex Siloxyphenyl) -4,6-diphenyltriazine, octyl-5-N, N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate, 2-hydroxy-4- (2 (Co) polymers of -acryloxyethoxy) benzophenone, (co) polymers of 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, and the like. You may use together 2 or more types of these organic type ultraviolet absorbers.

<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 azo bis compounds. Ketone peroxide, peroxy ketal, and hydroper are mentioned as the peroxide compounds. Oxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, etc. are mentioned.

<Surfactant>

It is preferable to comprise in the coloring photosensitive composition of this invention using various surfactant from a viewpoint of improving applicability | paintability. Liquid characteristics (especially fluidity) at the time of using a surfactant as a coating liquid can be improved, and the uniformity and liquid saving of coating thickness can be improved. That is, since the interfacial tension between the substrate and the coating liquid is decreased, the wettability to the substrate is improved, and the coating property to the substrate is improved, so that even when a thin film having a thickness of several μm is formed with a small amount of liquid, a uniform thickness is formed. This is valid in terms of possible. Moreover, it is effective also in slit application which is easy to drop liquid but is easy.

As surfactant, various surfactant of nonionic, cationic, and anionic type can be used. Especially, the fluorine-type surfactant which has a perfluoroalkyl group as a nonionic surfactant is preferable.

3-40 mass% is suitable for the fluorine-containing rate of a fluorine-type surfactant, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%. If the fluorine content is in the above range, it is effective in terms of coating thickness uniformity and liquid saving property, and the solubility in the composition is also good.

As a fluorine type surfactant, MEGAFACE F171, copper F172, copper F173, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437 (above, DIC Corporation), FLUORAD FC430, copper FC431 , FC171 (above, Sumitomo 3M product), Surflon S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC1068, East SC-381, East SC-383, East S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), and the like.

Examples of surfactants other than fluorine-based include phthalocyanine derivatives (commercially available EFKA-745 (manufactured by MORISHITA SANGYO KK), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer POLYFLOW) Cationic surfactants such as No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusu Co., Ltd.), polyoxyethylene lauryl ether, polyoxyethylene ste Aryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, produced by BASF Corporation, Nonionic surfactants such as L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1; and anionic surfactants such as W004, W005, W017 (manufactured by Yusu Co., Ltd.) ; Can be mentioned.

As for the addition amount of surfactant, 0.001-2.0 mass% is preferable with respect to the total mass of a pigment dispersion composition or a coloring photosensitive composition, More preferably, it is 0.005-1.0 mass%.

<Development accelerator>

In addition, when promoting the alkali solubility of an uncured part and further improving developability of a coloring photosensitive composition, addition of organic carboxylic acid, preferably low molecular weight organic carboxylic acid of molecular weight 1000 or less can be performed to a coloring photosensitive composition. have. Specific examples 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, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasilic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, kumaric acid and umbelic acid. Can be.

<Heat polymerization inhibitor>

It is preferable to further 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-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butyl phenol), 2-mercaptobenzoimidazole Etc. are useful.

<Dispersants, Fillers, Agglomeration Agents>

In addition to the above, the coloring photosensitive composition includes EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (more than MORISHITA SANGYO KK), DISPERSE AID 6, DISPERSE AID 8, Polymer dispersants such as DISPERSE AID 15 and DISPERSE AID 9100 (manufactured by San Nopco Limited);

Various SOLSPERSE dispersants (manufactured by Zeneca Corporation) such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000;

Fillers such as glass and alumina; And aggregation inhibitors such as sodium polyacrylate.

The coloring photosensitive composition of this invention is a (C) polymerizable monomer, (D) binder resin, and (E) photoinitiator to the solution or dispersion of the color material which has the (A) phthalocyanine frame | skeleton containing the (B) solvent of this invention mentioned above. And (F) The compound represented by General formula (1) can be prepared (preferably with (B) solvent), and it can prepare by mixing other additives, such as surfactant, as needed.

<Color filter and manufacturing method thereof>

The manufacturing method of the color filter of this invention gives the coloring photosensitive composition of this invention mentioned above on a board | substrate, and forms a colored layer, and after exposing the said colored layer in a pattern form, it develops and removes an uncured part with a developing solution, and coloring it. It is characterized by including a step of forming a pattern.

That is, the coloring photosensitive composition of this invention is provided directly on a board | substrate, such as glass, or another layer, for example, by the method of rotational application, slit application, casting | coating, roll coating, inkjet coating, etc., and a colored layer. It forms and exposes the formed colored layer by the method of exposing through a predetermined | prescribed mask pattern, and develops and removes the uncured part with a developing solution after exposure, and the coloring pattern of each color (for example, three or four colors) (for example, For example, by forming a colored pixel, a color filter can be produced most suitably.

Thereby, the color filter used for a liquid crystal display device, an organic electroluminescence display, a solid-state image sensor, etc. can be manufactured with little difficulty in a process, high quality, and low cost.

At this time, as radiation used for exposure, especially ultraviolet rays, such as g line | wire, h line | wire, i line | wire, j line | wire, are preferable.

Moreover, in exposure, the exposure system using a laser light source can be used suitably besides the general proximity exposure system. In the laser exposure method, an ultraviolet light laser is used as the light source. Laser is the acronym for English Light Amplification by Stimulated Emission of Radiation. Oscillators and amplifiers that produce monochromatic light with greater coherence and directivity by amplifying and oscillating light waves by using the phenomenon of induced emission occurring in a material having an inversion distribution, and crystals, glass, liquids, pigments, and gases as excitation media. From these mediums, lasers having an oscillation wavelength in known ultraviolet light such as solid lasers, liquid lasers, gas lasers, and semiconductor lasers can be used. Especially, a solid state laser and a gas laser are preferable from a viewpoint of a laser output and an oscillation wavelength.

As a wavelength which can be used for this invention, the ultraviolet light laser of the wavelength range of 300 nm-380 nm is preferable, More preferably, the ultraviolet light laser of the wavelength of 300 nm-360 nm range is preferable at the point which matches the photosensitive wavelength of a resist. Do.

Specifically, the third high-frequency (355 nm) of the Nd: YAG laser of the solid laser having a large output and relatively low cost, and the XeCl (308 nm) and XeF (353 nm) of the excimer laser can be suitably used.

As exposure amount of a to-be-exposed object (pattern), it is the range of 1mJ / cm <2> -100mJ / cm <2>, and the range of 1mJ / cm <2> -50mJ / cm <2> is more preferable. It is preferable at the point of productivity of pattern formation that an exposure amount is this range.

Although there is no restriction | limiting in particular as an exposure apparatus which can be used for this invention, As what is marketed, LE5565A (made by Hitachi High-Technologies Corporation), Callisto (made by V Technology Co., Ltd.) and EGIS (made by V Technology Co., Ltd.) Or DF2200G (manufactured by Dainippon Screen Mfg. Co., Ltd.) may be used. Moreover, the apparatus of that excepting the above is also used suitably.

It is also possible to use light emitting diodes (LED) and laser diodes (LD) as active radiation sources. In particular, when an ultraviolet source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation markets purple LEDs whose main emission spectrum has wavelengths between 365 nm and 420 nm. When even shorter wavelengths are needed, US Pat. No. 6,084,250 discloses LEDs capable of emitting active radiation centered between 300 nm and 370 nm. In addition, other ultraviolet LEDs are available and can irradiate radiation in different ultraviolet bands. Particularly preferred active radiation sources in the present invention are UV-LEDs, particularly preferably UV-LEDs having a peak wavelength at 340-370 m.

Since the ultraviolet light laser has good parallelism, it can be exposed in a pattern even when a mask is not used at the time of exposure. However, when exposing a pattern using a mask, since the linearity of a pattern becomes further high, it is more preferable.

Drying (prebaking) of the colored layer by the colored photosensitive composition of the present invention imparted on the substrate (preferably applied) is carried out under a condition of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate or an oven. I can do it.

In image development, the uncured part after exposure is eluted to a developing solution, and only a hardened part remains. As image development temperature, it is 20-30 degreeC normally, and as image development time, it is 20 to 90 second.

As the developing solution, any one can be used as long as it dissolves the colored layer of the colored photosensitive composition in the uncured portion and does not dissolve the cured portion. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

As said organic solvent, what was listed as the said solvent which can be used when preparing the pigment dispersion composition or colored photosensitive composition of this invention is mentioned.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium The concentration of the alkaline compounds such as hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001-10% by mass, preferably 0.01? The alkaline aqueous solution melt | dissolved so that it may become 1 mass% is mentioned.

In addition, when alkaline aqueous solution is used as a developing solution, washing | cleaning (rinsing) with water is generally performed after image development.

After image development, excess developer is wash | cleaned and removed, and after drying, heat processing (post-baking) is generally performed at the temperature of 100-250 degreeC.

Post-baking is the heating after image development to make hardening perfect, and usually performs heating (hard baking) of about 200 degreeC-250 degreeC. This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the colored layer after image development may become said condition.

By repeatedly performing the above operation for each color in accordance with the desired number of colors, a color filter in which a colored layer colored with a plurality of colors is formed can be produced.

When providing the colored photosensitive composition of this invention on a board | substrate and forming a colored layer, as a dry thickness of a colored layer, it is generally 0.3 micrometer-5.0 micrometers, Preferably it is 0.5 micrometer-3.5 micrometers, Most preferably, 1.0 micrometer. 2.5 μm.

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices and the like, and a transparent conductive film attached thereto, a photoelectric conversion substrate used for a solid state imaging device, and the like, For example, a silicon substrate etc. and a plastic substrate are mentioned. The black stripe which isolate | separates each pixel may be formed on these board | substrates.

The plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

The gas barrier layer, the solvent-resistant layer, etc. are mentioned as another layer at the time of providing a coloring photosensitive composition through another layer on a board | substrate.

<Liquid crystal display device, organic EL display device>

The color filter of the present invention is particularly suitable as a color filter for liquid crystal display devices and organic EL display devices. A liquid crystal display device and an organic EL display device provided with such a color filter can display high quality images.

The definition of the display device and the description of each display device are described in, for example, "Electronic display device" by Teru Sasaki, Kogyo Chosakai Publishing, Inc. 1990), "Display device (by Ibuki Sumiaki, Sangyo-Tosho 1989) Issuance). In addition, the liquid crystal display device is described, for example in "next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Chosakai Publishing, Inc. 1994 issuance)". There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

The color filter of the present invention is particularly effective for a color TFT type liquid crystal display device. About the liquid crystal display device of a color TFT system, it describes in a "color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd. 1996 issuance), for example." In addition, the present invention can be applied to liquid crystal display devices having an enlarged viewing angle such as lateral electric field driving methods such as IPS and pixel division methods such as MVA, STN, TN, VA, OCS, FFS, and R-OCB.

In addition, the color filter of the present invention can be provided in a bright and high-precision color filter on array (COA) method. In the COA type liquid crystal display device, the required characteristics for the color filter layer are required for the interlayer insulating film, that is, low dielectric constant and peeling liquid resistance, in addition to the usual required characteristics as described above. The color filter of the present invention is considered to improve the transmittance of the ultraviolet light laser which is exposure light by selecting the color and the film thickness of the pixel prescribed by the present invention in addition to the exposure method by the ultraviolet light laser. As a result, the curability of the colored pixel can be improved to form a pixel without missing, peeling, or kink. Thus, particularly the peeling liquid resistance of the colored layer formed directly or indirectly on the TFT substrate is improved, and the liquid crystal display of the COA system is improved. Useful for devices In order to satisfy the required characteristic of low dielectric constant, you may form a resin film on a color filter layer.

Further, in the colored layer formed by the COA method, a rectangular through hole or a U-shape having a length of about 1 to 15 µm on one side in order to conduct the terminal of the ITO electrode disposed on the colored layer and the terminal for driving the substrate below the colored layer. It is necessary to form a conductive path such as a concave portion of the groove, and it is preferable that the dimension of the conductive path (that is, the length of one side) is particularly 5 µm or less, but the conductive path of 5 µm or less is formed by using the present invention. It is also possible.

These image display methods are described, for example, on page 43 of "EL, PDP, LCD display technology and the latest trends in the market" (Research Study Division, Toray Research Center, Inc. 2001).

The liquid crystal display device and the organic EL display device of the present invention are composed of various members, such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle guarantee film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device and an organic EL display device composed of these known members.

For these members, for example, the '94 liquid crystal display peripheral materials and the chemical market (Kenta Shima, CMC Publishing Co., Ltd. 1994), the 2003 liquid crystal related market and future prospects (the lower volume) ( Omote Ryokichi, issued by Fuji Chimera Research Institute Inc. 2003).

Backlights are described in SID meeting Digest 1380 (2005) (A. Konno et al.), Pages 18-24 (Shima Yasuhiro), and pages 25-30 (Yagi Takaaki) of the December 2005 issue of the monthly display.

When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a three-wavelength tube of a conventionally known cold cathode tube, but the red, green, and blue LED light source (RGB-LED) is used as a backlight. A liquid crystal display device having high luminance and good color reproducibility with high color purity can be provided.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. In addition, "%" and "part" are mass references | standards unless there is particular notice.

Synthesis of phthalocyanine pigment

Zinc phthalocyanine was manufactured using phthalodinitrile and zinc chloride as a raw material.

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, after which the reaction mixture was poured into water to precipitate a partially zinc bromide phthalocyanine crude pigment. This aqueous slurry was filtered, washed with warm water at 80 ° C, and dried at 90 ° C to obtain 2.6 parts of purified partially zinc bromide phthalocyanine crude pigment.

1 part of this partial zinc bromide phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol, and 0.09 parts of xylene were added to a double arm kneader and kneaded at 100 ° C for 6 hours. After kneading, the mixture was extracted with 100 parts of water at 80 ° C., and stirred for 1 hour to obtain a partially zinc bromide phthalocyanine pigment obtained by filtration, hot water, drying and pulverization.

The obtained partial zinc bromide phthalocyanine pigment had an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) from halogen content analysis by mass spectrometry, and contained an average of 10 bromine and 4 chlorine in one molecule.

In addition, the average primary particle diameter measured by the transmission electron microscope (JEOL Co. Ltd. product, JEM-2010) was 65 nm.

Synthesis of Quinophthalone Compound

Quinophthalone pigment (4,5,6,7-tetrachloro-2- [2- (4,5,6,7-tetrachloro-2,3-dihydro-1,3-dioxo-1H-indene -2-yl) -8-quinolinyl] -1H-isoindole-1,3 (2H) -dione (BALI Corporation, "PALIOTOL" YELLOW K0961HD) 10g fuming lactic acid (25%) with stirring 10 g SO3) was added in 130 g. After stirring for 3 hours, it was added to 250 g of ice. After standing for 30 minutes, the resulting suspension was filtered and the resulting product was washed with 50 ml of water.

The product was added to 330 ml of water, and neutralized with an aqueous ammonia solution (added with an aqueous ammonia solution until pH reached 7). 75 g of ammonia chloride was added, the mixture was stirred at 80 ° C for 30 minutes, and the precipitate deposited was filtered at 60 ° C. After wash | cleaning the obtained wet crystal | crystallization with water, it dried at 80 degreeC and obtained the ammonium salt (3) of 17 g of quinophthalone derivative sulfonates.

The ammonium salt (3) of this quinophthalone derivative sulfonate was heat-treated at 180 degreeC for 3 hours, and 16g (yield 94%) of quinophthalone derivative sulfonates (compound (4) below) which ammonium salt was removed.

To 10 g of the compound (4) obtained above, 2.2 g of oxalyl chloride (from Wako Pure Chemical Industries) and 1 mL of N, N-dimethylformamide (from Wako Pure Chemical Industries) were added under ice cooling in chloroform, and the mixture was heated at 50 ° C for 2 hours. Stirred. The reaction mixture was added to 150 mL of water in an ice bath, and the precipitated crystals were filtered to yield 7.4 g of a sulfonic acid chloride compound (the following compound (5)). (Yield 72%)

To 5.0 g of the compound (5) obtained above, 0.9 g of 6-chloro-1-hexylamine (manufactured by Rare Chemicals) was added under ice cooling in chloroform, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 150 mL of water, and the precipitated crystals were filtered, washed with water, and dried under reduced pressure to obtain 4.3 g of a sulfoamide alkyl chloride compound (Compound (6)). (Yield 76%)

An excess amount of water and anhydrous sodium sulfite (manufactured by Kanto Chemical Co., Inc.) was added to 4.3 g of the compound (6) obtained above, and the mixture was heated at 180 ° C in an autoclave for 12 hours. After allowing to cool, the crystals were filtered to obtain 3.7 g of a sulfoamide alkyl sulfonic acid compound (compound (7) below). (Yield 82%)

Synthesis of Resin (J-1)

(1) Synthesis of Resin (i-1)

6.4 g of n-octanoic acid, 200 g of epsilon -caprolactone, and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1).

The synthetic scheme is shown below.

(2) Synthesis of Resin (J-1)

10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai Co Ltd, Ltd.) and 100 g of polyester resin (i-1) were mixed and heated at 120 ° C. for 3 hours to obtain an intermediate (J-1B). Thereafter, the mixture was allowed to cool to 65 ° C, and 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, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PGMEA) was added to obtain a 10 mass% PGMEA solution of resin (J-1). Resin (J-1) has a side chain derived from polyester resin (i-1), and a carboxyl group derived from succinic anhydride.

The synthetic scheme is shown below.

Preparation of pigment dispersion liquid of phthalocyanine pigment PG58

11.9 parts of the partially zinc bromide phthalocyanine pigment (called PG58), 3.1 parts of compound (7) as a quinophthalone compound, 9.0 parts of SOLSPERSE 24000GR (manufactured by Lubrizol Japan Limited) as a dispersant, 76 parts of PGMEA as a solvent, and then sand grinder The pigment dispersion liquid of PG58 was obtained by dispersing with wheat for 3 hours. When the viscosity of the obtained pigment dispersion liquid of PG58 was measured with the E-type viscosity meter, it was confirmed that it is very stable at 9.2 mPa * s and favorable dispersibility is obtained.

Preparation of Pigment Dispersion PY150 Containing Yellow Pigment PY150

A mixture of 40 parts (average primary particle diameter of 60 nm) and 223 parts of PGMEA 10% by mass solution (22.3 parts in terms of solid content) of C. I. pigment yellow 150 (PY150) as a yellow pigment. Was mixed and dispersed for 3 hours with a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion containing yellow pigment PY150.

Preparation of Pigment Dispersion Containing Yellow Pigment PY138

As a yellow pigment, C. I. Pigment Yellow 138 (PY138) was mixed with 40 parts (average primary particle diameter of 60 nm) and 223 parts (22.3 parts of solid content equivalent) of PGMEA 10% by mass solution of the resin (J-1). The pigment dispersion liquid containing yellow pigment PY138 was prepared by mixing and disperse | distributing for 3 hours with the bead mill (zirconia beads 0.3mm diameter).

Preparation of Pigment Dispersion Containing Green Pigment PG36

As a green pigment, 40 parts (average primary particle diameter of 60 nm) of C.I. pigment green 36 (PG36) and 200 parts (20 parts of solid content conversion) of PGMEA 10 mass% solution of resin (J-1) were beads. It was mixed and dispersed for 3 hours with a mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion containing green pigment PG36.

About the obtained pigment dispersion, the average primary particle diameter of the pigment was 25 nm when it measured using the dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (made by NIKKISO CO., LTD.)).

Synthesis of Compound 1 as a Photopolymerization Initiator

(1) Synthesis of Compound A

First, compound A was synthesize | combined with the following scheme.

Ethylcarbazole (100.0 g, 0.512 mol) is dissolved in 260 ml of chlorobenzene, cooled to 0 ° C. and aluminum chloride (70.3 g, 0.527 mol) is added. Subsequently, o-toluyl chloride (81.5g, 0.527mol) was dripped over 40 minutes, it heated up to room temperature and stirred for 3 hours. Then, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) was added. 4-chlorobutyryl chloride (79.4g, 0.563mol) was dripped over 40 minutes, it heated up to room temperature and stirred for 3 hours. The mixed solution of 156 ml of 35% hydrochloric acid aqueous solution and 392 ml of distilled water was cooled to 0 ° C, and the reaction solution was added dropwise. The precipitated solid was filtered off with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (amount 164.4 g, yield 77%) having the following structure.

(2) Synthesis of Compound B

Then, compound B was synthesized using the compound A in the following scheme.

Compound A (20.0 g, 47.9 mmol) was dissolved in 64 ml of tetrahydrofuran (THF), and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol) were added. Then, sodium hydroxide (2.0 g, 50.2 mmol) was added to the reaction solution, and the mixture was refluxed for 2 hours. Then, after cooling to 0 ° C, sodium methylate 28% methanol solution (Nippon Shokubai Co Ltd, product: SM-28) (11.1 g, 57.4 mmol) was added dropwise over 20 minutes, and the temperature was raised to room temperature. It stirred for hours. Then, after cooling to 0 degreeC, nitrous acid isopentyl (6.73 g, 57.4 mmol) was dripped over 20 minutes, it heated up to room temperature and stirred for 3 hours. The reaction solution was diluted in 120 ml of acetone and added dropwise to an aqueous 0.1N hydrochloric acid solution cooled to 0 ° C. The precipitated solid was filtered off with suction, and then washed with distilled water. Subsequently, it recrystallized with acetonitrile and the compound B (amount 17.0g, yield 64%) of the following structure was obtained.

(3) Synthesis of Compound 1

Subsequently, compound 1 was synthesize | combined using the compound B by the following scheme.

Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml of N-methylpyrrolidone and triethylamine (3.94 g, 38.9 mmol) was added. Then, after cooling to 0 degreeC, acetyl chloride (3.05g, 38.9 mmol) was dripped over 20 minutes, Then, it heated up to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was filtered off with suction, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then Compound 1 (amount 19.5 g, yield 99%) having the following structure: )

(Example 1)

<Preparation of a colored photosensitive composition>

The component shown in the following composition 1 was stirred and mixed, and the coloring photosensitive composition of Example 1 was prepared.

(Composition 1)

(A) Pigment Dispersion 1: 36.6 parts of pigment dispersion comprising green pigment PG58

Pigment dispersion 2: 12.6 parts pigment dispersion containing yellow pigment PY150

(B) Solvent: PGMEA Part 25.8

(B) Solvent: 16.7 parts of 3-ethoxyethyl propionate

(D) Binder resin (allyl methacrylate-methacrylic acid (= copolymerization molar ratio 8: 2) copolymer, weight average molecular weight 30000) 1.76 parts

(C) Polymerizable Monomer: 3.77 parts of ARONIX M-520 (manufactured by Toagosei Co., Ltd., acid-modified polyfunctional acrylate compound)

(E) Photoinitiator 1: 0.71 parts of IRGACURE OXE-01 from Ciba Specialty Chemicals Inc.

(E) Photoinitiator 2: 2-chlorophenyl-4,5-bisphenylimidazole dimer (manufactured by HODOGAYA CHEMICAL CO., LTD., B-CIM) 0.35 parts

Photosensitizer: 0.49 parts of the following Compound III

Photosensitizer: 0.11 part of N-phenyl mercaptobenzimidazole

(F) Specific Additives: 1.80 parts of 4,4'-azoxystyrene

Surfactant: Fluorine-based surfactant, manufactured by DIC Corporation, 0.033 parts of MEGAFACE F781-F

The structure of IRGACURE OXE-01 and compound III used above is shown below.

<Formation of a Colored Pattern Using a Colored Photosensitive Composition>

The coloring pattern was formed on the glass substrate as follows using the coloring photosensitive composition obtained by the above.

Formation of Colored Photosensitive Composition Layer

The obtained colored photosensitive composition was applied to a glass substrate (Corning Incorporated, Millennium, 0.7 mm thickness). Specifically, the interval between the slit nozzle and the substrate and the discharge amount were adjusted so as to be about 2.4 µm after drying of the colored photosensitive composition layer after postbaking, and the coating speed was applied at a coating speed of 120 mm / second.

Prebaking Process

Next, the colored photosensitive composition layer was dried in a vacuum drying apparatus until the degree of vacuum reached 66 Pa, and then heated (prebaked treatment) at 90 ° C. for 120 seconds using a hot plate.

Exposure process (proxy exposure)

After prebaking process, it exposed at 40 mJ / cm <2> using the proximity exposure machine (the LE5565A by Hitachi High-Technologies Corporation).

Development Process, Baking (Post Baking) Process

Then, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0% developer (1 part of CDK-1, pure water 99) of potassium hydroxide-based developer CDK-1 (manufactured by Fujifilm Electronics Materials Co., Ltd.) was used. Negative dilution liquid, 25 ° C) was developed for 60 seconds at a shower pressure of 0.2 MPa and washed with pure water.

After drying sufficiently, it was post-baked for 40 minutes in 230 degreeC oven.

(Examples 2-25, Comparative Examples 1-14)

In the composition 1 of Example 1, the kind of pigment dispersion liquid, the kind of photoinitiators 1 and 2, the kind of specific additive, and the addition amount were changed as shown in Table 1, and the Example was carried out similarly to Example 1 except for it. 2-25 and each coloring photosensitive composition of Comparative Examples 1-14 were prepared. In addition, the coloring pattern was produced like Example 1 except having changed the exposure system in an exposure process as shown in Table 1 using each obtained coloring photosensitive composition.

In Table 1, the detail of the exposure system shown as a proxy is the exposure system (proxy exposure) applied by the exposure process in Example 1. FIG. In addition, the detail of the exposure system represented by a laser in Table 1 is as follows.

Exposure process (laser exposure)

After the prebaking treatment, a pulse of about 1 mJ / cm 2 was applied to the surface of the colored photosensitive composition layer, using EGIS (V Technology Co., Ltd. product, YAG laser's third high frequency wavelength 355 nm, pulse width 6 nsec) as the prebaking treatment. The investigation was performed 20 times through a photomask.

In Tables 1-3, PG58, PG36, PB15: 6, PY150, and PY138 of the compartment of a pigment dispersion liquid represent the said pigment dispersion liquid containing each pigment. The two types described used the same amount as the pigment dispersion of PG58 in Example 1, and the pigment dispersion of PY150, respectively. In addition, in Example 19 and the comparative example 12, the pigment dispersion liquid of PG36 was substituted and used for the pigment dispersion liquid of PG58 in Example 1. In addition, in Examples 20-23 and the comparative example 13, the pigment dispersion liquid of PY138 was substituted and used for the pigment dispersion liquid of PY150 in Example 1. In addition, in Example 7, Example 24, Example 25, and the comparative example 14, it showed that the pigment dispersion liquid of a single pigment was used, and it adjusted so that a pigment content may be mass and it may be equal to the sum total of the pigment content of Example 1.

In addition, in Tables 1-3, "-" shows not adding, G shows the green coloring photosensitive composition, and B represents the blue coloring photosensitive composition, respectively.

The use of two photosensitizers in the compartment of the photosensitizer is the same as the photosensitizer in Example 1, but the photosensitization in Examples 11 to 13, 16 to 18, 22, and 23 using only one type. The amount of the agent is the same as the amount of N-phenylmercaptobenzimidazole added in Example 1.

In addition, the usage-amount of the other additive (uv absorber: octyl-5-N, N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate) in Examples 13 and 18 is 0.27 mass part. .

In addition, the 4,4'- azoxy styrene, the ethyl 4,4'- aoxy cycinnamate used in the Example and the comparative example, methyl 4,4'- aoxy cycinnamate have a polymerizable group, correspond to the specific additive of this invention, , Azoxybenzene, azoxyphenitol do not have a polymerizable group and do not correspond to the specific additive of the present invention.

Moreover, the structure of the compound 2 and the compound 3 which are photoinitiators is shown below.

<Evaluation>

About each color pattern obtained, each item of shape, light resistance, heat resistance, and solvent resistance was evaluated. Evaluation methods and evaluation criteria are shown below.

The evaluation results are collectively shown in Table 4.

1-1. Evaluation of the coloring pattern shape

(1) linearity

Evaluation of the coloring pattern shape was evaluated by the linearity and the missing part of the edge part of a coloring pattern. The edge part of a coloring pattern was photographed in the reflection mode 200 times using the optical microscope, and the pixel edge part was observed in the 5 cm x 5 cm photograph, and the following reference | standard evaluated.

Straightness Evaluation Criteria

(Circle): The edge part of a coloring pattern looks linear.

×: part or all of the coloring pattern is jagged

It is preferable that the edge part of a coloring pattern is linear.

That is, when the edge part of a coloring pattern becomes jagged based on a residual film, an undercut, etc., when forming the coloring pattern (pixel pattern) of a color filter with the coloring photosensitive composition of this invention, superimposition with a black matrix is prevented. It is necessary to make it large, and the width of the black matrix becomes wider, and the aperture ratio decreases. In addition, when the overlapping with the black matrix is not large, there is a fear that there is no colored pattern and voids are generated near the edge of the black matrix. In addition, when the edge portion of the colored pattern is jagged, a practical problem occurs such that the transparent electrode formed thereon is disconnected and the resistance value is increased.

1-2. Evaluation of the coloring pattern shape

(2) Missing

The fall of a coloring pattern evaluated each color filter obtained by the above by taking the edge part of a coloring pattern with a photograph in 200 times of reflection mode using the optical microscope, and performed the deletion by the following reference | standard. Here, in the case of missing, either (A) half-moon-shaped edge part disappears, (B) (A) thinner or longer than it is seen, but the line width is discontinuously thinner than the periphery, or any of the shapes recognized as missing. Even if it was observed. In this evaluation, it was said that there was a missing case when even one missing case was seen.

If a deletion occurs, the part is white and light is missing, which is not practically desirable.

Eligibility criteria

(Circle): (1) The shape of a coloring pattern is a forward taper or a rectangle, and (2) no missing is seen.

X: At least 1 item of the items of said (1) and (2) does not correspond.

1-3. Evaluation of the coloring pattern shape

(3) pattern shape comprehensive evaluation

In consideration of the two items of the linearity and missing, the evaluation of the shape was comprehensively evaluated by the following evaluation criteria.

-Pattern shape general evaluation standard-

○: in evaluation of both linearity and missing ○

(Triangle | delta): Any one item of linearity and a missing thing is a thing of evaluation.

×: Not all of the evaluations ○ in both linearity and missing

2-1. Reliability Assessment

(1) light resistance

The post-baking of the glass substrate in which the coloring pattern after completion | finish of image development process was formed was carried out by 230 degreeC x 30 minutes in the convection oven. The chromaticity of the substrate was measured by OSP-SP100 (Olympus Corporation), after which it was degassed under nitrogen substitution and encapsulated in a cell.

The enclosed substrate was put into a xenon weather meter "Sx-75" (Suga Test Instruments Co., Ltd.), and 180W 120 hours from the glass surface side under the conditions of temperature 30 degreeC, humidity 50%, and black panel temperature 63 degreeC. I did an investigation.

Then, the chromaticity of the board | substrate was measured by OSP-SP100 (Olympus Corporation), and (DELTA) E * ab was calculated | required from the chromaticity of the coloring pattern before and behind irradiation.

In this evaluation, it was evaluated that (DELTA) E * ab was 3.0 or less that it was excellent in light resistance.

2-2. Reliability evaluation

(2) heat resistance

In the same manner as in the evaluation of light resistance, the glass substrate having the colored pattern after postbaking was further heated in a convection oven for 230 ° C. × 40 minutes.

Then, the chromaticity of the board | substrate was measured with OSP-SP100 (Olympus Corporation), and (DELTA) E * ab was calculated | required from the chromaticity of the coloring pattern before and after a reheating process.

In this evaluation, it was evaluated that (DELTA) E * ab was 3.0 or less that it was excellent in heat resistance.

3. Evaluation of solvent resistance

The chromaticity of the glass substrate which has a coloring pattern after postbaking similarly to the said reliability evaluation was measured by OSP-SP100 (Olympus Corporation), and N-methyl- 2-pyrrolidone (it abbreviates as "NMP" hereafter). Was immersed at 23 degreeC for 30 minutes, and (DELTA) E * ab was calculated | required from the chromaticity of the coloring pattern before and behind immersion. Chromaticity was measured by OSP-SP100 (Olympus Corporation). Moreover, the change of the shape with the coloring pattern before and after immersion in NMP was observed by optical microscope observation.

The fact that ΔE * ab is 3 or more and shows a change in shape is insufficient in various solvent resistances that can be used for panel processing in the production of a liquid crystal display device and the like, which is a problem in practical use.

About the obtained result, it evaluated by the following evaluation criteria.

-Evaluation standard-

○: (1) ΔE * ab is 3.0 or less, and (2) no change was observed in the shape of the colored pattern.

X: At least 1 item of the items of said (1) and (2) does not correspond.

4. Comprehensive Evaluation

-Evaluation standard-

(Circle): (1) Evaluation of pattern shape and solvent resistance is (circle), and (2) All (DELTA) E * ab in light resistance evaluation and heat resistance evaluation are 3.0 or less.

X: At least 1 item of the items of said (1) and (2) does not correspond.

As shown in Table 4, each colored pattern obtained using the colored photosensitive composition of the Example was excellent in linearity, the shape was also good, there was no fallout, and also the various reliability and solvent resistance were favorable. On the other hand, in each coloring pattern obtained using the coloring photosensitive composition of Comparative Examples 1-14, (DELTA) E * ab before and after light resistance or heat resistance exceeded 3.0, and reliability deteriorated.

Since the azoxy compound which does not correspond to the specific additive of this invention which does not have a polymeric group from Comparative Examples 2-5, 7, 8, 10, and 11 has a light resistance improvement effect, but is accompanied by discoloration and decomposition in a heating process, It was a result of deterioration of heat resistance. Moreover, it turns out that the azoxy compound which is a specific additive in this invention improves light resistance, is effective also in heat resistance improvement, and can realize reliability comprehensively.

In addition, according to the contrast between Example 2 and Example 1, the same good results were obtained in all of the examples, and this also showed the excellent effect of the present invention as in the case of applying the pattern exposure by the laser exposure machine, similarly to the exposure by the high-pressure mercury lamp. It can be seen that it is obtained.

Claims (10)

(A) Colorant which has a phthalocyanine frame | skeleton, (B) solvent, (C) polymerizable monomer, (D) binder resin, (E) photoinitiator, and (F) containing compound represented by following General formula (1) The coloring photosensitive composition characterized by the above-mentioned.

[In General Formula (1), R <^1> and R <^2> represents a divalent tetravalent coupling group each independently, Y <^1> and Y <^2> respectively independently represent a single bond, an oxygen atom, an ester group, 2 or more carbon atoms, and 30 The following alkylene group, a C6 or more, 30 or less divalent aromatic group, a polyethyleneglycol group, or a bivalent coupling group formed by combining two or more types is shown. P ¹ and P ² each independently represent a polymerizable group. m and n each independently represent an integer of 1 or more and 3 or less] The method of claim 1,
Content of the compound represented by said (F) General formula (1) is 0.1 mass% or more and 5.0 mass% or less with respect to the total solid of a composition, The coloring photosensitive composition characterized by the above-mentioned. The method of claim 1,
In the general formula (1), at least one of the polymerizable groups represented by P ¹ and P ² is a polymerizable group selected from acryloyl group and methacryloyl group. The method of claim 1,
The coloring material which has said (A) phthalocyanine frame | skeleton contains the coloring material containing a metal in a molecule | numerator. The coloring photosensitive composition characterized by the above-mentioned. The method of claim 1,
The coloring material which has said (A) phthalocyanine frame | skeleton contains a green pigment, The coloring photosensitive composition characterized by the above-mentioned. The method of claim 1,
The coloring material which has said (A) phthalocyanine frame | skeleton contains C. I. pigment green 7, C. I. pigment green 36, or C. I. pigment green 58. The coloring photosensitive composition characterized by the above-mentioned. The process of providing the coloring photosensitive composition of any one of Claims 1-6 on a board | substrate, and forming a colored layer;
And exposing the colored layer in a pattern, and then developing and removing the uncured portion with a developer to form a colored pattern. The color filter manufactured by the manufacturing method of the color filter of Claim 7. A liquid crystal display device comprising the color filter according to claim 8. An organic EL display device comprising the color filter according to claim 8.