TW201300950A - Coloring photosensitive composition, color filter and fabricating method thereof, liquid crystal display device, and organic electroluminescent display device - Google Patents

Abstract

A coloring photosensitive composition is provided, which obtains excellent photo resistivity and thermal resistivity while sustaining good pattern formability. The coloring photosensitive composition contains: (A) a pigment having a body frame of phthalocyanine, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, (E) a photopolymerization initiator, and (F) a compound represented by the following formula (1). In formula (1), R1 and R2 independently represent 2-valent to 4-valent connecting groups respectively, Y1 and Y2 independently represent 2-valent connecting groups respectively, P1 and P2 independently represent polymerizable groups respectively, m and n independently represent integers of 1 or more and 3 or less respectively. Formula (1)

Description

Coloring photosensitive composition, color filter, manufacturing method thereof, liquid crystal display device, and organic EL display device

The present invention relates to a coloring photosensitive composition, a method of 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.

In the case of a small liquid crystal display device such as a mobile phone, a mobile game machine, or a PDA, or an organic EL display device, it is necessary to use a backlight having a capacitance limitation such as a battery or a dry battery. Therefore, the color filter used in these display devices is used. In the color material of the light sheet, it has been advantageous to use a color material having high brightness and allowing the bright line of the backlight to pass through well to perform color display.

In recent years, the increase in size of liquid crystal display devices and organic EL display devices has progressed in applications such as displays for personal computers and televisions, and RGB color reproduction has been emphasized in these display devices. Therefore, in addition to the previous brightness improvement, the color filter of the color filter requires a higher image quality, that is, an improvement in contrast and color purity.

In the pigment composition in which the particle size of the pigment is further refined, the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, and other components are further used as the coloring photosensitive composition, and the coloring is used. The photosensitive composition is formed into a color filter of a colored pattern such as red, green, or blue on a transparent substrate such as glass by a photolithography method or the like, and is put into practical use.

From the viewpoint of color tone and fastness, a green pigment such as a copper chloride phthalocyanine pigment (C.I. Pigment Green 7) or a copper bromide phthalocyanine pigment (C.I. Pigment Green 36) is usually used in the green coloring pattern. In recent years, in order to improve the color (color purity and color density) of pigments, polyhalogenated metal phthalocyanine pigments in which the central metal is not copper but aluminum, titanium, cobalt, nickel, zinc, tin, lead, etc., have been studied. It is a polybromide phthalocyanine pigment (CI Pigment Green 58, etc.) having a high chroma, and various pigments have been proposed. For example, the degree of substitution of Br and Cl is carried out (for example, refer to JP-A-2003-161823, JP-A-2007-284592), or a pigment treatment method using a betaine-type surfactant, and various crystal forms. A detailed study, etc., reports the color of polyhalogenated copper phthalocyanine having a maximum diffraction peak at 26.4° or 25.5° for the Bragg angle of the Cu-Kα line (2θ ± 0.2°) in the X-ray diffraction spectrum. The degree (color purity and color density) is high and is excellent in stability over time (for example, refer to JP-A-2008-24743). Further, it has been proposed to use these pigments to obtain a color filter having high transparency and high color purity.

On the other hand, the color filter must have various reliability in order not to be discolored or discolored by the light of the backlight or the heat of irradiation. In order to improve the reliability, a color-sensitive photosensitive composition which has been improved by the coloring matter itself has been reported (for example, refer to Japanese Patent Laid-Open No. 2008-138037, Japanese Patent Laid-Open No. 2009-149779, and Japanese Patent Laid-Open No. 2009-215380 A coloring photosensitive composition of a compound such as a matting agent or a light stabilizer is added (for example, see JP-A-2000-214580, JP-A-2004-139050). Further, in order to reduce the loss of the matting agent or the light stabilizer in the processing step, a polymerizable monomer or a polymer having a function of improving reliability has been reported (for example, refer to Japanese Patent Laid-Open No. 2004-155812, Japanese Patent Laid-Open Bulletin 2010-54808).

In general, when compared with a pigment, dye heat resistance and light resistance are inferior, and the reliability of the dye is particularly actively repeated. However, it is known that even if the pigment is refined to improve the brightness, the reliability is deteriorated, and it is necessary to improve the reliability of the pigment as described above while maintaining the characteristics of high transparency and high color purity.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a coloring photosensitive composition which can obtain excellent light resistance and heat resistance while maintaining good pattern formability. Further, the coloring photosensitive composition is used to provide a method for producing a color filter having excellent color characteristics, a color filter, and a liquid crystal display device and an organic EL display device including the color filter.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems are remarkably improved by the following means, and the present invention has been achieved.

<1> A colored photosensitive composition comprising: (A) a pigment having a phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, and (E) photopolymerization initiation And (F) a compound represented by the following formula (1);

[Chemical 1]

[In the general formula (1), R ¹ and R ² each independently represent a divalent to tetravalent linking group, and Y ¹ and Y ² each independently represent a single bond, an oxygen atom, an ester group, and have a carbon number of 2 or more. a divalent aromatic group having a carbon number of 30 or less, a divalent aromatic group having a carbon number of 6 or more and 30 or less, a polyethylene glycol group, or a combination of a plurality of such groups; P ¹ and P ² are each independently The ground indicates a polymerizable group; m and n each independently represent an integer of 1 or more and 3 or less].

The coloring photosensitive composition according to the above-mentioned item (1), wherein the content of the compound represented by the formula (1) is 0.1 wt% or more and 5.0 based on the total solid content of the composition. Below wt%.

(3) The colored photosensitive composition according to the above formula (1), wherein at least one of the polymerizable groups represented by P ¹ and P ² is selected from the group consisting of acrylonitrile groups and A polymerizable group of a methacrylonitrile group.

<4> The colored photosensitive composition according to <1>, wherein the (A) coloring matter having a phthalocyanine skeleton contains a coloring material containing a metal in a molecule.

<5> The colored photosensitive composition according to <1>, wherein the (A) coloring matter having a phthalocyanine skeleton contains a green pigment.

The colored photosensitive composition according to any one of the above aspects, wherein the (A) coloring matter having a phthalocyanine skeleton comprises CI Pigment Green 7, CI Pigment Green 36, or CI Pigment Green 58.

(7) A method of producing a color filter, comprising: applying a coloring photosensitive composition according to any one of <1> to <6> to a substrate to form a coloring layer; After the layer is exposed as a pattern, the uncured portion is developed and removed by a developing solution to form a colored pattern.

<8> A color filter manufactured by the manufacturing method according to <7>.

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

<10> An organic EL display device comprising the color filter according to <8>.

[Effects of the Invention]

According to the present invention, it is possible to provide a coloring photosensitive composition which can obtain excellent light resistance and heat resistance while maintaining good pattern formability. Further, the coloring photosensitive composition can provide a method for producing a color filter having excellent color characteristics, a color filter, and a liquid crystal display device and an organic EL display device including the color filter.

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

<Coloring photosensitive composition>

The colored photosensitive composition of the present invention is characterized by containing at least (A) a pigment having a phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, and (E) photopolymerization initiation. And (F) a compound represented by the formula (1).

Hereinafter, each component contained in the colored photosensitive composition of the present invention will be described.

<(A) Colorant having a phthalocyanine skeleton>

In the coloring photosensitive composition of the present invention, a coloring matter having a phthalocyanine skeleton is used as a coloring material, and thus a color filter having high color purity or high contrast is obtained.

The coloring matter having a phthalocyanine skeleton has 16 hydrogen atoms in the phthalocyanine ring, so that the hydrogen atoms can be substituted with up to 16 bromine atoms and/or chlorine atoms. These halogen atoms may be all the same or different.

The number of substitution of the halogen atom is preferably 8 or more and 16 or less, and more preferably 10 or more and 16 or less.

As a coloring material having a phthalocyanine skeleton in the present invention, a green pigment having a phthalocyanine skeleton is substituted with eight or more bromine atoms, and thus has a yellow color with a high brightness, and is suitable for use in a green color filter. Graphic pattern. In particular, a coloring matter having a bromine atom having 10 to 16 phthalocyanine skeletons has a higher brightness, and therefore can be suitably used in the present invention.

Further, in the present invention, as a coloring material having a phthalocyanine skeleton, a blue pigment having a phthalocyanine skeleton is also preferable.

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

The metal is not particularly limited as long as it can maintain the stability of the coloring material, and is preferably copper, aluminum, titanium, cobalt, nickel, zinc, tin, lead, etc., and further preferably contains zinc from the viewpoint of chromaticity. .

The phthalocyanine pigment can be produced, for example, by various known production methods such as a chlorosulfonic acid method, a halogenated phthalonitrile method, and a melting method. A more specific production method is described in detail in Japanese Laid-Open Patent Publication No. 2008-19383, Japanese Patent Laid-Open No. Hei. No. 2007-320986, and Japanese Patent Laid-Open No. 2004-70342.

Among these production methods, the zinc halide phthalocyanine pigment disclosed in Japanese Laid-Open Patent Publication No. 2004-70342, which is simple in the production process, is preferred from the viewpoint of cost. Further, in terms of stability, it is related to a combination method of other additives or post-treatment, but a zinc halide phthalocyanine pigment which has undergone crystallization conversion disclosed in Japanese Laid-Open Patent Publication No. 2008-19383 is preferable. Further, in particular, in order to improve the dispersibility, a resin-coated zinc halide phthalocyanine pigment disclosed in Japanese Laid-Open Patent Publication No. 2007-320986 is a preferred embodiment.

Examples of the coloring material having a phthalocyanine skeleton of the present invention include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, and the like, and examples of the blue pigment include CI Pigment Blue 15 and CI Pigment Blue 15:1. , Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:6, etc. The coloring material having a phthalocyanine skeleton may be used in combination of two or more kinds.

Among these pigments, the coloring matter having a phthalocyanine skeleton preferably contains C.I. Pigment Green 7, C.I. Pigment Green 36, or C.I. Pigment Green 58.

The average primary particle diameter of the phthalocyanine pigment of the present invention is preferably in the range of 10 nm to 100 nm, and more preferably in the range of 10 nm to 70 nm. By using a phthalocyanine-based pigment having an average primary particle diameter in this range, a coloring photosensitive composition for a color filter having excellent dispersibility stability or coloring power, high luminance, and high contrast can be obtained.

Further, in the average primary particle diameter in the present invention, a particle in a field of view is imaged by a transmission electron microscope, and a total of 100 primary particles of a phthalocyanine pigment constituting an aggregate on a two-dimensional image are obtained. The average value of the diameter (long diameter) and the short diameter (short diameter) and averaged them.

When the aspect ratio of the vertical and horizontal aspect ratio of the primary particles of the phthalocyanine pigment of the present invention is further in the range of 1 to 3, the viscosity characteristics are improved in each application field, and the fluidity is further increased. When the aspect ratio is obtained, the particles in the field of view are imaged using a transmission electron microscope or a scanning electron microscope in the same manner as in the case of obtaining the average particle diameter of the primary particles as described above. Next, a total of 100 primary particles of a phthalocyanine pigment constituting an aggregate on a two-dimensional image were obtained, and an average value of a long diameter (long diameter) and a short diameter (short diameter) was obtained and calculated using these values.

When a phthalocyanine pigment having an average primary particle diameter of 10 nm to 100 nm is obtained, it may be a phthalocyanine pigment formed by micronization by any method, whereby crystal growth can be easily suppressed, and an average primary particle diameter comparison is obtained. In terms of small pigment particles, it is preferred to employ a solvent salt milling treatment.

The solvent salt polishing means that the phthalocyanine pigment, the inorganic salt, and the organic solvent are kneaded and kneaded. The phthalocyanine pigment having a large particle size can also be subjected to solvent salt polishing after dry grinding. Specifically, a phthalocyanine pigment, an inorganic salt, and an organic solvent insoluble therein are charged into a kneading machine, and kneading is carried out therein. As the kneading machine at this time, for example, a kneader or a mix muller or the like can be used.

As the inorganic salt, a water-soluble inorganic salt can be suitably used, and for example, an inorganic salt such as sodium chloride, potassium chloride or sodium sulfate is preferably used. Further, it is more preferred to use an inorganic salt having an average particle diameter of 0.5 μm to 50 μm. Such an inorganic salt can be easily obtained by finely pulverizing a usual inorganic salt.

When a phthalocyanine pigment having an average primary particle diameter of 10 nm to 100 nm is obtained, it is preferred to increase the ratio of the amount of the inorganic salt used in the solvent salt polishing to the amount of the phthalocyanine pigment used. In other words, the amount of the inorganic salt used is preferably 5 parts to 20 parts, more preferably 7 parts to 15 parts, per part by weight of the phthalocyanine pigment.

The organic solvent is preferably an organic solvent which inhibits crystal growth, and such an organic solvent may suitably be a water-soluble organic solvent, for example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polymerization may be used. Propylene glycol, 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol monomethyl ether, diethyl 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.

The amount of the water-soluble organic solvent to be used in this case is not particularly limited, and is from 0.01 part by weight to 5 parts, preferably from 0.8 part to 2 parts, per part by weight of the phthalocyanine pigment.

The temperature at the time of solvent salt polishing is preferably from 30 ° C to 150 ° C, and more preferably from 80 ° C to 100 ° C. The solvent salt polishing time is preferably from 5 hours to 20 hours, more preferably from 8 hours to 18 hours.

Thus, a mixture containing a phthalocyanine pigment, an inorganic salt, and an organic solvent as a main component is obtained, and the organic solvent and the inorganic salt are removed from the mixture, and the solid matter mainly composed of the phthalocyanine pigment is washed, filtered, and dried, if necessary. A powder of fine phthalocyanine pigment can be obtained by pulverization or the like.

Any type of washing can be washed with water or hot water. The number of times of washing can be repeated in the range of 1 to 5 times. When the mixture of the water-soluble inorganic salt and the water-soluble organic solvent is used, the organic solvent and the inorganic salt can be easily removed by washing with water.

The above-mentioned filtration separation and drying after washing include, for example, batch or continuous dehydration and/or solvent removal of the pigment by heating at 80 ° C to 120 ° C using a heating source provided in a dryer. For the drying of the type, etc., the dryer usually has a box dryer, a belt dryer, a spray dryer, and the like. Further, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, for example, when a box dryer or a belt dryer is used for drying, when the pigment becomes a lamp or the like, In the case where the pigment is dispersed and powdered, for example, pulverization using a mortar, a hammer mill, a disk mill, a pin mill, a jet mill, or the like can be mentioned.

The coloring agent having the phthalocyanine skeleton of (A) of the present invention can be obtained, for example, by the above method, but a pigment or a pigment dispersion liquid which is usually distributed can also be used.

The coloring agent having the phthalocyanine skeleton (A) thus obtained has a property that the cohesive force of the primary particles is weak and is more likely to spread, so that the covering power is increased, and it is easy to produce a high-contrast coloring film.

In the present invention, these phthalocyanine pigments may be used singly or in combination of two or more. Further, in the case of use in combination, other halogenated phthalocyanine pigments having different bromination ratios or chlorination ratios or brominated phthalocyanines having different central metals may be used in combination. By changing the bromination rate and the chlorination rate or changing the center metal to change the color tone of the pigment, it is expected that the change in the color tone that can be reproduced is increased.

In the coloring photosensitive composition of the present invention, the other coloring materials can be combined with the coloring material having the phthalocyanine skeleton (A), and the color tone of the coloring photosensitive composition can be adjusted to increase the transmittance.

For example, in order to form a green pixel, a yellow pigment or an orange pigment may be used in combination with a phthalocyanine green pigment. Examples of the yellow pigment include a yellow pigment such as a disazo yellow pigment, an isoporphyrin yellow pigment, a quinophthalone yellow pigment, a benzimidazolone yellow pigment, or a nickel azo yellow pigment. An orange pigment such as a diketopyrrolopyrrole orange pigment or a purple ringtone orange pigment is used as needed.

If specific examples are given, there are: CI 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 CI 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.

Preferred in these specific examples are CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166. 173, 180, 185, etc., more preferably CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Pigment Yellow 139.

In particular, when C.I. Pigment Yellow 150, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 139 are used, the transmittance is high and the contrast is high, which is preferable.

Further, in order to form a blue pixel, a violet pigment may be used in combination with the phthalocyanine blue pigment. Examples of the purple pigment include a quinacridone violet pigment, an oxazine violet pigment, an anthraquinone violet pigment, an indigo violet pigment, a xanthene violet pigment, and the like.

Specific examples are C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38. In particular, C.I. Pigment Violet 23 is preferred because of its high transmittance and high contrast.

When the average primary particle diameter of these pigments is in the range of 10 nm to 40 nm, the transmittance is high and the contrast is high, which is preferable. More preferably, it is a range of 10 nm - 30 nm. In order to reduce the average primary particle size and to make it fine, the salt polishing method is effective similarly to phthalocyanine, and salt polishing may be carried out together with the phthalocyanine pigment, or salt polishing may be separately performed.

The average primary particle diameter can be obtained by observing by SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

In the colored photosensitive composition of the present invention, the total amount of the coloring matter having a phthalocyanine skeleton is the total amount of the solvent (B) removed from the coloring photosensitive composition of the present invention in terms of weight (hereinafter, The "total amount of the solvent (B) removed in the coloring photosensitive composition" is referred to as "all solids") is preferably 5% to 60%, more preferably 10% to 50%, and most preferably 15%. 45%. When the amount of addition is used in this range, a color filter excellent in color characteristics, high in contrast, and high in brightness can be obtained.

<Pigment Dispersion Composition>

In the preparation of the colored photosensitive composition of the present invention, it is preferred that the coloring material having the phthalocyanine skeleton (A) and the other coloring materials are dispersed together or separately to form a pigment dispersion composition.

The pigment dispersion composition is obtained by dispersing the pigment and the solvent, and a dispersant, a resin or the like may be added as needed. Further, it may be formed using a pigment derivative or the like and, if necessary, other components.

- Modulation of pigment dispersion composition -

The preparation form of the pigment dispersion composition of the present invention is not particularly limited, and can be obtained, for example, by using a vertical or horizontal type sand mill, a pin mill, a roll cutter, an ultrasonic disperser, or the like. The beads formed of glass, zirconia or the like having a particle diameter of 0.01 mm to 1 mm are microdispersed with the pigment and the pigment dispersant and the solvent.

It is also possible to use a two-roll mill, a three-roll mill, a ball mill, a tumbler, a disperser, a kneader, a worm kneader, a homogenizer, a mixer, a uniaxial or biaxial extrusion before performing bead dispersion. The machine is subjected to a kneading and dispersing treatment while imparting a strong shearing force.

In addition, the details of the kneading and dispersion are in "Paint Flow and Pigment Dispersion" by TCPatton (published by John Wiley & Sons Inc. in 1964). There are records.

- Pigment concentration -

The content of the pigment in the pigment dispersion composition is preferably from 10% by weight to 60% by weight, and more preferably from 15% by weight to 50% by weight based on all the solids (by weight) of the composition. If the content of the pigment is within the above range, it is effective for ensuring sufficient and excellent color characteristics of the color density.

-Dispersant-

The pigment dispersion composition preferably contains at least one dispersant. By containing the dispersant, the dispersibility of the pigment can be improved.

As the dispersing agent, for example, a known pigment dispersing agent or a surfactant can be appropriately selected.

Specifically, a plurality of compounds can be used, and examples thereof include an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a (meth)acrylic (co) polymer Polyflow No. 75, No. 90, and No. .95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yushang Co., Ltd.) and other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic interface such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Active agent; anionic surfactant such as W004, W005, W017 (manufactured by Yushang Co., Ltd.); amphoteric interfacial activity having a carboxylbetaine structure, a guanamine base structure, a sulfobetaine structure, a hydroxybetaine structure, etc. Fluoride surfactants such as Megafac F171, F172, F173 (manufactured by DIC); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (both manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by Sannoteco Co., Ltd.) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 Various Solsperse dispersants (manufactured by Lubrizol Corporation, Japan); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Kasei Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by BYK Chemie Co., Ltd.). Other examples include an acrylic copolymer, an oligomer or a polymer having a polar group such as an N,N-disubstituted amino group or an acidic group at a molecular terminal or a side chain, and a polyurethane resin modified with a tertiary amine. An AB type or ABA type block copolymer described in Japanese Laid-Open Patent Publication No. 2009-52010.

The content of the dispersant in the pigment dispersion composition is preferably from 1 wt% to 100 wt%, more preferably from 3 wt% to 70 wt%, based on the total weight of the pigment.

-Pigment derivatives -

Pigment dispersion group. The pigment derivative can be added as needed. The pigment derivative into which a moiety or a polar group having affinity with a dispersing agent is introduced is adsorbed on the surface of the pigment, and the pigment derivative is used as a point of adsorption of the dispersing agent to disperse the pigment in the form of fine particles in a coloring photosensitive composition. In the product, it is possible to prevent re-agglomeration, and it is possible to effectively form a color filter having high contrast and excellent transparency.

The pigment derivative is specifically a compound in which an organic pigment is used as a matrix and an acidic group or a basic group or an aromatic group is introduced as a substituent in a side chain. Specific examples of the organic pigment include a quinacridone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinoline pigment, and a diketone group. Pyrrolopyrrole pigments, benzimidazolone pigments, and the like. In general, a pale yellow aromatic polycyclic compound such as a naphthalene, an anthracene, a triazine or a quinoline which is not called a dye is also contained. The pigment derivative can be used, for example, in Japanese Laid-Open Patent Publication No. Hei 11-49974, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. a pigment described in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. derivative.

The content of the pigment derivative in the pigment dispersion composition is preferably from 1 wt% to 30 wt%, more preferably from 3 wt% to 20 wt%, based on the weight of the pigment. When the content of the pigment derivative is within this range, the viscosity of the pigment dispersion composition can be suppressed to be low, and the dispersion can be favorably dispersed, and the dispersion stability after dispersion can be improved.

Thus, a colored photosensitive composition having high transmittance and excellent color characteristics can be obtained. Therefore, when the colored photosensitive composition is applied to, for example, a color filter production use, it is possible to obtain a good color. Color filter with high contrast and contrast.

In addition, a polymer compound such as an alkali-soluble resin to be described later may be added to the pigment dispersion composition. It is considered that a polar group such as an acid group contained in the alkali-soluble resin is also effective for dispersion of a pigment, and is often effective for dispersion stability of a pigment dispersion liquid.

- solvent -

The solvent in the pigment dispersion composition is not particularly limited as long as it is an organic solvent used in a general 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, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene Wait for the solvent. Further, a solvent exemplified in the solvent (B) to be described later can also be used. In order to adjust the boiling point or viscosity, and the dispersibility of the pigment, a plurality of these solvents may be used in combination.

The content of the solvent in the pigment dispersion composition can be appropriately selected depending on the use of the pigment dispersion composition and the like. When the pigment dispersion composition is used in the preparation of the coloring photosensitive composition to be described later, the solid content concentration including the pigment and the pigment dispersant can be made from the viewpoint of workability (in the pigment dispersion composition, The solvent is contained in such a manner that the total amount of the solvent removed is from 5 wt% to 50 wt%.

The content of the pigment dispersion composition in the colored photosensitive composition of the present invention is preferably a pigment containing (A) a pigment having a phthalocyanine skeleton, based on all the solids (weight) of the colored photosensitive composition. The total content is in the range of 5 wt% to 70 wt%, and more preferably in the range of 15 wt% to 60 wt%. When the content of the pigment dispersion composition is within the above range, the color density is sufficient to effectively ensure excellent color characteristics.

<(B) Solvent>

The colored photosensitive composition of the present invention can be suitably prepared by using the components and the solvent contained in the colored 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, and butyl. Ethyl acetate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxy 3-oxopropane such as ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxopropionate and ethyl 3-oxopropionate Acid alkyl esters (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxopropionic acid alkyl esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, and propyl 2-oxopropionate (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxo-2-methylpropane Methyl ester, ethyl 2-oxo-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2-methylpropionic acid Ester), and, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. 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, etc.; ketones such as methyl ethyl ketone, ring Hexanone, 2-heptanone, 3-heptanone, etc.; aromatic hydrocarbons such as toluene, xylene, and the like.

Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and the like.

The solvent may be used singly or in combination of two or more.

<(C) Polymerizable monomer>

In the present invention, a polymerizable monomer is used as a hardening component of the coloring photosensitive composition.

The polymerizable monomer of the present invention is not particularly limited as long as it can be polymerized, and an addition polymerizable compound such as a low molecular compound, a dimer, a trimer or an oligomer having at least one ethylenic double bond can be suitably used. .

Examples of the compound having at least one ethylenic double bond include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound with an unsaturated carboxylic acid, and an aromatic polyhydroxy compound. An ester of an unsaturated carboxylic acid, which is obtained by esterification reaction of an unsaturated carboxylic acid and a polyvalent carboxylic acid with a polyvalent hydroxy compound such as a fatty acid polyhydroxy compound or an aromatic polyhydroxy compound, a polyisocyanate compound and a (meth) group. An ethylenic compound having a urethane skeleton obtained by reacting a hydroxy compound of an acrylonitrile group.

The specific polymerizable monomer can be listed by the number of the polymerizable groups in one molecule as shown below, but is not limited thereto.

Further, in the present specification, acrylate and methacrylate are collectively referred to as (meth) acrylate.

[Compound having a polymerizable group in one molecule]

Hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-n-butyl (meth)acrylate Cyclohexyl ester, borneyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexanediol (meth)acrylate, (A) Butyloxyethyl acrylate, 2-chloroethyl (meth)acrylate, cyanoethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, (meth)acrylic acid -2-(2-methoxyethoxy)ethyl ester, (2,2,2-trifluoroethyl (meth)acrylate, -1H,1H,2H,2H-perfluoroindole Ester, phenyl (meth)acrylate, 2,4,5-trimethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate , glycidyl (meth)acrylate, glycidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (A) 3-hydroxypropyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyl (meth)acrylate Butyl ester, 3-hydroxypropyl (meth)acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide Alkane (meth) acrylate, oligoethylene oxide (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified phenol (meth) acrylate, PO modified phenol (meth) acrylate, EO modified (meth) acrylate 2-ethylhexyl Ester and the like.

[Compound with two polymerizable groups in one molecule]

Examples of the compound having two (meth)acryl fluorenyl groups in the same molecule as a polymerizable group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol II. (Meth) acrylate, polyethylene glycol di(meth) acrylate, 1,3-butylene glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1 ,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(a) Acrylate, polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-dipropenyloxypropane, 2,2-bis[4-(acryloxyethoxy)phenyl] Propane, 2,2-bis[4-(propyleneoxydiethoxy)phenyl]propane, bis(acryloxyethyl)ether of bisphenol A, bisphenol A epoxy resin Acrylic acid modified product, 3-methylpentanediol di(meth)acrylate, 2-hydroxy-3-propenyloxypropyl methacrylate, dimethylol-tricyclodecane II Methyl) acrylate or the like is preferably dimethylol-tricyclodecane di(meth)acrylate, new Glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, bisphenol A type epoxy resin (meth) acrylic acid modified, and the like.

[A compound having three polymerizable groups in one molecule]

Examples thereof include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane, alkylene oxide-modified tri(meth)acrylate, and pentaerythritol. Tris(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tris((meth)acryloxypropyl)ether, isocyanuric acid alkylene oxide modified tris(methyl) Acrylate, dipentaerythritol tris(meth)acrylate, tris((meth)propenyloxyethyl)isocyanurate, hydroxytrimethylacetaldehyde modified dimethylolpropane III Methyl) acrylate, sorbitol tri(meth) acrylate, propoxylated trimethylolpropane tri(meth) acrylate, ethoxylated glycerin triacrylate, and the like.

[Compound having four or more polymerizable groups in one molecule]

Examples of the compound having four or more polymerizable groups in one molecule include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, Dipentaerythritol tetra(meth)acrylate propionate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, sorbitol five ( Methyl) acrylate, sorbitol hexa(meth) acrylate, phosphazene alkylene oxide modified hexa(meth) acrylate, lactone modified dipentaerythritol hexa (meth) acrylate, co-prosper Acrylic urethane such as UA-306H, UA-306T, UA-306I manufactured by Seika Chemical Co., Ltd.

The preferred amount of the polymerizable monomer is from 5 wt% to 80 wt%, preferably from 10 wt% to 60 wt%, more preferably 15%, based on all solids (by weight) of the color-sensitive photosensitive composition of the present invention. Range of wt% to 50 wt%.

From the viewpoint of suitably maintaining solvent resistance or ITO sputtering suitability in the post-treatment step, it is preferable that these compounds have a (meth) acrylate single having two or more (meth) acrylonitrile groups in the same molecule. The compound is more preferably a compound having three or more polymerizable groups. Particularly advantageous is a compound having four or more polymerizable groups, and for example, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or a mixture of these compounds can be suitably used from the viewpoint of solvent resistance or ITO sputtering suitability. (The weight conversion ratio is dipentaerythritol pentaacrylate: dipentaerythritol hexaacrylate = 2 to 4: 8 to 6).

Further, from the viewpoint of self-development latitude, it is advantageous that a compound having one to three hydrophilic groups in the same molecule, particularly a compound having a hydroxyl group or a carboxyl group in the molecule, contributes greatly to improvement of developability. . From this viewpoint, a compound having an acid group such as a carboxyl group at the terminal of the acrylate monomer is preferred. Specific examples thereof include an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or maleic acid, or an acid-based modified compound having an acid group such as a carboxyl group introduced at the terminal of the polyfunctional acrylate compound (for example, manufactured by Toagosei Co., Ltd.). Aronix M-520, Aronix M-520 manufactured by Toagosei Co., Ltd., Aronix TO-2349 manufactured by Toagosei Co., Ltd., etc.), in particular, Aronix M-520 and Aronix TO-2349 can be suitably used.

In addition to the compound containing three or more polymerizable groups and acid groups in the same molecule, it is also possible to have three or more polymerizable groups in one molecule in order to achieve compatibility with solvent resistance, ITO sputtering suitability, and development latitude. The compound and the acid group-containing compound are used in combination. In the case of use in combination, when the polymerizable monomer is 100 parts by weight, it is used in the range of 1 wt% to 50 wt%, preferably in the range of 1 wt% to 40 wt%, more preferably 5 wt% to 20 The range of wt%.

<(D) Adhesive Resin>

The (D) binder resin of the present invention can be used arbitrarily as a polymer compound which is soluble in a solvent. As a preferred binder resin, an alkali-soluble resin is preferred in consideration of alkali developability by photolithography.

The alkali-soluble resin may be contained in the preparation stage of the pigment dispersion composition, or may be added in two stages of preparation of the pigment dispersion composition and preparation of the colored photosensitive composition.

The alkali-soluble resin is a linear organic high molecular polymer, and is an alkali-soluble polymer having at least one alkali-soluble group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group or the like), and more preferably soluble in an organic solvent. An alkali-soluble resin developed using a weakly alkaline aqueous solution.

In the production of an alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent 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 experimentally determined.

The linear organic high molecular polymer is preferably a polymer having a carboxylic acid in a side chain. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer described in each of Japanese Laid-Open Patent Publication No. 59-71048 And a polymer obtained by adding an acid anhydride to an acid cellulose derivative having a carboxylic acid in a side chain or a polymer having a hydroxyl group, and the like, and having a high (meth)acryl fluorenyl group in a side chain. The molecular polymer is a preferred linear organic high molecular polymer.

Among these compounds, a benzyl (meth)acrylate/(meth)acrylic copolymer or a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer is particularly suitable. Other than this, a compound in which 2-hydroxyethyl methacrylate is copolymerized or the like can be mentioned as a useful compound. The polymer can be used in any amount by mixing.

In addition to the above, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer described in JP-A-7-140654 , 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/poly Styrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

The other alkali-soluble adhesive resin can be used in the Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A known polymer compound described in JP-A-H07-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020.

The specific structural unit of the alkali-soluble resin, in particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith can be suitably used because it can be easily obtained, and the alkali solubility and the like can be easily adjusted.

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

Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl acrylate , tolyl acrylate, naphthalene acrylate, cyclohexyl acrylate, and the like.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl (meth)acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, and (meth)acrylic acid. Hydroquinone ester, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ =CR ³¹ R ³² [here, R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms], and CH ₂ = C(R ³¹ )(COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

These other monomers which can be copolymerized may be used alone or in combination of two or more. Preferred other copolymerizable monomers are selected from the group consisting of CH ₂ =CR ³¹ R ³² , CH ₂ =C(R ³¹ )(COOR ³³ ), phenyl (meth)acrylate, benzyl (meth)acrylate, and At least one kind of styrene is particularly preferably CH ₂ =CR ³¹ R ³² and/or CH ₂ =C(R ³¹ )(COOR ³³ ). R ³¹ , R ³² and R ^{33 in} these compounds are each synonymous with the above.

In the present invention, the (D) binder resin may be a single compound or a plurality of compounds may be used in combination. The content of the binder resin such as an alkali-soluble resin in the coloring photosensitive composition is preferably from 1% by weight to 20% by weight, and more preferably from 2% by weight to 15% by weight based on the total solid content of the composition. It is particularly preferably from 3 wt% to 12 wt%.

Further, the blending of the (C) polymerizable monomer/(D) binder resin is preferably in the range of 0.1 to 10, more preferably in the range of 0.4 to 8, and still more preferably in the range of 0.5 to 5 by weight.

<(E) Photopolymerization initiator>

The (E) photopolymerization initiator in the present invention is a known compound having the ability to initiate polymerization by light irradiation, and can be widely used without limitation.

A known photopolymerization initiator which is usually used may also be, for example, camphorquinone, benzophenone, benzophenone derivative, mercaptophosphine, mercaptophosphine derivative, acetophenone; acetophenone derivative, For example, α-hydroxycycloalkylphenyl ketones or 2-hydroxy-2-methyl-1-phenyl-acetone, dialkoxyacetophenones, α-hydroxy- or 4-arylmercapto-1, 3-dioxolans; benzoin alkyl ethers and benzyl ketals, such as benzoin dimethyl ketal, phenyl glyoxylate and its derivatives, dimer phenyl aldehyde aldehyde; Acid esters such as benzophenone tetracarboxylic acid peresters (for example, the compounds described in EP 1126,541); halomethyltriazines such as 2-[2-(4-methoxy-phenyl) )-vinyl]-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl [ 1,3,5]triazine, 2-(3,4-dimethoxy-phenyl)-4,6-bis-trichloromethyl[1,3,5]triazine, 2-methyl- 4,6-bis-trichloromethyl[1,3,5]triazine; anthraquinones such as O-benzimidyl-4'-(phenylhydrazino)benzylidene-hexyl-ketooxime, O- Ethyl-1-[9-ethyl-6-(2-methylbenzylidenyl)-9-oxazol-3-yl]-ethane-1-one oxime; hexaaryl Biimidazole/co-initiator, for example o-chlorohexaphenylbisimidazole in combination with 2-mercaptobenzothiazole; ferrocene compound or titanocenes, such as dicyclopentadienyl-bis ( 2,6-Difluoro-3-pyrrolophenyl)titanium; for example, a mixture with an O-mercapto oxime ester compound as described in GB 2,339,571. A boric acid compound can also be used as the co-starting agent.

The content of the photopolymerization initiator in the coloring photosensitive composition of the present invention is preferably from about 0.05% by weight to about 30% by weight of all solids, more preferably from 0.1% by weight to 20% by weight, still more preferably from 0.2% by weight. ~10 wt%.

Preferably, the colored photosensitive composition of the present invention contains a co-sensitizer. In the present invention, the co-sensitizer has a function of further increasing the sensitivity of the sensitizing dye or the initiator to the active radiation, or suppressing polymerization inhibition of the photopolymerizable compound due to oxygen.

Examples of such a co-sensitizer include, for example, MRSander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), Japanese Patent Publication No. Sho 44-20189. Japanese Patent Laid-Open Publication No. SHO-52-82102, Japanese Patent Laid-Open No. Sho 52-134692, Japanese Patent Laid-Open Publication No. Sho 59-138205, Japanese Patent Laid-Open No. SHO-60-84305, Japanese Patent Laid-Open The compound and the like described in Research Disclosure No. 33825, and the like, specifically, triethanolamine and p-dimethylaminobenzoic acid ethyl ester, etc., may be mentioned in Japanese Patent Laid-Open Publication No. Sho 64-33104 , p-Mercaptodimethylaniline, p-methylthiodimethylaniline, and the like.

Other examples of the co-sensitizers include thiols and thioethers, and examples thereof include those disclosed in JP-A-53-702, JP-A-55-500806, and JP-A-5-142772. The thiol compound described in Japanese Laid-Open Patent Publication No. SHO 56-75643, and the like, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and N -phenylmercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, β-mercaptophthalene, butanediol bis(3-mercaptobutyrate), butanediol bis(3-mercaptopropionic acid) Ester, ethylene glycol bis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), and the like.

Further, other examples include an amino acid compound (for example, N-phenylglycine), an organometallic compound (for example, tributyltin acetate, etc.) described in Japanese Patent Publication No. Sho 48-42965, and Japan. A hydrogen compound (for example, trithiane) or a thioxanthone compound (2,4-dimethyl) described in Japanese Laid-Open Patent Publication No. Hei 6-308727. A thioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, etc.).

The content of the co-sensitizer is preferably from 0.1% by weight to 30% by weight based on the weight of all the solids of the colored photosensitive composition, from the viewpoint of increasing the curing speed and the chain transfer. The range is more preferably in the range of 1 wt% to 25 wt%, still more preferably in the range of 0.5 wt% to 20 wt%.

<(F) Compound represented by the formula (1)>

The colored photosensitive composition of the present invention contains (F) a compound represented by the following formula (1) (hereinafter referred to as "specific additive" as appropriate).

When the colored photosensitive composition of the present invention is used as a color filter as described later, in the step of forming the colored pattern, heat treatment (post-baking) is performed at a temperature of 100 ° C to 250 ° C. Therefore, in the case where an additive is used for the purpose of improving reliability, it is required to not lose the effect after the heat treatment. Since the additive is difficult to volatilize or decompose due to heat, it is particularly excellent in heat resistance, and exhibits remarkable effects in the aspect of the present invention.

By using the compound represented by the following general formula (1), the coloring photosensitive composition of the present invention can be used without loss of the original brightness and color purity of the coloring material, and is excellent in heat resistance and light resistance after heat treatment, and Both developability and solvent resistance can be achieved.

[Chemical 2]

[In the general formula (1), R ¹ and R ² each independently represent a divalent to tetravalent linking group, and Y ¹ and Y ² each independently represent a single bond, an oxygen atom, an ester group, and have a carbon number of 2 or more. An alkyl group having 30 or less alkyl groups, an aromatic group having 6 or more and 30 or less carbon atoms, a polyethylene glycol group, or a combination of a plurality of such groups. 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 divalent to tetravalent linking group in R ¹ and R ² in the formula (1) includes a hydrocarbon group having 2 or more and 10 or less carbon atoms, and an aromatic group having 6 or more and 10 or less carbon atoms.

The hydrocarbon group having 2 to 10 carbon atoms in the divalent to tetravalent R ¹ and R ² may be an exoethyl group, a propenyl group, a propane-1,3-diyl group or a propane-2,2-di. The alkyl group and the substituted alkyl group are preferably an ethyl group and a propyl group.

Further, examples of the aromatic group having a carbon number of 2 to 4 valent in R ¹ and R ² of 6 or more and 10 or less may be an extended aryl group such as a stretching phenyl group, a stretching naphthyl group, a methyl phenylene group or a benzene dimethyl group. And the substituted aryl group is preferably a phenyl group or a phenyl group.

The ester group in Y ¹ and Y ² in the formula (1) may, for example, be a carboxylate, a phosphate or a sulfonate, and is preferably a carboxylate.

Further, examples of the aliphatic alkyl group having 2 or more and 30 or less carbon atoms in Y ¹ and Y ² include an ethylene group, a propylene group, a propane-1,3-diyl group, a propane-2,2-diyl group, and the like. The alkylene group and the substituted alkylene group are preferably an ethyl group and a propyl group; and the aromatic group having a carbon number of 6 or more and 30 or less may be a phenyl group, a naphthyl group, a phenyl group, a phenyl group. The methyl aryl group and the substituted aryl group are preferably a phenyl group or a phenyl group.

In addition, as the polyethylene glycol group having a carbon number of 2 or more and 30 or less in Y ¹ and Y ² , the number of repetitions of the ethylene glycol residue is 1 to 15, more preferably 1 to 10.

The monovalent polymerizable group which can be polymerized by heat or light irradiation in P ¹ and P ² in the general formula (1) may, for example, be a (meth) acrylonitrile group, a (meth) propylene fluorenyl group, or a methyl group. a acrylamide group, a vinyl group, a vinyloxy group, a maleidino group, an epoxy group, a glycidyl group or the like, preferably a (meth) acrylonitrile group or a (meth) propylene fluorenyl group, particularly It is preferably a (meth) acrylonitrile group.

Further, m and n are each independently an integer of 1 or more and 3 or less.

The mechanism for improving the light resistance due to the addition of the oxidized azo compound as the specific additive represented by the general formula (1) is not clearly understood, and can be estimated as follows. It is presumed that the radical generated when the coloring matter having the phthalocyanine skeleton is excited by light irradiation is trapped by the oxidized azo compound represented by the general formula (1), and thus discoloration at the time of the light resistance test can be suppressed.

It is presumed that the oxidized azo compound having a polymerizable group is particularly light-irradiated after post-baking because it has less volatilization and decomposition due to heating and is excellent in heat resistance as compared with other non-polymerizable oxidized azo compounds. Medium, the most effective capture of free radicals.

The specific additive of the present invention comprises an oxidized azo moiety (a site containing an oxidized azo group and a chemical structure to which it is bonded, hereinafter referred to as an "oxidized azo site"), a polymerizable site, an oxidized azo site, and a polymerization. The sexual site can be directly bonded, or a joint site where the two are bonded can be introduced.

Further, in the coloring photosensitive composition of the present invention, two or more specific additives may be used in combination.

Next, each part of the specific additive of the present invention will be described.

The oxidized azo moiety includes a oxidized azo group at the center and a chemical structure linking the oxidized azo group (-N=NO-), and the light resistance of the colored photosensitive composition can be improved. The chemical structure to be bonded to the oxidized azo group is not particularly limited as long as it is a compound represented by the formula (1), and examples thereof include various hydrocarbon groups and various aromatic groups. Among them, from the viewpoint of the activity of the azo group, an aromatic group is preferred, and a benzene ring is particularly preferred.

The polymerizable portion has an effect of preventing volatilization or decomposition of an oxidized azo compound (the oxidized azo compound exhibits an effect of suppressing deterioration by light irradiation) and an effect of improving heat resistance. The polymerizable portion which is a specific additive of the present invention is a structure which is generally known to be used without any limitation as long as it is a polymerization reaction by heat or light irradiation. Specific examples of the polymerizable group include (meth) acrylonitrile, (meth) propylene decyloxy, (meth) acryl oxime, vinyl, vinyloxy, maleimine, and epoxy. , glycidyl groups, and the like. These polymerizable groups may be further partially substituted. Among them, a (meth) acrylonitrile group or a (meth) propylene decyloxy group is preferred from the viewpoint of ease of synthesis.

The linking site is not particularly limited, and a cyclic aliphatic group, a chain aliphatic group, an aromatic group or the like can be used widely, and an alkyl chain or a polyethylene glycol chain is particularly preferable. The organic group may further have a branch, and in the case of having a branch, it may have a plurality of polymerizable sites or oxidized azo sites at each end.

Examples of the alkylene chain include an exoethyl group, a propyl group, a propane-1,3-diyl group, and a propane-2,2-diyl group.

The carbon number of the alkylene chain is preferably from 1 to 30, more preferably from 1 to 10. With regard to the polyethylene glycol chain, the preferred carbon number range is the same as in the case of the alkyl chain.

In the present invention, the content of the compound represented by the formula (1) in the formula (1) is preferably from about 0.1% by weight to about 5.0% by weight, more preferably from 0.2% by weight to 4.0%, based on the total mass of the coloring photosensitive composition. The wt% is further more preferably 0.5 wt% to 2.0 wt%.

By setting it as the range, the effect of oxidizing the azo site is sufficiently exhibited, and the sensitivity to exposure is high, and when it is used as a color filter, a desired pattern can be formed, so that the following problems are not caused: surface roughness is generated. Or gap.

(F) The compound represented by the formula (1) is preferably a compound having a structure of the following formula (2) from the viewpoints of stability of the compound, activity of the azo group, and ease of handling. .

[Chemical 3]

In the formula (2), Y ¹ , Y ² , P ¹ , P ² , m and n are respectively synonymous with Y ¹ , Y ² , P ¹ , P ² , m and n in the formula (1).

P ¹ and P ² in the formula (2) are preferably a (meth) acrylonitrile group or a (meth) propylene fluorenyl group. Y ¹ and Y ² in the formula (2) are preferably a single bond or a linking group represented by the following. m and n in the formula (2) are each independently an integer of 1 or more and 3 or less.

In the following linking group, * indicates an aromatic ring attached to the oxidized azo moiety or a bonding position to a polymerizable portion. 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.

[Chemical 4]

Specific examples of the compounds represented by the general formulae (1) and (2) are shown below, but the specific additives in the present invention are not limited to these compounds.

[Chemical 5]

[Chemical 6]

[Chemistry 7]

Among the compounds represented by the formula (1), 4,4'-oxy azostyrene and 4,4'-oxyazophenyl acrylate alkyl ester compounds (for example, the following compound a, Compound b) and the like.

[化8]

<Other additives>

In the colored photosensitive composition of the present invention, various additions such as an ultraviolet absorber, a thermal polymerization initiator, a surfactant, a development accelerator, a thermal polymerization inhibitor, a filler, a dispersant, and a coagulation inhibitor may be contained as needed. Things.

<UV absorber>

In the compound represented by the above formula (1), it is also possible to add a usual ultraviolet absorber containing no polymerizable group to the extent that the disadvantage is not caused. In this case, when an organic ultraviolet absorber having good compatibility with the compound represented by the formula (1) is used, a multiplication effect can be expected, which is preferable. The main skeleton is preferably a derivative of a compound of a hydroxybenzophenone type, a benzotriazole type, a cyanoacrylate, a triazine type, or a diester type. Further, it may be a polymer such as an ethylene-based polymer containing a residue of these ultraviolet absorbers in a side chain.

Specific examples thereof include 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxyl group. 4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2- Hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethyl Oxybenzophenone, 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-butylphenyl)benzotriazole, 2-(2-hydroxy-5-th-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-hexyloxyphenyl)-4,6-diphenyltriazine, octyl-5 -N,N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate, 2-hydroxy-4-(2-propene oxime (co)polymerization of (co)polymer of 2-ethoxy(2)-benzophenone, (co)polymerization of 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole Things and so on. These organic ultraviolet absorbers may be used in combination of two or more kinds.

<Thermal polymerization initiator>

It is also effective to contain a thermal polymerization initiator in the coloring photosensitive composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds, and examples of the peroxide compounds include ketone peroxide and peroxyl condensation. Ketones, hydrogen peroxide, dialkyl peroxides, didecyl peroxides, peroxyesters, peroxydicarbonates, and the like.

<Surfactant>

The colored photosensitive composition of the present invention is preferably formed using various surfactants from the viewpoint of improving coatability. By using the surfactant, the liquid properties (especially fluidity) at the time of forming the coating liquid can be improved, and the uniformity of the coating thickness or the liquid-saving property can be improved. In other words, it is effective in that the surface tension of the substrate and the coating liquid is lowered to improve the wettability to the substrate, and the coating property to the substrate is improved. Therefore, even a small amount of liquid is formed to be several μm or so. In the case of a film, a film of uniform thickness having a small thickness unevenness can be formed. Moreover, it is also effective in the slit coating which is easy to generate a liquid removal.

As the surfactant, various surfactants of a nonionic, cationic or anionic type can be used. Among them, a fluorine-based surfactant having a perfluoroalkyl group among the nonionic surfactants is preferred.

The fluorine content of the fluorine-based surfactant is preferably from 3 wt% to 40 wt%, more preferably from 5 wt% to 30 wt%, particularly preferably from 7 wt% to 25 wt%. When the fluorine content is within the above range, it is effective in coating thickness uniformity or liquid-saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437 (manufactured by DIC Corporation), and Fluorad FC430. Fluorad FC431, Fluorad FC171 (above Sumitomo 3M Co., Ltd.), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above manufactured by Asahi Glass Co., Ltd.), etc.

Examples of the surfactant other than the fluorine-based phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Industrial Co., Ltd.)), organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (methyl) Acrylic surfactants such as acrylic acid (co)polymers Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoei Oil & Fat Chemicals Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether; Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate a nonionic surfactant such as an ester, a sorbitan fatty acid ester (manufactured by BASF Corporation), Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1; An anionic surfactant such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

The amount of the surfactant added is preferably 0.001% by weight to 2.0% by weight, and more preferably 0.005% by weight to 1.0% by weight based on the total weight of the pigment dispersion composition or the coloring photosensitive composition.

<Development accelerator>

In addition, when the alkali solubility of the uncured portion is promoted and the developability of the colored photosensitive composition is further improved, an organic carboxylic acid may be added to the colored photosensitive composition, and a low molecular weight organic having a molecular weight of preferably 1,000 or less is preferable. carboxylic acid. Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and caprylic acid; oxalic acid and malonic acid; Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethyl propyl Aliphatic dicarboxylic acid such as diacid, methyl succinic acid, tetramethyl succinic acid, citraconic acid; aliphatic tricarboxylic acid such as 1,2,3-propane tricarboxylic acid, aconitic acid, camphoric acid; benzene Aromatic monocarboxylic acids such as formic acid, methylbenzoic acid, cumene, perylenecarboxylic acid, m-dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, homobenzene Aromatic polycarboxylic acids such as tricarboxylic acid, benzoic acid, and pyromellitic acid; phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamic acid Other carboxylic acids such as ester, benzyl cinnamate, cinnamyl acetic acid, coumaric acid, and umbrella acid.

<thermal polymerization inhibitor>

In the coloring photosensitive composition of the present invention, it is preferred to further add a thermal polymerization inhibitor in advance, and for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, or the like may be used. Tert-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl- 6-tert-butylphenol), 2-mercaptobenzimidazole, and the like.

<dispersant, filler, coagulation inhibitor>

In addition to the above, it is also possible to add to the coloring photosensitive composition: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above by Morikawa Polymer company manufacturing), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannoteco Co., Ltd.) and other polymer dispersing agents; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (made by Jielikang); fillers such as glass and alumina; and aggregation inhibitors such as sodium polyacrylate.

The colored photosensitive composition of the present invention can be prepared by the following method: (B) a solution or dispersion of the (A) phthalocyanine-containing coloring material containing the (B) solvent of the present invention, (preferably with (B) (a solvent together) containing (C) a polymerizable monomer, (D) a binder resin, (E) a photopolymerization initiator, and (F) a compound represented by the formula (1), wherein a surfactant, etc. are mixed as needed. Other additives.

<Color filter and method of manufacturing the same>

The method for producing a color filter according to the present invention includes the step of applying the colored photosensitive composition of the present invention to a substrate to form a colored layer; and exposing the colored layer to a pattern, and developing the colored layer The step of developing and removing the uncured portion of the liquid to form a colored pattern.

In other words, the colored photosensitive composition of the present invention is applied to a substrate such as glass by a method such as spin coating, slit coating, cast coating, roll coating, or inkjet coating, directly or via another layer. The colored layer is exposed by a method of exposing the formed coloring layer by a predetermined mask pattern, and after exposure, the uncured portion is developed and removed by a developing solution to form respective colors (for example, three colors or four colors). A coloring pattern (for example, a color pixel) is used, whereby a color filter can be optimally produced.

As a result, a color filter used in a liquid crystal display device, an organic EL display device, a solid-state imaging device, or the like can be produced with less difficulty in the process, high quality, and low cost.

At this time, ultraviolet rays such as g-line, h-line, i-line, and j-line are particularly preferable for the radiation used in the exposure.

Further, in the exposure, in addition to the general proximity exposure method, an exposure method using a laser light source can be suitably used. In the laser exposure mode, an ultraviolet laser is used as a light source. Laser (LASER) is an acronym for English Light Amplification by Stimulated Emission of Radiation. A laser can be used which uses an oscillator and an amplifier (the oscillator and the amplifier are made by the phenomenon of stimulated radiation appearing in a substance having a reversed distribution, by the amplification and oscillation of the light wave) Produced by a more intense monochromatic light with interference and directivity, the excitation medium is provided with crystals, glass, liquid, pigment, gas, etc., and the laser is subjected to solid laser and liquid laser due to the medium. A known wavelength of ultraviolet light such as a gas laser or a semiconductor laser has an oscillation wavelength. Among them, solid lasers and gas lasers are preferred from the viewpoint of the output of the laser and the oscillation wavelength.

As the wavelength which can be used in the present invention, an ultraviolet laser having a wavelength range of preferably 300 nm to 380 nm is more preferably in the range of 300 nm to 360 nm in terms of the photosensitive wavelength of the resist. Wavelength ultraviolet laser.

Specifically, it is particularly preferable to use a third harmonic (355 nm) of a Nd:YAG laser that outputs a large, relatively inexpensive solid laser, or XeCl (308 nm) and XeF (353) of an excimer laser. Nm).

The exposure amount of the object to be exposed (pattern) is in the range of 1 mJ/cm ² to 100 mJ/cm ² , and more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² . If the amount of exposure is this range, it is preferable in terms of productivity in pattern formation.

The exposure apparatus usable in the present invention is not particularly limited, and a commercially available exposure apparatus may use LE5565A (manufactured by Hitachi High-Technologies Corporation), Callisto (manufactured by V Technology Co., Ltd.) or EGIS (V Technology Co., Ltd.). Manufactured) or DF2200G (manufactured by Dainippon Screen Co., Ltd.). Further, it is also possible to suitably use a device other than the above.

Moreover, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. Especially in the case where an ultraviolet source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Chemical Co., Ltd. has marketed a purple LED with a main emission spectrum having a wavelength between 365 nm and 420 nm. LEDs having a central active radiation between 300 nm and 370 nm are disclosed in U.S. Patent No. 6,084,250, the disclosure of which is incorporated herein by reference. Moreover, other ultraviolet LEDs can be obtained that can illuminate radiation in different ultraviolet bands. A particularly preferred active radiation source in the present invention is a UV-LED, and particularly preferably a UV-LED having a peak wavelength in the range of 340 nm to 370 nm.

Since the ultraviolet laser has a good parallelism, it can be exposed to a pattern even if a mask is not used at the time of exposure. However, in the case where the pattern is exposed using a mask, the linearity of the pattern is further increased and more preferable.

The drying (prebake) of the colored layer formed by imparting (preferably coating) the colored photosensitive composition of the present invention onto the substrate can be carried out using a hot plate, an oven or the like in a temperature range of 50 ° C to 140 ° C for 10 seconds. It is carried out under conditions of ~300 seconds.

In the development, the unhardened portion after the exposure is eluted into the developer, and only the hardened portion remains. The development temperature is usually from 20 ° C to 30 ° C, and the development time is from 20 seconds to 90 seconds.

If the developer is a coloring layer that dissolves the colored photosensitive composition in the uncured portion and does not dissolve the developer in the cured portion, any developer can be used. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used.

The organic solvent may be exemplified as the organic solvent which can be used in the preparation of the pigment dispersion composition of the present invention or the coloring photosensitive composition.

The alkaline aqueous solution may, for example, be an alkaline aqueous solution obtained by dissolving a basic compound in a concentration of 0.001 wt% to 10 wt%, preferably 0.01 wt% to 1 wt%: sodium hydroxide or potassium hydroxide. , sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium decanoate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Pyrrole, acridine, 1,8-diazabicyclo-[5,4,0]-7-undecene and the like.

Further, in the case where an alkaline aqueous solution is used as the developing solution, it is usually washed (rinsed) with water after development.

After the development, the remaining developer is washed and removed, and after drying, the heat treatment is usually performed at a temperature of 100 ° C to 250 ° C (post-baking).

Post-baking is heating after development to complete the hardening, and heating (hard baking) of about 200 ° C to 250 ° C is usually carried out. This post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate or a convection oven (hot air loop dryer) or a high-frequency wave heater in such a manner as to achieve the above conditions.

By repeating the above operations for each color in comparison with the desired number of tones, a color filter in which a colored layer (the colored layer is colored in a plurality of colors) can be produced.

When the coloring photosensitive composition of the present invention is applied to a substrate to form a colored layer, the dried thickness of the colored layer is usually 0.3 μm to 5.0 μm, preferably 0.5 μm to 3.5 μm, and most preferably 1.0 μm to ～ 2.5 μm.

Examples of the substrate include an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a transparent conductive film attached to the glass, or a solid. A photoelectric conversion element substrate used in an image pickup element or the like, for example, a tantalum substrate or the like, and a plastic substrate. Black stripes that separate the pixels can also be formed on these substrates.

On the plastic substrate, it is preferred to have a gas barrier layer and/or a solvent resistant layer on the surface thereof.

The other layer in the case where the coloring photosensitive composition is applied to the substrate via the other layer may be a gas barrier layer or a solvent resistant layer.

<Liquid crystal display device, organic EL display device>

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

The definition of the display device or the description of each display device is, for example, "Electronic display device (released by Kogyo Chosakai Publishing Co., Ltd., 1990)", "Display device (Ibuki Shunzhang) , Sangyo Tosho Publishing, published in the first year of Heisei (1989), etc. Further, the liquid crystal display device is described, for example, in "Next-generation liquid crystal display technology (issued by Uchida Ryuo, Industrial Investigations Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention is particularly effective for a liquid crystal display device of a color TFT type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd., 1996)". Further, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a transverse electric field driving method such as IPS (in-plane switching) or a pixel division method such as MVA (multi-domain vertical alignment) is expanded. , or STN (super twisted nematic), TN (twisted nematic), VA (vertical alignment), OCS (optically compensated splay), FFS (fringe field switching, Edge electric field switching), and R-OCB (reflected-optically compensated bend).

Moreover, the color filter of the present invention can also be used in a bright and high-resolution COA (Color-filter On Array) mode. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer must be required for the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance. Sex. The color filter of the present invention can improve the transmittance of the ultraviolet light as the exposure light by selecting the color tone or film thickness of the pixel specified by the present invention in addition to the exposure method using the ultraviolet light. Thereby, the curability of the colored pixel can be improved, and a pixel having no chipping or peeling or wrinkles can be formed. Therefore, the coloring layer directly or indirectly provided on the TFT substrate is particularly resistant to the peeling liquid, and can be used for the COA method. In a liquid crystal display device. In order to satisfy the required characteristics of a low dielectric constant, a resin coating film may be provided on the color filter layer.

Further, in the coloring layer formed by the COA method, in order to electrically connect the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer, it is necessary to form a rectangular pass having a length of about 1 μm to 15 μm. Hole or " It is preferable that the size of the conduction path (that is, the length of one side) of the shape of the sac is particularly 5 μm or less, and a conduction path of 5 μm or less can be formed by using the present invention.

These image display methods are described, for example, in "EL, PDP, LCD Display - Technology and Market Trends - (Dongli Research Center Research and Research Division, 2001)", page 43 and the like.

The liquid crystal display device and the organic EL display device of the present invention include various components such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing 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 including the known members.

Regarding these components, for example, "'94 Liquid Crystal Display Peripherals, Chemicals Market (Shima Kotaro, CMC Co., Ltd., issued in 1994), "2003 Liquid Crystal Related Market Status and Future Outlook (Vol. 2) , documented by Fuji Chimera Research Institute, Inc., issued in 2003).

Regarding the backlight, SID meeting Digest 1380 (2005) (A. Konno et al.) or Display Monthly, December 2005, pages 18 to 24 (Island Kang Yu), Display Monthly, December 2005 No. 25th to 30th (Yumu Longming), etc.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a previously known cold cathode tube, and by using red, green, and blue LED light sources (RGB- As a backlight, LED) can provide a liquid crystal display device having high luminance and high color reproducibility.

[Example]

Hereinafter, the present invention will be more specifically described by way of examples, but it is not limited to the examples below. In addition, "%" "parts" is a weight basis unless otherwise specified.

- Synthesis of phthalocyanine pigments -

Zinc phthalocyanine is produced by using sebaconitrile and zinc chloride as raw materials.

The halogenation was carried out by mixing 3.1 parts of sulfonium chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride, and 1 part of zinc phthalocyanine at 40 ° C, and adding 2.2 parts of bromine dropwise. The reaction was carried out at 80 ° C for 15 hours, after which the reaction mixture was poured into water to precipitate a part of the crude zinc bromide phthalocyanine pigment. The aqueous slurry was filtered, washed with hot water at 80 ° C, and dried at 90 ° C to obtain 2.6 parts of purified crude zinc bromide phthalocyanine pigment.

1 part of the crude zinc bromide phthalocyanine pigment, 7 parts of pulverized sodium chloride, 1.6 parts of diethylene glycol, and 0.09 parts of xylene were placed in a double-arm type kneader, and subjected to 100 hours at 100 ° C for 6 hours. Mixed. After kneading, the mixture was taken out to 100 parts of water at 80 ° C, stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a partially zinc bromide phthalocyanine pigment.

According to the analysis of the halogen content by gravimetric analysis, the obtained partial zinc bromide phthalocyanine pigment had an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc is phthalocyanine) and contained an average of 10 bromines and 4 chlorines in one molecule.

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

- Synthesis of quinophthalone compounds -

One facing quinacridone pigment (4,5,6,7-tetrachloro-2-[2-(4,5,6,7-tetrachloro-2,3-dihydro-1,3-dioxo) -1H-indol-2-yl)-8-quinolinyl]-1H-isoindole-1,3(2H)-dione) (Paliotol "Yellow K0961HD" manufactured by BASF Corporation) 10 g was stirred and put in To 15 ° C of fuming sulfuric acid (25% SO ₃ ) 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 obtained product was washed with 50 ml of water.

The product was poured into 330 ml of water, and neutralized with an aqueous ammonia solution (addition of an aqueous ammonia solution until the pH became 7). 75 g of ammonium chloride was added thereto, and the mixture was stirred at 80 ° C for 30 minutes, and the precipitate precipitated was filtered at 60 ° C. After the obtained wet crystals were washed with water, they were dried at 80 ° C to obtain 17 g of an ammonium salt (3) of a quinone derivative sulfonate.

The ammonium salt (3) of the quinone derivative sulfonate was heat-treated at 180 ° C for 3 hours to obtain a quinone derivative sulfonate (the following compound (4)) having an ammonium salt removed (16 g). The yield was 94%).

[Chemistry 9]

To the 10 g of the compound (4) obtained above, 2.2 g of N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 10 g of the compound (4) obtained in chloroform under ice-cooling. The mL was stirred at 50 ° C for 2 hours. The reaction mixture was added to 150 mL of water in an ice bath, and the precipitated crystals were filtered to obtain sulfonium chloride compound (Compound (5) below) 7.4 g. (yield 72%)

[化10]

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

[11]

Water and anhydrous sodium sulfite (manufactured by Kanto Chemical Co., Ltd.) were added in excess to 4.3 g of the compound (6) obtained above, and the mixture was heated in an autoclave at 180 ° C for 12 hours. After standing to cool, the crystals were filtered to obtain 3.7 g of a sulfonamide alkylsulfonic acid compound (Compound (7) below). (yield 82%)

[化12]

- Synthesis of resin (J-1) -

(1) Synthesis of Resin (i-1)

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

The synthesis process is as follows.

[Chemistry 13]

(2) Synthesis of Resin (J-1)

10 g of polyethyleneimine (SP-018, number average molecular weight: 1,800, manufactured by Nippon Shokubai Co., Ltd.) and 100 g of polyester resin (i-1) were mixed, and heated at 120 ° C for 3 hours to obtain a middle portion. Body (J-1B). Thereafter, the mixture was cooled 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 gradually added thereto, followed by stirring for 2 hours. Thereafter, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PGMEA) was added to obtain a PGMEA 10 wt% solution of the resin (J-1). The resin (J-1) is a resin having a side chain derived from the polyester resin (i-1) and a carboxyl group derived from succinic anhydride.

The synthesis process is as follows.

[Chemistry 14]

- Modulation of pigment dispersion of phthalocyanine pigment PG58 -

11.9 parts of the above-mentioned partial zinc bromide phthalocyanine pigment (referred to as PG58), 3.1 parts of the compound (7) as a quinophthalone compound, and 9.0 parts of Solsperse 24000GR (manufactured by Lubrizol Corporation, Japan) as a dispersing agent were used as After 76 parts of PGMEA of the solvent was mixed, it was dispersed by a sand mill for 3 hours to obtain a pigment dispersion liquid of PG58. The viscosity of the obtained pigment dispersion liquid of PG58 was measured with an E-type viscometer, and as a result, it was 9.2 mPa·s and was very stable, and it was confirmed that good dispersibility was obtained.

- Modulation of pigment dispersion PY150 containing yellow pigment PY150 -

Using a bead mill (zirconia beads, diameter 0.3 mm), 40 parts of CI Pigment Yellow 150 (PY150) as a yellow pigment (average primary particle diameter of 60 nm), PGMEA 10 of the resin (J-1) A mixed solution of 223 parts of a wt% solution (solid content: 22.3 parts) was mixed and dispersed for 3 hours to prepare a pigment dispersion liquid containing the yellow pigment PY150.

- Modulation of pigment dispersion containing yellow pigment PY138 -

Using a bead mill (zirconia beads, diameter 0.3 mm), 40 parts of CI Pigment Yellow 138 (PY138) as a yellow pigment (average primary particle diameter of 60 nm), PGMEA 10 of the resin (J-1) A mixed solution of 223 parts of a wt% solution (22.3 parts in terms of solid content) was mixed and dispersed for 3 hours to prepare a pigment dispersion liquid containing yellow pigment PY138.

- Modulation of pigment dispersion containing green pigment PG36 -

Using a bead mill (zirconia beads, diameter 0.3 mm), 40 parts of CI Pigment Green 36 (PG36) as green pigment (average primary particle size 60 nm), PGMEA 10 wt% solution of resin (J-1) A mixed liquid of 200 parts (in terms of solid content: 20 parts) was mixed and dispersed for 3 hours to prepare a pigment dispersion liquid containing green pigment PG36.

With respect to the obtained pigment dispersion liquid, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and it was 25 nm.

- Synthesis of Compound 1 as a photopolymerization initiator -

(1) Synthesis of Compound A

First, Compound A was synthesized by the following procedure.

Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C, aluminum chloride (70.3 g, 0.527 mol) was added. Next, o-toluene chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, and the mixture was heated to room temperature and stirred for 3 hours. Next, after cooling to 0 ° C, aluminum chloride (75.1 g, 0.563 mol) was added. 4-Chlorobutylphosphonium chloride (79.4 g, 0.563 mol) was added dropwise over 40 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of a 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 suction filtered, washed with distilled water and methanol, and recrystallized from acetonitrile to give Compound A (yield: 164.4 g, yield: 77%).

[化15]

(2) Synthesis of Compound B

Next, Compound B was synthesized by the following procedure using Compound A.

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. Next, sodium hydroxide (2.0 g, 50.2 mmol) was added to the reaction liquid, and the mixture was refluxed for 2 hours. Next, after cooling to 0 ° C, a 28% methanol solution of sodium methoxide (manufactured by Nippon Shokubai Co., Ltd.: SM-28) (11.1 g, 57.4 mmol) was added dropwise thereto over 20 minutes, and the temperature was raised to room temperature for 2 hours. Stir. Next, after cooling to 0 ° C, isoamyl nitrite (6.73 g, 57.4 mmol) was added dropwise over 20 minutes, and the mixture was heated to room temperature and stirred for 3 hours. The reaction solution was diluted with 120 ml of acetone, and a 0.1 N aqueous solution of hydrochloric acid cooled to 0 ° C was added dropwise. The precipitated solid was suction filtered, and then washed with distilled water. Next, recrystallization was carried out with acetonitrile to obtain Compound B having the following structure (yield: 17.0 g, yield: 64%).

[Chemistry 16]

(3) Synthesis of Compound 1

Next, Compound 1 was synthesized by the following procedure using Compound B.

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. Next, after cooling to 0 ° C, acetonitrile (3.05 g, 38.9 mmol) was added dropwise over 20 minutes, and the mixture was heated to room temperature and stirred for 2 hours. The reaction liquid droplets were added to 150 ml of distilled water cooled to 0 ° C, and the precipitated solid was suction filtered, washed with 200 ml of isopropanol cooled to 0 ° C, and dried to obtain Compound 1 having the following structure ( The yield was 19.5 g and the yield was 99%).

[化17]

(Example 1)

<Preparation of Colored Photosensitive Composition>

The components shown in the following composition 1 were stirred and mixed to prepare the colored photosensitive composition of Example 1.

(composition 1)

‧(A) Pigment Dispersion 1: Pigment Dispersion Containing Green Pigment PG58 36.6 parts

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

‧(B) Solvent: PGMEA 25.8 parts

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

‧(D) Adhesive resin (allyl methacrylate-methacrylic acid (copolymerization molar ratio: 8:2) copolymer, weight average molecular weight of 30,000) 1.76 parts

‧(C) Polymerizable monomer: Aronix M-520 (manufactured by Toagosei Co., Ltd., acid-modified polyfunctional acrylate compound) 3.77 parts

‧(E) Photopolymerization initiator 1: IRGACURE OXE-01 (manufactured by CIBA Co., Ltd.) 0.71 parts

‧ (E) Photopolymerization initiator 2: 2-chlorophenyl-4,5-bisphenylimidazole dimer (manufactured by Hodogaya Chemical Co., Ltd., B-CIM) 0.35 parts

‧ Photosensitizer: 0.49 of the following compound III

‧ Photosensitizer: N-phenylmercaptobenzimidazole 0.11 part

‧(F) Specific Additive: 4,4'-Azo styrene 1.80 parts

‧Interactive surfactant: Fluorine surfactant, manufactured by DIC, Megaafac F781-F 0.033

The structures of IRGACURE OXE-01 and Compound III used in the above are as follows.

[化18]

[Chemistry 19]

<Formation of Colored Pattern Using Colored Photosensitive Composition>

Using the colored photosensitive composition obtained above, a colored pattern was formed on the glass substrate as follows.

- Formation of a coloring photosensitive composition layer -

The obtained colored photosensitive composition was applied onto a glass substrate (Millium, manufactured by Corning Incorporated, 0.7 mm thick). Specifically, the film thickness after drying of the colored photosensitive composition layer after baking was adjusted to about 2.4 μm, and the interval between the slit nozzle and the substrate and the discharge amount were adjusted, and the coating was applied at a coating speed of 120 mm/sec.

- Prebake step -

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

- Exposure step (near exposure) -

After the prebaking treatment, exposure was performed at 40 mJ/cm ² using a proximity exposure machine (manufactured by Hitachi High-Technologies Corporation, LE5565A).

- development step, baking (post-baking) step -

Thereafter, a developing device (manufactured by Hitachi High-Technologies Corporation) was used, and a 1.0% developer solution of potassium hydroxide-based developer CDK-1 (manufactured by Fujifilm Electronic Materials Co., Ltd.) was used (99 parts of pure water was used for 1 part of CDK-1). The diluted liquid, 25 ° C), the shower pressure was set to 0.2 MPa, and developed for 60 seconds, and washed with pure water.

After sufficient drying, post-baking was carried out in an oven at 230 ° C for 40 minutes.

(Example 2 to Example 25, Comparative Example 1 to Comparative Example 14)

In the composition 1 of the example 1, the type of the pigment dispersion liquid, the type of the photopolymerization initiator 1, the type of the photopolymerization initiator 2, the type and amount of the specific additive, and the addition amount were changed as described in Table 1, and In Example 1, the colored photosensitive compositions of Examples 2 to 25 and Comparative Examples 1 to 14 were prepared in the same manner. In addition, the coloring pattern was produced in the same manner as in Example 1 except that the obtained coloring photosensitive composition was changed in the exposure method in the manner described in Table 1.

In Table 1, the details of the exposure mode marked as "near" are the exposure modes (proximity exposure) applied in the exposure step in Example 1. Further, in Table 1, the details of the exposure method of "laser" are as follows.

- Exposure step (laser exposure) -

After the prebaking treatment, EGIS (manufactured by V Technology Co., Ltd., third harmonic of YAG laser, wavelength of 355 nm, pulse width of 6 nsec) was used as a laser exposure device, and coloring was performed by a photomask. The surface of the composition layer was subjected to pulse irradiation of about 1 mJ/cm ² 20 times.

In Tables 1 to 3, PG58, PG36, PB15:6, PY150, and PY138 in one column of the pigment dispersion liquid indicate the above-described pigment dispersion liquid containing each pigment. When it is described as two types, it is used in the same amount as the pigment dispersion liquid of PG58 and the pigment dispersion liquid of PY150 in Example 1. Further, in Example 19 and Comparative Example 12, the pigment dispersion liquid of PG36 was replaced with the pigment dispersion liquid of PG58 in Example 1. Further, in Examples 20 to 23 and Comparative Example 13, the pigment dispersion liquid of PY138 was replaced with the pigment dispersion liquid of PY150 in Example 1. Further, in Example 7, Example 24, Example 25, and Comparative Example 14, a pigment dispersion liquid using a separate pigment was used, and the pigment component was the same as the total of the pigment components of Example 1.

Further, in Tables 1 to 3, "-" indicates that no color is added, G indicates a green coloring photosensitive composition, and B indicates a blue coloring photosensitive composition.

In the case where two photosensitizers are used in the photosensitizer column, as in the case of the photosensitizer in Example 1, in only one of Examples 11 to 13, Example 16 to Example 18, Example 22, and Example 23, The amount of the photosensitizer was the same as that of the N-phenylmercaptobenzimidazole in Example 1.

Moreover, the other additives of Example 13 and Example 18 (ultraviolet absorber: octyl-5-N,N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate) The amount used was 0.27 parts by weight.

Further, 4,4'-oxy azostyrene, 4,4'-oxyazo cinnamic acid ethyl ester, and 4,4'-oxyazo cinnamic acid methyl ester used in the examples and the comparative examples have a polymerizable group. Corresponding to the specific additive of the present invention, azobenzene and azobenzene ether have no polymerizable group and do not correspond to the specific additive of the present invention.

Further, the structures of the compound 2 and the compound 3 as a photopolymerization initiator are as follows.

[Chemistry 20]

[Chem. 21]

<evaluation>

Each of the obtained colored patterns was evaluated for each item of shape, light resistance, heat resistance, and solvent resistance. The evaluation method and evaluation criteria are as follows.

The evaluation results are collectively shown in Table 4.

1-1. Evaluation of the shape of the colored pattern (1) Linearity

The evaluation of the shape of the colored pattern can be evaluated by the linearity and the notch of the edge portion of the colored pattern. Using an optical microscope, the edge portion of the colored pattern was photographed on the photograph at 200 times in the reflection mode, and the pixel edge portion was observed in a 5 cm × 5 cm photograph, and evaluated according to the following criteria.

-Linearity evaluation benchmark -

○: The edge portion of the colored pattern can be seen as a straight line

×: a part or the whole of the colored pattern is jagged,

The edge portion of the colored pattern is preferably linear.

That is, if the edge portion of the colored pattern becomes jagged due to residual film or undercut or the like, the colored pattern (pixel pattern) of the color filter is formed by the colored photosensitive composition of the present invention. In the case of the case, it is necessary to increase the overlap with the black matrix, and the width of the black matrix is widened to cause a decrease in the aperture ratio. Moreover, when the overlap with the black matrix is not increased, there is a possibility that a portion having no coloring pattern and being hollow is generated in the vicinity of the edge of the black matrix. Further, when the edge portion of the colored pattern is serrated, there is a practical problem that the transparent electrode formed thereon is broken and the resistance value is increased.

1-2. Evaluation of the shape of the colored pattern (2) Notch

As for the notch of the colored pattern, the edge portion of the colored pattern was imaged on a photograph at 200 times in a reflection mode using the optical microscope for each of the obtained colored patterns, and the notch was evaluated based on the following criteria. Here, the term "notch" refers to a case where any one of the following shapes is observed: (A) a shape in which the edge portion is not changed in the half moon shape, and (B) a case where it is found to be more elongated than (A), but is surrounded by In contrast, the line width is discontinuously thinned and is considered to have a notched shape. In the case of this evaluation, when one notch was found, a gap was formed.

If a notch is formed, the portion is white and leaks light, so it is not preferable in practical use.

- Gap evaluation benchmark -

○: (1) The shape of the colored pattern was a trapezoidal or rectangular shape, and (2) no notch was found.

×: At least one item in the items (1) and (2) above does not match.

1-3. Evaluation of the shape of the colored pattern (3) Comprehensive evaluation of the shape of the pattern

Considering the above two items of linearity and notch, the evaluation of the shape is comprehensively evaluated by the following evaluation criteria.

- Pattern evaluation comprehensive evaluation benchmark -

○: ○ evaluation in both linearity and notch

△: Any project with linearity or notch is evaluated ○

×: Both linearity and notch are not in compliance with ○ evaluation

2-1. Evaluation of reliability (1) Light resistance

In a convection oven, the glass substrate on which the colored pattern was formed after the development step was post-baked at 230 ° C for 30 minutes. The chromaticity of the substrate was measured with OSP-SP100 (Olympus Co., Ltd.), and then degassed under nitrogen replacement, and sealed in a tank.

The sealed substrate was placed in a helium gas weathering tester "SX-75" (suga test instruments Co., Ltd.) at a temperature of 30 ° C, a humidity of 50%, and a blackboard temperature of 63 ° C, from the glass surface. The side was irradiated for 180 W and 120 hours.

Thereafter, the chromaticity of the substrate was measured by OSP-SP100 (Olympus Co., Ltd.), and ΔE ^* ab was obtained from the chromaticity of the colored pattern before and after the irradiation.

In the evaluation, the case where ΔE ^* ab was 3.0 or less was evaluated as excellent in light resistance.

2-2. Reliability evaluation (2) Heat resistance

The glass substrate having the colored pattern after post-baking in the same manner as the evaluation of the light resistance was further subjected to reheating at 230 ° C for 40 minutes in a convection oven.

Thereafter, the chromaticity of the substrate was measured by OSP-SP100 (Olympus Co., Ltd.), and ΔE ^* ab was determined from the chromaticity of the colored pattern before and after the reheating step.

In the evaluation, when ΔE ^* ab was 3.0 or less, it was evaluated that the heat resistance was excellent.

3. Evaluation of solvent resistance

The chromaticity of the glass substrate having a colored pattern after post-baking was measured by OSP-SP100 (Olympus Co., Ltd.) in the same manner as the evaluation of the reliability, and N-methyl-2-pyrrolidone (hereinafter) In the abbreviated as "NMP", it was immersed at 23 ° C for 30 minutes, and ΔE ^* ab was obtained from the chromaticity of the colored pattern before and after immersion. The color is measured by OSP-SP100 (Olympus Co., Ltd.). Further, the change in the shape of the colored pattern before and after immersion in NMP was observed by observation with an optical microscope.

When ΔE ^* ab is 3 or more, or a shape change occurs, various solvent resistances used for panel processing in production of a liquid crystal display device, etc., are insufficient, and it becomes a practical problem.

The results obtained were evaluated based on the following evaluation criteria.

- Evaluation criteria -

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

×: At least one item in the items (1) and (2) above does not match.

4. Comprehensive evaluation

- Evaluation criteria -

○: (1) The evaluation of the pattern shape and the solvent resistance was ○, and (2) the ΔE ^* ab in the light resistance evaluation and the heat resistance evaluation were both 3.0 or less.

×: At least one item in the items (1) and (2) above does not match.

As shown in Table 4, each of the colored patterns obtained by using the colored photosensitive composition of the examples was excellent in linearity, good in shape, and free from chipping, and was also excellent in various reliability and solvent resistance. On the other hand, the ΔE ^* ab before and after the light resistance or heat resistance of each of the colored patterns obtained by using the colored photosensitive compositions of Comparative Examples 1 to 14 was more than 3.0, and the reliability was poor.

According to Comparative Example 2 to Comparative Example 5, Comparative Example 7, Comparative Example 8, Comparative Example 10, and Comparative Example 11, it is understood that the oxidized azo compound which does not have a polymerizable group and does not correspond to the specific additive of the present invention has light resistance improvement. The effect is accompanied by discoloration or decomposition in the heating step, and as a result, heat resistance is poor. On the other hand, the oxidized azo compound which is a specific additive in the present invention can improve the light resistance and also has an effect of improving heat resistance, and can realize overall reliability.

Further, according to the comparison between Example 2 and Example 1, it is understood that any of the examples obtains equally good results, and in the case of pattern exposure to which a laser exposure machine is applied, the excellent effect of the present invention is obtained similarly to the exposure of the high pressure mercury lamp. .

Claims (10)

A colored photosensitive composition comprising: (A) a pigment having a phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, (E) a photopolymerization initiator, and (F) a compound represented by the following formula (1); [Chemical Formula 1] [In the general formula (1), R ¹ and R ² each independently represent a divalent to tetravalent linking group, and Y ¹ and Y ² each independently represent a single bond, an oxygen atom, an ester group, and have a carbon number of 2 or more. a divalent aromatic group having a carbon number of 30 or less, a divalent aromatic group having a carbon number of 6 or more and 30 or less, a polyethylene glycol group, or a combination of a plurality of such groups; P ¹ and P ² are each independently The ground indicates a polymerizable group; m and n each independently represent an integer of 1 or more and 3 or less]. The colored photosensitive composition according to claim 1, wherein the content of the compound represented by the above formula (1) is 0.1 wt% or more with respect to all solids of the composition. Below wt%. The colored photosensitive composition according to the first aspect of the invention, wherein, in the general formula (1), at least one of the polymerizable groups represented by P ¹ and P ² is selected from the group consisting of an acrylonitrile group and A polymerizable group of a methacrylonitrile group. The colored photosensitive composition according to claim 1, wherein the (A) coloring matter having a phthalocyanine skeleton contains a coloring material containing a metal in a molecule. The colored photosensitive composition according to claim 1, wherein the (A) coloring material having a phthalocyanine skeleton contains a green pigment. The colored photosensitive composition according to claim 1, wherein the (A) pigment having a phthalocyanine skeleton comprises C.I. Pigment Green 7, C.I. Pigment Green 36, or C.I. Pigment Green 58. A method of producing a color filter, comprising: applying a coloring photosensitive composition according to any one of claims 1 to 6 to a substrate to form a coloring layer; After the colored layer is exposed to a pattern, the uncured portion is developed and removed by a developing solution to form a colored pattern. A color filter manufactured by the manufacturing method as described in claim 7 of the patent application. A liquid crystal display device comprising the color filter according to item 8 of the patent application. An organic EL display device comprising the color filter according to item 8 of the patent application.