JP2002105326A - Red resin composition, photosensitive red resin composition, method for producing red-colored pixel and method for producing color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red resin composition having high light transmittance, to provide a red resin composition having high light transmittance, photocurability and excellent resolution, to provide a method for producing a red colored pixel having high light transmittance and excellent dimensional accuracy, and to provide a method for producing a high definition color filter having red colored pixels which have high light transmittance and dimensional accuracy. SOLUTION: This red resin composition comprising a resin, and C.I. pigment violet 19 and a yellow pigment dispersed in the resin. The photosensitive red resin composition comprising C.I. pigment violet 19, a yellow pigment, a resin, a photopolymerizable monomer, and a photopolymerization initiator. The method for producing the red colored pixel, characterized by laminating a photosensitive layer comprising the photosensitive red resin composition to a substrate and then exposing and developing the photosensitive layer. The method for producing the color filter, characterized by containing a process for forming red colored pixels by the method for producing the red colored pixel.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a red resin composition,
The present invention relates to a photosensitive red resin composition, a method for producing a red colored pixel, and a method for producing a color filter.

[0002]

2. Description of the Related Art In recent years, color filters have been frequently used in liquid crystal display devices, sensors, color separation devices, and the like. Conventionally, as a method of manufacturing this color filter,
A method has been adopted in which a dyeable resin, for example, natural gelatin or casein is patterned, and the resultant is dyed mainly with a dye to obtain pixels. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials.

[0003] Recently, attention has been paid to a method of using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance, and much research has been conducted. According to this method, the manufacturing method is simplified, and the obtained color filter is known to be stable and have a long life. However, when a pigment is used as compared with a dye, there is a problem that the light transmittance is low.

[0004]

SUMMARY OF THE INVENTION The first aspect of the present invention provides a red resin composition having a high light transmittance. The invention according to claim 2 provides a photosensitive red resin composition having high light transmittance, excellent photocurability and excellent resolution. The third aspect of the present invention provides a method for manufacturing a red colored pixel having high light transmittance and excellent dimensional accuracy. The fourth aspect of the present invention is to provide a method of manufacturing a high-quality color filter having red colored pixels having high light transmittance and excellent dimensional accuracy.

[0005]

According to the present invention, there is provided a C.I. I. Pigment Violet 19 and a yellow pigment dispersed in a resin. The present invention also relates to a photosensitive red resin composition comprising CI Pigment Violet 19, a yellow pigment, a resin, a photopolymerizable monomer, and a photopolymerization initiator. The present invention also relates to a method for producing a red colored pixel, comprising laminating a photosensitive layer comprising the above-described photosensitive red resin composition on a substrate, and exposing and developing the photosensitive layer. The present invention also relates to a method for manufacturing a color filter, comprising a step of forming a red colored pixel by the above-described method for manufacturing a red colored pixel.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, pigments include
A red (pigment name is purple) color pigment is combined with a yellow pigment,
CI pigment violet 19 (color index name) is used as an essential component for the red pigment.

As the red pigment in the present invention, other red pigments can be used in addition to CI Pigment Violet 19, and the amount of the red pigment used is 0 to 90% by weight based on the whole red pigment. Is preferred, and 0 to
More preferably, it is 50% by weight. If the amount of the red pigment other than CI Pigment Violet 19 is too large, the light transmittance tends to decrease. Other red pigments include CI Pigment Red 9, 123, 155, 168, 177, 180, 21 under the color index name.
7, 220, 224 and the like.

As the above-mentioned yellow pigment, any of an inorganic pigment and an organic pigment can be used, but an organic pigment is preferred from the viewpoint of abundant color tone. As organic pigments, color index names, CI Pigment Yellow 20, 24,
83, 93, 109, 110, 117, 125, 13
9, 147, 154 and the like.

In the present invention, the mixing ratio of the red pigment and the yellow pigment is such that the weight ratio of the red pigment / the yellow pigment is 90/10 to 10%.
40/60, preferably 80/20 to 50
/ 50 is more preferable.

The resin used in the present invention is not particularly limited as long as it has a pigment dispersing property. However, a resin having a film forming property is preferable, and a resin having a developing property without hindering photosensitivity is more preferable.

Examples of such a resin include cellulose resins such as carboxymethylhydroxyethylcellulose and hydroxyethylcellulose, polyvinyl alcohol,
Polyvinylpyrrolidone and the like can be used.

Further, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl methacrylate,
Propyl acrylate, acrylate or methacrylate such as butyl acrylate, styrene,
Homopolymers or copolymers of styrene derivatives and other polymerizable monomers can be used.

Further, (meth) acrylic acid (meaning acrylic acid and methacrylic acid; the same applies hereinafter), itaconic acid,
Carboxyl group-containing polymerizable monomers such as maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride, monoalkyl citraconic acid and (meth) acrylic acid ester, styrene,
A copolymer with a styrene derivative or another polymerizable monomer can be used, and this copolymer is preferable.

The monoalkyl maleate preferably has 1 to 12 carbon atoms in the alkyl group.
Monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate,
Mono-n-butyl maleate, mono-n-hexyl maleate, mono-n-octyl maleate, mono-2-maleate
Examples include ethylhexyl, mono-n-nonyl maleate, and mono-n-dodecyl maleate.

The monoalkyl citraconic acid ester preferably has 1 to 12 carbon atoms in the alkyl, and includes monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, monoisopropyl citraconic acid, and mono-n-citraconic acid. Examples thereof include butyl, mono-n-hexyl citraconic acid, mono-n-octyl citraconic acid, mono-2-ethylhexyl citraconic acid, mono-n-nonyl citraconic acid, and mono-n-dodecyl citraconic acid.

Examples of the styrene derivative include α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

Further, as the resin, a resin having a photopolymerizable unsaturated bond may be used. Preferred examples of such a resin include oxirane rings such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether itaconate in a high acid value carboxyl group-containing resin. And a compound having one ethylenically unsaturated bond,
A hydroxyl group such as allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, N-methylol acrylamide and an ethylenically unsaturated bond are each 1 Resin having a compound (unsaturated alcohol) having
A resin in which a free isocyanate group-containing unsaturated compound is reacted with a carboxyl group-containing resin having a hydroxyl group, a resin in which an addition reaction product of an epoxy resin and an unsaturated carboxylic acid is reacted with a polybasic anhydride, a conjugated diene polymer or Resins obtained by reacting a hydroxyl group-containing polymer monomer with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic anhydride are exemplified.

The unsaturated equivalent of these resins is 200 to
3,000, preferably 230 to
00, more preferably in the range of 250 to 750.
It is particularly preferred that If the unsaturated equivalent is too small, the photosensitive material tends to be partially cured when adjusting the photosensitive material, particularly when the pigment is dispersed in a resin. Not done. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

When the above resin has photopolymerizability itself, or when it is given photosensitivity as a composition such as a photosensitive red resin composition as described later, it exhibits alkali developability after exposure. From the viewpoint of having an acid value of 20 to
It is preferably in the range of 300, more preferably in the range of 40 to 200, and particularly preferably in the range of 60 to 170. If the acid value is less than 20, alkali developability tends to decrease, and if it exceeds 300, the shape of the pixel pattern after alkali development tends to be unclear.

The weight average molecular weight of the resin is 1,
It is preferably in the range of 500 to 200,000, more preferably in the range of 5,000 to 100,000, and particularly preferably in the range of 10,000 to 50,000. Weight average molecular weight of 1,500
If it is less than 200, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity becomes high when it is made into a photosensitive solution, and the coatability, especially the coatability when spin coating is reduced. is there. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

As the resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000, particularly, a resin represented by the following general formula (I):

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (II)

Embedded image (However, in the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 1
2) represents a repeating unit represented by formula (I) / general formula (II) in a ratio of 1/1 to 5/1 (molar ratio).
Is preferred in terms of pigment dispersion stability, photosensitivity and the like.

The following are more preferred as the resin. (I) a compound having a repeating unit in which R ¹ is a group having a photoreactive unsaturated bond, R ² is a hydrogen atom, and R ³ is a hydrogen atom in the general formula (I); Wherein R ¹ is a group having a photoreactive unsaturated bond, R ² is a hydrogen atom or a group having a photoreactive unsaturated bond, R ³ is a group having a hydrogen atom, and (iii) a compound represented by the general formula ( In I), a repeating unit wherein R ¹ is a group having a photoreactive unsaturated bond, R ² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ³ is a hydrogen atom. And (iv) In formula (I), R ¹ and R ² are each independently a hydrogen atom or a group having a photoreactive unsaturated bond, and R ³ is an alkyl group having 1 to 12 carbon atoms. Having a certain repeating unit.

As a method for producing a resin having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II), for example, the repeating unit represented by the general formula (I) As a precursor of the resin having a repeating unit represented by the general formula (II), unsaturated alcohols (allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol,
Hydroxyacrylate, 2-hydroxymethacrylate, N-methylolacrylamide, etc.) and a resin having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) Compounds each having one oxirane ring and one ethylenically unsaturated bond (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, etc.) Is produced by an addition reaction.

As the resin precursor having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II), styrene or a derivative thereof and a monoalkyl maleate (for maleic acid) (Half ester) and monoalkyl citraconic acid (half ester of citraconic acid).

Examples of the styrene derivative include α-methylstyrene, m or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

Examples of the monoalkyl maleate include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate and mono-n-maleate. Xyl, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like.

Examples of the monoalkyl citraconic acid ester include monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, mono-n-hexyl citraconic acid, mono-n-octyl citraconic acid, and mono-citraconic acid. Examples thereof include 2-ethylhexyl, mono-n-nonyl citraconic acid, and mono-n-dodecyl citraconic acid.

The resins used in the red resin composition of the present invention include those represented by the general formulas (I) and (II) described above.
When using a resin having a repeating unit represented by,
Other resins may be used in combination. As the other resin, a resin other than the resin having the repeating unit represented by the general formula (I) and the general formula (II) among the above-mentioned resins is used, and further, an acrylic resin, an epoxy resin, Urethane resin, melamine resin and the like may be used. The other resin is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the resin.

The photosensitive red resin composition is prepared by adding a photopolymerizable monomer (a compound having at least one photopolymerizable unsaturated bond in a molecule), a photopolymerization initiator, and the like to the red resin composition. Can be.

The photopolymerizable monomer is a compound having at least one photopolymerizable unsaturated bond in the molecule.
Although not particularly limited, for example, those described in JP-A-11-310714 as monomers having two or more photopolymerizable unsaturated bonds in a molecule are preferable.

Specific examples include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like. These photopolymerizable monomers can be used alone or in combination of two or more.

The photopolymerization initiator is not particularly limited, but for example, those described in JP-A-11-310714 as the photoinitiator are preferred. Specific examples include benzophenone and N, N'-tetraethyl-4,4'-diaminobenzophenone. These photopolymerization initiators are used alone or in combination of two or more.

The red resin composition and the photosensitive red resin composition of the present invention may contain an organic solvent.

Examples of the organic solvent include ketone compounds, alkylene glycol ether compounds, alcohol compounds, aromatic compounds and the like. In particular,
Ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, dioxane, methyl cellosolve, ethyl cellosolve, butisoreselsolve, methyl cellosolve acetate, ethyl solosolve acetate, butyl solosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene Alkylene glycol ether compounds such as glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, diethylene Recall ether acetate, diethylene glycol ethyl ether acetate,
Diethylene glycol propyl ether acetate, diethylene glycol-iso-propyl ether acetate, diethylene glycol butyl ether acetate,
Diethylene glycol-tert-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol-iso-propyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol-tert- Polyethylene glycol alkyl ether acetate compounds such as butyl ether acetate, alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol, tetrahydrofuran, benzene, toluene, xylene, N-methyl -2-pyrrolidone, N-hydroxymethyl-2-pyrrolide Aromatic compounds such as 3-
Methyl-3-methoxybutyl acetate, ethyl acetate and the like. These can be used alone or in combination of two or more.

A resin used in the photosensitive red resin composition,
The mixing ratio of the pigment, the photopolymerizable monomer and the photopolymerization initiator is preferably 10 to 85% by weight, more preferably 20 to 60% by weight, based on the total amount thereof.
Particularly preferably 25 to 50% by weight, (b) the pigment is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 15 to 30% by weight, and (c) the photopolymerizable monomer is Preferably 2 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight,
(D) The photopolymerization initiator is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight, particularly preferably 5 to 15% by weight.
To 10% by weight.

When the amount of the resin in the photosensitive red resin composition is too small, the dispersion stability of the pigment tends to decrease,
If the amount is too large, the viscosity of the photosensitive solution becomes high, and the coating properties, particularly the coating properties during spin coating, tend to decrease. When the amount of the pigment is too small, the color density of the pixel tends to decrease, and when the amount is too large, the light sensitivity tends to decrease.

When the amount of the photopolymerizable monomer is too small, the photosensitivity tends to decrease, and when the amount is too large, the dispersion stability of the pigment tends to decrease. Further, if the photopolymerization initiator is too small, the photosensitivity tends to decrease, and if it is too large, the adhesion tends to decrease.

The organic solvent used as necessary is used so that the total solid content of the photosensitive red resin composition including the resin, pigment, photopolymerizable monomer and photopolymerization initiator is in the range of 5 to 40% by weight. Preferably. If the total solid content exceeds 40% by weight, the viscosity tends to be high and the applicability tends to be poor. If the total solid content is less than 5% by weight, the viscosity tends to be low and the applicability tends to be poor.

The photosensitive red resin composition of the present invention contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for controlling the dark reaction, and for improving the adhesion to the substrate. Titanate coupling agents (silane coupling agents having vinyl group, epoxy group, amino group, mercapto group, etc., isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.), ultraviolet absorbers, antioxidants Various additives such as can be used as needed.

Next, the production of the red resin composition and the photosensitive red resin composition of the present invention will be described.

In the red resin composition, the pigment is mixed and dispersed with the resin, the optional organic solvent, and the optional dispersant. At this time, the mixture is preferably subjected to dispersion treatment by kneading using a dispersing / kneading apparatus such as an ultrasonic dispersing machine, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. At this time, it is preferable to use at least 20 parts by weight of the resin with respect to 100 parts by weight of the pigment. If the amount of the resin is too small, the dispersion stability of the pigment tends to decrease. It is preferable to use at least 100 parts by weight of the organic solvent at the time of dispersion based on 100 parts by weight of the total amount of the pigment and the resin at the time of dispersion. If less than 100 parts by weight, the viscosity at the time of dispersion is too high,
In particular, when dispersing by a ball mill, a sand mill, a bead mill, or the like, dispersion may be difficult.

In order to obtain a photosensitive red resin composition, a photopolymerizable monomer and a photopolymerization initiator are further mixed. These may be mixed before the dispersion treatment, or may be mixed after the dispersion treatment. Is also good. The resin is not used in total during the dispersion,
The remainder may be mixed later, especially during the production of the photosensitive liquid for forming colored pixels.

Examples of the dispersant include anionic dispersants such as polycarboxylic acid-type polymer surfactants and polysulfonic acid-type polymer surfactants; nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers; An organic dye derivative such as an anthraquinone-based, perylene-based, phthalocyanine-based, or quinacdrine-based organic dye into which a substituent such as a carboxyl group, a sulfonate group, a carboxylic acid amide group, or a marine group is introduced. It is preferable because the dispersibility and dispersion stability of the pigment are improved. These pigment dispersants and organic dye derivatives are preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the pigment. If it exceeds 50 parts by weight, the chromaticity tends to shift.

The color filter of the present invention uses a photosensitive red resin composition to form a red colored pixel, and in addition, uses a pigment system suitable for a colored pixel such as green, blue or black. It can be manufactured by forming each color colored pixel using a resin composition of each color.

For a green colored pixel, a single green pigment may be used, or a yellow pigment system may be mixed with a green pigment system for toning. As the green pigment, either an inorganic pigment or an organic pigment can be used, but an organic pigment is preferable in terms of abundant color tone and the like. Examples of the organic pigment include phthalocyanine-based pigments, for example, Pigment Green 7, 36, and 37 under the color index name.

As a yellow pigment system, as a yellow pigment,
For example, CI Pigment Yellow 20, 24, 83, 9
3, 109, 110, 117, 125, 139, 14
7, 154, etc. can be used.

For a blue colored pixel, a single blue pigment system may be used, or a violet pigment system may be mixed with a blue pigment system for toning. As blue pigments, for example, CI Pigment Blue 15, 15:
3, 15; 4, 16: 6, 22, 60 and the like.
As a purple pigment, for example, in the color index name,
CI Pigment Violet 19, 23, 29, 37,
50 and the like.

For the black colored pixels, for example, black pigments such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide are used.

When a pigment system other than the red pigment system is used, the preparation of the resin composition of each color and the photosensitive resin composition can be performed according to the preparation of the red resin composition and the photosensitive red resin composition.

The substrate in the present invention is selected according to the intended use. For example, a transparent glass plate such as white plate glass, blue plate glass, silica-coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin, etc. Examples include a resin sheet, film, or plate, a metal plate such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. On these substrates, a black matrix may be formed in advance by chromium evaporation or the like.

For laminating a photosensitive layer made of a photosensitive red resin composition on a substrate, the photosensitive red resin composition is applied directly to the substrate, or the photosensitive red resin composition is temporarily applied to a support. After coating and forming a film, the film can be transferred to a substrate and laminated.

The method for applying the photosensitive red resin composition to the substrate includes roll coater coating, spin coater coating, spray coating, whey coater coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, There is an air knife coater application and the like. After application, 1-30 at a temperature of 50-130 ° C
It is preferable to dry for minutes

The thickness of the photosensitive layer formed in this manner is appropriately determined depending on the application, but is preferably in the range of 0.1 to 300 μm. When used for a color filter, the thickness is preferably in the range of 0.2 to 5 μm.

A photosensitive layer can be formed on a support in the same manner as described above. In order to laminate the photosensitive layer on the substrate, there is a method in which a film is laminated on the substrate and pressure-bonded through a roller. At this time, it is preferable to slightly heat the roller. Further, it is preferable to perform the pressure bonding under reduced pressure. The support is preferably peeled off after the photosensitive layer is laminated on the substrate. As the support, a polyethylene film, an acrylic resin film, a polyester film, or the like can be used.

Exposure to the photosensitive layer laminated on the substrate can be performed by irradiating the photosensitive layer with actinic rays in the form of pixels. Thereby, the film in the exposed portion can be cured. At the time of exposure, an oxygen shielding film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm, and then the film may be exposed.

As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a visible light laser and the like are suitable. Using these light sources, active light rays are irradiated in a pixel shape by pattern exposure through a photomask or direct depiction by scanning.

Following the above exposure, development is performed. Aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, or the like, or an organic base or salt such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-butylamine ( An unexposed portion is removed by spraying a developer such as an alkali developer) or an organic solvent or dipping the developer into the developer to obtain a colored pixel pattern of a cured film corresponding to the pixel.

After development, post-baking is preferably performed to further harden the pattern of the colored pixels. The post-bake temperature is preferably from 60 to 280C, and the heating time is preferably from about 1 to 60 minutes.

A colored pixel is formed by such a colored pixel forming step. In particular, in a method of manufacturing a color filter, the colored pixel forming step is performed for three to four different colored pixels including a red pixel forming step. It is preferable to repeat. For example, colored pixels of red, green, and blue are formed on a black matrix previously formed by chromium evaporation or the like. After a black matrix is formed using a black colored pixel forming material, red, green, and blue colored pixels are formed. Further, after forming the red, green, and blue colored pixels, a black matrix is formed in a gap between these colored pixels using a black pixel forming material. Red,
The order of forming green and blue colored pixels is arbitrary. The colored pixels are adapted to form pixels for each color.

[0060]

Next, the present invention will be described with reference to examples.

(1) Resin used: 50 mol% of styrene
-20% by mole of maleic acid monopropyl ester-30% by mole of maleic acid derivative, having a weight average molecular weight of 110
A copolymer having a value of 00 and an acid value of 65 (hereinafter referred to as copolymer A). (2) The repeating unit based on the maleic acid derivative has the following structure.

Embedded image

Example 1 (1) Production of red resin composition and photosensitive red resin composition 20 g of copolymer A as a resin, 12 g of CI Pigment Violet 19 as a pigment, 5 g of CI Pigment Yellow 83, and 200 g of diethylene glycol dimethyl ether were added. Dispersion treatment was performed for 2 hours using a bead mill to obtain a red resin composition. To this red resin composition were added 32 g of trimethylolpropane triacrylate as a photopolymerizable monomer, 6 g of benzophenone as a photopolymerization initiator, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, and 200 g of diethylene glycol dimethyl ether as an organic solvent. To obtain a photosensitive red resin composition.

(2) Production of Red Colored Pixel The photosensitive red resin composition is applied on a glass substrate (Corning Corp., trade name: 7059) by spin coating, and further dried at 110 ° C. for 5 minutes. 2.0 μm thick
(Photosensitive layer) was formed. The obtained film was exposed to 400 mJ / cm ² on the pixel with an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.3% by weight of potassium hydroxide. Table 1 and FIG. 1 show the transmittance, the chromaticity, and the transmission curve of the obtained red color pixel.

Example 2 (1) Production of Red Resin Composition and Photosensitive Red Resin Composition 30 g of copolymer A as a resin, 8 g of CI Pigment Violet 19 as a pigment, and CI Pigment Red 1
5 g of 77 and 10 g of CI Pigment Yellow 139 were added to 200 g of diethylene glycol dimethyl ether, and the mixture was dispersed using a bead mill for 2 hours to obtain a red resin composition. To this red resin composition, 32 g of pentaerthritol tetraacrylate as a photopolymerizable monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photopolymerization initiator, and 200 g of diethylene glycol dimethyl ether as an organic solvent. The resulting mixture was mixed to obtain a photosensitive red resin composition.

(2) Production of Red Colored Pixel The photosensitive red resin composition is applied on a glass substrate (Corning Corp., trade name: 7059) by spin coating, and further dried at 110 ° C. for 5 minutes. 2.0 μm thick
Was formed. The obtained film was exposed to 100 mJ / cm ² on a pixel by an ultra-high pressure mercury lamp through a negative mask,
Next, development was performed using an aqueous solution containing 0.6% by weight of sodium carbonate. Table 1 shows the transmittance and chromaticity of the obtained red color pixel.

Example 3 (1) Production of red resin composition and photosensitive red resin composition 40 g of copolymer A as a resin, 15 g of CI Pigment Violet 19 as a pigment, 4 g of CI Pigment Red 177, and CI Pigment Yellow 83 as a pigment 8g,
In addition to 200 g of diethylene glycol dimethyl ether, dispersion treatment was performed for 2 hours using a bead mill to obtain a red resin composition. To this red resin composition were added 32 g of trimethylolpropane triacrylate as a photopolymerizable monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photopolymerization initiator, and 200 g of diethylene glycol dimethyl ether as an organic solvent. To obtain a photosensitive red resin composition.

(2) Production of Red Colored Pixel The obtained photosensitive red resin composition was applied to a 6 μm-thick polyethylene terephthalate film by a gravure coating method, and dried at 100 ° C. for 12 minutes to obtain a film having a thickness of 2 μm.
A layer containing a 0 μm red-colored pixel forming material was formed, and a 40 μm-thick polyethylene film was applied thereon to obtain a photosensitive element. After peeling off the polyethylene film from the obtained photosensitive element, it was laminated on the same glass substrate as that used in Example 1. Laminating conditions were as follows: glass substrate temperature 40 ° C., laminating roll temperature 110 ° C., laminating pressure 3.4 × 10 ⁵ Pa
(3.5 kgf / cm ² ) at a lamination speed of 1.5 m / min.

Next, through a negative type photomask, the pixels were exposed to 60 mJ / cm ² from above the polyethylene terephthalate film with an ultra-high pressure mercury lamp, and then the polyethylene terephthalate film was peeled off. Development was performed under the conditions. Table 1 shows the transmittance and chromaticity of the obtained red color pixel.

Example 4 (1) Production of Green Resin Composition and Photosensitive Green Resin Composition 30 g of Copolymer A as a resin, 21 g of CI Pigment Green 36 as a pigment and 4 g of CI Pigment Yellow 154 were added to 200 g of diethylene glycol dimethyl ether. The mixture was dispersed using a bead mill for 2 hours to prepare a green resin composition. To this, 32 g of pentaerythritol tetraacrylate as a monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photopolymerization initiator and 200 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed. A green resin composition was obtained.

(2) Production of Blue Resin Composition and Photosensitive Blue Resin Composition 30 g of copolymer A as a resin, 17 g of CI Pigment Blue 15: 6 as a pigment, 1 g of CI Pigment Violet 23, and 200 g of diethylene glycol dimethyl ether The mixture was dispersed for 2 hours using a bead mill to prepare a blue resin composition. In addition, pentaerythritol tetraacrylate 32 was used as a monomer.
g, 6 g of benzophenone as a photopolymerization initiator and N,
2 g of N'-tetraethyl-4,4'-diaminobenzophenone and 200 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a photosensitive blue resin composition.

(3) Production of Color Filter A red-colored pixel was formed on a glass substrate on which a black matrix was formed with chromium by the same method and under the same conditions as in Example 1, and then heated at 180 ° C. for 10 minutes. Next, a green colored pixel was formed next to the red colored pixel using the photosensitive green resin composition in the same manner and under the same conditions as in Example 1, and then heated at 180 ° C. for 10 minutes. Next, a blue colored pixel was formed next to the green pixel pattern using the photosensitive blue resin composition in the same manner and under the same conditions as in Example 1, and then heated at 180 ° C. for 10 minutes.
As described above, a color filter in which one pixel was arranged in a mosaic shape of three colors of red, green, and blue of 30 μm × 100 μm was created.

Comparative Example 1 A photosensitive red resin composition was prepared in the same manner and under the same conditions as in Example 1 except that Pigment Red 177 was used instead of Pigment Bio Red 19, and the same as in Example 1. A red-colored pixel was formed by various methods and conditions, and its transmittance, chromaticity, and transmission curve are shown in Table 1 and FIG.

Comparative Example 2 A photosensitive red resin composition was prepared in the same manner and under the same conditions as in Example 1 except that Pigment Red 155 was used instead of Pigment Bio Red 19, and the same as in Example 1. A red colored pixel by various methods and conditions,
The transmittance and chromaticity are shown in Table 1.

[0074]

[Table 1]

The transmittance and chromaticity are measured using a color techno system.
The measurement was performed using a spectrocolorimeter JP7200F manufactured by Co., Ltd. The measured values Y, x, and y are the Y value, x value, and y value based on the XYZ (Yxy) color system, which is the CIE standard color system, where the Y value is the transmittance, and x and y are Chromaticity.

From Table 1, it can be seen that when Pigment Yellow Bio Red 19 is used as the red pigment, the chromaticity Y value is large and the color purity is good. (Examples 1 to 3). In contrast, when Pigment Bio Red 19 is not used (Comparative Examples 1 and 2), it is recognized that the value of Y of the chromaticity is low and the light transmittance is not good.

FIG. 1 shows a transmission curve of a red-colored pixel, curve 1 shows a transmission curve of a red-colored pixel of Example 1, and curve 2 shows a transmission curve of a red-colored pixel of Comparative Example 1. FIG.
As is clear from Example 1, Example 1 is superior to Comparative Example 1 in light transmittance. Thus, a color filter (Example 4) prepared using a photosensitive element having a photosensitive layer made of a photosensitive red resin composition having a higher light transmittance than ever before has excellent optical characteristics and is effective as a pixel display element. Was confirmed.

[0078]

The red resin composition according to the first aspect has a high light transmittance. The photosensitive red resin composition according to claim 2 has a high light transmittance, and is excellent in photocurability and resolution. The method for producing a red colored pixel according to claim 3 has a high light transmittance and an excellent dimensional accuracy. The method for manufacturing a color filter according to the fourth aspect is a high-quality one including a red colored pixel having high light transmittance and excellent dimensional accuracy.

[Brief description of the drawings]

FIG. 1 is a light transmission curve of a red-colored pixel prepared in Example 1 and Comparative Example 1.

[Explanation of symbols]

 1 Light transmission curve of red colored pixel created in Example 1 2 Light transmission curve of red colored pixel created in Comparative example 1

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 5/00 C08K 5/00 G02B 5/20 101 G02B 5/20 101 5/22 5/22 G03F 7/004 505 G03F 7/004 505 7/027 502 7/027 502 (72) Inventor Liu Junlin 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Works of Hitachi Chemical Co., Ltd. (72) Inventor Seiji Sunohara Goi Minami, Ichihara City, Chiba Prefecture 14 Kaigan, Hitachi Chemical Industry Co., Ltd., Goi Works (72) Inventor Tetsuya Okazaki 14 Goi Minami Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd., Goi Works (72) Inventor Seigo Yokochi 14, Goi Minami Coast, Ichihara City, Chiba Prefecture Address Hitachi Chemical Co., Ltd. Goi Works F-term (reference) 2H025 AA02 AA10 AA11 AB13 AC01 AD01 BC13 BC31 CB04 CB10 CB43 CC12 FA17 2H048 BA02 BA11 BA45 BA47 BA48 BB02 BB42 BB46 CA04 CA09 CA14 GA04 GA13 GA17 GA02 GA03 GA62 BC041 BC081 BC091 BC121 BG 041 BG051 BG061 EE039 EH078 EQ017 EU016 EU017 FD096 FD097 GP03 4J011 PA38 PA43 PA53 PA65 PA69 PA70 PB25 PB30 PC02 QA21 QA23 QA24 RA03 RA04 RA09 SA22 SA25 SA28 TA03 UA01 UA06 VA01 WA01 AAA ABA AA ABA AA ABA AA ABA AA ABA AA AA ABA AA AA ABA AA

Claims (4)

[Claims] A red resin composition comprising CI pigment violet 19 and a yellow pigment dispersed in a resin. 2. A photosensitive red resin composition comprising CI Pigment Violet 19, a yellow pigment, a resin, a photopolymerizable monomer and a photopolymerization initiator. 3. A method for producing a red-colored pixel, comprising laminating a photosensitive layer comprising the photosensitive red resin composition according to claim 2 on a substrate, exposing and developing. 4. A method for producing a color filter, comprising a step of forming a red colored pixel by the method for producing a red colored pixel according to claim 3.