JP2009210870A - Colored composition for color filter, method for manufacturing color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter with excellent productivity through 405 nm-wavelength laser exposure capable of reducing the size of a mask or making a mask unnecessary, and to provide a high-sensitivity colored composition suitable for the manufacturing of the color filter by 405 nm-wavelength laser exposure. <P>SOLUTION: The colored composition comprises a pigment (A), resin (B), a monomer (C) having an ethylenically unsaturated double bond, and a photopolymerization initiator (D) represented by a general formula (1), wherein the colored composition is cured upon irradiation with a laser of a 405 nm wavelength. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored composition used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a method for producing a color filter using the colored composition.

  In recent years, color liquid crystal display devices have formed a large market as liquid crystal color televisions, car navigation and liquid crystal display device-integrated notebook personal computers. Monitors and televisions for desktop personal computers that take advantage of energy-saving and space-saving features It is also popular.

  The filter segment constituting the color filter used in the color liquid crystal display device is generally coated with a photosensitive material on a glass substrate or the like, dried and removed excess solvent, and then passed through a photomask for pixel formation. It is formed by irradiating an active energy ray, curing (negative type) or increasing alkali solubility (positive type), and removing a portion that dissolves with an alkali solution or the like. By repeating this for each color, a color filter is created.

  With the recent increase in size of products using color filters, the size of photomasks for forming filter segments is inevitably increased. In particular, when the substrate size is increased, it is necessary to manufacture a large photomask with high accuracy, and the cost of the photomask becomes very high, leading to an increase in manufacturing cost. Therefore, research and development of a filter segment forming method that does not require mask miniaturization or a mask is actively performed. Examples of the filter segment forming method that does not require mask miniaturization or a mask include a printing method, an ink jet method, and a laser ablation method.

  The printing method does not require a photomask, but has a problem of printing alignment and blurring. The inkjet method needs to process too many dots and has a problem of yield.

  The laser ablation method is a method of forming a pattern by irradiating a colored resin film with high-energy laser light and evaporating the colored resin film in the irradiated region. With the laser ablation method, the photomask can be eliminated or reduced, but when the resin film is evaporated with laser light, the modified product of the resin film may remain in the surrounding area or burrs may be formed on the evaporated edge. Causes defects when assembled into the device. In particular, the modified product of the resin film is difficult to remove and tends to be defective.

In recent years, with the development of laser light sources of various wavelengths, research has been conducted to use them for curing colored resin films rather than ablation. In particular, a laser using a 405 nm laser requires a mask because a direct drawing method is possible, so that practical application is desired. In Patent Document 1, studies have been made to expose a cured composition using a laser having a wavelength of 405 nm as an exposure light source. However, the 405 nm laser is weak in energy and requires a long time for curing a colored resin film, or oxygen blocking. There are many problems such as requiring a film.
Japanese Patent No. 3912405

  From such a background, the present invention aims to provide a method for producing a color filter with excellent productivity by laser exposure at a wavelength of 405 nm capable of reducing the size of the mask or maskless, and is suitable for manufacturing a color filter by laser exposure at a wavelength of 405 nm. An object is to provide a highly sensitive coloring composition.

  The problems include a pigment (A), a resin (B), a monomer (C) having an ethylenically unsaturated double bond, and a photopolymerization initiator (D) represented by the following general formula (1). This is solved by a coloring composition characterized by being cured by irradiation with a laser having a wavelength of 405 nm.

General formula (1):
[In general formula (1),
R ¹ and R ² are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, or an alicyclic group. A substituted alicyclic group, an alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an amino group, a substituted amino group, or a substituted R ¹ and R ² bonded together. A heterocyclic ring that may be
R ³ and R ⁴ are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, or an alicyclic group. A substituted alicyclic group, an alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an amino group, a substituted amino group, or a substituted R ¹ and R ² bonded together; Is a good heterocycle,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkenyl group, or a substituted group. An alkenyl group. (However, not all of R ⁵ , R ⁶ , R ⁷ and R ⁸ become an aryl group or a substituted aryl group.)]
In the preferable aspect of the coloring composition by this invention, a benzophenone derivative and / or a thioxanthone derivative are further included as a sensitizer (E).

In a preferred embodiment of the coloring composition according to the present invention, the content of the sensitizer is 5 to 150% by weight based on the photopolymerization initiator represented by the general formula (1). A step of forming a colored coating film on the substrate using the colored composition, a step of irradiating a portion of the colored coating film to be a filter segment with a laser having a wavelength of 405 nm, and a step of forming the colored coating film. The present invention relates to a method for manufacturing a color filter, in which an uncured portion is removed and a filter segment is formed a plurality of times to form at least two color filter segments.

  The present invention also relates to a color filter comprising at least two color filter segments formed from the colored composition.

  Since the coloring composition of the present invention can be sufficiently cured to the inside of the coating film in a short time, even when a laser having a wavelength of 405 nm, which has low energy, is used, downsizing of an expensive photomask or photo Maskless can be realized, and a color filter can be manufactured at low cost.

First, the coloring composition of the present invention will be described.
The coloring composition of the present invention is a coloring composition used for forming a filter segment of a color filter, and is a pigment (A), a resin (B), and a monomer (C) having an ethylenically unsaturated double bond. And a photopolymerization initiator (C) represented by the general formula (1) and, if necessary, a sensitizer (D).

[Pigment (A)]
As the pigment contained in the colored composition of the present invention, a commercially available organic pigment can be used, and a dye, a natural pigment, or an inorganic pigment can be used in combination according to the hue of the filter segment to be formed. .

As the organic pigment, those having high color developability and high heat resistance, particularly high heat decomposition resistance are preferably used. An organic pigment can be used individually by 1 type or in mixture of 2 or more types.
Further, the organic pigment may be refined by salt milling, acid pasting or the like.

  Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown by a color index (C.I.) number.

  In the case of forming a red filter segment using the colored composition of the present invention, C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 168, 177, Red pigments such as 178, 179, 184, 185, 187, 192, 200, 202, 208, 210, 216, 220, 223, 224, 226, 240, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  In the case of forming a green filter segment using the colored composition of the present invention, C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37, and 58 can be used. A yellow pigment can be used in combination with the green coloring composition.

  When forming a blue filter segment using the colored composition of the present invention, C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 64, and 80 can be used. A purple pigment can be used in combination with the blue coloring composition.

  In the case of forming a yellow filter segment using the colored composition of the present invention, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 82,185,187,188,193,194,198,199,213, and it can be used yellow pigment 214, and the like.

  In the case of forming a purple filter segment using the coloring composition of the present invention, C.I. I. Pigments such as pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used.

  In the case of forming a magenta color filter segment using the colored composition of the present invention, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 146, 177, 178, 184, 185, 187, 200, Pigments such as 202, 208, 210, 246, 254, 255, 264, 270, and 272 can be used. A yellow pigment can be used in combination with the magenta colored composition.

  In the case of forming a cyan filter segment using the colored composition of the present invention, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, and 80 pigments can be used.

  In the case of forming an orange filter segment using the colored composition of the present invention, C.I. I. Pigment oranges 36, 43, 51, 55, 59, 61, 71, 73, and the like can be used.

  The coloring composition can contain an inorganic pigment in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness. Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium Examples thereof include black, synthetic iron black, and carbon black. An inorganic pigment can be used individually by 1 type or in mixture of 2 or more types. The inorganic pigment can be used in an amount of 0.1 to 10% by weight based on the total weight of the pigment (100% by weight).

  Moreover, the coloring composition of this invention can be made to contain a dye within the range which does not reduce heat resistance for color matching. The dye can be used in an amount of 0.1 to 10% by weight based on the total weight of the pigment (100% by weight).

[Resin (B)]
The colored composition of the present invention contains a transparent resin in order to improve the dispersibility of the pigment and increase the adhesion to the coated substrate. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in combination of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  The upper limit of the content of the resin (B) in the colored composition of the present invention is preferably 500% by weight or less, more preferably 300% by weight or less, based on the pigment. If it exceeds 500% by weight, the film thickness becomes too thick to obtain a coating film having the required chromaticity. On the other hand, the lower limit is preferably 15% by weight or more, more preferably 25% by weight or more, based on the pigment. If it is 15% by weight or less, it is difficult to disperse the pigment, and the storage stability may be impaired.

[Monomer (C) having an ethylenically unsaturated double bond]
A monomer having an ethylenically unsaturated double bond is a component that is cured by irradiation with a laser having a wavelength of 405 nm.

Examples of monomers having an ethylenically unsaturated double bond include
Singles such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecanyl (meth) acrylate Functional (meth) acrylic acid ester monomers;
Monofunctional (meth) acrylic acid ester monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Monofunctional monomers having a carboxyl group such as (meth) acrylic acid and β-carboxyethyl (meth) acrylate;
Other monofunctional monomers such as styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile;
Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, or neopentyl glycol modified Trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) Multifunctional such as acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid ester of methylolated melamine Meth) acrylic acid esters;
Other functional epoxy (meth) acrylic esters such as 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and neopentyl glycol diglycidyl ether di (meth) acrylate ;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, etc .; and
A mixture of two or more of these may be mentioned, but is not necessarily limited thereto.

  The upper limit of the content of the monomer (C) having an ethylenically unsaturated double bond in the colored composition of the present invention is preferably 300% by weight or less, more preferably 200% by weight or less, based on the resin (B). If it is more than 300% by weight, the shape of the formed filter segment may become an overhang shape or the linearity may deteriorate. On the other hand, the lower limit is preferably 10% by weight or more, more preferably 20% by weight or more, based on the pigment resin (B). If it is 10% by weight or less, the coating film may not be cured.

[Photopolymerization initiator (D)]
The photopolymerization initiator (D) used in the present invention is represented by the following general formula (1).

General formula (1):
[In General Formula (1), R ¹ and R ² are
Each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, an alicyclic group, a substituted alicyclic group , An alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an amino group, a substituted amino group, or an optionally substituted heterocyclic ring in which R ¹ and R ² are bonded to each other ,
R ³ and R ⁴ are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, or an alicyclic group. A substituted alicyclic group, an alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an amino group, a substituted amino group, or a substituted R ¹ and R ² bonded together; Is a good heterocycle,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkenyl group, or a substituted group. An alkenyl group. (However, not all of R ⁵ , R ⁶ , R ⁷ and R ⁸ become an aryl group or a substituted aryl group.)]
Since the initiator represented by the general formula (1) has an absorption at 405 nm and is less susceptible to oxygen inhibition than other general photopolymerization initiators, it has oxygen characteristics for 405 nm laser exposure. High sensitivity can be obtained without using a blocking film. Particularly preferred is the compound (1a) represented by the following formula (1a).

General formula (1a):

  The upper limit of the content of the photopolymerization initiator (D) in the colored composition of the present invention is preferably 1,000% by weight or less, and preferably 800% by weight or less, based on the monomer (C) having an ethylenically unsaturated double bond. Is more preferable. If it is more than 1,000% by weight, the developability may be deteriorated, and the heat resistance and solvent resistance of the coating film may be inferior. On the other hand, the lower limit is preferably 1% by weight or more, more preferably 5% by weight or more, based on the monomer (C) having an ethylenically unsaturated double bond. If it is 1% or less, the coating film may not be cured.

[Sensitizer (E)]
The coloring composition of the present invention is further enhanced in sensitivity by using an appropriate sensitizer in combination with a photopolymerization initiator. As the sensitizer, a compound having absorption at 405 nm is preferable. In particular, benzophenone derivatives and thioxanthone derivatives are preferably used. First, as benzophenone derivatives, benzophenone, dibenzosuberone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′- Dimethyl-4-methoxybenzophenone, 2,4-dichlorobenzophenone, 2,4′-dichlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-morpholinobenzophenone, 4,4′-dimethylaminobenzophenone, 4, 4 '-Diethylaminobenzophenone (EAB), bis [9,9- (2,3,6,7-tetrahydro-1H, 5H-benzo [i, j] quinolidinyl)] methanone, bis (N-ethyl-1,2, 3,4-tetrahydro-6-ki Noryl) ketone, 3,3,4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4 ′, 4 ″ -diethylisophthalone, and the like. Next, as thioxanthone derivatives, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone (DETX), 2,4 -Diisopropyl thioxanthone etc. are mentioned. These sensitizers can be used individually by 1 type or in mixture of 2 or more types. The content of the sensitizer is preferably 1 to 200% by weight, more preferably 5 to 150% by weight, based on the photopolymerization initiator (D). If the amount is less than 1% by weight, there is no effect as a sensitizer. If the amount is more than 150% by weight, the light absorption of the sensitizer increases, and the light absorption of the photoinitiator is inhibited.

(Optional component)
The coloring composition of the present invention can further contain a polyfunctional thiol that functions as a chain transfer agent.

  The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimerca DOO -s- triazine, and 2-(N, N-dibutylamino) -4,6-dimercapto -s- triazine.

  These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types. The content of the polyfunctional thiol is preferably 1 to 300% by weight, more preferably 5 to 200% by weight, based on the monomer (C) in the colored composition. If it is less than 1% by weight, there is no effect of the chain transfer agent, and if it is more than 300% by weight, curing becomes insufficient.

  The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time.

  Examples of the storage stabilizer include benzyltrimethyl chloride; quaternary ammonium chloride such as diethylhydroxyamine hydrochloride; organic acids such as lactic acid and oxalic acid; methyl esters of the organic acids; t-butylpyrocatechol, tetraethylphosphine, And organic phosphines such as tetraphenylphosphine; and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on the colored composition.

  The colored composition of the present invention may contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the transparent substrate.

As a silane coupling agent, for example,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane;
(meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane;
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3, 4-epoxycyclohexyl) epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane;
and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight in the colored composition. If the amount is less than 0.01% by weight, the effect of the silane coupling agent is not obtained. If the amount is more than 10% by weight, the stability over time may be deteriorated or the coated surface may be repelled.

  In the colored composition of the present invention, a pigment is sufficiently dispersed in the composition, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. In order to facilitate the process, a solvent can be contained.

  Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,5,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ -Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol Ether monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, Cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether Ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexane Examples include sanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester, but are not limited to these. Used.

  The organic solvent can be used in an amount of 800 to 4,000 parts by weight, preferably 1,000 to 2,500 parts by weight with respect to 100 parts by weight of the dye in the photosensitive coloring composition.

  When dispersing the pigment in the monomer having an ethylenically unsaturated double bond, a dispersant such as a surfactant, a resin-type pigment dispersant, and a dye derivative can be appropriately used. The dispersant is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in a transparent resin and an organic solvent using the dispersant is used. In this case, a color filter having excellent transparency can be obtained. The pigment dispersant can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on the pigment in the coloring composition.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate. , Anionic surface activity such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Agent;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines;
A fluorosurfactant; and
Examples include silicone-based surfactants.

  The resin-type pigment dispersant is a resin having a pigment affinity part having a property of adsorbing to a pigment and a part compatible with a monomer having an ethylenically unsaturated double bond. It functions to stabilize dispersion in a monomer having an ethylenically unsaturated double bond.

Specifically, as a resin-type pigment dispersant,
Polycarboxylic acid ester such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamidophosphoric acid Oily dispersants such as salts, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and amides formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group and salts thereof;
(Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, and other water-soluble polymer compounds, Aqueous dispersants such as polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compound-based, and phosphate ester-based are used. These can be used alone or in admixture of two or more.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used, and these can be used alone or in admixture of two or more.

(Manufacturing method of coloring composition)
The coloring composition of the present invention comprises a pigment, if necessary, a monomer having an ethylenically unsaturated double bond together with the pigment dispersant, a three-roll mill, a two-roll mill in a transparent resin and an organic solvent as necessary, It can be finely dispersed using various dispersing means such as a sand mill, a kneader, and an attritor, and can be manufactured by adding a photopolymerization initiator. Moreover, the coloring composition for color filters containing 2 or more types of pigment | dyes can also mix and manufacture what disperse | distributed each pigment | dye separately in the monomer etc. which have an ethylenically unsaturated double bond separately.
The colored composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

Next, a method for manufacturing the color filter of the present invention will be described.
The method for producing a color filter of the present invention comprises a step of forming a colored coating film on the substrate using the colored composition, and a portion of the colored coating film that becomes a filter segment is irradiated with a laser having a wavelength of 405 nm and cured. And the step of removing the uncured portion of the colored coating film and the step of forming a filter segment are repeated a plurality of times to form filter segments of at least two colors.

  The color filter produced by the method of the present invention comprises a filter segment on a substrate, and for example, at least two colors selected from the group consisting of a black matrix and red, green, blue, yellow, orange, and cyan. Filter segments.

(Colored coating film forming process)
In the colored coating film forming process, the colored composition of the present invention is applied by spin coating or die coating, and an excess solvent is removed as necessary to form a colored coating on the substrate.

  As a substrate for the color filter, glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc., which have high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A plate is used.

  In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

(Exposure and curing process)
In the exposure / curing step, the portion that becomes the filter segment of the colored coating film is irradiated with a laser having a wavelength of 405 nm to be cured. At this time, direct writing without a mask is possible by irradiating the portion to be the filter segment while scanning with laser light.

(Uncured part removal process)
In the uncured portion removing step, the uncured portion of the colored coating film is removed to form a filter segment. When removing the uncured portion, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

  In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

  First, preparation of the acrylic resin solutions and pigment dispersions used in the examples and comparative examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(Preparation of acrylic resin solution)
In a reaction vessel, 800 parts of cyclohexanone was heated to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of 2-hydroxyethyl methacrylate, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate. A mixture of 65.0 parts of butyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction.

  After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an acrylic resin solution. Obtained. The weight average molecular weight of the acrylic resin was about 40,000.

  After cooling to room temperature, sample about 2 g of the resin solution, heat and dry at 180 ° C. for 20 minutes to measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. To prepare an acrylic resin solution.

(Preparation of pigment dispersion)
The mixture having the composition shown in Table 1 is stirred and mixed uniformly, dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, filtered through a 5 μm filter, and dispersed with a red pigment dispersion R-1 and a green pigment. Body G-1 was prepared.

PR254: Diketopyrrolopyrrole pigment (CI Pigment Red 254)
("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals)
PR177: Anthraquinone pigment (CI Pigment Red 177)
("Chromophthal Red A2B" manufactured by Ciba Specialty Chemicals)
PG36: Copper halide phthalocyanine pigment (CI Pigment Green 36)
("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
・ PY150: Nickel azo complex pigment (CI Pigment Yellow 150)
("E4GN" manufactured by LANXESS)
・ Pigment dispersant: “Solsperse 20000” manufactured by Nippon Lubrizol
・ Acrylic resin solution: previously prepared acrylic resin solution ・ Solvent: cyclohexanone

[Examples 1 to 9, Comparative Examples 1 to 10]
After stirring and mixing the mixture having the blending ratios shown in Tables 2 to 4 including the pigment dispersions R-1 and G-1 prepared previously so as to be uniform, each color coloring composition is filtered through a 1 μm filter. I got a thing.
Tables 2 to 4 show the composition of the coloring composition.

Initiator 1: Compound (a) Dimethyl (2-oxo-2-phenylethyl) sulfonium butyltriphenylborate Initiator 2: α-aminoalkylphenone photopolymerization initiator 2- (dimethylamino) -2- [ (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379” manufactured by Ciba Specialty Chemicals)
Initiator 3: α-aminoalkylphenone photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907” manufactured by Ciba Specialty Chemicals) ")
Initiator 4: Carbazole-based photopolymerization initiator 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole (“Adeka Arcles N-1414” manufactured by Asahi Denka Kogyo Co., Ltd.)
Initiator 5: Acylphosphine oxide photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide ("Lucirin TPO" manufactured by BASF)
Initiator 6: Oxime ester photopolymerization initiator 1,2-octadion-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“Irgacure OXE-01” manufactured by Ciba Specialty Chemicals) ")
Sensitizer 1: 4,4'-bis (diethylamino) benzophenone ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Sensitizer 2: 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Monomer 1: Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)

[Evaluation of sensitivity at 405 nm]
The compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were applied to a thickness of about 3 μm on a 10 cm × 10 cm glass substrate with a spin coater, and allowed to stand in an oven at 70 ° C. for 15 minutes. Was removed and dried. The film thickness at this time was defined as the film thickness after coating. Subsequently, stripe pattern exposure was performed using a direct-drawing type 405 nm laser exposure apparatus. This time was varied in 50 mJ / cm ² increments the exposure dose from 50 mJ / cm ² to 500 mJ / cm ^2. The direct-drawing 405 nm laser exposure apparatus used was DXP-3101 manufactured by Oak Seisakusho. The light source was a 405 nm semiconductor laser manufactured by Nichia Chemical Co., Ltd., 3 W module slot, and the illuminance was 898 mW / cm ² . After the exposure, spray development was performed with a developer comprising a 0.2% aqueous sodium carbonate solution to remove the unexposed portion, and the membrane was washed with ion-exchanged water. Thereafter, the thickness of the cured coating film was measured. The film thickness at this time was defined as the film thickness after development. The exposure amount at which the post-development film thickness was 90% or more with respect to the post-coating film thickness was defined as the required minimum exposure amount. The smaller the required minimum exposure, the higher the sensitivity.
Table 5 shows the results.

  Examples 1 to 9 using the initiator 1 had a small necessary minimum exposure amount and high sensitivity as compared with Comparative Examples 1 to 10. Further, among the examples, those containing an appropriate amount of a sensitizer were more sensitive.

[Preparation of color filter]
The red colored composition of Example 3 was applied on a 10 cm × 10 cm glass substrate with a spin coater to a thickness of about 3 μm, and left in an oven at 70 ° C. for 15 minutes to remove excess solvent and dry. Subsequently, stripe pattern exposure was performed using the direct drawing type 405 nm laser exposure apparatus. The exposure amount was 150 mJ / cm ² . Furthermore, after spray development with a developer composed of a 0.2% sodium carbonate aqueous solution to remove the unexposed portion, the substrate was washed with ion-exchanged water, and this substrate was heated at 230 ° C. for 30 minutes to have a line width of about 50 μm A red filter segment was formed. Next, a filter segment was formed using the green coloring composition of Example 8 next to the red filter segment by the same operation, and a color filter including two color filter segments was produced.

Claims (5)

Containing a pigment (A), a resin (B), a monomer (C) having an ethylenically unsaturated double bond, and a photopolymerization initiator (D) represented by the following general formula (1) A colored composition, which is cured by irradiation with a laser having a wavelength of 405 nm.
General formula (1):
[In general formula (1),
R ¹ and R ² are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, or an alicyclic group. A substituted alicyclic group, an alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an amino group, a substituted amino group, or a substituted R ¹ and R ² bonded together. A heterocyclic ring that may be
R ³ and R ⁴ are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, or an alicyclic group. A substituted alicyclic group, an alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an amino group, a substituted amino group, or a substituted R ¹ and R ² bonded together; Is a good heterocycle,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkenyl group, or a substituted group. An alkenyl group. (However, not all of R ⁵ , R ⁶ , R ⁷ and R ⁸ become an aryl group or a substituted aryl group.)]   Furthermore, the coloring composition of Claim 1 formed by containing a benzophenone derivative and / or a thioxanthone derivative as a sensitizer (E).   The coloring composition according to claim 2, wherein the content of the sensitizer is 5 to 150% by weight based on the photopolymerization initiator represented by the general formula (1).   A step of forming a colored coating film using the colored composition according to any one of claims 1 to 3 on a substrate, and a step of irradiating and curing a wavelength 405 nm laser to a portion to be a filter segment of the colored coating film; And a step of forming a filter segment by removing an uncured portion of the colored coating film a plurality of times to form a filter segment of at least two colors.   The color filter which comprises the filter segment of at least 2 colors formed from the coloring composition in any one of Claims 1-3.