JP2010015111A - Colored curable composition for ultraviolet laser exposure, pattern forming method, method for manufacturing color filter, color filter and display including the same - Google Patents

Abstract

A colored curable composition for ultraviolet laser exposure capable of forming a pattern having high adhesion to a substrate, a pattern forming method using the same, a method for producing a color filter, a color filter obtained thereby, and the color Provided is a display element including a filter.
At least (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a resin, wherein the (D) resin has a glycidyl group in the molecule, A colored curable composition for ultraviolet laser exposure comprising a resin having at least one selected from the group consisting of oxetanyl groups and N-substituted maleimide groups.
[Selection figure] None

Description

  The present invention relates to a colored curable composition for ultraviolet laser exposure, a pattern forming method, a color filter manufacturing method, a color filter, and a display device including the same.

  Color filters are indispensable components for liquid crystal displays. The liquid crystal display is compact compared to the CRT as a display device, and can save power, and has become more than equivalent in terms of performance due to technological advancement. Therefore, TV screens, personal computer screens, and other display devices It is being replaced by CRT.

In recent years, the development of liquid crystal displays has been expanded from the use of personal computers and monitors having a relatively small screen area to TV applications that require a large screen and high image quality.
In TV applications, higher image quality, that is, improvement in contrast and color purity is required compared to conventional monitor applications. In order to improve contrast, a finer particle size of a colorant (such as an organic pigment) used in a colored curable composition used for forming a color filter is required. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of this colored curable composition for color purity improvement.

  In response to the above requirements, a pigment dispersion composition having a finer particle diameter and higher dispersibility is required. In order to improve the dispersibility of the pigment, for example, the surface of the phthalocyanine pigment is usually modified with the derivative compound thereof, and the dispersion of a low molecular weight resin having a polar functional group that is easily adsorbed on the modified surface. A pigment dispersion composition containing a pigment, a surface modifier, and a dispersant is obtained while dispersing or stabilizing the pigment using the agent. Then, the obtained pigment dispersion composition further contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and other components to form a photosensitive composition, and a color filter is obtained by using this to obtain a color filter. ing.

If the pigment is made finer and the pigment content is increased, there is a problem that the stability of the line width is impaired when an image pattern is formed by the photolithography method. For TV applications, it is particularly required to provide a color filter at a low cost. However, the above-described problems centered on the development process have been required to be improved because the yield is lowered and the productivity is deteriorated.
In order to solve the above problems, many attempts have been made to improve the sensitivity by improving the photopolymerization initiator used in the photocurable composition for color filters. For example, a photopolymerizable composition using a triazine compound having a specific structure (see, for example, Patent Document 1), or a photo filter for a color filter using a mixture of one or more benzophenone, acetophenone, and thioxanthone compounds. A resist (see, for example, Patent Document 2) is disclosed.

In addition, as another proposal, the average double bond equivalent in the organic compound formed by summing the binder resin and the polymerizable monomer in the colored curable composition is specified, and further, the molecular weight of the binder resin is specified, and the firing is performed. Discloses a technique for forming a forward tapered shape (see Patent Document 3).
However, these techniques are inferior in productivity in the exposure process and the development process, cannot secure sufficient productivity, and therefore cannot reduce the price of the color filter.

In order to increase the productivity of the exposure process and the development process, it has been proposed to perform pattern formation by exposing with laser light (see Patent Document 4). Unlike mercury lamps that are normally used, lasers are expected to have characteristics that they have high linearity, high output, can be focused, and do not require a mask for pattern formation in the exposure process. Has been. However, even with the above prior art, the properties required for the color filter, such as insufficient adhesion to the substrate, were not satisfied. Also, an exposure apparatus that does not use a large photomask has been proposed in terms of reducing the total cost of the color filter. However, there is no specific material presentation, and a proposal of a material suitable for these devices has been desired.
JP-A-6-289611 Japanese Patent Laid-Open No. 9-80225 JP 2007-93811 A JP 2003-287614 A JP 2008-76709 A JP 2008-51866 A

The present invention relates to a colored curable composition for ultraviolet laser exposure capable of forming a pattern having high adhesion to a substrate and a pattern forming method using the same, particularly suitable for forming colored pixels of a color filter. It is an object of the present invention to provide a colored curable composition for optical laser exposure and a pattern forming method.
Another object of the present invention is to provide a method for producing a color filter having a colored pattern with excellent adhesion to a substrate using the pattern forming method of the present invention, a color filter obtained thereby, and the color filter. It is to provide a display element provided.

As a result of intensive studies, the present inventor has found that the above problems can be solved by the following method.
<1> At least (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a resin. The (D) resin has a glycidyl group and an oxetanyl in the molecule. A colored curable composition for ultraviolet laser exposure, comprising a resin having at least one selected from the group consisting of a group and an N-substituted maleimide group.
<2> The colored curable composition for ultraviolet light laser exposure according to <1>, wherein the (D) resin includes at least one resin selected from an acrylic copolymer, an epoxy resin, an oxetane resin, and a maleimide resin. .
<3> The colored curable composition for ultraviolet laser exposure according to <1> or <2>, which contains at least one of a hexaarylbiimidazole compound and an oxime ester compound as the (B) photopolymerization initiator.
<4> The colored curable composition for ultraviolet laser exposure according to any one of <1> to <3>, further comprising a silane coupling agent.
<5> The coloring for ultraviolet laser exposure according to any one of <1> to <4>, wherein the silane coupling agent is a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group. Curable composition.

<6> The colored curable composition according to any one of <1> to <5> is applied on a substrate to form a colored curable composition layer, and pattern exposure is performed with an ultraviolet laser. The pattern formation method including the process of hardening an exposure area | region.
<7> The pattern forming method according to <6>, wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm.
<8> A method for producing a color filter comprising a step of forming a colored pattern on a substrate by the pattern forming method according to <6> or <7>.
<9> A color filter manufactured by the method for manufacturing a color filter according to <8>.
<10> A display device comprising the color filter according to <9>.

In the present invention, an ultraviolet laser is used as exposure light. Since the output of the ultraviolet laser is high, productivity is improved, but there is a problem that adhesion to the substrate is deteriorated. The reason for this is presumed to be that the polymerization at the bottom of the film is not promoted because the output of the ultraviolet laser is high, and the degree of cure at the bottom of the film is insufficient.
In the present invention, by adding a resin having at least one group selected from the group consisting of a glycidyl group, an oxetanyl group, and an N-substituted maleimide group to the colored curable composition used for pattern formation in the present invention. The adhesion to the substrate could be improved.
Although this effect is not clear, one of the characteristics of the ultraviolet laser is that the illuminance is high, and heat is generated in the ultraviolet laser exposure process. The generated heat causes a reaction of a glycidyl group, oxetanyl group or N-substituted maleimide group present in the resin, promotes polymerization at the bottom of the film, and improves the degree of cure at the bottom of the film, thereby It is presumed that the adhesion could be improved.

According to the present invention, a colored curable composition for ultraviolet laser exposure and a pattern forming method having high adhesion to a substrate, and particularly suitable for forming colored pixels of a color filter, etc. Composition and a pattern forming method can be provided.
In addition, according to the present invention, it is possible to provide a method for producing a color filter having a colored pattern with excellent adhesion to a substrate, a color filter obtained thereby, and a display element including the color filter.

Hereinafter, the best mode for carrying out the invention will be described in detail.
[Pattern formation method]
The pattern forming method of the present invention includes at least (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a resin. As the (D) resin, a glycidyl group in the molecule, Exposing a colored curable composition for ultraviolet laser exposure containing a resin having at least one of oxetanyl group or N-substituted maleimide group in a pattern with an ultraviolet laser to cure the exposed region It is characterized by.

  In the pattern formation method of this invention, it has the exposure process exposed to a pattern shape with an ultraviolet light laser. By this exposure step, (A) the polymerization curing reaction of the polymerizable compound occurs and proceeds by the initiation species generated from the (B) photopolymerization initiator in the patterned exposure region in the colored curable composition, and at the same time, ultraviolet light. (D) Glycidyl group, oxetanyl group, or N-substituted maleimide group present in the resin molecule undergoes a thermal reaction due to heat generated by laser exposure, and a curing reaction occurs and proceeds. By curing, a pattern composed of a cured region and an uncured region is formed. After this exposure step, a development step may be performed as desired to remove the uncured region and form a pattern.

[Exposure process]
In the exposure method of the present invention, an ultraviolet laser is used as a light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  The wavelength that can be used in the present invention is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm. This is preferable in that it matches the photosensitive wavelength.

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
As the exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available ones such as EGIS (buoy technology) or DF2200G (Dainippon Screen Co., Ltd.) can be used. These devices are also preferably used.

  The ultraviolet laser has good light parallelism, and pattern exposure can be performed without using a mask during exposure, but the pattern shape is affected by the shape and profile of the output light. Therefore, it is preferable to expose the pattern using a mask because the linearity of the pattern becomes high.

<Colored curable composition>
The colored curable composition for ultraviolet laser exposure of the present invention contains at least (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a resin. ) A colored curable composition characterized in that the resin contains a resin having at least one selected from the group consisting of a glycidyl group, an oxetanyl group and an N-substituted maleimide group in the molecule.
The colored curable composition for ultraviolet light laser exposure has a minimum exposure amount of 50 mJ / cm ² or less that gives a residual film ratio of 90% or more when a step edge pattern is exposed with either a laser of 08 nm or 355 nm. It is a curable composition. The exposure is usually performed by irradiating 1 to 100 nS pulsed light 1 to 100 times.
Below, each structural component of the colored curable composition of this invention is explained in full detail.

[(A) polymerizable compound]
The colored curable composition for ultraviolet laser exposure of the present invention contains (A) a polymerizable compound.
The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

General formula (V)
^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(Wherein, ^{R 4} and ^{R 5} each independently represent H or CH _3.)

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount, etc. can be arbitrarily set in accordance with the performance design of the final photosensitive material. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the colored image portion, that is, the colored curable composition layer, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic ester, methacrylic ester, A method of adjusting both sensitivity and strength by using a styrene compound or a vinyl ether compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection and use method of the addition polymerization compound is also an important factor for compatibility with other components of the colored curable composition (for example, an alkali-soluble resin and an initiator). For example, the use of a low-purity compound The compatibility may be improved by using two or more kinds in combination, and a specific structure may be selected for the purpose of improving the adhesion to the substrate.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha) are preferred.

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha) Manufactured) is more preferable.

  (A) The content of the polymerizable compound is preferably 5% by mass to 55% by mass and preferably 10% by mass to 50% by mass in the total solid content in the colored curable composition layer of the present invention. Is more preferable, and it is still more preferable that it is 15 mass%-45 mass%.

[(B) Photopolymerization initiator]
The colored curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator that can be used in the present invention is preferably a compound that is sensitized by exposure light and initiates and accelerates the polymerization of the polymerizable compound (A), and has absorption at the exposure wavelength of the ultraviolet laser.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

Specific examples of organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc.
Japan 42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55-3070, JP JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243 JP, 63-298339, M .; P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. It is done.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol Forinophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4 -Acetophenone derivatives such as morpholinobyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples thereof include benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl dimethyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4- Di (9-acridinyl) butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di ( 9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9- Acridinyl) dodecane and other di (9-acridinyl) alkanes.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, oxalic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 -Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), And carbonyldi (t-hexylperoxydihydrogen diphthalate).

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- -Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaph Orofen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include, for example, JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, and JP-A-9-188710. Publications, JP 2000-131837 A, JP 2002-107916 A, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin “Rad Tech '98. Proceeding April 19 -22, 1998, Chicago ”etc., organic boron sulfonium complexes or organic boron described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561. Oxosulfonium complex, JP-A-6-175554 JP, JP-A-6-175553, organoboron iodonium complex, JP-A-9-188710, organoboron phosphonium complex, JP-A-6-348011, JP-A-7-128785, JP Specific examples include organoboron transition metal coordination complexes such as 7-140589, JP-A-7-306527, and JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797 And the compounds described. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, phosphonium salts described in European Patent Nos. 104,143, U.S. Pat. Nos. 339,049, 410,201. And iodonium salts described in JP-A-2-150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297. 442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013 No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604 Examples thereof include sulfonium salts described in each specification of No. 581. From the viewpoint of stability, it is preferably substituted with an electron-withdrawing group. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello
et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt, C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As photopolymerization initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime ester compounds, hexaarylbiimidazole compounds, onium compounds, benzophenones And acetophenone compounds are preferred.

  More preferably, it is at least one compound selected from the group consisting of oxime ester compounds, hexaarylbiimidazole compounds, and benzophenone compounds.

  Specific examples of the preferable photopolymerization initiator include CGI242 (manufactured by Ciba Specialty Chemicals), 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (black metal conversion). Product), EABF (manufactured by Hodogaya Chemical Co., Ltd.), and the compounds shown below.

  A photoinitiator can be used 1 type or in combination of 2 or more types. Moreover, when using the photoinitiator which does not have absorption in an exposure wavelength, it is necessary to use the compound which has absorption in an exposure wavelength as a sensitizer.

  The content of the photopolymerization initiator used in the present invention is preferably in the range of 0.1% by mass to 30% by mass and more preferably in the range of 1% by mass to 25% by mass with respect to the total solid content of the colored curable composition. The range of 0.5% by mass to 20% by mass is more preferable.

(Chain transfer agent)
The colored curable composition used in the present invention can optionally contain a chain transfer agent. In the present invention, the chain transfer agent has functions such as further improving the sensitivity of the sensitizing dye and the initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such chain transfer agents include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Another example of the chain transfer agent includes a thiol compound and the like, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline. , Β-mercaptonaphthalene and the like.

  Other examples of chain transfer agents include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), and JP-B-55-34414. And a hydrogen compound described in JP-A-6-308727 (eg, trithiane).

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

[(C) Colorant]
When forming a coloring pattern with the colored curable composition of this invention, it is preferable that a coloring agent is contained in a colored curable composition.
As the colorant, dyes and pigments can be appropriately selected and used. From the viewpoint of heat resistance and the like, a pigment is more preferable.

The pigment used as the colorant may be an inorganic pigment or an organic pigment, but it is preferable to use a pigment having a particle size as small as possible from the viewpoint of high transmittance. The average particle size is preferably 10 nm to 100 nm, and more preferably 10 nm to 50 nm.
In the colored curable composition used in the present invention, the use of a polymer dispersant described later improves the pigment dispersibility and dispersion stability even when the pigment size is small. A colored pixel having excellent color purity can be formed even if it is thin.

  Furthermore, in the present invention, among the pigments contained in the colored curable composition, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% in the total amount of the pigment, and the primary particles. The proportion of the pigment having a diameter exceeding 0.08 μm is preferably less than 5% in the total amount of the pigment.

When the ratio of the pigment having a primary particle diameter of less than 0.02 μm is less than 10%, the heat resistance and chromaticity change can be prevented, and the ratio of the pigment having a primary particle diameter exceeding 0.08 μm is 5 When it is less than%, the contrast is good, the temporal stability of the colored curable composition is good, and further, foreign matter failure can be prevented.
The proportion of the pigment having a primary particle size of less than 0.02 μm is preferably less than 5% from the viewpoints of heat resistance and chromaticity change prevention.
The proportion of the pigment having a primary particle diameter exceeding 0.08 μm is preferably less than 3% from the viewpoint of improving the contrast.

  The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, the TEM photograph is subjected to image analysis to examine the particle size distribution. For example, the particle size distribution can be grasped by measuring the total number of particles in the observation sample at 3 to 100,000 times and the number of pigment particles less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder is observed with a transmission electron microscope at 3 to 100,000 times, photographed, the major axis of 1000 primary particles is measured, less than 0.02 μm, and more than 0.08 μm Calculate the percentage of primary particles. This operation was performed for a total of three locations by changing the location of the pigment powder, and the results were averaged.

  Examples of the inorganic pigment that can be used as a colorant for forming a colored pattern (colored pixel) include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium And metal oxides such as lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

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

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66
C. I. Pigment Green 7, 36, 37

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a pigment for the red phase (R), an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment A pigment or a mixture with a perylene red pigment, an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is less than 100: 4, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

In addition, as a pigment for the green phase (G), a halogenated phthalocyanine pigment alone or a mixture thereof with a bisazo yellow pigment, quinophthalone yellow pigment, azomethine yellow pigment or isoindoline yellow pigment may be used. Can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the pigment for the blue phase (B), a phthalocyanine pigment can be used alone or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  As content of (C) coloring agent in the colored curable composition of this invention, 25 mass%-75 mass% are preferable with respect to the total solid (mass) of this composition, and 32 mass%-70 mass%. The mass% is more preferable. When the content of the colorant is within the above range, the color density is sufficient to ensure excellent color characteristics.

  In the present invention, it is particularly preferable to use an organic pigment as a colorant and to coat the pigment with a polymer compound in the pigment miniaturization step or dispersion step. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles Further, it is possible to use a coated pigment excellent in dispersion stability in which primary particles are stably maintained.

  A coated pigment which is a preferred embodiment in the present invention is a pigment coated with a polymer compound, but the coating is a new interface of a highly active pigment formed by miniaturization, and a heterocyclic ring is present in the side chain. It is considered that a coating pigment having higher dispersion stability can be obtained because a strong coating layer of the polymer compound is formed by a strong electrostatic action with the polymer compound having the above. That is, in the present invention, the coated polymer compound is hardly liberated even when the pigment after coating treatment is washed with an organic solvent that dissolves the polymer compound.

  The coated pigment as used in the present invention is one in which pigment particles such as organic pigments are coated with a polymer compound having a polar group such as a heterocyclic ring in the side chain, and the polymer compound is a part of the pigment particle surface or By being firmly coated all over, a higher dispersion stability effect can be obtained, which is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent described below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a surface-coated pigment as in the present invention, the liberation rate Is very small, 30% or less.

  The pigment after the coating treatment is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours using a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. And calculated as “mass of the polymer compound used in the initial treatment”. Separately, the pigment is washed with 1-methoxy-2-propanol, and the obtained liberation amount is divided by the “mass of the polymer compound used in the initial treatment” to obtain the liberation rate (%). .
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The coating treatment is preferably performed at the same time in the step of refining the pigment. Specifically, i) the pigment, ii) the water-soluble inorganic salt, and iii) a small amount of water-soluble that does not substantially dissolve ii). An organic solvent, and iv) a step of adding a polymer compound and mechanically kneading with a kneader or the like (referred to as a salt milling step), adding this mixture into water, stirring the mixture with a high-speed mixer or the like to form a slurry, The slurry is filtered, washed with water, and dried if necessary.

  The salt milling described above will be described more specifically. First, a small amount of iii) a water-soluble organic solvent as a wetting agent is added to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is poured into water. Stir with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When used in an oily varnish, it is possible to disperse the treated pigment before drying (referred to as filter cake) in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

During salt milling, iii) by using an organic solvent in combination with iv) at least partly soluble resin, the pigment is agglomerated during drying, and the surface is further coated with iv) at least partly soluble resin. Can be obtained.
Note that iv) the polymer compound may be added at the initial stage of the salt milling process, or may be added separately. It is also possible to add in the dispersion step.

  The polymer compound used for coating the pigment may be anything as long as it has an adsorptive group for the pigment. In particular, those coated with a polymer compound having a heterocyclic ring in the side chain are preferred. Such a polymer compound is preferably a monomer represented by the following general formula (1) or a polymer containing a polymer unit derived from a monomer comprising a maleimide or a maleimide derivative. A polymer containing a polymer unit derived from the monomer represented by the general formula (1) is particularly preferable.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.

As the alkyl group for R ¹ , an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of the preferred alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ¹ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
The alkylene group represented by R ² may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

  In general formula (1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

  Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, the alkyl group when RB represents an alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as methyl group, Examples include an ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formulas (2), (3), and (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  Specific examples of these compounds include the following MA-1 to MA-13 and the following M-1 to M-33, but the present invention is not limited thereto.

  In addition to the MA-1 to MA-13 and M-1 to M-33, the following compounds can be exemplified.

Even in the case of using the above-described coated pigment, it is more preferable to disperse the pigment using at least one dispersant and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, polymer dispersants such as Disperse Aid 9100 (both manufactured by San Nopco);

Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 161, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (bit Chemie Co., Ltd.) and the like. In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

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

  A pigment derivative is added to the above-described pigment dispersion composition as necessary. The pigment is introduced into the curable composition as fine particles by adsorbing a pigment derivative having a part having affinity for the dispersant or a polar group to the pigment surface and using it as an adsorption point of the dispersant. The re-aggregation can be prevented, and it is effective for constructing a color filter having high contrast and excellent transparency.

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

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

  The dispersion method can be performed, for example, by finely dispersing a pigment and a dispersant previously mixed with a homogenizer or the like using a bead disperser using zirconia beads or the like.

In the present invention, when a dye is used as the colorant, a uniformly curable colored curable composition is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

[(D) resin]
The colored curable composition of the present invention has the purpose of reacting with heat generated by an ultraviolet laser in addition to improving film properties, imparting development properties, etc., and has the purpose of accelerating curing, so that glycidyl group, oxetanyl group and A resin having at least one selected from the group consisting of N-substituted maleimide groups (hereinafter referred to as a specific resin as appropriate) is contained. The resin having the specific functional group used here is preferably a resin selected from polymer compounds such as acrylic copolymers, epoxy resins, oxetane resins, and maleimide resins.
Resin used for the colored curable composition of this invention can be used individually or in mixture of 2 or more types. In consideration of imparting development characteristics with an alkali, it is preferable to include at least an alkali-soluble resin in addition to the specific resin. Hereinafter, these other resins that can be used in combination with the specific resin will be described in detail.

  The alkali-soluble resin in the present invention acts as a binder for the colorant, and has a solubility in a developer used in the development processing step, particularly preferably an alkaline developer, when producing a color filter. As long as it is not particularly limited, an acrylic copolymer having a carboxyl group is preferred, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group-containing”). (Hereinafter referred to as “unsaturated monomer”) and other copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “copolymerizable unsaturated monomer”) (hereinafter referred to as “carboxyl group”). "Containing acrylic copolymer").

As a carboxyl group-containing unsaturated monomer,
For example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride Unsaturated dicarboxylic acids such as acids and mesaconic acids or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as [2- (meth) acryloyloxyethyl]; both ends of ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group.
Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name.
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Examples of the copolymerizable unsaturated monomer include:
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Unsaturation such as (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, etc. Carboxylic acid esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; unsaturated carboxylic acid oxetanyl esters such as oxetanyl (meth) acrylate; vinyl acetate, Carboxylic acid vinyl esters such as vinyl propionate, vinyl butyrate and vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  As the carboxyl group-containing acrylic copolymer in the present invention, a carboxyl group-containing acrylic copolymer having at least one group among glycidyl group, oxetanyl group and N-substituted maleimide group (hereinafter referred to as “acrylic copolymer”). And a carboxyl group-containing acrylic copolymer having no glycidyl group, oxetanyl group and N-substituted maleimide group (hereinafter referred to as “acrylic copolymer (D2)”). Exists. From the viewpoint of adhesion to the substrate, an acrylic copolymer (D1) is preferred.

As a specific example of the acrylic copolymer (D1),
Styrene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Styrene / acrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl acrylate copolymer,
Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane / t-butyl methacrylate copolymer,
Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) -3-ethyloxetane / styrene copolymer,
Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane / N-phenylmaleimide copolymer,
Styrene / methacrylic acid / N-phenylmaleimide / glycidyl methacrylate copolymer,
Styrene / acrylic acid / N-phenylmaleimide / glycidyl acrylate copolymer,
Styrene / methacrylic acid / N-cyclohexylmaleimide / glycidyl methacrylate copolymer,

Butadiene / styrene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Butadiene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Styrene / methacrylic acid / tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl / methacrylic acid-6,7-epoxyheptyl copolymer,
Styrene / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,
t-butyl methacrylate / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,
Styrene / methacrylic acid / methyl methacrylate / glycidyl methacrylate copolymer,
p-methoxystyrene / methacrylic acid / cyclohexyl acrylate / glycidyl methacrylate copolymer methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / styrene / benzyl (meth) acrylate / Glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
Examples thereof include (meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

Preferably, styrene / methacrylic acid / tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer, benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane. / T-butyl methacrylate copolymer, styrene / methacrylic acid / N-cyclohexylmaleimide / glycidyl methacrylate copolymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer.
These acrylic copolymers can be used alone or in admixture of two or more.

As a specific example of the acrylic copolymer (D2),
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
Etc.
These acrylic copolymers can be used alone or in admixture of two or more.

The carboxyl group-containing acrylic copolymer can be synthesized by polymerization in a suitable solvent in the presence of a radical polymerization initiator.
Examples of the solvent used for the polymerization include alcohol, ether, ethylene glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol ether, propylene glycol ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, and aromatic hydrocarbon. , Ketones, esters and the like.

Solvents used for the synthesis are preferably ethylene glycol alkyl ether acetate, diethylene glycol ether, propylene glycol ether, propylene glycol alkyl ether acetate and the like, and particularly, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate and the like. preferable.
These solvents can be used alone or in admixture of two or more.

Examples of the radical polymerization initiator used for the polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile); organic peroxidation such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane Thing; hydrogen peroxide etc. can be mentioned. When a peroxide is used as the radical polymerization initiator, it may be used as a redox initiator by using it together with a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing acrylic copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. Within this range, it is preferable from the viewpoint of solubility in an alkaline developer.
Mw measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the carboxyl group-containing acrylic copolymer is usually 3,000 to 300,000, preferably 5,000 to 100,000.
The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the carboxyl group-containing acrylic copolymer is usually 3,000-60. 5,000, preferably 5,000 to 25,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the carboxyl group-containing acrylic copolymer is preferably 1 to 5, and more preferably 1 to 4.
In the present invention, by using such a carboxyl group-containing acrylic copolymer having specific Mw and Mn, a colored curable composition excellent in developability can be obtained, and thereby a sharp pattern edge can be obtained. Can be formed, and residues, background stains, film residues, and the like are less likely to occur on the unexposed substrate and the light shielding layer during development.

  The acid value of the carboxyl group-containing acrylic copolymer is preferably in the range of 10 mgKOH / g to 200 mgKOH / g, preferably 30 mgKOH / g to 180 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g.

  The addition amount of the carboxyl group-containing acrylic copolymer is preferably in the range of 3 to 40% by mass in the total solid content of the colored curable composition, and 5 to 30% by mass is soluble in an alkali developer. From the viewpoint of

<Specific resin>
In the present invention, it is necessary to use a resin having at least one group selected from the group consisting of an epoxy group, an oxetanyl group and an N-substituted maleimide group as the specific resin. Specifically, epoxy resin, oxetanyl resin, and maleimide resin can be used as the specific resin.

(Epoxy resin)
Examples of the epoxy resin include bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compounds.

For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103, etc. (more from Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (more from Daicel Chemical) and their similarities The bisphenol F type and bisphenol S type can also be mentioned. Ebecryl
Epoxy acrylates such as 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

  Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and biphenyl type 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl and the like.

  Examples of the alicyclic epoxy compounds include Celoxide 2021, 2081, 2083, 2085, Eporide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries), Santo Tote ST-3000, ST. -4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like. In addition, Epototo YH-434 and YH-434L, which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin can be used.

  Among these epoxy resins, preferably novolak type epoxy compounds and alicyclic epoxy compounds are preferable, and those having an epoxy equivalent of 180 to 250 are particularly preferable. Examples of such materials include epiclone N-660, N-670, N-680, N-690, YDCN-704L (manufactured by DIC) and EHPE3150 (manufactured by Daicel Chemical).

In the colored curable composition of this invention, you may contain 2 or more types of epoxy resins.
As content in the colored curable composition of the epoxy resin which concerns on this invention, 0.5-15 mass% is preferable with respect to the total solid of a colored curable composition, and 1-10 mass% is based on an alkali. It is preferable from the viewpoint of compatibility between solubility and adhesion to the substrate.

(Oxetane resin)
As the oxetane resin, Aron oxetane OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Oxetane resins can be used alone or mixed with acrylic copolymers, epoxy resins and maleimide resins. In particular, when used in combination with an epoxy resin, the reactivity due to heat generated by ultraviolet laser exposure is high, which is preferable from the viewpoint of adhesion to the substrate.
As content in the colored curable composition of the oxetane resin which concerns on this invention, 0.5-15 mass% is preferable with respect to the total solid of a colored curable composition, and 1-10 mass% is with respect to an alkali. It is preferable from the viewpoint of compatibility between solubility and adhesion to the substrate.

(Maleimide resin)
As maleimide resin, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI-2400, BMI-3000, BMI-4000, BMI-5100, BMI-6000, BMI-7000, BMI-8000, BMI- TMH (manufactured by Daiwa Kasei) can be used.
The maleimide resin can be used alone or mixed with an acrylic copolymer, an epoxy resin and an oxetane resin.
As content in the colored curable composition of the maleimide resin which concerns on this invention, 0.5-15 mass% is preferable with respect to the total solid of a colored curable composition, and 1-10 mass% is based on an alkali. It is preferable from the viewpoint of compatibility between solubility and adhesion to the substrate.

〔solvent〕
The colored curable composition used in the present invention can generally be prepared using a solvent. The pigment dispersion composition described above is also prepared using a solvent.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, -2-oxypropionic acid alkyl esters such as ethyl oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion) Acid methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate, etc.), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl Ether acetate, propylene glycol propyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n -Propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether Acetate, tripropylene glycol mono n-butyl ether, tripropylene glycol methyl ether acetate and the like;

  Alkoxyalkyl acetates such as 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 2- Ethoxybutyl acetate, 4-ethoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3- Methyl-4-methoxypentyl acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether,
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like are preferable.
You may use a solvent in combination of 2 or more types besides using independently.

[Other additives]
In addition to the above components, various known additives can be used in the colored curable composition used in the present invention depending on the purpose.
Hereinafter, such additives will be described.

(Surfactant)
When the pigment concentration is increased, the thixotropy of the coating solution is generally increased. Therefore, film thickness unevenness after the colored curable composition is applied or transferred onto the substrate to form the colored curable composition layer (colored layer coating film). It is easy to produce. In particular, in the formation of the colored curable composition layer (colored layer coating film) by the slit coating method, the coating liquid for forming the colored curable composition layer is leveled before drying to form a uniform thickness coating film. is important. For this reason, it is preferable to contain an appropriate surfactant in the colored curable composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polystyrylated ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, Adeka Pluronic series, Adecanol series i, Tetronic series (above made by ADEKA Co., Ltd.), Emulgen series, Leodole series (above made by Kao Co., Ltd.), Eleminor series, Nonipole Series, Octapole series, Dodecapole series, New Pole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.), etc. is there. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08 (Dainippon Ink Co., Ltd.), Florard FC -135, FC-170C, FC-430, FC-431 (Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801 and 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.).

  These surfactants are preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the coating liquid for forming the colored curable composition layer. When the amount of the surfactant exceeds 5 parts by mass, surface roughness due to coating and drying tends to occur, and smoothness tends to deteriorate.

  Further, in order to promote the alkali solubility of the uncured part and further improve the developability of the colored curable composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. be able to. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

(Silane coupling agent)
A silane coupling agent can be used for the coloring curable composition used for this invention from a viewpoint of the adhesive improvement with the further board | substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material. In addition, it preferably has a group that interacts or forms a bond with an organic resin and exhibits an affinity, and such a group has a (meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group. Among them, those having a (meth) acryloyl group or a glycidyl group are preferable.
That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group, and specifically, a (meth) acryloyl-tri having the following structure. Examples include methoxysilane compounds and glycidyl-trimethoxysilane compounds.

  In the case of using a silane coupling agent, the addition amount is preferably in the range of 0.2% by mass to 5.0% by mass in the total solid content in the colored curable composition used in the present invention. More preferably, it is 5 mass%-3.0 mass%.

(Polymerization inhibitor)
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the ethylenically unsaturated compound that can be polymerized during the production or storage of the colored curable composition.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, phenoxazine, phenothiazine and the like.

  The addition amount of the thermal polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the colored curable composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide can be added to prevent polymerization inhibition due to oxygen and can be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The addition amount of the higher fatty acid derivative is preferably 0.5% by mass to 10% by mass of the colored curable composition.

(Plasticizer)
Furthermore, in this invention, in order to improve the physical property of a colored curable composition, you may add an inorganic filler, a plasticizer, etc.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like (A) polymerizable compound ( D) 10 mass% or less can be added with respect to the total mass with resin.

  By using the components described above, the colored curable composition of the present invention is cured with high sensitivity by exposure to an ultraviolet laser, and exhibits high adhesion to the substrate. Furthermore, since the film is formed with high sensitivity, the smoothness of the surface is maintained even by high-power exposure with an ultraviolet laser. Therefore, the colored curable composition containing the various components can be preferably used for forming a colored pattern of a color filter by applying it to the method of the present invention.

The colored curable composition for ultraviolet laser exposure and the pattern forming method of the present invention are suitable for a color filter for liquid crystal display devices. Hereinafter, the colored curable composition for ultraviolet laser exposure and the pattern forming method of the present invention will be described as a colored pattern forming composition and a forming method in a method for producing a color filter for a liquid crystal display device. The method is not limited.
<Method for producing color filter for liquid crystal display element>
Although it manufactures by forming a colored pattern using a colored curable composition on a light-transmitting board | substrate, another process can also be provided as needed.

[Pattern formation process]
In the present invention, the colored pattern is formed by forming a colored curable composition layer on the light-transmitting substrate using the colored curable composition (colored curable composition layer forming step), and the colored curable composition layer. Is exposed to a pattern with an ultraviolet laser (exposure process), the colored curable composition layer after exposure is developed to remove an uncured region (development process), and the developed colored curable resin is developed as desired. The composition layer can be formed by baking (baking step). In addition to the above steps, the pattern forming step may further include other steps such as a pre-baking step as necessary.

-Colored curable composition layer forming step-
Examples of the light-transmitting substrate (hereinafter also simply referred to as “substrate”) include, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and transparent conductive films used in liquid crystal display devices and the like. And a photoelectric conversion element substrate used for a solid-state imaging device or the like. Furthermore, a plastic substrate is also possible. In these substrates, a black matrix is formed in a lattice shape or the like, and a colored pattern is formed in an empty portion of the lattice.

  Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with an upper layer, prevent diffusion of substances, or planarize the substrate surface. It is preferable that the substrate is large (generally 1 m or more per side) in that the effects of the present invention are further exhibited.

As a method of forming the colored curable composition layer on the substrate, various application methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. . Of these, slit coating is preferred from the viewpoints of accuracy and speed.
Moreover, the method of transferring on the board | substrate the coating film previously provided and formed by the said application | coating method on the temporary support body can also be applied.
Regarding the transfer method, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 are used. It can be suitably used in the present invention.

  The thickness of the colored curable composition layer (for example, coating thickness) is 0.5 μm to 3.0 μm after drying in order to obtain a sufficient color reproduction region and sufficient panel brightness. It is preferable to form so that it may become, and it is more preferable to set it as 1.5 micrometers-2.5 micrometers.

-Exposure process-
In the pattern formation method of this invention, the said colored curable composition layer is exposed using an ultraviolet laser as a light source at an exposure process. In this case, pattern exposure may be performed through a mask, or exposure may be performed in a pattern with the focus of exposure light being reduced. From the viewpoint of the pattern shape, it is preferable to perform exposure using a mask. Preferred illuminance and exposure amount are as described above.

-Development process-
In the development step, the colored curable composition layer after exposure is developed. The exposed area is cured in a pattern shape, and in the development process, the unexposed part (uncured part) in the above exposure process is removed by elution into an alkaline aqueous solution and photocured by performing an alkali development process. By leaving only the part, a pattern can be formed.

As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is used.
Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkali compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline compounds is 0.001 to 0.001. An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

The development temperature is preferably 20 ° C to 35 ° C, more preferably 23 ° C to 30 ° C. The development time is preferably 30 seconds to 120 seconds, and more preferably 40 seconds to 90 seconds. Among these, a preferable combination of the development temperature and the development time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C. and 40 seconds to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and preferably 0.1 MPa to 0.3 MPa. By selecting these conditions, it is possible to arbitrarily design the pattern shape to be rectangular or forward tapered.

-Bake process-
In the baking process, the developed colored curable composition layer is baked in order to complete the curing of the colored curable composition. The baking method is such that a substrate having a colored curable composition pattern layer after development and rinsing is heated continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like. This can be done by heating with the formula.
As conditions for baking, the temperature is preferably 150 ° C to 260 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 ° C to 240 ° C. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 30 minutes to 90 minutes.

  In addition, when forming a colored pattern of a plurality of hues such as RGB3 hue, light shielding layer, etc., the cycle of forming the colored curable composition layer, exposure, development, and baking may be repeated as many times as desired. After forming the colored curable composition layer for each hue, exposing, and developing, finally, all the hues may be collectively baked. As a result, a color filter including colored pixels having a desired hue is produced.

-Other processes-
Before the exposure step, a prebaking step may be provided in order to dry the colored curable composition layer formed by coating or the like.
The prebaking temperature of the colored curable composition layer is preferably 60 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The pre-bake time is preferably 30 seconds to 300 seconds, and more preferably 80 seconds to 200 seconds.

<Liquid crystal display device>
A color filter for a liquid crystal display device is suitable for producing a liquid crystal display device, and a liquid crystal display device using a color filter produced by the pattern forming method of the present invention can display a high-quality image.
For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)). The liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Issued in 1994 by Industrial Research Co., Ltd.)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”.

The color filter for a liquid crystal display device is particularly effective for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Applicable. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".
In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter for a liquid crystal display element of the present invention can be applied to a liquid crystal display device composed of these known members.
For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi Co., Ltd.) Fuji Chimera Research Institute, published in 2003) ”.

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, 18-24 pages (Yasuhiro Shima), 25-30 pages (Yukiaki Yagi), etc. Are listed.

  When the color filter produced by the pattern forming method of the present invention is used in a liquid crystal display device and combined with a conventionally known three-wavelength tube of a cold-cathode tube, high contrast can be realized. By using a light source (RGB-LED) as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

Example 1
(C) 100 parts by weight of a 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, BYK163 (solid content concentration 45%) 55 parts by weight as a dispersant, (D ) Styrene / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer (resin 1, copolymer weight ratio = 7/15/42) as specific resin / 36, Mw = 25,000, Mn = 10,000) 70 parts by weight, (A) 80 parts by weight of dipentaerythritol hexaacrylate as a polymerizable compound, (B) Compound 1 (trade name: CGI242) as a photopolymerization initiator , Ciba Specialty Chemicals) and 15 parts by weight propylene glycol monomethyl ether acetate ( GMEA) were mixed 1300 parts by weight, the liquid composition of the colored curable composition (B1) was prepared.

<Pixel formation>
The liquid composition (B1) was applied on the surface of an alkali-free glass substrate (Corning, 1737, 550 mm × 660 mm) using a slit coater (Hirata Kiko Co., Ltd., HC-6000), and then heated to 90 ° C. Pre-baking was performed for 120 seconds in a clean oven to form a coating film having a film thickness of 1.7 μm.
Next, using EGIS (Bui Technology Co., Ltd., third harmonic of YAG laser (355 nm), pulse width 6 nS) as a laser exposure apparatus, the surface of the photosensitive resin composition layer is irradiated with a pulse of about 1 mJ / cm2. This was performed 20 times through a photomask. Then, using this developing device (manufactured by Hitachi High-Technologies Corporation), 1.0% developer (CDK-1) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) is used. The shower pressure was set at 0.20 MPa with 1 part by mass, 99 parts by mass of pure water diluted at 25 ° C.), developed for 50 seconds, washed with pure water, and then air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a blue stripe pixel array on the substrate.

(Example 2)
(B) A liquid composition (B2) was prepared in the same manner as in Example 1 except that 6 parts by mass of Compound 2 as a photopolymerization initiator, 6 parts by mass of Compound 3 and 3 parts by mass of Compound 4 as a chain transfer agent were added. Was prepared. In addition, stripe-like pixels were formed using the liquid composition (B2) as in Example 1.

(Example 3)
A liquid composition (B3) was prepared in the same manner as in Example 1 except that 3 parts by mass of Compound 5 was added as a silane coupling agent. Similarly to Example 1, stripe-like pixels were formed using the liquid composition (B3).

Example 4
(D) Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane / t-butyl methacrylate copolymer (resin 2, copolymer weight ratio = 42/15/36/7, Mw = 22,000 as specific resin , Mn = 10,000) A liquid composition (B4) was prepared in the same manner as in Example 1 except for adding 70 parts by weight. Similarly to Example 1, stripe-like pixels were formed using the liquid composition (B4).

(Example 5)
(B) 6 parts by mass of compound 2 as a photopolymerization initiator, 6 parts by mass of compound 3 and 3 parts by mass of compound 4 as a chain transfer agent are added, and (D) benzyl methacrylate / methacrylic acid / 3- ( Methacryloyloxymethyl) oxetane / t-butyl methacrylate copolymer (resin 2, copolymer weight ratio = 42/15/36/7, Mw = 22,000, Mn = 10,000) In the same manner as in Example 1, a liquid composition (B5) was prepared. In addition, stripe-like pixels were formed using the liquid composition (B5) as in Example 1.

(Example 6)
(D) Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane / t-butyl methacrylate copolymer (resin 2, copolymer weight ratio = 42/15/36/7, Mw = 22,000, Mn = 10,000) 70 parts by weight was added, and a liquid composition (B6) was prepared in the same manner as in Example 1 except that 3 parts by weight of Compound 5 was added as a silane coupling agent. In addition, stripe-like pixels were formed using the liquid composition (B6) as in Example 1.

(Example 7)
(D) Methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer (resin 3, copolymer weight ratio = 15/15/35/35, Mw = 23,000, Mn = 9 as specific resin , 000) A liquid composition (B7) was prepared in the same manner as in Example 1 except that 70 parts by weight was added. In addition, stripe-like pixels were formed using the liquid composition (B7) as in Example 1.

(Example 8)
(B) 6 parts by mass of compound 2 as a photopolymerization initiator, 6 parts by mass of compound 3 and 3 parts by mass of compound 4 as a chain transfer agent are added, and (D) methacrylic acid / styrene / benzyl (meth) acrylate as a resin / N-phenylmaleimide copolymer (resin 3, copolymer weight ratio = 15/15/35/35, Mw = 23,000, Mn = 9000) 70 parts by weight were added in the same manner as in Example 1 Thus, a liquid composition (B8) was prepared. In addition, stripe-like pixels were formed as in Example 1.

Example 9
(D) Methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer (resin 3, copolymer weight ratio = 15/15/35/35, Mw = 23,000, Mn = 9, 000) 70 parts by weight was added, and a liquid composition (B9) was prepared in the same manner as in Example 1 except that 3 parts by weight of Compound 5 was added as a silane coupling agent. In addition, stripe-like pixels were formed using the liquid composition (B9) as in Example 1.

(Example 10)
(D) Styrene / methacrylic acid / N-phenylmaleimide / glycidyl methacrylate copolymer as resin (resin 4, copolymer weight ratio = 15/15/35/35, Mw = 21,000, Mn = 9,000) A liquid composition (B10) was prepared in the same manner as in Example 1 except that 70 parts by weight was added. In addition, stripe-like pixels were formed using the liquid composition (B10) as in Example 1.

(Example 11)
(B) 6 parts by mass of compound 2 as a photopolymerization initiator, 6 parts by mass of compound 3 and 3 parts by mass of compound 4 as a chain transfer agent are added. (D) Styrene / methacrylic acid / N-phenylmaleimide as a specific resin / Glycidyl methacrylate copolymer (resin 4, copolymer weight ratio = 15/15/35/35, Mw = 21,000, Mn = 9000) 70 parts by weight, except that 70 parts by weight were added A liquid composition (B11) was prepared. In addition, stripe-like pixels were formed using the liquid composition (B11) as in Example 1.

Example 12
(D) Styrene / methacrylic acid / N-phenylmaleimide / glycidyl methacrylate copolymer (resin 4, copolymer weight ratio = 15/15/35/35, Mw = 21,000, Mn = 9,000 as specific resin ) A liquid composition (B12) was prepared in the same manner as in Example 1 except that 70 parts by weight was added and 3 parts by weight of Compound 5 was added as a silane coupling agent. In addition, stripe-like pixels were formed using the liquid composition (B12) as in Example 1.

(Example 13)
(D) As resin, benzyl methacrylate / methacrylic acid copolymer (resin 5, copolymer weight ratio = 80/20, Mw = 18,000, Mn = 8,000), which is a combined resin, and specific resin An epoxy resin: A liquid composition (B13) was prepared in the same manner as in Example 1 except that 20 parts by mass of EHPE3150 (resin 6, manufactured by Daicel Chemical Industries) was added. Similarly to Example 1, stripe-like pixels were formed using the liquid composition (B13).

(Example 14)
(B) 6 parts by mass of compound 2 as a photopolymerization initiator, 6 parts by mass of compound 3 and 3 parts by mass of compound 4 as a chain transfer agent are added. (D) benzyl methacrylate / methacrylic acid 50 parts by weight of polymer (resin 5, copolymer weight ratio = 80/20, Mw = 18,000, Mn = 8,000) and epoxy resin as specific resin: EHPE3150 (resin 6, manufactured by Daicel Chemical) 20 parts by weight A liquid composition (B14) was prepared in the same manner as Example 1 except for the addition. In addition, stripe-like pixels were formed as in Example 1.

(Example 15)
(D) As resin, benzyl methacrylate / methacrylic acid copolymer (resin 5, copolymer weight ratio = 80/20, Mw = 18,000, Mn = 8,000), which is a combined resin, and specific resin A certain epoxy resin: 20 parts by mass of EHPE3150 (resin 6, manufactured by Daicel Chemical Industries) was added, and a liquid composition (B15) was prepared in the same manner as in Example 1 except that 3 parts by mass of compound 5 was added as a silane coupling agent. . In addition, stripe-like pixels were formed using the liquid composition (B15) as in Example 1.

(Comparative Example 1)
(D) Except that 70 parts by weight of benzyl methacrylate / methacrylic acid copolymer (resin 5, copolymer weight ratio = 80/20, Mw = 18,000, Mn = 8,000) as a comparative resin was added as a resin. A liquid composition (B16) was prepared in the same manner as in Example 1. In addition, stripe-like pixels were formed using the liquid composition (B16) as in Example 1.

(Comparative Example 2)
(B) 6 parts by mass of compound 2 as a photopolymerization initiator, 6 parts by mass of compound 3 and 3 parts by mass of compound 4 as a chain transfer agent are added, and (D) benzyl methacrylate / methacrylic acid which is a comparative resin as a resin A liquid composition (B17) was prepared in the same manner as in Example 1 except that 70 parts by weight of a copolymer (resin 5, copolymer weight ratio = 80/20, Mw = 18,000, Mn = 8,000) was added. did. In addition, stripe-like pixels were formed using the liquid composition (B17) as in Example 1.

(Comparative Example 3)
(D) 70 parts by weight of benzyl methacrylate / methacrylic acid copolymer (resin 5, copolymer weight ratio = 80/20, Mw = 18,000, Mn = 8,000), which is a comparative resin, is added as a resin, and silane A liquid composition (B18) was prepared in the same manner as in Example 1 except that 3 parts by mass of Compound 5 was added as a coupling agent. Similarly to Example 1, stripe-like pixels were formed using the liquid composition (B18).

  Details of the liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 3 are shown in Table 1.

  The structures of the compounds used in Table 1 are shown below.

(Evaluation of adhesion to the substrate)
The cross section of the formed pixel pattern was observed with a field emission scanning electron microscope S-4800 (manufactured by HITACHI) to evaluate the adhesion with the substrate.
A: There is no gap between the substrate and the pixel and the adhesion is good. ○: There is a slight gap between the substrate and the pixel, but there is no adhesion problem. Δ: There is a small gap between the substrate and the pixel. Table 2 below shows the results of evaluation of adhesion to the substrates of Examples 1 to 15 and Comparative Examples 1 to 3 with a large gap between the substrate and the pixels.

From the above results, it is clear that the colored curable composition for ultraviolet laser exposure of the present invention can form a cured film having extremely good adhesion to the substrate. In addition, the colored curable composition for ultraviolet laser exposure of the present invention is further improved in adhesion when used in combination with a silane coupling agent.
By the pattern forming method of the present invention, it is possible to provide a color filter having good color characteristics and high productivity, and a display device having high image quality with high contrast and color purity provided with the color filter.

Claims (10)

  It contains at least (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a resin, and the (D) resin has a glycidyl group, an oxetanyl group, and N in the molecule. A colored curable composition for ultraviolet laser exposure, comprising a resin having at least one selected from the group consisting of position-substituted maleimide groups.   2. The colored curable composition for ultraviolet laser exposure according to claim 1, wherein the (D) resin includes at least one resin selected from an acrylic copolymer, an epoxy resin, an oxetane resin, and a maleimide resin.   The colored curable composition for ultraviolet laser exposure according to claim 1 or 2, comprising at least one of a hexaarylbiimidazole compound and an oxime ester compound as the (B) photopolymerization initiator.   Furthermore, the colored curable composition for ultraviolet laser exposure of any one of Claims 1-3 containing a silane coupling agent.   The colored curable composition for ultraviolet laser exposure according to any one of claims 1 to 4, wherein the silane coupling agent is a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group. object.   The colored curable composition according to any one of claims 1 to 5 is applied on a substrate to form a colored curable composition layer, and pattern exposure is performed with an ultraviolet laser to expose an exposure region. The pattern formation method including the process of hardening.   The pattern forming method according to claim 6, wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm.   The manufacturing method of the color filter which has the process of forming a colored pattern on the board | substrate by the pattern formation method of Claim 6 or Claim 7.   A color filter manufactured by the method for manufacturing a color filter according to claim 8.   A display device comprising the color filter according to claim 9.