JP4902369B2 - Curable composition, color filter and method for producing the same - Google Patents

Abstract

The invention provides a solidified composite which has excellent film-coating ability, high-sensitive solidification, remarkable image dissection degree, great pattern forming ability, large tolerance level while developing, and outstanding adhesiveness with a support body. The solidified composite is characterized in that: the composite is a sensitive composite comprising (A) a colorant, (B) aninitiator of light polymerization, (C) an alkaline solubility resin and (D) a multifunctional monomer including olefins unsaturated bonds, (B) the initiator of light polymerization comprises (I) united imidazole compounds, (II) mercapto compound and (iii) at least one compound selected from the group consisting of amino benzene derivatives, alkoxyl benzene derivatives, thioxanthone derivatives and coumarin derivatives; (D) the multifunctional monomer including olefins unsaturated bonds includes hydroxyl, and comprises at least one multifunctional monomer whose double bond density is 9.6mmol/gto 11.5mmol/g in a molecule.

Description

  The present invention relates to a curable composition suitable for producing a color filter used for a liquid crystal display element (LCD) or a solid-state imaging element (CCD, CMOS, etc.), a color filter using the same, and a method for producing the same.

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
A liquid crystal display is more compact than a CRT as a display device and is equivalent or better in terms of performance, and is thus being replaced by a CRT as a television screen, a personal computer screen, or other display device. In recent years, the development trend of liquid crystal displays has been widened from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

Liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor applications. Also, with the recent spread of mobile phones and car navigation systems, the monitor size of the liquid crystal display used is becoming smaller, and a display with higher resolution is required. Further, higher definition is also desired for color filters for solid-state imaging devices.
In order to improve the contrast among the above-mentioned advanced image quality, a finer particle size is demanded as the particle size of the colorant (organic pigment etc.) used in the curable composition used in the production of the color filter (for example, (See Patent Document 1). Accordingly, the amount of dispersant added for dispersing the pigment tends to increase.
In addition, in order to improve color purity among advanced image quality, a higher content of colorant (organic pigment) in the solid content of the curable composition is required. Therefore, the content of the photopolymerization initiator and the photopolymerizable monomer in the solid content in the curable composition tends to decrease. Therefore, the curable composition has to be highly sensitive.

Increasing the concentration of the colorant for improving the sensitivity is accompanied by a decrease in the content of the photopolymerization initiator and the photopolymerizable monomer, resulting in a decrease in resolution and an increase in pattern line width, resulting in display display. Defects become a problem. Furthermore, it is remarkable in reducing the monitor size.
In order to improve the sensitivity described above, a combination of a chain transfer agent such as a polyfunctional thiol and a photosensitive resin is recommended (see Patent Document 1). However, since these materials have low alkali solubility, the sensitivity is increased. And proper pattern formability are difficult to achieve. Furthermore, polyfunctional thiols are highly reactive and it is difficult to ensure resist aging stability.
Japanese Patent No. 3120547

By the way, regarding the resolution and pattern line width control, when a resolution is required such as a mobile phone or car navigation, it is particularly important to reduce the width of the fine line width. To reduce the line width, it is effective to reduce the amount of the initiator, but the shape deteriorates and it is difficult to achieve both the line width and the shape.
The present invention was made in order to improve the above-mentioned disadvantages of the prior art, and the purpose thereof is excellent even when the colorant is contained in a high concentration, and is cured with high sensitivity, An object of the present invention is to provide a curable composition having excellent resolution, good pattern forming properties, wide latitude during development, and excellent adhesion to a support.
Furthermore, this invention aims at providing the manufacturing method which can manufacture the color filter which has the pixel excellent in the resolution which uses the curable composition of this invention, and this color filter with high productivity.

In view of the above circumstances, the present inventors have conducted extensive research and found that the use of a curable composition containing a specific photopolymerization initiator and a specific polyfunctional monomer can solve the above problems. Was completed.
That is, the present invention is achieved by the following means.

<1> In the curable composition comprising (A) a colorant, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a polyfunctional monomer having an ethylenically unsaturated bond, The polymerization initiator includes a biimidazole compound, a mercapto compound represented by the following formula (2), and a compound B represented by the following formula (1), and (D) an ethylenically unsaturated bond. The polyfunctional monomer has a hydroxyl group in the molecule and contains at least one polyfunctional monomer having a double bond density of 9.6 mmol / g or more and 11.5 mmol / g or less. object.

<2> The curable composition as described in <1> above, wherein the (D) polyfunctional monomer having an ethylenically unsaturated bond is trifunctional or more.
<3> A color filter having pixels formed using the curable composition according to <1> or <2>.

<4> A step of applying the curable composition according to <1> or <2> on the support to form a curable composition layer, and the curable composition layer through a mask. A method for producing a color filter, comprising: a step of exposing; and a step of developing a curable composition layer after exposure to form a colored pattern.

The present invention was made in order to improve the above-mentioned disadvantages of the prior art, and the purpose thereof is excellent even when the colorant is contained in a high concentration, and is cured with high sensitivity, A curable composition that exhibits good pattern-forming properties, has a wide latitude during development, has excellent adhesion to the support, and has a small line width with respect to the mask width, so that the resolution is high. Can be provided.
Furthermore, this invention can provide the manufacturing method which can manufacture the color filter which has the pixel excellent in the resolution which uses the said curable composition, and can manufacture this color filter with high productivity.

Hereinafter, the curable composition of the present invention, a color filter using the curable composition, and a production method thereof will be described in detail.
[Curable composition]
The curable composition of the present invention is a radiation-sensitive composition, and is particularly suitable for curing by light. (A) a colorant, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) A polyfunctional monomer having an ethylenically unsaturated bond, and (B) the photopolymerization initiator is selected from a biimidazole compound and a mercapto compound, and at least an aminobenzene derivative, an alkoxybenzene derivative, a thioxanthone derivative, and a coumarin derivative. And (D) the polyfunctional monomer having an ethylenically unsaturated bond has a hydroxyl group in the molecule and has a double bond density of 9.6 mmol / g or more and 11.5 mmol / g. It contains at least one polyfunctional monomer that is:
The curable composition of the present invention may contain a solvent and other components as desired.
Hereinafter, each compound contained in the curable composition of this invention is demonstrated one by one. First, the (D) polyfunctional monomer having an ethylenically unsaturated bond will be described.

<(D) Polyfunctional monomer having an ethylenically unsaturated bond>
The curable composition of the present invention contains (D) a polyfunctional monomer having an ethylenically unsaturated bond (hereinafter also referred to as “polyfunctional monomer in the present invention”).
The polyfunctional monomer having an ethylenically unsaturated bond (D) which is an addition polymerizable compound having at least one ethylenically unsaturated double bond that can be used in the present invention has one hydroxyl group in the molecule. The double bond density is not less than 9.6 mmol / g and not more than 11.5 mmol / g.
By using the curable composition having the polyfunctional monomer to expose and develop the formed curable composition layer, no increase in line width or deterioration of the pattern shape observed in the past is observed, Both line width and pattern shape can be achieved. Furthermore, there is an effect that an unexposed part is quickly removed by development (break time).
The bonding position in the molecule of the hydroxyl group of the polyfunctional monomer in the present invention is not particularly limited.

The double bond density in the present invention needs to be within the above range in order to achieve the effects of the present invention, but from the viewpoints of sensitivity, pattern shape, fine adjustment of line width, and improvement of resolution, unsaturated per molecule. The group content is preferably a specific value, preferably 10.0 mmol / g or more and 11.5 mmol / g or less, more preferably 10.2 mmol / g or more and 11.5 mmol / g or less, and particularly preferably 10.5 mmol / g or more and 11.5 mmol / g or less.
Here, the “double bond density (mmol / g)” in the present invention refers to the number of millimoles (mmol) of double bonds per polyfunctional monomer (1 g). For example, with respect to exemplary compound A-1, since the molecular weight is 298.29 and the double bond is 3000 mmol, the double bond density is 10.1 (3000 (mmol) /298.29 (g)).

The polyfunctional monomer in the present invention has only to have the hydroxyl group and the double bond density in the specific range. From the viewpoint of pattern shape, line width, and resolution, it is preferably trifunctional or higher. More than trifunctional and 8 functionals are more preferable, 3 functionals and 6 functionals are more preferable, 3 functionals and 4 functionals are especially preferable.
It is preferable that the polyfunctional monomer in the present invention has three or more functional groups because the pattern forming property is excellent and the pattern is not easily chipped or peeled off.
The polyfunctional monomer in the present invention may be used alone or in combination of two or more. However, in order to increase the strength of the image portion, that is, the cured film, different functional numbers and different polymerizable groups are used in combination. This is effective in controlling both sensitivity and intensity.
Examples of the monomer having a different functional number / different polymerizable group include a polyfunctional monomer having an ethylenically unsaturated bond other than the polyfunctional monomer in the present invention described later.

  Specific examples of the polyfunctional monomer in the present invention include the following, but are not limited thereto.

  As the polyfunctional monomer in the present invention, a commercially available product may be used, or an appropriately synthesized monomer may be used.

The content of the polyfunctional monomer in the present invention is preferably 1% by mass or more and 90% by mass or less, and preferably 5% by mass or more and 80% by mass or less in the solid content of the curable composition of the present invention. More preferably, it is 10 mass% or more and 70 mass% or less.
In particular, when the curable composition of the present invention is used for forming a coloring pattern of a color filter, the content is preferably 5% by mass to 50% by mass, and more preferably 7% by mass to 40% by mass. The content is more preferably 10% by mass or more and 35% by mass or less.

In this invention, it is also a preferable aspect to add the polyfunctional monomer which has ethylenically unsaturated bond other than the polyfunctional monomer in this invention.
The compound containing an ethylenically unsaturated double bond that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, Preferably, it is selected from compounds having two or more. 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, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with 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 tetraacrylate, dipentaerythritol hexaa Relate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomers, and isocyanuric acid EO-modified triacrylate.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Examples include hexanediol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, and bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane.

  Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and the like. Examples of crotonic acid esters include ethylene glycol dicrotonate and tetramethylene glycol dicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate and triethylene glycol dimaleate.

  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-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 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-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.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, 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, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like 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 addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc., can be arbitrarily set according to 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 image area, that is, the cured film, those having three or more functionalities are preferable. A method of adjusting both sensitivity and strength by using a 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 and dispersibility with other components in the polymerizable layer (for example, binder polymer, initiator, colorant (pigment, dye, etc.)). For example, the compatibility may be improved by using a low-purity compound or a combination of two or more types, and a specific structure may be used for the purpose of improving the adhesion of the substrate and an overcoat layer described later. It can also be selected.

  From the above viewpoints, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol tetra Preferred examples include acrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, dipentaerythritol hexaacrylate EO modified, and the like. Moreover, as a commercial item, urethane oligomer UAS-10 UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) preferable.

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. As a commercial item, DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha) are more preferable.

  The content of the compound having an ethylenic double bond other than the polyfunctional monomer in the present invention is preferably contained within the range of the content of the polyfunctional monomer in the present invention.

<(B) Photopolymerization initiator>
The photopolymerization initiator (B) contained in the curable composition of the present invention is at least one selected from a biimidazole compound, a mercapto compound, and an aminobenzene derivative, an alkoxybenzene derivative, a thioxanthone derivative, and a coumarin derivative. A photopolymerization initiation system containing a compound (hereinafter also referred to as “specific sensitizing dye”).
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of the polyfunctional monomer having the (D) ethylenically unsaturated bond, and has an absorption in a wavelength region of 300 to 500 nm. It is preferable that
The photopolymerization initiator in the present invention can be highly sensitive by combining a biimidazole compound, a mercapto compound, and a specific sensitizing dye.

In the present invention, a hexaarylbiimidazole compound is preferable as the biimidazole compound. For example, various compounds described in JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. 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'-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4, Examples include 4 ', 5,5'-tetraphenylbiimidazole.
Among these, 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole is preferable. These can be used alone or in combination of two or more.

  The mercapto compound used for the photopolymerization initiator further improves the sensitivity of the sensitizing dye and biimidazole compound to actinic radiation, or suppresses the inhibition of polymerization of the polymerizable compound (polyfunctional monomer) by oxygen. A co-sensitizer.

Specific examples of the mercapto compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate (TMTP) PETP), mercaptopropionic acid derivatives such as THEIC-BMPA; mercapto ethers such as di (mercaptoethyl) ether; hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthioglycolate, trimethylolpropane tris Aliphatic polyfunctional mercapto compounds such as thioglycolate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, mercapto Nzuchiazoru, 2-mercaptobenzoxazole, aromatic mercapto compounds such as 2-mercaptobenzimidazole, 2-mercapto -4 (3H) - quinazoline, can be exemplified β- -mercaptonaphthalene. These can be used alone or in combination of two or more.
Furthermore, the compound which has a structure below is illustrated.

Examples of photopolymerization initiators other than biimidazole compounds and mercapto compounds in the present invention include the aminobenzene derivatives (for example, Michler's ketone, N-aryloxazolidinones, ((4-N, N-diethylaminophenyl) buta-1,3). -Dienyl) benzene, 7-diethylamino-4-methyl-chromen-2-one, Michler's ketone and compound B are preferred), alkoxybenzene derivatives (for example, 9,10-dialkoxyanthracene, 3- (4- (Alkoxyphenyl) -chromen-2-one, ((4-alkoxyphenyl) buta-1,3-dienyl) benzene, ((3,4-alkoxyphenyl) buta-1,3-dienyl) benzene, ((3, 4,5-alkoxyphenyl) buta-1,3-dienyl) benzene ((4-methoxyphenyl) buta-1,3-dienyl) benzene is preferred), thioxanthone derivatives (for example, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4- Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like are mentioned, and 2-ethylthioxanthone and 2-isopropylthioxanthone are preferable.) And a coumarin derivative (for example, 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-dimethyl Amino-((s-triazine-2-yl ) Amino) -3-phenylcoumarin and the like, and at least one compound selected from 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin is preferred.) It is.
Among these, Michler's ketone, compound B, and those described in paragraph numbers [0022] to [0042] of JP-A No. 2006-171689 are preferable, and the following compound B is particularly preferable.

  The specific sensitizing dyes in the present invention can be used alone or in combination.

Among these, as a suitable combination of a biimidazole compound, a mercapto compound, and a sensitizing dye, a combination of each suitable compound is more preferable.
Below, the specific example of the said suitable combination is shown.
For example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole can be mentioned as a biimidazole compound, and N as a mercapto compound. Examples of the phenyl mercaptobenzimidazole and sensitizing dye include Michler's ketone and Compound B.
Each of the biimidazole compound, the mercapto compound, and the specific sensitizing dye may be used alone or in combination of two or more.

The ratio of combining the biimidazole compound, mercapto compound, and sensitizing dye is as follows: the biimidazole compound (particularly 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole) is preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents.
The mercapto compound is 0.5 to 10 equivalents relative to the biimidazole compound (particularly 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole). 1 to 3 equivalents are more preferable.
The content of the (B) photopolymerization initiator in the curable composition of the present invention is preferably 3% by mass or more and 20% by mass or less, more preferably based on the total solid content of the curable composition. It is the range of 5 mass% or more and 10 mass% or less.
As described above, as a photopolymerization initiator in the present invention, high sensitivity can be achieved by combining a biimidazole compound, a mercapto compound, and a specific sensitizing dye, and further, curable with the polyfunctional monomer in the present invention. When used in the composition, the composition can be cured with high sensitivity, excellent resolution, good pattern forming properties, wide latitude during development, and excellent adhesion to the support.

In the present invention, the mass ratio of the photopolymerization initiator in the present invention to the polyfunctional monomer in the present invention (photopolymerization initiator / polyfunctional monomer) is 0.25 or more from the viewpoint of line width controllability and pattern formability. Is preferable, 0.25 or more and 0.4 or less is more preferable, and 0.25 or more and 0.3 or less is particularly preferable.
When the mass ratio is less than 0.25, the pattern formability is poor, and chipping and peeling tend to occur.

<(A) Colorant>
The curable composition of the present invention contains (A) a colorant. By using a colorant, a colored cured body made of a curable composition can be formed and applied to the formation of a colored pattern of an image forming material or a color filter.
There is no restriction | limiting in particular in the coloring agent added to the curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance.

As the pigment that can be used in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 μm. ˜0.1 μm is preferable, and 0.01 μm to 0.06 μm is more preferable.
Here, in the present invention, the average primary particle size is a value measured as follows.
In the present invention, the average particle size means a volume average particle size obtained by measurement using a light scattering particle size distribution analyzer (trade name: Microtrac UPA (manufactured by Nikkiso Co., Ltd.)).
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As the organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the dispersibility mechanism has not been fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component containing the polyfunctional monomer and the pigment in the present invention is affected.

  Examples of pigments that can be preferably used in the present invention 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 Black 1

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. 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. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, 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. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, 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 to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

  When the composition of the present invention is used for a color filter, the primary particle diameter of the pigment is preferably from 10 to 100 nm, more preferably from 10 to 70 nm, and more preferably from 10 to 60 nm, from the viewpoint of color unevenness and contrast. More preferably, 10 to 50 nm is particularly preferable, and 10 to 40 nm is most preferable.

Moreover, when using the composition of this invention for color filters, it is preferable to use the dye which melt | dissolves uniformly in a composition from a viewpoint of uneven color and contrast.
The dye that can be used as the colorant contained in the curable composition of the present invention is not particularly limited, and conventionally known dyes for color filters 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 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In addition, after pattern exposure of the curable composition and curing of the exposed portion, unexposed portions are removed by water or alkali development to form a pattern, for example, when a colored pattern of a resist or a color filter is formed. From the viewpoint of completely removing the binder, dye, and the like in the non-light-irradiated part due to the acid dye, an acid dye and / or a derivative thereof may be suitably used.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

  The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, other in the composition. It is selected in consideration of all the required performances such as interaction with the components, light resistance and heat resistance.

Hereinafter, although the specific example of an acidic dye is given, in this invention, it is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes mentioned above, acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Dyes such as Acid Green 25 and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.

  Among them, as the colorant (A), triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo A colorant selected from pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferable.

As content in the case of using a coloring agent for the curable composition of this invention, it is preferable that it is 5-80 mass% in the total solid of a curable composition, 10-70 mass% is more preferable, 20 -70 mass% is still more preferable. 40-70 mass% is still more preferable.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the colorant is preferably 20% by mass or more in the range of the content, and more preferably, It is 30% by mass or more and 40% by mass or more.
By setting it as the said range, it is preferable at the point from which the color purity and contrast when producing a color filter using the curable composition of this invention are excellent.

<(C) Alkali-soluble resin>
In the curable composition of the present invention, an alkali-soluble resin is used as a binder polymer for the purpose of improving film properties.
It is preferable to use a linear organic polymer as the alkali-soluble resin. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (13).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the alkali-soluble resin that can be used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more. More preferably, it is in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These polymers may be random polymers, block polymers, graft polymers or the like.
As addition amount of alkali-soluble resin, it is preferable that it is the range of 5-20 mass% in the total solid of the curable composition of this invention, and 5-12 mass% is more preferable.

  Hereinafter, other preferable additives will be described.

<Co-sensitizer>
The curable composition of the present invention preferably contains a co-sensitizer if desired. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers 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.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the 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 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

<Solvent>
The curable composition of the present invention can contain at least one solvent.
Specifically, the solvent is preferably selected from glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, and chlorine-containing solvents.

  Examples of the glycol ether solvent include ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methylmethoxybutanol (3-methyl-3-methoxybutanol), butyl Carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1 -Ethoxy-2-propanol), propylene glycol monoethyl ether Seteto, and the like are preferable.

  As the alcohol solvent, methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, and the like are preferable.

  Examples of the ester solvent include ethyl acetate, normal butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, 3- Ethyl ethoxypropionate (EEP) and lactic acid esters (for example, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, etc.) are preferred.

  Examples of the ketone solvent include 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, acetone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and isophorone (3, 3). 5,5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone) and the like are preferable.

  As the amide solvent, dimethylformamide (DMF), N-methylpyrrolidone (4-methylaminolactam or NMP) and the like are preferable.

  As the chlorine-containing solvent, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, methylene chloride, carbon tetrachloride, chloroform, dichloroethane, dichlorobenzene and the like are preferable.

As content in the curable composition of the solvent in this invention, 15-60 mass% is preferable with respect to this curable composition, 20-50 mass% is more preferable, 30-40 mass% is especially preferable. When the content is within the above range, the solubility of the colorant in the composition and the temporal stability during storage after dissolution can be effectively improved.

  Among the above solvents, ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methylmethoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol ( Diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy- 2-propanol), propylene glycol monoethyl ether acetate,

  Ethyl acetate, normal butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP) , Methyl lactate, ethyl lactate, propyl lactate, butyl lactate,

  2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5,5-trimethyl-2-cyclo) Hexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone),

  N-methylpyrrolidone (4-methylaminolactam or NMP),

Methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, and the like are preferable.
Moreover, in the curable composition of this invention, the said solvent can be used individually or in combination of 2 or more types.

  Furthermore, when preparing the curable composition of this invention, you may use together other solvents other than the solvent mentioned above. The other solvent is not particularly limited as long as the solubility of each component and the applicability of the curable composition are satisfied, but in particular, the solubility, applicability, and safety of the colorant and the alkali-soluble resin (binder). Is preferably selected in consideration of

  Examples of the other solvent include esters other than those exemplified above, such as amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl oxyacetate, ethyl oxyacetate, oxy Butyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

  3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.); 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate 2-ethoxy-2- Chirupuropion ethyl, etc.); methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

  Ethers other than those exemplified above, such as diethylene glycol dimethyl ether, tetrahydrofuran, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol propyl ether acetate, etc .;

  Ketones other than those exemplified above, for example, methyl ethyl ketone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons, for example, toluene, xylene and the like.

  Of these, methyl 3-ethoxypropionate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, and the like are preferable.

<Dispersant>
When the curable composition of this invention contains a pigment as (c) a coloring agent, it is preferable to add a dispersing agent from a viewpoint of improving the dispersibility of this pigment.

Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the dispersing agent in this invention, it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, and 10-60 mass% is still more preferable.
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment. In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  In the present invention, when using a pigment and a dispersant as a colorant, the total content of the colorant and the dispersant is based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 25% by mass or more and 95% by mass or less, more preferably 25% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass or less.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
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 and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Adhesion improver>
In the present invention, an adhesion improver can be added in order to improve the adhesion to the hard surface (substrate) as a base material. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  0.1-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of an adhesive improvement agent, 0.5-10 mass% is more preferable.

<Other additives>
Furthermore, in the present invention, a known additive such as an inorganic filler, a plasticizer, or a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added to improve the physical properties of the cured film. Good.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

  The curable composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown. Accordingly, the curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coating agents.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof are described.
The color filter of the present invention has a pixel (colored pattern) formed using the curable composition of the present invention on a support.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

A step of applying the curable composition of the present invention on a support to form a curable composition layer (hereinafter abbreviated as “curable composition layer forming step” as appropriate), and the curable composition. A step of exposing the layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and a step of developing the curable composition layer after exposure to form a colored pattern (hereinafter referred to as “development” as appropriate). The process is abbreviated as “step”.).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Curable composition layer forming step>
In the curable composition layer forming step, the curable composition of the present invention is applied on the support to form a curable composition layer.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, an image sensor, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

  As a coating film thickness of a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is further more preferable.

  Drying (prebaking) of the curable composition layer applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven or the like.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, the pattern of the coating film is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, developed with a developer, and each color (three colors or four colors). This can be done by forming a pattern-like film consisting of these pixels. As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
If the color filter of the present invention is a liquid crystal display element is preferably 5 to 200 mJ / cm ² within the above range, more preferably 10~150mJ / cm ^2, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is a solid-state imaging element is preferably 30~1500mJ / cm ² within the above range, more preferably 50~1000mJ / cm ^2, and most preferably 80~500mJ / cm ² .

<Development process>
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Is preferably used as a 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.
Next, excess developer is washed away and dried, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured.
Thereby, a color filter is obtained.
The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  In the production method of the present invention, after performing the above-described curable composition layer forming step, exposure step, and development step, if necessary, the formed colored pattern is cured by heating and / or exposure. A process may be included.

  By repeating the curable composition layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

  The application of the curable composition of the present invention has been described mainly with respect to the application to the pixels of the color filter, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix is patterned exposure and alkaline development in the same manner as the above pixel manufacturing method except that a black colorant such as carbon black or titanium black is added to the curable composition of the present invention as a colorant. Further, after that, post-baking can be performed to promote the curing of the film.

  Since the color filter of the present invention uses the curable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. It is possible to form a high-resolution pattern that is excellent in exposure sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

[Comparative Example 1]
≪Preparation of green curable composition≫
-GREEN composition A-Dispersion-Pigment Green 36 (average particle size 19 nm in SEM observation) 11 parts-Pigment Yellow 150 (average particle size 22 nm in SEM observation-7 parts-Dispersant (trade name: Disperbyk-161, Big Chemie) Propylene glycol monomethyl ether acetate solution (solid content) of 6 parts alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) : 50% by mass) 4 parts · Solvent B (3-ethoxypropionic acid methyl ether acetate) 70 parts

-GREEN composition B-Coating liquid-GREEN composition A-Dispersion 100 parts-Epoxy resin (trade name EHPE3150, manufactured by Daicel Chemical Industries) 2 parts-Polymerizable compound (dipentaerythritol hexaacrylate) 8 parts-Polymerization initiator 1 (2 , 2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (biimidazole compound)) 2.2 parts polymerization initiator 2 (compound D, specific sensitizing dye below) 0.8 part polymerization initiator 3 (compound M, mercapto compound below) 0.5 part polymerization inhibitor (p-methoxyphenol) 0.001 part fluorinated surfactant (trade name: Megafac R08, Dainippon Ink Chemical Industries Co., Ltd.) 0.02 part Nonionic surfactant (trade name: Emulgen A-60, manufactured by Kao Corporation) 0.5 part Solvent A (1,3-buty Lenglycol diacetate) 50 parts / solvent B (3-ethoxypropionic acid methyl ether acetate) 100 parts The above GREEN composition B-coating solution was mixed and stirred to obtain a colored curable composition.

[Example 1]
In Comparative Example 1, a colored curable composition was obtained in the same manner as in Comparative Example 1 except that 8 parts of dipentaerythritol hexaacrylate was changed to 4 parts of dipentaerythritol pentaacrylate and 4 parts of Compound A-1. It was.

[Example 2]
In Comparative Example 1, a colored curable composition was obtained in the same manner as Comparative Example 1 except that 8 parts of dipentaerythritol hexaacrylate was changed to 4 parts of dipentaerythritol pentaacrylate and 4 parts of compound A-4. It was.

[Example 3]
In Comparative Example 1, a colored curable composition was obtained in the same manner as Comparative Example 1, except that 8 parts of dipentaerythritol hexaacrylate was changed to 4 parts of dipentaerythritol pentaacrylate and 4 parts of Compound A-5. It was.

[Example 4]
In Comparative Example 1, a colored curable composition was obtained in the same manner as in Comparative Example 1 except that 8 parts of dipentaerythritol hexaacrylate was changed to 4 parts of dipentaerythritol pentaacrylate and 4 parts of compound A-9. It was.

[Comparative Example 2]
In Comparative Example 1, a colored curable composition was obtained in the same manner as in Comparative Example 1 except that dipentaerythritol hexaacrylate was changed to the following compound A-12.

[Comparative Example 3]
In Comparative Example 1, a colored curable composition was obtained in the same manner as in Comparative Example 1 except that dipentaerythritol hexaacrylate was changed to the following compound A-13.

[Comparative Example 4]
In Comparative Example 1, a colored curable composition was obtained in the same manner as in Comparative Example 1, except that dipentaerythritol hexaacrylate was changed to the following compound A-14.

[Production of color filters]
<1-1. Formation of curable composition layer>
Each curable composition obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate with slits under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and prebaking (prebake) 100 degreeC80 second) was given, and the curable composition coating film (curable composition layer) was formed.
(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

<1-2. Exposure and development>
Thereafter, the photocurable coating film (curable composition coating film) was exposed in a pattern using a test photomask having a line width of 20 μm using a 2.5 kw ultra-high pressure mercury lamp, and after the exposure, The entire surface was covered with a 10% aqueous solution of an organic developer (trade name: CDK-1, manufactured by FUJIFILM Electromaterials Co., Ltd.) and allowed to stand for 90 seconds.

<1-3. Heat treatment>
After standing still, pure water was sprayed in the form of a shower to wash away the developer, and the coating film subjected to the photo-curing treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, a colored resin film (color filter) was formed on the glass substrate.

[2. (Curable composition and color filter performance evaluation)
Storage stability of the curable composition adjusted as described above, line width thickening amount of the curable composition coating film (colored layer) formed on the glass substrate using the curable composition, substrate adhesion, The developability and the pattern cross-sectional shape were evaluated as follows. The results are shown in Table 1.

<2-1. Storage stability of curable composition>
After the curable composition as the coating solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters was evaluated by visual observation according to the following evaluation criteria.
-Evaluation criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

<2-2. Line width thickening>
The dimension of the formed pattern was measured with a dimension measuring instrument (ICRON, manufactured by Olympus Corporation), and the width of the width with respect to the mask of 20 μm is shown in the table. The smaller the value, the better.

<2-3. Exposure sensitivity of coating film (colored layer)>
The exposure amount was changed to various exposure amounts of 10 to 200 mJ / cm ² shown in Table 1, and exposure was performed. The exposure amount at which the pattern line width after post-baking was 20 μm was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

<2-4. Developability, pattern cross-sectional shape, substrate adhesion>
The substrate surface and the cross-sectional shape after post-baking were confirmed by an ordinary method using an optical microscope and SEM photograph observation.
<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed, and the developability was evaluated according to the following criteria.
-Evaluation criteria-
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was observed.
-Evaluation criteria-
A: Tapered angle in the range of 30 to less than 70 degrees (forward taper)
○: Tapered angle in the range of 70 to less than 90 degrees (forward taper)
Δ: Taper angle is 90 degrees (rectangular)
X: The taper angle exceeds 90 degrees (reverse taper)

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. These evaluation items were evaluated based on the following criteria.
-Evaluation criteria-
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

  As is apparent from Table 1 above, the color filter in which colored pixels are formed using the curable composition of the present invention can form a pattern with high sensitivity, is excellent in developability and pattern formability, and has good substrate adhesion. The performance was the same as that of the comparative example, and the line width thickening amount was 1 to 3 μm thinner than that of the comparative example, so that the resolution was improved and it was suitable as a color filter.

Claims (4)

In the curable composition comprising (A) a colorant, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a polyfunctional monomer having an ethylenically unsaturated bond,
The (B) photopolymerization initiator includes a biimidazole compound, a mercapto compound represented by the following formula (2), and a compound B represented by the following formula (1), and (D) ethylene The polyfunctional monomer having a polymerizable unsaturated bond contains at least one polyfunctional monomer having a hydroxyl group in the molecule and having a double bond density of 9.6 mmol / g or more and 11.5 mmol / g or less. A curable composition.

The curable composition according to claim 1, wherein the (D) polyfunctional monomer having an ethylenically unsaturated bond is trifunctional or more. A color filter comprising pixels formed using the curable composition according to claim 1. The process of apply | coating the curable composition of Claim 1 or 2 on a support body, forming a curable composition layer, the process of exposing the said curable composition layer through a mask, and exposure And a step of developing a later curable composition layer to form a colored pattern.