JP5019833B2 - Curable composition, color filter and method for producing the same - Google Patents

Description

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

  In color filter applications for liquid crystal displays (LCDs), the substrate size is increasing for large TV production, and low energy curing is desired to improve productivity when large substrates are used. In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor use. That is, improvement in contrast and color purity. In order to improve the contrast, the curable composition used for the production of the color filter is required to have a finer particle size of the colorant (organic pigment or the like) used. (For example, refer to Patent Document 1.) Along with this, the amount of dispersant added for dispersing the pigment tends to increase. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of a curable composition for color purity improvement. Therefore, the content of the photopolymerization initiator and the photopolymerizable monomer in the solid content in the curable composition tends to decrease.

On the other hand, curing with low energy is also desired in color filter applications for solid-state imaging devices. Moreover, the pattern thinning is progressing and the pigment density | concentration in a composition is improving with this. Furthermore, in the pigment-based color filter, the proportion of the pigment dispersant in the composition tends to increase as the pigment becomes finer. Due to such factors, the content of the photopolymerization initiator and the photopolymerizable monomer, which are components necessary for curing the curable composition, is limited in both cases for liquid crystal displays and solid-state imaging devices. In addition, since the colorant concentration is high, there are problems such as low sensitivity and insufficient curing, insufficient adhesion to the substrate, and extremely difficult pattern formation. It was. As a countermeasure against this problem, in order to improve the substrate adhesion, a technique of introducing a silane coupling agent (see, for example, Patent Documents 2 and 3) or a technique of using a photopolymerization initiator having a specific functional group ( For example, Patent Document 4) has been proposed, but further improvement in practical use is desired.
JP 2006-30541 A (fine particle size pigment) JP-A-11-38226 (Silane coupling agent) Japanese Patent No. 2874091 (Silane coupling agent) JP-A-2005-99488 (specific initiator, fine particle size pigment)

The present invention was made in order to improve the above-mentioned drawbacks of the prior art, and the object of the present invention is to provide excellent coating properties and high sensitivity even when the colorant is contained in a high concentration. It is an object to provide a curable composition that exhibits good pattern forming properties, has a wide latitude during development, and has excellent adhesion to a hard surface as a substrate.
A further object of the present invention is to provide a color filter having a colored pattern excellent in resolving power and adhesion to a support using the curable composition of the present invention, and production capable of producing the color filter with high productivity. It is to provide a method.

As a result of intensive studies, the present inventor has found that the above problems can be solved by using a compound having a specific binding structure, and has completed the present invention. That is, the means for solving the above problems are as follows.
<1> (A) a compound having at least one ethylenically unsaturated double bond, (B) a photopolymerization initiator, (C) a colorant, (D) an alkali-soluble resin , ( E) a compound having an isocyanate bond, the following general formula obtained by reaction of the alcohol compound represented by the formula (I), urethane in the molecule, amide, and compounds having a partial structure selected from urea, and contains (F) an alkoxysilane compound the relative solids content of (C) is 30% to 70% by mass Ru curable composition of the colorant.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. R ³ represents a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, a functional group represented by the following general formula (II), or a functional group represented by the following general formula (III).

In the said general formula (II), n shows the integer of 1-10. In general formula (II) and general formula (III), R ⁴ represents a hydrogen atom or an alkyl group, and in general formula (III), a plurality of R ⁴ present in the molecule may be the same or different from each other. Good.
<2> It has a partial structure selected from urethane, amide, and urea in the molecule obtained by the reaction of the compound (E) having an isocyanate bond and the alcohol compound represented by the general formula (I). <1> The curable composition according to <1>, wherein the compound has a molecular weight of 100 to 5,000.
<3> The curable composition according to <1> or <2>, wherein the (B) photopolymerization initiator is a bisimidazole compound.
<4> as before SL (B) a photopolymerization initiator, further mercapto compounds and aminobenzene derivatives, alkoxy benzene derivatives, alkyl thio benzene derivatives, thioxanthone derivatives, <1> to include at least one compound selected from coumarin derivative < The curable composition according to any one of 3 >.

< 5 > A color filter having a colored pattern formed using the curable composition according to any one of <1> to < 4 >.
< 6 > A step of applying a curable composition according to any one of <1> to < 4 > on a support to form a colored curable composition layer, and the curable composition layer. And a step of exposing through a mask, and a step of developing the curable composition layer after exposure to form a colored pattern.

According to the present invention, even when the colorant is contained in a high concentration, it has excellent coating properties, is cured with high sensitivity, exhibits good pattern forming properties, has a wide latitude during development, and has a base material. The curable composition excellent in adhesiveness with the hard surface which is can be provided.
Furthermore, according to the present invention, by using the curable composition of the present invention, a color filter having a colored pattern excellent in resolving power and adhesion between the support and the color filter is produced with high productivity. A possible manufacturing method can be provided.

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 compound having at least one ethylenically unsaturated double bond (polymerizable compound), (B ) A photopolymerization initiator, (C) a colorant, (D) an alkali-soluble resin , ( E) a compound having a partial structure selected from urethane, amide, and urea in the molecule , and (F) an alkoxysilane compound. The content of the colorant (C) with respect to the solid content is 30% by mass to 70% by mass, and 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, (E) a compound having a partial structure selected from urethane, amide, and urea in the molecule (hereinafter, appropriately referred to as component (E)), which is an important constituent of the present invention, will be described.

<(E) Compound obtained by reaction of compound having isocyanate bond and alcohol compound represented by general formula (I), having a partial structure selected from urethane, amide, and urea in the molecule>
In the present invention, (E) the compound having a partial structure selected from urethane, amide, and urea in the molecule is selected from a compound having a urethane bond, a compound having an amide group, and a compound having a urea bond in the molecule. what der those, isocyanate bond may be any one as Re reaction products der obtained by reaction of an alcohol compound represented by the following general formula described below as compound (I) having a but the pattern From the viewpoint of formability, those having a urethane bond as a partial structure in the molecule are preferred. The component (E) is preferably a compound having a nitrogen-containing heterocycle in its structure, and isocyanurate is more preferable.
In view of the influence of the component (E) on the physical properties of the curable composition of the present invention, for example, from the viewpoint of developability, it is preferable to have an alkylene oxide group in the molecule in addition to the above structure. As the alkylene oxide group, ethylene oxide and propylene oxide are preferable, and an ethylene oxide group is particularly preferable.
Furthermore, from the viewpoint of improving curability of the composition, it is more preferable to have an ethylenically unsaturated double bond group in the molecule.
Incidentally, Keru Contact to the present invention (E) is preferably used as the component, a urethane compound having an ethylenically unsaturated bond group, and specific examples of the isocyanurate compound, a compound having an isocyanate bond and the following general formula (I) in the reaction product of an alcohol compound represented it can be mentioned up.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. R ¹ and R ² are more preferably a hydrogen atom or a methyl group, respectively.

R ³ represents a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, a functional group represented by the following general formula (II), or a functional group represented by the following general formula (III). Especially, it is preferable that they are a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a functional group represented by general formula (III), More preferably, a methyl group, Or it is a functional group represented by general formula (III).

In the said general formula (II), n shows the integer of 1-10, Preferably, it is 1-5. In the general formulas (II) and (III), R ⁴ represents a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. In the general formula (III), a plurality of R ⁴ present in the molecule may be the same or different from each other. More preferable R ⁴ here includes a hydrogen atom or a methyl group.

The alcohol compound represented by the general formula (I), the compounds exemplified below (MA-1) ~ (MA -4) , etc., but are exemplified, but the invention is not limited thereto.
[Alcohols: Exemplified compounds (MA-1) to (MA- 4 )]

As the component (E) requires that the the alcohol is selected from the exemplified compounds, the reaction product of a compound selected from the isocyanate, the following compounds (MU-1) ~ (MU -27) .
The reaction between the compound having an isocyanate bond and the alcohol compound is performed, for example, under the following conditions.
As preparation amount of an isocyanate compound and an alcohol compound, it adjusted so that the isocyanate group mole number of an isocyanate compound and the hydroxyl group mole number of an alcohol compound might become equal.
The reaction catalyst is not particularly limited, but is preferably an organic tin (meth) acrylate such as bismuth tris (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin acetate, dibutyltin dichloride, tin octylate, octyl acid (Meth) acrylates having amidine skeletons such as organic zinc (meth) acrylates such as zinc and zinc naphthenate, tertiary amines such as triethylenediamine and triethylamine, and 1,8-azabicyclo [5,4,0] undecene-7 Can be added in the range of 0.0001 to 10 parts by weight per 100 parts by weight of thiol or isocyanate.
In the present specification, “(meth) acrylate” may be used to represent both or either acrylate or methacrylate.

As reaction conditions, a temperature range of −50 ° C. to 100 ° C. is usually applied. Below -50 ° C, the progress of the reaction is extremely slow. Above 100 ° C, not only the by-products increase and the yield decreases, but also there is a possibility of gelation, which is not preferable. Dilute with solvent if necessary. Solvents used can be used except alcohols, carboxylic acids, amines and the like that react with isocyanates. From the viewpoint of reaction rate and solubility, acetonitrile, N, N-dimethylformamide (DMF), N, Polar solvents such as N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP), chlorinated solvents such as chloroform, and aromatic solvents such as toluene and xylene are preferably used. A dehydrated solvent is preferably used to prevent the reaction between residual water and isocyanate.
After completion of the reaction, the reaction solution was concentrated under reduced pressure and purified by a silica gel column (eluent: ethyl acetate / n-hexane = 1/1). It can also be purified by chromatography, recrystallization, reprecipitation.

Specific compounds of the isocyanates MU capable of producing an urethane compound having an ethylenically unsaturated bond group, which is the component (E) in the present invention, and an isocyanurate compound are shown below.
[Isocyanates: exemplary compounds (MU-1) to (MU-27)]

The component (E) thus obtained is preferably contained in an amount of 0.3 to 5.0% by mass, more preferably 0.5 to 2.0% by mass, in the total solid content of the curable composition of the present invention. % Range.
Further, the component (E) is preferably contained in an amount of 2 parts by weight or more and less than 25 parts by weight, more preferably 5 parts per 100 parts by weight of the (A) ethylenically unsaturated double bond compound described later.
More than 10 parts by mass.

<(A) Compound containing ethylenically unsaturated double bond>
The curable composition of the present invention contains (A) a compound containing an ethylenically unsaturated double bond.
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, 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-59-5241, 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 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.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

  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-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 are commercially available products. (Manufactured by Kyoeisha) is more preferred.

(A) The content of the compound having an ethylenic double bond is preferably 1 to 90% by mass and more preferably 5 to 80% by mass in the solid content of the curable composition of the present invention. Preferably, it is 10-70 mass%.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content is preferably 5 to 50% by mass, more preferably 7 to 40% by mass. More preferably, it is 10-35 mass%.

<(B) Photopolymerization initiator>
The curable composition of the present invention contains (B) a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates the polymerization of the compound (A) containing an ethylenically unsaturated bond, and has absorption in a wavelength region of 300 to 500 nm. Preferably there is. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

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, hexaaryls. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds. In the present invention, 2,2′-bis (O-chlorophenyl) -4 is used. , 4 ′, 5,5′-tetraphenylbiimidazole is preferable, and by using a photopolymerization initiation system in which a sensitizing dye and a mercapto compound are combined in this polymerization initiator, further enhancement of sensitivity can be achieved.
The ratio of the initiator, the sensitizing dye, and the mercapto compound is 1 to 5 for 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole with respect to the sensitizing dye. Equivalents are preferable, and 1-2 equivalents are more preferable.
The mercapto compound is preferably 0.5 to 10 equivalents, more preferably 1 to 3 equivalents with respect to 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole. Is preferred.
The content of the (B) photopolymerization initiator in the cured composition of the present invention is preferably about 3 to 20% by mass, more preferably 5 to 10% by mass in terms of solid content.
As the sensitizing dye used in the photopolymerization initiation system in the present invention, Michler's ketone is preferable, and those described in paragraphs [0022] to [0042] of JP-A No. 2006-171689 are preferable. B is preferred.

The mercapto compound used in the photopolymerization initiation system is preferably a compound having the following structure in addition to the mercaptobenzothiazole used in the examples described later.
The SH group in the following compounds is monofunctional, but is not limited to this, and even the polyfunctional compound can achieve the effects of the present invention.

<(D) Colorant>
In the curable composition of the present invention, a colorant (D) can be used as desired. 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 by necessity 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. As the colorant,
From the viewpoint of durability such as heat resistance and light resistance, a pigment is preferable.

  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 fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable. 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 cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

  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 10 to 100 nm, more preferably 10 to 70 nm, still more preferably 10 to 50 nm, from the viewpoint of color unevenness and contrast. Most preferred is ˜40 nm.

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 (D), 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.

The content of the case of using a coloring agent to the curable composition of the present invention, the total solid content of the curable composition is from 30 to 70 wt%.

<(D) Alkali-soluble resin>
In the curable composition of the present invention, an alkali-soluble resin is used as the binder polymer for the purpose of improving the 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. Yes, more preferably in the range of 2,000-250,000. 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.

<(F) alkoxysilane compound>
Although the curable composition of this invention contains the said (A)-(E) component as an essential component, from a viewpoint of adhesiveness improvement with a board | substrate further, an alkoxysilane compound is included. Of the alkoxysilane compounds, silane coupling agents are preferred.
The silane coupling agent is preferably an alkoxysilyl group as a hydrolyzable group capable of chemically bonding with an inorganic material, and the bonding group with an organic resin is preferably (meth) acryloyl, phenyl, mercapto, or epoxysilane. (Meth) acryloylpropyltrimethoxysilane is more preferable.
The addition amount in the case of using a silane coupling agent is preferably in the range of 0.2 to 3.0% by mass in the total solid content of the curable composition of the present invention, 0.5 to 1.0 The 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.

<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.

<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 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 is characterized by having a 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 photocurable 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 device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, 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.
[Example 1]
<1-1. Pigment kneading dispersion treatment>
First, the following components were kneaded and dispersed with two rolls.
・ C. I. Pigment Red 254 100 parts by mass I. Pigment Red 177 40 parts by mass Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000,
Solvent: 60% propylene glycol methyl ether acetate,
Resin solid content concentration: 40%) 60 parts by mass Solvent: propylene glycol methyl ether acetate 140 parts by mass

  After the obtained kneaded product was pulverized, 10% of dispersant: (trade name: EFKA-46) was added to the pigment, and propylene glycol monomethyl ether acetate was added so that the pigment concentration was 15%, and the bead mill The pigment dispersion R was obtained by dispersing with (Dynomill: Disperser manufactured by Shinmaru Enterprises).

<1-2. Preparation of colored curable composition>
[Colored curable composition 1]
-Pigment dispersion R (pigment concentration 15 wt%) [(C) component] 150 parts-Dipentaerythritol hexaacrylate [(A) component] 10 parts-Isocyanurate compound M1 [(E) component] 5 parts 2, 2 '-Bis (O-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole [component (B)] 2.0 parts, Michler's ketone 0.6 parts, mercaptobenzothiazole 0.6 parts, methacryloylpropyl Trimethoxysilane [silane coupling agent] 0.6 parts benzyl methacrylate / methacrylic acid = 80/20 mol ratio
[Alkali-soluble resin: Component (D)] 8 parts ・ Hydroquinone monomethyl ether 0.005 part ・ Propylene glycol monomethyl ether acetate 100 parts

[Examples 5, 7, 8 Reference Examples 2-4, 6 ]
The curable compositions of Examples 5 , 7 , and 8 and Reference Examples 2 to 4 , and 6 except that each compound used in the colored curable composition 1 of Example 1 was changed as described in Table 1 below. I got a thing.

In addition, the detail of (E) component of Table 1 is as follows. [Synthesis example 1]: Synthesis | combination of M1 M1 is alcohol compound (MA-2), (MA-3), and an isocyanate type (MU-). 22).
After MA-2 (0.1 mol) and MA-3 (0.2 mol) are dissolved in 100 ml of acetonitrile, bismuth tris (2-ethylhexanoate) (trade name: Neostan U-600 (Nitto Kasei Co., Ltd.) 100 mg) was added to make a uniform solution. It heated to 60 degreeC and the acetonitrile 10 ml solution of MU-22 (0.1 mol) was dripped. After completion of dropping, the mixture was stirred at 55 to 65 ° C. for 8 hours. After completion of the reaction, the reaction solution is cooled to room temperature and then the solvent is distilled off. The residue is purified by silica gel column chromatography, and (E) a compound having a partial structure selected from urethane, amide, and urea in the molecule. Some (M1) was obtained.

[Synthesis Example 2]: Synthesis of M2 M2 is a condensation reaction product of an alcohol compound (MA-8) and an isocyanate compound (MU-27).
MA-8 (0.2 mol) is dissolved in 100 ml of acetonitrile, and then 100 mg of bismuth tris (2-ethylhexanoate) (trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.)) is added to obtain a homogeneous solution. It was. It heated to 60 degreeC and the acetonitrile 10 ml solution of MU-27 (0.1 mol) was dripped. After completion of dropping, the mixture was stirred at 55 to 65 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain component (E) (M2).

Similarly, the following compounds were reacted to obtain (M3) to (M6).
M3: a reaction product of an amine compound (A-2) and an isocyanate compound (MU-27).
M4: reaction product of amine compound (A-2) and halogen-containing compound (C-2).
M5: a reaction product of an alcohol compound (MA-1) and an isocyanate compound (MU-21).
M6: reaction product of alcohol compound (MA-11) and isocyanate compound (MU-23).

[Comparative Example 1]
<Preparation of curable composition>
-Pigment dispersion R (pigment concentration 15 wt%) [component (C)] 150 parts-Dipentaerythritol hexaacrylate [component (A)] 15 parts-4- {o-bromo-pN, N-di ( Ethoxycarbonyl) aminophenyl}
2,6-di (trichloromethyl) -S-triazine (component (B)) 3.2 parts benzyl methacrylate / methacrylic acid = 70/30 molar ratio,
50% PGMEA solution) [Alkali-soluble resin: Component (D)] 8 parts Hydroquinone monomethyl ether 0.005 parts PGMEA (propylene glycol monomethyl ether acetate) 100 parts Comparative Example 1 in the same manner as in Example 1 according to the above composition A curable composition was prepared.

[Comparative Example 2]
<Preparation of curable composition>
-Pigment dispersion R (pigment concentration 15 wt%) [(C) component] 150 parts-Dipentaerythritol hexaacrylate [(A) component] 15 parts-Irgacure 369 [(B) component] 2.4 parts-Michler's ketone 0 8 parts benzyl methacrylate / methacrylic acid = 70/30 molar ratio,
50% PGMEA solution) [alkali-soluble resin: component (D)] 8 parts Hydroquinone monomethyl ether 0.005 parts PGMEA (propylene glycol monomethyl ether acetate) 100 parts Comparative Example 2 in the same manner as in Example 1 according to the above composition A curable composition was prepared.

[Comparative Example 3]
<Preparation of curable composition>
-Pigment dispersion R (pigment concentration 15 wt%) [component (C)] 150 parts-Dipentaerythritol hexaacrylate 15 parts-2,2'-bis (O-chlorophenyl) -4,4 ', 5,5' −
Tetraphenylbiimidazole 2.0 parts, Michler's ketone 0.6 parts, mercaptobenzothiazole 0.6 parts, alkali-soluble resin (benzyl methacrylate / methacrylic acid = 70/30
Molar ratio 50% PGMEA solution) 8 parts Hydroquinone monomethyl ether 0.005 parts PGMEA (propylene glycol monomethyl ether acetate) 100 parts According to the above composition, a curable composition of Comparative Example 3 was prepared in the same manner as Example 1. .

[2. (Production of color filter)
<2-1. 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

<2-2. Exposure and development>
Thereafter, the photocurable 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. After the exposure, the entire surface of the coating film was exposed to an organic developer (product). Name: CDK-1, manufactured by Fuji Film Arch Co., Ltd.) and covered with a 10% aqueous solution, and rested for 90 seconds.
<2-3. 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.

[3. (Evaluation of color filter)
Storage stability of the colored curable composition coating solution prepared above, exposure sensitivity of the curable composition coating film (colored layer) formed on the glass substrate using the colored curable composition, and substrate adhesion Property, developability, and pattern cross-sectional shape were evaluated as follows. The results are shown in Table 1.
<3-1. Exposure sensitivity of coating film (colored layer)>
The exposure amount was changed in the range of 10 to 200 mJ / cm ² and exposed, and the exposure amount at which the pattern line width after post-baking was 20 μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

<3-2. 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.
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
<3-2-1. Developability>
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.
The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred.
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:

<3-2-2. Substrate adhesion>
○: 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.
<3-2-3. Pattern cross-section shape>
A: Tapered angle in the range of 30 to 70 degrees (forward taper)
○: Tapered angle in the range of 70 to 90 degrees (forward taper)
Δ: Taper angle is 90 degrees (rectangular)
X: The taper angle exceeds 90 degrees (reverse taper)

  As is apparent from Table 2, a color filter formed with a colored pattern using the curable composition of the present invention can be patterned with high sensitivity, has excellent developability and pattern formability, and is suitable as a color filter. there were.

Claims (6)

(A) Compound having at least one ethylenically unsaturated double bond, (B) Photopolymerization initiator, (C) Colorant, (D) Alkali-soluble resin , ( E) Compound having isocyanate bond and the following general formula obtained by reaction of the alcohol compound represented by the formula (I), urethane in the molecule, amide, and compounds having a partial structure selected from urea, and contains (F) an alkoxysilane compound, solids wherein (C) content of 30% to 70% by mass Ru curable composition of the coloring agent to.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. R ³ represents a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, a functional group represented by the following general formula (II), or a functional group represented by the following general formula (III).

In the general formula (II), n represents an integer of 1 to 10. In general formula (II) and general formula (III), R ⁴ represents a hydrogen atom or an alkyl group, and in general formula (III), a plurality of R ⁴ present in the molecule may be the same or different from each other. Good.   Molecular weight of the compound having a partial structure selected from urethane, amide, and urea in the molecule, obtained by the reaction of the compound having an isocyanate bond (E) with the alcohol compound represented by the general formula (I) Is 100-5000, The curable composition of Claim 1 characterized by the above-mentioned.   The curable composition according to claim 1 or 2, wherein the (B) photopolymerization initiator is a bisimidazole compound. Along with the (B) photopolymerization initiator, it contains a mercapto compound and at least one compound selected from an aminobenzene derivative, an alkoxybenzene derivative, an alkylthiobenzene derivative, a thioxanthone derivative, and a coumarin derivative, The curable composition according to any one of claims 1 to 3 . Color filter characterized by having a colored pattern formed by using the curable composition according to any one of claims 1 to 4. A step of applying a curable composition according to any one of claims 1 to 4 to form a colored curable composition layer on a support, and the curable composition layer as a mask. And a step of developing the curable composition layer after exposure to form a colored pattern, and a method for producing a color filter.