JP2007128060A - Photocurable composition and color filter using the same - Google Patents

Abstract

A photocurable composition having sufficient color density, spectral characteristics, sensitivity, and curability, and having excellent pixel pattern rectangularity and developability when used in a color filter, and a color filter using the same I will provide a.
In a photocurable composition containing a colorant, a photopolymerizable compound, and a photopolymerization initiator, the content of the colorant is 40% by mass or more based on the total solids, and the photopolymerizable compound comprises: A photocurable composition having an alkali-soluble group.
[Selection figure] None

Description

  The present invention relates to a photocurable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display element (LCD), a solid-state image sensor (CCD, CMOS, etc.), and the photocurable composition. It relates to the color filter used.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. Colored pixels are formed, and a color filter can be obtained by repeating this operation for each color.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 5).

  In recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution in the conventional pigment dispersion system, and there is a problem in color uniformity between pixels, such as color unevenness caused by coarse particles of the pigment. For this reason, it was not suitable for uses requiring a fine pattern such as a solid-state imaging device.

  In order to solve such a problem, a technique of using a dye instead of a pigment has been conventionally proposed (for example, see Patent Document 6). However, in general, a curable composition containing a dye is inferior to a curable composition using a pigment in terms of various properties such as light resistance, heat resistance, solubility, and coating uniformity. there were.

  In particular, color filters for solid-state imaging devices (image sensors) tend to be thinned to a thickness of 1.5 μm or less in order to cope with improved shading and device miniaturization. However, when such a thin film is formed, the content of the colorant contained in the film inevitably decreases, which causes a problem in terms of color density. Such a tendency is particularly remarkable when a dye is used rather than when a pigment is used as a colorant.

  That is, when an organic pigment is used, the molecules that form a chromophore are present in an aggregated state in the color filter, whereas when a dye is used, the molecules are dispersed in a molecular state. In addition to the chromophore molecules, molecular chains that improve their properties are bound to increase durability and light resistance, so the molecular chains that become chromophores are further diluted. Therefore, the color density is lowered accordingly.

  As described above, in order to meet the demand for thinning the color filter in the solid-state imaging device, it is necessary to increase the content ratio of the colorant in the color filter. This requirement is particularly important when dyes are used rather than when pigments are used as colorants.

  However, increasing the content ratio of the colorant inevitably decreases the ratio of other components contained in the composition. In this case, as a matter of course, when the ratio of the other components is lowered, the photocurability and the alkali developability are lowered, so that there is a limit to the improvement of the content ratio of the colorant. In particular, when a dye is used as the colorant, the color density is significantly reduced as the film is made thinner than when a pigment is used, and it is very difficult to balance with practical properties other than the color density.

Further, in the radiation-sensitive colored composition containing a radiation-sensitive component, a binder resin, a pigment, and a solvent, the radiation-sensitive component is selected from a specific compound group containing an ethylene oxide chain or a propylene oxide chain as a polymerizable component. A radiation-sensitive colored composition containing at least one (meth) acrylate compound selected has been proposed (see, for example, Patent Document 7).
JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 Japanese Patent Laid-Open No. 10-332929 JP-A-6-75375 Japanese Patent Laid-Open No. 10-62986

An object of the present invention is to provide a photocurable composition that can provide sufficient color density, spectral characteristics, sensitivity, and curability, and that has excellent pixel pattern rectangularity and developability when used in a color filter. With the goal.
Another object of the present invention is to provide a color filter having a sufficient color density and excellent in the rectangularity of a pixel pattern.

In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> In the photocurable composition containing a colorant, a photopolymerizable compound, and a photopolymerization initiator, the content of the colorant is 40% by mass or more of the total solid content, and the photopolymerizable compound is an alkali. A photocurable composition having a soluble group.
<2> The total content of the colorant, the photopolymerizable compound, and the photopolymerization initiator is 80% by mass or more based on the total solid content in the photocurable composition. The photocurable composition as described in <1>.
<3> The photocurable composition as described in <1> or <2> above, wherein the number of polymerizable functional groups of the photopolymerizable compound is 3 or more.

<4> The photocurable composition according to any one of <1> to <3>, wherein the colorant is mainly composed of a dye.
<5> The photocurable composition according to any one of <1> to <4>, wherein 25% by mass or more of the colorant is an acidic dye.
<6> The above-mentioned <1> to <5>, wherein the alkali-soluble group of the photopolymerizable compound is at least one of a carboxyl group, a phosphoric acid group, and a sulfonic acid group. The photocurable composition as described.

<7> Pixels formed by forming a coating film made of the photocurable composition according to any one of <1> to <6> above on a substrate and patterning by a photolithography method using alkali development. A color filter comprising:
<8> In the wavelength range of 400 nm to 700 nm, the minimum transmittance is 10% or less, and the difference between the maximum transmittance and the minimum transmittance in the wavelength range is 65% or more. Color filter.
<9> The color filter according to <7> or <8>, wherein the pixel has a thickness of 0.3 μm to 1.5 μm.

<10> The color filter according to any one of <7> to <9>, wherein a maximum side of the pixel is 5.0 μm or less.

According to the present invention, it is possible to provide a photocurable composition that has sufficient color density, spectral characteristics, sensitivity, and curability, and that has excellent pixel pattern rectangularity and developability when used in a color filter. Can do.
In addition, according to the present invention, it is possible to provide a color filter having a sufficient color density and excellent in pixel pattern rectangularity.

  Hereinafter, the photocurable composition of this invention and the color filter comprised using it are explained in full detail.

<< Photocurable composition >>
The photocurable composition of the present invention contains a colorant, a photopolymerizable compound, and a photopolymerization initiator, and the content of the colorant is 40% by mass or more of the total solids, and the photopolymerization is performed. The organic compound has an alkali-soluble group, and includes an alkali-soluble resin or an organic solvent as necessary.
The photocurable composition of the present invention is a photocurable composition containing a colorant, a photopolymerizable compound, and a photopolymerization initiator, and the content of the colorant is 40% by mass or more based on the total solid content. And since the photopolymerizable compound has an alkali-soluble group, an alkali-soluble resin is not substantially used. Therefore, even if the content of the colorant is as large as 40% by mass with respect to the total solid content, The contents of the photopolymerizable compound and the photopolymerization initiator, which are curable components, can be maintained.
In addition, the photocurable composition of the present invention ensures practical characteristics (color density, spectral characteristics, sensitivity, curability, etc.) as a coating film for a color filter, and the transmittance and pattern profile of the pixel of the obtained color filter. (Pattern rectangularity) can be improved.

Furthermore, the total content of the colorant, the photopolymerizable compound and the photopolymerization initiator in the photocurable composition of the present invention is preferably 80% by mass or more based on the total solid content. In other words, the total content of solid components other than the colorant, photopolymerizable compound, and photopolymerization initiator in the photocurable composition of the present invention is preferably less than 20% by mass.
When the total content of the colorant, photopolymerizable compound and photopolymerization initiator is 80% by mass or more based on the total solid content, the color density, sensitivity, curability and the like can be further sufficiently improved.
Hereinafter, each component contained in the photocurable composition of the present invention will be described.

<Colorant>
The colorant in the present invention is not particularly limited, and various conventionally known dyes and pigments can be used alone or in combination of two or more.
The colorant is preferably substantially composed mainly of a dye. By using the dye as a main component of the colorant, the uniformity of color characteristics can be improved and the variation in color density distribution between pixels can be reduced. .
Here, “substantially the main component of the dye” refers to a degree that does not impair the characteristics of the dye in terms of color characteristics. Specifically, the dye content is 60% by mass or more based on the total amount of the colorant. It means that.
The content of the dye in the colorant is 60% by mass or more, desirably 65% by mass or more, and more desirably 70% by mass or more.

(dye)
As the dye as the colorant in the present invention, an organic solvent-soluble dye or the like can be used without particular limitation, and examples thereof include conventionally known dyes for color filters. Examples of the known dye include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, US Patent. No. 4,808,501, U.S. Pat.No. 5,667,920, U.S. Pat.No. 5,059,500, JP-A-5-333207, JP-A-6-35183, Examples thereof include dyes described in JP-A-6-51115 and JP-A-6-194828. From the viewpoint of chemical structure, triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, etc. can be mentioned. . Particularly preferable dyes in the present invention include pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes, and anthrapyridone dyes.

In the case of a resist system that performs water or alkali development, acidic dyes and / or derivatives thereof can be suitably used as the dye in the present invention from the viewpoint of completely removing the binder and / or dye by development. In addition, as the dye in the present invention, 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 also be used.
It is preferable that 25 mass% or more of the photocurable composition of this invention is an acidic dye with respect to all the coloring agents. Thereby, alkali developability can be maintained and the rectangularity and developability of the pattern can be achieved.
Hereinafter, the acid dye will be described.

(Acid dyes)
The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the acidic dye in the present invention is not limited to these. Examples thereof include the following dyes and derivatives of these dyes.
Acid Black 24;
Acid Blue 1,7,9,15,83,86,90,103,108,113,120,249;
Acid Green 1, 3, 5, 9, 16, 50;
Acid Orange 7, 8, 10, 12, 50, 51, 52, 63;

Acid Red 4, 8, 14, 17, 18, 26, 27, 51, 66, 73, 80, 87, 88, 91, 92, 94, 103, 111, 114, 145, 150, 151;
Acid Violet 9, 17, 49;
Acid Yellow 1,7,9,11,17,23,34,36,38,40,65,72,76,135,228;

Direct Yellow 34;
Direct Orange 41, 61, 70;
Direct Violet 54;
Direct Blue 86, 108, 109, 199;
Modern Yellow 8, 10, 20;
Modern Red 9, 32;
Modern Violet 2,41;
Modern Blue 1,3;
Modern Green 4;
Food Yellow 3;

Solvent Yellow 14;
Solvent Orange 2, 7, 15;
Solvent Red 49;
Valentine Blue 2620

As the acidic dye that can be used as the colorant in the present invention, the following compounds can also be used.
-Heterocyclic azo compounds-
A heterocyclic azo compound is a compound in which an azo group (—N═N—) is directly connected to a heterocyclic ring.
Here, the heterocyclic ring has a hetero atom (for example, nitrogen atom, sulfur atom, oxygen atom) in the ring. Either a saturated ring or an unsaturated ring may be used, but an unsaturated ring is preferable. Further, it may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent.

  Specific examples of the heterocyclic ring include furan, pyrrole, pyrazole, pyrazoline, imidazole, oxazole, thiazole, triazole, pyran, pyridine, pyrimidine, pyrazine, triazine, pyridone, isothiazole, thiadiazole, benzothiazole, benzoxazole, benzoisothiazole. Etc. Among these, a heterocyclic ring containing a nitrogen atom in the ring (a nitrogen-containing heterocyclic ring) is preferable, and among them, pyrazole, pyridone, pyridine, and pyrimidine are preferable.

  Moreover, it is preferable to contain an acid group at any position of the heterocyclic azo compound. Here, the acid group is not particularly limited as long as it is a functional group that can be dissociated with an alkaline aqueous solution, and specific examples include sulfonic acid, carboxylic acid, phenolic hydroxyl group, sulfonamide, phosphoric acid, and the like. It is done. These acid groups may be a salt of a metal having a valence of 2 or more, and examples of the metal include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, and iron. It is done.

Examples of the heterocyclic azo compound include: 1) a heterocycle directly connected to one bond of an azo group is a pyrazole ring, and a heterocycle is also directly connected to the other bond of the azo group; A compound having an acid group at the position of
2) The heterocycle directly connected to one bond of the azo group is a pyrazole ring, the heterocycle directly connected to the other bond of the azo group is a pyridine ring, and a carboxylic acid and / or at any position in the structure A compound having a sulfonamide,
3) The heterocycle directly connected to one bond of the azo group is a pyrazole ring, the heterocycle directly connected to the other bond of the azo group is a pyrimidine ring, and a carboxylic acid and / or at any position in the structure A compound having a sulfonamide,
Is preferred.

  Hereinafter, specific examples of the heterocyclic azo compound (Exemplary Compounds A1-1 to A1-24, A2-1 to A2-24, A3-1 to A3-24) are shown. However, the present invention is not limited to these specific examples.

-Phthalocyanine compounds-
The phthalocyanine compound is generally a compound represented by the following general formula 1.

General formula 1:

In the general formula 1, M represents a metal, and examples of the metal include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe. and _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl metal chlorides such as _2, TiO, metal oxides such as VO, and Si _(OH) include metal hydroxides _2. M is preferably Zn, Pd, Cu, Ni, Co, or VO, more preferably Zn, Cu, Co, or VO, and most preferably Cu.

Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent an atomic group necessary for forming a 6-membered ring containing a carbon atom. The 6-membered ring may be a saturated ring or an unsaturated ring, may be a heterocyclic ring containing a nitrogen atom or the like, and may be unsubstituted or have a substituent. Further, another 5-membered or 6-membered ring may be condensed, and the condensed ring may further have a substituent. Specifically, a benzene ring, a cyclohexane ring, a cyclohexene ring, a pyridine ring, a naphthalene ring and the like are included.

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ each independently represent a substituent described later. In the present invention, it is preferable that at least one of the substituents represented by R ^{101 to} R ¹⁰⁴ is an organic group described later. Furthermore, the organic group is preferably an organic group containing a sulfur atom (a sulfur-containing organic group).

  n1, n2, n3, and n4 each independently represents an integer of 0 to 4. The sum of the values of n1 to n4 is preferably 1 or more, and more preferably 2 or more.

The phthalocyanine compound preferably has an acid group at an arbitrary position in the structure. The acid group may be any functional group as long as it is dissociable with respect to an alkaline aqueous solution, and specific examples include sulfonic acid, carboxylic acid, phenolic hydroxyl group, sulfonamide, and phosphoric acid. .
In addition, these acid groups may be a salt of a metal having a valence of 2 or more. Examples of the metal include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, and iron. Can be mentioned.

As the phthalocyanine compound, any of the following cases is preferable.
1) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is a sulfur-containing organic group. Compound,
2) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring and / or a pyridine ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is halogen. A compound that is an atom or a sulfur-containing organic group. Furthermore,
3) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is —SR (R is described later) A compound containing an acid group at an arbitrary position of the organic group R,
4) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring and / or a pyridine ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is halogen. Compounds that are atoms or sulfonamide groups are preferred.

  Hereinafter, specific examples (Exemplary Compounds A4-1 to A4-19) of the phthalocyanine compounds will be shown. However, the present invention is not limited to these specific examples.

  In the following specific examples (A5-1 to A5-38), ring A1, ring A2, ring A3, and ring A4 each independently represent a benzene ring or a pyridine ring. In the case of a pyridine ring, there are positional isomers having different N positions depending on the direction of the condensed ring. In addition, isomers having different substitution positions of substituents also exist in each.

-Azomethine compounds-
An azomethine compound refers to a compound having an azomethine group [RaC (Rb) = N-] in the molecule. Here, Ra and Rb represent arbitrary organic groups.

  As the azomethine compound, those containing a heterocycle are preferable. Examples of the heterocyclic ring include those similar to the heterocyclic ring in the above-described heterocyclic azo compound. In these, the heterocyclic ring (nitrogen-containing heterocyclic ring) which contains a nitrogen atom in a ring is preferable.

  In the present invention, those having a structure in which a plurality of the aforementioned heterocycles are condensed are preferable. Among these, a structure in which two heterocycles selected from pyrazole, pyrazoline, imidazole, triazole, and oxazole are condensed is preferable.

  The azomethine compound preferably has an acid group at an arbitrary position in the structure. The acid group is not particularly limited as long as it is a functional group dissociable with an alkaline aqueous solution, and specific examples include sulfonic acid, carboxylic acid, phenolic hydroxyl group, sulfonamide, and phosphoric acid. The acid group may be a salt of a metal having a valence of 2 or more, and examples of the metal include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, and iron.

As the azomethine compound, 1) a compound having a condensed structure of pyrazoline and triazole, an aromatic ring substituted on the nitrogen atom of the azomethine group, and an acid group at an arbitrary position in the structure is preferable, Furthermore,
2) A structure in which pyrazoline and 1,2,4-triazole shown below are condensed [from the left side, 7H-pyrazolo [1,5-b] [1,2,4] triazole or 7H-pyrazolo [5,1 -C] [1,2,4] triazole], a compound in which the aromatic ring substituted on the nitrogen atom of the azomethine group is a quinoline skeleton, and has a carboxylic acid and / or a sulfonamide at any position in the structure, Is preferred.

  Hereinafter, specific examples (exemplary compounds A6-1 to A6-28) of azomethine compounds will be shown. However, the present invention is not limited to these specific examples.

-Description of substituents-
The “substituent” in the present specification will be described.
In the present specification, the “substituent” represents an arbitrary group regardless of inorganic or organic, and specifically includes a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxylic acid group, and a sulfonic acid group. , Sulfinic acid group, alkyl group (including linear, branched, and cyclic), alkenyl group (including linear, branched, and cyclic), alkynyl group, aryl group, heterocyclic group, formyl group, or And a group obtained by arbitrarily combining one partial structure selected from the following group (A) and one partial structure selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. It is done.
Group (A): ether group, amino group, thioether group, ketone group, ester group, amide group, urethane group [carbamoyl group -O-CO-N (R)-], urea group [-N (R) -CO -N (R) -], a sulfinyl group [-SO-], a sulfonyl group [-SO ₂ -], a sulfonic acid ester group _[-SO 2 -O-], a sulfonamide group _[-SO 2 -N (R) -], imide group [-CO-N (R) -CO-], sulfonyl amido groups _[-SO 2 -N (R) -CO-], disulfonylimide groups _[-SO 2 -N (R) _{-SO 2-} ]

  R bonded to the nitrogen atom in the group (A) represents any of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

  In the “substituent”, the alkyl group may be linear, branched or cyclic. In the case of a ring, it may be monocyclic or polycyclic. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, or a norbornyl group. And an adamantyl group. Moreover, you may have a substituent further in the arbitrary positions of these alkyl groups, and all the above-mentioned "substituents" are included in the further substituents including said alkyl group itself. In the case of a cyclic alkyl group, a partial structure selected from the above group (A) may be inserted at any position of the carbon-carbon bond constituting the ring.

  In the “substituent”, the alkenyl group may be linear, branched or cyclic. In the case of a ring, it may be monocyclic or polycyclic. As the alkenyl group, an alkenyl group having 1 to 30 carbon atoms is preferable, and specifically, a vinyl group, an allyl group, a 1-methylvinyl group, a 3-buten-1-yl group, a cyclopentan-2-ene-1 -Yl group, cyclohexane-2-en-1-yl group, cyclohexane-1-en-1-yl group and the like. Further, the alkenyl group may further have a substituent at any position, and the additional substituent includes all of the above-mentioned “substituents”. In the case of a cyclic alkenyl group, a partial structure selected from the above group (A) may be inserted at any position of the carbon-carbon bond constituting the ring.

  In the “substituent”, the alkynyl group is an ethynyl group, but may be substituted by a hydrogen atom of the ethynyl group. The substituents herein include all of the above “substituents”.

  In the “substituent”, the aryl group may be either a single ring or a condensed ring as long as it is an aromatic ring, and is preferably an aryl group having 6 to 20 carbon atoms. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. Further, the aryl group may further have a substituent at any position, and examples of the further substituent include all of the above-mentioned “substituents”.

  In the “substituent”, the heterocyclic group has a hetero atom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring. It may be a single ring or a condensed ring. For example, tetrahydrofuranyl group, dihydrofuranyl group, dihydrofuranyl group, tetrahydropyranyl group, dihydropyranyl group, oxocanyl group, dioxanyl group, tetrahydrothiophenyl group, dithianyl group, pyrrolidinyl group, pyrrolinyl group, tetrahydropyridinyl Group, piperazinyl group, homopiperazinyl group, piperidinyl group, pyrrolyl group, furyl group, thiophenyl group, benzopyrrolyl group, benzofuryl group, benzothiophenyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, indazolyl group, benzoisoxazolyl group, Benzoisothiazolyl, imidazolyl, oxazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, pyridyl, quinolinyl, isoquinolinyl, pyrida Nyl group, pyrimidinyl group, pyrazinyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, acridinyl group, phenanthridinyl group, phthalazinyl group, carbazolyl group, uracil group, dithiouracil group, carbolinyl group, purinyl group, thiadiazolyl Groups and the like. Further, the heterocyclic group may further have a substituent at any position, and the additional substituent includes all of the above-mentioned “substituents”.

In addition, the above-mentioned “organic group” refers to an “substituent” containing at least a carbon atom.
In the above, the organic group represented by R ^{101 to} R ¹⁰⁴ in the phthalocyanine-based compound is preferably a sulfur-containing organic group, and may further have an alkylthio group, arylthio group, alkyl group which may have a substituent. A sulfonyl group, an arylsulfonyl group, and a sulfonamide group are preferable. Moreover, as an organic group represented by Ra and Rb in the azomethine-based compound, it is preferable that Ra and Rb together form a nitrogen-containing heterocycle.

-Other dyes-
Next, other dyes than those described above that can be contained in the composition of the present invention will be described.
Further, other dyes (including organic solvent-soluble dyes) that may be contained are 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 The dyes described in JP-A-6-194828 can be used.

  The chemical structure includes azo dyes other than the above, triphenylmethane, anthraquinone, benzylidene, oxonol, phenothiazine, azomethine other than the above, xanthene, phthalocyanine other than the above, benzopyran, indigo And pigments such as anthrapyridone.

  When the resist system is subjected to water or alkali development, at least one of acid dyes and derivatives thereof may be suitably used in that the dye is completely removed by development. In addition, it is also useful to select and use at least one of direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof as appropriate. is there.

  Hereinafter, the acid dye and its derivative will be described. The acidic dye is not particularly limited as long as it is a pigment having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developer used for the preparation of a composition or a development process, It is selected in consideration of all required performances such as salt formation with a basic compound, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

  Specific examples and preferred examples of the acid dye include dyes described in JP-A-2005-227722, but the invention is not limited thereto.

  As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye, or the like can be used. The acid dye derivative is not particularly limited as long as it can be dissolved as a curable composition solution. However, the solubility in an organic solvent or a developer, absorbance, and mutual relationship with other components in the curable composition. It is selected in consideration of all required performance such as action, light resistance and heat resistance.

The salt of the acidic dye and the nitrogen-containing compound will be described.
The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

The nitrogen-containing compound that forms a salt with the acid dye and the nitrogen-containing compound that forms an amide bond with the acid dye will be described.
Nitrogen-containing compounds are the solubility of salts or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / transmittance, interaction with other components in the curable composition, and heat resistance as a colorant. In addition, it is selected in consideration of all of light resistance and the like. When selecting only from the viewpoint of absorbance / transmittance, the nitrogen-containing compound preferably has a molecular weight as low as possible, preferably a molecular weight of 300 or less, more preferably a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

The molar ratio (hereinafter referred to as “n”) of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound will be described.
Said n is a value which determines the molar ratio of an acidic dye molecule and the amine compound which is a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.

Since the acidic dye shown above is an acidic dye due to the introduction of an acidic group in its structure, it can be made a non-acidic dye by changing its substituent.
In some cases, the acid dye works favorably during alkali development, but on the other hand, it may become over-developed, and a non-acid dye may be preferably used.
These dyes use single-color dyes when forming the complementary colors of yellow, magenta, and cyan, respectively. When forming the primary colors of red, green, and blue, two or more dyes are combined. Is used. In the present invention, it is preferable to assemble a primary color system by combining two or more kinds of dyes.

(Pigment)
As the pigment that can be used as the colorant in the present invention, various conventionally known 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. Specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

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

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

CI pigment yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CI pigment orange 36, 71,
CI pigment leads 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CI pigment violet 19, 23, 32,
CI pigment blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CI Pigment Green 7, 36, 37;
CI pigment black 1

The photocurable colored resin composition in the present invention preferably contains a green, red, or blue organic pigment as the organic pigment.
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.
Examples of red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or mixed pigments combining these red pigments, at least one of them, disazo yellow pigments, isoindoline yellow pigments A mixed pigment with a quinophthalone yellow pigment 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: 75. If it is out of this range, it may be difficult to suppress the light transmittance and the color purity may not be increased. A more preferable mass ratio is 100: 10 to 100: 50.

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 36 alone or 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.

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.

In the photocurable composition of the present invention, the content of the colorant in all solid components is 40% by mass or more. When the content of the colorant is less than 40% by mass, a sufficient color density cannot be obtained when the film thickness of the pixel is 1.5 μm or less. For example, an image sensor using the same (solid-state image sensor) ).
As content of the said coloring agent, it is 40 mass% or more with respect to the total solid, Preferably it is 45 mass% or more, More preferably, it is 50 mass% or more. The upper limit of the content of the colorant is not particularly limited, but is 80% by mass from the viewpoint of securing a certain amount of the photopolymerizable compound and the photopolymerization initiator in order to prevent a decrease in curability and sensitivity. It is preferable that it is below, and 70 mass% or less is still more preferable.

(Photopolymerizable compound)
Next, the photopolymerizable compound will be described.
The photopolymerizable compound in the present invention needs to have an alkali-soluble group in the molecule. Here, having an alkali-soluble group in the molecule means a compound having a form in which an alkali-soluble group is bonded to the side chain even if the alkali-soluble group is bonded to the main chain of a conventionally known photopolymerizable compound. However, it is not particularly limited.
The photocurable composition of the present invention eliminates the need to use a commonly used alkali-soluble resin by using a photopolymerizable compound having an alkali-soluble group in the molecule. As a result, the colorant, photopolymerizable The total content of the compound and the photopolymerizable initiator can be increased, and film curability can be ensured by light irradiation.
Also in the thinning of the color filter of the present invention, by using the photocurable composition of the present invention, the color filter has a sufficient color density, retains alkali developability, and has a rectangular pixel pattern profile. It can be made excellent in properties.

The alkali-soluble group is not particularly limited, and is an acidic group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group. Among these, a carboxyl group is preferable.
The side chain to which the alkali-soluble group is bonded is not particularly limited, and examples thereof include an ethylene oxide chain, vinyl alcohol, vinyl pyrrolidone, hydroxy group, and styrene group.
The position of the side chain to which the alkali-soluble group is bonded is not particularly limited, whether it is the terminal part of the side chain or the center part of the side chain.

Examples of the known photopolymerizable compound include radical polymerizable monomers. The photopolymerizable compound used in the present invention preferably has at least one addition polymerizable ethylenic double bond (polymerizable functional group), and the number of polymerizable functional groups is 2 or more, Preferably they are 3 or more and 20 or less, More preferably, they are 3 or more and 15 or less, Most preferably, they are 3 or more and 10 or less. A too large number of functional groups is not preferable because the reactivity is lowered.
Further, the photopolymerizable compound is preferably a compound having a boiling point of 100 ° C. or higher under normal pressure, and more preferably a combination with the polymerizable functional group.

  Examples of the radical polymerizable monomer include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate , Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane and then (meth) acrylated after addition of ethylene oxide or propylene oxide; Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, Polyester acrylates described in JP-B Nos. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof; Can be mentionedFurthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be mentioned.

  Specific examples of the photopolymerizable compound in the present invention are given below. However, the photopolymerizable compound in the present invention is not limited to these.

  As described above, the content of the photopolymerizable compound in the photocurable composition of the present invention is determined so that the total content of the colorant and the photopolymerization initiator is 80% by mass or more. Preferably, from the viewpoint of color density and the like, 85% by mass or more is more preferable and 90% by mass or more is particularly preferable with respect to the total solid content.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include halomethyloxadiazole described in JP-A-57-6096; halomethyl-s-- described in JP-B-59-1281 and JP-A-53-133428. Active halogen compounds such as triazines; aromatic carbonyl compounds such as ketals, acetals or benzoin alkyl ethers described in US Pat. No. US Pat. No. 4,318791 and European Patent Publication EP-88050A; aromatics such as benzophenones described in US Pat. No. 4,1994,420 Group ketone compounds; (thio) xanthones or acridine compounds described in Fr-2456541; compounds such as coumarins or lophine dimers described in JP-A-10-62986; sulfoniums described in JP-A-8-015521 Use organic boron complex, etc. Rukoto can.

  In the present invention, as the photopolymerization initiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, lophine dimer It is preferable to use a photopolymerization initiator such as a series or biimidazole.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferred examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferable examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl bezoate.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferable examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole and 2,2′-benzothiazolyl disulfide.

  Other examples of the photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2, Examples include 4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt, and the like.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatics substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallyl disclosed in US Pat. No. 3,549,367 Combination of imidazole dimer / p-aminophenyl ketone, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Thial-s-triazine compounds are exemplified.
Moreover, these photoinitiators can also be used together.

  The usage-amount of the said photoinitiator is 0.1-10.0 mass% of the total solid of a photocurable coloring resin composition, Preferably it is 0.5-5.0 mass%. When the amount of the photopolymerization initiator used is less than 0.1% by mass, the polymerization may not proceed easily, and when it exceeds 10.0% by mass, the film strength may be weakened.

(Other additives)
In the photocurable composition of the present invention, an additive can be contained in addition to the above-described colorant, photopolymerizable compound and photopolymerization initiator. However, the total content other than the colorant, the photopolymerizable compound and the photopolymerization initiator is preferably less than 20% by mass, more preferably less than 15% by mass, based on the total solid content of the composition. Preferably, it is less than 10% by mass.
Hereinafter, additives other than the colorant, photopolymerizable compound and photopolymerization initiator that can be used in the photocurable composition of the present invention will be described.

-Alkali-soluble binder-
First, the alkali-soluble binder will be described.
In the photocurable composition of the present invention, an alkali-soluble binder can be added as long as the effects of the present invention are not impaired.
The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

In addition to the above, the alkali-soluble binder includes a polymer having a hydroxyl group and an acid anhydride added thereto, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful.
Further, the linear organic polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

-Crosslinking agent-
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the (b) melamine compound, guanamine compound, glycoluril compound and urea compound are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) according to (b).

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to the above (c) uses a compound in which the phenolic OH group has a hydrogen atom at the 2nd or 4th position as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide. It can be obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ Bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, compound obtained by methoxymethylating 1 to 5 methylol groups of hexamethylol of TrisP-PA, bishydroxymethylnaphthalenediol, etc. Is mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  The total content of the crosslinking agent in the photocurable composition varies depending on the material, but from the viewpoint of improving curability, 0.1 to 7 with respect to the solid content (mass) of the photocurable composition. % By mass is preferable, 0.1 to 6% by mass is more preferable, and 0.15 to 5% by mass is most preferable.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photocurable composition of the present invention. For example, 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-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.
As content of a thermal-polymerization inhibitor, 0.1-15 mass% is desirable with respect to solid content (mass) of the said photocurable composition from a viewpoint of stability of a photocurable composition.

-Organic solvent-
The organic solvent that can be used in the present invention is not particularly limited as long as it satisfies the solubility of each component and the applicability of the photocurable composition, but in particular, the solubility, applicability, and safety of colorants and the like. Is preferably selected in consideration of Moreover, when preparing the photocurable composition of this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, 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, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  As described above, these organic solvents may be used in combination of two or more from the viewpoints of solubility of the components contained in the photocurable composition of the present invention and improvement of the coated surface, and in particular, the 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl A mixed solution composed of two or more selected from ether and propylene glycol methyl ether acetate is preferably used.

  The amount of the organic solvent used in the present invention is preferably such that the total solid concentration of the photocurable composition of the present invention is 5 to 80% by mass from the viewpoint of applicability, and 5 to 60% by mass. More preferably, 10-50 mass% is especially preferable.

-Various additives-
The photocurable composition of the present invention further contains various additives such as fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like. be able to.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when promoting the alkali solubility of the non-image area and further improving the developability of the photocurable composition of the present invention, the composition is an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

《Color filter》
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described photocurable composition of the present invention is used.
The color filter of the present invention has a pixel formed by forming a coating film made of the photocurable composition on a substrate and patterning the coating film by a photolithography method using alkali development. And
By adopting such a configuration, the color filter of the present invention is excellent in color uniformity between pixels, and the rectangularity of the pixel pattern profile can also be improved.

The color filter of the present invention preferably has a minimum transmittance of 10% or less in a wavelength range of 400 nm to 700 nm, and a difference between the maximum transmittance and the minimum transmittance in the wavelength range of 65% or more. .
Among these, the minimum transmittance is preferably 8% or less, and particularly preferably 6% or less, from the viewpoint of color separation property and transmittance of the color filter.
Further, the difference between the maximum transmittance and the minimum transmittance in the wavelength range is more preferably 70% or more, and particularly preferably 75% or more.
Among these combinations, a more preferable combination is more preferable.

In the color filter of the present invention, the thickness of the pixel formed on the substrate is preferably 1.5 μm or less, more preferably 1.3 μm or less, from the viewpoint of thinning the color filter. It is especially preferable that it is 2 micrometers or less.
The lower limit of the thickness of the pixel is not particularly limited, but is preferably 0.3 μm or more, and more preferably 0.5 μm or more from the viewpoint of the function as a color filter, productivity, and smoothness.

Further, the length of the maximum side of the pixel (the maximum side when the pixel is observed from above) is preferably 5.0 μm or less from the viewpoint of realizing high resolution by increasing the pixel density. More preferably, it is more preferably 3.5 μm or less.
The lower limit value of the maximum side of the pixel is not particularly limited, but is preferably 0.4 μm or more in view of the function of the filter that transmits visible light.

The color filter production method of the present invention is specifically a coating layer in which the photocurable composition of the present invention is first coated on a substrate by a coating method such as spin coating, cast coating, roll coating or the like. (A photocurable composition layer) is formed, the layer is exposed through a predetermined mask pattern, and is alkali-developed with a developer such as an alkaline aqueous solution to form a negative colored pattern (pixel). (Image forming step).
Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  Further, in the production of the color filter of the present invention, a color filter having a desired hue can be produced by repeating the image forming step (and the curing step if necessary) for the desired number of hues. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

As the substrate, for example, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, photoelectric conversion element substrates used for image pickup devices, etc. For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

Any developer may be used as long as it has a composition that dissolves the unirradiated part (uncured part) of the photocurable composition of the present invention while the irradiated part (cured part) does not dissolve. it can.
Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the photocurable composition of this invention is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be 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, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Note that “part” is “part by mass” unless otherwise specified.

[Example 1]
1) Fabrication of transparent layer Transparent layer coating solution CT-2000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto a 6-inch diameter silicon substrate on which a photodiode is formed by a spin coating method, and then in an oven. And dried at 220 ° C. for 1 hour to obtain a transparent layer having a thickness of 2 μm.

2) Preparation of photocurable composition Solvent: Cyclohexanone: 800 parts Photopolymerizable compound A: 70 parts Photopolymerization initiator: o-acyloxime compound (CGI-124: Ciba Specialty Chemicals ( 30 parts acidic dye A: Varifast Blue 2620 (manufactured by Orient Chemical Co., Ltd.)
... 25 parts dye B: The following dye (B) ... 75 parts were mixed and dissolved to prepare a photocurable composition.

Dye (B)

  The dye B was synthesized according to the following scheme.

(Synthesis of Compound B)
25.0 g (0.162 mol) of the above compound A was dissolved in 100 ml of methanol and 23 ml of triethylamine, and 9 ml of 30% aqueous hydrogen peroxide was added dropwise while maintaining the internal temperature at 25 ° C. with cooling and stirring at 5 ° C. The reaction solution was further stirred at 25 ° C. for 30 minutes, cooled again to 5 ° C., 15 ml of concentrated hydrochloric acid was added dropwise with stirring, 200 ml of water was further added, and the mixture was stirred at 25 ° C. for 1 hour. The precipitated crystals were filtered, washed thoroughly with water, and the obtained crystals were dried to obtain 24.7 g of white crystals (Compound B). The yield was 99.5%.

(Synthesis of compounds C, D and E)
100 ml of toluene and 0.25 m of dimethylacetamide were added to 17.5 parts by mass (0.114 mol) of the compound B, and 25 ml of thionyl chloride was added dropwise over 10 minutes under reflux. The mixture was further heated under reflux for 1 hour and then concentrated under reduced pressure to obtain a viscous liquid. On the other hand, 10 ml of dimethylacetamide and 100 ml of acetonitrile were added to 38.0 parts by mass (0.235 mol) of diethoxyethylamine, and the viscous liquid was added dropwise with stirring at 10 ° C. while maintaining the viscosity at 15 ° C. for 15 minutes. The mixture was further stirred for 30 minutes, poured into 100 ml of water and 100 ml of ethyl acetate, the ethyl acetate layer was separated, and washed twice with 100 ml of water. The ethyl acetate layer was dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a pale yellow viscous liquid (Compound C).

  To this pale yellow viscous liquid (Compound C), 50 ml of water, 200 ml of ethanol and 12 parts by mass (0.200 mol) of zinc powder were added, and a solution obtained by diluting 10 ml of sulfuric acid in 40 ml of water was added dropwise over 20 minutes while heating under reflux. did. The mixture was further stirred with heating for 30 minutes, then cooled, and insolubles were filtered off. To the resulting solution were added 50 ml of saturated brine and 100 ml of ethyl acetate, liquid separation was performed, and the ethyl acetate layer was washed twice with 100 ml of water. The ethyl acetate layer was dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a pale yellow viscous liquid (Compound D).

To this viscous liquid (Compound D), 70 ml of dimethylacetamide and 15 parts by mass (0.108 mol) of potassium carbonate were added with stirring under a nitrogen atmosphere, and 3-nitrophthalonitrile 19.7 was stirred at 20 ° C. Mass parts (0.113 mol) were gradually added at 25 ° C. or lower. The mixture was further stirred for 30 minutes and then poured into 300 ml of water with stirring, and the resulting crystals were filtered and thoroughly washed with water. The obtained crystals were recrystallized with 70 ml of methanol, and the precipitated crystals were washed with 30 ml of cold methanol and dried to obtain 35.0 parts by mass (0.082 mol) of white crystals (Compound E). The yield of Compound E was 72.6%.

<Synthesis of Dye B>
150 mL of butanol, 6.7 parts by mass (0.070 mol) of ammonium carbonate, and 4.7 parts by mass (0.035 mol) of copper chloride are added to 34.4 parts by mass (0.081 mol) of Compound E, and the mixture is heated for 7 hours. Stir. Thereafter, butanol was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 25 parts by mass (0.020 mol) of the above-mentioned dye B powder. The yield was 72.7%.
Absorption of the obtained dye B in ethyl acetate was λmax 70, 6.8 nm, and ε55.600.

3) Preparation and exposure / development of photocurable coating film 2) The coating solution of the photocurable composition was applied onto the transparent layer obtained in 1) by spin coating, and 100 ° C. × 120 sec with a hot plate. A photocurable coating film was obtained by heat treatment (Prebake) so that the film thickness was 1 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the coating film was irradiated at an exposure dose of 3000 mJ / cm ² through an Island pattern mask having a wavelength of 365 nm and a maximum side of 2 μm.
After the exposure, a substrate having a photocurable coating film formed thereon is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemtronics), and a developer CD-2000 (FUJIFILM Electronics Materials) The paddle development was performed at 23 ° C. for 60 sec.
After that, it is fixed to the horizontal rotary table by a vacuum chuck method, and the substrate is rotated at 50 rpm by a rotating device, and pure water is supplied from the upper part of the center of rotation to the shower nozzle, Rinse treatment is performed, and then spray drying is performed. Thus, a color filter was obtained.

4) Color filter pattern profile and residue evaluation method For the color filter, one pattern was observed from directly above using SEM (manufactured by Hitachi, Ltd., S-9260A), and the pattern profile was rectangular. The case was evaluated as “◯”, the case with inferior rectangularity as “Δ”, and the case with blurred and unclear outline as “X”. The shape of the pixel pattern is shown in FIG. In FIG. 1, 1 represents a pixel and 2 represents a transparent layer surface. Moreover, about the residue, the thing without a residue in an unexposed part was evaluated as "(circle)", the thing with a little residue remaining evaluated as "(triangle | delta)", and the thing with a residue remaining evaluated as "x". The evaluation results are shown in Table 2.

5) Evaluation method of absorption maximum transmittance and absorption minimum transmittance of coating film for color filter A photocurable composition is applied onto a glass substrate by a spin coating method, and is heated (prebaked) at 100 ° C. for 120 seconds using a hot plate. Thus, a color filter coating film was obtained so that the film thickness was 1.0 μm.
The transmittance | permeability of wavelength 400nm -700nm was measured for the said coating film for color filters using the spectrophotometer (The Otsuka Electronics Co., Ltd. make, MCPD-2000).
Among the transmittances, the minimum transmittance was the absorption minimum transmittance, the maximum transmittance was the absorption maximum transmittance, and the difference was calculated. The evaluation criterion is that it is practically problematic if it is less than 65%, practically problematic if it is less than 65% and less than 75%, and excellent if it is 75% or more. The evaluation results are shown in Table 2.

[Examples 2 to 7]
In Example 1, a photocurable composition was prepared in the same manner as in Example 1 except that each composition contained in the photocurable composition was changed to the composition shown in Table 1 below, and a color filter was prepared. Were prepared and evaluated in the same manner as in Example 1.
Furthermore, the resist layer in the evaluation method of Example 1 was evaluated by forming a coating film for a color filter using the photocurable composition.

[Comparative Examples 1-4]
In Example 1, a photocurable composition for comparison was prepared in the same manner as in Example 1 except that each composition contained in the photocurable composition was changed to the composition shown in Table 1 below. A comparative color filter was prepared and evaluated in the same manner as in Example 1. The shape of the pixel pattern in Comparative Example 1 is shown in FIG. In FIG. 2, 1 represents a pixel and 2 represents a transparent layer surface.
In addition, the color filter coating film in the evaluation method of Example 1 was formed using the photocurable composition, and evaluated in the same manner as in Example 1.

In Table 1 above, each compound is as follows.
Photopolymerizable compound C: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Acid dye A: Varifast Blue 2620 (manufactured by Orient Chemical Co., Ltd.)
Dye B: Dye B above
Resin A: benzyl methacrylate / methacrylic acid copolymer (70/30 copolymerization ratio average molecular weight 30,000)
The photopolymerizable compound A, photopolymerizable compound B, and photopolymerizable compound D in Table 1 are as shown below.

The pigment dispersion used in Example 7 shown in Table 1 above was prepared as follows.
<Preparation of pigment dispersion>
The following composition was stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.1 mm zirconia beads to obtain a dispersion.

-Composition of pigment dispersion-
Pigment Blue 15: 6 15 parts. Dispersion resin: benzyl methacrylate / methacrylic acid copolymer (= 75/25 [mass ratio], weight average molecular weight Mw: 16000) propylene glycol monomethyl ether acetate solution (solid content: 50) (Part by mass): 9 parts ・ Propylene glycol monomethyl ether acetate (30%) solution of dispersant (trade name: Disperbyk-161, manufactured by Big Chemie)… 3 parts ・ Propylene glycol monomethyl ether acetate: 73 parts

As shown in Table 2 above, in the examples of the present invention, the pattern profile shows a good rectangle, no development residue, good color separation, and color density (difference between absorption maximum transmittance and absorption minimum transmittance). ) Was able to obtain a high pixel.
In contrast, the pattern profiles of the color filters of Comparative Example 1 and Comparative Example 3 were blurred and the outline was not clear and did not become rectangular. Furthermore, there was a residue in the unexposed area of Comparative Example 1, and development was insufficient. In Comparative Examples 2 and 3, the color separability was insufficient.
Further, as is clear from FIGS. 1 and 2, in the first embodiment of the present invention shown in FIG. 1, the outline of the pixel is sharp and more angular than the corner of the pixel viewed from above, whereas the comparative example of FIG. In FIG. 1, it can be seen that the outline of the pixel is blurred and the shape is widened at the interface with the underlying transparent layer surface, and the corner of the viewed pixel is more rounded.

It is a 1st figure which shows the pixel pattern shape of the color filter of Example 1 (use of the pentafunctional monomer which introduce | transduced the carboxyl group). It is a 2nd figure which shows the pixel pattern shape of the color filter of the comparative example 1 (use of the hexafunctional monomer which does not have an alkali-soluble group).

Explanation of symbols

1 pixel 2 transparent layer surface

Claims (10)

  In a photocurable composition comprising a colorant, a photopolymerizable compound and a photopolymerization initiator, the content of the colorant is 40% by mass or more of the total solids, and the photopolymerizable compound has an alkali-soluble group. A photocurable composition comprising:   The total content of the colorant, the photopolymerizable compound and the photopolymerization initiator is 80% by mass or more based on the total solid content in the photocurable composition. The photocurable composition as described.   The photocurable composition according to claim 1 or 2, wherein the number of polymerizable functional groups of the photopolymerizable compound is 3 or more.   The photocurable composition according to any one of claims 1 to 3, wherein the colorant is mainly composed of a dye.   The photocurable composition according to any one of claims 1 to 4, wherein 25% by mass or more of the colorant is an acid dye.   The photocurable composition according to any one of claims 1 to 5, wherein the alkali-soluble group of the photopolymerizable compound is at least one of a carboxyl group, a phosphoric acid group, and a sulfonic acid group. object.   A coating film made of the photocurable composition according to any one of claims 1 to 6 is formed on a substrate, and pixels are formed by patterning by a photolithography method using alkali development. Color filter to be used.   The color filter according to claim 7, wherein a minimum transmittance is 10% or less in a wavelength range of 400 nm to 700 nm, and a difference between the maximum transmittance and the minimum transmittance in the wavelength range is 65% or more.   The color filter according to claim 7 or 8, wherein the pixel has a thickness of 0.3 µm or more and 1.5 µm or less.   The color filter according to claim 7, wherein a maximum side of the pixel is 5.0 μm or less.

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