JP2009175724A - Colored curable composition, color filter and method for manufacturing the same, and solid-state image pickup device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition having a wide DOF margin (a large depth of a focus). <P>SOLUTION: The colored curable composition comprises a colorant and two or more polymerizable compounds including a polymerizable compound having ≥2C alkyleneoxy groups, wherein the number of polymerizable groups in the two or more polymerizable compounds is ≥4.5 on a mass average and the number of ≥2C alkyleneoxy groups is 2.0-10.0 on a mass average. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored curable composition, a color filter, a method for producing the same, and a solid-state imaging device.

The color filter is a member used for a solid-state imaging device or a liquid crystal display device.
A color filter is generally produced by forming a colored pattern on a support using a colored curable composition.

  As a technique relating to the colored curable composition, for improving alkali developability, a technique using a carboxyl group-containing polyfunctional photocurable compound or the like (for example, see Patent Documents 1 to 3), or an alkylene such as ethylene oxide or propylene oxide. A technique using a radiation-sensitive colored composition containing a (meth) acrylate compound having an oxide structure (for example, see Patent Document 4) is known.

Moreover, as a monomer mix | blended with a solder resist (solder resist), the compound which introduce | transduced the acid group into dipentaerythritol and pentaerythritol is known (for example, refer patent document 5, 6). Also, a solder resist ink composition using a tetrafunctional acrylate monomer in which acryloyl groups are linked by a ring-opening structure such as ethylene oxide or propylene oxide (for example, see Patent Document 7), or the solder A photosensitive resin composition similar to a resist ink composition is known (see, for example, Patent Document 8). Moreover, the coating composition which is a photopolymerizable composition containing polyfunctional acrylates, such as polypentaerythritol polyacrylate, is also known (for example, refer patent document 9).
Japanese Patent Laid-Open No. 10-332929 Japanese Patent Laid-Open No. 2004-287230 JP-A-2005-148717 Japanese Patent Laid-Open No. 10-62986 JP-A-8-123027 JP-A-8-123028 JP-A-2-38471 JP-A 64-25147 JP-A-1-126345

In recent years, the color pattern of color filters tends to be thinner, and the size of the color pattern tends to be finer. In particular, these tendencies are remarkable in the color filter for the solid-state image sensor.
With the miniaturization of the coloring pattern, roughness of the end of the coloring pattern and development residue in the unexposed area have become a problem.
In addition, in order to obtain a spectral sensitivity equivalent to that of the conventional color filter, the thinned color filter has to increase the composition ratio of the colorant in the colored curable composition. However, at that time, components other than the colorant (components contributing to photolithography performance) are relatively reduced.
Accordingly, there is a need to develop a colored curable composition capable of maintaining the conventional photolithography performance even if the components contributing to the photolithography performance are relatively reduced.

In addition, when obtaining the spectral sensitivity by increasing the composition ratio of the colorant, the composition ratio of the colorant dispersion is also increased. As the composition ratio of the colorant dispersion increases, the thixotropy of the colored curable composition itself containing the colorant dispersion increases, so that the colored layer is formed by coating the colored curable composition on a support. When formed, the film thickness uniformity in the support surface tends to decrease. When the film thickness uniformity of the colored layer is reduced, the focal length may vary during exposure, and fine pattern peripheral portions may be roughened, or development residues may be generated in uncured portions.
Accordingly, there is a need to develop colored curable compositions having a wide DOF (Depth of Focus) margin (ie, deep depth of focus).

  However, in the above-described conventional curable composition, in particular, when the composition ratio of the colorant in the composition is high, when the thickness of the color pattern to be formed is thin, or when the size of the color pattern is small, DOF It is clear that the margin tends to narrow.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a colored curable composition having a wide DOF margin (deep depth of focus).
Another object of the present invention is to provide a color filter in which the generation of development residues and the occurrence of roughness around the pattern are suppressed, and a method for manufacturing the color filter.
Another object of the present invention is to provide a solid-state imaging device having excellent color reproducibility.

Specific means for solving the above problems are as follows.
<1> A colorant and two or more polymerizable compounds including a polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, wherein the number of polymerizable groups of the two or more polymerizable compounds is a mass average. 4.5 or more, and the number of alkyleneoxy groups having 2 or more carbon atoms is a colored curable composition having a mass average of 2.0 or more and 10.0 or less.

<2> The colored curable composition according to <1>, wherein the two or more polymerizable compounds include a polymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms.

<3> The polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms is at least one selected from the group of compounds represented by formula (i) or formula (ii) <1> or It is a colored curable composition as described in <2>.

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents, Each y independently represents an integer of 1 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (i), the sum total of an acryloyl group and a methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 1-40.
In general formula (ii), the sum total of an acryloyl group and a methacryloyl group is five or six, n represents the integer of 0-10 each independently, and the sum of each n is an integer of 1-60.

<4> The colored curable composition according to any one of <1> to <3>, wherein the content of the colorant is 30% by mass or more based on the total solid content.

<5> After the colored curable composition according to any one of <1> to <4> is applied on a support, the applied coating film is exposed through a mask and developed to form a colored pattern. A method of manufacturing a color filter having a step of:

<6> A color filter using the colored curable composition according to any one of <1> to <4>.
<7> A solid-state imaging device including the color filter according to <6>.

According to the present invention, a colored curable composition having a wide DOF margin (deep depth of focus) can be provided.
In addition, according to the present invention, it is possible to provide a color filter in which the occurrence of development residue and the occurrence of roughness around the pattern are suppressed, and a method for manufacturing the color filter.
In addition, according to the present invention, it is possible to provide a solid-state imaging device having excellent color reproducibility.

≪Colored curable composition≫
The colored curable composition of the present invention includes a colorant and two or more polymerizable compounds including a polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, and the two or more polymerizable compounds are The number of polymerizable groups is 4.5 or more by mass average, and the number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 or more and 10.0 or less by mass average.

When only one kind of polymerizable compound (for example, polyfunctional polymerizable compound) is used, the developability in the non-cured portion is lowered, the exposure dose dependency is increased, and the line width is increased in a high exposure region (dot gain). As a result, the DOF margin tends to be narrow (that is, the depth of focus is shallow).
Further, even when two or more polymerizable compounds are used, if the number of polymerizable groups is less than 4.5 in terms of mass average, the sensitivity is insufficient and the remaining film ratio of the cured portion is reduced. There is a tendency for the DOF margin to narrow.
Further, even when two or more polymerizable compounds are used, if the number of alkyleneoxy groups having 2 or more carbon atoms is less than 2.0 in terms of mass average, the solubility of the developing solution in the non-cured portion decreases, As a result, the DOF margin tends to be narrowed.
Even when two or more polymerizable compounds are used, if the number of alkyleneoxy groups having 2 or more carbon atoms exceeds 10.0 by mass average, the solubility of the developer in the cured portion increases, and the As a result, the residual film ratio is lowered, and as a result, the DOF margin tends to be narrowed.
The tendency for the DOF margin to become narrower becomes more prominent particularly when the content of the colorant in the colored curable composition is high, when the thickness of the colored pattern to be formed is thin, or when the size of the colored pattern is small. .

Therefore, the DOF margin can be increased by using the colored curable composition of the present invention. In particular, the configuration of the present invention is effective when the composition ratio of the colorant in the colored curable composition is large, when the thickness of the colored pattern to be formed is thin, or when the size of the colored pattern is small.
The DOF margin is preferably as wide as possible, but the specific value is preferably 0.5 μm or more, more preferably 0.7 μm or more, and particularly preferably 0.9 μm or more.

In the present invention, the polymerizable group is not particularly limited as long as it is a group contributing to polymerization. From the viewpoint of obtaining the effect of the present invention more effectively, a group having an ethylenically unsaturated double bond is preferable, and a (meth) acryloyl group is more preferable.
In the present specification, a (meth) acryloyl group represents an acryloyl group or a methacryloyl group, (meth) acrylate represents an acrylate or methacrylate, and (meth) acryl represents acryl or methacryl.

In the present invention, the number of polymerizable groups in the mass average of two or more kinds of polymerizable compounds is the number of polymerizable groups that each polymerizable compound has, and the respective polymerizable compounds in the colored curable composition. The mass average value calculated based on mass.
In the present invention, the number of alkyleneoxy groups having 2 or more carbon atoms in mass average of two or more polymerizable compounds is the number of “alkyleneoxy groups having 2 or more carbon atoms” possessed by each polymerizable compound, The mass average value calculated based on the mass of each polymerizable compound in the colored curable composition.

For example, when the colored curable composition of the present invention contains n kinds of polymerizable compounds consisting of the polymerizable compound 1, the polymerizable compound 2,..., The polymerizable compound n, the n kinds of polymerizable compounds. The number of polymerizable groups (J _AVE ) in the mass average is calculated by the following formula (1).

Formula (1):
J _AVE = (J ₁ · W ₁ + J ₂ · W ₂ ... + J _n · W _n ) / (W ₁ + W ₂ ... + W _n )

However, in the formula (1), J ₁ is a polymerizable groups in one molecule of the polymerizable compound 1, W ₁ is the total mass of the polymerizable compound 1 in the colored curable composition, J ₂ Polymerization W ₂ is the total mass of the polymerizable compound ₂ in the colored curable composition, and J _n is the number of polymerizable groups in one molecule of the polymerizable compound n. Yes, W _n is the total mass of the polymerizable compound _n in the colored curable composition.

Similarly, when the colored curable composition of the present invention contains n kinds of polymerizable compounds composed of the polymerizable compound 1, the polymerizable compound 2,..., The polymerizable compound n, the n kinds of polymerizable compounds. The number of alkyleneoxy groups having 2 or more carbon atoms in mass average (A _AVE ) of the compound is calculated by the following formula (2).

Formula (2):
A _AVE = (A ₁ · W ₁ + A ₂ · W ₂ ... + A _n · W _n ) / (W ₁ + W ₂ ... + W _n )

However, in formula (2), A ₁ is in one molecule of the polymerizable compound 1 "having two or more alkyleneoxy groups carbon", W ₁ is the total mass of the polymerizable compound 1 in the colored curable composition A ₂ is “the number of alkyleneoxy groups having 2 or more carbon atoms” in one molecule of the polymerizable compound 2, W ₂ is the total mass of the polymerizable compound ₂ in the colored curable composition, and _An Is the number of polymerizable groups in one molecule of the polymerizable compound n, and W _n is the total mass of the polymerizable compound _n in the colored curable composition.

In the present invention, the number of polymerizable groups in the two or more polymerizable compounds needs to be 4.5 or more on a mass average. From the viewpoint of more effectively obtaining the effect of the present invention, the number of the polymerizable groups is preferably 5.0 or more and more preferably 5.5 or more in terms of mass average.
Moreover, as an upper limit of the number of polymerizable groups in a mass average, 12 is preferable from the viewpoint of more effectively suppressing a decrease in crosslinking density due to an increase in molecular size.

  In the present invention, the number of “alkyleneoxy group having 2 or more carbon atoms” in the two or more polymerizable compounds needs to be 2.0 or more and 10.0 or less in terms of mass average. From the viewpoint of obtaining the effect of the present invention more effectively, the number of the “alkyleneoxy group having 2 or more carbon atoms” is preferably 3.0 or more and 9.0 or less in terms of mass average, and is 4.0 or more and 8.0. The following is more preferable.

Hereinafter, the polymerizable compound, the colorant, and other components will be described.
<Polymerizable compound>
The colored curable composition of the present invention contains two or more polymerizable compounds.
The two or more polymerizable compounds include at least one polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, and the number of polymerizable groups of the two or more polymerizable compounds is 4.5 or more in terms of mass average. There is no particular limitation as long as it is selected so that the number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 to 10.0 in terms of mass average.

Two or more kinds of polymerizable compounds in the present invention can be used by selecting two or more kinds from the following compounds.
That is, monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc .; polyethylene glycol di (meth) acrylate, trimethylolethanetri (meth) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxy) Propyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane and other polyfunctional al (Meth) acrylate after addition of ethylene oxide or propylene oxide to a rubber; as described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193 Urethane acrylates; polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490; reaction products of epoxy resin and (meth) acrylic acid Polyfunctional acrylates and methacrylates such as certain epoxy acrylates. Furthermore, 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 used.

(Polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms)
The colored curable composition of the present invention contains at least one of “a polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms”.
When such a polymerizable compound is not contained (for example, when only a polyfunctional polymerizable compound is contained), the developability of the non-cured portion is insufficient and the DOF margin tends to be lowered.
The “polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms” in the present invention is not particularly limited. For example, at least selected from the group of compounds represented by the following general formula (i) or (ii) One type is also preferred.

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents, y represents the integer of 1-10 each independently.
In general formula (i) and (ii), X represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group each independently.

In general formula (i), the sum total of an acryloyl group and a methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 1-40.
In general formula (ii), the sum total of an acryloyl group and a methacryloyl group is five or six, n represents the integer of 0-10 each independently, and the sum of each n is an integer of 1-60.

In general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends Is preferred in which X is bonded to X.

  The compound represented by the general formula (i) or (ii) has a ring-opening skeleton by a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide, which is a conventionally known process. It can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and (b) ), (E), (f) are preferred.

  Examples of commercially available compounds represented by the general formula (i) or the general formula (ii) include SR-494 manufactured by Sartomer, DPCA-60 manufactured by Nippon Kayaku Co., Ltd., and TPA-330.

(Polymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms)
The colored curable composition of the present invention preferably contains at least one polymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms.
By containing such a polymerizable compound, it is possible to more effectively suppress the phenomenon that the solubility of the cured portion in the developer is increased and the phenomenon that the line width sensitivity is decreased.
The number of polymerizable groups in the polymerizable compound is preferably 2 or more, and more preferably 3 or more.
The “polymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms” is not particularly limited, and examples thereof include monofunctional acrylates and methacrylates (for example, polyethylene glycol mono (meth) acrylate). , Polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
In addition, as the “polymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms”, a compound represented by the following general formula (iii) or general formula (iv) is also preferably used. it can.

In general formulas (iii) and (iv), Z each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (iii), the total number of acryloyl groups and methacryloyl groups is 3 or 4. In general formula (iv), the total number of acryloyl groups and methacryloyl groups is 5 or 6.

As mentioned above, although the polymerizable compound in this invention was demonstrated, from a viewpoint of obtaining the effect of DOF margin expansion more effectively, preparing content of all the polymerizable compounds contained in the colored curable composition of this invention. Is also preferable.
From such a viewpoint, the content of the total polymerizable compound contained in the colored curable composition of the present invention is preferably 5 to 50% by mass with respect to the total solid content of the colored curable composition, and 10 to 40%. % By mass is more preferable, and 20 to 30% by mass is particularly preferable.

  Further, for example, the colored curable composition of the present invention has an A part by mass of a polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, and does not have an alkyleneoxy group having a polymerizable group and having 2 or more carbon atoms. And B parts by mass of the polymerizable compound, the mass ratio [A: B] in the colored curable composition is not particularly limited, but is preferably 9: 1 to 1: 9, and 8: 2-2. : 8 is more preferable. When the mass ratio [A: B] is within the above range, the adjustment of the number of polymerizable groups on the mass average and the adjustment of the number of “alkyleneoxy groups having 2 or more carbon atoms” on the mass average become easier and more effective. The DOF margin can be expanded.

<Colorant>
The photocurable composition of the present invention contains at least one colorant. As the colorant, conventionally known various dyes, inorganic pigments or organic pigments can be used singly or in combination.

  There is no restriction | limiting in particular as said dye, A well-known dye can be used for conventional color filters. 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, US Pat. No. 5, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like. Can be used. The chemical structure uses dyes such as pyrazole azo, anilino azo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. it can. In particular, since the photocurable composition can be cured at a relatively low temperature, even a dye that is inferior in heat resistance as compared with a pigment is subjected to a high temperature during post-baking for imparting durability to the cured film. It is possible to reduce problems such as decomposition even when exposed to water.

  Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And composite oxides of the above metals.

As an organic pigment,
C. I. Pigment Yellow 11,24,31,53,83,85,99,108,109,110,138,139,150,151,154,167,185;
C. I. Pigment Orange 36, 38, 43, 71;
C. I. Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 224, 242, 254;
C. I. Pigment Violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 16, 22, 60, 66, 15: 3, 15: 6;
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Brown 25, 28;
C. I. Pigment Black 1, 7;
Examples thereof include carbon black.

  These organic pigments may be used alone or in various combinations in order to increase color purity. As a specific example, as a pigment for a red pattern, an anthraquinone pigment alone, a perylene pigment alone, or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used. Can do. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, and C.I. I. Pigment yellow 83 or C.I. I. A mixture with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment in the red pattern pigment is preferably 100: 5 to 100: 50. When the mass ratio is within this range, the light transmittance of 400 nm to 500 nm can be suppressed and the color purity can be increased, which is preferable.

  As the pigment for the green pattern, a halogenated phthalocyanine pigment alone or a mixture of a disazo yellow pigment, a quinophthalone yellow dye or an isoindoline yellow pigment is used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Mixing with pigment yellow 83, 138, 139 is preferred. The mass ratio of the green pigment to the yellow pigment in the green pattern pigment is preferably 100: 5 to 100: 100. When the mass ratio is within this range, the light transmittance of 400 nm to 450 nm can be suppressed and good color purity can be obtained.

  As a pigment for a blue pattern, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. A mixture with Pigment Violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment in the blue pattern pigment is preferably 100: 0 to 100: 50. When the mass ratio is within this range, the light transmittance of 400 nm to 420 nm can be suppressed and the color purity can be increased.

  Further, a pigment-containing photosensitive resin having good dispersibility and dispersion stability by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like. Can be obtained.

  In addition, as the pigment for the black matrix, carbon, titanium oxide, and iron oxide are used alone or in combination, and carbon and titanium oxide are preferable. The mass ratio of carbon to titanium oxide is preferably in the range of 100: 5 to 100: 40. Within this range, the light transmittance at long wavelengths is small, and the dispersion stability is also good.

  There is no limitation in particular as content of the total coloring agent with respect to the total solid of the colored curable composition of this invention. From the viewpoint of thinning and miniaturization of the color filter, 30% by mass or more is preferable, 35% by mass or more is more preferable, 38% by mass or more is further preferable, and 40% by mass or more is particularly preferable.

<Photopolymerization initiator>
The colored curable composition of the present invention may contain at least one photopolymerization initiator.
Although it does not specifically limit as a photoinitiator, As an appropriate thing, an oxime type compound and an oxime ester type compound; At least 1 active halogen compound selected from the halomethyl oxadiazole compound and the halomethyl-s-triazine compound; 3-aryl substituted coumarin compounds; lophine dimers; benzophenone compounds; acetophenone compounds and derivatives thereof; cyclopentadiene-benzene-iron complexes and salts thereof;

  Examples of oxime compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6. -(2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone is most preferred. Examples of such oxime photopolymerization initiators include CGI-124 and CGI-242 (manufactured by Ciba Specialty Chemicals).

  Examples of oxime ester compounds include J. Org. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like. Examples of commercially available oxime ester photopolymerization initiators include IRGACURE OXE01 (manufactured by Ciba Specialty Chemicals).

  Examples of the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in JP-B-57-6096, 2-trichloromethyl-5-styryl- 1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1, 3,4-oxadiazole and the like can be mentioned.

  Examples of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphth-1-yl)-described in JP-A-53-133428. Examples include 4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

  Other examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-) ) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphth-2 Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7- Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine,

2- (6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyla) Nophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p- N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminopheny ] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o- Chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-FLUORO -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine.

  In addition, TAZ series manufactured by Midori Chemical Co., TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123; T series manufactured by PANCHIM, T-OMS IRGACURE series, IRGACURE 651, IRGACURE 184, IRGACURE 500, IRGACURE 1000, IRGACURE 149, IRGACURE 819, IRGACURE 261; Ciba Specialty, manufactured by Ciba Specialty Chemicals Co., Ltd. -DALOCURE series, DAROCURE 11734, 4'-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2 manufactured by Chemicals 2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- ( o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl Dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, etc. Useful.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. .

  When the colored curable composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.05% by mass to 2.0% by mass with respect to the total amount of the polymerizable compound, 0.2 mass%-1.0 mass% is more preferable.

<Other ingredients>
The colored curable composition of the present invention may contain other components as necessary.
For example, the colored curable composition of the present invention may contain at least one sensitizer.
Specific examples thereof include 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, and 9,10-anthraquinone. 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl Examples thereof include ketones, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzoanthrone, and benzothiazole compounds described in Japanese Patent Publication No. 51-48516.

The colored curable composition of the present invention may contain at least one resin.
Examples of the resin include known benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / acrylic acid copolymer, benzyl methacrylate / methacrylic acid copolymer / and multi-component copolymers with other monomers. Resin can be used.
When the colored curable composition of this invention contains resin, 0.1 mass%-2.0 mass% are preferable with respect to the whole quantity of the said polymeric compound, and resin content is 0.3 mass%-. 1.0 mass% is more preferable.

The colored curable composition of the present invention may contain at least one solvent.
As the solvent, a known solvent such as propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, cyclohexanone, 2-heptanone, etc. should be used. Can do.
Other additives include polymerization inhibitors such as p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane. Further, known additives such as an adhesion promoter such as an anion, a cation, and a nonionic surfactant can be used.

  The colored curable composition of the present invention can be prepared by mixing and dispersing the above components using various mixers and dispersers.

Although there is no limitation in particular as a use of the colored curable composition of this invention demonstrated above, From the viewpoint of acquiring the effect of this invention more effectively, the use of the color filter preparation for a liquid crystal display device or a solid-state image sensor. It is preferably used for the purpose of manufacturing a color filter for a solid-state image sensor.
Especially, the colored curable composition of this invention is suitable for the use of the color filter for solid-state image sensors of a high resolution which exceeds 1 million pixels especially.
When the thickness of the colored pattern to be formed is thin or the size of the colored pattern is small, considering that the DOF margin tends to be narrow, the thickness of the colored pattern in the color filter for the solid-state imaging device is as follows. 2.0 μm or less is preferable, and 1.0 μm or less is more preferable. The size of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

≪Color filter and its manufacturing method≫
The color filter of the present invention is formed using the above-described colored curable composition of the present invention. For example, it is configured to have a coloring pattern of one or more colors (preferably three colors or four colors) using the above-described colored curable composition of the present invention on a support described later.
Since the color filter of the present invention uses the colored curable composition of the present invention having a wide DOF margin, the occurrence of development residues and the occurrence of roughness around the pattern are suppressed.

  Here, as the film thickness of the colored pattern, from the viewpoint of forming a finer pattern and preventing the adjacent image sensor from receiving light that passes through the color filter in an oblique direction, 0.1 μm to 2. 0 μm is preferable, and 0.2 μm to 1.0 μm is more preferable.

The method for producing the color filter of the present invention is not particularly limited. For example, there is provided a method for producing a color filter, which comprises a step of applying a colored curable composition of the present invention described above on a support, exposing the coated film formed through a mask, and developing to form a colored pattern. Is preferred. When a three-color or four-color color filter is used, it can be produced by repeating the above steps for each color to form a pattern for each color.
Hereinafter, an example of a more specific method for manufacturing a color filter will be described.
That is, an application step of applying the colored curable composition of the present invention on a support, and (if necessary, a pre-baking step of pre-baking the applied colored curable composition), an applied colored cure An exposure step of pattern-exposing the curable composition through a mask, a development step of alkali-developing the pattern-exposed colored curable composition, and, if necessary, a post-baking of the alkali-developed colored curable composition And a post-baking step to be manufactured).

  More specifically, for example, in the coating step, the colored curable composition of the present invention is dried on a suitable support by a spinner or the like, and the film thickness upon drying is generally 0.1 μm to 5 μm, preferably 0. Apply 2 μm to 2 μm to obtain a smooth coating film.

After applying the colored curable composition, the solvent is evaporated to perform a normal pre-bake to obtain a dry coating film (pre-baking step). Examples of the pre-baking method include indirect heat drying using high-temperature air or the like, direct heat drying using a hot plate or the like (about 80 to 140 ° C., 50 seconds to 200 seconds), and the like. You may dry under reduced pressure before prebaking.
In addition, post-baking is performed in order to sufficiently cure the pattern obtained after development to increase the mechanical strength and form a permanent film (post-baking step). For example, when a three-color filter is manufactured, the first formed pattern is then subjected to application, exposure, and development of another color resist solution twice. At this time, post-baking is performed so as not to cause pattern omission due to color mixing with the applied resist solution, exposure, and development. This post-baking uses the same method as pre-baking, but is performed at a higher temperature and for a longer time than the pre-baking conditions. For example, in the case of indirect heating by an oven, the heating is performed at about 180 to 250 ° C. for about 0.5 hours to 2 hours, and in the case of direct heating by a hot plate, it is performed at about 180 to 250 ° C. for about 2 minutes to 10 minutes.

  The light source for pattern exposure in the exposure process is not particularly limited. As a light source that brings about a remarkable effect on pattern formation, light having a wavelength of 410 nm or less is preferable, and i-line (365 nm) of a mercury lamp is particularly preferable.

  There is no restriction | limiting in particular in the developing solution used for image development of a colored curable composition, A conventionally well-known developing solution can be used. Among them, an organic alkaline developer of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) is preferable for achieving the object of the present invention.

Although it does not specifically limit as a support body, the base material of electronic components, such as a glass substrate, a plastics board | substrate, an aluminum board | substrate, a silicon wafer for solid-state image sensors, Furthermore, a transparent resin substrate, a resin film, a cathode-ray tube display surface, an imaging tube A semiconductor wafer on which a light receiving surface and a solid-state imaging device (CCD, CMOS, BBD, CID, BASIS, etc.) are formed can be used. In addition, a contact image sensor using a thin film semiconductor, a liquid crystal display surface, a color electrophotographic photoreceptor, and an electrochromic (EC) display device can be used.
Moreover, in order to improve adhesiveness with a color filter layer, it is preferable to perform a high adhesion process on the support. Specifically, a colored curable composition pattern may be formed after thinly applying a silane coupling agent or the like on the support in advance, or the colored curable composition may contain a silane coupling agent in advance. Good.

In addition, when there exists a level | step difference on a support body, after apply | coating the coloring curable composition of this invention after apply | coating the planarization film | membrane for eliminating the level | step difference and smoothing a coating surface on a support body. be able to.
For example, a solid-state imaging device (image sensor) such as a CCD or CMOS has a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate in accordance with the amount of received light, and a read gate unit for outputting the generated electrons. It consists of and. A light shielding film layer is formed on the upper part of the readout gate part because it causes noise and accurate data is not output when light strikes the readout gate part, and there is a step between the photodiode part without the light shielding film layer. May have occurred. When a color resist is applied on such a step and a color filter is directly formed, the optical path length becomes long, so that the image becomes dark and the light condensing property becomes inferior. In order to improve this, it is preferable to form a transparent flattened film between the CCD, CMOS or the like and the color filter in order to fill the step. Examples of the material for the planarizing film include a photo-curable resist solution such as the colored curable composition of the present invention, and an acrylic or epoxy thermosetting resin.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention is configured to include the above-described color filter of the present invention.
Since the solid-state imaging device of the present invention includes the color filter of the present invention in which the colored pixels have a cross-sectional shape close to a rectangle, the color image reproducibility is excellent.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on the support, and the transfer electrodes are formed on the photodiodes and the transfer electrodes. Having a light-shielding film made of tungsten or the like that is opened only in the light-receiving part of the photodiode, and having a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, In this configuration, the color filter of the present invention is provided on the device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.

Examples of the present invention will be described below, but the present invention is not limited thereto.
[Example 1]
<Preparation of resist solution for flattening film>
The following components were mixed with a stirrer to prepare a planarization film resist solution.
-Components of the resist solution for flattening film-
・ Benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])
... 16.4 parts by mass-Dipentaerythritol pentaacrylate ... 6.5 parts by mass-Propylene glycol monomethyl ether acetate ... 13.8 parts by mass-Ethyl-3-ethoxypropionate ... 12.3 parts by mass Agent: 0.3 parts by mass

<Fabrication of wafer with flattening film>
On the 6-inch silicon wafer, the flattening film resist solution obtained above is uniformly applied by spin coating to form a coating film. The formed coating film is formed on a hot plate having a surface temperature of 120 ° C. on a 120-degree hot plate. For 2 seconds. Here, the spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 1 μm.
The coating film after the heat treatment was further treated in an oven at 220 ° C. for 1 hour to cure the coating film to obtain a flattened film.
As described above, a wafer with a planarization film in which a planarization film was formed on a 6-inch silicon wafer was obtained.

<Preparation of color resist solution (colored curable composition)>
The following components were mixed with a stirrer to prepare a color resist solution.
-Color resist solution components-
・ Benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])
... 3.27 parts by mass-C.I. I. Pigment Blue 15: 6 5.33 parts by mass I. Pigment Violet 23 ... 1.33 parts by mass Polymer dispersing agent (Disper Aid 163 (pigment dispersant manufactured by Big Chemie) ... 2.56 parts by mass Propylene glycol monomethyl ether acetate 81 parts by mass IRGACURE OXE01 (Ciba Specialty) Chemicals, Inc .; photopolymerization initiator) ... 1.65 parts by mass p-methoxyphenol (polymerization inhibitor) 0.002 parts by mass Exemplified compound (b) (polymerizable compound) ... 3.42 parts by mass・ ARONIX M-305 (manufactured by Toagosei Co., Ltd .; polymerizable compound)
... 1.47 parts by mass

<Production of color filter>
On the planarizing film of the wafer with the planarizing film, the color resist solution obtained above is uniformly applied by spin coating to form a coating film, and the formed coating film is formed on a hot plate having a surface temperature of 100 ° C. A color resist layer was formed by heat treatment (pre-baking) for 120 seconds. Here, the spin coating speed was adjusted so that the film thickness of the coating film after the heat treatment was about 0.8 μm.

Next, the color resist layer was subjected to pattern exposure through a photomask described later using an i-line stepper (Canon FPA-3000i5 +).
Pattern exposure was performed in a matrix form at a total of 399 locations in an arrangement of 21 rows × 19 columns.
Here, the above-mentioned 21 rows are conditions in which the exposure dose is increased for each row at intervals of the minimum exposure dose of 500 J / m ² to 250 J / m ² .
On the other hand, the 19th column is a condition in which the focal length is changed at intervals of 0.1 μm with the focal length optimum value (Focus 0.0 μm) as the center. Specifically, the condition is such that the central column is the optimum focal length and the focal length is changed for each column.
As a photomask, a square pixel pattern of 6 sizes (1.0 μm square, 1.5 μm square, 2.0 μm square, 3.0 μm square, 4.0 μm square, 7.0 μm square) is in a range of 4 mm × 3 mm. A photomask having a mask pattern arranged therein was used.

The pattern-exposed color resist layer was developed with a paddle method for 60 seconds at room temperature using an organic alkaline developer CD-2060 (manufactured by FUJIFILM Electronics Materials). Then, it rinsed with the pure water for 20 seconds with the spin shower, and also washed with the pure water. Thereafter, water droplets were blown with high-pressure air, and the substrate was naturally dried to obtain a colored pattern.
Thus, a blue color filter was obtained.

<Evaluation>
A colored pattern formed by exposure through a square pixel pattern (mask pattern) of 1.5 μm square was measured using a critical dimension SEM (Critical-Dimension Scanning Electron Microscope) (Hitachi S-9260). The range of the focal length in which the dimension is resolved in the range of 1.5 μm ± 0.1 μm was defined as the DOF margin.
Larger numbers indicate better performance.

[Examples 2-7, Comparative Examples 1-5]
Example 1 is the same as Example 1 except that the types and / or amounts of the polymerizable compounds (Exemplary Compound (b) and Aronics M-305) used in the preparation of the color resist solution are changed as shown in Table 1. A color filter was prepared in the same manner and evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Details of the types of polymerizable compounds in Table 1 and Table 2 and Table 3 described below are as follows.
DPHA: Dipentaerythritol hexaacrylate M-305: Aronix M-305 manufactured by Toagosei Co., Ltd.
SR-494 ... Sartomer SR-494

As shown in Table 1, the colored curable compositions of the examples had a wide DOF margin.
In addition, in the color filter produced using the colored curable composition of the example, generation of development residue and generation of roughness around the pattern were suppressed.

Example 8
A color filter was produced in the same manner as in Example 1 except that the components of the color resist solution were changed to the components shown below, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2.
-Color resist solution components-
・ Benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])
... 3.00 parts by mass I. Pigment Blue 15: 6 ... 5.78 parts by mass C.I. I. Pigment Violet 23: 1.44 parts by mass Polymer dispersing agent (Disper Aid 163 (pigment dispersant manufactured by Big Chemie) ... 2.78 parts by mass Propylene glycol monomethyl ether acetate: 81 parts by mass IRGACURE OXE01 (Ciba Specialty) Chemicals Co .; photopolymerization initiator) 1.50 parts by mass p-methoxyphenol (polymerization inhibitor) 0.002 parts by mass Exemplified compound (b) (polymerizable compound) 3.15 parts by mass Aronix M-305 (manufactured by Toagosei Co., Ltd .; polymerizable compound) ... 1.35 parts by mass

[Examples 9 to 14, Comparative Examples 6 to 10]
Example 8 is the same as Example 8 except that the types and / or amounts of the polymerizable compounds (Exemplary Compound (b) and Aronix M-305) used in the preparation of the color resist solution are changed as shown in Table 2. A color filter was produced in the same manner and evaluated in the same manner as in Example 8.
The evaluation results are shown in Table 2.

As shown in Table 2, the colored curable compositions of the examples had a DOF margin.
In addition, in the color filter produced using the colored curable composition of the example, generation of development residue and generation of roughness around the pattern were suppressed.

Example 15
A color filter was produced in the same manner as in Example 1 except that the components of the color resist solution were changed to the components shown below, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 3.
-Color resist solution components-
・ Benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])
... 2.73 parts by mass-C.I. I. Pigment Blue 15: 6 ... 6.23 parts by mass-C.I. I. Pigment Violet 23 1.56 parts by mass Polymer dispersant (Disperse Aid 163 (pigment dispersant manufactured by Big Chemie) ... 3.00 parts by mass Propylene glycol monomethyl ether acetate 81 parts by mass IRGACURE OXE01 (Ciba Specialty) Chemicals Co .; photopolymerization initiator) 1.37 parts by mass p-methoxyphenol (polymerization inhibitor) 0.002 parts by mass Exemplified compound (b) (polymerizable compound) 2.88 parts by mass Aronix M-305 (manufactured by Toagosei Co., Ltd .; polymerizable compound) ... 1.23 parts by mass

[Examples 16 to 21, Comparative Examples 11 to 15]
Example 15 is the same as Example 15 except that the types and / or amounts of the polymerizable compounds (Exemplary Compound (b) and Aronics M-305) used in the preparation of the color resist solution are changed as shown in Table 3. A color filter was produced in the same manner and evaluated in the same manner as in Example 15.
The evaluation results are shown in Table 3.

As shown in Table 3, the colored curable compositions of the examples had a DOF margin.
In addition, in the color filter produced using the colored curable composition of the example, generation of development residue and generation of roughness around the pattern were suppressed.

As described above, two or more kinds of polymerizable compounds having a polymerizable group number of 4.5 or more on a mass average and an alkyleneoxy group number of 2 or more carbon atoms on a mass average of 2.0 or more and 10.0 or less. By using it, the DOF margin was expanded.
The effect of increasing the DOF margin was also obtained under conditions where the colorant content is high and the DOF margin tends to be narrow.

As described above, in Examples 1 to 21, the case where the exemplified compound (b) is mainly used as the polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms has been mainly described, but the example compound (b) is used instead. In addition, the “compound represented by the general formula (i) or general formula (ii) (including exemplary compounds (a) and (c) to (f))” other than the exemplary compound (b), and other “ Similarly, when the “polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms” is used, the effect of expanding the DOF margin of the present invention can be obtained.
Moreover, in Examples 1-21, although the example which produced the blue color filter was demonstrated, by changing the coloring agent used for the colored curable composition, similarly to Examples 1-21, it is the development residue. It is possible to manufacture a color filter having three colored pixels of red, green, and red, in which the occurrence of occurrence and roughness around the pattern is suppressed.
In addition, a solid-state imaging device having excellent color reproducibility by producing a color filter having the colored pixels of the three colors on a substrate for a solid-state imaging device on which a photodiode, a light-shielding film, a device protective film, and the like are formed. Can be produced.
For example, on a silicon substrate on which a photodiode and a transfer electrode are formed, a light shielding film made of tungsten having an opening only in the light receiving portion of the photodiode is formed, and the entire surface of the formed light shielding film and the photodiode light receiving portion (openings in the light shielding film). A device protective layer made of silicon nitride so as to cover the color filter (colored pixels of R, G, and B) by the same method as in Examples 1 to 21 on the formed device protective layer And a microlens that is a condensing means is formed on the formed color filter, so that a solid-state imaging device with good color reproducibility can be manufactured.

Claims (7)

A colorant and two or more polymerizable compounds including a polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms,
The colored curable composition in which the number of polymerizable groups of the two or more kinds of polymerizable compounds is 4.5 or more in terms of mass average, and the number of alkyleneoxy groups having 2 or more carbon atoms is in the range of 2.0 to 10.0 in terms of mass average. object.   The colored curable composition according to claim 1, wherein the two or more polymerizable compounds include a polymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms. The polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms is at least one selected from the group of compounds represented by formula (i) or formula (ii). The colored curable composition described in 1.

[In the general formula (i) and (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - a represents , Y each independently represents an integer of 1 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (i), the sum total of an acryloyl group and a methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 1-40.
In general formula (ii), the sum total of an acryloyl group and a methacryloyl group is five or six, n represents the integer of 0-10 each independently, and the sum of each n is an integer of 1-60. ]   The colored curable composition according to any one of claims 1 to 3, wherein the content of the colorant is 30% by mass or more based on the total solid content.   A step of applying a colored curable composition according to any one of claims 1 to 4 on a support, exposing the applied coating film through a mask, and developing to form a colored pattern. A method for producing a color filter.   The color filter which uses the colored curable composition of any one of Claims 1-4.   A solid-state imaging device comprising the color filter according to claim 6.