KR20090073035A - Colored curable composition, color filter and method of producing the same, and solid-state imaging device - Google Patents

Abstract

A colored curing composition, and a color filter using the composition are provided to inhibit the generation of development residue and the inaccuracy of pattern surrounding. A colored curing composition comprises a colorant; and at least two kinds of polymerizable compounds which comprise a polymerizable compound having an alkyleneoxy group of the carbon number 2 or more, wherein the number of the polymerizable group of the at least two kinds of polymerizable compounds is 4.5 or more by mass average, and the number of the alkyleneoxy group of the carbon number 2 or more is 2.0-10.0 by mass average.

Description

Colored curable composition, a color filter, and its manufacturing method, and a solid-state image sensor TECHNICAL FIELD: COLORED CURABLE COMPOSITION, COLOR FILTER AND METHOD OF PRODUCING THE SAME, AND SOLID-STATE IMAGING DEVICE

This invention relates to a colored curable composition, a color filter, its manufacturing method, and a solid-state image sensor.

A color filter is a member used for a solid-state image sensor and a liquid crystal display device.

A color filter is generally produced by forming a coloring pattern using a colored curable composition on a support.

As a technique regarding a coloring curable composition, the technique which uses a carboxyl group-containing polyfunctional photocurable compound etc. for alkali developability improvement (for example, Unexamined-Japanese-Patent No. 10-332929, Unexamined-Japanese-Patent No. 2004-287230, Japanese patent) Japanese Patent Application Laid-Open No. 10-148717 or a technique using a radiation-sensitive coloring composition containing a (meth) acrylate compound having an alkylene oxide structure such as ethylene oxide or propylene oxide (for example, see Japanese Patent Application Laid-Open No. 10). (See -62986).

Moreover, as a monomer mix | blended with a solder resist, the compound which introduce | transduced an acidic radical into dipentaerythritol and pentaerythritol is known (for example, Unexamined-Japanese-Patent No. 8-123027 and Unexamined-Japanese-Patent No. 8-H). See 123028). Moreover, the soldering resist ink composition (For example, refer Unexamined-Japanese-Patent No. 2-38471) using what the acryloyl group connected by ring-opening structures, such as ethylene oxide and a propylene oxide, as a tetrafunctional acrylate monomer, A photosensitive resin composition similar to the above solder resist ink composition is known (see, for example, Japanese Patent Laid-Open No. 64-25147). Moreover, the coating composition which is a photopolymerizable composition containing polyfunctional acrylates, such as polypentaerythritol polyacrylate, is also known (for example, refer Unexamined-Japanese-Patent No. 1-26345).

In recent years, the coloring pattern of a color filter tends to be thin, and the size of a coloring pattern tends to become fine. In particular, these tendencies are remarkable in the color filter for solid-state image sensors.

As the coloring pattern becomes smaller, inaccuracies in the tip of the coloring pattern and developing residues of the unexposed portions are more problematic than before.

In addition, the thinned color filter has to increase the composition ratio of the colorant in the colored curable composition in order to obtain spectral sensitivity equivalent to that of the conventional color filter. However, then components other than the colorant (components contributing to photolithographic performance) are relatively reduced.

Therefore, there is a need to develop a colored curable composition capable of maintaining a conventional photolithographic performance even if the component contributing to photolithographic performance is relatively reduced.

In addition, when trying to obtain spectral sensitivity by increasing the composition ratio of the colorant, the composition ratio of the colorant dispersion is also increased. Since the thixotropy of the colored curable composition itself containing the colorant dispersion increases when the composition ratio of the colorant dispersion increases, the film thickness uniformity in the surface of the support when the colored curable composition is applied onto the support to form a colored layer. This tends to be lowered. When the film thickness uniformity of a colored layer falls, the focal length may be varied during exposure, and inaccurate fine pattern periphery may occur, or development residue may occur in an uncured portion.

Thus, there is a need to develop colored curable compositions having a wide depth of focus (DOF) margin (i.e. deep depth of focus).

However, in the above-mentioned conventional curable composition, it is clear that especially when the composition ratio of the coloring agent in a composition is high, DOF margin tends to become narrow when the film thickness of the coloring pattern to form is small, or when the size of a coloring pattern is small. did.

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).

Further, the present invention is to provide a color filter in which the occurrence of developing residue and the occurrence of inaccuracy around a pattern are suppressed and a manufacturing method thereof.

Moreover, this invention is providing the solid-state image sensor which was excellent in color reproducibility.

The specific means for solving the said subject is as follows.

<1> 2 or more types of polymeric compounds containing a coloring compound and the polymeric compound which has a C2 or more alkyleneoxy group, The number of polymeric groups of the said 2 or more types of polymeric compounds is 4.5 or more in mass mean, C2 It is colored curable composition whose number of the above-mentioned alkyleneoxy group is 2.0 or more and 10.0 or less in mass mean.

<2> The said 2 or more types of polymeric compound is a colored curable composition as described in <1> containing a polymeric compound which has a polymeric group and does not have a C2 or more alkyleneoxy group.

<3> The colored curable as described in <1> or <2> which is at least 1 sort (s) chosen from the group of the compound represented by general formula (i) or general formula (ii) whose said C2 or more alkyleneoxy group is an alkyleneoxy group. Composition.

In formulas (iii) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, and y each represents Independently, the integer of 1-10 is represented, X represents acryloyl group, methacryloyl group, a hydrogen atom, or a carboxyl group each independently.

In the general formula (V), the sum of the acryloyl group and the methacryloyl group is three or four, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 1 to 40.

In general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6 pieces, 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 in any one of <1>-<3> whose content of the <4> said coloring agent is 30 mass% or more with respect to a total solid.

<5> The manufacturing method of the color filter which has a process of exposing and apply | coating the formed coating film through a mask, and developing a coloring pattern after apply | coating the coloring curable composition in any one of <1>-<4> on a support body. to be.

<6> It is a color filter formed using the colored curable composition in any one of <1>-<4>.

<7> It is a solid-state image sensor provided with the color filter as described in <6>.

(Effects of the Invention)

According to the present invention, a colored curable composition having a wide DOF margin (deep depth of focus) can be provided.

Moreover, according to this invention, the color filter and the manufacturing method which suppressed generation | occurrence | production of image development residue and inaccuracy of the pattern periphery can be provided.

Moreover, according to this invention, the solid-state image sensor which is excellent in color reproducibility can be provided.

≪Coloring curable composition≫

The colored curable composition of this invention contains a 2 or more types of polymeric compound containing a coloring agent and the polymeric compound which has a C2 or more alkyleneoxy group, and the said 2 or more types of polymeric compounds have 4.5 or more by mass mean number of polymeric groups. The number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 or more and 10.0 or less on a mass average.

When only one type of polymerizable compound (for example, a polyfunctional polymerizable compound) is used, developability in the non-cured portion decreases, exposure dose dependency increases, and line gain increases in a high exposure region. As a result, the DOF margin tends to be narrower (i.e., the depth of focus becomes shallower).

Moreover, even when two or more types of polymerizable compounds are used, if the number of polymerizable groups is less than 4.5 on a mass average, the sensitivity is insufficient and the residual film ratio of the hardened portion is lowered, and as a result, the DOF margin tends to be narrowed.

Moreover, even when using 2 or more types of polymeric compounds, when the number of C2-C2 alkyleneoxy groups is less than 2.0 by mass mean, the solubility of the developing solution of a non-hardened part will fall, and as a result, DOF margin tends to become narrow.

In addition, even when two or more types of polymerizable compounds are used, when the number of alkyleneoxy groups having 2 or more carbon atoms exceeds 10.0 by mass average, the developer solubility of the hardened portion is increased, and the residual film ratio of the hardened portion is decreased, and as a result, the DOF margin tends to be narrowed. have.

The tendency of narrowing the DOF margin is remarkable especially when the content rate of the colorant in the colored curable composition is high, when the film thickness of the colored pattern to be formed is thin, or when the size of the colored pattern is small.

Therefore, DOF margin can be enlarged by making colored curable composition into the structure of the said 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 wider the DOF margin is, the more preferable it is. However, 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 contributes to polymerization. From a viewpoint of obtaining the effect by this invention more effectively, it is preferable that it is a group which has an ethylenically unsaturated double bond, and it is more preferable that it is a (meth) acryloyl group.

In addition, in this specification, a (meth) acryloyl group represents an acryloyl group or a methacryloyl group, (meth) acrylate represents an acrylate or a methacrylate, and (meth) acryl represents an acryl or methacryl .

In addition, in this invention, the number of polymeric groups in the mass mean of 2 or more types of polymeric compounds is based on the number of the polymeric groups which each polymeric compound has, and the mass of each polymeric compound in a colored curable composition, respectively. Point out the calculated mass mean value.

In addition, in this invention, the number of C2 or more alkyleneoxy groups in the mass mean of 2 or more types of polymeric compounds is the number of "C2 or more alkyleneoxy groups" which each polymeric compound has, and in a colored curable composition. The mass mean value calculated based on the mass of each polymerizable compound is indicated.

For example, the colored curable composition of this invention is a polymeric compound 1, a polymeric compound 2,... When the n-type polymerizable compound consisting of the polymerizable compound n is contained, the number of polymerizable groups (J _AVE ) in the mass average of the n-type polymerizable compounds is calculated by the following formula (1).

Equation (1):

J _AVE = (J ₁ · W ₁ + J ₂ · W ₂ … + J _n · W _n ) / (W ₁ + W ₂ … + W ₃ )

However, in Formula (1), J <_1> is the number of polymeric groups in 1 molecule of polymeric compound 1, W <_1> is the total mass of polymeric compound 1 in colored curable composition, and J <_2> is 1 molecule of polymeric compound 2 Is the number of polymerizable groups in the compound, W ₂ is the total mass of the polymerizable compound 2 in the colored curable composition, J _n is the number of polymerizable groups in one molecule of the polymerizable compound n, and W _n is the amount of the polymerizable compound n in the colored curable composition. Is the total mass.

Similarly, the colored curable composition of this invention is a polymeric compound 1, polymeric compound 2,... In the case of containing n polymerizable compounds composed of polymerizable compound n, the number of alkyleneoxy groups having 2 or more carbon atoms (A _AVE ) in the mass average of the n polymerizable compounds is calculated by the following formula (2). do.

Equation (2):

A _AVE = (A ₁ · W ₁ + A ₂ · W ₂ … + A _n · W _n ) / (W ₁ + W ₂ … + W ₃ )

In this formula (2) A ₁ is a polymerizable Compound 1 "having 2 can more alkyleneoxy group" in one molecule of the, W ₁ is the total mass of the first polymerizable compound in the colored curable composition, A ₂ is polymerized in the "C2 or more alkyleneoxy group numbers" in one molecule of the compound 2, W ₂ is the total mass of the polymerizable compound 2 in the colored curable composition, A _n is the number of polymerizable groups in one molecule of the polymerizable compound n, 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 in terms of mass average. From the viewpoint of obtaining the effect of the present invention more effectively, the number of the polymerizable groups is preferably 5.0 or more, more preferably 5.5 or more in terms of mass average.

In addition, as an upper limit of the number of polymerizable groups in a mass mean, 12 is preferable from a viewpoint which suppresses the fall of crosslinking density more effectively as molecular size becomes large.

In the present invention, the number of "carbon number 2 or more alkyleneoxy groups" in the two or more polymerizable compounds is required to be 2.0 or more and 10.0 or less by mass average. From a viewpoint of obtaining the effect by this invention more effectively, the number of said "C2 or more alkyleneoxy groups" is preferably 3.0 or more and 9.0 or less, more preferably 4.0 or more and 8.0 or less in terms of mass average.

Hereinafter, a polymeric compound, a coloring agent, and another component are demonstrated.

<Polymerizable compound>

The colored curable composition of this invention contains 2 or more types of polymeric compounds.

The 2 or more types of polymeric compounds contain at least 1 type of polymeric compounds which have a C2 or more alkyleneoxy group, and the number of polymeric groups of 2 or more types of polymeric compounds is 4.5 or more by mass average, and the number of C2 or more alkyleneoxy groups is There is no restriction | limiting in particular if it selects so that it may become 2.0 or more and 10.0 or less by mass mean.

Two or more types of polymeric compounds in this invention can select and use 2 or more types from the following compounds.

That is, monofunctional acrylates and methacrylates, such as polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane, etc. (Meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol of; Urethane acrylates as described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. In addition, Japan Adhesion Society Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also be used.

(Polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms)

The colored curable composition of this invention contains at least 1 sort (s) of "polymerizable compound which has a C2 or more alkyleneoxy group."

When it does not contain such a polymeric compound (for example, when it contains only a polyfunctional polymeric compound), there exists a tendency for DOF margin to fall because of lack of developability of a non-hardened part.

Although there is no limitation in particular as "the polymeric compound which has a C2 or more alkyleneoxy group" in this invention, For example, it is also at least 1 sort (s) chosen from the group of the compound represented by following General formula (i) or (ii). desirable.

In formulas (iii) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, and y each represents Independently, the integer of 1-10 is represented.

X in general formula (iii) and (ii) represents acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group each independently.

In the general formula (V), the sum of the acryloyl group and the methacryloyl group is three or four, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 1 to 40.

In general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6 pieces, n represents the integer of 0-10 each independently, and the sum of each n is an integer of 1-60.

In general formula (m), the integer of 0-6 is preferable and, as for m, the integer of 0-4 is more preferable. Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In General Formula (ii), the integer of 0-6 is preferable and, as for n, the integer of 0-4 is more preferable. Moreover, the integer of 3-60 is preferable, as for the sum total of each n, the integer of 3-24 is more preferable, and the integer of 6-12 is especially preferable.

Further, the general formula (ⅰ) or general formula (ⅱ) of - the ends of the oxygen atom side of _{- ((CH 2) y CH} 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) Forms bound to X are preferred.

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

Among the compounds represented by the formulas (iii) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

Specifically, the compound (henceforth a "exemplified compound (a)-(f)") represented by following formula (a)-(f) is mentioned, Especially, exemplary compound (a), (b) , (e) and (f) are preferred.

As a commercial item of the compound represented by general formula (i) or general formula (ii), SR-494 by a Satomer company, DPCA-60 by Nippon Kayaku Co., Ltd., TPA-330, etc. are mentioned, for example.

(Polymerizable compound having a polymerizable group and no alkyleneoxy group having 2 or more carbon atoms)

It is preferable that the colored curable composition of this invention contains a polymeric group and at least 1 sort (s) of the polymeric compound which does not have a C2 or more alkylene oxy group.

By containing such a polymeric compound, the phenomenon which the solubility of the hardening part to a developing solution becomes high, and the phenomenon which a line width sensitivity falls, can be suppressed more effectively.

2 or more are preferable and, as for the number of the polymerizable groups in the said polymeric compound, 3 or more are more preferable.

Although it does not specifically limit as said "polymerizable compound which has a polymeric group and does not have a C2 or more alkyleneoxy group", For example, Monofunctional acrylate and methacrylate (for example, polyethyleneglycol mono (meth) acrylate) , Polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), trimetholethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylic The rate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. can be used.

Moreover, as a "polymerizable compound which has a polymeric group and does not have a C2 or more alkyleneoxy group", the compound represented by the following general formula (i) or general formula (i) can also be used preferably.

In General Formulas (VIII) and (VIII), each Z independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In general formula, the total number of acryloyl group and methacryloyl group is three or four. In addition, the total number of acryloyl group and methacryloyl group in general formula (5) is five or six.

As mentioned above, although the polymeric compound in this invention was demonstrated, it is also preferable to prepare content of the all polymeric compound contained in the colored curable composition of this invention from a viewpoint of obtaining the effect of DOF margin enlargement more effectively.

From such a viewpoint, as content of the total polymeric compound contained in the colored curable composition of this invention, 5-50 mass% is preferable with respect to the total solid of a colored curable composition, 10-40 mass% is more preferable, 20-30 Mass% is particularly preferred.

Moreover, for example, when the colored curable composition of this invention contains the polymeric compound A mass part which has a C2 or more alkyleneoxy group, and the polymeric compound B mass part which has a polymeric group and does not have a C2 or more alkylene oxy group, Although there is no limitation in particular as mass ratio [A: B] in a colored curable composition, 9: 1-1: 9 are preferable and 8: 2-2: 8 are more preferable. When mass ratio [A: B] is in the said range, adjustment of the number of polymeric groups in a mass mean, and control of the number of "carbon number 2 or more alkyleneoxy groups" in a mass mean will become easier, and DOF margin can be expanded more effectively.

<Colorant>

The photocurable composition of this invention contains at least 1 type of coloring agents. As a coloring agent, 1 type, or 2 or more types of conventionally well-known various dye, inorganic pigment, or organic pigment can be used.

There is no restriction | limiting in particular as said dye, A conventionally well-known dye can be used for a color filter. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Registration 2592207, US Patent 4808501, US Patent 5667920, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. 6-194828 The pigment | dye disclosed in the publication etc. can be used. Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine and pyrrolopyrazole azomethine. Dye, such as a system, can be used. In particular, since the photocurable composition can be cured at a relatively low temperature, even a dye having a lower heat resistance than the pigment can alleviate problems such as decomposition even when exposed to a high temperature during post-baking for imparting durability to the cured film.

As an inorganic pigment, it is a metal compound represented by metal oxide, metal complex salt, etc., Specifically, Metal oxide, such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the said metal complex And oxides.

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;

Carbon black etc. are mentioned.

These organic pigments may be used alone, or may be used in various combinations to increase color purity. When a specific example is shown, as an pigment for a red pattern, an anthraquinone type pigment alone, a perylene type pigment alone, or at least 1 sort (s) and a disazo yellow pigment or an isoindolin type yellow pigment etc. can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 is mentioned as a perylene pigment, A mixture with CI pigment yellow 83 or CI pigment yellow 139 is preferable at the point of color reproducibility. . As for the mass ratio of the red pigment and a yellow pigment in the pigment for red patterns, 100: 5-100: 50 are preferable. If the mass ratio is within this range, it is preferable because the light transmittance of 400 nm to 500 nm can be suppressed and the color purity can be increased.

As the pigment for the green pattern, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow dye or an isoindolin yellow pigment is used. For example, a mixture of C. I. Pigment Green 7, 36, 37 and C. I. Pigment Yellow 83, 138, 139 is preferable. As for the mass ratio of the green pigment and yellow pigment in the pigment for green patterns, 100: 5-100: 100 are preferable. If mass ratio is in this range, the light transmittance of 400 nm-450 nm can be suppressed and favorable color purity can be obtained.

As the pigment for the blue pattern, a phthalocyanine-based pigment alone or a mixture with a dioxadine-based purple pigment is used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 is preferable. As for the mass ratio of the blue pigment and purple pigment in the pigment for blue patterns, 100: 0-100: 50 are preferable. If the mass ratio is within this range, light transmittance of 400 nm to 420 nm can be suppressed and color purity can be increased.

In addition, a pigment-containing photosensitive resin having good dispersibility and dispersion stability can be obtained by using a powdery processing pigment in which the pigment is finely dispersed in an acrylic resin, maleic acid resin, vinyl chloride-vinyl acetate copolymer, and ethyl cellulose resin.

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

 There is no restriction | limiting in particular as content of the all coloring agent with respect to the total solid of the coloring curable composition of this invention. From a viewpoint of the thinning and refinement | miniaturization of a color filter, 30 mass% or more is preferable, 35 mass% or more is more preferable, 38 mass% or more is more preferable, 40 mass% or more is especially preferable.

<Photoinitiator>

The colored curable composition of this invention may contain at least 1 sort (s) of a photoinitiator.

Although it does not specifically limit as a photoinitiator, As a preferable thing, An oxime compound and an oxime ester compound; At least one active halogen compound selected from halomethyloxadiazole compounds, halomethyl-s-triazine compounds; 3-aryl substituted coumarin compound; Ropin dimer; Benzophenone compounds; Acetophenone compounds and derivatives thereof; Cyclopentadiene-benzene-iron complexes and salts thereof; Etc. can be mentioned.

Examples of the oxime compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6- Most preferred is (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone. As such an oxime system photoinitiator, CGI-124 and CGI-242 (above, Chiba Specialty Chemicals make) are mentioned.

As an oxime ester type compound, it is J.C.S. Perkin II (1979) 1653-1660, J.C.S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Compounds described in Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797 The compound of the publication, etc. are mentioned. As a commercial item of an oxime ester photoinitiator, IRGACURE OXE01 (made by Chiba Specialty Chemicals) is mentioned, for example.

As said halomethyloxadiazole compound, the 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound of Unexamined-Japanese-Patent No. 57-6096, etc., 2-trichloromethyl-5-sty Yl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-meth Oxystyryl) -1,3,4-oxadiazole, etc. are mentioned.

As said halomethyl-s-triazine compound, the vinyl-halomethyl-s-triazine compound of Unexamined-Japanese-Patent No. 59-1281 and 2- (naphtho-1 of Unexamined-Japanese-Patent No. 53-133428 are described. -Yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

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- (naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis-trichloro Romethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphtho- 1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl -s-triazine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2- Butoxyethyl) -naphtho-1-yl] -4,6-bis-trichloro Methyl-s-triazine, 2- (2-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl- Naphto-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s -Triazine, 2- (5-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphtho-1- Il) -4,6-bis-trichloromethyl-s-triazine,

2- (6-ethoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphtho-1-yl) -4 , 6-bis-trichloromethyl-s-triazine, 4- [pN, 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- [pN, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloro Ethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl ] 2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-tri Azine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -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-pN, 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-ethoxycar Bonylmethylaminophenyl) -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 ( Trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylamino phenyl) -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 (trichloro Methyl) -s-triazine, 4- (m-fluoro-pN-chloro Ethylaminophenyl) -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-pN-chloroethylaminophenyl)- 2, 6- di (trichloromethyl) -s-triazine etc. are mentioned.

In addition, the TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123 made by Midori Kagaku Corporation; T series, T-OMS, T-BMP, T-R, T-B manufactured by PANCHIM; IRGACURE series by Chiba Specialty Chemicals, Ilgacure 651, Illucure 184, Illucure 500, Illucure 1000, Illucure 149, Illucure 819, Illucure 261; Chiro Specialty Chemicals' DALOCURE series, Darocure 11734; 4'-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyllophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chloro Phenyl) -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 and the like are also usefully used.

A sensitizer and a light stabilizer can be used together for these photoinitiators.

Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone , 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-diethyl thioxanthone, acridon, 10-butyl-2-chloro Acridon, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (or US Hilerketone), p- (diethylamino) benzophenone, benzoanthrone and the like, and the benzothiazole compound described in Japanese Patent Application Laid-open No. 51-48516, etc., tinubin 1130, tinubin 400, and the like.

When the colored curable composition of this invention contains a photoinitiator, 0.05 mass%-2.0 mass% are preferable with respect to whole quantity of the said polymeric compound, and, as for content of a photoinitiator, 0.2 mass%-1.0 mass% are more preferable.

<Other ingredients>

The colored curable composition of this invention may contain another component as needed.

For example, the colored curable composition of this invention may contain at least 1 type of sensitizers.

Specific examples thereof include 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-an Tron, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, benzyl, di Benzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzoanthrone and the like, and the benzothiazole compound described in Japanese Patent Publication No. 51-48516 Can be mentioned.

The colored curable composition of this invention may contain at least 1 sort (s) of resin.

As the resin, a known resin such as a benzyl methacrylate / methacrylic acid copolymer, a benzyl methacrylate / acrylic acid copolymer, a benzyl methacrylate / methacrylic acid copolymer / and a multicomponent copolymer with other monomers can be used.

When the colored curable composition of this invention contains resin, 0.1 mass%-2.0 mass% are preferable with respect to whole quantity of the said polymeric compound, and, as for content of resin, 0.3 mass%-1.0 mass% are more preferable.

The colored curable composition of this invention may contain at least 1 sort (s) of solvent.

As the solvent, known solvents such as propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, cyclohexanone and 2-heptanone It is available.

Other additives include polymerization inhibitors such as p-methoxyphenol, hydroquinone and hydroquinone monomethyl ether, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyl triethoxysilane and 3-glycidoxy Adhesion promoters, such as propyl trimethoxysilane, and well-known additives, such as an anion, a cation, and a nonionic surfactant, can be used.

The colored curable composition of this invention can be prepared by mixing-dispersing said each component 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 a viewpoint of obtaining the effect of this invention more effectively, it is preferable to use for the use of the color filter preparation for liquid crystal display devices or a solid-state image sensor, and solid-state imaging It is especially preferable to use for the use of the color filter preparation for elements.

Especially, the colored curable composition of this invention is suitable for the use of the color filter for solid-state image sensors of high resolution exceeding 1 million pixels especially.

Considering the fact that the DOF margin tends to be narrow when the film thickness of the colored pattern to be formed is thin or the size of the colored pattern is small, the film thickness of the colored pattern in the color filter for a solid-state image sensor is 2.0 µm. The following is preferable and 1.0 micrometer or less is more preferable. As a size of a coloring pattern (color pixel), 2.5 micrometers or less are preferable, 2.0 micrometers or less are more preferable, 1.7 micrometers or less are especially preferable.

≪Color filter and its manufacturing method≫

The color filter of this invention is made using the coloring curable composition of this invention described. For example, it is comprised with the coloring pattern of one or more colors (preferably three or four colors) which use the coloring curable composition of this invention described on the support body mentioned later.

Since the color filter of this invention is made using the coloring curable composition of this invention which has a wide DOF margin, generation | occurrence | production of a development residue and the occurrence of inaccuracy around a pattern are suppressed.

Here, as a film thickness of a coloring pattern, 0.1 micrometer-2.0 micrometers are preferable from a viewpoint of forming a finer pattern, or from the viewpoint of preventing an adjacent imaging element from receiving light which passes through a color filter in an inclined direction, and 0.2 Μm to 1.0 µm are more preferable.

There is no limitation in particular as a method of manufacturing the color filter of this invention. For example, the manufacturing method of the color filter which has the process of apply | coating the coloring curable composition of this invention described above on a support body, exposing the developed coating film through a mask, and developing and forming a coloring pattern is preferable. In the case of using a color filter of three or four colors, the above steps can be repeated for each color to form a pattern of each color.

Hereinafter, the example of the manufacturing method of a more specific color filter is demonstrated.

That is, the pattern exposure of the application | coating process of apply | coating the coloring curable composition of this invention on a support body, the prebaking process of prebaking the colored curable composition applied as needed, and the apply | coated coloring curable composition through a mask. The manufacturing method comprised by the exposure process mentioned above and the image development process (also the post-baking process of post-baking the color curable composition alkali-developed as needed) which alkali-develops the colored curable composition exposed by the pattern exposure is mentioned.

More specifically, for example, in the application | coating process, the film thickness at the time of drying the colored curable composition of this invention on a suitable support body by a spinner etc. is 0.1 micrometer-5 micrometers, Preferably it is 0.2 micrometer-2 micrometers so that It is apply | coated and a smooth coating film is obtained.

After apply | coating a colored curable composition, in order to evaporate a solvent and to obtain a dry coating film, prebaking is normally performed (prebaking process). As a method of this prebaking, indirect heat drying by hot air etc., direct heat drying by a hotplate etc. (about 80-140 degreeC, 50 second-200 second), etc. are mentioned. You may dry under reduced pressure before prebaking.

In addition, post-baking is performed in order to fully harden the pattern obtained after image development, to raise mechanical strength, and to make a permanent film (post-baking process). For example, when manufacturing a three-color color filter, the pattern formed initially receives two times application | coating, exposure, and image development of the resist liquid of a different color. At this time, post-baking is performed so that a pattern may not be eliminated due to color mixing, exposure, and development with the applied resist solution. This post-baking is carried out in the same manner as in the pre-baking, but is performed at a higher temperature and longer time than the conditions of the pre-baking. For example, in the case of indirect heating by an oven, about 180 to 250 ° C, about 0.5 hours to 2 hours, and in the case of direct heating by a hot plate, it is about 180 to 250 ° C and about 2 to 10 minutes.

The light source for pattern exposure in an exposure process is not specifically limited. As a light source which brings about a remarkable effect regarding pattern formation property, the light of wavelength 410 nm or less is preferable, and i line | wire (365 nm) of a mercury lamp is especially 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. Especially, the organic alkali type developing solution of quaternary ammonium salts, such as tetramethylammonium hydroxide (TMAH), is preferable in order to achieve the objective of this invention.

Although it does not specifically limit as a support body, The base material of electronic components, such as a glass substrate, a plastic substrate, an aluminum substrate, and the silicon wafer for solid-state image sensors, a transparent resin substrate, a resin film, a CRT display surface, the light receiving surface of an imaging tube, a solid-state image sensor ( CCD, CMOS, BBD, CID, BASIS and the like) can be used. Further, a close-up image sensor using a thin film semiconductor, a liquid crystal display surface, a photosensitive member for color electrophotography, and an electrochromic (EC) display device may be used.

Moreover, in order to improve adhesiveness with a color filter layer, it is preferable to give a high adhesion process to a support body. Specifically, after apply | coating thinly a silane coupling agent etc. on a support body previously, you may form the pattern of a colored curable composition, or may contain a silane coupling agent in a colored curable composition beforehand.

In addition, when there is a step on the support, after applying the flattening film for eliminating the step and smoothing the coated surface on the support, the colored curable composition of the present invention can be applied.

For example, a solid-state imaging element (image sensor) such as a CCD or a CMOS is composed of a photoelectric conversion unit (photodiode) for generating electrons on the silicon substrate in accordance with the amount of light received, and a read gate portion for outputting the generated electrons. . When light reaches the read gate part, noise causes noise and accurate data is not output. Therefore, a light shielding film layer is formed on the upper part of the read gate part, and a step may occur between the photodiode part having no light shielding film layer. have. If a color filter is directly formed by applying a color resist on such a step, the optical path length becomes longer, resulting in darker images and lower light collection. In order to improve this, it is preferable to form a transparent flattening film between the color filter and the CCD or CMOS in order to fill the step. As a material of this planarization film, thermosetting resins, such as a photocurable resist liquid like the colored curable composition of this invention, an acryl type, and an epoxy type, etc. are mentioned.

≪Solid-state imaging device≫

The solid-state imaging device of the present invention includes the color filter of the present invention described above.

The solid-state imaging device of the present invention is excellent in color reproducibility because the color filter of the present invention is provided in which the colored pixels have a cross-sectional shape close to a rectangle.

As a structure of the solid-state image sensor of this invention, if it is a structure with the color filter of this invention, and it is a structure which functions as a solid-state image sensor, there is no limitation in particular, For example, the following structures are mentioned.

It has a transfer electrode which consists of a some photodiode, polysilicon, etc. which comprise the light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a support body, The light-receiving part of a photodiode is carried out on the said photodiode and the said transfer electrode. It has the light shielding film which consists of tungsten etc. opened only, and has the device protective film which consists of silicon nitride etc. formed so that the light shielding film whole surface and the photodiode light-receiving part may be coat | covered on the light shielding film, and has the color filter of this invention on the said device protective film.

Moreover, the structure which has a condensing means (for example, a microlens etc .. is the same below) on the said device protective layer and under a color filter (side close to a support body), the structure which has a condensing means on a color filter, etc. may be sufficient.

(Example)

Hereinafter, although the Example of this invention is shown, this invention is not limited to these.

Example 1

<Preparation of resist liquid for flattening film>

The following component was mixed with the stirrer and the resist liquid for planarization films was prepared.

Component ... of resist liquid for ...

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

· Triazine initiator as described below. 0.3 parts by mass

<Preparation of wafer with flattening film>

The flattening film resist liquid obtained above was uniformly apply | coated by spin coating on a 6-inch silicon wafer, and the coating film was formed, and the formed coating film was heat-processed for 120 second on the hotplate of surface temperature 120 degreeC. Here, the application | coating rotation speed of a spin coat was adjusted so that the film thickness of the coating film after the said heat processing might be set to about 1 micrometer.

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 flattening film.

As described above, a wafer with a flattening film having a flattening film formed on a 6-inch silicon wafer was obtained.

<Preparation of color resist liquid (color curable composition)>

The following components were mixed with the stirrer and the color resist liquid was prepared.

Component ... of ... color resist liquid

Benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])... 3.27 parts by mass

C.I. pigment blue 15: 6. 5.32 parts by mass

C.I. pigment violet 23... 1.33 parts by mass

· Polymer dispersant (disperade 163 (pigchem dispersant pigment dispersant)) 2.56 parts by mass

Propylene glycol monomethyl ether acetate... 81 parts by mass

IRGACURE OXE01 (manufactured by Chiba Specialty Chemicals; Photopolymerization Initiator). 1.65 parts by mass

P-methoxyphenol (polymerization inhibitor). 0.002 parts by mass

Exemplary compound (b) (polymerizable compound) described above. 3.42 parts by mass

ARONIX M-305 (made by Toagosei Co., Ltd .; polymeric compound). 1.47 parts by mass

<Production of color filter>

The color resist liquid obtained above was uniformly coated on the planarization film of the wafer with the planarization film by spin coating to form a coating film, and the formed coating film was heated (prebaked) for 120 seconds on a hot plate having a surface temperature of 100 ° C. The color resist layer was formed. Here, the application | coating rotation speed of a spin coat was adjusted so that the film thickness of the coating film after the said heat processing might be about 0.8 micrometer.

Next, the said color resist layer was pattern-exposed through the photomask mentioned later using i line | wire stepper (FPA-3000i5 + by Canon).

Pattern exposure was performed in matrix form at 399 places in total by arrangement of 21 rows x 19 columns.

Here, the above 21 lines are set under the condition that the exposure amount is increased for every row at the interval of 250 J / m 2 from the minimum exposure amount of 500 J / m 2.

On the other hand, the 19th column is a condition in which the focal length is changed at an interval of 0.1 mu m centering on the focal length optimum value (Foucus 0.0 mu m). In detail, the center column is set as an optimum focal length value, and the focal length is changed for each column.

As a photomask, a mask pattern in which a square pixel pattern of 6 sizes (1.0 square µm, 1.5 square µm, 2.0 square µm, 3.0 square µm, 4.0 square µm, 7.0 square µm) is arranged within a range of 4 mm x 3 mm The photomask which had was used.

The pattern-exposed color resist layer was developed by the Puddle method for 60 seconds at room temperature using the organic alkaline developing solution CD-2060 (made by FUJIFILM Electronics). Thereafter, the resultant was rinsed with pure water in a spin shower for 20 seconds, and washed with pure water again. Thereafter, the water droplets were blown with high pressure air to naturally dry the substrate to obtain a colored pattern.

The blue color filter was obtained by the above.

<Evaluation>

The colored pattern formed by exposure through a square pixel pattern (mask pattern) of 1.5 square µm was measured using a longitudinal-dimension scanning electron microscope (SEM) (Hitachi S-9260), and the dimension of the colored pattern was 1.5 µm ± 0.1. The range of the focal length resolved in the range of micrometers was made into DOF margin.

The larger this number, the better the performance.

[Examples 2-7, Comparative Examples 1-5]

In Example 1, except having changed the kind and / or quantity of the polymeric compound (Example compound (b) and Aronix M-305) used for preparation of a color resist liquid as shown in Table 1, Similarly, the color filter was produced and evaluation similar to Example 1 was performed.

The evaluation results are shown in Table 1.

The detail of the kind of polymeric compound in the said Table 1, the following Table 2, and Table 3 is as follows.

DPHA… Dipentaerythritol hexaacrylate

M-305... Toa Kosei Co., Ltd. aronix M-305

SR-494... Sartomer SR-494

As shown in Table 1, the colored curable composition of the Example had wide DOF margin.

Moreover, in the color filter produced using the colored curable composition of an Example, generation | occurrence | production of the image development residue and generation | occurrence | production of the inaccuracy of the pattern periphery were suppressed.

Example 8

The color filter was produced like Example 1 except having changed the component of the color resist liquid into the component shown below, and the same evaluation as Example 1 was performed. The evaluation results are shown in Table 2.

Component ... of ... color resist liquid

Benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])

                                                         … 3.00 parts by mass

C.I. pigment blue 15: 6. 5.78 parts by mass

C.I. pigment violet 23... 1.44 parts by mass

· Polymeric dispersant (disperade 163 (pigchem dispersant pigment dispersant)) 2.78 parts by mass

Propylene glycol monomethyl ether acetate... 81 parts by mass

IRGACURE OXE01 (manufactured by Chiba Specialty Chemicals; Photopolymerization Initiator). 1.50 parts by mass

P-methoxyphenol (polymerization inhibitor). 0.002 parts by mass

Example compound (b) (polymerizable compound). 3.15 parts by mass

Aronix M-305 (made by Toagosei Co., Ltd .; polymeric compound). 1.35 parts by mass

[Examples 9-14, Comparative Examples 6-10]

In Example 8, except having changed the kind and / or quantity of the polymeric compound (Example compound (b) and Aronix M-305) used for preparation of a color resist liquid as shown in Table 2, Similarly, the color filter was produced and evaluation similar to Example 8 was performed.

The evaluation results are shown in Table 2.

As shown in Table 2, the colored curable composition of the Example had DOF margin.

Moreover, in the color filter produced using the colored curable composition of an Example, generation | occurrence | production of the image development residue and generation | occurrence | production of the inaccuracy of the pattern periphery were suppressed.

Example 15

The color filter was produced like Example 1 except having changed the component of the color resist liquid into the component shown below, and the same evaluation as Example 1 was performed. Table 3 shows the results of the evaluation.

Component ... of ... color resist liquid

Benzyl methacrylate / methacrylic acid copolymer (= 70/30 [molar ratio])

                                                         … 2.73 parts by mass

C.I. pigment blue 15: 6. 6.23 parts by mass

C.I. pigment violet 23... 1.56 parts by mass

· Polymeric dispersant (disperade 163 (pig dispersant pigment dispersant)) 3.00 parts by mass

Propylene glycol monomethyl ether acetate... 81 parts by mass

IRGACURE OXE01 (manufactured by Chiba Specialty Chemicals; Photopolymerization Initiator). 1.37 parts by mass

P-methoxyphenol (polymerization inhibitor). 0.002 parts by mass

Example compound (b) (polymerizable compound). 2.88 parts by mass

Aronix M-305 (made by Toagosei Co., Ltd .; polymeric compound). 1.23 parts by mass

[Examples 16-21, Comparative Examples 11-15]

In Example 15, except that the kind and / or amount of the polymerizable compound (Example compound (b) and Aronix M-305) used for preparing the color resist liquid were changed as shown in Table 3, Similarly, the color filter was produced and evaluation similar to Example 15 was performed.

Table 3 shows the results of the evaluation.

As shown in Table 3, the colored curable composition of the Example had DOF margin.

Moreover, in the color filter produced using the colored curable composition of an Example, generation | occurrence | production of a development residue and generation | occurrence | production of the inaccuracy of the pattern periphery were suppressed.

As indicated above, DOF margin was expanded by using 2 or more types of polymeric compounds whose number of polymeric groups is 4.5 or more in mass mean, and the number of alkyleneoxy groups of 2 or more carbon atoms is 2.0 or more and 10.0 or less in mass mean.

Moreover, the effect of DOF margin enlargement was acquired also on the conditions where a coloring agent content rate is high and DOF margin tends to become narrow.

As mentioned above, although Examples 1-21 mainly demonstrated the case where illustration compound (b) was mainly used as a polymeric compound which has a C2 or more alkyleneoxy group, it replaces the above-mentioned example compound (b) other than the above-mentioned example compound (iii). "Compound represented by general formula (i) or general formula (ii) (Including compound (a), (c)-(f)), or other" polymerizable compound which has a C2 or more alkyleneoxy group. " Also in the same manner, the effect of increasing the DOF margin of the present invention can be obtained.

In addition, although the example which produced the blue color filter was demonstrated in Examples 1-21, the development residue and generation of inaccuracy around a pattern are produced similarly to Examples 1-21 by changing the coloring agent used for the colored curable composition. This suppressed red color filter, green color filter, and a color filter having colored pixels of three colors of red, green, and blue can be produced.

Moreover, the solid-state image sensor which is excellent in color reproducibility can be manufactured by producing the color filter which has the said three color pixels on the board | substrate for solid-state image elements in which the photodiode, the light shielding film, the device protective film, etc. were formed.

For example, a light shielding film made of tungsten in which only the light receiving portion of the photodiode is opened is formed on the silicon substrate on which the photodiode and the transfer electrode are formed, and the entire surface of the formed light shielding film and the photodiode light receiving portion (opening in the light shielding film) are formed to be made of silicon nitride. Forming a device protective layer, and forming color filters (colored pixels of R, G, and B) on the formed device protective layer by the same method as Examples 1 to 21, and forming a color filter; By forming a lens, a solid-state imaging device with good color reproducibility can be produced.

Claims (7)

2 or more types of polymeric compounds containing a coloring agent and the polymeric compound which has a C2 or more alkyleneoxy group; The number of polymerizable groups of the said 2 or more types of polymeric compounds is 4.5 or more in mass mean, and the number of C2 or more alkyleneoxy groups is 2.0 or more and 10.0 or less in mass mean, The coloring curable composition characterized by the above-mentioned. The colored curable composition according to claim 1, wherein the two or more polymerizable compounds contain 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 member selected from the group of compounds represented by the general formula (i) or (ii). Coloring curable composition.

[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 the, y is Each independently represents an integer of 1 to 10, and each X independently represents an acryloyl group, methacryloyl group, a hydrogen atom, or a carboxyl group. In the general formula (V), the sum of the acryloyl group and the methacryloyl group is three or four, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 1 to 40. In the general formula (ii), the sum of the acryloyl group and the methacryloyl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the sum of each n is an integer of 1 to 60.] Content of the said coloring agent is 30 mass% or more with respect to a total solid, The colored curable composition of any one of Claims 1-3 characterized by the above-mentioned. After apply | coating the coloring curable composition of any one of Claims 1-4 on a support body, it has the process of exposing and developing the apply | coated coating film through a mask and forming a coloring pattern, The manufacturing method of the color filter characterized by the above-mentioned. Way It uses the colored curable composition in any one of Claims 1-4, The color filter characterized by the above-mentioned. The color filter of Claim 6 was provided. The solid-state image sensor characterized by the above-mentioned.