TWI611219B - Method for manufacturing color filter, color filter and solid-state imaging sensing device - Google Patents

Abstract

The invention provides a color filter with a good pattern shape. The method for producing a color filter of the present invention includes: (a) a step of forming a colored layer using a colored radiation-sensitive composition containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent; b) a step of exposing the colored layer into a pattern through a barrier mask; and (c) a step of developing the exposed colored layer using a developing solution containing an organic solvent, in the total amount of the colored radiation-sensitive composition. The solid content contains 65% by mass or more of the above dye.

Description

Manufacturing method of color filter, color filter and solid-state imaging element

The invention relates to a method for manufacturing a color filter, a color filter and a solid-state imaging element.

For example, in a solid-state imaging element, a color filter formed by arranging colored pixels of a plurality of colors such as red pixels, green pixels, and blue pixels on a support such as a semiconductor substrate is provided in two dimensions. In this solid-state imaging device, the number of pixels has increased significantly in recent years, and its pixel size has been significantly reduced when compared with the inch size and the same solid-state imaging element as before. In addition, with the reduction in pixel size, the performance requirements for color separation have become stricter. In order to maintain the characteristics of elements such as color shading and prevent color mixing, the performance required for color filters requires thinning and rectangularization. And eliminating overlapping areas where colors overlap each other between the colored pixels.

As for a method for manufacturing such a color filter, a photolithography method has been used in the past. In this photolithography method, organic pigments of red pigment, green pigment, and blue pigment are used as colored materials, and alkali is used. Sex aqueous solution as Developer. The photolithography method is a method in which a colored radiation-sensitive composition is coated on a support and dried to form a colored layer, and then the colored layer is subjected to pattern exposure, development, and the like to form a first color (for example, green). The pixels are similarly formed in the remaining colors (for example, refer to Patent Document 1).

In addition, a technique using a dye has been proposed in place of a technique using a pigment (for example, refer to Patent Documents 2 and 3).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-68076

[Patent Document 2] Japanese Patent Laid-Open No. 6-75375

[Patent Document 3] Japanese Patent Laid-Open No. 2011-148950

In the technology described in Patent Document 1, with the miniaturization of pixels of a solid-state imaging device, it is difficult to make a color filter finer and thinner when a pattern is formed by the photolithography method described above. The spectral characteristics of the filter and the pattern forming ability coexist. Specifically, in a color filter for a solid-state imaging element, the thickness of a colored pattern is reduced, for example, to achieve a thickness of 0.8 μm or less and a pixel pattern size of 1.4 μm or less (for example, 0.5 μm to 1.4 μm). The tendency to miniaturization.

In particular, with the advancement of thin film, the relative amount of colorants such as pigments in the film has increased, but the amount of components other than colorants that contribute to photolithography in the film has relatively decreased, and the thickness of the film is 0.8 μm or less. Picture with pixel pattern size less than 1.4 μm According to the requirements of the case, there is a problem in that the pattern forming property caused by the above reduction is accompanied by a residue due to poor development. The reason is that, for a color filter using a pigment dispersion (a color filter produced by a photolithography method using a color-sensitive radioactive composition obtained by dispersing a pigment in various compositions), The original pigment itself does not have developability. In addition, even when corrections such as Optical Proximity Correction (OPC) are performed, although the effect of improving the shape of the pattern viewed from the upper surface can be improved, when the cross section is observed, the edge of the pattern of the shape of the pattern becomes round and lacks. Rectangle and other issues. In this case, it is known that the rounding of the edge of a pattern becomes noticeable by the influence of light scattering at the time of exposure by a pigment.

In particular, recently, in accordance with the requirements for further refinement of color filters for solid-state imaging elements, for example, the formation of 1.1 μm patterns has been sought, and a conventional method for developing a colored composition using an organic pigment using an alkaline developer has been developed. In terms of resolution, its resolution is close to the limit.

Further, a color filter for a solid-state imaging element is desired to have a higher definition. However, it has been difficult to further improve the resolution of the conventional pigment dispersion system, and there are problems of color unevenness due to the coarse particles of the pigment. Therefore, it is not suitable for applications requiring fine patterns such as solid-state imaging elements.

In addition, as in the techniques described in Patent Documents 2 and 3, a system using a dye that is soluble in an organic solvent as a colorant is also difficult to satisfy the required spectrum while achieving a thin film thickness of 0.8 μm or less.

In this way, the conventional color filter formed by the photolithography process has a problem that sufficient resolution cannot be obtained, that is, the pattern shape is not good, resulting in solid A problem that the characteristics of a photographic element are reduced.

This invention is made in view of the said subject, The objective is to provide the manufacturing method of the color filter with favorable pattern shape.

The inventors of the present application conducted intensive studies based on the above-mentioned conditions, and found that (i) a colored layer was formed using a color-sensitive radiation composition containing 65% by mass or more of a dye soluble in an organic solvent, and exposed, Developing using a developer containing an organic solvent; or (ii) patterning the first colored layer obtained from the colored composition to form a colored pattern by dry etching, and on the patterned first colored layer, Patterning is performed by photolithography to form other colored patterns. In the step of patterning by photolithography, an organic solvent containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent is used. The colored radiation-sensitive composition is used to perform a colored layer, expose it, and develop using a developer containing an organic solvent, thereby obtaining a color filter with a good pattern shape, and completed the present invention.

Specifically, the above-mentioned problems are solved by the following solution <1>, preferably solution <2> to solution <14>.

<1> A method for manufacturing a color filter, comprising: (a) forming a colored layer using a color-sensitive radiation composition containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent; (B) a step of exposing the colored layer into a pattern through a barrier mask; and (c) a step of developing the exposed colored layer using a developer containing an organic solvent, The total solid content of the colored radiation-sensitive composition contains 65% by mass or more of the dye.

<2> The method for producing a color filter according to <1>, wherein the dye soluble in the organic solvent is a pigment multimer.

<3> The method for producing a color filter according to <1> or <2>, wherein the developer containing the organic solvent contains 95% by mass or more of an organic solvent.

<4> The method for producing a color filter according to any one of <1> to <3>, wherein a solubility parameter (SP) value of the developer containing the organic solvent is 15.1 to 18.9 or 23.1 to 42.0.

<5> The method for producing a color filter according to any one of <1> to <4>, wherein an SP value of the developer containing the organic solvent is 15.1 to 17.5 or 30.0 to 42.0.

<6> A method for manufacturing a color filter, which is a method for manufacturing a color filter having a plurality of colored layers formed on a substrate, and includes a step of forming a first colored layer obtained from a colored composition; A step of patterning the first colored layer to form a colored pattern by dry etching; and patterning by photolithography on the patterned first colored layer to form another colored pattern The step of patterning by photolithography includes: (a) forming a colored layer using a color-sensitive radioactive composition containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent; A step of; (b) a step of exposing the colored layer into a pattern through a mask; and (c) a step of developing the exposed colored layer using a developer containing an organic solvent.

<7> The method for producing a color filter according to <6>, wherein the colored radiation-sensitive composition contains 65% by mass or more of the dye in a total solid content of the colored radiation-sensitive composition.

<8> The method for producing a color filter according to <6> or <7>, wherein the dye soluble in the organic solvent is a dye polymer.

<9> The method for producing a color filter according to any one of <6> to <8>, wherein the developer containing the organic solvent contains 95% by mass or more of an organic solvent.

<10> The method for producing a color filter according to any one of <6> to <9>, wherein the SP value of the developer containing the organic solvent is 15.1 to 18.9 or 23.1 to 42.0.

<11> The method for producing a color filter according to any one of <6> to <10>, wherein the SP value of the developer containing the organic solvent is 15.1 to 17.5 or 30.0 to 42.0.

<12> The method for producing a color filter according to any one of <6> to <11>, wherein the first colored layer is a green transmission layer.

<13> A color filter obtained by the method for producing a color filter according to any one of <1> to <12>.

<14> A solid-state imaging element having the color filter according to <13> sheet.

According to the present invention, a color filter having a good pattern shape can be provided.

10‧‧‧Solid Photographic Element

11‧‧‧ the first colored layer

12‧‧‧ the first coloring pattern

13, 100‧‧‧ color filters

14‧‧‧ flattening film

15‧‧‧ micro lens

20B, 20G, 20R‧‧‧ pixels

21‧‧‧The second colored radiation-sensitive layer

21A‧‧‧ A position corresponding to the first removal section group 121 provided in the first colored layer 11

22‧‧‧ 2nd coloring pattern

22R‧‧‧ A plurality of second colored pixels provided inside each of the removal sections of the second removal section group 122

31‧‧‧The third colored radiation-sensitive layer

31A‧‧‧ is a position corresponding to the second removal group group 122 provided in the first colored layer 11

32‧‧‧ 3rd coloring pattern

41‧‧‧P Well

42‧‧‧Light receiving element (light diode)

43‧‧‧ impurity diffusion layer

44‧‧‧ electrode

45‧‧‧Wiring layer

46‧‧‧BPSG film

47‧‧‧ insulating film

48‧‧‧P-SiN film

49‧‧‧ flattening film

51‧‧‧Photoresistive layer

51A‧‧‧resist removal group

52‧‧‧resist pattern

120‧‧‧ removal group

121‧‧‧ the first removal group

122‧‧‧ The second removal group

FIG. 1 is a schematic cross-sectional view showing a configuration example of a color filter and a solid-state imaging element.

FIG. 2 is a schematic cross-sectional view of a first colored layer.

3 is a schematic cross-sectional view showing a state where a photoresist layer is formed on a first colored layer.

FIG. 4 is a schematic cross-sectional view showing a state where a resist pattern is formed on the first colored layer.

5 is a schematic cross-sectional view showing a state where a first colored pattern is formed by providing a group of removed portions in the first colored layer by etching.

FIG. 6 is a schematic cross-sectional view showing a state where the resist pattern of FIG. 5 is removed.

FIG. 7 is a schematic cross-sectional view showing a state where a second colored pattern and a second colored radiation-sensitive layer are formed.

FIG. 8 is a schematic cross-sectional view of a state in which a part of the second colored radiation-sensitive layer of FIG. 7 and a portion of the second colored pixels constituting the second colored pattern are removed.

9 is a schematic cross-sectional view showing a state where a third colored pattern and a third colored radiation-sensitive layer are formed.

FIG. 10 is a schematic cross-sectional view showing a state where the third colored radiation-sensitive layer of FIG. 9 is removed.

Hereinafter, the content of this invention is demonstrated in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the specification of this application, "~" is used to mean that the numerical value described before and after is used as a lower limit value and an upper limit value.

In the description of the group (atomic group) in this specification, the descriptions that are not substituted and unsubstituted include a group having no substituent and also include a group having a substituent. For example, the "alkyl group" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acryl" refers to acryl and methyl Acrylic acid.

In this specification, the "colored layer" refers to a pixel used in a color filter.

The pigment in the present invention refers to, for example, an insoluble pigment compound that is insoluble in a solvent. Examples of the solvent herein include solvents exemplified in the column of solvents described later. Therefore, the pigment compound which is insoluble in these solvents corresponds to the pigment of the present invention.

In the present invention, the "dye soluble in organic solvent" means, for example, that the solubility of the dye in the organic solvent at 23 ° C is 1% by mass or more, preferably 1 to 50% by mass, and more preferably 5 to 50% by mass is dissolved, and further preferably 10 to 50% by mass is dissolved. The "organic solvent" means, for example, at least one of esters, ethers, ketones, and aromatic hydrocarbons.

Hereinafter, a method for manufacturing a color filter of the present invention will be described in the order of the first embodiment and the second embodiment.

According to the method for manufacturing a color filter of the present invention, a color filter having a good pattern shape can be obtained. In addition, according to the method for manufacturing a color filter of the present invention, even when the color filter is made thinner, the pattern shape of the color filter can be made good. In addition, according to the method for manufacturing a color filter of the present invention, a color filter with little unevenness in reflectance between pixels can be provided.

In addition, according to the method for producing a color filter of the present invention, a color filter having a good pattern shape, good developability in an unexposed portion, and further excellent decoloring resistance can be obtained.

<First Embodiment>

The method for producing a color filter of the present invention includes: (a) a step of forming a colored layer using a colored radiation-sensitive composition containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent; b) a step of exposing the coloring layer into a pattern through a barrier mask; and (c) a step of developing the exposed coloring layer using a developing solution containing an organic solvent, in the total amount of the coloring radiation-sensitive composition. The solid content contains 65% by mass or more of the above dye.

In the manufacturing method of the color filter of this invention, it is preferable to perform patterning by photolithography.

In addition, a method for manufacturing a color filter may be provided to perform coloring on the colored layer as necessary. A baking step (pre-baking step), and a step of baking the developed colored layer (post-baking step). Hereinafter, these steps may be collectively referred to as a pattern forming step.

Here, in order to reduce the thickness of the color filter, it is necessary to increase the concentration of the colorant (dye), but the amount of components other than the colorant that contribute to the photolithography in the film is relatively reduced. It is difficult to make the pattern shape good because the number of components contributing to photolithography other than the colorant is reduced in the film.

In the present invention, by setting the color filter manufacturing method as described above, even when the color filter is made thinner, the pattern shape can be made good.

<< Procedure for forming colored layer using colored radiation-sensitive composition >>

In the coloring layer forming step, a coloring layer (preferably a coating film) is formed using a color-sensitive radiation composition containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent. For example, it is preferable to dissolve each component of the radiation-sensitive resin composition in a solvent, filter the filter if necessary, and impart a colored radiation-sensitive composition to the support to form a colored layer.

The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less.

The support that can be used in this step can be, for example, a photography provided with a Charge Coupled Device (CCD) or a Complementary Metal-Oxide Semiconductor (CMOS) on a substrate (such as a silicon substrate). Element (light-receiving element) substrate for solid-state imaging element.

The colored pattern of the present invention may be formed on the side (front surface) on which the imaging element is formed of the substrate for a solid-state imaging element, or may be formed on the side (back surface) where the imaging element is not formed.

A light-shielding film may be provided between the colored patterns of the solid-state imaging element or on the back surface of the substrate for the solid-state imaging element.

In addition, if necessary, an undercoat layer may be provided on the support to improve the adhesion with the upper layer, prevent the diffusion of substances, and achieve planarization of the substrate surface. Especially when using a resist as an undercoat layer, mixing of an undercoat layer and an upper layer can be further suppressed.

The method for imparting the colored radiation-sensitive composition of the present invention to a support is preferably a slit coat, an ink-jet method, a spin coat, or a cast coating. Various coating methods, such as roll coating, screen printing method, and the like, are more preferably slit coating and spin coating.

The film thickness (thickness of the coating film before heating) of the colored radiation-sensitive composition layer is not particularly limited, but is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm.

The heating (pre-baking) time is not particularly limited, but is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and further preferably 30 seconds to 130 seconds.

Heating can be performed by a mechanism provided in a general exposure-developing machine, and can be performed using a hot plate, an oven, or the like.

The thickness of the colored radiation-sensitive composition layer after heating is preferably 0.1 μm to 1.5 μm, and more preferably 0.1 μm to 0.8 μm.

<< Exposure steps >>

In the exposing step, the coloring layer formed above is exposed into a pattern through a blocking mask. In the exposure step, for example, it is preferable to use an exposure device such as a stepper to pattern-expose the colored layer formed in the colored layer forming step through a mask having a predetermined mask pattern. Thereby, a colored hardened film obtained by curing a colored radiation-sensitive composition can be obtained.

The radiation (light) that can be used during exposure is particularly preferably ultraviolet rays such as g-rays and i-rays (i-rays are particularly preferred). Irradiation amount (exposure amount) is preferably ^{30mJ / cm 2 ~ 3000mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 2500mJ / cm} 2, particularly preferably ^{100mJ / cm 2 ~ 500mJ / cm} 2.

<< Pattern forming step >>

In the pattern forming step, the exposed colored layer is developed using a developer containing an organic solvent. Thereby, the colored layer in a portion not irradiated with light is eluted into the developing solution, and only the light-hardened portion remains.

The vapor pressure of the developer containing the organic solvent (the overall vapor pressure in the case of a mixed solvent) is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup can be suppressed, and the temperature uniformity in the wafer surface can be improved. As a result, the size uniformity in the wafer surface changes. good.

As the organic solvent used in the developing solution, various organic solvents can be widely used, and examples thereof include solvents such as ester solvents, ketone solvents, alcohol solvents, amidine solvents, ether solvents, and hydrocarbon solvents.

In the present invention, the term “ester-based solvent” refers to a solvent having an ester group in the molecule. Agent.

The ketone-based solvent refers to a solvent having a ketone group in the molecule. The alcohol-based solvent refers to a solvent having an alcoholic hydroxyl group in the molecule. The amidine solvent is a solvent having an amidine group in the molecule. The ether-based solvent refers to a solvent having an ether bond in the molecule. Among these solvents, there are also solvents having a plurality of the above-mentioned functional groups in one molecule, and in this case, they also correspond to any solvents containing the functional groups of the solvents. For example, diethylene glycol monomethyl ether also corresponds to the alcohol-based solvents and ether-based solvents in the above classification.

The hydrocarbon solvent refers to a hydrocarbon solvent having no substituent.

In particular, in the present invention, a developer containing at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an ether solvent is preferred, and more preferably a developer solution containing a solvent selected from a ketone solvent, an ester solvent, and an alcohol A developer of at least one of the solvents.

A plurality of organic solvents used in the developing solution may be mixed and used, or may be mixed with a solvent or water other than those described above. In order to achieve the effect of the present invention more effectively, the overall water content of the developer is preferably 30% by mass or less, more preferably less than 10% by mass, and further preferably substantially free of water. By setting the water content of the entire developing solution to 30% by mass or less as described above, the developability of the unexposed portion can be made better, and for example, the development residue in the unexposed portion can be further suppressed.

The concentration of the organic solvent (total amount when a plurality of types are mixed) in the developer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 95% by mass or more, and most preferably substantially organic Solvent situation. In addition, the case where substantially only an organic solvent is included means the case where a trace amount of a surfactant, an antioxidant, a basic compound, a stabilizer, a defoamer, etc. are included.

The organic solvent used in the developing solution preferably contains an organic solvent selected from the group consisting of ethyl acetate, butyl acetate, amyl acetate, isoamyl acetate, diisopropyl ketone, methylhexyl ketone, methylpentyl ketone (MAK), One or more of methyl ethyl ketone (MEK), γ-butyrolactone, methanol, propylene glycol monomethyl ether acetate, 2-heptanone, and anisole, and more preferably contains ethyl acetate Butyl acetate, diisopropyl ketone, methylhexyl ketone, methylpentyl ketone, methyl ethyl ketone, γ-butyrolactone, and methanol, and more preferably one selected from the group consisting of acetic acid One or more of the group of butyl ester, diisopropyl ketone, methylhexyl ketone, and methylpentyl ketone.

For the developer containing an organic solvent, for example, the developer described in paragraphs 0021 to 0043 of Japanese Patent Application Laid-Open No. 2010-217884 may be used, and the contents thereof are incorporated into the description of the present application.

The organic solvent in the developer containing the organic solvent can be specified by a solubility parameter (Solubility Parameter, SP) value. The SP value of the organic solvent can be, for example, the SP value described in VII / 675 to 714 of the "Polymer Handbook Fourth Edition Volume 2" (more specifically, Table) SP value described in 7). The SP value is preferably 15.1 to 18.9 or 23.1 to 42.0, more preferably 15.1 to 18.0 or 26.0 to 42.0, even more preferably 15.1 to 17.5 or 30.0 to 42.0, and even more preferably 15.7 to 17.5 or 30.0 to 42.0.

By setting the SP value of the organic solvent to 18.9 or less and 23.1 or more, it is possible to prevent the compatibility between the organic solvent and the dye from becoming too good, and to prevent the dye from escaping from the hardened portion. In addition, by setting the SP value of the organic solvent to 15.1 or more and 42.0 or less, the affinity between the organic solvent and the dye can be improved, and the developability is good.

In addition, by setting the SP value of the organic solvent to 15.7 or more, the developability of the unexposed portion can be made better.

In addition, a nitrogen-containing compound may be contained in the developing solution containing an organic solvent. The nitrogen-containing compound can be referred to, for example, the descriptions in paragraphs 0042 to 0063 of Japanese Patent Laid-Open No. 2013-011833, and the contents thereof are incorporated into the description of the present application.

The developing method can be applied, for example, by immersing a substrate in a tank filled with a developing solution for a certain period of time (immersion method); and developing the solution by accumulating the developing solution on the surface of the substrate by surface tension and allowing it to stand for a certain period of time (immersion Method); spraying the developer solution on the surface of the substrate (spray method); scanning the developer ejection nozzle at a constant speed on the substrate rotating at a certain speed, and continuously ejecting the developer (dynamic distribution method), etc., especially The immersion method is preferred.

The development time is not particularly limited as long as the coloring layer of the unexposed portion is sufficiently dissolved, and is usually 10 seconds to 300 seconds. It is preferably 20 seconds to 120 seconds.

The temperature of the developing solution is preferably 0 ° C to 50 ° C, and more preferably 15 ° C to 35 ° C.

In the method for manufacturing a color filter of the present invention, after developing using a developer containing an organic solvent, the method may include a step of washing with an eluent containing an organic solvent.

The vapor pressure of the eluent (total vapor pressure in the case of a mixed solvent) is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less at 20 ° C. the following. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and swelling caused by the penetration of the eluent is suppressed, and the size in the wafer surface is uniform. The uniformity becomes better.

Various eluents can be used for the eluent. It is preferable to use an eluent containing at least one organic solvent or water selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, ammonium solvents, and ether solvents. Lotion.

Regarding the leaching treatment, for example, paragraphs 0045 to 0054 of Japanese Patent Laid-Open No. 2010-217884 can be referred to, and the contents thereof are incorporated into the specification of the present application.

<< Colored radiation-sensitive composition >>

Next, the composition used in the present invention will be described.

<<< Dye soluble in organic solvents >>>

The colored radiation-sensitive composition used in the present invention contains a dye (hereinafter simply referred to as a dye) soluble in an organic solvent.

The dye is not particularly limited as long as it is a dye that is soluble in an organic solvent. For example, a dye that has been conventionally known as a color filter can be used. For example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, and Japanese Patent Registration No. 2592207 can be used. , US Patent No. 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115 The pigments described in the gazette, Japanese Patent Application Laid-Open No. 6-194828, and the like are incorporated into the specification of the present application.

For example, pyrazole azo-based, aniline azo-based, triphenylmethane-based, Anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazoleazo, pyridoneazo, cyanine, phenothiazine, pyrrolopyrazol Dyes such as azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, pyrromethene-based, and methine-based dyes.

The dye used in the present invention preferably has a partial structure (pigment structure) derived from a pigment selected from the group consisting of dipyrrole methylene pigment, azo pigment, anthraquinone pigment, triphenylmethane pigment, and dibenzopiperan Pigments in pigments, cyanine pigments, squarylium pigments, quinophthalone pigments, phthalocyanine pigments, and sub-phthalocyanine pigments. The partial structure derived from a pigment refers to a specific pigment (hereinafter also referred to as a pigment compound) that can form a pigment structure, which can remove a hydrogen atom and can be connected to a pigment polymer (a polymer chain or a dendrimer). Core (core), etc.).

Among the dyes used in the present invention, each of the aforementioned dyes constituting a partial structure derived from the dye is preferably a dye skeleton having a maximum absorption wavelength in the range of 400 nm to 780 nm. In the colored radiation-sensitive composition of the present invention, the dye functions as a colorant, for example.

The structure of the dye is preferably a pigment polymer structure. The pigment polymer may have two or more pigment structures in the molecule, and is preferably a pigment polymer containing a repeating unit having a pigment structure. By using such a pigment polymer, the decoloring resistance of a color filter can be further improved.

The pigment polymer may contain, in addition to a repeating unit having a pigment structure, There are other repeating units. Examples of other repeating units include repeating units having an ethylenically unsaturated bond, repeating units having an alkali-soluble group, and repeating units having a hydrophilic group. From the viewpoint of reducing device pollution and suppressing generation of residues, it is preferable to include a repeating unit having an ethylene unsaturated bond.

In addition, for more specific examples of the structure of the pigment polymer, refer to, for example, Japanese Patent Laid-Open No. 2010-250291, Japanese Patent Laid-Open No. 2011-95732, Japanese Patent Laid-Open No. 2012-13945, and Japan Patent Publication No. 2012-46708, Japanese Patent Publication No. 2012-46712, Japanese Patent Publication No. 2012-181502, Japanese Patent Publication No. 2012-208494, Japanese Patent Publication No. 2013-28764, Japan Paragraphs 0022 to 0133 of Japanese Patent Laid-Open No. 2013-29760 are incorporated into the description of this application.

<<< The better structure of the dye >>>

The dye used in the colored radiation-sensitive composition of the present invention is preferably a pigment multimer containing at least one of the structural units represented by the following general formula (A), general formula (B), and general formula (C) Or a pigment polymer represented by the general formula (D).

Structural unit represented by general formula (A)

In the general formula (A), X ¹ represents a linking group formed by polymerization, and L ¹ represents a single bond or a divalent linking group. DyeI represents a pigment structure described later.

In the general formula (A), X ₁ represents a linking group formed by polymerization. That is, it means the part which forms the repeating unit equivalent to a main chain formed by a polymerization reaction. It should be noted that the portions indicated by 2 * become repeating units. X ₁ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, and is particularly preferably a linking group represented by the following (XX-1) to (XX-24), and most preferably ( (XX-1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains and (XX-24) Vinyl chain. (XX-1) ~ (XX -24) , a * represents the portion indicated in the link to L _1. Me represents a methyl group. In addition, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

[Chemical 2]

In the general formula (A), L ₁ represents a single bond or a divalent linking group. When L ₁ represents a divalent linking group, the divalent linking group represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., methylene, ethylene, trimethylene, or propylene) , Butyl, etc.), substituted or unsubstituted arylene (e.g., phenyl, naphthyl, etc.) having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, -CO _2- , -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -and so on A linking group formed by linking two or more of them. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. In General Formula (A), DyeI represents the pigment structure.

For details of the general formula (A), reference may be made to paragraphs 0138 to 0152 of Japanese Patent Laid-Open No. 2013-29760, and the contents are incorporated into the specification of the present application.

Structural unit represented by general formula (B)

In the general formula (B), X ² has the same meaning as X ¹ in the general formula (A). L ² has the same meaning as L ¹ in the general formula (A). Y ² represents a group capable of forming an ionic or coordination bond with DyeII. DyeII represents a pigment structure described later.

Formula (B) in, X ₂ in the general formula (A) is the same meaning as X _2, preferred ranges are also the same. L ₂ has the same meaning as L ₁ in the general formula (A), and the preferred range is also the same. Y ₂ may be any group that can form an ionic or coordination bond with DyeII, and may be any of an anionic group and a cationic group. Include anionic groups ^{_{COO -, PO 3 H -,}} SO 3 -, -SO 3 NH -, -SO 3 N - CO- and the like, preferably ^{_{COO -, PO 3 H -,}} SO 3 -.

Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium, and sulfonium), and particularly preferred are ammonium cations.

Y ₂ may be bonded to an anion part (COO ⁻ , SO ₃ ⁻ , O ^−, etc.) or a cationic part (the onium cation or metal cation, etc.) that DyeII has.

For details of the general formula (B), reference may be made to paragraphs 0156 to 0161 of Japanese Patent Laid-Open No. 2013-29760, and the contents are incorporated into the specification of the present application.

Structural unit represented by general formula (C)

In the general formula (C), L ³ represents a single bond or a divalent linking group. DyeIII represents a pigment structure described later. m represents 0 or 1.

In the above general formula (C), the divalent linking group represented by L ₃ may be preferably exemplified by a substituted or unsubstituted linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene (E.g., ethylene, trimethylene, propyl, butyl, etc.), substituted or unsubstituted aryl (e.g., phenyl, naphthyl, etc.) having 6 to 30 carbon atoms, substituted Or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -NR- (R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C ( = O)-, -SO-, -SO ₂ -and a linking group formed by linking two or more of these. m represents 0 or 1, preferably 1.

Specific examples of the divalent linking group represented by L ₃ in the general formula (C) are described below, but L _{3 of the} present invention is not limited to these specific examples.

For details of the general formula (C), reference may be made to paragraph 0165 to paragraph 0167 of Japanese Patent Laid-Open No. 2013-29760, and the contents are incorporated into the specification of the present application.

Pigment polymer represented by general formula (D) [Chem. 6]

(In the general formula (D), L ⁴ represents an n-valent linking group. N represents an integer of 2 to 20. When n is 2 or more, the structures of DyeIV may be the same or different. DyeIV represents a pigment structure described later.)

In the general formula (D), n is preferably 3 to 15, and particularly preferably 3 to 6.

In the general formula (D), when n is 2, the divalent linking group represented by L ₄ may be preferably listed as a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, methylene (E.g., ethylene, trimethylene, propyl, butyl, etc.), substituted or unsubstituted aryl (e.g., phenyl, naphthyl, etc.) having 6 to 30 carbon atoms, substituted Or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -NR- (R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C ( = O)-, -SO-, -SO ₂ -and a linking group formed by linking two or more of these.

Examples of n-valent linking groups in which n is 3 or more include: substituted or unsubstituted arylene (1,3,5-phenylene, 1,2,4-phenylene, 1,4,5, 8-naphthyl, etc.), a heterocyclic linking group (e.g., 1,3,5-triazinyl, etc.), an alkylene linking group, etc. as the central parent core and the above-mentioned divalent linking group is substituted and formed.

Specific examples of L ₄ in the general formula (D) are shown below, but the present invention is not limited thereto.

For details of the general formula (D), refer to Japanese Patent Laid-Open No. 2013-29760 The contents of paragraphs 0173 to 0178 of the Gazette are incorporated into the specification of the present application.

A pigment polymer containing a structural unit represented by any one of the general formula (A), the general formula (B), and the general formula (C), and a pigment polymer represented by the general formula (D) In the pigment polymer containing the structural unit represented by the general formula (A) and the general formula (C), and the pigment polymer represented by the general formula (D) are linked by covalent bonds, The polymer colored radiation-sensitive composition is excellent in heat resistance. When the colored radiation-sensitive composition is used to form colored patterns of a plurality of colors, it is effective in suppressing the movement of colors to adjacent colored patterns. Better. In addition, the compound represented by the general formula (A) is particularly preferable because it is easy to control the molecular weight of the pigment polymer.

The dye used in the present invention may have a polymerizable group. As the polymerizable group, a known polymerizable group which can be crosslinked by a radical, an acid, or heat can be used, and examples thereof include a group containing an ethylenically unsaturated bond and a cyclic ether group (epoxy group, oxetan group). Alkyl), methylol and the like are particularly preferably a group containing an ethylenically unsaturated bond, more preferably a (meth) acrylfluorenyl group, and particularly preferably a glycidyl (meth) acrylate and (methyl) ) (Meth) acrylfluorenyl group of 3,4-epoxy-cyclohexyl methyl acrylate.

The introduction method of the polymerizable group includes (1) a method of introducing a polymerizable group by modifying a pigment polymer using a polymerizable group-containing compound, and (2) copolymerizing a pigment monomer and a polymerizable group-containing compound. In addition, a method of introducing a polymerizable group and the like. For these methods, reference may be made to paragraph 0181 to paragraph 0188 of Japanese Patent Laid-Open No. 2013-29760, and the contents are incorporated into the specification of the present application.

With respect to 1 g of the dye, the polymerizable group content of the dye is preferably 0.1 mmol to 2.0 mmol, more preferably 0.2 mmol to 1.5 mmol, and even more preferably 0.3 mmol to 1.0 mmol.

The dye used in the present invention may also contain other functional groups. About other officials The energy group is preferably an alkali-soluble group having a carboxylic acid group, a sulfonic acid group, a phosphate group, and a phenolic hydroxyl group. The alkali-soluble group is particularly preferably a carboxylic acid group.

Regarding other functional groups that the polymer of the dye used in the present invention may have, for example, paragraphs 0195 to 0201 of Japanese Patent Laid-Open No. 2013-29760 can be referred to, and the contents thereof are incorporated into the specification of the present application.

The weight average molecular weight of the dye used in the present invention is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 5,000 or more. In particular, since the weight-average molecular weight of the dye is 5,000 or more, the solubility of the colored radiation-sensitive composition of the present invention in a developing solution is improved, and thus the developability can be further improved. The upper limit of the weight average molecular weight of the dye is not particularly limited, but is preferably 20,000 or less, more preferably 15,000 or less, and even more preferably 10,000 or less.

In the present specification, the weight average molecular weight and the number average molecular weight are values measured in terms of styrene by a gel permeation chromatography (GPC) method.

In addition, the ratio of the weight average molecular weight (Mw) of the (A) pigment polymer to the number average molecular weight (Mn) [(Mw) / (Mn)] is preferably 1.0 to 3.0, more preferably 1.6 to 2.5, and particularly preferably It is 1.6 ~ 2.0.

The Tg of the dye used in the present invention is preferably 50 ° C or higher, and more preferably 100 ° C or higher. The 5% weight reduction temperature obtained by Thermal Gravimetric Analysis (TGA measurement) is preferably 120 ° C or higher, more preferably 150 ° C or higher, and even more preferably 200 ° C or higher. When the temperature is within this range by 5% weight reduction, the color-sensitive radiation composition of the present invention is used to make a color filter. Isochronous, can reduce the concentration change caused by the heating process.

In addition, the light absorption coefficient per unit weight of the dye used in the present invention (hereinafter referred to as ε ^'. Ε ^' = ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, more preferably 60 or more, Furthermore, it is preferably 100 or more. When the light absorption coefficient per unit weight is within this range, when a color filter is produced using the color-sensitive radiation composition of the present invention, a color filter with good color reproducibility can be produced.

From the viewpoint of tinting power, the molar absorption coefficient of the (A) pigment polymer used in the colored radiation-sensitive composition of the present invention is preferably as high as possible. The maximum absorption wavelength and the absorption coefficient were measured by a spectrophotometer cary 5 (manufactured by Varian).

The content of the dye in the colored radiation-sensitive composition of the present invention is 65% by mass or more, and preferably 70% by mass or more, with respect to the total solid content of the colored radiation-sensitive composition. By setting the content of the dye in the colored radiation-sensitive composition to 65% by mass or more based on the total solid content of the colored radiation-sensitive composition, the color filter can be made thinner. The upper limit of the content of the dye in the color-sensitive radiation composition of the present invention is not particularly limited, but is preferably 95% by mass or less, and more preferably 90% by mass or less. Only one kind of dye may be used, or two or more kinds may be used in combination. Moreover, you may use a well-known pigment together with a dye.

<<< Photocurable Compound >>>

The colored radiation-sensitive composition of the present invention contains a photocurable compound. The photocurable compound is preferably a polymerizable compound containing, for example, an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane), or a methylol group. In the following, it can be used as photohardenable The polymerizable compound of the compound will be described.

From the viewpoint of sensitivity, the polymerizable compound can be preferably selected from polymerizable compounds having at least one terminal ethylenically unsaturated bond, and preferably at least two. Among these, a tetrafunctional or more polyfunctional polymerizable compound is preferable, and a polyfunctional or more polyfunctional polymerizable compound is more preferable. In the present invention, these compounds can be used without particular limitation. These compounds may be, for example, any of the following chemical forms: monomers, prepolymers, such as dimers, trimers, and oligomers, or mixtures thereof, and such polymer forms. The polymerizable compound of the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and its prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylic acid, maleic acid, etc.) or their esters, The amidines and these polymers are preferably esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amidines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and such polymers .

In addition, it is also preferable to use the following reactants: addition of unsaturated carboxylic acid esters or amidoamines having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy Reactants, or dehydration condensation reactants with monofunctional or polyfunctional carboxylic acids, and the like.

In addition, the following reactants are also preferred: the addition of unsaturated carboxylic acid esters or amidines having an electrophilic substituent such as an isocyanate group or an epoxy group, and the addition of monofunctional or polyfunctional alcohols, amines, and thiols. Unreacted unsaturated carboxylic acid esters or amidoamines which form a reactant and further have a detachable substituent such as a halogen group or tosyloxy group and a monofunctional Or polyfunctional alcohols, amines, and thiols.

In addition, as another example, a compound group obtained by replacing an unsaturated carboxylic acid with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like may be used.

Such specific compounds can be referred to the compounds described in paragraph number 0095 to paragraph number 0108 of Japanese Patent Laid-Open No. 2009-288705, and the contents are incorporated into the specification of the present application.

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one vinyl group capable of addition polymerization and having a boiling point of 100 ° C. or higher under normal pressure. For an example, reference may be made to paragraph 0227 of Japanese Patent Laid-Open No. 2013-29760, and the content is incorporated into the specification of the present application. A compound having a boiling point of 100 ° C. or more under normal pressure and having at least one ethylenically unsaturated group capable of addition polymerization can be referred to those described in paragraph number 0254 to paragraph number 0257 of Japanese Patent Laid-Open No. 2008-292970. Compounds, the contents of which are incorporated into the specification of this application.

Among them, the polymerizable compound is preferably a polyfunctional (meth) acrylate, for example, dipentaerythritol triacrylate (a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) ), Dipentaerythritol tetraacrylate (commercial product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is Kayarad (KAYARAD) D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product is KAYARAD) DPHA; manufactured by Nippon Kayaku Co., Ltd.), and the structure of these (meth) acrylfluorene groups via ethylene glycol and propylene glycol residues. Such oligomer types can also be used.

The polymerizable compound can be referred to, for example, the descriptions of paragraphs 0466 to 0495 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to [0571] to [0606] of the specification of U.S. Patent Application Publication No. 2012/0235099). Incorporated into the specification of this application.

The content of the photocurable compound in the colored radiation-sensitive composition of the present invention is preferably 0.1% to 70% by mass, and more preferably 1.0% to 40% of the total solid content in the colored radiation-sensitive composition. Mass%, particularly preferably 2.0% to 20% by mass.

<<< Photopolymerization initiator >>>

The colored radiation-sensitive composition used in the present invention further contains a photopolymerization initiator. When the colored radiation-sensitive composition used in the present invention contains a photopolymerization initiator, the sensitivity can be further improved.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and may be appropriately selected from known photopolymerization initiators. For example, those having a sensitivity in the ultraviolet range to visible light are preferred. In addition, it may be an active agent that generates some active radicals by interacting with a photo-excited sensitizer, or an initiator that initiates cationic polymerization depending on the type of monomer.

The photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), fluorenylphosphine compounds such as a fluorenylphosphine oxide, hexaarylbiimidazole, and oxime derivatives Such as oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like.

In addition, from the viewpoint of exposure sensitivity, a compound selected from the group consisting of a trihalomethyltriazine compound, a benzophenone dimethyl ketal compound, an α-hydroxy ketone compound, α-Aminoketone compound, fluorenylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triallyl imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone Compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl substituted coumarin compounds.

In particular, when the colored radiation-sensitive composition of the present invention is used to produce a color filter for a solid-state imaging element, it is necessary to form a fine pattern in a sharp shape, so it is important that the composition is hardenable. Development was performed in the exposure section without residue. From such a viewpoint, the polymerization initiator is particularly preferably an oxime compound.

In particular, when a fine pattern is formed in a solid-state imaging element, a stepper is used for exposure during hardening. However, the exposure machine may be damaged by halogen, and it is necessary to reduce the addition amount of the polymerization initiator to a low level. . Taking these points into consideration, it is particularly preferable to use an oxime compound as the photopolymerization initiator when forming a fine pattern like a solid-state imaging element.

Specific examples of the oxime compound include, for example, Japanese Patent Laid-Open No. 2001-233842 The compounds described in the gazette, the compounds described in Japanese Patent Laid-Open No. 2000-80068, and the compounds described in Japanese Patent Laid-Open No. 2006-342166. In addition, the oxime compound can refer to, for example, formula (OX-1) or formula (OX- 2) A description of the compound represented, which is incorporated into the specification of the present application.

Examples of the oxime compound such as an oxime derivative which can be preferably used as the photopolymerization initiator of the present invention include 3-benzyloxyiminobutane-2-one and 3-acetamidoxyimine Butane-2-one, 3-propionyloxyiminobutane-2-one, 2-ethoxymethyliminopentane-3-one, 2-ethoxymethylimino- 1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- Ketones and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-ones.

Examples of oxime ester compounds are: "Journal of the Chemical Society (JCS) Perkin II" (1979) pp. 1653-1660, "Journal of the Chemical Society , JCS) Perkin II (1979) pp. 156-162, "Journal of Photopolymer Science and Technology" (1995) pp. 202-232, Japan Compounds described in JP 2000-66385, compounds described in JP 2000-80068, JP 2004-534797, and JP 2006-342166 . Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and Iluca can also be preferably used. (IRGACURE) -OXE02 (manufactured by BASF).

The content of the photopolymerization initiator contained in the colored radiation-sensitive composition used in the present invention is preferably 0.1% to 50% by mass, and more preferably 0.5% by mass relative to the total solid content of the colored radiation-sensitive composition. % To 30% by mass, particularly preferably 1% to 10% by mass.

<<< polymerization inhibitor >>>

In the colored radiation-sensitive composition used in the present invention, a polymerization inhibitor is preferably added in order to suppress unnecessary polymerization of the photocurable compound during the production or storage of the colored radiation-sensitive composition.

Examples of polymerization inhibitors usable in the present invention include hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, third-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), N- Nitrophenylhydroxylamine cerium salt and the like.

The addition amount of the polymerization inhibitor is preferably from 0.01% by mass to 5% by mass relative to the total solid content of the colored radiation-sensitive composition used in the present invention.

<<< Solvent >>>

The colored radiation-sensitive composition used in the present invention may contain a solvent (organic solvent). The solvent is not particularly limited as long as the solubility of the dye is satisfied.

The organic solvent is preferably exemplified by esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate Esters, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-oxypropanoic acid alkyl esters (e.g. Methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, etc.)), 2-oxypropionate alkyl esters (e.g. methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-propoxypropionate Esters (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl acetate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, 2-oxobutanoic acid Methyl esters, ethyl 2-oxobutanoate, and the like; and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl cellosolve acetate Ethyl cellulose Acid esters, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetates and the like; and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; and aromatic hydrocarbons such as toluene and xylene.

The content of the solvent in the colored radiation-sensitive composition is preferably set to an amount such that the total solid content concentration of the colored radiation-sensitive composition becomes 5 to 80% by mass, and more preferably set to the colored radiation-sensitive composition. The total solid content concentration is an amount of 5 to 60% by mass, and it is more preferable to set the total solid content concentration of the colored radiation-sensitive composition to an amount of 10 to 50% by mass.

<<< Other ingredients >>>

The colored radiation-sensitive composition used in the present invention may contain components other than the components described above. For example, paragraphs 0182 to 0184 of Japanese Patent Laid-Open No. 2006-243173 can be referred to, and the contents are incorporated into the specification of the present application.

<Second Embodiment>

The present invention is a method for manufacturing a color filter having a plurality of colored layers formed on a substrate. The method includes the steps of: forming a first colored layer obtained from a colored composition; and performing dry etching on the first colored layer. A step of patterning in a manner of forming a plurality of patterns; and a step of patterning other colored layers by photolithography on the patterned first colored layer; the above described other colored layers by photolithography The patterning step includes: (a) forming the other colored layer using a color-sensitive radiation composition containing a dye, a polymerizable compound, and a photopolymerization initiator which are soluble in an organic solvent; (b) a spacer A step of exposing the other colored layer into a pattern by a mask; and (c) a step of developing the exposed other colored layer using a developer containing an organic solvent.

According to the method for manufacturing a color filter according to the second embodiment, compared with the method for manufacturing a color filter according to the first embodiment, when the color filter is made thinner, the The pattern shape is better.

In the method for manufacturing a color filter of the present invention, the first colored layer is patterned by dry etching at first, thereby being more reliable than the case where the first colored layer is patterned by photolithography. Set a desired shape of the removal part. In addition, after the first colored layer is patterned by dry etching, the other colored layers are patterned by photolithography, so that the number of steps can not be increased as compared with the case where all steps are performed by dry etching.

In the method for manufacturing a color filter of the present invention, the coloring composition used in the step of forming the first colored layer is not particularly limited as long as it contains a hardening compound, a colorant (pigment or dye), a solvent, and the like, A known composition can be used. Regarding each component, for example, paragraphs 0072 to 0387 of Japanese Patent Laid-Open No. 2013-54081 can be referred to, and the contents are incorporated into the specification of the present application.

As the curable compound in the coloring composition used in the step of forming the first colored layer, a polymerizable compound (for example, a thermosetting compound) can be used.

The solvent in the coloring composition used in the step of forming the first colored layer is not particularly limited, and for example, the above-mentioned photocurable compound or solvent can be used.

The content of the coloring agent in the coloring composition used in the step of forming the first coloring layer with respect to the total solid content of the coloring composition is preferably 65% by mass or more, and more preferably 70% by mass or more. The upper limit of the content of the coloring agent in the coloring composition used in the step of forming the first colored layer is not particularly limited, but is preferably 95% by mass or less, and more preferably 90% by mass or less. The coloring agent in the coloring composition used in the step of forming the first coloring layer may be a pigment or a dye, preferably a pigment, and more preferably used as a pigment dispersion in which the pigment is dispersed in a solvent. . another The coloring agent in the coloring composition used in the step of forming the first coloring layer may be used alone or in combination of two or more.

The so-called patterning by dry etching to form a plurality of patterns is not particularly limited as long as it is a method capable of patterning the first colored layer by forming a removal portion in the first colored layer. The removed portions formed in the first colored layer are arranged in a checkerboard shape (bayer shape).

Dry etching is not particularly limited, and from the viewpoint of forming a pattern cross section closer to a rectangle or further reducing damage to a support, for example, dry etching is preferably performed using an etching gas.

The other coloring layer used in the step of patterning other coloring layers by photolithography refers to a coloring layer having a color different from that of the first coloring layer. The color-sensitive radioactive composition used in the step of patterning other colored layers by photolithography has the same meaning as the color-sensitive radioactive composition of the first embodiment described above, and its preferred range is also the same.

Hereinafter, specific examples of the method for manufacturing the color filter of the present invention will be described.

The manufacturing method of the color filter of this invention uses a coloring composition (henceforth a 1st coloring composition) to form a 1st coloring layer.

Here, as an example, a solid-state imaging element will be briefly described with reference to FIG. 1.

As shown in FIG. 1, the solid-state imaging element 10 includes a light-receiving element (photodiode) 42, a color filter 13, a flattening film 14, a microlens 15, and the like provided on a silicon substrate. In the present invention, the planarizing film 14 is not necessarily provided. Again, Figure 1 In order to clearly show each part, the ratios of the thickness and width of each other are ignored and are partially exaggerated.

The support is not particularly limited as long as it is used in a color filter other than a silicon substrate, and examples include soda glass, borosilicate glass, quartz glass, and A transparent conductive film is attached to these glasses, or a photoelectric conversion element substrate used in a solid-state imaging device, such as an oxide film, silicon nitride, or the like. In addition, an intermediate layer or the like may be provided between these supports and the color filter 13 within a range that does not impair the present invention.

A P-well 41 is provided on the silicon substrate, and a light-receiving element (photodiode) 42 is provided on a part of the surface of the P-well 41. On the surface of the P-well 41 of the silicon substrate and in a region different from the above, there is an impurity diffusion layer 43 having a higher N-type impurity concentration than the light receiving element (photodiode) 42.

An insulating film 47 such as SiO ₂ or SiO ₂ / SiN / SiO _{2 is provided} on the P well 41, the light receiving element (photodiode) 42, and the impurity diffusion layer 43. The insulating film 47 is provided with polycrystalline silicon, tungsten, Electrodes 44 such as tungsten silicide, Al, Cu, and the like. A wiring layer 45 is formed above the electrode 44. A Boro-phospho-silicate glass (BPSG) film 46 and a P-SiN film 48 are provided above the wiring layer 45. A planarizing film layer 49 is formed on the BPSG film 46 in order to planarize uneven portions other than the surface of the P-SiN film 48 or the pixel region.

A color filter 13 is formed on the planarizing film layer 49. Furthermore, in the following description, a colored film formed on a silicon substrate without dividing a region is referred to as a "coloring (radiation for coloring)", and a colored film formed by dividing regions into patterns. (For example, a film patterned in a striped pattern) is called a "colored pattern". In addition, in the coloring pattern, a coloring pattern (for example, a coloring pattern formed by patterning a square or a rectangle) that is an element constituting the color filter 13 is referred to as "coloring (red, green, blue) pixels" .

The color filter 13 is composed of a plurality of green pixels (first color pixels) 20G, red pixels (second color pixels) 20R, and blue pixels (third color pixels) 20B arranged two-dimensionally. Made up. Each of the colored pixels 20R, 20G, and 20B is formed above the light receiving element (light diode) 42. A green pixel 20G is formed in a checkerboard pattern, and a blue pixel 20B and a red pixel 20R are formed between the green pixels 20G. In addition, in FIG. 1, in order to explain that the color filter 13 is composed of pixels of three colors, each of the colored pixels 20R, 20G, and 20B is shown in a row.

The planarizing film 14 is formed so as to cover the upper surface of the color filter 13 and flatten the surface of the color filter.

The microlens 15 is a condenser lens arranged with the convex surface facing upward. The microlens 15 is a light receiving element (light diode) 42 provided above the planarizing film 14 (color filter in the case of not having a planarizing film). Up. Each microlens 15 efficiently guides light from a subject to each light receiving element (photodiode) 42.

Next, a method for manufacturing a color filter of the present invention will be described.

As for the manufacturing method of the color filter of this invention, as shown in the schematic sectional drawing of FIG. 2, the 1st coloring layer 11 is first formed with the 1st coloring composition (step (A)). The first coloring composition will be described later.

The first colored layer 11 is preferably a green transmissive layer. By setting the first colored layer 11 as a green transmission layer, the color sensitivity can be further improved.

The coloring agent in the first coloring composition is preferably selected from one or more of the following pigments: Color Index (CI) Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58 and CI Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 11 , CI pigment yellow 12, CI pigment yellow 13, CI pigment yellow 14, CI pigment yellow 15, CI pigment yellow 16, CI pigment yellow 17, CI pigment yellow 18, CI pigment yellow 20, CI pigment yellow 24, CI pigment yellow 31 , CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35: 1, CI Pigment Yellow 36, CI Pigment Yellow 36: 1, CI Pigment Yellow 37, CI Pigment Yellow 37: 1, CI Pigment Yellow 40. CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, CI Pigment Yellow 199, CI Pigment Yellow 213, CI Pigment Yellow 214.

The first colored layer 11 can be formed, for example, by applying a colored composition to a support by a coating method such as spin coating, slit coating, or spray coating, and drying the colored composition to form a colored layer.

The thickness of the dried first colored layer 11 is preferably in a range of 0.3 μm to 1 μm, more preferably in a range of 0.35 μm to 0.8 μm, and even more preferably in a range of 0.35 μm to 0.7 μm.

When the 1st coloring composition contains a photocurable compound, it is preferable to heat and harden the 1st coloring layer 11 with heating apparatuses, such as a hot plate and an oven. The heating temperature is preferably 90 ° C to 250 ° C, and more preferably 100 ° C to 230 ° C. The heating time varies depending on the heating mechanism. When heating on a hot plate, it is usually about 3 minutes to 30 minutes. When heating in an oven, it is usually about 30 minutes to 90 minutes.

Then, patterning is performed by dry etching so that the removal group group is formed in the first colored layer 11 (step (B)). Thereby, a first coloring pattern is formed. According to this method, as compared with the case where the first colored layer is formed by using a color-sensitive radiation composition, and the first colored layer is exposed and developed, the removal group group can be provided more reliably. Groups of removal parts to be shaped.

The patterned photoresist layer can be used as a mask to dry-etch the first colored layer 11 using an etching gas. For example, as shown in the schematic cross-sectional view of FIG. 3, a photoresist layer 51 is first formed on the first colored layer 11.

Specifically, a positive-type or negative-type radiation-sensitive composition is coated on the first colored layer 11 and dried to form a photoresist layer. When the photoresist layer 51 is formed, a pre-baking process is preferably further performed. In particular, the formation process of the photoresist is preferably in the form of performing a heat treatment (PEB) after exposure and a heat treatment (post-baking treatment) after development.

As the photoresist, for example, a positive radiation-sensitive composition can be used. The positive-type radiation-sensitive composition can be used: a positive type suitable for sensing ultraviolet rays (g-rays, h-rays, i-rays), extreme ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays Positive resist composition for photoresist. Among the radiations, g-rays, h-rays, and i-rays are preferable, and i-rays are preferable.

Specifically, the positive radiation-sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. Examples of the quinonediazide compound include naphthoquinonediazide compounds.

The thickness of the dried photoresist layer 51 is preferably 0.1 μm to 3 μm, and more preferably 0.2. μm to 2.5 μm, more preferably 0.3 μm to 2 μm. The application of the photoresist layer 51 can be preferably performed using a coating method of the first colored layer 11.

Then, as shown in the schematic cross-sectional view of FIG. 4, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist removal section group 51A. .

The formation of the resist pattern 52 is not particularly limited, and a conventionally known photolithography technique can be used. The resist removal portion group 51A is provided in the photoresist layer 51 by exposure and development, and a resist pattern 52 serving as an etching mask used in subsequent etching is provided on the first colored layer 11.

The exposure of the photoresist layer 51 can be performed by interposing a predetermined mask pattern, and using g-rays, h-rays, i-rays, and the like, preferably using i-rays for a positive or negative radiation-sensitive composition. exposure. After the exposure, a developing solution is used to perform a development process, thereby removing the photoresist corresponding to the area where a colored pattern is to be formed.

The developer may be used arbitrarily as long as it does not affect the first colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, various organic solvents may be used. Combination or alkaline aqueous solution.

The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound at a concentration of 0.001% to 10% by mass, and preferably 0.01% to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc. In addition, in the case of using an alkaline aqueous solution as a developing solution At the time of forming, a washing treatment is usually performed with water after development.

Then, as shown in the schematic cross-sectional view of FIG. 5, the resist pattern 52 is used as an etching mask, and patterning is performed by dry etching so that the removal group group 120 is formed in the first colored layer 11. Thereby, the first coloring pattern 12 is formed. Here, the removal portion group 120 includes a first removal portion group 121 and a second removal portion group 122.

The removal portion group 120 is provided in a checkerboard pattern on the first coloring layer 11. Therefore, the first coloring pattern 12 in which the removal group group 120 is provided in the first coloring layer 11 has a plurality of quadrangular first coloring pixels in a checkerboard shape.

Specifically, when dry etching is performed, the first colored layer 11 is dry-etched using the resist pattern 52 as an etching mask. Representative examples of dry etching include Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. 59-46628, Japanese Patent Laid-Open No. 58-9108, and Japanese Patent Laid-Open No. 58-2809. The methods described in Japanese Patent Application Laid-Open No. 57-148706 and Japanese Patent Application Laid-Open No. 61-41102 are incorporated into the specification of the present application.

From the viewpoint of forming the pattern cross section closer to a rectangle or further reducing damage to the support, the dry etching is preferably performed in the following manner.

Preferably, the form includes the following steps: in the first stage of etching, a mixed gas of fluorine-based gas and oxygen (O ₂ ) is used to etch to a region (depth) where the support body is not exposed; in the second stage of etching, After the above-mentioned first-stage etching, a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) is preferably used to etch to the vicinity (depth) of the exposed area of the support; Over etching. Hereinafter, the specific method of dry etching, the etching in the first step, the etching in the second step, and the over-etching will be described.

Dry etching is performed by obtaining the etching conditions in advance by the following method.

(1) The etching rate (nm / min) of the first-stage etching and the etching rate (nm / min) of the second-stage etching are calculated, respectively.

(2) Calculate the time required for the thickness required for etching in the first-stage etching and the time required for the thickness required for etching in the second-stage etching.

(3) The first-stage etching is performed in accordance with the etching time calculated in the above (2).

(4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Alternatively, the etching time is determined by end point detection, and the second-stage etching is performed in accordance with the determined etching time.

(5) The over-etching time is calculated with respect to the total time of said (3) and (4), and over-etching is performed.

From the viewpoint of processing the organic material to be etched into a rectangular shape, it is preferable that the mixed gas used in the first-step etching step contains a fluorine-based gas and oxygen (O ₂ ). In addition, by setting the etching step in the first stage to a form in which etching is performed to a region where the support body is not exposed, damage to the support body can be avoided.

In addition, in the first-stage etching step, after the etching is performed with a mixed gas of a fluorine-based gas and an oxygen gas to an area where the support body is not exposed, the second-stage etching step is to prevent damage to the support body. And the over-etching step is preferably performed by using a mixed gas of nitrogen and oxygen.

Regarding the ratio of the etching amount in the first-stage etching step to the etching amount in the second-stage etching step, it is important not to damage the first-stage etching step. The method of rectangularity obtained by the etching process in this step is determined. In addition, the ratio of the latter of the total etching amount (the sum of the etching amount in the first step etching step and the etching amount in the second step etching step) is preferably in a range of greater than 0% and 50% or less, More preferably, it is 10% to 20%. The etching amount is an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

The etching preferably includes an over-etching process. The over-etching process is preferably performed by setting an over-etching ratio. The over-etching ratio is preferably calculated based on the etching process time that is performed first. The over-etching ratio can be arbitrarily set. In terms of maintaining the photoresist resistance and the rectangularity of the pattern to be etched, it is preferably 30% or less of the etching processing time in the etching step, and more preferably 5% to 25%. .

Then, as shown in the schematic sectional view of FIG. 6, the resist pattern (that is, the etching mask) 52 remaining after the etching is removed. The removal of the resist pattern 52 preferably includes the steps of applying a peeling solution or a solvent to the resist pattern 52, adjusting the resist pattern 52 to a removable state, and using a washing water to remove the resist pattern 52. Removal steps. For example, a step of applying a peeling solution or a solvent to at least the resist pattern 52 and stopping the resist pattern 52 for a predetermined period of time to perform immersion development may be mentioned. The time for which the peeling solution or the solvent is stagnation is not particularly limited, but it is preferably several tens of seconds to several minutes. In addition, for example, the resist pattern 52 may be sprayed with washing water from a spray type or spray type spray nozzle onto the resist pattern 52.

As the washing water, pure water is preferably used. Examples of the spray nozzle include a spray nozzle that includes the entire support body in its spray range, or a spray nozzle that is a movable spray nozzle and whose movable range includes the entire support body.

Next, as shown in the schematic cross-sectional view of FIG. 7, the second colored radiation-sensitive composition is embedded in each of the removal sections of the first removal section group 121 and the second removal section group 122 to form a plurality of first sections. In the method of coloring pixels, the first coloring layer (that is, the first coloring pattern 12 formed by removing the group 120 in the first coloring layer 11) is laminated with a second coloring radiation-emitting composition. The second colored radiation-sensitive layer 21 (step (C)). As a result, a second colored pattern 22 having a plurality of second colored pixels is formed in the removal portion group 120 of the first colored layer 11. Here, the second colored pixel is a quadrangular pixel. The formation of the second colored radiation-sensitive layer 21 can be performed in the same manner as the step of forming the colored layer using the colored radiation-sensitive composition according to the first embodiment.

The thickness of the second colored radiation-sensitive layer 21 after the post-baking is preferably in a range of 0.1 μm to 1 μm, more preferably in a range of 0.2 μm to 0.8 μm, and even more preferably in a range of 0.3 μm to 0.6 μm.

Next, the second colored radiation-sensitive layer 21 is exposed and developed at a position 21A corresponding to the first removed portion group 121 provided in the first colored layer 11, thereby exposing the second colored radiation-sensitive layer 21. And removing a plurality of second colored pixels 22R provided inside each of the removal sections of the second removal section group 122 (step (D)) (see a schematic cross-sectional view of FIG. 8). This step can be performed in the same manner as the exposure step and pattern formation step in the first embodiment.

Then, as shown in the schematic cross-sectional view of FIG. 9, a third colored radiation-sensitive composition is embedded in each of the removal sections in the second removal section group 122 to form a plurality of third colored pixels. On the first colored layer (that is, on the first removing portion On the first colored pattern 12) in which the second colored pattern 22 is formed in the group 121, a third colored radiation-sensitive composition 31 is formed with a third colored radiation-sensitive composition (step (E)). Thereby, in the second removal portion group 122 of the first colored layer 11, a third colored pattern 32 having a plurality of third colored pixels is formed. Here, the third colored pixel is a quadrangular pixel. The formation of the third colored radiation-sensitive layer 31 can be performed in the same manner as the step of forming the colored layer using the colored radiation-sensitive composition according to the first embodiment.

The thickness of the third colored radiation-sensitive layer 31 after the post-baking is preferably in a range of 0.1 μm to 1 μm, more preferably in a range of 0.2 μm to 0.8 μm, and even more preferably in a range of 0.3 μm to 0.6 μm.

Next, the third colored radiation-sensitive layer 31 is exposed and developed at a position 31A corresponding to the second removed portion group 122 provided in the first colored layer 11, thereby exposing the third colored radiation-sensitive layer 31. As a result, the color filter 100 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is manufactured as shown in the schematic cross-sectional view of FIG. 10 (step (F)). This step can be performed in the same manner as the exposure step and pattern formation step in the first embodiment.

In the color filter of the present invention, the arrangement of the colored patterns is preferably arranged in a so-called checkerboard pattern, that is, a green transmission layer is disposed every other pixel, and a red transmission is disposed every other row between the green transmission layers. Layer and blue transmission layer.

The color filter of the present invention preferably has a thickness of 0.8 μm or less, and more preferably has a thickness of 0.6 μm or less. The color filter of the present invention preferably has a pixel pattern size of 1.4 μm or less, more preferably 0.5 μm to 1.4 μm, and even more preferably 0.5 μm. ~ 1.1 μm. By setting the size of such a pixel pattern, the resolution can be further improved.

Except for the content of the dye in the colored radiation-sensitive composition, the above-mentioned second colored radiation-sensitive composition and the third colored radiation-sensitive composition have the same meaning as the colored radiation-sensitive composition of the first embodiment, and are preferably The range is the same.

The content of the dye in the second colored radiation-sensitive composition and the third colored radiation-sensitive composition is generally 50% by mass or more, and preferably 65% by mass or more, with respect to the total solid content of the colored radiation-sensitive composition. It is more preferably 70% by mass or more. The upper limit of the content of the dye in the color-sensitive radiation composition of the present invention is not particularly limited, but is preferably 95% by mass or less, and more preferably 90% by mass or less.

Preferably, one of the second colored pixel and the third colored pixel is a red transmitting portion, and the other is a blue transmitting portion.

As the coloring agent contained in the coloring composition for forming the red transmitting portion, a dye that is soluble in an organic solvent according to the first embodiment can be used. Moreover, as a coloring agent contained in the coloring composition for forming a red transmission part, you may use a pigment together with the said dye which is soluble in an organic solvent. As the pigment, for example, one or more selected from the following pigments: CI Pigment Orange 2, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17: 1, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 52, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 60, CI Pigment Orange 61, CI Pigment Orange 62, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, and CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 14, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI Pigment Red 52: 1, CI Pigment Red 52: 2, CI Pigment Red 53: 1, CI Pigment Red 57: 1, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 66, CI Pigment Red 67, CI Pigment Red 81: 1, CI Pigment Red 81: 2, CI Pigment Red 81: 3, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90, CI Pigment Red 105, CI Pigment Red 112, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 279.

As the coloring agent contained in the coloring composition for forming the blue transmitting portion, a dye soluble in an organic solvent according to the first embodiment can be used. In addition, as The coloring agent contained in the coloring composition that forms the blue transmission portion can be used in combination with the dye that is soluble in the organic solvent as described above. As the pigment, for example, one or more selected from the group consisting of CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37, and CI Pigment Violet 42 and CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15: 1, CI Pigment Blue 15: 2 , CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 16, Pigment Blue 22. CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Blue 66, CI Pigment Blue 79, CI Pigment Blue 80.

<Solid-state imaging element>

The solid-state imaging element of the present invention includes a color filter obtained by the method for producing a color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration including the color filter for a solid-state imaging device of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

The solid-state imaging element of the present invention has a structure including a plurality of photodiodes and a transmission electrode including polycrystalline silicon and the like on a support having a light-receiving area constituting the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.), Tungsten and the like having openings in only the light receiving portion of the photodiode on the photodiode and the transmission electrode The light-shielding film includes an element protection film including silicon nitride and the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and the color of the solid-state imaging element of the present invention is provided on the element protection film. Filter.

Furthermore, it may be a structure having a light-concentrating mechanism (such as a micro lens, etc. below) on the element protective layer and under the color filter (on the side close to the support), or on the color filter. It has a structure of a light-concentrating mechanism and the like.

<Image display device>

The color filter of the present invention can be used not only for the above-mentioned solid-state imaging element, but also for an image display device such as a liquid crystal display device or an organic EL display device, and is particularly suitable for use in a liquid crystal display device.

When it is used in a liquid crystal display device, it contains a metal complex pigment having excellent spectral characteristics and heat resistance as a colorant, and the liquid crystal molecules with less resistivity are less misaligned, and the hue of a displayed image is good and displayed. Excellent characteristics.

Therefore, the liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good hue and excellent display characteristics.

The definition of the display device or the details of each display device can be referred to, for example, paragraph 0364 of Japanese Patent Application Laid-Open No. 2013-29760, and the contents are incorporated into the specification of the present application.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the present invention does not exceed the gist thereof. In addition, unless otherwise specified, "%" and "part" are the basis of quality.

(Synthesis of dye a, dye b, and dye c) (Synthesis example 1)

The dye a (pigment monomer M1) was obtained by the method described in paragraphs 0413 to 0423 of Japanese Patent Laid-Open No. 2012-158739.

(Synthesis example 2)

A mixed solution of 50 g of dye a, 3.67 g of methacrylic acid, 1.05 g of dodecanethiol, polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), and 50 g of cyclohexanone was prepared. Into a reaction vessel, 50 g of dye a, 3.67 g of methacrylic acid, 1.05 g of dodecanethiol, and 50 g of cyclohexanone were added. Nitrogen was passed through the reaction vessel, and the mixture was kept at 80 ° C. and stirred. The prepared mixed solution was added dropwise thereto over 1 hour, and after stirring for 3 hours, the reaction was stopped. After cooling to room temperature, a solution obtained by mixing the obtained reaction solution with 1038 mL of methanol was added dropwise to 6200 mL of acetonitrile over 20 minutes, and stirred for 10 minutes. The obtained precipitate was filtered and then dried to obtain 70 g of dye b as a dye polymer. The weight average molecular weight (Mw) of the dye b confirmed by GPC measurement was 6,000, and the ratio of weight average molecular weight / number average molecular weight (Mw / Mn) was 2.0. The acid value was 82 mgKOH / g by titration using a 0.1 N sodium hydroxide aqueous solution.

(Synthesis example 3)

15 g of dye b, 2.08 g of glycidyl methacrylate, 0.38 g of tetrabutylammonium bromide, and 0.017 g of p-methoxyphenol were added to 96.8 g of propylene glycol methyl ether acetate, and the mixture was heated and stirred at 100 ° C for 8 hours. The obtained dye solution was added dropwise to a mixed solution of 180 g of acetonitrile and 900 g of ion-exchanged water, and then filtered and dried to obtain 15 g The dye c as a pigment polymer. The weight average molecular weight (Mw) of the dye c confirmed by GPC measurement was 9,000, and the ratio of weight average molecular weight / number average molecular weight (Mw / Mn) was 2.2. The acid value was 28 mgKOH / g by titration using a 0.1 N sodium hydroxide aqueous solution.

The structure of the dye a (pigment monomer M1), the structure of the dye b (formula (101)), and the structure of the dye c (formula (102)) are shown below.

(Synthesis of dye d and dye e)

A dye e, which is a dye polymer having a structure represented by the following formula (103), was synthesized using a dye monomer M2, which is a triphenylmethane dye, as a dye. The following description is detailed Operation.

(Synthesis example 4)

The dye d (pigment monomer M2) was synthesized by a method described in Japanese Patent Laid-Open No. 2000-162429.

Pigment monomer M2 (15g), 2-acrylamido-2-methylpropanesulfonic acid (6.5g), hydroxyethyl methacrylate (23g), methacrylic acid (5.5g), 28% by mass ammonia water ( 2g) and azobisisobutyronitrile (5g) were added to N-ethylpyrrolidone (70g), and they were dissolved by stirring at room temperature for 30 minutes (polymerization solution for dropwise addition).

In addition, pigment monomer M2 (15 g), 2-acrylamido-2-methylpropanesulfonic acid (6.5 g), hydroxyethyl methacrylate (23 g), methacrylic acid (5.5 g), and 28% by mass Aqueous ammonia (2 g) was dissolved in N-ethylpyrrolidone (70 g) and stirred at 95 ° C. The prepared polymerization solution for dropwise addition was added dropwise over 3 hours, and after stirring for 1 hour, azoisobutyronitrile (2.5 g) was added, and the reaction was stopped after 2 hours. After cooling to room temperature, the solvent was distilled off. The weight average molecular weight (Mw) of the obtained copolymer (dye e) was 28,000. According to the titration using a 0.1N sodium hydroxide aqueous solution, the acid value was 190 mgKOH / g.

(Synthesis of dye i)

A dye i having a structure represented by formula (104) was synthesized as follows using a dye monomer M3, which is an anthraquinone dye, as a dye.

Add pigment monomer M3 (8.21g), methacrylic acid (1.08g), dodecyl mercaptan (0.20g), and propylene glycol to the reaction vessel. 1-monomethyl ether 2-acetate (PGMEA) (23.3 g) was heated to 80 ° C. under a nitrogen atmosphere. To this solution, pigment monomer M3 (8.21 g), methacrylic acid (1.08 g), dodecyl mercaptan (0.25 g), and 2,2'-azobis (isobutyric acid) were added dropwise over 2 hours. A mixed solution of dimethyl ester (0.46 g) and PGMEA (23.3 g) (the turbidity of the mixed solution was 8 ppm at room temperature). After stirring for 3 hours, the temperature was raised to 90 ° C., and after heating and stirring for 2 hours, it was left to cool to obtain a PGMEA solution of (MD-1). Next, glycidyl methacrylate (1.42 g), tetrabutylammonium bromide (80 mg), and p-methoxyphenol (20 mg) were added, and heated at 100 ° C for 15 hours in an air environment, and methacrylic acid was confirmed. The glycidyl ester disappeared. After cooling, it was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL to reprecipitate, and 17.6 g of a pigment polymer 13 was obtained. According to GPC measurement, the weight average molecular weight (Mw) was 9,000, and the weight average molecular weight / number average molecular weight (Mw / Mn) ratio was 1.9. In addition, based on a titration using a 0.1N sodium hydroxide aqueous solution, the acid value was 42 mgKOH / g, and the nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) measurement revealed that the pigment polymer 13 (1 g) contained in the pigment polymer The polymerizable group content was 22 mg / g.

(Synthesis of dye j to dye u)

A dye j to a dye u were synthesized in the same manner as the synthesis of the dye i except that the type of the pigment monomer was set as shown in Table 1 below.

In the following Table 1, the pigment monomers M4 to M15 and the formulae (105) to (116) are as follows.

Here, the pigment monomer M4 and the pigment monomer M5 are anthraquinone pigments, the pigment monomer M6 is a squarylium pigment, the pigment monomer M7 is a cyanine pigment, the pigment monomer M8, The pigment monomer M17 is a phthalocyanine pigment, the pigment monomer M9 is a subphthalocyanine pigment, the pigment monomer M10 is a quinophthalone pigment, the pigment monomer M11 is a dibenzopiperan pigment, the pigment monomer M12 to the pigment monomer M15 For azo pigments.

[Chemical 12]

[Chemical 13]

[Chemical 14]

In Table 1 below, the types of pigment monomers (M1 to M15) that can form a pigment structure contained in dyes c to dye u, which are pigment polymers, are described, and the structure of the pigment polymer (formula (101) to Formula (117)) and the acid value and weight average molecular weight (Mw) of the obtained pigment polymer.

[First embodiment]

1) Preparation of primer solution

The following components were mixed and dissolved to prepare a resist solution.

． Propylene glycol monomethyl ether acetate ... 19.20 parts

(PGMEA)

． Ethyl lactate ... 36.67 parts

． Resin ... 30.51

[40% PGMEA solution of benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (Molar ratio = 60: 22: 18)]

． Dipentaerythritol hexaacrylate ... 12.20 parts

(Photopolymerizable compound)

． Polymerization inhibitor (p-methoxyphenol) ... 0.0061 parts

． Fluorine surfactant ... 0.83 parts

(F-475, made by Dainippon Ink Chemical Industry Co., Ltd.)

． Photopolymerization initiator ... 0.586 parts

(TAZ-107 (trihalomethyltriazine-based photopolymerization initiator), manufactured by Bichem Corporation)

2) Fabrication of a silicon wafer substrate (support) with an undercoat layer

An 8-inch silicon wafer was heated in an oven at 200 ° C for 30 minutes. Then, the above-mentioned resist solution was coated on the silicon wafer so that the dry film thickness became 0.5 μm, and further dried by heating in an oven at 220 ° C. for 1 hour to form an undercoat layer to obtain silicon with an undercoat layer. Wafer substrate.

3) Preparation of colored radiation-sensitive composition

A compound having the following composition was mixed and dissolved to prepare a colored radiation-sensitive composition.

The dipentaerythritol hexaacrylate was purified using a column beforehand.

Preparation of colored radiation-sensitive composition

The compounds represented by the following compositions are mixed and dissolved to prepare a color-sensitive radiation composition for use in the present invention.

[Composition of colored curable composition]

． Cyclohexanone ... 88 servings

． Organic solvent-soluble dyes

Dye (X) ... x

Dye (Y) ... y

． Polymerization inhibitor: p-methoxyphenol ... 0.01 parts

． Photocurable compound: dipentaerythritol hexaacrylate ... 1.4 parts

． Photopolymerization initiator: IRGACURE OXE 02 (manufactured by Ciba Specialty Chemicals) ... 0.8 parts

4) Evaluation of coating, exposure, development, developability of unexposed portions, and pattern rectangularity of the color-sensitive radiation composition

The undercoat layer of the silicon wafer substrate with an undercoat layer obtained in the above 2) was coated with the composition obtained in the above 3) to form a photocurable coating film. The coating film was subjected to a heat treatment (pre-baking) for 120 seconds using a hot plate at 100 ° C so that the dry film thickness of the coating film became 0.4 µm.

Next, an i-ray stepper exposure device FPA-3000i5 + (manufactured by Canon) was used, which was masked at a wavelength of 365 nm through an island pattern with a square pattern of 0.9 μm at 50 mJ / cm ^In the range of ² to 2500 mJ / cm ² , the exposure amount was changed in units of 50 mJ / cm ² and irradiation was performed. After that, the irradiated silicon wafer substrate on which the coating film was formed was placed on a horizontal rotary table of a spin-spray developing machine (type DW-30; manufactured by Chemitronics) and used. The solvent described in the table was immersed and developed at 23 ° C for 30 seconds to form a colored pattern on a silicon wafer substrate.

The evaluation of the developability and pattern rectangularity of the unexposed area was performed using a scanning electron microscope (SEM) at 25,000 times. The shadowed pattern was evaluated according to the following evaluation criteria.

-Evaluation criteria for developability of unexposed areas-

A: Unexposed parts can be completely removed.

B: There is almost no residue in the unexposed portion.

C: Although there is a little residue, it is within the allowable range.

D: The residue is too much to be tolerated.

-Evaluation criteria for pattern rectangularity-

A: A square island pattern of 0.9 μm can be formed in a rectangular shape.

B: A square island pattern of 0.9 μm is slightly arc-shaped.

C: A square island pattern of 0.9 μm has an arc but is within an allowable range.

D: The square island pattern of 0.9 μm is rounded and unacceptable.

5) Evaluation of coating, exposure, and decoloring resistance of a colored radiation-sensitive composition

Using a spin coater, apply the colored radiation-sensitive composition obtained in the above 3) to the undercoat layer of the glass substrate with an undercoat layer obtained in the above 2) so that the film thickness becomes 0.4 μm. Pre-bake at 120 ° C for 120 seconds.

Then, the coating film was irradiated with an exposure device with a wavelength of 365 nm at an exposure amount of 2000 mJ / cm ² , and the obtained sample was used as a sample.

The coating films obtained in the respective examples and comparative examples were evaluated for decoloring resistance as follows.

The spectrum (spectrum A) of each coating film after the measurement after baking. Then, this coating film was immersed in cyclohexane for one minute, and the spectrum (spectrum B) was measured again. According to the obtained spectrum A and spectrum B were calculated by evaluating the dye residual ratio (%; B / A × 100). The closer this value is to 100%, the better the resistance. The results are shown in the following table.

In the following table, the mixed solvent A represents heptane / diisopropyl ketone = 50% by weight / 50% by weight. The mixed solvent B represents γ-butyrolactone (γBL) / water = 75% by weight / 25% by weight. The mixed solvent C represents methanol / water = 75% by weight / 25% by weight. In addition, the addition amount of the pigment dispersion liquid of the comparative example 1 and the comparative example 2 was adjusted so that it might become 9.8 parts as a pigment solid content. CV-2000 represents an aqueous alkaline developer (manufactured by FUJIFILM Electronic Materials).

It is clear from the above table that according to the present invention, the colored layer is formed using the following colored radiation-sensitive composition, and the colored layer is exposed to a pattern through a mask, and the exposed colored layer is developed using a developer containing an organic solvent. The developed color filter has good rectangularity (pattern shape), and the colored radiation-sensitive composition contains a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent. The total solid content of the colored radiation-sensitive composition contains 65% by mass or more of a dye. It was also found that the developability of the unexposed portion of the obtained color filter was also good, and the decoloring resistance was also good.

[Second embodiment] <Dry etching>

-Preparation of Green Pigment Dispersion-

A bead mill was used to mix and disperse the following mixed liquid for 15 hours to prepare a green pigment dispersion liquid. The mixed liquid contained Pigment Green 36 (8.6 parts) and Pigment Yellow 185 as phthalocyanine pigments. Pigment (5.7 Parts) as a pigment, and derivative A (the following compound) (1.4 parts) as a pigment derivative, dispersant A (the following compound) (4.3 parts) as a dispersing resin, and propylene glycol monomethyl ether ethyl as a solvent Acid ester (PGMEA, 80 parts).

<Preparation of green pigment-containing composition (coating liquid)>

Using the green pigment dispersion, mix and stir so as to have the following composition. Stir to prepare a colored radiation-sensitive composition.

<Composition>

． Pigment dispersion: 85.0 parts of the above green pigment dispersion

． Hardening compound: Additive A (the following compound) 3.24 parts

． Solvent: PGMEA 8.76 parts

． Surfactant: F-781 (manufactured by DIC) (polymeric surfactant: PGMEA 0.2% solution with a mass average molecular weight of 30,000 and a solid content acid value of 0 mgKOH / g) 3.0 parts

Preparation of colored radiation-sensitive composition other than green

The compound represented by the following composition is mixed and dissolved to prepare a color-sensitive radiation composition for use in the present invention.

[Composition of coloring radiation-sensitive composition]

． Cyclohexanone ... 88 servings

． Organic solvent-soluble dyes

Exemplified compound (X) ... x parts

Exemplified compound (Y) ... y parts

． Polymerization inhibitor: p-methoxyphenol ... 0.01 parts

． Photocurable compound: dipentaerythritol hexaacrylate ... 1.4 parts

． Photopolymerization initiator: IRGACURE OXE 02 (manufactured by Ciba Specialty Chemicals) ... 0.8 parts

(Comparative Example: Preparation of Red Pigment Dispersion Liquid R1)

A bead mill was used to mix and disperse the following mixed liquid for 15 hours to prepare a red pigment dispersion liquid R1. The mixed liquid contained Pigment Red 254 (8.3 parts) and Pigment Yellow 139 (Pigment Yellow) 139 ( 3.7 parts), BYK-161 (manufactured by BYK) (4.8 parts) as a pigment dispersant, and PGMEA (83.2 parts).

(Comparative Example: Preparation of Blue Pigment Dispersion B1)

A bead mill was used to mix and disperse the following mixed liquid for 15 hours to prepare a blue pigment dispersion liquid B1. The mixed liquid contained Pigment Blue 15: 6 (9.5 parts) and Pigment Violet as a pigment. ) 23 (2.4 parts), BYK-161 (manufactured by BYK) (5.6 parts) as a pigment dispersant, and PGMEA (82.5 parts).

<Green pattern (green pixel) formation step by dry etching> (Formation of green layer)

The coloring composition for green filter formation of an Example or a comparative example was apply | coated on the glass wafer by the spin coater so that it might become a coating film with a film thickness of 0.40 micrometer, and it dried at 100 degreeC using the hot plate After drying for 180 seconds, a green layer was formed by performing a heat treatment (post-baking) for 480 seconds using a 200 ° C. hot plate. The green The thickness of the color layer was 0.36 μm.

(Coating of resist for mask)

Next, a positive photoresist "FHi622BC" (manufactured by FUJIFILM Electronic Materials) was coated on the green layer, and pre-baking was performed to form a photoresist layer having a film thickness of 0.8 μm.

(Pattern exposure and development of mask resist)

Next, pattern exposure was performed on the photoresist layer using an i-ray stepper (manufactured by Canon) with an exposure amount of 350 mJ / cm ² , and the photoresist layer was subjected to a temperature at which the temperature of the photoresist layer or the ambient temperature reached 90 ° C. 1 minute heat treatment. Thereafter, a developing solution "FHD-5" (manufactured by FUJIFILM Electronic Materials) was subjected to a development process for 1 minute, and then a post-baking process was performed at 110 ° C for 1 minute to form a resist pattern. In consideration of the difference in etching conversion (reduction in the pattern width due to etching), this resist pattern is a pattern in which square-shaped resist films formed with a side of 0.90 μm are arranged in a checkerboard pattern.

(Dry etching)

Then, using the resist pattern as an etching mask, the green layer was dry-etched in the following order.

Using a dry etching device (Hitachi High-Technologies, U-621), the radio frequency (RF) power is set to 800W, the antenna bias is set to 400W, and the wafer bias is set. Set 200W, the internal pressure of the chamber to 4.0Pa, the substrate temperature to 50 ° C, the gas type and flow rate of the mixed gas to 80 mL / min. For CF ₄ , 40 mL / min. For O ₂ , and 800 mL for Ar. / min., the first-stage etching process was performed for 80 seconds.

The cutting amount of the green layer under this etching condition was 356 nm (89% of the etching amount), and it was in a state having a residual film of about 44 nm.

Then, in the same etching chamber, the RF power was set to 600W, the antenna bias was set to 100W, the wafer bias was set to 250W, the internal pressure of the chamber was set to 2.0Pa, the substrate temperature was set to 50 ° C, and the The gas type and flow rate are set to 500 mL / min. For N ₂ , 50 mL / min. For O ₂ , and 500 mL / min. For Ar. (N ₂ / O ₂ / Ar = 10/1/10). The etching rate was set to 20%, and the second-stage etching process and over-etching process were performed.

The etching rate of the green layer under the etching conditions in the second stage is 600 nm / min or more, and it takes about 10 seconds to etch the residual film of the green layer. 80 seconds of the etching time in the first stage and 10 seconds of the etching time in the second stage were added to calculate the etching time. As a result, the etching time was 80 + 10 = 90 seconds, the over-etching time was 90 × 0.2 = 18 seconds, and the total etching time was set to 90 + 18 = 108 seconds.

After performing dry etching under the above conditions, use a photoresist stripping solution "MS230C" (FUJIFILM Electronic Materials) (Manufactured by the company), performing a 120-second peeling process to remove the resist pattern, and then performing washing with pure water and spin-drying. Thereafter, a dehydration baking treatment was performed at 100 ° C for 2 minutes. By the above operation, a green pattern obtained by arranging square green pixels having a side of 0.9 μm in a checkerboard pattern was obtained.

In the above step of forming a green pattern (green pixel) using dry etching In step>, green patterns each prepared by using the green coloring composition for forming a green filter for each example and having a square green pixel with a side of 0.9 μm arranged in a checkerboard pattern are prepared. A method of burying a color-sensitive radiation composition for forming a red filter in each of the removal portions of the green pattern, and coloring the color for forming a red filter so that the thickness after drying and post-baking becomes 0.36 μm. A radiation-sensitive composition is coated on the green pattern to obtain a laminated color filter (corresponding to the state of FIG. 7) obtained by forming a red radiation-sensitive layer on the green layer.

The red radiation-sensitive layer of the laminated color filter thus obtained was pattern-exposed using an i-ray stepper (manufactured by Canon (KK)) at an exposure amount of 350 mJ / cm ² . Here, the exposure area is an area corresponding to the removal portion located in an even-numbered line in the checkerboard pattern of the green pattern (corresponding to the second color-sensitive radiation layer 21 and the first color layer 11 provided in the first color layer 11 The position 21A (refer to FIG. 7) corresponding to the 1 removal section group 121).

Next, the laminated color filter after the exposure was placed on a horizontal rotary table of a rotary-spray developing machine (type DW-30, manufactured by Chemitronics), using a solution containing the components described in the following table. The solvent developer was immersed and developed at 23 ° C for 60 seconds. Thereafter, the color filter is fixed on the horizontal rotary table by a vacuum chuck method, while the color filter is rotated at a speed of 50 rpm by a rotating device, and from above the center of rotation, from the ejection nozzle to spray Pure water was supplied in the form of a shower to perform a rinsing treatment, followed by spray drying.

Through the above operations, a color filter precursor (equivalent to the state shown in FIG. 8) is obtained, and the color filter precursor is a red-radiating layer that laminates the color filters, And the red pixels set inside the removing portion of the odd-numbered rows in the checkerboard pattern of the green pattern are removed.

Next, a blue color filter-forming colored radioactive composition was embedded in each of the removal portions of the green pattern of the color filter precursor, and the thickness after drying and post-baking was 0.40 μm. In a method, a colored radiation-sensitive composition for forming a blue filter is coated on the color filter precursor, and a laminated color filter (equivalent to a blue-ray radiation layer formed on a green layer) is obtained. (In the state of FIG. 9).

The blue radiation-sensitive layer of the laminated color filter thus obtained was pattern-exposed using an i-ray stepper (manufactured by Canon (KK)) at an exposure amount of 350 mJ / cm ² . Here, the exposed area is an area corresponding to the removal portion located on an odd-numbered line in the checkerboard pattern of the green pattern (corresponding to the third color-sensitive radiation layer 31 and the first color layer 11 provided in the first color layer 11). 2A 31A (see FIG. 9) corresponding to the removal group group 122.

Next, the laminated color filter after the exposure was placed on a horizontal rotary table of a rotary-spray developing machine (type DW-30, manufactured by Chemitronics), using a solution containing the components described in the following table. The solvent developer was immersed and developed at 23 ° C for 60 seconds. Thereafter, the color filter is fixed on the horizontal rotary table by a vacuum chuck method, while the color filter is rotated at a speed of 50 rpm by a rotating device, and from above the center of rotation, from the ejection nozzle to spray Pure water was supplied in a shower form to perform a rinse treatment, followed by spray drying.

By the above operation, a blue-sensitive radiation layer obtained by stacking color filters is obtained. The removed color filter (equivalent to the state of FIG. 10).

The evaluation of the unexposed area developability and pattern rectangularity was performed by observing the developed pattern at 25,000 times using an SEM, and the evaluation was performed according to the following evaluation criteria.

The evaluation of the discoloration resistance of the colored radiation-sensitive composition was performed in the same manner as in "5) Evaluation of the coating, exposure, and decolorization resistance of the colored radiation-sensitive composition in the first example described above.

The results are shown in the following table.

-Evaluation criteria for developability of unexposed areas-

A: Unexposed parts can be completely removed.

B: There is almost no residue in the unexposed portion.

C: Although there is a little residue, it is within the allowable range.

D: The residue is too much to be tolerated.

-Evaluation criteria for pattern rectangularity-

A: A square island pattern of 0.9 μm can be formed in a rectangular shape.

B: The square island pattern of 0.9 μm is slightly arc-shaped but within the allowable range.

C: The square island pattern of 0.9 μm is rounded and unacceptable.

In the following table, the mixed solvent A represents heptane / diisopropyl ketone = 50% by weight / 50% by weight. The mixed solvent B represents γ-butyrolactone (γBL) / water = 75% by weight / 25% by weight. The mixed solvent C represents methanol / water = 75% by weight / 25% by weight. In addition, the addition amount of the pigment dispersion liquid of the comparative example 1 and the comparative example 2 was adjusted so that it might become 9.8 parts as a pigment solid content. In addition, CV-2000 indicates an aqueous alkaline developer (FUJIFILM Electronic Materials). Manufacturing).

It is clear from the above table that according to the present invention, the first colored layer obtained from the colored composition is patterned to form a colored pattern by dry etching, and the patterned first colored layer is The method of forming other colored patterns is patterned by photolithography. In the step of patterning by photolithography, a coloring containing a dye, a polymerizable compound, and a photopolymerization initiator soluble in an organic solvent is used. The radiation-sensitive composition is used to form a colored layer, the colored layer is exposed to a pattern through a mask, and the exposed colored layer is developed using a developing solution containing an organic solvent, whereby the rectangularity of the pattern of the color filter obtained (Pattern shape) Good. It was also found that the developability of the unexposed portion of the obtained color filter was also good, and the decoloring resistance was also good.

10‧‧‧Solid Photographic Element

13‧‧‧ color filters

14‧‧‧ flattening film

15‧‧‧ micro lens

20B, 20G, 20R‧‧‧ pixels

41‧‧‧P Well

42‧‧‧Light receiving element (light diode)

43‧‧‧ impurity diffusion layer

44‧‧‧ electrode

45‧‧‧Wiring layer

46‧‧‧BPSG film

47‧‧‧ insulating film

48‧‧‧P-SiN film

49‧‧‧ flattening film

Claims (21)

A method for manufacturing a color filter, comprising: (a) forming a colored layer using a color-sensitive radiation composition containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent; (b) ) A step of exposing the colored layer into a pattern through a barrier mask; and (c) a step of developing the exposed colored layer using a developer containing an organic solvent, and developing a total solid of the colored radiation-sensitive composition The component contains 65% by mass or more of the above-mentioned organic solvent-soluble dye, and the entire water content of the developing solution is 30% by mass or less, and the concentration of the organic solvent is 70% by mass or more. The method for manufacturing a color filter according to item 1 of the scope of the patent application, wherein the dye soluble in the organic solvent is a pigment polymer. The method for manufacturing a color filter according to item 1 or item 2 of the scope of patent application, wherein the developer containing the organic solvent contains 95% by mass or more of an organic solvent. The method for manufacturing a color filter according to item 1 or item 2 of the scope of patent application, wherein the solubility parameter (SP) value of the developer containing the organic solvent is 15.1 to 18.9 or 23.1 to 42.0. The method for manufacturing a color filter according to item 1 or item 2 of the scope of patent application, wherein the SP value of the developer containing the organic solvent is 15.1 to 17.5 or 30.0 to 42.0. The method for manufacturing a color filter according to item 3 of the scope of patent application, wherein the SP value of the developer containing the organic solvent is 15.1 to 18.9 or 23.1 to 42.0. The method for manufacturing a color filter according to item 3 of the scope of patent application, wherein the SP value of the developer containing the organic solvent is 15.1 to 17.5 or 30.0 to 42.0. A method for manufacturing a color filter, which is a method for manufacturing a color filter having a plurality of coloring layers formed on a substrate, and includes a step of forming a first coloring layer obtained from a coloring composition; A step of patterning the first colored layer to form a colored pattern by etching; and a step of patterning by light lithography on the patterned first colored layer to form another colored pattern by light lithography, The step of patterning by photolithography includes: (a) the step of forming the colored layer using a color-sensitive radiation composition containing a dye, a polymerizable compound, and a photopolymerization initiator that are soluble in an organic solvent; (B) a step of exposing the coloring layer into a pattern through a barrier mask; and (c) a step of developing the exposed coloring layer using a developer containing an organic solvent, and the overall moisture content of the developer The concentration is 30% by mass or less, and the concentration of the organic solvent is 70% by mass or more. The method for manufacturing a color filter according to item 8 of the scope of patent application, wherein in the total solid content of the coloring radiation-sensitive composition, the coloring The radioactive composition contains 65% by mass or more of the above-mentioned dyes soluble in an organic solvent. The method for manufacturing a color filter according to item 8 or item 9 of the scope of patent application, wherein the dye soluble in the organic solvent is a pigment polymer. The method for manufacturing a color filter according to item 8 or item 9 of the scope of patent application, wherein the developer containing the organic solvent contains 95% by mass or more of an organic solvent. The method for manufacturing a color filter according to item 8 or item 9 of the scope of patent application, wherein the SP value of the developer containing the organic solvent is 15.1 to 18.9 or 23.1 to 42.0. The method for manufacturing a color filter according to item 8 or item 9 of the scope of patent application, wherein the SP value of the developer containing the organic solvent is 15.1 to 17.5 or 30.0 to 42.0. The method for manufacturing a color filter according to item 8 or item 9 of the scope of patent application, wherein the first colored layer is a green transmission layer. The method for manufacturing a color filter according to item 10 of the scope of patent application, wherein the developer containing an organic solvent contains 95% by mass or more of an organic solvent. The method for manufacturing a color filter according to item 10 of the scope of the patent application, wherein the SP value of the developer containing the organic solvent is 15.1 to 18.9 or 23.1 to 42.0. The method for manufacturing a color filter according to item 10 of the scope of patent application, wherein the first colored layer is a green transmission layer. The method for manufacturing a color filter according to item 11 of the scope of patent application, wherein the SP value of the developer containing the organic solvent is 15.1 to 18.9 or 23.1 to 42.0. The method for manufacturing a color filter according to item 11 of the scope of patent application, wherein the first colored layer is a green transmission layer. A color filter obtained by the method for manufacturing a color filter according to any one of claims 1 to 19 in the scope of patent application. A solid-state imaging element has a color filter as described in claim 20 of the scope of patent application.