JP2023053991A - Structure production method, color filter production method, solid state imaging element production method, and image display device production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a structure production method, a color filter production method, a solid state imaging element production method, and an image display device production method.

SOLUTION: A structure production method includes the steps of: coating a coloring photosensitive composition on a support provided with a plurality of regions divided by partition walls to form a coloring photosensitive composition layer over the support including the interior of the regions divided by the partition walls; exposing the coloring photosensitive composition layer formed on the support to light in a patterned manner; and using a development solution to develop/eliminate the coloring photosensitive composition layer in non-exposed portions to form pixels in the regions divided by the partition walls. In the structure production method, an alkali water solution containing 0.02 to 0.22 mass% of an alkaline agent and a chelator as the development solution. A color filter production method, a solid state imaging element production method, and an image display device production method, which includes the structure production method, are provided.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to a method of manufacturing a structure in which pixels are formed in regions partitioned by partition walls. The present invention also relates to methods for manufacturing color filters, solid-state imaging devices, and image display devices.

2. Description of the Related Art In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements.

A color filter is formed, for example, by forming a colored photosensitive composition layer on a support using a colored photosensitive composition, exposing the colored photosensitive composition layer in a pattern, and then using a developer to form an unexposed area. is developed and removed to form pixels. As a developer, an alkaline aqueous solution containing an alkaline agent and a chelating agent is known, as described in Patent Documents 1 and 2 (see Patent Documents 1 and 2).

JP-A-03-198046 JP-A-2000-162785

When forming pixels by performing exposure and development, it is desired that there be little development residue and that the surface roughness of the surface of the pixels after development is small.

Further, in recent years, attempts have been made to provide partition walls between pixels to improve the light collecting property of the light transmitted through the pixels, or to prevent color mixture with adjacent pixels. When forming pixels between partition walls, a higher standard is required for the rectangularity of the formed pixels.

Moreover, in recent years, solid-state imaging devices are sometimes used in harsher environments. Along with this, there is a demand for color filters used in solid-state imaging devices that have excellent characteristics in terms of temperature cycle resistance. Here, "temperature cycle resistance" means the degree of adhesion of a pixel to a support when the pixel formed on the support is subjected to cycles of repeated high and low temperatures.

According to the studies of the present inventors, when pixels are formed in regions partitioned by partition walls using a conventionally known developing solution, it is difficult to bring these characteristics side by side at a high level. Do you get it.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for manufacturing a structure capable of suppressing development residue, forming pixels with small surface roughness, excellent rectangularity and temperature cycle resistance in regions partitioned by partition walls. , a method for manufacturing a color filter, a method for manufacturing a solid-state imaging device, and a method for manufacturing an image display device.

As a result of extensive studies, the inventors of the present invention have found that the above object can be achieved by the method described below, and have completed the present invention. Accordingly, the present invention provides the following.
<1> A colored photosensitive composition is applied onto a support provided with a plurality of regions partitioned by partition walls to form a colored photosensitive composition layer on the support including the regions partitioned by the partition walls. process and
a step of patternwise exposing a colored photosensitive composition layer formed on a support;
A step of developing and removing the colored photosensitive composition layer in the unexposed areas using a developer to form pixels in the regions partitioned by the partition walls;
A method of manufacturing a structure comprising
A method for producing a structure, wherein an alkaline aqueous solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent is used as a developer.
<2> The method for producing a structure according to <1>, wherein the developer contains 0.10 to 0.18% by mass of an alkaline agent.
<3> The method for producing a structure according to <1> or <2>, wherein the developer contains 0.01 to 0.20% by mass of a chelating agent.
<4> The method for producing a structure according to any one of <1> to <3>, wherein the alkaline agent is an organic base compound.
<5> The method for producing a structure according to any one of <1> to <4>, wherein the developer further contains a surfactant.
<6> The method for producing a structure according to <5>, wherein the surfactant is a nonionic surfactant.
<7> The method for producing a structure according to <6>, wherein the nonionic surfactant is a compound having an alkyl group having 10 to 20 carbon atoms.
<8> The method for producing a structure according to <6>, wherein the nonionic surfactant is a compound having an alkyl group having 12 to 15 carbon atoms.
<9> The method for producing a structure according to any one of <6> to <8>, wherein the nonionic surfactant is a compound containing a polyoxyalkylene structure.
<10> The method for producing a structure according to any one of <1> to <9>, wherein the colored photosensitive composition contains 30 to 70% by mass of a colorant in the total solid content.
<11> The colored photosensitive composition contains a resin having an acid value of 10 to 100 mgKOH/g and an ethylenically unsaturated bond value of 1.0 to 2.0 mmol/g, <1> to <10> A method for manufacturing a structure according to any one of .
<12> The method for producing a structure according to any one of <1> to <11>, wherein the colored photosensitive composition contains a polymerizable compound having 6 or more polymerizable groups.
<13> Any one of <1> to <12>, wherein after forming an organic layer on the surface of the partition wall, a colored photosensitive composition is applied onto the support to form the colored photosensitive composition layer. 10. A method of manufacturing the structure according to claim 1.
<14> The method for producing a structure according to <13>, wherein the organic layer is formed on the partition walls using an organic layer-forming composition containing a compound having an ethylenically unsaturated bond group.
<15> A method for producing a color filter, including the method for producing the structure according to any one of <1> to <14>.
<16> A method for manufacturing a solid-state imaging device, including the method for manufacturing the structure according to any one of <1> to <14>.
<17> A method for manufacturing an image display device, including the method for manufacturing the structure according to any one of <1> to <14>.

According to the present invention, a method for manufacturing a structure capable of suppressing development residue, forming pixels with small surface roughness, excellent rectangularity and temperature cycle resistance in a region partitioned by partition walls, A method for manufacturing a color filter, a method for manufacturing a solid-state imaging device, and a method for manufacturing an image display device can be provided.

FIG. 4 is a plan view of the support as seen from directly above; FIG. 2 is a cross-sectional view taken along the line AA of FIG. 1; It is a figure which shows the state which formed the coloring photosensitive composition layer. It is a figure which shows the state which formed the pixel in the area|region divided by the partition. It is a figure which shows the state which each formed the pixel of each color in the area|region divided by the partition.

The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, a (meth)allyl group represents both or either allyl and methallyl, and "(meth)acrylate" represents both or either acrylate and methacrylate, and "(meth) "Acrylic" represents both or either of acrylic and methacrylic, and "(meth)acryloyl" represents both or either of acryloyl and methacryloyl.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, infrared light refers to light with a wavelength of 700 to 2500 nm.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "process" does not refer only to an independent process, and even if it cannot be clearly distinguished from other processes, the term can be used as long as the intended action of the process is achieved. included.

<Method for manufacturing structure>
The method for manufacturing the structure of the present invention comprises:
A step of applying a colored photosensitive composition onto a support provided with a plurality of regions partitioned by partition walls to form a colored photosensitive composition layer on the support including the regions partitioned by the partition walls;
a step of patternwise exposing a colored photosensitive composition layer formed on a support;
a step of developing and removing the colored photosensitive composition layer in the unexposed areas using a developer to form pixels in the regions partitioned by the partition walls;
The developer is characterized by using an alkaline aqueous solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent.

According to the present invention, an alkaline aqueous solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent is used as a developer to develop and remove the colored photosensitive composition layer in the unexposed area, It is possible to form pixels that suppress development residues, have small surface roughness, and are excellent in rectangularity and temperature cycle resistance in the regions partitioned by the partition walls.

In the method for manufacturing a structure of the present invention, a support having partition walls on its surface and partitioning the surface of the support into a plurality of regions by the partition walls is used. First, a support having partition walls will be described with reference to the drawings. FIG. 1 is a plan view of the support 1 viewed from directly above, and FIG. 2 is a cross-sectional view taken along the line AA of FIG.

1 and 2, reference numeral 1 is a support. The material for the support 1 is not particularly limited. It can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, an undercoat layer may be provided on the silicon substrate for improving the adhesion with the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.

As shown in FIGS. 1 and 2, partition walls 2 are provided on the support 1 , and the surface of the support 1 is partitioned into a plurality of regions by the partition walls 2 . The above-mentioned "area" means a space surrounded by partition walls on the support. The partition wall 2 may be provided in direct contact with the support 1 . In addition, when an undercoat layer is provided on the support 1, partition walls may be provided on the undercoat layer. In FIGS. 1 and 2, the shape of the region surrounded by the partition walls 2 on the support 1 (hereinafter also referred to as the shape of the opening of the partition walls) is rectangular. good. For example, a circular shape, an elliptical shape, a polygonal shape with pentagons or more, and the like can be mentioned.

The material of the partition wall 2 is not particularly limited. Examples include organic materials such as siloxane resins and fluorine resins, and inorganic particles such as silica particles. As the silica particles, those in which a plurality of spherical silica particles are linked in a beaded shape are preferably used. In this specification, the term “spherical” means that the shape may be substantially spherical, and may be deformed within the scope of the effects of the present invention. For example, it includes a shape having unevenness on the surface and a flat shape having a long axis in a predetermined direction. Moreover, "a plurality of spherical silica particles are linked in a beaded shape" means a structure in which a plurality of spherical silica particles are linked in a linear and/or branched form. For example, there is a structure in which a plurality of spherical silica particles are connected to each other by a junction having an outer diameter smaller than that of the spherical silica particles. In addition, in the present invention, the structure in which "a plurality of spherical silica particles are connected in a beaded shape" includes not only a structure connected in a ring shape but also a chain-like structure having an end. It also includes structures that are Moreover, the partition wall 2 can also be formed using a composition containing colloidal silica particles described in WO2019/017280.

Moreover, the partition wall 2 may be made of a metal such as tungsten or aluminum. Alternatively, a laminate of a metal and a black matrix may be used. In the case of the laminate, the order of lamination of the metal and the black matrix is not particularly limited.

The height H1 of the partition wall 2 is preferably 0.3 to 1.2 μm. The lower limit is preferably 0.35 μm or more, more preferably 0.4 μm or more. The upper limit is preferably 1.1 μm or less, more preferably 1.0 μm or less, and even more preferably 0.8 μm or less.

The width W1 of the partition wall 2 is preferably 0.05 to 0.2 μm. The lower limit is preferably 0.06 μm or more, more preferably 0.08 μm or more, and even more preferably 0.10 μm or more. The upper limit is preferably 0.18 μm or less, more preferably 0.15 μm or less, and even more preferably 0.12 μm or less.

The ratio of the height H1 to the width W1 of the partition wall 2 (height H1/width W1) is preferably 1.5 to 20.0. The lower limit is preferably 1.8 or more, more preferably 2.0 or more, and even more preferably 4.0 or more. The upper limit is preferably 15.0 or less, more preferably 10.0 or less, and even more preferably 8.0 or less.

The pitch width P1 of the partition walls 2 is preferably 0.5 to 2.0 μm. The lower limit is preferably 0.6 μm or more, more preferably 0.7 μm or more, and even more preferably 0.8 μm or more. The upper limit is preferably 1.8 μm or less, more preferably 1.4 μm or less, and even more preferably 1.2 μm or less. The pitch width P1 of the partition walls 2 is the arrangement pitch of adjacent partition walls. As the pitch width P1 becomes shorter, the pixel size becomes smaller. Although there is a tendency that the smaller the size of the formed pixel is, the more easily the temperature cycle resistance is lowered, according to the present invention, excellent temperature cycle resistance can be obtained even if the size of the formed pixel is small. Therefore, when the pitch width P1 of the partition walls 2 is narrow and the pixel size to be formed is small, the effect of the present invention is exhibited remarkably.

An organic layer may be provided on the surface of the partition wall 2 . The organic layer can be formed by applying a composition for forming an organic layer onto the partition walls and drying the composition. The organic layer is preferably a layer formed using an organic layer-forming composition containing a compound having an ethylenically unsaturated bond group. According to this aspect, the adhesion between the organic layer and the pixels can be enhanced, and better moisture resistance and temperature cycle resistance can be obtained. The composition for forming an organic layer will be described later.

The partition wall 2 can be formed using a conventionally known method. For example, the partition wall 2 can be formed as follows. First, a barrier rib material layer is formed on a support. The partition wall material layer can be formed, for example, by coating a composition containing inorganic particles such as silica particles on a support and then curing the composition to form a film. Such compositions include optical functional layer-forming compositions described in paragraphs 0012 to 0133 of WO 2015/190374, the contents of which are incorporated herein. In addition, the barrier rib material layer can be formed by depositing an inorganic material such as silicon dioxide on the support by a deposition method such as chemical vapor deposition (CVD) or vacuum deposition, or a method such as sputtering. Next, a resist pattern is formed on the barrier rib material layer using a mask having a pattern along the shape of the barrier rib. Next, using this resist pattern as a mask, the barrier rib material layer is etched to form a pattern. The etching method includes a dry etching method and a wet etching method. Etching by the dry etching method can be performed under the conditions described in paragraphs 0114 to 0120, 0129, and 0130 of JP-A-2016-014856. Next, the resist pattern is removed from the barrier rib material layer. The partition wall 2 can be formed in this way.

In the method for producing a structure of the present invention, as shown in FIG. A colored photosensitive composition layer 10 is formed on the support 1 including the region. As the colored photosensitive composition, one containing a polymerizable compound, a photopolymerization initiator, and a resin is preferably used. Types of the colored photosensitive composition include, for example, a pixel-forming composition selected from red pixels, green pixels, blue pixels, yellow pixels, cyan pixels, magenta pixels, transparent pixels, infrared-transmitting pixels, and light-shielding pixels. A pixel-forming composition selected from red pixels, green pixels and blue pixels is preferred. Details of the colored photosensitive composition will be described later. In this specification, the concept of "coloration" in the colored photosensitive composition includes "transparency".

A known method can be used as a method for applying the colored photosensitive composition. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, as a method for applying the colored photosensitive composition, the methods described in WO2017/030174 and WO2017/018419 can also be used, the contents of which are incorporated herein.

The colored photosensitive composition layer 10 formed on the support 1 may be dried (pre-baked). When pre-baking is performed, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher. The pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

Next, the colored photosensitive composition layer 10 formed on the support is exposed in a pattern (exposure step). For example, the colored photosensitive composition layer 10 can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferred. A long-wave light source of 300 nm or more can also be used.

The dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be selected as appropriate, and in addition to exposure in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free) or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m ² to 100000 W/m ² (eg, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). can be done. The oxygen concentration and exposure illuminance may be appropriately combined. For example, the illuminance may be 10000 W/m ² at an oxygen concentration of 10% by volume and 20000 W/m ² at an oxygen concentration of 35% by volume.

Next, a developing solution is used to develop and remove the colored photosensitive composition layer 10 in the unexposed areas to form pixels in the regions partitioned by the partition walls (developing step). As a result, the unexposed portion of the colored photosensitive composition layer in the exposure step is eluted into the developer, leaving only the photocured portion.

In the present invention, an alkaline aqueous solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent is used as a developer. By developing with such a developer, it is possible to suppress the development residue and form pixels with small surface roughness, rectangularity and temperature cycle resistance in the regions partitioned by the partition walls. . Although the detailed reason is unknown, by making the content of the alkaline agent in the alkaline aqueous solution 0.02 to 0.22% by mass and further containing the chelating agent, excellent developability can be obtained and development can be achieved. It is presumed that pixels with reduced residue, small surface roughness, and excellent rectangularity could be formed. Furthermore, it is presumed that part of the chelating agent permeates into the film during development, thereby relieving the stress applied to the film during the temperature cycle test, and as a result, it is presumed that excellent temperature cycle resistance was obtained. Further, when the content of the chelating agent is 0.01 to 0.20% by mass, in addition to the above properties, excellent moisture resistance can be obtained. Although the detailed reason is unknown, even if a part of the chelating agent permeates into the film during development, the content of the chelating agent is within the above range. It is presumed that this is because it could be suppressed.

Washing (rinsing) with pure water after development is also preferred. After development, it is preferable to carry out additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Also, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

Thus, as shown in FIG. 4, pixels 11 are formed within the regions partitioned by the partition walls. In FIG. 4, the height H1 of the partition 2 and the thickness H2 of the pixel 11 are substantially the same, but the height H1 of the partition 2 may be lower than or higher than the thickness H2 of the pixel 11. good too.

By repeating the above steps for pixels of the second and subsequent colors, as shown in FIG. 5, pixels 11, 21, and 31 of a plurality of colors can be formed in regions partitioned by partition walls.

<Developer>
Next, the developer used in the present invention will be described. In the present invention, an alkaline aqueous solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent is used as a developer. The pH of the developer is preferably 10-14, more preferably 11-13.5, and even more preferably 12-13.

<<Alkaline agent>>
Examples of the alkali agent include organic base compounds and inorganic base compounds, and organic base compounds are preferred from the viewpoint of suppressing development residue. The organic base compound is preferably an organic base compound having an ammonium salt structure, more preferably a tetraalkylammonium salt, and even more preferably a tetramethylammonium salt.

Specific examples of organic base compounds include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium. hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, etc. is mentioned. Specific examples of inorganic base compounds used as alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like.

The content of the alkaline agent in the alkaline aqueous solution is 0.02 to 0.22% by mass, preferably 0.10 to 0.18% by mass, and 0.12 to 0.17% by mass. is more preferable, and 0.13 to 0.16% by mass is even more preferable. When the content of the alkaline agent is 0.02% by mass or more, the developer penetrates well into the colored photosensitive composition layer in the unexposed areas, and the occurrence of development residuals can be suppressed. Further, when the content of the alkaline agent is 0.22% by mass or less, it is easy to form pixels with small surface roughness and excellent rectangularity, temperature cycle resistance, and moisture resistance.

<<Chelating agent>>
The alkaline aqueous solution used as the developer contains a chelating agent. As used herein, a chelating agent refers to a compound (ligand) that forms a complex by coordinating with a metal ion.

The chelating agent is preferably a bidentate or higher polydentate ligand, more preferably a didentate to hexadentate polydentate ligand, and preferably a didentate to tetradentate polydentate ligand. More preferred.

The chelating agent is preferably a compound having at least one group selected from an amino group, a carboxyl group, a sulfo group and a phosphate group. more preferably a compound having an amino group and a carboxyl group (hereinafter, a compound having an amino group and a carboxyl group is also referred to as an aminocarboxylic acid compound).

The aminocarboxylic acid compound is preferably a compound having 2 to 4 amino groups and 2 to 8 carboxyl groups. The number of amino groups is preferably 2-3, more preferably 2. The number of carboxyl groups is preferably 2-8, more preferably 2-4.

Specific examples of chelating agents include polyamine compounds such as ethylenediamine and propylenediamine; -N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6- Hexamethylene-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10 -tetraazacyclododecane-tetraacetic acid, diaminopropanol tetraacetic acid, and aminocarboxylic acid compounds such as (hydroxyethyl)ethylenediaminetriacetic acid. Among them, ethylenediaminetetraacetic acid (EDTA) and ethylenediamine are preferable from the viewpoint of temperature cycle resistance and humidity resistance, and ethylenediaminetetraacetic acid (EDTA) is more preferable from the viewpoint of pattern shape in addition to the above properties.

The content of the chelating agent in the alkaline aqueous solution is preferably 0.01 to 0.20% by mass, more preferably 0.02 to 0.10% by mass, and 0.04 to 0.10% by mass. % is more preferred. If the content of the chelating agent is within the above range, the effects of the present invention can be obtained more remarkably.
In addition, the content of the chelating agent is preferably 5 to 130 parts by mass, more preferably 10 to 100 parts by mass, and further preferably 30 to 70 parts by mass with respect to 100 parts by mass of the alkaline agent. preferable. If the ratio of the chelating agent and the alkaline agent is within the above range, the effects of the present invention can be obtained more remarkably. Although the detailed reason is unknown, it is presumed that the ratio of the chelating agent and the alkaline agent is within the above range, so that the chelating agent can moderately permeate into the colored photosensitive composition layer. .

<<Surfactant>>
The alkaline aqueous solution used as the developer preferably further contains a surfactant. By containing a surfactant, generation of development residue can be more effectively suppressed. Furthermore, temperature cycle resistance can also be improved.

Examples of surfactants include nonionic surfactants, cationic surfactants, and anionic surfactants, and nonionic surfactants are preferred from the viewpoint of penetration of the developer into the colored photosensitive composition layer. .

The nonionic surfactant is preferably a compound having an alkyl group having 1 to 30 carbon atoms, more preferably a compound having an alkyl group having 5 to 30 carbon atoms, and an alkyl group having 5 to 20 carbon atoms. and more preferably a compound having an alkyl group having 10 to 20 carbon atoms, for the reason that better moisture resistance is likely to be obtained, and an alkyl group having 12 to 15 carbon atoms. It is particularly preferred that the compound has

In addition, the nonionic surfactant is preferably a compound containing a polyoxyalkylene structure because it tends to more effectively suppress development residues. The oxyalkylenes constituting the polyoxyalkylene structure are preferably oxyalkylenes having 2 to 6 carbon atoms, more preferably oxyalkylenes having 2 to 4 carbon atoms, and still more preferably oxyethylene and oxypropylene. The number of repeating oxyalkylenes in the polyoxyalkylene structure is preferably 2-40, more preferably 5-30, even more preferably 10-20.

The polyoxyalkylene structure is preferably a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, or a mixed structure thereof, more preferably a polyoxyethylene structure, a polyoxypropylene structure, or a mixed structure thereof. A mixed structure of structure and polyoxypropylene structure is more preferred. Further, when the polyoxyalkylene structure is a mixed structure of a polyoxyethylene structure and a polyoxypropylene structure, the mass ratio of the polyoxyethylene structure and the polyoxypropylene structure is polyoxyethylene structure:polyoxypropylene structure=100. : 1 to 1000, more preferably 100:10 to 100, still more preferably 100:10 to 50, particularly preferably 100:20 to 30.

The molecular weight of the nonionic surfactant is preferably 500-3000. The upper limit is preferably 2000 or less, more preferably 1000 or less, from the viewpoint of permeability of the developer into the colored photosensitive composition layer. From the viewpoint of moisture resistance, the lower limit is preferably 600 or more, more preferably 700 or more.

The nonionic surfactant used in the developer is preferably a compound containing no fluorine atoms or silicon atoms.

The nonionic surfactant used in the developer is preferably a compound represented by formula (W1) or formula (W2), more preferably a compound represented by formula (W1).
R ^W1 −(OR ^W2 ) _m −R ^W3 (W1)
R ^W1 -Ph-(OR ^W2 ) _m -R ^W3 (W2)

In Formulas (W1) and (W2), R ^W1 represents an alkyl group having 1 to 30 carbon atoms. The number of carbon atoms in the alkyl group is preferably 5-30, more preferably 5-20, even more preferably 10-20, and particularly preferably 12-15. The alkyl group is preferably a linear or branched alkyl group.

In formula (W2), Ph represents a phenylene group.

In Formulas (W1) and (W2), R ^W2 represents an alkylene group. The alkylene group preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms. In Formula (W1) and Formula (W2), m R ^W2 may be the same or different. In particular, it is preferable that at least one of m R ^W2 is an ethylene group and the rest are propylene groups.
represents an alkylene group.

In formulas (W1) and (W2), m represents an integer of 2 or more, preferably 2 to 40, more preferably 5 to 30, and even more preferably 10 to 20.

In Formulas (W1) and (W2), R ^W3 represents a hydrogen atom or a substituent. A hydroxy group, an alkyl group, etc. are mentioned as a substituent.

The compound represented by formula (W1) is preferably a compound represented by formulas (W1-1) to (W1-3), more preferably a compound represented by (W1-3). .
R ^W1 −(OC ₂ H ₅ ) _m1 −R ^W3 (W1-1)
R ^W1 −(OC ₃ H ₇ ) _m1 −R ^W3 (W1-2)
R ^W1 - (OC ₂ H ₅ ) _m2 (OC ₃ H ₇ ) _m3 - R ^W3 (W1-3)

In the formula, R ^W1 represents an alkyl group having 1 to 30 carbon atoms, R ^W3 represents a hydrogen atom or a substituent, m1 represents an integer of 2 or more, m2 represents an integer of 1 or more, and m3 represents Represents an integer of 1 or more. m1 is preferably 2 to 40, more preferably 5 to 30, even more preferably 10 to 20. m2 and m3 are each independently preferably 1 to 39, more preferably 5 to 30, even more preferably 10 to 20. The sum of m2 and m3 is preferably 2-40, more preferably 5-30, and even more preferably 10-20.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, 2,4,7,9-tetramethyl-5- Decyne-4,7-diol ethoxylate, NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto oil Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), BLAUNON EL-1515, WONDERSURF NDR-1400, WONDERSURF 140, WONDERSURF S-1400, WONDERSURF SA-30/ 70 2000R, WONDERSURF NPP-0802R, FINESURF TDE1055, FINESURF TDP-04K (manufactured by Aoki Yushi Kogyo Co., Ltd.) and the like.

The content of the surfactant in the alkaline aqueous solution is preferably 0.03 to 0.25% by mass, more preferably 0.05 to 0.20% by mass, and 0.10 to 0.15% by mass. % by mass is more preferred. If the content of the chelating agent is within the above range, the generation of development residue can be more effectively suppressed.

<Colored photosensitive composition>
Next, the colored photosensitive composition used in the method for producing a structure of the present invention will be described. The colored photosensitive composition includes a pixel-forming composition selected from red pixels, green pixels, blue pixels, yellow pixels, cyan pixels, magenta pixels, transparent pixels, infrared-transmitting pixels, and light-shielding pixels. Compositions for forming pixels selected from red pixels, green pixels and blue pixels are preferred.

<<coloring agent>>
The colored photosensitive composition preferably contains a coloring agent. Colorants include chromatic colorants such as red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. The coloring agent may be a pigment or a dye. A pigment and a dye may be used in combination. Moreover, the pigment may be either an inorganic pigment or an organic pigment. As the pigment, an inorganic pigment or a material in which a part of an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.

The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. When the average primary particle size of the pigment is within the above range, the dispersion stability of the pigment in the colored photosensitive composition is good. In the present invention, the primary particle diameter of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment. Further, the primary particles of the pigment refer to independent particles without agglomeration.

The colorant preferably contains a pigment. The content of the pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 90% by mass or more. Especially preferred. Examples of pigments include those shown below.

Color Index (C.I.) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 231, 232 (methine) etc. (above, yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, orange pigment),
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (xanthene , Organo Ultramarine, Bluish Red) etc. (above, red pigment),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (the above are green pigments),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), etc. (purple pigments),
C. I. Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87 (monoazo), 88 (methine-based), etc. (above, blue pigments);

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used. Specific examples include compounds described in International Publication No. 2015/118720. Further, as the green pigment, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO2012/102395, and the like can also be used.

Also, an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.

Further, as the yellow pigment, the pigment described in JP-A-2017-201003, the pigment described in JP-A-2017-197719, the paragraph numbers 0011-0062, 0137- of JP-A-2017-171912 0276, the pigments described in paragraph numbers 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, paragraph numbers 0011-0062 and 0139-0190 of JP-A-2017-171914 Pigments described in JP-A-2017-171915, paragraphs 0010 to 0065 and 0142 to 0222 can also be used.

Further, as a yellow pigment, compounds described in JP-A-2018-062644 can also be used. This compound can also be used as a pigment derivative.

As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, The diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, the diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, and the naphthol azo compounds described in JP-A-2012-229344 can also be used. can. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.

A dye can also be used as the coloring agent. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used. Further, thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can also be preferably used. Further, as the yellow dye, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraph numbers 0013-0058 of JP-A-2014-026228, and the like can also be used.

A pigment multimer can also be used as a coloring agent. The dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent. The particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682. A dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. A plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.

Moreover, as a coloring agent, the fused-ring type quinophthalone compound described in WO2012/128233 and the coloring agent described in WO2011/037195 can also be used.

The content of the coloring agent is preferably 30 to 70% by mass based on the total solid content of the colored photosensitive composition. The lower limit is preferably 35% by mass or more, more preferably 40% by mass or more. The upper limit is preferably 60% by mass or less.

<<Pigment derivative>>
The colored photosensitive composition can contain pigment derivatives. Pigment derivatives include compounds having a structure in which a portion of the chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. Chromophores constituting pigment derivatives include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, iso Examples thereof include indoline skeleton, isoindolinone skeleton, quinophthalone skeleton, threne skeleton, metal complex skeleton, and the like, and quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, quinophthalone skeleton, isoindoline skeleton and phthalocyanine skeleton. Preferred are an azo skeleton and a benzimidazolone skeleton. The acid group possessed by the pigment derivative is preferably a sulfo group or a carboxyl group, more preferably a sulfo group. The basic group possessed by the pigment derivative is preferably an amino group, more preferably a tertiary amino group.

As the pigment derivative, a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be used. The maximum value (εmax) of the molar extinction coefficient of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L·mol ⁻¹ ·cm ⁻¹ or less, and 1000 L·mol ⁻¹ ·cm ⁻¹ or less. is more preferable, and 100 L·mol ⁻¹ ·cm ⁻¹ or less is even more preferable. The lower limit of εmax is, for example, 1 L·mol ⁻¹ ·cm ⁻¹ or more, and may be 10 L·mol ⁻¹ ·cm ⁻¹ or more.

Specific examples of pigment derivatives include compounds described in paragraphs 0162 to 0183 of JP-A-2011-252065, compounds described in JP-A-2003-081972, and compounds described in Japanese Patent No. 5299151. is mentioned.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. The total content of the pigment derivative and the colorant is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on the total solid content of the colored photosensitive composition. . The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<<polymerizable compound>>
The colored photosensitive composition preferably contains a polymerizable compound. The polymerizable compound is preferably a radically polymerizable compound.

The polymerizable compound may be in any chemical form such as monomer, prepolymer, oligomer, etc., but monomer is preferred. The molecular weight of the polymerizable compound is preferably 100-3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, even more preferably 250 or more.

The polymerizable compound is preferably a compound containing 3 or more polymerizable groups, more preferably a compound containing 4 or more polymerizable groups, and further preferably a compound containing 5 or more polymerizable groups. A compound containing 6 or more polymerizable groups is particularly preferred because it is easier to improve the temperature cycle resistance and humidity resistance of the formed pixel. When a compound containing 6 or more polymerizable groups is used as the polymerizable compound, the curability at the time of exposure is good, and the cross-linking density of the film in the exposed portion can be further increased. It is presumed that the permeation of the developer can be moderately suppressed, and the pixels firmly adhered to the support and partition wall can be formed. As a result, it is presumed that the temperature cycle resistance and humidity resistance of the formed pixels can be further improved.

The upper limit of the number of polymerizable groups contained in the polymerizable compound is preferably 15 or less, more preferably 10 or less. The type of polymerizable group possessed by the polymerizable compound is preferably an ethylenically unsaturated bond group. Examples of ethylenically unsaturated bond groups include vinyl groups, allyl groups, and (meth)acryloyl groups, with allyl groups and (meth)acryloyl groups being preferred, and (meth)acryloyl groups being more preferred.

The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 4- to 15-functional (meth)acrylate compound, and a 5- to 15-functional (meth)acrylate compound. More preferably, it is a 6- to 15-functional (meth)acrylate compound, even more preferably a 6- to 10-functional (meth)acrylate compound, and a 3- to 6-functional (meth)acrylate Compounds are particularly preferred. Specific examples of the polymerizable compound include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2008-292970. Paragraph numbers 0034 to 0038 of 2013-253224, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662 Compounds described in publications are included, the contents of which are incorporated herein.

As the polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. ), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues Compounds (eg, SR454, SR499, commercially available from Sartomer) can be used.

Further, as the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A -TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) , NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. can also

In addition, as the polymerizable compound, trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, isocyanuric acid ethyleneoxy-modified tri(meth)acrylate. , pentaerythritol tri(meth)acrylate and other trifunctional (meth)acrylate compounds can also be used. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) etc.

A compound having an acid group can also be used as the polymerizable compound. By using a polymerizable compound having an acid group, the colored photosensitive composition layer in the unexposed area is easily removed during development, and the generation of development residue can be more effectively suppressed. The acid group includes a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferred. Commercially available polymerizable compounds having an acid group include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The acid value of the polymerizable compound having an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the solubility in the developer is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling.

A compound having a caprolactone structure can also be used as the polymerizable compound. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

A polymerizable compound having an alkyleneoxy group can also be used as the polymerizable compound. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and a trifunctional compound having 4 to 20 ethyleneoxy groups. The above (meth)acrylate compounds are more preferred. Commercially available polymerizable compounds having an alkyleneoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups and a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Sartomer Co., Ltd. KAYARAD TPA-330, which is an acrylate, and the like.

A polymerizable compound having a fluorene skeleton can also be used as the polymerizable compound. Commercially available polymerizable compounds having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

As the polymerizable compound, it is also preferable to use a compound that does not substantially contain environmental regulation substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the polymerizable compound include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. It is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-A-01-105238. Further, the polymerizable compound includes UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

The content of the polymerizable compound in the total solid content of the colored photosensitive composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less. The polymerizable compound may be used singly or in combination of two or more.

<<Photoinitiator>>
The colored photosensitive composition preferably contains a photoinitiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet range to the visible range are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazoles. dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, α-hydroxyketone compounds , α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and Japanese Patent No. 6301489, the contents of which are incorporated herein.

Commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF). Commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2000-080068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, Patent No. Compounds described in WO 2015/152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, WO 2017/164127 and the compounds described in paragraphs 0025 to 0038 of No. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), and Adeka Optomer N-1919. (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-014052). As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

An oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A-2014-137466.

As a photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505.

An oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.

An oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.

An oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

Specific examples of the oxime compound are shown below, but the present invention is not limited thereto.

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photopolymerization initiator, a bifunctional or trifunctional photopolymerization initiator may be used. Good sensitivity can be obtained by using such a photoinitiator. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered and the solubility in a solvent or the like is improved, making it difficult to precipitate over time, thereby improving the stability over time of the colored photosensitive composition. can be done. Specific examples of bifunctional or trifunctional or higher photopolymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, paragraph of Japanese Patent Publication No. 2016-532675. Numbers 0412 to 0417, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound (G) described in JP 2013-522445 ), Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, paragraph of JP 2017-167399 Photoinitiators described in numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, and the like.

The content of the photopolymerization initiator in the total solid content of the colored photosensitive composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. A photoinitiator may use only 1 type and may use 2 or more types.

<<Resin>>
The colored photosensitive composition preferably contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigment in the colored photosensitive composition and for the purpose of binder. A resin that is mainly used to disperse particles such as pigments is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is more preferably 1,000,000 or less, and even more preferably 500,000 or less. The lower limit is more preferably 4000 or more, and even more preferably 5000 or more.

Resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, and polyamideimide resins. , polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and the like. One of these resins may be used alone, or two or more may be mixed and used. In addition, the resin described in paragraph numbers 0041 to 0060 of JP-A-2017-206689, the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856, the resin described in JP-A-2017-057265, Resins described in JP-A-2017-032685, resins described in JP-A-2017-075248, and resins described in JP-A-2017-066240 can also be used.

In the present invention, it is preferable to use a resin having an acid group as the resin. According to this aspect, the developability of the colored photosensitive composition can be improved. The acid group includes a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferred. A resin having an acid group can be used, for example, as an alkali-soluble resin.

The resin having an acid group preferably contains a repeating unit having an acid group in its side chain, and more preferably contains 1 to 70 mol % of repeating units having an acid group in its side chain in all repeating units of the resin. The upper limit of the content of repeating units having acid groups in side chains is preferably 50 mol % or less, more preferably 40 mol % or less. The lower limit of the content of repeating units having acid groups in side chains is preferably 2 mol % or more, more preferably 5 mol % or more.

The acid value of the resin having an acid group is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less, and particularly preferably 100 mgKOH/g or less. Moreover, the acid value of the resin having an acid group is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and still more preferably 20 mgKOH/g or more.

The acid group-containing resin preferably further has an ethylenically unsaturated bond group. According to this aspect, it is easy to form a pixel excellent in moisture resistance. Examples of ethylenically unsaturated bond groups include vinyl groups, allyl groups, and (meth)acryloyl groups, with allyl groups and (meth)acryloyl groups being preferred, and (meth)acryloyl groups being more preferred.

The resin having an ethylenically unsaturated bond group preferably contains a repeating unit having an ethylenically unsaturated bond group in its side chain, and the repeating unit having an ethylenically unsaturated bond group in its side chain is included in all the repeating units of the resin. It is more preferable to contain 5 to 80 mol %. The upper limit of the content of repeating units having ethylenically unsaturated bond groups in side chains is preferably 60 mol % or less, more preferably 40 mol % or less. The lower limit of the content of repeating units having ethylenically unsaturated bond groups in side chains is preferably 10 mol % or more, more preferably 15 mol % or more.

The ethylenically unsaturated bond value of the resin is preferably 0.5 to 3 mmol/g. The upper limit is preferably 2.5 mmol/g or less, more preferably 2 mmol/g or less. The lower limit is preferably 0.9 mmol/g or more, more preferably 1.0 mmol/g or more. The ethylenically unsaturated bond group value of the resin is a numerical value representing the molar amount of the ethylenically unsaturated bond groups per 1 g of the solid content of the resin.

The colored photosensitive composition has an acid value of 10 to 100 mgKOH/g (preferably 20 to 80 mgKOH/g, more preferably 30 to 50 mgKOH/g) and an ethylenically unsaturated bond value of 1.0 to 2.0 mmol. /g (preferably 1.2 to 1.8 mmol/g) of resin (hereinafter also referred to as resin X). By including the resin X in the colored photosensitive composition, development residue is suppressed, and pixels with small surface roughness and excellent rectangularity and temperature cycle resistance are easily formed in the regions partitioned by the partition walls. The content of the resin X in the resin contained in the colored photosensitive composition is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more. is more preferable. The upper limit can be 100% by mass, 75% by mass or less, or 50% by mass or less.

The resin used in the present invention includes a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds are sometimes referred to as "ether dimer"). It is also preferred that repeating units derived from monomer components are included.

式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の詳細については、特開２０１０－１６８５３９号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), the description in JP-A-2010-168539 can be referred to, the contents of which are incorporated herein.

Specific examples of the ether dimer, for example, paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.

式（Ｘ）中、Ｒ_１は、水素原子またはメチル基を表し、Ｒ_２は炭素数２～１０のアルキレン基を表し、Ｒ_３は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 The resin also preferably contains a repeating unit derived from a compound represented by formula (X) below.

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, R ₃ represents a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring. represents an alkyl group of n represents an integer of 1-15.

Resins having an acid group and/or an ethylenically unsaturated bond group include, for example, resins having the following structures. In the following structural formulas, Me represents a methyl group.

The colored photosensitive composition can also contain a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably from 40 to 105 mgKOH/g, more preferably from 50 to 105 mgKOH/g, even more preferably from 60 to 105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol % when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group.

It is also preferable that the resin used as the dispersant is a graft resin. Graft resins include resins described in paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

It is also preferable that the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. A resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Polyimine-based dispersants include resins described in paragraphs 0102 to 0166 of JP-A-2012-255128, the contents of which are incorporated herein.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion. Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

Moreover, the above-described resin having an acid group (alkali-soluble resin) can also be used as a dispersant.

Dispersants are also commercially available, and specific examples thereof include BYK Chemie's DISPERBYK series (e.g., DISPERBYK-111, 161, etc.), Lubrizol's Solsperse series (e.g., Solsperse 36000, etc.). etc. Also, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can be used, the contents of which are incorporated herein. In addition, the resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.

When the colored photosensitive composition contains a resin, the content of the resin in the total solid content of the colored photosensitive composition is preferably 5 to 50% by mass. The lower limit is more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less. Moreover, the content of the resin having an acid group in the total solid content of the colored photosensitive composition is preferably 5 to 50% by mass. The lower limit is more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less. Moreover, the content of the resin having an acid group in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit can be 100% by mass, 95% by mass, or 90% by mass or less.

<<Compound Having a Cyclic Ether Group>>
The colored photosensitive composition can contain a compound having a cyclic ether group. Cyclic ether groups include epoxy groups and oxetanyl groups. The compound having a cyclic ether group is preferably a compound having an epoxy group. Compounds having an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of epoxy groups is more preferably two or more. As the compound having an epoxy group, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408 The compounds described in JP-A-2017-179172 can also be used. The contents of these are incorporated herein.

The compound having an epoxy group may be a low-molecular compound (e.g., molecular weight less than 2000, further molecular weight less than 1000), or a macromolecule (e.g., molecular weight 1000 or more, in the case of a polymer, weight-average molecular weight 1000 or more). The weight average molecular weight of the epoxy group-containing compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and still more preferably 3,000 or less.

Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (these are epoxy group-containing polymers manufactured by NOF Corporation) and the like.

When the colored photosensitive composition contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group in the total solid content of the colored photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Only one kind of compound having a cyclic ether group may be used, or two or more kinds thereof may be used.

<<Silane coupling agent>>
The colored photosensitive composition can contain a silane coupling agent. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred. Specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. the contents of which are incorporated herein.

The content of the silane coupling agent in the total solid content of the colored photosensitive composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The number of silane coupling agents may be one, or two or more.

<<Organic solvent>>
The colored photosensitive composition preferably contains an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the colored photosensitive composition. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a mass ppt (parts per trillion) level organic solvent may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The content of the organic solvent in the colored photosensitive composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 90% by mass.

<<Curing accelerator>>
A curing accelerator may be added to the colored photosensitive composition for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. Curing accelerators include methylol compounds (for example, compounds exemplified as cross-linking agents in paragraph number 0246 of JP-A-2015-034963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, JP-A Curing agent described in paragraph number 0186 of 2013-041165), base generator (e.g., ionic compound described in JP-A-2014-055114), cyanate compound (e.g., JP-A-2012-150180 Compounds described in paragraph number 0071), alkoxysilane compounds (e.g., alkoxysilane compounds having an epoxy group described in JP-A-2011-253054), onium salt compounds (e.g., paragraph numbers of JP-A-2015-034963 0216 as examples of acid generators, compounds described in JP-A-2009-180949), and the like can also be used.

When the colored photosensitive composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9 mass% in the total solid content of the colored photosensitive composition, 0.8 ~6.4% by mass is more preferred.

<<polymerization inhibitor>>
The colored photosensitive composition can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the colored photosensitive composition is preferably 0.0001 to 5% by mass.

<<Surfactant>>
The colored photosensitive composition can contain a surfactant. As the surfactant, various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicon surfactants can be used. For surfactants, reference can be made to paragraphs 0238-0245 of WO 2015/166779, the contents of which are incorporated herein.

The surfactant is preferably a fluorosurfactant. By incorporating a fluorine-based surfactant into the colored photosensitive composition, the liquid properties (especially fluidity) are further improved, and the liquid saving property can be further improved. In addition, it is also possible to form a film with less unevenness in thickness.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and has good solubility in the colored photosensitive composition.

As the fluorine-based surfactant, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- 132503, paragraphs 0117-0132, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. .

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. For such fluorine-based surfactants, the description in JP-A-2016-216602 can be referred to, the content of which is incorporated herein.

上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 A block polymer can also be used as the fluorosurfactant. Examples thereof include compounds described in JP-A-2011-089090. The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorosurfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.

A fluoropolymer having an ethylenically unsaturated bond group in a side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, such as Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorine-based surfactant.

The surfactant content in the total solid content of the colored photosensitive composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Ultraviolet absorber>>
The colored photosensitive composition can contain an ultraviolet absorber. A conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used as the ultraviolet absorber. For details of these, paragraph numbers 0052 to 0072 of JP 2012-208374, paragraph numbers 0317 to 0334 of JP 2013-068814, paragraph numbers 0061 to 0080 of JP 2016-162946 are described. The contents of which can be referred to are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). Further, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as the ultraviolet absorber. The content of the ultraviolet absorber in the total solid content of the colored photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Antioxidant>>
The colored photosensitive composition can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. The content of the antioxidant in the total solid content of the colored photosensitive composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Other Ingredients>>
The colored photosensitive composition may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, fillers, antifoaming agents, A retardant, a leveling agent, a release accelerator, a fragrance, a surface tension modifier, a chain transfer agent, etc.) may be contained. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. Moreover, the colored photosensitive composition may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available products include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).

<Composition for Forming Organic Layer>
Next, a composition for forming an organic layer that can be used to form an organic layer on the surface of the partition wall in the method for producing a structure of the present invention will be described. The composition for forming an organic layer preferably contains a compound having an ethylenically unsaturated bond group. Examples of ethylenically unsaturated bond groups include vinyl groups, allyl groups, and (meth)acryloyl groups, with allyl groups and (meth)acryloyl groups being preferred, and (meth)acryloyl groups being more preferred.

A compound having an ethylenically unsaturated bond group may be a monomer or a resin such as a polymer. The compound having an ethylenically unsaturated bond group is preferably a resin having an ethylenically unsaturated bond group. When a resin having an ethylenically unsaturated bond group is used, it is easier to apply the organic layer-forming composition to the partition walls more uniformly. Therefore, the film formability of the composition for forming an organic layer can be improved. Furthermore, the adhesion between the organic layer and the pixels can be enhanced, and better moisture resistance and temperature cycle resistance can be obtained. Hereinafter, the monomer-type compound having an ethylenically unsaturated bond group is also referred to as a monomer A. A resin-type compound having an ethylenically unsaturated bond group is also referred to as resin A.

The molecular weight of the monomer A is preferably 100-3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more. The weight average molecular weight of Resin A is preferably 5,000 to 20,000. The upper limit is preferably 19000 or less, more preferably 18000 or less. The lower limit is preferably 8,000 or more, more preferably 10,000 or more.

The content of the compound having an ethylenically unsaturated bond group is preferably 0.01 to 1% by mass with respect to the total mass of the composition for forming an organic layer. The lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. The upper limit is preferably 0.9% by mass or less, more preferably 0.8% by mass or less.

The content of the compound having an ethylenically unsaturated bond group in the total solid content of the organic layer-forming composition is preferably 50 to 100% by mass. The lower limit is preferably 70% by mass or more, more preferably 90% by mass or more.

The content of the resin A compound in the compound having an ethylenically unsaturated bond group is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and 90 to 100% by mass. is more preferred, and it is particularly preferred that it consists essentially of resin A only. According to this aspect, the film formability of the organic layer is good, and more excellent moisture resistance is likely to be obtained. In addition, when the compound having an ethylenically unsaturated bond group is substantially composed only of the resin A, the content of the resin A in the compound having an ethylenically unsaturated bond group should be 99% by mass or more. It is preferably 99.5% by mass or more, more preferably 99.9% by mass or more, and particularly preferably composed of resin A only.

It is also preferable to use the monomer A and the resin A together as the compound having an ethylenically unsaturated bond group.

(Monomer A)
Monomer A is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2013-253224. Paragraph numbers 0034 to 0038 of the publication, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662 and the contents of which are incorporated herein. Moreover, as the monomer A, the compounds described in the section of the polymerizable compound of the colored photosensitive composition can also be used.

式中、Ｒ^１は、水素原子又はアルキル基を表し、Ｌ^１は、単結合または２価の連結基を表し、Ｐ^１はエチレン性不飽和結合基を表す。 (Resin A)
Resin A is preferably a polymer containing a repeating unit having an ethylenically unsaturated bond group in its side chain, and more preferably a polymer having a repeating unit represented by formula (1).

In the formula, ^R1 represents a hydrogen atom or an alkyl group, ^L1 represents a single bond or a divalent linking group, and ^P1 represents an ethylenically unsaturated bond group.

The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. R ¹ is preferably a hydrogen atom or a methyl group.

L ¹ represents a single bond or a divalent linking group. The divalent linking group is selected from an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -CO-, -OCO-, -O-, -NH- and -SO ₂ -. and a group formed by combining one of the above. An alkylene group and an arylene group may have a substituent or may be unsubstituted. Examples of substituents include halogen atoms, alkyl groups, aryl groups, hydroxy groups, carboxyl groups, alkoxy groups, and aryloxy groups. Hydroxy groups are preferred. The alkylene group may be linear, branched or cyclic.

^P1 represents an ethylenically unsaturated bond group. As the ethylenically unsaturated bond group, a vinyl group, an allyl group, and a (meth)acryloyl group are preferable, and the (meth)acryloyl group is more preferable because it has high polymerization reactivity and is likely to provide better moisture resistance. preferable.

In resin A, the content of repeating units having ethylenically unsaturated bond groups in side chains is preferably 5 to 100 mol % of all repeating units. The lower limit is preferably 10 mol % or more, more preferably 15 mol % or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less, and particularly preferably 70 mol% or less.

The ethylenically unsaturated bond value of Resin A is preferably 0.5 to 3 mmol/g. The upper limit is preferably 2.5 mmol/g or less, more preferably 2 mmol/g or less. The lower limit is preferably 0.9 mmol/g or more, more preferably 1.0 mmol/g or more.

Resin A preferably further contains a repeating unit having an acid group. Examples of acid groups include carboxyl groups, sulfo groups, and phosphoric acid groups. Only one type of acid group may be contained, or two or more types may be contained. The proportion of repeating units having an acid group is preferably 1 to 50 mol % of all repeating units constituting the polymer. The lower limit is more preferably 2 mol % or more, still more preferably 3 mol % or more. The upper limit is more preferably 35 mol% or less, even more preferably 30 mol% or less.

When resin A has an acid group, the acid value of resin A is preferably 10 to 100 mgKOH/g. The lower limit is preferably 15 mgKOH/g or more, more preferably 20 mgKOH/g or more. The upper limit is preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 70 mgKOH/g or less, and particularly preferably 60 mgKOH/g or less.

It is also preferred that the resin A further contains a repeating unit having an aryl group on its side chain. The proportion of repeating units having an aryl group in their side chains is preferably 1 to 80% by mass of all repeating units constituting the polymer. The lower limit is more preferably 10 mol % or more, still more preferably 15 mol % or more. The upper limit is more preferably 70 mol % or less, and even more preferably 60 mol % or less.

Resin A also preferably contains a repeating unit derived from the ether dimer described above.

Specific examples of resin A include polymers having the following structures. In the structural formulas below, Me represents a methyl group.

Resin A can also use a commercial item. For example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.) , Cychromer P series (eg, ACA230AA), Praxel CF200 series (both manufactured by Daicel Corporation), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

The organic layer-forming composition may contain a surfactant. As the surfactant, various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicon surfactants can be used. Among them, fluorine-based surfactants are preferred. The details of the surfactant are the same as those described in the section on the surfactant of the colored photosensitive composition. The content of the surfactant is preferably 0.0001 to 0.1% by mass with respect to the total mass of the composition for forming an organic layer. The lower limit is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more. The upper limit is preferably 0.05% by mass or less, more preferably 0.01% by mass or less. Further, the content of the surfactant in the total solid content of the organic layer-forming composition is preferably 0.01 to 2.0% by mass. The lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. The upper limit is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. Only one surfactant may be used, or two or more surfactants may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.

The composition for forming an organic layer preferably contains an organic solvent. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. The details of the organic solvent are the same as those described in the section on the organic solvent of the colored photosensitive composition. The content of the organic solvent is preferably 99 to 99.99% by mass with respect to the total mass of the composition for forming an organic layer. The lower limit is preferably 99.2% by mass or more, more preferably 99.4% by mass or more. The upper limit is preferably 99.95% by mass or less, more preferably 99.9% by mass or less. When the content of the organic solvent is within the above range, the coating property of the composition for forming an organic layer is good, and it is easy to form a thin organic layer with less variation in thickness.

The organic layer-forming composition may further contain other additives such as photopolymerization initiators and polymerization inhibitors, but the content of these other additives is It is preferably 1% by mass or less, more preferably 0.1% by mass or less, and more preferably not substantially contained relative to the solid content. When the other additive is not substantially contained, the content of the other additive is preferably 1% by mass or less with respect to the total solid content of the organic layer-forming composition, and is preferably 0.1% by mass. It is more preferably 0.01% by mass or less, and particularly preferably not contained.

<Manufacturing method of color filter>
Next, a method for manufacturing the color filter of the present invention will be described. The method for manufacturing the color filter of the present invention includes the method for manufacturing the structure of the present invention described above. Color filters can be used in solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), image display devices, and the like.

<Manufacturing method of solid-state imaging device>
A method for manufacturing a solid-state imaging device of the present invention includes the above-described method for manufacturing a structure of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.

<Method for manufacturing image display device>
A method for manufacturing an image display device of the present invention includes the above-described method for manufacturing a structure of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. For a definition of an image display device and details of each image display device, see, for example, "Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) of sample>
The weight average molecular weight of the sample was measured by gel permeation chromatography (GPC) under the following conditions.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 connected Column developing solvent: Tetrahydrofuran Column temperature: 40°C
Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1% by mass)
Device name: Tosoh HLC-8220GPC
Detector: RI (refractive index) detector calibration curve Base resin: polystyrene resin

<Measurement of acid value of sample>
The acid value of a sample represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. The acid value of the sample was measured as follows. That is, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and the resulting solution was measured at 25°C using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry). was neutralized and titrated with a 0.1 mol/L sodium hydroxide aqueous solution. Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated by the following formula.
A = 56.11 x Vs x 0.5 x f/w
A: Acid value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L aqueous sodium hydroxide solution required for titration
f: titer of 0.1 mol / L sodium hydroxide aqueous solution w: mass of sample (g) (converted to solid content)

<Colored photosensitive composition>
(Production of Dispersion Green-1)
C. I. Pigment Green 36, 8 parts by weight, C.I. I. 6.5 parts by mass of Pigment Yellow 150, 1.5 parts by mass of Resin B-1, 4.5 parts by mass of Resin B-4, and 79.5 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) After mixing and dispersing the mixed solution for 3 hours using a bead mill (zirconia beads 0.3 mm diameter), a high-pressure disperser NANO-3000-10 with a pressure reduction mechanism (manufactured by Nippon BEE Co., Ltd.) was used to disperse the mixture to 2000 kg / cm. Dispersion treatment was carried out at a pressure of ³ and a flow rate of 500 g/min. This dispersing treatment was repeated 10 times to obtain dispersion Green-1.

(Production of Dispersion Green-2)
C. I. A mixture of 9.5 parts by mass of Pigment Green 36, 1.5 parts by mass of Resin B-1, 4.5 parts by mass of Resin B-4, and 84.5 parts by mass of PGMEA was prepared in a bead mill (zirconia After mixing and dispersing for 3 hours using beads with a diameter of 0.3 mm, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism is used under a pressure of 2000 kg/cm ³ at a flow rate of 500 g. /min. This dispersing treatment was repeated 10 times to obtain a dispersion Green-2.

(Production of Dispersion Green-3)
C. I. Pigment Green 36, 8 parts by weight, C.I. I. A mixture of 6.5 parts by mass of Pigment Yellow 150, 6 parts by mass of Resin B-4, and 79.5 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.3 mm). After that, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, dispersion treatment was carried out under a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersing treatment was repeated 10 times to obtain dispersion Green-3.

(Production of Dispersion Green-4)
C. I. A mixture of 9.5 parts by mass of Pigment Green 36, 6 parts by mass of Resin B-4, and 84.5 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.3 mm). After that, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, dispersion treatment was carried out under a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersing treatment was repeated 10 times to obtain dispersion Green-4.

(Production of dispersion Red-1)
C. I. Pigment Red 254, 7.3 parts by mass, C.I. I. 3.6 parts by weight of Pigment Yellow 139, 1.5 parts by weight of pigment derivative X-1, 4.3 parts by weight of Resin B-1, 1.1 parts by weight of Resin B-5, and PGMEA. After mixing and dispersing the mixed liquid with 82.2 parts by mass for 3 hours using a bead mill (zirconia beads 0.3 mm diameter), a high-pressure disperser NANO-3000-10 with a pressure reduction mechanism (manufactured by Nippon BEE Co., Ltd.) was added. Dispersion treatment was carried out with a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersing treatment was repeated 10 times to obtain dispersion liquid Red-1.

(Production of dispersion Blue-1)
C. I. Pigment Blue 15:6 with 10 parts by weight of C.I. I. A mixture of 2.3 parts by mass of Pigment Violet 23, 3 parts by mass of Resin B-1, 2 parts by mass of Resin B-6, and 82.7 parts by mass of PGMEA was prepared in a bead mill (0.3 mm zirconia beads After mixing and dispersing for 3 hours using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), the mixture was dispersed under a pressure of 2000 kg/cm ³ at a flow rate of 500 g/min. processed. This dispersing treatment was repeated 10 times to obtain dispersion Blue-1.

The details of the raw materials indicated by abbreviations among the raw materials used in the preparation of the dispersion are as follows.
Pigment derivative X-1: a compound having the following structure

樹脂Ｂ－４：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２１０００、酸価３６ｍｇＫＯＨ／ｇ）

分散剤Ｂ－５：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２００００、酸価７７ｍｇＫＯＨ／ｇ）

分散剤Ｂ－６：Ｓｏｌｓｐｅｒｓｅ ３６０００（Ｌｕｂｒｉｚｏｌ製） Resin B-1: Resin having the following structure (numerical values attached to the main chain are molar ratios: Mw = 11000, acid value 32 mgKOH/g, ethylenically unsaturated bond value 1.42 mmol/g)

Resin B-4: A resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 21000, acid value 36 mgKOH/g)

Dispersant B-5: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 20000, acid value 77 mgKOH/g)

Dispersant B-6: Solsperse 36000 (manufactured by Lubrizol)

(Production of colored photosensitive composition)
A colored photosensitive composition was prepared by mixing the following raw materials. The units of numerical values in the table below are parts by mass. In addition, the value of the content of the colorant in the total solid content of the colored photosensitive composition is also shown.

The details of the raw materials indicated by abbreviations among the raw materials described in the above table are as follows.

(solvent)
PGMEA: propylene glycol monomethyl ether acetate

(resin)
B-1: Resin B-1 described above
B-2: Resin having the following structure (numerical values attached to the main chain are molar ratios: Mw = 30000, acid value 112 mgKOH/g, ethylenically unsaturated bond value 0 mmol/g)

(Polymerizable compound)
M-1: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-2: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)
M-3: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(Photoinitiator)
Ini-1: IRGACURE-OXE01 (manufactured by BASF)

(Additive)
U-1: a compound having the following structure

(Surfactant)
F-1: A compound having the following structure (Mw = 14000, % values indicating the ratio of repeating units are mol%, fluorosurfactant)

(dispersion liquid)
Green-1, Green-2, Green-3, Green-4, Red-1, Blue-1: the dispersion prepared above Green-1, Green-2, Green-3, Green-4, Red-1, Blue-1

<Production of Composition for Forming Organic Layer>
(Organic Layer-Forming Composition 1)
As a compound having an ethylenically unsaturated bond group, 12 parts by mass of Cychromer P (manufactured by Daicel Ornex, 54% by mass of solid content), 87.99 parts by mass of PGMEA, and 0.2 parts by mass of surfactant F-1. 01 parts by mass were mixed to prepare a composition 1 for forming an organic layer.

<Production of developer>
A developer was prepared by mixing raw materials shown in the table below. The blending amount of each raw material described in the table below is shown in parts by mass.

The raw materials listed in the above table are as follows.
(Alkaline agent)
Alkaline agent 1: Tetramethylammonium hydroxide Alkaline agent 2: Diglycolamine Alkaline agent 3: Diethanolamine

(chelating agent)
Chelating agent 1: ethylenediaminetetraacetic acid Chelating agent 2: ethylenediamine

(Surfactant)
Surfactant 1: BLAUNON EL-1515 (nonionic surfactant, manufactured by Aoki Oil Industry Co., Ltd., a compound having an alkyl group having 12 carbon atoms and a polyoxyalkylene structure (oxyethylene repeating number 15))
Surfactant 2: WONDERSURF NDR-1400 (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., an alkyl group having 10 carbon atoms and a polyoxyalkylene structure (a mixed structure of a polyoxyethylene structure and a polyoxypropylene structure (polyoxyethylene structure: polyoxypropylene structure = 80: 20 (mass ratio)), weight average molecular weight (Mw) 650)
Surfactant 3: WONDERSURF 140 (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., an alkyl group having 12 carbon atoms and a polyoxyalkylene structure (a mixed structure of a polyoxyethylene structure and a polyoxypropylene structure (poly Oxyethylene structure: polyoxypropylene structure = 80:20 (mass ratio)), weight average molecular weight (Mw) 750)
Surfactant 4: WONDERSURF S-1400 (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., an alkyl group having 13 carbon atoms and a polyoxyalkylene structure (a mixed structure of a polyoxyethylene structure and a polyoxypropylene structure (Polyoxyethylene structure: polyoxypropylene structure = 80: 20 (mass ratio)) compound, weight average molecular weight (Mw) 800)
Surfactant 5: WONDERSURF SA-30/70 2000R (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., an alkyl group having 18 carbon atoms and a polyoxyalkylene structure (polyoxyethylene structure and polyoxypropylene structure A compound having a mixed structure (polyoxyethylene structure: polyoxypropylene structure = 30: 70 (mass ratio)), weight average molecular weight (Mw) 2000)
Surfactant 6: WONDERSURF NPP-0802R (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., a phenyl group having an alkyl group having 9 carbon atoms as a substituent and a polyoxyalkylene structure (polyoxyethylene structure and poly A compound having a mixed structure with an oxypropylene structure (polyoxyethylene structure: polyoxypropylene structure = 75:25 (mass ratio)), weight average molecular weight (Mw) 620)
Surfactant 7: FINESURF TDE1055 (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., an alkyl group having 13 carbon atoms and a polyoxyalkylene structure (a mixed structure of a polyoxyethylene structure and a polyoxypropylene structure (poly Oxyethylene structure: polyoxypropylene structure = 80:20 (mass ratio)), weight average molecular weight (Mw) 770)
Surfactant 8: FINESURF TDP-04K (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., a compound having an alkyl group having 13 carbon atoms and a polyoxyalkylene structure (oxypropylene repeating number 4), weight Average molecular weight (Mw) 430)
Surfactant 9: 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate (manufactured by Sigma-Aldrich, number average molecular weight (Mn) 670, nonionic surfactant)

[Production of structure] (Examples 1 to 39, Comparative Examples 1 to 3)
A silicon oxide layer was formed on a silicon wafer by plasma CVD (chemical vapor deposition). Next, this silicon oxide layer was patterned by a dry etching method to form barrier ribs (width 100 nm, thickness 500 nm) made of silicon oxide in a grid pattern at intervals of 0.8 μm. The dimensions of the opening of the partition on the silicon wafer (the area partitioned by the partition on the silicon wafer) were 0.8 μm long and 0.8 μm wide. Next, the organic layer-forming composition 1 was applied by spin coating onto the silicon wafer on which the barrier ribs were formed, then heated at 110° C. for 2 minutes using a hot plate, and then heated to 230° C. using a hot plate. C. for 5 minutes to form an organic layer with a thickness of 13 nm. Next, on the organic layer of the silicon wafer on which the organic layer is formed, the colored photosensitive composition described in the table below is applied by spin coating so that the film thickness after forming the film is 0.6 μm. , and heated at 110° C. for 2 minutes using a hot plate. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed through a mask having an island pattern of 0.8 μm at an exposure amount of 50 to 2000 mJ/cm ² . Next, development processing was carried out using a developing device (Act-8 manufactured by Tokyo Electron). A developer shown in the table below was used, and puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower using pure water, further washed with pure water, and heated at 220° C. for 5 minutes using a hot plate to form pixels in the regions partitioned by the partition walls. to manufacture the structure.

[Production of structure] (Example 40)
A silicon oxide layer was formed on a silicon wafer by plasma CVD (chemical vapor deposition). Next, this silicon oxide layer was patterned by a dry etching method to form barrier ribs (width 100 nm, thickness 500 nm) made of silicon oxide in a grid pattern at intervals of 0.8 μm. The dimensions of the opening of the partition on the silicon wafer (the area partitioned by the partition on the silicon wafer) were 0.8 μm long and 0.8 μm wide. Next, on the silicon wafer on which the barrier ribs were formed, the colored photosensitive composition shown in the table below was applied by a spin coating method so that the film thickness after forming the film was 0.6 μm, and then a hot plate was applied. and heated at 110° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed through a mask having an island pattern of 0.8 μm at an exposure amount of 50 to 2000 mJ/cm ² . Next, development processing was carried out using a developing device (Act-8 manufactured by Tokyo Electron). A developer shown in the table below was used, and puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower using pure water, further washed with pure water, and heated at 220° C. for 5 minutes using a hot plate to form pixels in the regions partitioned by the partition walls. to manufacture the structure.

<Evaluation of surface roughness>
The surface roughness (Ra) of the pixels of the obtained structure was measured using an atomic force microscope Dimension FastScan AFM (manufactured by Bruker). The evaluation criteria for surface roughness are as follows. If the evaluation is A to D, it is judged that there is no practical problem.
A: Surface roughness (Ra) is 0 nm or more and less than 3 nm B: Surface roughness (Ra) is 3 nm or more and less than 5 nm C: Surface roughness (Ra) is 5 nm or more and less than 7 nm D: Surface roughness (Ra) is 7 nm or more Less than 10 nm E: Surface roughness (Ra) is 10 nm or more

<Evaluation of temperature cycle resistance>
A step of alternately exposing the obtained structure to −65° C. and 150° C. for 15 minutes each using a cycle thermo tester (LTS-150-W [trade name] manufactured by Hutech) is defined as one cycle. A temperature cycle test was conducted for 2000 cycles. Using a focused ion beam (FIB) every 100 cycles, a cross-sectional sample of the portion where the pixels are embedded in the partition was prepared, and scanned with a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation). , and the presence or absence of peeling of the pixels was observed to evaluate the temperature cycle resistance. In addition, when the pixel was completely peeled off from the silicon wafer, or when the interface between the pixel and the silicon wafer was cracked, it was determined that there was peeling. Evaluation criteria for temperature cycle resistance are as follows. If the evaluation is A to D, it is judged that there is no practical problem.
A: No peeling observed at 1500 cycles or more B: Peeling observed at 1000 cycles or more and less than 1500 cycles C: Peeling observed at 750 cycles or more and less than 1000 cycles D: Peeling observed at 500 cycles or more and less than 750 cycles E: Peeling was observed in less than 500 cycles

<Evaluation of moisture resistance>
The resulting structure was left at rest for 500 hours, 750 hours, 1000 hours, and 1500 hours in an atmosphere with a temperature of 85° C. and a relative humidity of 85% using a constant temperature and humidity machine (EHS-221M, manufactured by Yamato Scientific Co., Ltd.). Then, a moisture resistance test was performed. After the test, using a focused ion beam (FIB), a cross-sectional sample of the portion where the pixels are embedded in the partition was prepared, and scanned with a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation). Humidity resistance was evaluated by observing the presence or absence of peeling of pixels. In addition, when the pixel was completely peeled off from the silicon wafer, or when the interface between the pixel and the silicon wafer was cracked, it was determined that there was peeling. Evaluation criteria for moisture resistance are as follows. If the evaluation is A to D, it is judged that there is no practical problem.
A: No peeling observed after 1500 hours of humidity test B: No peeling observed after 1000 hours of humidity test but peeling observed after 1500 hours C: No peeling observed after 750 hours of humidity test but peeling observed after 1000 hours D: Peeling was not observed after 500 hours of humidity resistance test, but peeling was observed after 750 hours E: Peeling was observed after 500 hours of humidity resistance test

<Evaluation of Development Residue>
The presence or absence of residues in the portions (non-pixel portions) where pixels are not embedded in the partition walls of the obtained structure was evaluated by observation with a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation). . Evaluation criteria for the development residue are as follows. If the evaluation is A to D, it is judged that there is no practical problem.
A: No residue in the non-pixel portion B: A residue of less than 0.01 μm was observed in the non-pixel portion C: A residue of 0.01 μm or more and less than 0.05 μm was observed in the non-pixel portion D: Non-pixel portion E: A residue of 0.10 μm or more was observed in the non-pixel area

<Evaluation of Rectangularity>
Using a focused ion beam (FIB), a cross-sectional sample of the portion where the pixels are embedded in the partition wall was prepared from the obtained structure, and a scanning electron microscope (SEM) (S-4800H, Hitachi High Technologies), the cross-sectional shape of the pixel was observed, the taper angle of the pixel was measured, and the rectangularity was evaluated according to the following criteria. If the evaluation is A to D, it is judged that there is no practical problem. It should be noted that the taper angle of a pixel is the angle formed by the partition side surface (side surface) of the pixel and the silicon wafer (substrate surface).
A: taper angle of 88 degrees or more and 90 degrees or less B: taper angle of 85 degrees or more and less than 88 degrees C: taper angle of 80 degrees or more and less than 85 degrees D: taper angle of 75 degrees or more and less than 80 degrees E: taper angle of 75 degrees less than degree

As shown in the table above, the examples were all evaluated as D or higher in terms of surface roughness, temperature cycle resistance, development residue, and rectangularity, and these characteristics could be combined. In contrast, at least one of these properties of the comparative example was evaluated as E, indicating poor performance. Regarding these evaluations, it is important from the viewpoint of performance balance that there is no evaluation of E.

1: Support 2: Partition walls 10: Colored photosensitive composition layers 11, 21, 31: Pixels

Claims (16)

A step of applying a colored photosensitive composition onto a support provided with a plurality of regions partitioned by partition walls to form a colored photosensitive composition layer on the support including the regions partitioned by the partition walls. and,
exposing the colored photosensitive composition layer formed on the support to light in a pattern at an exposure amount of 0.03 to 2.5 J/cm ² ;
a step of performing puddle development using a developer to develop and remove the colored photosensitive composition layer in the unexposed areas to form pixels in the regions partitioned by the partition walls;
A method of manufacturing a structure comprising
Using a coloring agent, a polymerizable compound, a photopolymerization initiator, a resin, and an organic solvent as the colored photosensitive composition,
The coloring agent contains a pigment, the content of the pigment in the coloring agent is 50% by mass or more, and the content of the coloring agent in the total solid content of the colored photosensitive composition is 30 to 70% by mass. can be,
The polymerizable compound contains a 3- to 15-functional (meth)acrylate compound, and the content of the polymerizable compound in the total solid content of the colored photosensitive composition is 1 to 40% by mass,
The photopolymerization initiator in the total solid content of the colored photosensitive composition is 1 to 15% by mass,
The content of the resin in the total solid content of the colored photosensitive composition is 5 to 50% by mass,
The content of the organic solvent in the colored photosensitive composition is 30 to 90% by mass, and the developer contains 0.02 to 0.22% by mass of an alkaline agent and 0.02 to 0.02% by mass of a chelating agent. A method for producing a structure using an alkaline aqueous solution containing 0.10% by mass and containing 30 to 70 parts by mass of a chelating agent with respect to 100 parts by mass of an alkaline agent. 2. The method for manufacturing a structure according to claim 1, wherein the developer contains 0.10 to 0.18% by mass of an alkaline agent. 3. The method for producing a structure according to claim 1, wherein said alkaline agent is an organic base compound. 4. The method for producing a structure according to claim 1, wherein said developer further contains a surfactant. 5. The method of manufacturing a structure according to claim 4, wherein said surfactant is a nonionic surfactant. 6. The method for producing a structure according to claim 5, wherein the nonionic surfactant is a compound having an alkyl group with 10 to 20 carbon atoms. 6. The method for producing a structure according to claim 5, wherein the nonionic surfactant is a compound having an alkyl group having 12 to 15 carbon atoms. The method for producing a structure according to any one of claims 5 to 7, wherein the nonionic surfactant is a compound containing a polyoxyalkylene structure. Production of the structure according to any one of claims 5 to 7, wherein the nonionic surfactant is a compound containing a polyoxyalkylene structure, and the molecular weight of the nonionic surfactant is 700 to 1000. Method. Any one of claims 1 to 9, wherein the colored photosensitive composition contains a resin having an acid value of 10 to 100 mgKOH/g and an ethylenically unsaturated bond value of 1.0 to 2.0 mmol/g. 3. A method for manufacturing the structure according to . 11. The method according to any one of claims 1 to 10, wherein after forming an organic layer on the surface of the partition wall, a colored photosensitive composition is applied onto the support to form the colored photosensitive composition layer. A method of manufacturing a structure. 12. The method of manufacturing a structure according to claim 11, wherein the organic layer is formed on the partition walls using an organic layer-forming composition containing a compound having an ethylenically unsaturated bond group. The barrier ribs provided on the support have a height of 0.3 to 1.2 μm, a width of 0.05 to 0.2 μm, and a pitch width of 0.05 to 0.2 μm. 13. The method for producing a structure according to any one of claims 1 to 12, wherein the thickness is 5 to 2.0 µm. A method for manufacturing a color filter, comprising the method for manufacturing the structure according to any one of claims 1 to 13. A method for manufacturing a solid-state imaging device, comprising the method for manufacturing a structure according to any one of claims 1 to 13. A method for manufacturing an image display device, comprising the method for manufacturing a structure according to any one of claims 1 to 13.

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