JPWO2020179648A1 - A method for manufacturing a structure, a method for manufacturing a color filter, a method for manufacturing a solid-state image sensor, and a method for manufacturing an image display device. - Google Patents

Abstract

A step of applying a colored photosensitive composition on a support provided with a plurality of regions partitioned by a partition wall to form a colored photosensitive composition layer on the support including the inside of the region partitioned by the partition wall. In the step of exposing the colored photosensitive composition layer formed on the support in a pattern, and by developing and removing the colored photosensitive composition layer in the unexposed portion using a developing solution, the colored photosensitive composition layer is contained in the region partitioned by the partition wall. A method for producing a structure including a step of forming pixels, wherein a structural solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent is used as a developing solution. .. A method for manufacturing a color filter including the above-mentioned method for manufacturing a structure, a method for manufacturing a solid-state image sensor, and a method for manufacturing an image display device.

Description

The present invention relates to a method for manufacturing a structure in which pixels are formed in a region partitioned by a partition wall. The present invention also relates to a method for manufacturing a color filter, a solid-state image sensor, and an image display device.

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

In the color filter, for example, a colored photosensitive composition layer is formed on a support using a colored photosensitive composition, the colored photosensitive composition layer is exposed in a pattern, and then an unexposed portion is used with a developing solution. It is manufactured by developing and removing the colored photosensitive composition layer of the above to form pixels. As the developing solution, as described in Patent Documents 1 and 2, an alkaline aqueous solution containing an alkaline agent and a chelating agent is known (see Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 03-198046 Japanese Unexamined Patent Publication No. 2000-162785

In forming pixels by exposure and development, it is desired that the amount of development residue is small and the surface roughness of the pixel surface after development is small.

Further, in recent years, attempts have been made to provide a partition wall between pixels to improve the light condensing property of light transmitted through the pixels and to prevent color mixing with adjacent pixels. When forming pixels between partition walls, a higher level of rectangularity of the formed pixels is required.

Further, in recent years, the solid-state image sensor may be used in a harsher environment. Along with this, color filters used in solid-state image sensors are desired to have excellent temperature cycle resistance. Here, the "temperature cycle resistance" is the high degree of adhesion to the support indicated by the pixels when the pixels formed on the support are subjected to a cycle in which high temperature and low temperature are repeated.

According to the study of the present inventor, when pixels are formed in a region partitioned by a partition wall using a conventionally known developer, it is difficult to make these characteristics juxtaposed at a high level. Do you get it.

Therefore, an object of the present invention is a method for manufacturing a structure capable of suppressing development residue, forming pixels having a small surface roughness, excellent rectangularity and temperature cycle resistance, in a region partitioned by a partition wall. , A method of manufacturing a color filter, a method of manufacturing a solid-state image sensor, and a method of manufacturing an image display device.

As a result of diligent studies by the present inventor, it was found that the above object can be achieved by the method described later, and the present invention has been completed. Therefore, the present invention provides the following.
<1> The 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 inside of the regions partitioned by partition walls. Process and
A step of exposing the colored photosensitive composition layer formed on the support in a pattern, and
A step of developing and removing the colored photosensitive composition layer of the unexposed portion using a developing solution to form pixels in the region partitioned by the partition wall, and
It is a manufacturing method of a structure containing
A method for producing a structure, which uses an alkaline aqueous solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent as a developing solution.
<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 base value of 1.0 to 2.0 mmol / g, <1> to <10>. The method for manufacturing a structure according to any one of the above.
<12> The method for producing a structure according to any one of <1> to <11>, wherein the colored photosensitive composition contains a polymerizable compound containing 6 or more polymerizable groups.
<13> Any of <1> to <12>, wherein the organic material layer is formed on the surface of the partition wall, and then the colored photosensitive composition is applied onto the support to form the colored photosensitive composition layer. The method for manufacturing a structure according to one.
<14> The method for producing a structure according to <13>, wherein the organic layer is formed on the surface of the partition wall using a composition for forming an organic layer containing a compound having an ethylenically unsaturated bond group.
<15> A method for manufacturing a color filter, which comprises the method for manufacturing a structure according to any one of <1> to <14>.
<16> A method for manufacturing a solid-state image sensor, which comprises the method for manufacturing the structure according to any one of <1> to <14>.
<17> A method for manufacturing an image display device, which comprises the method for manufacturing a structure according to any one of <1> to <14>.

According to the present invention, a method for manufacturing a structure capable of forming pixels having a small surface roughness and excellent rectangularity and temperature cycle resistance in a region partitioned by a partition wall while suppressing development residue. It is possible to provide a method for manufacturing a color filter, a method for manufacturing a solid-state image sensor, and a method for manufacturing an image display device.

It is a top view from the direction directly above the support. FIG. 3 is a cross-sectional view taken along the line AA of FIG. It is a figure which shows the state which formed the colored photosensitive composition layer. It is a figure which shows the state which formed the pixel in the region divided by a partition wall. It is a figure which shows the state which formed the pixel of each color in the region partitioned by the partition wall.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "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. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, the (meth) allyl group represents both allyl and metharyl, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either, "(meth). "Acrylic" represents both acrylic and methacrylic, or either, and "(meth) acryloyl" represents both acryloyl and methacrylic, or either.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method.
In the present specification, infrared rays refer to light having a wavelength of 700 to 2500 nm.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, the term "process" does not only refer to an independent process, but also to the present term if the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. included.

<Manufacturing method of structure>
The method for manufacturing the structure of the present invention is as follows.
A step of applying a colored photosensitive composition on a support provided with a plurality of regions partitioned by a partition wall to form a colored photosensitive composition layer on the support including the inside of the region partitioned by the partition wall.
A step of exposing the colored photosensitive composition layer formed on the support in a pattern, and
It comprises the steps of developing and removing the colored photosensitive composition layer of the unexposed portion using a developing solution to form pixels in the region partitioned by the partition wall.
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 developing solution to develop and remove the colored photosensitive composition layer in the unexposed portion. It is possible to form pixels having a small surface roughness, excellent rectangularity and temperature cycle resistance, in a region partitioned by a partition wall, while suppressing development residue.

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

In FIGS. 1 and 2, reference numeral 1 is a support. The material of the support 1 is not particularly limited. It can be selected as appropriate according to the application. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, 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 in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.

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

The material of the partition wall 2 is not particularly limited. Examples thereof include organic materials such as siloxane resin and fluororesin, and inorganic particles such as silica particles. As the silica particles, those in which a plurality of spherical silica particles are connected in a bead shape are preferably used. In addition, in this specification, "spherical" means that it may be substantially spherical and may be deformed as long as the effect of the present invention is exhibited. For example, it is meant to include a shape having irregularities on the surface and a flat shape having a long axis in a predetermined direction. Further, "a plurality of spherical silica particles connected in a bead shape" means a structure in which a plurality of spherical silica particles are connected in a linear and / or branched form. For example, there is a structure in which a plurality of spherical silica particles are connected by a joint having a smaller outer diameter. Further, in the present invention, the structure in which "a plurality of spherical silica particles are connected in a bead shape" is not only a structure in which the particles are connected in a ring shape but also a chain shape having an end. Structure is also included. Further, the partition wall 2 can also be formed by using the composition containing the colloidal silica particles described in International Publication No. 2019/017280.

Further, the partition wall 2 may be made of a metal such as tungsten or aluminum. Further, it may be a laminate of a metal and a black matrix. In the case of a laminated body, the stacking order 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, and 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 further 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 further preferably 0.10 μm or more. The upper limit is preferably 0.18 μm or less, more preferably 0.15 μm or less, and further preferably 0.12 μm or less.

The ratio of the height H1 and 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 wall 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 further preferably 0.8 μm or more. The upper limit is preferably 1.8 μm or less, more preferably 1.4 μm or less, and further preferably 1.2 μm or less. The pitch width P1 of the partition wall 2 is the arrangement pitch of the adjacent partition walls. The shorter the pitch width P1, the smaller the pixel size. The smaller the formed pixel size, the more likely it is that the temperature cycle resistance will decrease. However, according to the present invention, even if the formed pixel size is small, excellent temperature cycle resistance can be obtained. Therefore, the effect of the present invention is remarkably exhibited when the pitch width P1 of the partition wall 2 is narrow and the formed pixel size is small.

An organic substance layer may be provided on the surface of the partition wall 2. The organic layer can be formed by applying and drying the composition for forming the organic layer on the partition wall. The organic layer is preferably a layer formed by using a composition for forming an organic layer containing a compound having an ethylenically unsaturated bond group. According to this aspect, the adhesion between the organic material layer and the pixel 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 by using a conventionally known method. For example, the partition wall 2 can be formed as follows. First, a partition wall material layer is formed on the support. The partition wall material layer can be formed by, for example, applying a composition containing inorganic particles such as silica particles onto a support and then curing the composition to form a film. Examples of such a composition include the compositions for forming an optical functional layer described in paragraphs 0012 to 0133 of International Publication No. 2015/190374, and the contents thereof are incorporated in the present specification. Further, an inorganic material such as silicon dioxide can be formed on the support by a vapor deposition method such as chemical vapor deposition (CVD) or vacuum deposition, or a method such as sputtering to form a partition wall material layer. A resist pattern is then formed on the bulkhead material layer using a mask with a pattern that follows the shape of the bulkhead. Next, using this resist pattern as a mask, the partition wall material layer is etched to form a pattern. Examples of the etching method include 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, 0130 of JP-A-2016-014856. The resist pattern is then stripped off from the bulkhead material layer. In this way, the partition wall 2 can be formed.

In the method for producing a structure of the present invention, as shown in FIG. 3, a colored photosensitive composition was applied onto a support 1 provided with a plurality of regions partitioned by the partition wall 2 and partitioned by the partition wall 2. The colored photosensitive composition layer 10 is formed on the support 1 including the inside of the region. As the colored photosensitive composition, a composition containing a polymerizable compound, a photopolymerization initiator, and a resin is preferably used. The type of the colored photosensitive composition is, for example, a composition for forming a pixel selected from red pixels, green pixels, blue pixels, yellow pixels, cyan pixels, magenta pixels, transparent pixels, infrared transmissive pixels, and light-shielding pixels. Examples thereof include, and a composition for forming a pixel selected from a red pixel, a green pixel, and a blue pixel is preferable. Details of the colored photosensitive composition will be described later. In addition, in this specification, "transparency" is included in the concept of "coloring" in a colored photosensitive composition.

As a method for applying the colored photosensitive composition, a known method can be used. For example, a drop method (drop cast); a slit coat method; a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nano-imprint method and the like can be mentioned. The method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumitomo Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, as a method for applying the colored photosensitive composition, the methods described in International Publication No. 2017/030174 and International Publication No. 2017/018419 can also be used, and these contents are incorporated in the present specification.

The colored photosensitive composition layer 10 formed on the support 1 may be dried (prebaked). When prebaking is performed, the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. The prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Pre-baking can be performed on 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 it to a colored photosensitive composition layer 10 through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured.

Examples of the radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm) and the like, and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.

Irradiation dose (exposure dose), for example, preferably ^{0.03~2.5J / cm 2, 0.05~1.0J / cm} 2 is more preferable. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment), or may be exposed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, or, 35000W / ^{m 2)} selected from the range of Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined with each other. For example, the oxygen concentration may be 10% by volume and the illuminance may be 10,000 W / m ² , and the oxygen concentration may be 35% by volume and the illuminance may be 20000 W / m ² .

Next, the colored photosensitive composition layer 10 in the unexposed portion is developed and removed using a developing solution to form pixels in the region partitioned by the partition wall (development step). As a result, the colored photosensitive composition layer in the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains.

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 developing solution. By developing with such a developer, it is possible to suppress the development residue, form pixels having a small surface roughness, excellent rectangularity and temperature cycle resistance, in the region partitioned by the partition wall. .. Although the detailed reason is unknown, excellent developability can be obtained by setting the content of the alkaline agent in the alkaline aqueous solution to 0.02 to 0.22% by mass and further containing the chelating agent. It is presumed that the residue was suppressed, the surface roughness was small, and pixels with excellent rectangularity could be formed. Furthermore, it is presumed that the stress applied to the film during the temperature cycle test is alleviated by the permeation of a part of the chelating agent into the film during development, and as a result, it is presumed that excellent temperature cycle resistance is obtained. Further, when the content of the chelating agent is 0.01 to 0.20% by mass, in addition to the above characteristics, excellent moisture resistance can be obtained. Although the detailed reason is unknown, since the content of the chelating agent is in the above range, even if a part of the chelating agent permeates into the membrane during development, the chelating agent permeating into the membrane takes in water. It is presumed that this was because it could be suppressed.

It is also preferable to wash (rinse) with pure water after development. It is preferable to perform additional exposure treatment or heat treatment (post-baking) after development and drying. Additional exposure processing and post-baking are post-development curing treatments to complete the curing. The heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. .. When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

In this way, as shown in FIG. 4, the pixel 11 is formed in the region partitioned by the partition wall. In FIG. 4, the height H1 of the partition wall 2 and the thickness H2 of the pixel 11 are substantially the same, but the height H1 of the partition wall 2 may be lower or higher than the thickness H2 of the pixel 11. May be good.

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

<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 developing solution. The pH of the developer is preferably 10 to 14, more preferably 11 to 13.5, and even more preferably 12 to 13.

<< Alkaline agent >>
Examples of the alkaline agent include an organic base compound and an inorganic base compound, and the organic base compound is preferable from the viewpoint of suppressing the development residue. Further, as the organic base compound, an organic base compound having an ammonium salt structure is preferable, a tetraalkylammonium salt is more preferable, and a tetramethylammonium salt is further preferable.

Specific examples of the organic base compound include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium. Hydroxydo, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxydo, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc. Can be mentioned. Specific examples of the inorganic base compound used as an alkaline agent include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, 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 preferably 0.12 to 0.17% by mass. Is more preferable, and 0.13 to 0.16% by mass is further preferable. When the content of the alkaline agent is 0.02% by mass or more, the developer is well permeated into the colored photosensitive composition layer in the unexposed portion, and the generation of development residuals can be suppressed. Further, when the content of the alkaline agent is 0.22% by mass or less, the surface roughness is small, and it is easy to form pixels having excellent rectangularity, temperature cycle resistance and moisture resistance.

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

The chelating agent is preferably a polydentate ligand of 2 or more loci, more preferably a polydentate ligand of 2 to 6 loci, and a polydentate ligand of 2 to 4 locus. 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 phosphoric acid group, and the amino group is used because it is easy to obtain an interaction with an alkaline agent. It is more preferably a compound having an amino group, and further preferably a compound having an amino group and a carboxyl group (hereinafter, a compound having an amino group and a carbonicyl 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 to 3, more preferably 2. The number of carboxyl groups is preferably 2 to 8, and more preferably 2 to 4.

Specific examples of the chelating agent include polyamine compounds such as ethylenediamine, propylenediamine, etc .; butylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexacetic acid, 1,3-diamino-2-hydroxypropane. -N, N, N', N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediaminetetraacetic acid, ethylenediaminediaminedipropionic acid, 1,6- Hexylenediamine-diamine-N, N, N', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetate, diaminopropanetetraacetic acid, 1,4,7,10 Examples thereof include aminocarboxylic acid compounds such as −tetraazacyclododecane-4-acacetic acid, diaminopropanol tetraacetic acid, and (hydroxyethyl) ethylenediaminetriacacetic acid. Of these, ethylenediaminetetraacetic acid (EDTA) and ethylenediamine are preferable from the viewpoint of temperature cycle resistance and moisture resistance, and ethylenediaminetetraacetic acid (EDTA) is more preferable from the viewpoint of pattern shape in addition to the above characteristics.

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 preferable. When the content of the chelating agent is in the above range, the effect of the present invention can be obtained more remarkably.
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. When the ratio of the chelating agent to the alkaline agent is in the above range, the effect 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 to the alkaline agent is within the above range, so that the chelating agent can be appropriately permeated into the colored photosensitive composition layer. ..

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

Examples of the surfactant include nonionic surfactants, cationic surfactants and anionic surfactants, and nonionic surfactants are preferable from the viewpoint of permeability of the developing solution 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. It is more preferable that the compound has an alkyl group having 10 to 20 carbon atoms, and an alkyl group having 12 to 15 carbon atoms is more preferable because it is easy to obtain better moisture resistance. It is particularly preferable that the compound has.

Further, the nonionic surfactant is preferably a compound containing a polyoxyalkylene structure because it is easy to suppress the development residue more effectively. As the oxyalkylene constituting the polyoxyalkylene structure, oxyalkylene having 2 to 6 carbon atoms is preferable, oxyalkylene having 2 to 4 carbon atoms is more preferable, and oxyethylene and oxypropylene are further preferable. The number of repetitions of oxyalkylene in the polyoxyalkylene structure is preferably 2 to 40, more preferably 5 to 30, and even more preferably 10 to 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, and polyoxyethylene. A mixed structure of the structure and the polyoxypropylene structure is more preferable. When the polyoxyalkylene structure is a mixed structure of a polyoxyethylene structure and a polyoxypropylene structure, the mass ratio of the polyoxyethylene structure to the polyoxypropylene structure is the polyoxyethylene structure: polyoxypropylene structure = 100. : 1 to 1000 is preferable, 100: 10 to 100 is more preferable, 100: 10 to 50 is further preferable, and 100: 20 to 30 is particularly preferable.

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

The nonionic surfactant used in the developing solution is preferably a compound containing no fluorine atom and a silicon atom.

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

Wherein (W1) and the formula ^{(W2), R W1} represents an alkyl group having 1 to 30 carbon atoms. The number of carbon atoms of the alkyl group is preferably 5 to 30, more preferably 5 to 20, still more preferably 10 to 20, and particularly preferably 12 to 15. The alkyl group is preferably a linear or branched alkyl group.

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

In the formula (W1) and the formula (W2), ^RW2 represents an alkylene group. The alkylene group preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably 2 or 3 carbon atoms. In the formula (W1) and the formula (W2), the m ^RW2s may be the same or different. Among them, it is preferable that at least one of the m ^RW2s is an ethylene group and the rest are propylene groups.
Represents an alkylene group.

In the formula (W1) and the formula (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 formula (W1) and formula (W2), ^RW3 represents a hydrogen atom or a substituent. Examples of the substituent include a hydroxy group and an alkyl group.

The compound represented by the formula (W1) is preferably a compound represented by the formulas (W1-1) to (W1-3), and more preferably a compound represented by the formula (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)

^{Wherein, 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, m3 is Represents an integer greater than or equal to 1. The m1 is preferably 2 to 40, more preferably 5 to 30, and even more preferably 10 to 20. Independently, m2 and m3 are preferably 1 to 39, more preferably 5 to 30, and even more preferably 10 to 20. The total of m2 and m3 is preferably 2 to 40, more preferably 5 to 30, and even more preferably 10 to 20.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, 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- Decin-4,7-diol ethoxylate, NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Junyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil and Fat) (Manufactured by Co., Ltd.), Orfin E1010, Surfinol 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 Oil & Fat Industry Co., Ltd.) and the like can be mentioned.

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. It is more preferably by mass%. When the content of the chelating agent is within the above range, the generation of development residue can be suppressed more effectively.

<Colored photosensitive composition>
Next, the colored photosensitive composition used in the method for producing the structure of the present invention will be described. Examples of the colored photosensitive composition include compositions for forming pixels selected from red pixels, green pixels, blue pixels, yellow pixels, cyan pixels, magenta pixels, transparent pixels, infrared transmissive pixels, and light-shielding pixels. Pixel-forming compositions selected from red pixels, green pixels and blue pixels are preferred.

<< Colorant >>
The colored photosensitive composition preferably contains a colorant. Examples of the colorant include chromatic colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. The colorant may be a pigment or a dye. Pigments and dyes may be used in combination. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or a material in which a part of the organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, the 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, still more preferably 100 nm or less. When the average primary particle size of the pigment is in the above range, the dispersion stability of the pigment in the colored photosensitive composition is good. In the present invention, the primary particle size of the pigment can be obtained from an 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 obtained, 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 an arithmetic average value of the primary particle size for the primary particles of 400 pigments. Further, the primary particles of the pigment refer to independent particles without aggregation.

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, further preferably 80% by mass or more, and preferably 90% by mass or more. Especially preferable. Examples of the pigment include those shown below.

Color Index (CI) 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-based), 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. (The above is 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 system) , Organo Ultramarine, Bluesh Red), etc. (above, red pigment),
C. I. Pigment Green 7,10,36,37,58,59,62,63 etc. (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42,60 (triarylmethane type), 61 (xanthene type), etc. (above, purple pigment),
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 system), 88 (methine-based) and the like (above, blue pigment).

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. Further, as the green pigment, the compound described in Chinese Patent Application No. 1069090227, the phthalocyanine compound having a phosphate ester as a ligand according to International Publication No. 2012/10395, and the like can also be used.

Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.

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

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

As the red pigment, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, The diketopyrrolopyrrole compound described in WO2012 / 102399, the diketopyrrolopyrrole compound described in WO2012 / 117965, the naphtholazo compound described in JP2012-229344 can also be used. can. Further, as the red pigment, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. can.

Dyes can also be used as the colorant. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo system, anilino azo system, triarylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolopyrazole azomethine system, xanthene system, Examples thereof include phthalocyanine-based, benzopyran-based, indigo-based, and pyromethene-based dyes. Further, the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, and the azo compound described in JP-A-2011-145540 can also be preferably used. Further, as the yellow dye, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-054339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can also be used.

A pigment multimer can also be used as the colorant. The dye multimer is preferably a dye that is used by dissolving it in a solvent. Further, the dye multimer may form particles. When the dye multimer is a particle, it is usually used in a state of being dispersed in a solvent. The dye multimer in the particle state can be obtained, for example, by emulsion polymerization, and specific examples thereof include the compounds described in JP-A-2015-214682 and the production method. The 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. The plurality of dye structures contained in one molecule may have the same dye structure or may have different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 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. The dye multimer is described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, International Publication No. 2016/031442, and the like. Compounds can also be used.

Further, as the colorant, the condensed ring type quinophthalone compound described in International Publication No. 2012/128233 and the colorant described in International Publication No. 2011/307195 can also be used.

The content of the colorant is preferably 30 to 70% by mass in the total solid content of the colored photosensitive composition. The lower limit is preferably 35% by mass or more, and 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 a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is replaced with an acid group, a basic group or a phthalimide methyl group. The chromogens constituting the pigment derivative include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthracinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, and iso. Indoline skeleton, isoindolinone skeleton, quinophthalone skeleton, slene skeleton, metal complex skeleton, etc. Preferably, azo skeletons and benzoimidazolone skeletons are more preferred. As the acid group of the pigment derivative, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable.

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 of the molar extinction coefficient at the wavelength region of 400~700nm transparent pigment derivative (.epsilon.max) is that it is preferable, 1000L ^· mol ^{-1 · cm} -1 or less is not more than 3000L ^· mol ^{-1 · cm} -1 Is more preferable, and 100 L · mol ^-1 · cm ^-1 or less is further 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 the pigment derivative include the compounds described in paragraphs 0162 to 0183 of JP-A-2011-52065, the compounds described in JP-A-2003-081972, and the compounds described in Japanese Patent No. 5299151. Can be mentioned.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 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 further preferably 40% by mass or more in 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. As the pigment derivative, only one kind may be used, or two or more kinds 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 a monomer, a prepolymer or an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 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, and 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. It is particularly preferable that the compound contains 6 or more polymerizable groups because it is easy to further improve the temperature cycle resistance and moisture resistance of the formed pixels. 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 crosslink density of the film of the exposed part can be further increased. It is presumed that the penetration of the developing solution can be appropriately suppressed and the pixels firmly adhered to the support and the partition wall can be formed. As a result, it is presumed that the temperature cycle resistance and moisture 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, and more preferably 10 or less. The type of the polymerizable group contained in the polymerizable compound is preferably an ethylenically unsaturated bond group. Examples of the ethylenically unsaturated bonding group include a vinyl group, an allyl group, a (meth) acryloyl group, and the like, an allyl group and a (meth) acryloyl group are preferable, and a (meth) acryloyl group is more preferable.

The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, more preferably a (meth) acrylate compound having 4 to 15 functionalities, and a (meth) acrylate compound having 5 to 15 functionalities. It is even more preferably a 6 to 15 functional (meth) acrylate compound, even more preferably a 6 to 10 functional (meth) acrylate compound, and even more preferably a 3 to 6 functional (meth) acrylate. It is particularly preferred that it is a compound. Specific examples of the polymerizable compound include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and JP-A. 2013-253224, Paragraph Nos. 0034 to 0038, Japanese Patent Application Laid-Open No. 2012-208494, Paragraph Nos. 0477, Japanese Patent Laid-Open No. 2017-048637, Japanese Patent No. 6057891, Japanese Patent No. 6031807, Japanese Patent Application Laid-Open No. 2017-194662. Examples include the compounds described in the publication, the contents of which are incorporated herein.

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

As the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic), 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 Toa Synthetic 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. You can also.

Further, as the polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy-modified tri (meth) acrylate. , A trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate can also be used. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, 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 Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.

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

As the polymerizable compound, a compound having a caprolactone structure can also be used. The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. 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 compound is more preferable. Commercially available products of the polymerizable compound having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330 which is an acrylate.

As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. Examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).

As the polymerizable compound, it is also preferable to use a compound that does not substantially contain an environmentally regulatory substance such as toluene. Examples of 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 as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, 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 No. 01-105238. The polymerizable compounds are UA-7200 (manufactured by Shin-Nakamura Chemical Industry 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, and LINK-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, further preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, further preferably 40% by mass or less. The polymerizable compound may be used alone or in combination of two or more.

<< Photopolymerization Initiator >>
The colored photosensitive composition preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an α-hydroxyketone compound. , Α-Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, the contents of which are incorporated in the present specification.

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

Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2000-080068, compounds described in JP-A-2004-534977, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, Patent No. 6065596, the compound described in International Publication No. 2015/152153, the compound described in International Publication No. 2017/051680, the compound described in JP-A-2017-198865, the compound described in International Publication No. 2017/164127. Examples thereof include the compounds described in paragraph numbers 0025 to 0038 of the issue. Specific examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, 2-acetoxyimiminopentane-3-one, and the like. 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA PTOMER N-1919. (Photopolymerization initiator 2) manufactured by ADEKA Corporation and described in JP2012-014552A. Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and difficult to discolor. Examples of commercially available products include ADEKA ARCLUS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

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

Further, as the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.

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

As the photopolymerization initiator, an oxime compound having a nitro group can be used. 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 paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).

An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication No. 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, and 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, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and 5000 to 20000. It is particularly preferable to have. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure 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 or higher functional photopolymerization initiator may be used. Good sensitivity can be obtained by using such a photopolymerization initiator. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the colored photosensitive composition with time is improved. Can be done. Specific examples of the bifunctional or trifunctional or higher functional photopolymerization initiator include paragraphs of Japanese Patent Laid-Open No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Nos. 0412 to 0417, dimers of oxime compounds described in paragraphs Nos. 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds (G) described in JP-A-2013-522445. ), Cmpd1-7 described in International Publication No. 2016/034943, paragraph No. 0007 of JP-A-2017-523465, an oxime ester photoinitiator, paragraph of JP-A-2017-167399. Examples thereof include the photoinitiator described in Nos. 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 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. Only one kind of photopolymerization initiator may be used, or two or more kinds may be used.

<< Resin >>
The colored photosensitive composition preferably contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in a colored photosensitive composition or for a binder. A resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such use of the resin is an example, and it can be used for purposes other than such use.

The weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000. The upper limit is more preferably 1,000,000 or less, still more preferably 500,000 or less. The lower limit is more preferably 4000 or more, further preferably 5000 or more.

Examples of the resin include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used. Further, the resin described in paragraphs 0041 to 0060 of JP-A-2017-206689, the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856, and the resin described in JP-A-2017-057256. The resin described in JP-A-2017-032685, the resin described in JP-A-2017-075248, and the resin 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. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable. The 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 the side chain, and more preferably contains 1 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 40 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 2 mol% or more, and 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, further preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. 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 even more preferably 20 mgKOH / g or more.

The resin having an acid group preferably further has an ethylenically unsaturated bond group. According to this aspect, it is easy to form a pixel having excellent moisture resistance. Examples of the ethylenically unsaturated bonding group include a vinyl group, an allyl group, a (meth) acryloyl group, and the like, an allyl group and a (meth) acryloyl group are preferable, and a (meth) acryloyl group is more preferable.

The resin having an ethylenically unsaturated bond group preferably contains a repeating unit having an ethylenically unsaturated bond group in the side chain, and the repeating unit having an ethylenically unsaturated bond group in the 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 the repeating unit having an ethylenically unsaturated bond group in the side chain is preferably 60 mol% or less, more preferably 40 mol% or less. The lower limit of the content of the repeating unit having an ethylenically unsaturated bond group in the side chain is preferably 10 mol% or more, more preferably 15 mol% or more.

The ethylenically unsaturated bond base value of the resin is preferably 0.5 to 3 mmol / g. The upper limit is preferably 2.5 mmol / g or less, and more preferably 2 mmol / g or less. The lower limit is preferably 0.9 mmol / g or more, and more preferably 1.0 mmol / g or more. The ethylenically unsaturated bond base value of the resin is a numerical value representing the molar amount of the ethylenically unsaturated bond group 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 base value of 1.0 to 2.0 mmol. It is particularly preferable to contain a resin of / g (preferably 1.2 to 1.8 mmol / g) (hereinafter, this resin is also referred to as resin X). When the colored photosensitive composition contains the above resin X, it is easy to form pixels having a small surface roughness, rectangularity and excellent temperature cycle resistance in the region partitioned by the partition wall. 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 may be 100% by mass, 75% by mass or less, or 50% by mass or less.

The resin used in the present invention contains a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable to include repeating units derived from the monomer component.

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 hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.

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

As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-209760A can be referred to, and the content thereof is incorporated in the present specification.

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 preferably contains a repeating unit derived from the compound represented by the following formula (X).

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, and R ₃ represents a hydrogen atom or a benzene ring having 1 to 20 carbon atoms. Represents the alkyl group of. n represents an integer of 1 to 15.

Examples of the resin having an acid group and / or an ethylenically unsaturated bond group include a resin having the following structure. In the following structural formula, Me represents a methyl group.

The colored photosensitive composition may also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acid dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially acid. A resin consisting only of a group is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger 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 the amount of acid groups and the amount of basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

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

The resin used as the dispersant is also preferably a graft resin. Examples of the graft resin include the resins described in paragraphs 0025 to 0094 of JP2012-255128, the contents of which are incorporated in the present specification.

The resin used as the dispersant is also preferably 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 of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. The resin to have is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Examples of the polyimine-based dispersant include the resins described in paragraphs 0102 to 0166 of JP2012-255128A, the contents of which are incorporated in the present specification.

The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.

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

The dispersant is also available as a commercial product, and specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161 etc.) and Solsperse series manufactured by Lubrizol (for example, Solsperse 36000). And so on. Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification. 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, further preferably 15% by mass or more. The upper limit is more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. 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, further preferably 15% by mass or more. The upper limit is more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. 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, further 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 with cyclic ether group >>
The colored photosensitive composition can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group. Examples of the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group may be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group is more preferably two or more. Examples of the compound having an epoxy group include paragraph numbers 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP-A-2014-0435556, and paragraph numbers 0083-0092 of JP-A-2014-089408. The described compound and the compound described in JP-A-2017-179172 can also be used. These contents are incorporated herein.

The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is less than 1000). 1000 or more) may be used. The weight average molecular weight of the compound having an epoxy group 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 5000 or less, and even more preferably 3000 or less.

Commercially available products of compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G. Examples thereof include -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by NOF CORPORATION, epoxy group-containing polymer) 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, further preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, further preferably 10% by mass or less. The compound having a cyclic ether group may be only one kind or two or more kinds.

<< Silane Coupling Agent >>
The colored photosensitive composition can contain a silane coupling agent. In the present invention, the 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 linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group. , A phenyl group and the like, preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. The contents of are incorporated herein by reference.

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 silane coupling agent may be only one kind or two or more kinds.

<< 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 coatability of the colored photosensitive composition. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like. For these details, paragraph No. 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein by reference. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent 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, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropaneamide and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per tension) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015). Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter 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 filter material 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, and further preferably 30 to 90% by mass.

<< Curing Accelerator >>
In the colored photosensitive composition, a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. The curing accelerator is a methylol-based compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-034963), amines, a phosphonium salt, an amidin salt, and an amide compound (for example, JP-A-2015). The curing agent described in paragraph No. 0186 of Japanese Patent Application Laid-Open No. 2013-041165), the base generator (for example, the ionic compound described in JP-A-2014-0551114), and the cyanate compound (for example, JP-A-2012-150180). The compound described in paragraph No. 0071), the alkoxysilane compound (for example, the alkoxysilane compound having an epoxy group described in JP-A-2011-253504), and the onium salt compound (for example, the paragraph number of JP-A-2015-0349463). A compound exemplified as an acid generator in 0216, a compound 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% by mass, preferably 0.8, based on the total solid content of the colored photosensitive composition. ~ 6.4% by mass is more preferable.

<< Polymerization inhibitor >>
The colored photosensitive composition can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable. 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 a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. For surfactants, paragraphs 0238-0245 of WO 2015/16677 can be referred to, the contents of which are incorporated herein.

The surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the colored photosensitive composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.

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

Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-. The surfactants described in paragraphs 0117 to 0132 of the Publication No. 132503 are mentioned and their contents are incorporated herein by reference. Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS. -330 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like. ..

Further, as the fluorine-based surfactant, 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. For such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the content thereof is incorporated in the present specification.

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。As the fluorine-based surfactant, a block polymer can also be used. For example, the compounds described in JP-A-2011-089090 can be mentioned. The fluorine-based surfactant 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) (meth). 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 the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compounds is preferably 3000 to 50000, for example 14000. Among the above compounds,% indicating the ratio of the repeating unit is mol%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond group in the side chain can also be used. As specific examples, the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965 can be used, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

The content of the surfactant 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 to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount is within the above range.

<< UV absorber >>
The colored photosensitive composition can contain an ultraviolet absorber. As the 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 and the like can be used. For details thereof, refer to paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. It can be taken into consideration and these contents are incorporated in the present specification. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used. 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 kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount is within the above range.

<< Antioxidant >>
The colored photosensitive composition can contain an antioxidant. Examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. 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 may be used. When two or more kinds are used, it is preferable that the total amount is within the above range.

<< Other ingredients >>
The colored photosensitive composition may be a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliaries (eg, conductive particles, fillers, defoaming agents, difficulties, as required). It may contain a fueling agent, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjusting agent, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The descriptions of Nos. 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. Further, the colored photosensitive composition may contain a latent antioxidant, if necessary. The latent antioxidant is a compound whose site that functions as an antioxidant is protected by a protecting group and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.

<Composition for forming an organic layer>
Next, a composition for forming an organic substance layer that can be used for forming an organic substance layer on the surface of a 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 the ethylenically unsaturated bonding group include a vinyl group, an allyl group, a (meth) acryloyl group, and the like, an allyl group and a (meth) acryloyl group are preferable, and a (meth) acryloyl group is more preferable.

The 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 easy to more uniformly apply the composition for forming an organic layer to the partition wall. Therefore, the film-forming property of the composition for forming an organic layer can be improved. Furthermore, the adhesion between the organic material layer and the pixel can be enhanced, and better moisture resistance and temperature cycle resistance can be obtained. Hereinafter, the compound having a monomer-type ethylenically unsaturated bond group is also referred to as monomer A. Further, the compound having a resin type ethylenically unsaturated bond group is also referred to as resin A.

The molecular weight of the monomer A is preferably 100 to 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. The weight average molecular weight of the resin A is preferably 5000 to 20000. The upper limit is preferably 19000 or less, more preferably 18000 or less. The lower limit is preferably 8000 or more, and 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 composition for forming an organic substance 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 compound of the resin A 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. It is more preferable, and it is particularly preferable that the resin A is substantially composed of the resin A alone. According to this aspect, the film-forming property of the organic substance layer is good, and more excellent moisture resistance can be easily obtained. 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 may be 99% by mass or more. It is more preferably 99.5% by mass or more, more preferably 99.9% by mass or more, and particularly preferably composed only of the resin A.

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

(Monomer A)
The monomer A is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities. Specific examples thereof include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and paragraphs 0254 to 0257 of JP2013-253224. It is described in paragraph numbers 0034 to 0038 of Japanese Patent Application Laid-Open No. 2012-208494, paragraph numbers 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 6057891, Japanese Patent Application Laid-Open No. 6031807, and Japanese Patent Application Laid-Open No. 2017-194662. These compounds are incorporated herein by reference. Further, as the monomer A, the compound described in the above-mentioned 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)
The resin A is preferably a polymer containing a repeating unit having an ethylenically unsaturated bond group in the side chain, and more preferably a polymer having a repeating unit represented by the formula (1).

In the formula, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a single bond or a divalent linking group, and P ¹ represents an ethylenically unsaturated bond group.

The ^{alkyl group represented by R 1} is preferably an alkyl group having 1 to 3 carbon atoms, and 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-. There is a group consisting of a combination of one of the above. The alkylene group and the arylene group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxy group, a carboxyl group, an alkoxy group, an aryloxy group and the like. Hydroxy groups are preferred. The alkylene group may be linear, branched or cyclic.

P ¹ 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 a (meth) acryloyl group is more preferable because it has a high polymerization reactivity and more excellent moisture resistance can be easily obtained. preferable.

In the resin A, the content of the repeating unit having an ethylenically unsaturated bond group in the side chain is preferably 5 to 100 mol% of the total repeating unit. 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, further preferably 75 mol% or less, and particularly preferably 70 mol% or less.

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

The resin A preferably further contains a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group. 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, further preferably 3 mol% or more. The upper limit is more preferably 35 mol% or less, further preferably 30 mol% or less.

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

The resin A further preferably contains a repeating unit having an aryl group in the side chain. The proportion of repeating units having an aryl group in the side chain is preferably 1 to 80% by mass of all the repeating units constituting the polymer. The lower limit is more preferably 10 mol% or more, further preferably 15 mol% or more. The upper limit is more preferably 70 mol% or less, further preferably 60 mol% or less.

It is also preferable that the resin A contains a repeating unit derived from the above-mentioned ether dimer.

Specific examples of the resin A include a polymer having the following structure. In the following structural formula, Me represents a methyl group.

As the resin A, a commercially available product can also be used. For example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., manufactured by Ltd), Viscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.). , Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Catalyst Co., Ltd.) and the like.

The composition for forming an organic layer can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Of these, a fluorosurfactant is preferable. The details of the surfactant are the same as those described in the section of 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 composition for forming the organic substance layer 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 type of surfactant may be used, or two or more types may be used in combination. When two or more kinds are used in combination, the total amount is preferably in the above range.

The composition for forming an organic layer preferably contains an organic solvent. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like. The details of the organic solvent are the same as those described in the section of 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 the organic substance 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 substance layer is good, and it is easy to form an organic substance layer which is a thin film and has little variation in film thickness.

The composition for forming an organic layer may further contain other additives such as a photopolymerization initiator and a polymerization inhibitor, but the content of these other additives is the total content of the composition for forming an organic layer. It is preferably 1% by mass or less, more preferably 0.1% by mass or less, and more preferably substantially not contained in the solid content. When substantially no other additives are contained, the content of the other additives is preferably 1% by mass or less, preferably 0.1% by mass, based on the total solid content of the composition for forming an organic layer. It is more preferably less than or equal to, 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 a color filter of the present invention includes the above-mentioned method for manufacturing a structure of the present invention. The color filter can be used for a solid-state image pickup device such as a CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor), an image display device, or the like.

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

<Manufacturing method of image display device>
The method for manufacturing an image display device of the present invention includes the method for manufacturing the structure of the present invention described above. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For details on the definition of image display devices and the details of each image display device, see, for example, "Electronic Display Devices (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Devices (Junaki Ibuki, Industrial Books). Co., Ltd. (issued in 1989) ”. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<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 linked column developing solvent: tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 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 the sample represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g 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 obtained solution was used at 25 ° C. using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo). The titration was neutralized with a 0.1 mol / L aqueous sodium hydroxide solution. The acid value was calculated by the following equation with the inflection point of the titration pH curve as the titration end point.
A = 56.11 x Vs x 0.5 x f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)
f: Titer of 0.1 mol / L sodium hydroxide aqueous solution w: Mass of sample (g) (in terms of solid content)

<Colored photosensitive composition>
(Manufacturing of dispersion Green-1)
C. I. 8 parts by mass of Pigment Green 36 and C.I. I. 6.5 parts by mass of Pressure 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). Was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter), and then 2000 kg / cm using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. ^The dispersion treatment was performed at a flow rate of 500 g / min under the pressure of 3. This dispersion treatment was repeated 10 times to obtain a dispersion liquid Green-1.

(Manufacturing of dispersion Green-2)
C. I. A bead mill (zirconia) is a mixture of 9.5 parts by mass of Pressure 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. with further pressure reducing mechanism after 3 hours mixing and dispersing using beads 0.3mm diameter) high-pressure dispersing machine NANO-3000-10 with (Nippon Biii Co.), flow rate 500g under a pressure of 2000 kg / cm ³ Dispersion processing was performed with / min. This dispersion treatment was repeated 10 times to obtain a dispersion liquid Green-2.

(Manufacturing of dispersion Green-3)
C. I. 8 parts by mass of Pigment Green 36 and C.I. I. A mixed solution 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 0.3 mm diameter). After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to carry ^{out a dispersion treatment at a pressure of 2000 kg / cm 3} at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a dispersion liquid Green-3.

(Manufacturing of dispersion Green-4)
C. I. A mixed solution of 9.5 parts by mass of Pressure 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 0.3 mm diameter). After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to carry ^{out a dispersion treatment at a pressure of 2000 kg / cm 3} at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a dispersion liquid Green-4.

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

(Manufacturing of dispersion liquid Blue-1)
C. I. 10 parts by mass of Pigment Blue 15: 6 and C.I. I. A bead mill (zirconia beads 0.3 mm) is a mixture of 2.3 parts by mass of Pressure 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. After mixing and dispersing for 3 hours using (diameter), further disperse at a flow rate of 500 g / min under a pressure of ^{2000 kg / cm 3} using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. Processing was performed. This dispersion treatment was repeated 10 times to obtain a dispersion liquid Blue-1.

Of the raw materials used in the production of the dispersion, the details of the raw materials indicated by abbreviations 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 (the numerical value added to the main chain is the molar ratio. Mw = 11000, acid value 32 mgKOH / g, ethylenically unsaturated bond base value 1.42 mmol / g)

Resin B-4: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added 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 added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 20000, acid value 77 mgKOH / g)

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

(Manufacturing of Colored Photosensitive Composition)
The following raw materials were mixed to prepare a colored photosensitive composition. The unit of numerical values shown in the table below is 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 described.

Of the raw materials listed in the above table, the details of the raw materials indicated by abbreviations 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 (the numerical value added to the main chain is the molar ratio. Mw = 30,000, acid value 112 mgKOH / g, ethylenically unsaturated bond base value 0 mmol / g)

(Polymerizable compound)
M-1: NK Ester A-TMMT (manufactured by Shin Nakamura Chemical Industry 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 Industry Co., Ltd.)
M-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(Photopolymerization initiator)
Ini-1: IRGACURE-OXE01 (manufactured by BASF)

(Additive)
U-1: Compound with the following structure

(Surfactant)
F-1: A compound having the following structure (Mw = 14000, the numerical value of% indicating the ratio of the repeating unit is mol%, a fluorine-based surfactant).

(Dispersion)
Green-1, Green-2, Green-3, Green-4, Red-1, Blue-1: Dispersions prepared above Green-1, Green-2, Green-3, Green-4, Red-1, Blue-1

<Manufacturing of composition for forming organic layer>
(Composition for Forming Organic Layer 1)
As compounds having an ethylenically unsaturated bond group, 12 parts by mass of Cyclomer P (manufactured by Dycel Ornex, solid content 54% by mass), 87.99 parts by mass of PGMEA, and 0. The composition 1 for forming an organic layer was produced by mixing with 01 parts by mass.

<Manufacturing of developer>
The raw materials listed in the table below were mixed to produce a developer. 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 Yushi Kogyo Co., Ltd., a compound having an alkyl group having 12 carbon atoms and a polyoxyalkylene structure (repeated number of oxyethylene 15))
Surfactant 2: WONDERSURF NDR-1400 (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., a mixed structure of an alkyl group having 10 carbon atoms and a polyoxyalkylene structure (polyoxyethylene structure and polyoxypropylene structure) (Polyoxyethylene structure: Polyoxypropylene structure = 80:20 (mass ratio)) and 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 (polyoxyethylene structure and polyoxypropylene structure mixed 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 (mixed structure of polyoxyethylene structure and polyoxypropylene structure) (Polyoxyethylene structure: Polyoxypropylene structure = 80:20 (mass ratio)) and weight average molecular weight (Mw) 800)
Surfactant 5: WONDERSURF SA-30 / 70 2000R (nonionic surfactant, manufactured by Aoki Yushi Kogyo Co., Ltd., alkyl group with 18 carbon atoms and polyoxyalkylene structure (polyoxyethylene structure and polyoxypropylene structure) 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., phenyl group having an alkyl group having 9 carbon atoms as a substituent, and polyoxyalkylene structure (polyoxyethylene structure and poly) 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., a mixed structure of an alkyl group having 13 carbon atoms and a polyoxyalkylene structure (polyoxyethylene structure and 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., compound having an alkyl group having 13 carbon atoms and a polyoxyalkylene structure (repeated number of oxypropylene 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)

[Manufacturing of Structure] (Examples 1 to 39, Comparative Examples 1 to 3)
A silicon oxide layer was formed on a silicon wafer by a plasma CVD (chemical vapor deposition) method. Next, this silicon oxide layer was patterned by a dry etching method to form partition walls (width 100 nm, thickness 500 nm) made of silicon oxide in a grid pattern at intervals of 0.8 μm. The size of the opening of the partition wall on the silicon wafer (the area partitioned by the partition wall on the silicon wafer) was 0.8 μm in length and 0.8 μm in width. Next, the composition 1 for forming an organic layer is applied onto a silicon wafer having a partition wall formed by a spin coating method, then heated at 110 ° C. for 2 minutes using a hot plate, and then 230 using a hot plate. It was heated at ° C. for 5 minutes to form an organic layer having a film thickness of 13 nm. Next, the colored photosensitive composition described in the table below is applied onto the organic material layer of the silicon wafer on which the organic material layer is formed by a spin coating method so that the film thickness after film formation is 0.6 μm, and then is applied. , 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 at an exposure amount of ^{50 to 2000 mJ / cm 2 through a mask having an island pattern of 0.8 μm.} Then, a developing process was performed using a developing device (Act-8 manufactured by Tokyo Electron). As the developer, the developers listed in the table below were used, and paddle development was performed at 23 ° C. for 60 seconds. Then, after rinsing with a spin shower using pure water, washing with pure water, and then heating at 220 ° C. for 5 minutes using a hot plate, pixels are formed in the region partitioned by the partition wall. The structure was manufactured.

[Manufacturing of Structure] (Example 40)
A silicon oxide layer was formed on a silicon wafer by a plasma CVD (chemical vapor deposition) method. Next, this silicon oxide layer was patterned by a dry etching method to form partition walls (width 100 nm, thickness 500 nm) made of silicon oxide in a grid pattern at intervals of 0.8 μm. The size of the opening of the partition wall on the silicon wafer (the area partitioned by the partition wall on the silicon wafer) was 0.8 μm in length and 0.8 μm in width. Next, the colored photosensitive composition described in the table below is applied onto a silicon wafer on which a partition wall is formed by a spin coating method so that the film thickness after film formation is 0.6 μm, and then a hot plate is applied. It was heated at 110 ° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure amount of ^{50 to 2000 mJ / cm 2 through a mask having an island pattern of 0.8 μm.} Then, a developing process was performed using a developing device (Act-8 manufactured by Tokyo Electron). As the developer, the developers listed in the table below were used, and paddle development was performed at 23 ° C. for 60 seconds. Then, after rinsing with a spin shower using pure water, washing with pure water, and then heating at 220 ° C. for 5 minutes using a hot plate, pixels are formed in the region partitioned by the partition wall. The structure was manufactured.

<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>
Using a cycle thermo tester (LTS-150-W [trade name] manufactured by Hutech), the obtained structure is alternately exposed to -65 ° C and 150 ° C for 15 minutes each in one cycle. The temperature cycle test was performed for 2000 cycles. A focused ion beam (FIB) is used every 100 cycles to prepare a cross-sectional sample of the part where the pixels are embedded in the partition wall, and a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation). The temperature cycle resistance was evaluated by observing the presence or absence of peeling of the pixels. When the pixel is completely peeled off from the silicon wafer, or when the interface of the pixel with the silicon wafer is cracked, it is determined that the pixel is peeled off. The 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 is observed in 1500 cycles or more B: Peeling is observed in 1000 cycles or more and less than 1500 cycles C: Peeling is observed in 750 cycles or more and less than 1000 cycles D: Peeling is observed in 500 cycles or more and less than 750 cycles E: Peeling was observed in less than 500 cycles

<Evaluation of moisture resistance>
The obtained structure was allowed to stand for 500 hours, 750 hours, 1000 hours, and 1500 hours in an atmosphere at a temperature of 85 ° C. and a relative humidity of 85% using a constant temperature and humidity machine (EHS-221M, manufactured by Yamato Kagaku Co., Ltd.). Then, a moisture resistance test was conducted. After the test, a focused ion beam (FIB) was used to prepare a cross-sectional sample of the part where the pixels were embedded in the partition wall, and a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation) was used. The moisture resistance was evaluated by observing the presence or absence of peeling of the pixels. When the pixel is completely peeled off from the silicon wafer, or when the interface of the pixel with the silicon wafer is cracked, it is determined that the pixel is peeled off. The 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 is observed in the moisture resistance test 1500 hours B: No peeling is observed in the moisture resistance test 1000 hours, but peeling is observed in 1500 hours C: No peeling is observed in the moisture resistance test 750 hours, but peeling is observed in 1000 hours. D: No peeling was observed in 500 hours of the moisture resistance test, but peeling was observed in 750 hours. E: Peeling was observed in 500 hours of the moisture resistance test.

<Evaluation of development residue>
The presence or absence of a residue in the portion (non-pixel portion) in which pixels are not embedded in the partition wall of the obtained structure was evaluated by observation with a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation). .. The 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 part B: Residue less than 0.01 μm was observed in the non-pixel part C: Residue of 0.01 μm or more and less than 0.05 μm was observed in the non-pixel part D: Non-pixel part A residue of 0.05 μm or more and less than 0.10 μm was observed in E: A residue of 0.10 μm or more was observed in the non-pixel portion.

<Evaluation of rectangularness>
For the obtained structure, a focused ion beam (FIB) was used to prepare a cross-sectional sample of the portion where the pixels were embedded in the partition wall, and a scanning electron microscope (SEM) (S-4800H, Hitachi High Co., Ltd.) was prepared. The cross-sectional shape of the pixel was observed with (Technology's) to measure the taper angle of the pixel, 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. The taper angle of the pixel is an angle formed by the surface (side surface) of the pixel on the partition wall side and the silicon wafer (board surface).
A: Taper angle is 88 degrees or more and 90 degrees or less B: Taper angle is 85 degrees or more and less than 88 degrees C: Taper angle is 80 degrees or more and less than 85 degrees D: Taper angle is 75 degrees or more and less than 80 degrees E: Taper angle is 75 degrees Less than degree

As shown in the above table, in the examples, the surface roughness, the temperature cycle resistance, the development residue and the rectangularity were all evaluated to be D or higher and were good, and these characteristics could be made parallel. On the other hand, in the comparative example, at least one of these characteristics was an evaluation of E, and the performance was inferior. Regarding these evaluations, it is important that there is no evaluation of E in terms of performance balance.

1: Support 2: Partition 10: Colored photosensitive composition layer 11, 21, 31: Pixel

Claims (17)

A step of applying a colored photosensitive composition on a support provided with a plurality of regions partitioned by a partition wall to form a colored photosensitive composition layer on the support including the inside of the region partitioned by the partition wall. When,
A step of exposing the colored photosensitive composition layer formed on the support in a pattern, and
A step of developing and removing the colored photosensitive composition layer of the unexposed portion using a developing solution to form pixels in the region partitioned by the partition wall.
It is a manufacturing method of a structure containing
A method for producing a structure, which uses an alkaline aqueous solution containing 0.02 to 0.22% by mass of an alkaline agent and a chelating agent as the developing solution. The method for producing a structure according to claim 1, wherein the developer contains 0.10 to 0.18% by mass of an alkaline agent. The method for producing a structure according to claim 1 or 2, wherein the developer contains 0.01 to 0.20% by mass of a chelating agent. The method for producing a structure according to any one of claims 1 to 3, wherein the alkaline agent is an organic base compound. The method for producing a structure according to any one of claims 1 to 4, wherein the developer further contains a surfactant. The method for producing a structure according to claim 5, wherein the surfactant is a nonionic surfactant. The method for producing a structure according to claim 6, wherein the nonionic surfactant is a compound having an alkyl group having 10 to 20 carbon atoms. The method for producing a structure according to claim 6, 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 6 to 8, wherein the nonionic surfactant is a compound containing a polyoxyalkylene structure. The method for producing a structure according to any one of claims 1 to 9, wherein the colored photosensitive composition contains 30 to 70% by mass of a colorant in the total solid content. Any one of claims 1 to 10, wherein the colored photosensitive composition contains a resin having an acid value of 10 to 100 mgKOH / g and an ethylenically unsaturated bond base value of 1.0 to 2.0 mmol / g. A method for manufacturing a structure according to. The method for producing a structure according to any one of claims 1 to 11, wherein the colored photosensitive composition contains a polymerizable compound containing 6 or more polymerizable groups. The method according to any one of claims 1 to 12, wherein a colored photosensitive composition is applied onto the support after forming an organic layer on the surface of the partition wall to form the colored photosensitive composition layer. How to manufacture the structure. The method for producing a structure according to claim 13, wherein the organic layer is formed on the surface of the partition wall using a composition for forming an organic layer containing a compound having an ethylenically unsaturated bond group. A method for manufacturing a color filter, which comprises the method for manufacturing a structure according to any one of claims 1 to 14. A method for manufacturing a solid-state image sensor, which comprises the method for manufacturing the structure according to any one of claims 1 to 14. A method for manufacturing an image display device, which comprises the method for manufacturing the structure according to any one of claims 1 to 14.

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