JP7190508B2 - Structure Manufacturing Method, Color Filter Manufacturing Method, Solid-State Imaging Device Manufacturing Method, and Image Display Device Manufacturing Method - Google Patents

Description

The present invention relates to a method of manufacturing a structure in which pixel regions each composed of a plurality of pixels of the same color are formed in a pattern. The present invention also relates to a method of manufacturing a color filter, a solid-state imaging device, and an image display device, including the method of manufacturing the structure described above.

2. Description of the Related Art In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements. A color filter is manufactured by forming a pattern by photolithography using a colored photosensitive composition, for example. For example, in Patent Document 1, a radical polymerization type colored photosensitive composition is irradiated with exposure energy in an atmosphere having an oxygen concentration of more than 21% by volume so as to form a pattern with a width of 5 μm or less, and then the exposed portion is removed. Developing to form the pixel portion of the color filter is described.

In recent years, it has also been considered to use partition walls between pixels of each color of a color filter. For example, in Patent Document 2, on a semiconductor substrate on which a plurality of photoelectric conversion elements are arranged, a transparent planarization layer, a plurality of color filters arranged corresponding to each photoelectric conversion element, and each photoelectric conversion element A plurality of corresponding microlenses are laminated in this order, and a pixel partition having a lower refractive index than the resin of the color filter is formed on the transparent flattening layer side of the boundary between the color filters adjacent to each other. a solid-state imaging device, wherein the color filter includes a color filter main body disposed on the transparent flattening layer, and a convex lens formed on the color filter main body, the height of the color filter main body describes an invention relating to a solid-state imaging device in which the height is at least twice as high as the height of the pixel partition, and the convex lens portion is formed in a convex lens shape with the convex surface facing the microlens. Paragraph No. 0006 of Patent Document 2 describes that the height of the main body of the color filter is at least twice as high as the height of the pixel partition, so that light outside the transmission wavelength can be sufficiently absorbed, and color separation can be improved. ing.

In recent years, in order to improve the dynamic range of a multi-pixel color filter and to form phase difference detection pixels for imaging pixel sensitivity and autofocus, adjacent pixels are made the same color, and the same color filter is used. It has also been studied to arrange and use a pixel region composed of a plurality of pixels in a pattern (see FIGS. 3 and 4 of Patent Document 3).

JP 2015-052753 A JP 2017-120816 A JP 2016-213622 A

As one mode of the color filter, a structure in which a partition is provided between pixels of each color of the color filter is known. However, in a conventionally known color filter having a structure in which partition walls are provided between pixels, adjacent pixels are pixels of different colors. Also, in Patent Document 3, adjacent pixels are pixels of different colors.

Further, in recent years, the pixel size is becoming finer. Therefore, in forming pixels between the partition walls by photolithography using a colored photosensitive composition, it is becoming difficult to embed the pixels between the partition walls and expose the upper surfaces of the partition walls from the pixels. . For example, the design of masks used for exposure and the pattern formation process tend to be complicated. In Patent Document 2, since the height of the pixels is set to be at least twice the height of the partitions, the upper surfaces of the partitions between the pixels are also covered with the pixels as shown in FIG.

On the other hand, Patent Document 3 describes a color filter in which a plurality of adjacent pixels are of the same color and pixel regions each composed of a plurality of pixels of the same color are arranged in a pattern. does not provide a detailed description of a method for manufacturing a color filter or the like. Furthermore, there is no description or suggestion regarding formation of pixels on a support provided with partition walls.

Moreover, Japanese Patent Laid-Open No. 2002-200000 does not include any description or suggestion regarding formation of pixels on a support provided with partition walls.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel manufacturing method for a structure in which pixel regions each composed of a plurality of pixels of the same color are formed in a pattern. Another object of the present invention is to provide a method for manufacturing a color filter, a method for manufacturing a solid-state imaging device, and a method for manufacturing an image display device, including the method for manufacturing the structure described above.

The present invention provides the following.
<1> A colored photosensitive composition is applied onto a support provided with a plurality of regions partitioned by partition walls to form a colored photosensitive composition layer on the support including the regions partitioned by the partition walls. process and
a step of patternwise exposing the colored photosensitive composition layer formed on the support through a mask having openings capable of simultaneously exposing the colored photosensitive composition layer formed in adjacent regions;
Along with developing and removing the colored photosensitive composition layer in the unexposed area, a part of the colored photosensitive composition layer in the exposed area was also developed and removed so that at least a part of the surface of the partition wall was exposed, and partitioned by the partition wall. forming pixels in the region, forming a pixel region in a pattern, which is composed of a plurality of pixels of the same color and in which at least part of a surface of a partition wall between the pixels is exposed from the pixels;
A method of manufacturing a structure comprising
<2> The method for manufacturing a structure according to <1>, wherein the opening of the mask is provided with a light shielding portion that shields at least part of the position corresponding to the partition.
<3> The method for manufacturing a structure according to <2>, wherein the width of the light shielding portion is 1.0 to 5.0 times the width of the partition.
<4> The colored photosensitive composition contains a radically polymerizable compound and a photoradical polymerization initiator,
The structure according to any one of <1> to <3>, wherein the colored photosensitive composition layer formed on the support is exposed patternwise in an atmosphere having an oxygen concentration exceeding 21% by volume. Production method.
<5> The method for producing a structure according to <4>, wherein the oxygen concentration is 55% by volume or less.
<6> Any one of <1> to <5>, wherein the colored photosensitive composition layer formed on the support is exposed in a pattern at an exposure illuminance of 2500 to 50000 W/m ² . A method of manufacturing a structure.
<7> The method for producing a structure according to any one of <1> to <6>, wherein the partition walls have a height of 0.3 to 1.2 μm.
<8> The method for manufacturing a structure according to any one of <1> to <7>, wherein the partition walls have a width of 0.05 to 0.2 μm.
<9> A method for producing a color filter, including the method for producing the structure according to any one of <1> to <8>.
<10> A method for manufacturing a solid-state imaging device, including the method for manufacturing the structure according to any one of <1> to <8>.
<11> A method for manufacturing an image display device, including the method for manufacturing the structure according to any one of <1> to <8>.

INDUSTRIAL APPLICABILITY The present invention can provide a novel manufacturing method for a structure in which a pixel region composed of a plurality of pixels of the same color is formed in a pattern. Further, it is possible to provide a method for manufacturing a color filter, a method for manufacturing a solid-state imaging device, and a method for manufacturing an image display device, including the method for manufacturing the structure described above.

FIG. 2 is a plan view of the support 1 as seen from directly above; FIG. 2 is a cross-sectional view taken along the line AA of FIG. 1; FIG. 2 is a diagram showing a state in which a colored photosensitive composition layer is formed on a support; FIG. 10 illustrates an embodiment of an exposure process; FIG. 5 is a diagram showing an embodiment of a mask, and is a plan view of the portion surrounded by the dashed line in FIG. FIG. 10 is a diagram showing another embodiment of the exposure process; FIG. 7 is a diagram showing an embodiment of a mask used in the exposure process, and is a plan view of the portion surrounded by the dashed line in FIG. FIG. 4 is a diagram showing the state after the development process, and is a plan view of the support 1 as seen from directly above. FIG. 9 is a cross-sectional view taken along line AA of FIG. 8; FIG. 11 illustrates one embodiment of a structure; 1 is a cross-sectional view of a mask 1; FIG. FIG. 4 is a cross-sectional view of masks 2-6;

Principal embodiments of the present invention are described below. However, the invention is not limited to the illustrated embodiments.

In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.

As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.

Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or unsubstituted means that not only those not having substituents but also those having substituents are included. For example, when simply describing an "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Meaning.

In this specification, the term “exposure” includes not only drawing using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, the energy rays used for exposure include the emission line spectrum of mercury lamps, far ultraviolet rays (ArF, KrF, etc.) represented by excimer lasers, extreme ultraviolet rays (EUV light) and actinic rays such as X-rays, and electron beams and Particle beams such as ion beams are included.

As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.

As used herein, the concentration of solids in a composition is represented by the mass percentage of other components, excluding solvent, relative to the total mass of the composition.

In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are shown as polystyrene equivalent values according to gel permeation chromatography (GPC measurement), unless otherwise specified. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are measured by using, for example, HLC-8220 (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). In addition, unless otherwise stated, measurements are taken using THF (tetrahydrofuran) as an eluent. Unless otherwise specified, a UV ray (ultraviolet) wavelength detector of 254 nm is used for detection in GPC measurement.

In this specification, unless otherwise specified, the direction in which the layers are stacked with respect to the support is referred to as "up", and the opposite direction is referred to as "down". It should be noted that such setting of the vertical direction is for the sake of convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from the vertical upward direction.

<Method for manufacturing structure>
The method for manufacturing the structure of the present invention comprises:
A step of applying a colored photosensitive composition onto a support provided with a plurality of regions partitioned by partition walls to form a colored photosensitive composition layer on the support including the regions partitioned by the partition walls;
a step of patternwise exposing the colored photosensitive composition layer formed on the support through a mask having openings capable of simultaneously exposing the colored photosensitive composition layer formed in adjacent regions;
Along with developing and removing the colored photosensitive composition layer in the unexposed area, a part of the colored photosensitive composition layer in the exposed area was also developed and removed so that at least a part of the surface of the partition wall was exposed, and partitioned by the partition wall. forming pixels in the region, forming a pixel region in a pattern, which is composed of a plurality of pixels of the same color and in which at least part of a surface of a partition wall between the pixels is exposed from the pixels;
characterized by comprising

According to the present invention, a structure is manufactured in which a pixel region is formed in a pattern, and is composed of a plurality of pixels of the same color, and at least a part of the surface of the partition between the pixels is exposed from the pixels. can be done. In addition, since at least part of the surface of the partition wall between the individual pixels constituting the pixel region is exposed from the pixel, this structure effectively improves the color separation performance and the leakage of light to the adjacent pixel. can also be effectively suppressed.

Further, according to the present invention, the colored photosensitive composition layer formed in a plurality of adjacent regions is exposed using a mask having openings that can be exposed simultaneously, and the colored photosensitive composition layer and the unexposed portion of the colored photosensitive composition layer are exposed at the same time. Since pixels are formed by removing part of the colored photosensitive composition layer in the exposed areas by development, individual pixels constituting one pixel region can be formed at the same time, and the manufacturing process of the structure is simple. . Furthermore, even if the size of each pixel constituting one pixel region becomes finer, the process of mask processing design and pattern formation can be simplified. For example, as shown in FIGS. 8 and 10, when a pixel region 35 made up of four pixels 30 is formed in a pattern, an area of four pixels is set as one exposure area, which is divided into four by development and divided into individual areas. This is for forming a pixel of .

It is also preferable that the opening of the mask used in the manufacturing method of the structure of the present invention is provided with a light shielding part for shielding at least part of the position corresponding to the partition wall. By using such a mask, the colored photosensitive composition layer on the partition wall can be more effectively removed by development during development.

As a means for developing and removing a part of the colored photosensitive composition layer in the exposed area so that at least a part of the surface of the barrier ribs is exposed during development, for example, a radically polymerizable compound and light as the colored photosensitive composition are used. and a radical polymerization initiator, and exposing such that the radical polymerization reaction of the surface layer of the colored photosensitive composition layer is deactivated. By deactivating the radical polymerization reaction of the colored photosensitive composition layer of the surface layer, the surface layer of the colored photosensitive composition layer of the exposed portion is easily removed during development, and at least a part of the surface of the partition wall is exposed. Then, part of the colored photosensitive composition layer in the exposed area can be removed by development together with the unexposed area.

As a means for performing exposure so as to deactivate the radical polymerization reaction of the surface layer of the colored photosensitive composition layer, a method of exposing in an atmosphere with an oxygen concentration exceeding 21% by volume, and a method of exposing the material in the composition to an oxygen environment. and a method of using a photoradical polymerization initiator having high radical quenching properties, and a method of using a radically polymerizable compound having a small ethylenically unsaturated bond value.

As a preferred embodiment of the method for producing a structure of the present invention, the colored photosensitive composition contains a radically polymerizable compound and a photoradical polymerization initiator, and the colored photosensitive composition layer is formed on a support. and patternwise exposure in an atmosphere with an oxygen concentration exceeding 21% by volume. According to this aspect, the radical polymerization reaction of the surface layer of the colored photosensitive composition layer is easily inhibited by oxygen and deactivated, and the surface layer of the colored photosensitive composition layer is easily removed during development. The oxygen concentration is preferably 25% by volume or more, more preferably 30% by volume or more. The upper limit is preferably 55 vol% or less, more preferably 50 vol% or less, and 40 vol. % or less. Also, the exposure illuminance at the time of exposure is preferably 2500 to 50000 W/m ² . If the exposure illuminance is within the above range, the radical polymerization reaction of the surface colored photosensitive composition layer can be more effectively deactivated. The upper limit is preferably 30,000 W/m ² or less, more preferably 15,000 W/m ² or less, because the deactivation effect of the radical polymerization reaction due to oxygen inhibition is likely to be obtained more remarkably. The lower limit is preferably 3000 W/m ² or more, more preferably 5000 W/m ² or more, from the viewpoint of pixel formability. Also, the exposure energy during exposure is preferably 1000 to 10000 J/m ² . The upper limit is preferably 8,000 J/m ² or less, more preferably 6,000 J/m ² or less, because the deactivation effect of the radical polymerization reaction due to oxygen inhibition is likely to be obtained more remarkably. From the viewpoint of adhesion, the lower limit is preferably 2000 J/m ² or more, more preferably 3000 J/m ² or more.

Hereinafter, the method for manufacturing the structure of the present invention will be described in more detail with reference to the drawings.

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

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

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

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

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

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

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

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

The pitch width P1 of the partition walls 2 is preferably 0.5 to 2.0 μm. The lower limit is preferably 0.6 μm or more, more preferably 0.7 μm or more, and even more preferably 0.8 μm or more. The upper limit is preferably 1.8 μm or less, more preferably 1.4 μm or less, and even more preferably 1.2 μm or less. The pitch width P1 of the partition walls 2 is the arrangement pitch of adjacent partition walls. As the pitch width P1 becomes shorter, the pixel size becomes smaller.

A protective layer may be provided on the surface of the partition wall 2 . Various inorganic materials and organic materials can be used as the material of the protective layer. Examples of organic materials include acrylic resins, polystyrene resins, polyimide resins, and organic SOG (Spin On Glass) resins. A protective layer can also be formed using a composition containing a compound having a group having an ethylenically unsaturated bond. The group having an ethylenically unsaturated bond includes a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a styryl group and the like, and a (meth)allyl group and a (meth)acryloyl group are preferred. A compound having a group having an ethylenically unsaturated bond may be a monomer or a resin such as a polymer. Inorganic materials include silicon dioxide and the like.

The protective layer can be formed using a conventionally known method. When forming a protective layer composed of an organic material, for example, a composition containing an organic material can be applied onto the partition walls and dried to form the protective layer. When forming a protective layer composed of an inorganic material, for example, the inorganic material constituting the protective layer is deposited on the surface of the protective layer by a vapor deposition method such as chemical vapor deposition (CVD) or vacuum deposition, or a method such as sputtering. It can be formed as a film.

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

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

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

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

(Exposure process)
Next, as shown in FIG. 4, a colored photosensitive composition layer 10a formed in an adjacent region is exposed simultaneously through a mask 20 having openings 25. The composition layer 10 is exposed (exposure step). That is, in this step, a plurality of pixels are exposed as one exposure area. For example, in FIGS. 4 and 5, four pixels at positions corresponding to the openings 25 of the mask 20 are the exposure area. Further, as shown in FIGS. 6 and 7, even when the light shielding portion 22 is formed in a part of the opening 25a of the mask 20a, four pixels at the position corresponding to the opening 25a of the mask 20a are It corresponds to the exposure area.

The number of colored photosensitive composition layers 10a to be exposed simultaneously in one exposure area can be appropriately selected. For example, when the number of pixels forming one pixel region is four, four adjacent colored photosensitive composition layers are exposed at the same time. That is, four pixels of the colored photosensitive composition layer 10a are simultaneously exposed.

FIG. 5 is an embodiment of a mask having openings that allow simultaneous exposure of four adjacent colored photosensitive composition layers, and is the portion of the mask 20 shown in FIG. 2 is a plan view of the support 1 as seen from directly above. FIG. This mask 20 has colored photosensitive composition layers 10a in four adjacent regions partitioned by partition walls 2, and openings 25 at positions corresponding to the partition walls 2a between the colored photosensitive composition layers 10a. formed. By using such a mask 20, it is possible to irradiate and expose the colored photosensitive composition layer 10a formed in four adjacent regions with the light h.

Further, in the present invention, as shown in FIG. 6, as a mask 20a, light shielding portions 22 are provided in the openings 25a of the mask 20a to shield at least part of the positions corresponding to the partition walls 2a between the colored photosensitive composition layers 10a. may be used. The light shielding portion 22 may be made of the material forming the mask 20a. When such a mask is used, the colored photosensitive composition layer on the partition walls 2a can be more effectively removed by development during development. The width of the light shielding portion 22 is preferably 0.5 to 5.0 times the width of the partition wall, more preferably 1.0 to 4.0 times, even more preferably 1.0 to 3.0 times. The light shielding portion 22 preferably has a transmittance of 1.0% or less, more preferably 0.5% or less, and even more preferably 0.1% or less for light having a wavelength used for exposure. .

FIG. 7 shows an embodiment of a mask having openings capable of simultaneously exposing four adjacent colored photosensitive composition layers and having the light shielding portions provided in the openings, which is the mask shown in FIG. FIG. 2 is a plan view of a portion surrounded by a dashed line including an opening 25a of 20a, viewed from directly above the support 1; The mask 20a is provided with light shielding portions 22 at positions corresponding to the partition walls 2a between the colored photosensitive composition layers 10a.

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

The exposure illuminance during exposure (in the case of pulse exposure, the average value within the exposure time) is preferably 2,500 to 50,000 W/m ² . The upper limit is preferably 30000 W/m ² or less, more preferably 15000 W/m ² or less. The lower limit is preferably 3000 W/m ² or more, more preferably 5000 W/m ² or more.

Exposure energy during exposure is preferably 1000 to 10000 J/m ² . The upper limit is preferably 8000 J/m ² or less, more preferably 6000 J/m ² or less. The lower limit is preferably 2000 J/m ² or more, more preferably 3000 J/m ² or more.

The oxygen concentration at the time of exposure can be appropriately selected, and the exposure may be performed in the atmosphere (oxygen concentration is 20 to 21% by volume), or the exposure may be performed in an oxygen atmosphere with an oxygen concentration of less than 20% by volume. , the exposure may be performed in an oxygen atmosphere with an oxygen concentration exceeding 21% by volume. In the present invention, exposure is preferably performed in an oxygen atmosphere with an oxygen concentration of more than 21% by volume. Among them, when the colored photosensitive composition layer is formed using a colored photosensitive composition containing a radically polymerizable compound and a photoradical polymerization initiator, the oxygen concentration exceeds 21% by volume in an oxygen atmosphere. is preferred. By exposing in an atmosphere with a high oxygen concentration, the radical polymerization reaction of the surface layer of the colored photosensitive composition layer is inhibited by oxygen and is easily deactivated, and the surface layer of the colored photosensitive composition layer is unexposed during development. Easy to remove along with the part. The oxygen concentration is preferably 25% by volume or more, more preferably 30% by volume or more. The upper limit is preferably 55 vol% or less, more preferably 50 vol% or less, and 40 vol. % or less.

(Step of forming pixel regions in a pattern (development step))
Next, as shown in FIGS. 8 and 9, the colored photosensitive composition layer in the unexposed area is developed and removed, and at least a part of the surface (preferably the upper surface) of the partition walls is exposed. A part of the organic composition layer is also developed and removed to form pixels 30 in the regions partitioned by the partition walls, thereby forming a plurality of pixels of the same color and the surface of the partition walls 2a between the pixels 30. At least part of the pixel region 35 exposed from the pixel 30 is formed in a pattern. 8 is a plan view of the support 1 as seen from directly above, and FIG. 9 is a sectional view taken along the line AA of FIG.

Development and removal of the colored photosensitive composition layer can be performed using a developer. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

Examples of the developer include organic solvents and alkaline developers, and the alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene. Alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. A nonionic surfactant is preferable as the surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times.

A known method can be used as the developing method. Examples thereof include immersion development, puddle development, shower development, spray development, ultrasonic development, and dip development. Paddle development and spray development are preferred, and spray development is more preferred because residues can be efficiently removed. Note that spray development is a method in which a developer pressurized by a gas such as N ₂ or air is discharged from a nozzle, and the developer is spray-coated onto a target for development. In the spray development, the target is developed by the spray pressure while a spray-like developer discharged from a nozzle is heaped up on the target. A composite development method including a step of puddle development after liquid development by spray development may be used.

The flow rate of the developer in the spray development, the flow rate ratio of the developer and the gas, the spray pressure, etc. can be appropriately adjusted. For example, the developer flow rate is preferably 30 to 500 mL/min, more preferably 50 to 400 mL/min, and even more preferably 200 to 350 mL/min. Further, the flow ratio of the developer and the gas is, for example, preferably developer:gas = 1:1.5 to 1:50, more preferably 1:2 to 1:30. :2.5 to 1:20 is more preferable. Also, the spray pressure is preferably 3 to 15 MPa, more preferably 5 to 12 MPa, and even more preferably 7 to 9 MPa.

It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the support after development while rotating the support after development. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.

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

In this manner, a pixel region 35 composed of a plurality of pixels of the same color and having at least a portion (preferably the upper surface) of the surface of the partition wall 2a between the pixels 30 exposed from the pixels 30 is formed in a pattern. can do. In FIG. 8, one pixel region 35 is composed of four pixels 30, but the number of pixels that constitute one pixel region may be two or three. Well, it may be 5 or more. In FIG. 8, the individual pixels 30 forming one pixel region 35 are arranged two in the x direction and two in the y direction of FIG. The arrangement method of pixels is not particularly limited, and various arrangements can be adopted. For example, when one pixel region is composed of four pixels, in addition to the arrangement method shown in FIG. 8, one pixel region is formed by continuously arranging four pixels in the x direction. Alternatively, one pixel region may be formed by continuously arranging four pixels in the y direction.

In FIG. 9, the height H1 of the partition wall 2 and the thickness (height) H2 of the pixel 30 are substantially the same, but the height H1 of the partition wall 2>the thickness (height) H2 of the pixel 30 is satisfied. Alternatively, the height H1 of the partition wall 2<thickness (height) H2 of the pixel 30 may be satisfied. The thickness (height) H2 of the pixel 30 is preferably 0.8 to 1.3 times, more preferably 0.9 to 1.2 times, the height H1 of the partition wall 2 because color mixing is easily suppressed. is more preferable, and 0.9 to 1.1 times is even more preferable. In addition, although the upper surface of the pixel 30 is substantially flat in FIG. 9, the surface may have unevenness.

In the case of forming a structure in which pixel regions of a plurality of colors are formed in a pattern as shown in FIG. 10, it can be manufactured by repeating the above steps for each pixel of each color. FIG. 10 is a plan view of a structure in which three-color pixel regions 35, 45, and 55 are formed in patterns. Pixels 30, 40 and 50 are pixels of different hues. For example, the pixel 30 may be a green pixel, the pixel 40 may be a red pixel, and the pixel 50 may be a blue pixel. The type and arrangement of pixels can be appropriately selected according to the application and purpose.

A structure manufactured according to the present invention can be preferably used for a color filter or the like. Moreover, the structure manufactured by the present invention can be used by incorporating it into a solid-state imaging device, an image display device, or the like. Examples of image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices. It can also be used by incorporating it into an imaging device mounted on a digital still camera, a digital video camera, a surveillance camera, an in-vehicle camera, or the like.

<Colored photosensitive composition>
Next, the colored photosensitive composition used in the method for producing a 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-transmitting pixels, and light-shielding pixels. , red pixels, green pixels and blue pixels. Further, when a film having a thickness of 0.3 to 1.0 μm is formed using the colored photosensitive composition, at least one of the above film thicknesses has a transmittance of 0.5% or more for light with a wavelength of 365 nm. is preferably 1.0% or more, and even more preferably 5.0% or more.

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

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

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

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

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

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

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

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

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

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

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

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

The content of the colorant is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 40% by mass or more, based on the total solid content of the colored photosensitive composition. . The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less.

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

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

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

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

<<Radical polymerizable compound>>
The colored photosensitive composition preferably contains a radically polymerizable compound. The radically polymerizable compound is preferably, for example, a compound having an ethylenically unsaturated bond group. Examples of ethylenically unsaturated bond groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

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

The radical polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond groups, and an ethylenically unsaturated bond group. is more preferably a compound containing 3 to 6 The radically polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of the radically polymerizable compound include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and Paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662 Nos. 2004/0130001 and 2004/0000009, the contents of which are incorporated herein.

Examples of radically polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku ( Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Yaku Co., Ltd., NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (for example, SR454, SR499, commercially available from Sartomer) are preferred.

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

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

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

It is also a preferred embodiment that the radically polymerizable compound is a compound having a caprolactone structure. Radically polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

A radically polymerizable compound having an alkyleneoxy group can also be used as the radically polymerizable compound. The radically polymerizable compound having an alkyleneoxy group is preferably a radically polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a radically polymerizable compound having an ethyleneoxy group, and has 4 to 20 ethyleneoxy groups. 3- to 6-functional (meth)acrylate compounds having Examples of commercially available radically polymerizable compounds having an alkyleneoxy group include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth)acrylate having three isobutyleneoxy groups. ) KAYARAD TPA-330, which is an acrylate.

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

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

Examples of radically polymerizable compounds include urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. , JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. In addition, it is also preferable to use a radically polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. . Further, the radically polymerizable compound includes UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, and AH-600. , T-600, AI-600, and LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

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

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

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

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

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

In the present invention, an oxime compound having a fluorene ring can also be used as a radical photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A-2014-137466.

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

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

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

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a radical photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.

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

As the radical photopolymerization initiator, a difunctional or trifunctional or higher radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered and the solubility in a solvent or the like is improved, making it difficult to precipitate over time, thereby improving the stability over time of the colored photosensitive composition. can be done. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0412 to 0417, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, and the like.

The content of the radical 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 type of radical photopolymerization initiator may be used, or two or more types 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 pigment in the colored photosensitive composition and for the purpose of binder. A resin that is mainly used to disperse particles such as pigments is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

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

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

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

The resin having an acid group preferably contains a repeating unit having an acid group on its side chain, and more preferably contains 5 to 70 mol % of repeating units having an acid group on its side chain in the total repeating units of the resin. The upper limit of the content of repeating units having an acid group in the side chain is more preferably 50 mol % or less, particularly preferably 30 mol % or less. The lower limit of the content of repeating units having an acid group in the side chain is more preferably 10 mol % or more, particularly preferably 20 mol % or more.

As the resin having an acid group, for example, a resin containing a repeating unit derived from an ether dimer described in paragraphs 0313 to 0317 of JP-A-2013-029760 can also be used.

For the resin having an acid group, JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408 The descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein. Moreover, resin which has an acid group can also use a commercial item.

The acid value of the resin having acid groups is preferably 30-500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, still more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the acid group-containing resin is preferably 5,000 to 100,000. Moreover, the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.

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

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, it is possible to further suppress the generation of development residues when forming a pattern by photolithography.

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

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

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

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

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in its side chain. The content of repeating units having an ethylenically unsaturated bond group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70 mol, of the total repeating units of the resin. % is more preferred.

Dispersants are also available as commercial products, and specific examples thereof include BYK Chemie's DISPERBYK series (e.g., DISPERBYK-111, 161, etc.), Nippon Lubrizol Co., Ltd.'s Solsperse series ( For example, Solsperse 76500, etc.). Also, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can be used, the contents of which are incorporated herein. In addition, the resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.

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

The total content of the radically polymerizable compound and the resin in the total solid content of the colored photosensitive composition is preferably 10 to 65% by mass from the viewpoint of curability, developability and film formation. The lower limit is more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more. The upper limit is more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less. Moreover, it is preferable to contain 30 to 300 parts by mass of the resin with respect to 100 parts by mass of the polymerizable compound. The lower limit is more preferably 50 parts by mass or more, and even more preferably 80 parts by mass or more. The upper limit is more preferably 250 parts by mass or less, and even more preferably 200 parts by mass or less.

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

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

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

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

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

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

<<Surfactant>>
The colored photosensitive composition can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicon surfactants can be used. Surfactants include those described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.

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

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, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- 132503, paragraphs 0117-0132, the contents of which are incorporated herein. In addition, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

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

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

<<Ultraviolet absorber>>
The colored photosensitive composition can contain an ultraviolet absorber. A conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used as the ultraviolet absorber. Such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, paragraph numbers 0317-0334 of JP-A-2013-068814, Examples include compounds described in paragraphs 0061-0080 of JP2016-162946, the contents of which are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). Further, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as the ultraviolet absorber.

The content of the ultraviolet absorber in the total solid content of the colored photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used.

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

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

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

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

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

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

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

<Production of support having partition walls>
A silicon wafer having a diameter of 8 inches (20.32 cm) was spin-coated with the following barrier rib-forming composition, heated on a hot plate at 100° C. for 2 minutes, and further heated at 230° C. for 2 minutes to form a film. A barrier rib material layer having a thickness of 0.5 μm was formed. A positive photoresist (FFPS-0283, manufactured by Fuji Film Electronic Materials Co., Ltd.) was spin-coated on the barrier rib material layer and heated at 90° C. for 1 minute to form a photoresist layer with a thickness of 1.0 μm. did. Next, using a KrF scanner exposure machine (FPA6300ES6a, manufactured by Canon Inc.), exposure was performed through a mask with an exposure energy of 16 J/cm ² , followed by heat treatment at 100° C. for 1 minute. After that, after developing for 1 minute with a developer (FHD-5, manufactured by Fujifilm Electronic Materials Co., Ltd.), heat treatment is performed at 100 ° C. for 1 minute to form a mesh with a line width of 0.12 μm and a pitch width of 1 μm. formed a pattern. Using this pattern as a photomask, patterning is performed by a dry etching method under the conditions described in paragraphs 0129 to 0130 of Japanese Patent Application Laid-Open No. 2016-014856. They were formed in a grid shape at intervals to form partition walls having the shape shown in FIGS. 1 and 2 (W1=0.1 μm, H1=0.5 μm, P1=1 μm in FIG. 2). The size of the opening of the partition on the silicon wafer (the area for one pixel separated by the partition on the silicon wafer) was 0.9 μm long×0.9 μm wide. Together with the 0.1 μm barrier rib width, this example defines a 1.0 μm pixel size.

[Partition-forming composition]
A composition for forming partition walls was prepared by the following method.
First, tetraethoxysilane (TEOS) was prepared as silicon alkoxide (A), and trifluoropropyltrimethoxysilane (TFPTMS) was prepared as fluoroalkyl group-containing silicon alkoxide (B). Weighed so that the ratio (mass ratio) of the fluoroalkyl group-containing silicon alkoxide (B) was 0.6 when the mass of the silicon alkoxide (A) was 1, and put them into a separable flask. A mixture was obtained by mixing. A first liquid was prepared by adding propylene glycol monomethyl ether (PGME) in an amount of 1.0 part by mass to 1.0 part by mass of this mixture and stirring at a temperature of 30°C for 15 minutes. Separately from the first liquid, 1.0 parts by mass of ion-exchanged water and 0.01 parts by mass of formic acid are added to 1.0 parts by mass of the above mixture, and mixed. and stirred at a temperature of 30° C. for 15 minutes to prepare a second liquid. Next, the first liquid prepared above was maintained at a temperature of 55° C. in a water bath, the second liquid was added to the first liquid, and the mixture was stirred for 60 minutes while maintaining the temperature. Thus, a solution F containing a hydrolyzate of the silicon alkoxide (A) and the fluoroalkyl group-containing silicon alkoxide (B) was obtained. The solid content concentration of this solution F was 10% by mass in terms of SiO ₂ . Next, 100 parts by mass of an aqueous dispersion containing 30% by mass of commercially available colloidal silica having an average diameter of 15 nm (manufactured by Nissan Chemical Industries, Ltd., trade name ST-30) was added with 0.1 of an aqueous solution of calcium nitrate having a concentration of 30% by mass. The mixed liquid added by mass parts was heated at 120° C. for 5 hours in a stainless steel autoclave. This mixed solution is subjected to ultrafiltration, the solvent is replaced with propylene glycol monomethyl ether, the mixture is stirred for 30 minutes at a rotational speed of 14000 rpm using a homomixer (manufactured by Primix), and propylene glycol monomethyl ether is added. Thus, a colloidal silica particle liquid G having a solid content concentration of 15% by mass was obtained. 30 parts by mass of the solution F and 70 parts by mass of the colloidal silica particle liquid G are mixed, further heated at 40° C. for 10 hours, and centrifuged at 1000 G for 10 minutes to remove sediments to obtain spherical particles. The average particle size of silica (equivalent circle diameter in a projected image of a spherical portion measured by a transmission electron microscope (TEM)) is 15 nm, and the average particle size of colloidal silica particles measured by a dynamic light scattering method is 80 nm. A colloidal silica particle liquid P1 was obtained.

Next, using the colloidal silica particle liquid obtained above, each component was mixed so as to have the composition shown in the following table to obtain a composition for forming partition walls. After preparation of the colloidal silica particle liquid and after preparation of the partition forming composition, filtration was performed using DFA4201NIEY (0.45 μm nylon filter) manufactured by Nippon Pall.

The numerical values of the compounding amounts shown in the above table are parts by mass. Also, the amount of the colloidal silica particle liquid to be blended is the amount of SiO ₂ in the particle liquid. The numerical value of the blending amount of the solvent is the total amount of the solvent contained in the colloidal silica particle liquid. The raw materials listed in the above table are as follows.

（溶剤）
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＬＣ－ＯＨ：エタノール、メタノールまたはそれらの混合物
Ｗ：水(Colloidal silica particle liquid)
P1: Colloidal silica particle liquid P1 described above
(Surfactant)
F1: a compound having the following structure (Mw=14000, % indicating the ratio of repeating units is mol%)

(solvent)
PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate LC-OH: ethanol, methanol or a mixture thereof W: water

<Preparation of colored photosensitive composition>
(Green colored photosensitive composition)
The following raw materials were mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.1 mm) to prepare a pigment dispersion. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism, dispersion treatment was carried out under conditions of a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersing treatment was repeated up to 10 times to obtain a pigment dispersion liquid G1.
PG58 8.5 parts by mass PY185 2.9 parts by mass Pigment derivative 1 1.6 parts by mass Dispersant 1 4.7 parts by mass PGMEA (propylene glycol monomethyl ether acetate) 82.3 part by mass

Subsequently, after stirring a mixed liquid obtained by mixing the following raw materials, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to obtain a green colored photosensitive composition.
Pigment dispersion liquid G1...69.0 parts by mass 40% by mass PGMEA solution of resin 1...1.2 parts by mass Polymerizable monomer 1...1.1 parts by mass Photopolymerization initiator 1 0.5 parts by mass 1% by mass PGMEA solution of surfactant 1 4.2 parts by mass UV absorber 1 0.5 parts by mass Epoxy group-containing compound 1 0 .2 parts by mass PGMEA ... 23.3 parts by mass

(Red colored photosensitive composition)
A mixed liquid obtained by mixing the following raw materials was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.1 mm) to prepare a pigment dispersion liquid. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism, dispersion treatment was carried out under conditions of a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersing treatment was repeated up to 10 times to obtain a pigment dispersion liquid R1.
・PR254 10.5 parts by mass ・PY139 0.9 parts by mass ・Pigment derivative 1 1.6 parts by mass ・Dispersant 1 4.7 parts by mass ・PGMEA 82.3 parts by mass

Subsequently, after stirring a mixed liquid obtained by mixing the following raw materials, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to obtain a red colored photosensitive composition.
Ingredients of the composition:
Pigment dispersion liquid R1...58.9 parts by mass 40% by mass PGMEA solution of resin 1...2.0 parts by mass Polymerizable monomer 1...0.9 parts by mass Photopolymerization initiator 1 0.5 parts by mass 1% by mass PGMEA solution of surfactant 1 4.2 parts by mass UV absorber 1 0.1 parts by mass Epoxy group-containing compound 1 0 .1 parts by mass PGMEA ・・・33.3 parts by mass

(Blue colored photosensitive composition)
A mixed liquid obtained by mixing the following raw materials was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.1 mm) to prepare a pigment dispersion liquid. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism, dispersion treatment was carried out under conditions of a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersing treatment was repeated up to 10 times to obtain a pigment dispersion B1.
PB15: 6 9.6 parts by mass PV23 2.4 parts by mass Pigment derivative 1 1.0 parts by mass Dispersant 1 4.7 parts by mass PGMEA 82.3 parts by mass

Subsequently, after stirring a mixed liquid obtained by mixing the following raw materials, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to obtain a blue colored photosensitive composition.
・Pigment dispersion liquid B1 ... 54.1 parts by mass ・40% by mass PGMEA solution of resin 1 ... 1.0 parts by mass ・Polymerizable monomer 1 ... 0.9 parts by mass ・Photopolymerization initiator 1 ・0.6 parts by mass 1% by mass PGMEA solution of surfactant 1 4.2 parts by mass UV absorber 1 0.1 parts by mass Epoxy group-containing compound 1 0 .1 parts by mass PGMEA ・・・39.0 parts by mass

・分散剤１：下記構造の樹脂。主鎖に付記された数値は繰り返し単位のモル比であり、側鎖に付記された数値は繰り返し単位の数である。Ｍｗ＝２００００

Details of raw materials used in the colored photosensitive composition are as follows.
・PG58: C.I. I. Pigment Green 58
- PY185: C.I. I. Pigment Yellow 185
・PR254: C.I. I. Pigment Red 254
・PY139: C.I. I. Pigment Yellow 139
・PB15:6: C.I. I. Pigment Blue 15:6
・PV23: C.I. I. Pigment Violet 23
- Pigment derivative 1: a compound having the following structure

- Dispersant 1: A resin having the following structure. The numerical value attached to the main chain is the molar ratio of the repeating units, and the numerical value attached to the side chain is the number of repeating units. Mw=20000

・重合性モノマー１：下記構造の化合物

・光重合開始剤１：下記構造の化合物

・界面活性剤１：下記構造の化合物（Ｍｗ＝１４０００、繰り返し単位の割合を示す％はモル％である）

・紫外線吸収剤１：下記構造の化合物

- Resin 1: Resin having the following structure. The numerical value attached to the main chain is the molar ratio of repeating units. Mw = 60000

-Polymerizable monomer 1: a compound having the following structure

- Photoinitiator 1: a compound having the following structure

- Surfactant 1: a compound having the following structure (Mw = 14000, % indicating the ratio of repeating units is mol%)

- Ultraviolet absorber 1: a compound having the following structure

- Compound 1 having an epoxy group: EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol)

<Production of structure>
On the support having barrier ribs prepared as described above, the colored photosensitive composition shown in the table below was spin-coated and heated at 100° C. for 2 minutes using a hot plate to form a film having a thickness of 0.6 μm. A colored photosensitive composition layer was formed. Next, using a reduction projection type stepper (i-line stepper FPA5510iZs, manufactured by Canon Inc.) capable of controlling the oxygen concentration, exposure was performed through the following mask under the following exposure conditions. Next, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, using a hot plate, it was heated at 200° C. for 5 minutes to pattern and form pixels, thereby manufacturing a structure.

(Mask used)
Mask 1: A mask in which 1.9 μm square openings are arranged in a Bayer array, and is a binary mask having openings 25 shown in FIGS. 5 and 11 (mask having openings for four pixels).
Mask 2: A mask in which 1.9 μm square openings are arranged in a Bayer array (mask having openings for four pixels), and the openings 25a are provided with the light shielding portions 22 shown in FIGS. of W10)=0.10 μm). The line width of the light shielding portion is 1.0 times the line width of the partition wall.
Mask 3: A mask in which 1.9 μm×1.9 μm square openings are arranged in a Bayer array (mask having openings for four pixels), and the light shielding portion 22 (line width (FIG. 12)) shown in FIGS. (W10)=0.20 μm) is formed on the binary mask. The line width of the light shielding portion is 2.0 times the line width of the partition wall.
Mask 4: A mask in which 1.9 μm×1.9 μm square openings are arranged in a Bayer array (mask having openings for four pixels), and light shielding portions 22 (line width (FIG. 12)) shown in FIGS. of W10)=0.30 μm) is formed. The line width of the light shielding portion is 3.0 times the line width of the partition wall.
Mask 5: A mask in which 1.9 μm square openings are arranged in a Bayer array (a mask having openings for four pixels), and the light shielding portion 22 (line width (FIG. 12)) shown in FIGS. of W10)=0.35 μm). The line width of the light shielding portion is 3.5 times the line width of the partition wall.
Mask 6: A mask in which 1.9 μm square openings are arranged in a Bayer array (mask having openings for four pixels), and the light shielding portion 22 (line width (FIG. 12)) shown in FIGS. (W10)=0.50 μm) is formed on the binary mask. The line width of the light shielding portion is 5.0 times the line width of the partition wall.

11 is a cross-sectional view of mask 1, and FIG. 12 is a cross-sectional view of masks 2-6. 11 and 12 also show the dimensions of the partition walls. The partition pitch is 1.0 μm, and the area for two pixels is 2.0 μm. The edge of each mask opening was aligned with the center line on the partition wall.

(Exposure conditions)
Illumination conditions: NA/σ=0.57/0.50
Exposure illuminance: 7500 W/m ² , 10000 W/m ^{2 , 20000 W/m 2 , 30000 W/m 2 , 36000} W/m ²
Exposure energy: 100 mJ/cm ² , 200 mJ/cm ² , 400 mJ/cm ² , 600 mJ/cm ² , 800 mJ/cm ² , 1000 mJ/cm ²
Oxygen concentration: 22% by volume, 30% by volume, 40% by volume, 50% by volume, 55% by volume

<Evaluation 1>
For the resulting structure, the surface of the formed pixels was observed using a critical dimension-scanning electron microscope (S9260A, manufactured by Hitachi High-Technologies Corporation) at a magnification of 30,000. Observation areas were set at two locations, one at the center of the wafer and the other near the notch portion of the wafer. Evaluation was made according to the following criteria.
A: Partitions between pixels are exposed from the pixels, individual pixels are firmly separated by the partitions, there is no residue on the partitions, voids are not generated in the partitions, and pixels of the desired size are formed. It is
B: Partitions between pixels are exposed from the pixels, individual pixels are firmly separated by the partitions, there is no residue on the partitions, and there are slight voids at the corners of the pixels (edges at the corners of the pattern). It has occurred. This level is practically acceptable.
C: Partitions between pixels are exposed from the pixels and individual pixels are separated by the partitions, but there is a slight residual on the partitions. This level is practically acceptable.
D: Part of the composition remains on the partition wall, or there is a gap between the pixel and the partition wall.
E: Pixels could not be formed. Alternatively, the partition wall was buried in the pixel and the pixel could not be separated. Alternatively, the thickness of the pixels formed between the partition walls was too thin to form the pixels with the desired dimensions.

<Evaluation 2>
The cross section of the resulting structure was observed using an SEM (S4800A, manufactured by Hitachi High-Technologies Corporation) at a magnification of 30,000 times to determine the height of the partition (H1 in FIG. 8) and the thickness of the partition. The absolute value (ΔH) of the difference between the heights of adjacent pixels (H2 in FIG. 9) was obtained, and the maximum value of ΔH was obtained. Evaluation was made according to the following criteria.
A: The maximum value of ΔH is 0.05 μm or less.
B: The maximum value of ΔH exceeds 0.05 µm.

As shown in the above table, according to the present invention, a pixel region is formed in a pattern, which is composed of a plurality of pixels of the same color, and at least part of the surface of the partition between the pixels is exposed from the pixels. We were able to form a structure with
In each test example, a mask with an opening size of 1.9 μm was used, but the opening size of the mask need not be 1.9 μm due to the relationship between exposure illuminance, exposure energy, and oxygen concentration. , may be set with a timely bias. For example, the size of the opening of the mask can be 1.95 μm square or 1.85 μm square. In addition, although the barrier rib structure of the low refractive index material is shown in the present invention, it is also useful for barrier ribs in which a metal (tungsten, aluminum, etc.) and a low refractive index material are laminated, or a metal barrier.

In the above examples, a green colored photosensitive composition, a blue colored photosensitive composition, or a red colored photosensitive composition is used as the colored photosensitive composition, and is composed of a plurality of pixels of the same color, and the pixels A structure was produced in which pixel regions in which at least part of the surface of the partition between the partition walls was exposed from the pixels were formed in a pattern. Colored photosensitive composition for forming cyan pixels, Colored photosensitive composition for forming magenta pixels, Colored photosensitive composition for forming transparent pixels, Colored photosensitive composition for forming infrared pixels, Light shielding The structure can also be produced using a colored photosensitive composition for pixel formation.

1: Support 2, 2a: Partition 10, 10a: Colored photosensitive composition layer 20, 20a: Mask 22: Light shielding part 25, 25a: Opening 30, 40, 50: Pixel 35, 45, 55: Pixel region

Claims (11)

A colored photosensitive composition containing a radically polymerizable compound and a photoradical polymerization initiator is applied onto a support provided with a plurality of regions partitioned by partition walls, and the above-mentioned forming a colored photosensitive composition layer on a support;
The colored photosensitive composition layer formed on the support is exposed through a mask having openings capable of simultaneously exposing the colored photosensitive composition layer formed in the adjacent regions, and the oxygen concentration is 21% by volume. a step of patternwise exposing in an atmosphere exceeding
Along with developing and removing the colored photosensitive composition layer in the unexposed areas, part of the colored photosensitive composition layer in the exposed areas is also developed and removed so that at least a part of the surface of the partition walls is exposed, and partitioned by the partition walls. a step of forming a pixel region in a pattern in which a plurality of pixels of the same color are formed, and at least part of a surface of a partition wall between the pixels is exposed from the pixels; ,
A method of manufacturing a structure comprising 2. The method of manufacturing a structure according to claim 1, wherein said opening of said mask is provided with a light shielding portion for shielding at least part of a position corresponding to said partition wall. 3. The method of manufacturing a structure according to claim 2, wherein the width of said light shielding portion is 1.0 to 5.0 times the width of said partition wall. 3. The method of manufacturing a structure according to claim 2, wherein the width of said light shielding portion is 1.0 to 3.0 times the width of said partition wall. 5. The method for manufacturing a structure according to claim 1, wherein said oxygen concentration is 55% by volume or less. The structure according to any one of claims 1 to 5, wherein the colored photosensitive composition layer formed on the support is exposed in a pattern at an exposure illuminance of 2500 to 50000 W/m ² . Production method. The method for manufacturing a structure according to any one of claims 1 to 6, wherein the partition walls have a height of 0.3 to 1.2 µm. The method for manufacturing a structure according to any one of claims 1 to 7, wherein the partition wall has a width of 0.05 to 0.2 µm. A method for manufacturing a color filter, comprising the method for manufacturing the structure according to any one of claims 1 to 8. A method for manufacturing a solid-state imaging device, comprising the method for manufacturing a structure according to any one of claims 1 to 8. A method for manufacturing an image display device, comprising the method for manufacturing the structure according to any one of claims 1 to 8.

Images