TWI750383B - Device manufacturing method - Google Patents

Abstract

The present invention provides a method of manufacturing a device capable of improving sensitivity to target light and capable of detecting noise-reducing light. A method of manufacturing a device includes forming a pattern of a resist film having a thickness of 5 μm or more on a support using a resist composition, and then ion implanting the support using the pattern of the resist film as a mask A step of manufacturing a light-receiving element; a step of forming a layer of a pixel-forming composition of an optical filter on at least a part of the ion-implanted region of the light-receiving element; a step of irradiating the layer of the pixel-forming composition with a wavelength A step of exposing in a pattern with light of 300 nm or less; and a step of developing the layer of the exposed pixel formation composition to form a pixel.

Description

Method of manufacturing the device

The present invention relates to a method of manufacturing a device including a light-receiving element and an optical filter.

A CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor) is used in video cameras, digital cameras, mobile phones with camera functions, and the like. In the manufacturing steps of these solid-state imaging elements, a resist pattern is formed on a support, and a light-receiving element is manufactured by ion-implanting the support with the resist pattern as a mask.

In addition, filters such as color filters and infrared transmission filters are used in solid-state imaging elements. These filters are formed using various compositions for forming filters.

For example, Patent Document 1 describes an invention related to a colored photosensitive resin composition for producing a color filter of a solid-state imaging element using an ultra-short wavelength exposure device of 300 nm or less. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2012-532334

In a device including a light-receiving element and an optical filter, in order to improve sensing accuracy, image quality, and the like, it is desirable to improve the signal-to-noise ratio (S/N ratio) of target light for detection.

On the other hand, conventionally, when manufacturing a light-receiving element, after forming a pattern of a resist film having a thickness of 4 μm or less on a support, the pattern of the resist film is used as a mask to perform ion implantation on the support. to manufacture the light-receiving element. However, according to the research of the present inventors, it is found that the noise of the device using the light-receiving element manufactured by this method is easily increased.

In addition, according to the invention described in Patent Document 1, although it is described that by using a photopolymerization initiator containing a compound that reacts with light of 300 nm or less as a photopolymerization initiator, the photopolymerization initiator can be It is hardened at ultra-short wavelengths, but there is no record or suggestion of noise reduction.

Accordingly, an object of the present invention is to provide a method of manufacturing a device capable of improving sensitivity to target light and capable of detecting noise-reduced light.

According to the research of the present inventors, it was found that the above-mentioned object can be achieved by having the following structure, and the present invention has been completed. Thereby, the present invention provides the following. <1> A method of manufacturing a device, comprising: forming a pattern of a resist film having a thickness of 5 μm or more on a support using a resist composition, and then using the pattern of the resist film as a mask to A step of ion implanting a support to manufacture a light-receiving element; A step of forming a layer of a composition for forming a pixel of an optical filter on at least a part of the region of the light-receiving element where the ion implantation has been performed; The layer of the composition is irradiated with light having a wavelength of 300 nm or less and exposed in a pattern; and the layer of the composition for forming a pixel after exposure is developed to form a pixel. <2> The method of manufacturing a device according to <1>, wherein the exposure step is patterned by irradiating the layer of the composition for pixel formation with KrF line. <3> The method for producing a device according to <1> or <2>, wherein the composition for forming a pixel is at least one selected from the composition for forming a coloring pixel and a composition for forming an infrared ray transmissive layer A sort of. <4> The method for producing a device according to any one of <1> to <3>, wherein the composition for forming a pixel comprises a polymerizable compound and a photopolymerization initiator, and the photopolymerization initiator comprises an alkyl group selected from the group consisting of: At least one compound selected from a benzophenone compound, an acylphosphine compound, a benzophenone compound, a thioxanthone compound, a trioxanthine compound and an oxime compound. <5> The method for producing the device according to any one of <1> to <4>, wherein the composition for forming a pixel contains a color material. <6> The manufacturing method of the apparatus as described in <5> which contains 40 mass % or more of color materials with respect to the total solid content of the composition for pixel formation. <7> The method for producing the device according to any one of <1> to <6>, wherein the size of the pixel is 2.0 μm or less. <8> The method for producing the device according to any one of <1> to <7>, wherein the film thickness of the pixel is 1.0 μm or less. <9> The method for producing an apparatus according to any one of <1> to <8>, wherein the solid content concentration of the resist composition is 25% by mass or more. <10> The method for producing a device according to any one of <1> to <9>, wherein the resist composition has a viscosity of 30 to 1000 mPa·s at 25°C. <11> The method for producing a device according to any one of <1> to <10>, wherein the resist composition contains a resin, and the content of the resin in the solid content of the resist composition is 95.0 to 99.9 mass %. <12> The method for producing an apparatus according to <11>, wherein the Ohnishi parameter of the resin is 3.0 or less. <13> The method for producing an apparatus according to <11>, wherein the Onishi parameter of the resin is 2.8 or less. <14> The method for producing a device according to any one of <1> to <13>, wherein the resist composition is a positive-type photosensitive composition. <15> The method for producing a device according to any one of <1> to <10>, wherein the resist composition contains a resin having a repeating unit and a photoacid generator, the repeating unit having a A group that decomposes and produces polar groups. <16> The method for producing the device according to any one of <11> to <14>, wherein the resist composition further comprises a photoacid generator, and the resin is a resin having a repeating unit having a The action of acid decomposes and generates polar groups. [Inventive effect]

According to the present invention, it is possible to provide a method of manufacturing a device capable of improving sensitivity to target light and capable of detecting noise-reduced light.

Hereinafter, the content of the present invention will be described in detail. In this specification, "-" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit. In the labeling of groups (atomic groups) in this specification, the labels not describing substituted and unsubstituted also include groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In this specification, "exposure" means not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, the light used for exposure includes actinic rays such as bright-line spectroscopy of mercury lamps and excimer lasers, extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams, and radiation. In this specification, "(meth)allyl" means both or either of allyl and methallyl, and "(meth)acrylate" means both acrylate and methacrylate Alternatively or either, "(meth)acrylic" means both or either of acrylic acid and methacrylic acid, and "(meth)acryloyl" means both acryl and methacryloyl or either. In this specification, the weight average molecular weight and the number average molecular weight are polystyrene conversion values measured by GPC (gel permeation chromatography) method. Regarding GPC, the following method can be used: HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mmID (inner diameter) × 30.0 cm) as the column, and THF as the eluent (tetrahydrofuran). In this specification, the term "infrared" refers to light having a wavelength of 700 to 2500 nm. In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition. In this specification, the term "step" includes not only an independent step, but also includes the term as long as the desired effect of the step can be achieved even if it cannot be clearly distinguished from other steps.

<Method of Manufacturing Device> The method of manufacturing a device of the present invention is characterized by comprising: forming a pattern of a resist film having a thickness of 5 μm or more on a support using a resist composition, and then forming the resist film A step of ion-implanting a support body as a mask to manufacture a light-receiving element; at least a part of the ion-implanted region of the light-receiving element, forming a layer of the pixel-forming composition of the filter. Steps: irradiating the layer of the composition for forming a pixel with light with a wavelength of 300 nm or less and exposing in a pattern; and developing the layer of the composition for forming a pixel after exposure to form a pixel.

In the light-receiving element manufacturing step in the method of manufacturing the device of the present invention, a pattern of a resist film having a thickness of 5 μm or more is formed on a support, and ion implantation is performed on the support. In the portion of the support covered with the resist film, it is considered that implanted ions are effectively shielded by the resist film when ion implantation is performed, thereby effectively suppressing implantation of ions into a portion that does not require ion implantation. Therefore, it is considered that ions can be more selectively implanted into the portion exposed from the resist film of the support. As a result, it is presumed that the sensitivity to target light such as visible rays and infrared rays can be improved, and the sensitivity to impurities can be reduced. information sensitivity. Further, in the present invention, after the light-receiving element is formed in this manner, a layer of the composition for forming a pixel of the filter is formed on at least a part of the region of the light-receiving element where the ion implantation has been performed, and then, this The layer of the composition for forming a pixel is irradiated with light having a wavelength of 300 nm or less and exposed in a pattern, and then the layer of the composition for forming a pixel after exposure is developed to form a pixel. By forming the pixel in this way, it is possible to form a pixel with good rectangularity on the light-receiving element. In particular, even if the size of the pixel is further reduced, it is possible to form a pixel with good rectangularity. The reason why the rectangularity of the obtained pixel can be improved by forming the pixel in this manner is presumed as follows. That is, it is presumed that the layer of the composition for forming a pixel tends to have high absorptivity with respect to light having a wavelength of 300 nm or less, and that the layer of the composition for forming a pixel is irradiated with light having a wavelength of 300 nm or less and then has a high absorptivity. At the time of exposure, the surface layer of the layer of the composition for forming a pixel tends to be hardened more easily than the inside. Therefore, it is presumed that by irradiating and exposing the layer of the composition for forming a pixel with light having a wavelength of 300 nm or less, the surface layer of the layer of the composition for forming a pixel is rapidly hardened, and by the surface layer being rapidly hardened, the exposure light As a result, the scattering and springback of the particles are suppressed, and as a result, pixels with good squareness and fine pattern size can be formed. By forming the pixels as described above, the squareness of the obtained pixels can be improved. Therefore, it is considered that the stray light caused by the irregular reflection of the received light when the device is produced can be suppressed, and the sensitivity to the target light can be improved. And reduce the sensitivity to noise. For the above reasons, according to the present invention, it is possible to manufacture a device capable of detecting light with reduced noise.

Furthermore, according to the present invention, a pixel excellent in chemical resistance and scratch resistance can also be formed. The reason why such an effect can be obtained is presumed to be that by irradiating and exposing the layer of the composition for pixel formation with light having a wavelength of 300 nm or less, the surface layer of the layer of the composition for pixel formation can be further improved Harden effectively. In addition, according to the present invention, it is possible to suppress the generation of residues during pixel formation. As described above, the reason for this is presumed to be that the surface layer of the layer of the composition for forming a pixel can be rapidly hardened at the time of exposure, so that scattering and rebound of the exposure light can be suppressed.

Hereinafter, the manufacturing method of the apparatus of this invention is demonstrated in detail.

(Procedure of manufacturing a light-receiving element) [Pattern formation of a resist film] First, the process of manufacturing a light-receiving element will be described. In the step of manufacturing a light-receiving element, first, a pattern (hereinafter, also referred to as a resist pattern) 2 of a resist film having a thickness of 5 μm or more is formed on a support 1 using a resist composition ( FIG. 1 ). In the present invention, it is preferable to apply a resist composition on the support 1 to form a resist film, and to pattern the resist film to form the resist pattern 2 .

The type of the support is not particularly limited. For example, a known semiconductor substrate such as a silicon substrate and a ZnO substrate can be used. In addition, it is also preferable to use an InGaAs substrate as a support. Since the sensitivity of the InGaAs substrate to light with a wavelength exceeding 1000 nm is good, by using InGaAs, a light-receiving element with excellent sensitivity to light with a wavelength exceeding 1000 nm can be manufactured. Impurities such as boron, aluminum, phosphorus, and arsenic may be doped into the substrates.

The thickness of the resist pattern 2 is 5 μm or more, preferably 6 μm or more, more preferably 7 μm or more, and even more preferably 8 μm or more. The upper limit is not particularly limited, but from the viewpoint of the pattern shape, 15 μm or less is preferable, and 10 μm or less is more preferable. When the thickness of the resist pattern 2 is 5 μm or more, the implanted ions can be effectively shielded during ion implantation. When the thickness of the resist pattern 2 is 15 μm or less (preferably 10 μm or less), a favorable pattern shape can be maintained, and as a result, ions can be efficiently implanted in a target range during ion implantation, and further Improve the S/N ratio with respect to infrared rays. The resist pattern 2 of the above-mentioned thickness can be formed by repeating the application of the resist composition twice or more, but from the viewpoint of the manufacturing cost, it is preferably formed by one application. That is, a resist film with a thickness of 5 μm or more is formed by one coating of the resist composition, and the resist film is patterned to form a resist pattern with a thickness of 5 μm or more. 2 is better.

The resist composition may be either a positive-type photosensitive composition or a negative-type photosensitive composition, but a positive-type photosensitive composition is preferable because it is easy to form a fine pattern.

The solid content concentration of the resist composition is preferably 25% by mass or more, more preferably 30% by mass or more, more preferably 31% by mass or more, and particularly preferably 32% by mass or more. When the solid content concentration of the resist composition is 25% by mass or more, a resist film having a thickness of 5 μm or more can be easily formed by one coating. In particular, when the solid content concentration of the resist composition is 30 mass % or more, it is easy to form a resist pattern with a favorable pattern shape. The upper limit of the solid content concentration of the resist composition is preferably 45% by mass or less, more preferably 42.5% by mass or less, and even more preferably 40% by mass or less.

The viscosity of the resist composition at 25°C is preferably 30 to 1000 mPa･s, more preferably 100 to 1000 mPa･s, from the viewpoint of coatability. The upper limit is preferably 800 mPa･s or less, more preferably 700 mPa･s or less, and even more preferably 600 mPa･s or less. The lower limit is preferably 150 mPa･s or more, more preferably 200 mPa･s or more, and still more preferably 300 mPa･s or more.

The resist composition used in the present invention contains resin, and the content of the resin in the solid content of the resist composition is preferably 95 to 99.9 mass %, more preferably 96 to 99.9 mass %, and 97 to 99.9 mass % % is further preferred.

The Onishi parameter of the resin contained in the resist composition is preferably 3.0 or less, more preferably 2.9 or less, further preferably 2.8 or less, and particularly preferably 2.7 or less. The lower limit is preferably 2.5 or more, for example. When the Onishi parameter of the resin contained in the resist composition is 3.0 or less, it is easy to manufacture a device having a high S/N ratio with respect to target light. The reason why such an effect can be obtained is presumed to be that a resist film that can more effectively shield ions implanted at the time of ion implantation can be formed. In addition, the so-called Onishi parameter is a value defined by the following formula. Onishi parameter = the sum of the atomic numbers of C, H and O / (the number of C atoms - the number of O atoms)

In the present invention, the case where the Onishi parameter of the resin contained in the resist composition is 3.0 or less means the following cases. That is, when there is only one resin contained in the resist composition, it means that the Onishi parameter of the resin itself is 3.0 or less. In addition, when the resin contained in a resist composition is two or more types, it means the value calculated from the sum of the product of the content of each resin and the Onishi parameter. In addition, about the Onishi parameter of each resin, the value calculated by the said calculation formula was used.

In the case where the resist composition used in the present invention contains two or more kinds of resins, the resin having an Onishi parameter of 3.0 or less in the total amount of resins (preferably a resin having an Onishi parameter of 2.8 or less, more preferably Onishi parameter) The content of the parameter is 2.7 or less resin) is preferably 50 to 100 mass %, more preferably 60 to 100 mass %, and even more preferably 75 to 100 mass %.

Details of the resist composition will be described later.

It does not specifically limit as a coating method of a resist composition, A well-known coating method can be used. For example, drop coating method (drop coating); slit coating method; spray coating method; roll coating method; spin coating method; casting coating method; slit and spin method; The method described in Japanese Patent Laid-Open No. 2009-145395); ink jet method (for example, drop-on-demand method, piezoelectric method, thermal method), jet printing such as nozzle spray, flexographic printing, screen printing, gravure printing , reverse offset printing, metal mask printing and other printing methods; transfer methods using molds, etc., spin coating is preferred. Moreover, it is preferable to carry out at the rotation speed of 1000-2000 rpm about the application|coating by the spin coating method. In addition, as for coating by spin coating, as described in Japanese Patent Application Laid-Open No. 10-142603, Japanese Patent Application Laid-Open No. 11-302413, and Japanese Patent Application Laid-Open No. 2000-157922, for spreading into a thin film or for applying Spin dry to increase spin speed during coating. In addition, the spin coating process described in "Process Technology and Chemicals of the Most Advanced Color Filters" published by CMC on January 31, 2006 can also be preferably used.

After coating the resist composition on the support, drying treatment may be performed. Drying conditions can be appropriately adjusted depending on the type of resist composition. For example, the drying temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

Next, a pattern forming method will be described. It does not specifically limit as a pattern formation method, It is preferable to use the conventionally well-known photolithography method. The pattern forming method using photolithography includes a step of exposing a resist film formed on a support with actinic rays or radiation (exposure step), and using a developer to expose the resist film to light It is preferable to carry out the step of developing (developing step).

The exposure step is a step of exposing the resist film, and can be performed, for example, by the following method. The resist film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. In addition, in the irradiation of electron beams, drawing (direct drawing) is generally performed without interposing a mask. The actinic ray or radiation is not particularly limited, but for example, KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV, Extreme Ultra Violet), electron beam (EB, Electron Beam), etc., extreme ultraviolet or Electron beams are particularly preferred. The exposure may be liquid immersion exposure.

When forming a resist film using a positive-type photosensitive composition, it is preferable to bake (heat) after exposure and before developing. The reaction of the exposure part is accelerated by baking, and the sensitivity and pattern shape become more favorable. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

The developing step is a step of developing the exposed resist film with a developing solution. In addition, in the case of forming a resist film using a positive-type photosensitive composition, the exposed portion of the resist film is developed and removed. On the other hand, in the case of forming a resist film using a negative photosensitive composition, the unexposed portion of the resist film is developed and removed.

As a developing solution, the developing solution (organic type developing solution) containing an organic solvent, the aqueous solution (alkali developing solution) containing an alkali agent, etc. are mentioned. It can be appropriately selected depending on the type of resist film.

As the organic solvent used in the organic developer, various organic solvents are widely used, but, for example, solvents such as ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents can be used. . The organic solvent is selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, and an organic solvent containing at least one of a fluorine atom and a silicon atom. At least one organic solvent is preferred, hydrocarbon-based solvents, ester-based or ketone-based solvents are more preferred, ester-based or ketone-based solvents are more preferred, and from the viewpoint of suppressing penetration into the resist film, the number of carbon atoms is 5 or more. The hydrocarbon-based solvent or the ketone-based solvent with 5 or more carbon atoms is more preferable, and the hydrocarbon-based solvent with 7 or more carbon atoms or the ketone-based solvent with 7 or more carbon atoms is particularly preferable. Further, in the present invention, an ester-based solvent refers to a solvent having an ester bond in the molecule, a ketone-based solvent refers to a solvent having a ketone group in the molecule, and an alcohol-based solvent refers to a solvent having an alcoholic hydroxyl group in the molecule. The solvent, the so-called amide-based solvent, is a solvent having an amide group in the molecule, and the so-called ether-based solvent is a solvent having an ether bond in the molecule. Among these, there are also solvents having a plurality of the above-mentioned functional groups in one molecule, but in this case, it corresponds to any kind of solvent including the functional groups possessed by the solvent. For example, diethylene glycol monomethyl ether corresponds to either of the alcohol-based solvent and the ether-based solvent in the above classification. In addition, the so-called hydrocarbon-based solvent refers to a hydrocarbon-based solvent having no substituent. Specific examples of ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents can be referred to the descriptions in paragraphs 0021 to 0026 of International Publication No. WO2016/104565, which are described in incorporated into this manual.

The above-mentioned organic solvent may be mixed with a plurality of types, and may be used in combination with a solvent other than the above or water. However, in order to fully exhibit the effect of this invention, it is preferable that the water content of the whole developer is less than 10 mass %, and it is more preferable that it does not contain water substantially. The concentration of the organic solvent in the developer (in the case of mixing a plurality of kinds, the total amount) is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass, and still more preferably 90 to 100 mass %, particularly preferably 95 to 100 mass %. The most preferable is the case where only the organic solvent is contained substantially. In addition, the case where only an organic solvent is contained substantially means the case where a trace amount of surfactant, antioxidant, stabilizer, antifoaming agent, etc. are contained.

It is also preferable that the organic developer contains an antioxidant, an alkaline compound, and a surfactant. As antioxidants and basic compounds, reference can be made to the descriptions of paragraphs 0047 to 0078 of International Publication WO2016/104565, the contents of which are incorporated in the present specification. As the surfactant, the same surfactant as that which can be contained in the resist composition described later can be used.

As the alkaline developer, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, primary amines such as ethylamine and n-propylamine, diethylamine, di-n-butylamine and the like can be used. Secondary amines such as amine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylamine ammonium hydroxide, tetrabutyl ammonium hydroxide, tetrapentyl ammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, butyl trimethyl ammonium hydroxide, methyl ammonium hydroxide Tetraalkyl ammonium hydroxide such as triamyl ammonium hydroxide, dibutyl dipentyl ammonium hydroxide, dimethyl bis(2-hydroxyethyl) ammonium hydroxide, trimethylphenyl ammonium hydroxide, trimethyl ammonium hydroxide Aqueous solutions (alkaline aqueous solutions) containing alkaline agents, such as quaternary ammonium salts such as methylbenzylammonium hydroxide and triethylbenzylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. The alkaline developer can also be used by adding an appropriate amount of alcohols and surfactants to the above-mentioned alkaline aqueous solution. The alkaline agent concentration of the alkaline developer is preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10.0 to 15.0. As the alkaline developing solution, the alkaline developing solution described in paragraph No. 0460 of Japanese Patent Laid-Open No. 2014-048500 can also be used, the contents of which are incorporated in this specification.

As the developing method, for example, a method of immersing a support body in a tank filled with a developer solution for a certain period of time (dipping method); a method of developing by depositing the developer solution on the surface of the support body using surface tension and standing still for a certain period of time. Method (puddle method); method of spraying developer on the surface of the support (spraying method); while scanning the developer spray nozzle at a constant speed on the support rotating at a constant speed, while continuously spraying the developer. method (dynamic allocation method), etc. Moreover, after image development, you may implement the process of stopping image development, substituting with another solvent. The development time is not particularly limited, but is usually 10 to 300 seconds, preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

In the development step, both development using an organic developer and development using an alkali developer can be performed (so-called dual development can be performed). Thereby, a finer pattern can be formed.

In the case of developing with a developing solution, it is also preferable to perform a rinsing treatment. When developing using an alkali developing solution, pure water can be used as the rinsing solution in the rinsing treatment, and an appropriate amount of surfactant can be added and used. In the case of developing with an organic developer, it is preferable to use a rinse containing an organic solvent as the rinse in the rinse treatment. As the organic solvent used in the rinsing solution, at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is preferred. . For details of the organic solvent used in the rinsing solution, reference can be made to the descriptions of paragraph numbers 0081 to 0084 of International Publication WO2016/104565, which are incorporated in the present specification.

The method of the rinsing treatment is not particularly limited, but for example, a method of continuously spraying the rinsing liquid on a support that rotates at a constant speed (rotary spray method); immersing the support in a tank filled with the rinsing liquid for a certain period of time The method (dipping method); and the method of spraying the rinsing liquid on the surface of the support (spraying method), etc. The rinsing time is not particularly limited, preferably 10 seconds to 300 seconds, more preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds. The temperature of the rinsing liquid is preferably 0 to 50°C, and further preferably 15 to 35°C.

In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing solution adhering to the pattern by the supercritical fluid can be performed. Furthermore, after developing treatment or rinsing treatment or treatment with a supercritical fluid, heat treatment can be performed in order to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a favorable resist pattern can be obtained, but it is usually 40 to 160°C. The heating temperature is preferably 50 to 150°C, and most preferably 50 to 110°C. The heating time is not particularly limited as long as a favorable resist pattern can be obtained, but it is usually 15 to 300 seconds, preferably 15 to 180 seconds.

[Ion Implantation] Next, ion implantation is performed on the support 1 using the resist pattern 2 formed as described above as a mask ( FIG. 2 ). As a result, impurities are introduced into the exposed portions of the resist pattern on the surface of the support body, whereby the photodiode portion 3 is formed on the support body 1 .

Here, the so-called ion implantation is a method of ionizing an impurity serving as a donor or an acceptor, accelerating the implantation into a support, and introducing the impurity. Examples of the above-mentioned impurities include p-type impurities such as boron and aluminum, and n-type impurities such as phosphorus and arsenic, and it is preferable to select them appropriately according to the purpose. For example, in the case of using an n-type semiconductor substrate or a substrate on which n-type wells are formed as a support, and performing ion implantation on the support, it is better to select p-type impurities such as boron and aluminum, and boron is more preferred . Furthermore, in the case where a p-type semiconductor substrate or a substrate in which a p-type well is formed is used as a support and ion implantation is performed on the support, n-type impurities such as phosphonium and arsenic are preferably selected.

The ion implantation conditions are not particularly limited. For example, as the energy, 100 to 5000 KeV is preferable. The upper limit is preferably 400 KeV or less, more preferably 300 KeV or less, and even more preferably 200 KeV or less. The lower limit is preferably 150 KeV or more, more preferably 200 KeV or more, and still more preferably 300 KeV or more. The doping amount is preferably ^{1×10 12} to 1×10 ¹⁴ cm ^{-2 .} The upper limit ^{is preferably 8×10 13} cm ^-2 or less, more preferably 5×10 ¹³ cm ^-2 or less, and even more preferably 3×10 ¹³ cm ^-2 or less. The lower limit ^{is preferably 2 × 10 12} cm ^-2 or more, more preferably 3 × 10 ¹² cm ^-2 or more, and even more preferably 5 × 10 ¹² cm ^-2 or more.

In addition, the ion implantation may be performed by decreasing the energy stepwise or increasing the energy step by step. When ion implantation is performed by reducing the energy stepwise, an effect of reducing noise caused by damage to the resist pattern can be expected. In the case of performing ion implantation by increasing the energy stepwise, ions can be implanted deeper, and thus the effect of increasing the strength of the extracted signal can be expected.

Through such steps, a light-receiving element can be manufactured. In the present invention, after the ion implantation is performed, the resist pattern is preferably stripped from the support. It does not specifically limit as a lift-off method of a resist pattern, A well-known method can be used. For example, it is preferable to perform peeling using a resist removal liquid. As the resist removal solution, reference can be made to paragraphs 0011 to 0043 of Japanese Patent Application Laid-Open No. 2014-142635, the contents of which are incorporated in the present specification. Moreover, it is also preferable to form an insulating film on the surface of the support before peeling off the resist pattern from the support or after peeling the resist pattern from the support. The material of the insulating film include SiO _2, ZrO ₂ and the like. Further, after the resist pattern is peeled off from the support, a step of forming an insulating film, a control electrode, a metal wiring layer, a source electrode, a drain electrode, and the like may be further included.

(Pixel Formation) [Steps of Forming the Layer of the Composition for Pixel Formation] Next, the steps until pixel formation will be described. First, at least a part of the region where the ion implantation of the light-receiving element manufactured as described above is performed is formed as a layer of the composition for forming a pixel of the optical filter. In addition, in the present invention, the term "optical filter" refers to a filter that transmits light. It does not specifically limit as light which a filter transmits, An ultraviolet-ray, a visible light, an infrared-ray etc. are mentioned. The filter in the present invention only needs to transmit light having a wavelength of at least a part of the incident light. That is, the optical filter of the present invention may be one that selectively transmits or shields light of a specific wavelength in the incident light, or one that transmits the incident light almost completely.

The layer of the composition for pixel formation can be formed by applying the composition for pixel formation to the light-receiving element. Examples of the composition for forming a pixel include a composition for forming a coloring pixel, a composition for forming a pixel for an infrared transmissive layer, a composition for forming a pixel for an infrared cut layer, and the like, which are selected from those for forming a coloring pixel. At least one of the composition and the composition for forming a pixel of the infrared transmitting layer is preferred. Details of the composition for forming a pixel will be described later.

The layer of the composition for pixel formation may be directly formed on the light-receiving element, but other layers such as a base layer may be formed on the light-receiving element, and the layer of the composition for pixel formation may be formed on these layers. In addition, it is possible to use a method other than the method specified in the present invention (for example, a method of forming a pixel by patterning by a dry etching method, exposure with light having a wavelength exceeding 300 nm (for example, i-ray, etc.) A method of forming a pixel by developing, etc.), a pixel is formed on a light-receiving element in advance, and a layer of a composition for forming a pixel is formed on the pixel.

As an application method of the composition for pixel formation, a known method can be used. For example, a drop coating method (drop coating); a slit coating method; a spray coating method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; Wet method (for example, the method described in Japanese Patent Application Laid-Open No. 2009-145395); inkjet method (for example, drop-on-demand method, piezoelectric method, thermal method), ejection-type printing such as nozzle spraying, flexographic printing, Various printing methods such as screen printing, gravure printing, reverse offset printing, and metal mask printing methods; transfer methods using molds, etc.; nanoimprinting methods, etc. The applicable method based on the inkjet method is not particularly limited. For example, "Inkjet that can be promoted and used - Infinite Possibilities Seen in Patents-", issued in February 2005, SB RESEARCH CO., LTD. " (particularly pages 115 to 133) or JP 2003-262716 A, JP 2003-185831 A, JP 2003-261827 A, JP 2012-126830 A The method described in the gazette, Japanese Unexamined Patent Application Publication No. 2006-169325, and the like.

The layer (hereinafter, also referred to as a composition layer) of the pixel formation composition to which the pixel formation composition is applied may be dried (pre-baking). In the case of pre-baking, 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-baking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. The prebaking can be performed using a hot plate, an oven, or the like.

[Exposure Step] Next, the composition layer formed as described above is irradiated with light having a wavelength of 300 nm or less and exposed in a pattern. For example, the composition layer can be subjected to pattern exposure by using an exposure apparatus such as a stepper and exposing the composition layer through a mask having a predetermined mask pattern. Thereby, the exposed part can be hardened. The light that can be used during exposure may be light having a wavelength of 300 nm or less, and preferably light having a wavelength of 180 to 300 nm. Specifically, KrF line (wavelength: 248 nm), ArF (wavelength: 193 nm), etc. are mentioned, and KrF line (wavelength: 193 nm) is difficult to break because of the reason that the bond of resin or the like contained in the composition for forming a pixel is difficult to break. 248 nm) is better. The exposure amount is preferably 1 to 2000 mJ/cm ^{2 ,} for example. The upper limit is preferably 1000 mJ/cm ² or less, and more ^{preferably 500 mJ/cm 2} or less from the viewpoint of productivity. The lower limit is preferably 5 mJ/cm ² or more, more preferably 10 mJ/cm ² or more, and more preferably 20 mJ/cm ² or more from the viewpoint of pixel formability and adhesion to a substrate. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to performing in the atmosphere, for example, it may be performed in a low-oxygen environment with an oxygen concentration of 19 vol % or less (for example, 15 vol %, 5 vol %, substantially no oxygen concentration) Oxygen) for exposure, and exposure can also be performed under a high oxygen environment with an oxygen concentration exceeding 21 vol % (eg, 22 vol %, 30 vol %, 50 vol %). In addition, the exposure illuminance can be appropriately set, and can usually be selected from the range of 1,000 W/m ² to 100,000 W/m ² (for example, 5,000 W/m ² , 15,000 W/m ² , and 35,000 W/m ² ). The oxygen concentration and exposure illuminance can be appropriately combined conditions, for example, oxygen concentration of 10 vol% and illuminance of 10000 W/m ² , oxygen concentration of 35 vol % and illuminance of 20000 W/m ² .

[Step (Development) of Pixel Formation] Next, the exposed composition layer is developed. More specifically, the composition layer of the unexposed portion in the exposed composition layer is removed by development to form a pixel (pattern). The development of the composition layer can be performed using a developer. Thereby, the composition layer of the unexposed part in the exposure step is dissolved in the developing solution, and only the photohardened part remains on the light-receiving element. As the developing solution, an alkali developing solution that does not damage the light-receiving element of the base and the like is preferable. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal property, the following steps may be repeated several times: the developer is thrown off every 60 seconds, and the developer is supplied again.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, and tetramethylhydroxide Ammonium, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethylammonium hydroxide) base) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic basic compounds, sodium hydroxide, potassium hydroxide, sodium carbonate , sodium bicarbonate, sodium silicate, sodium metasilicate and other inorganic alkaline compounds. Regarding the alkali agent, a compound having a large molecular weight is preferable from the viewpoint of the environment and safety. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water can be preferably used. 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, a surfactant can also be used for a developer. From the viewpoint of convenient transportation, storage, etc., the developer can be temporarily prepared as a concentrated solution and diluted to a concentration required for use. The dilution ratio is not particularly limited, but can be set to, for example, a range of 1.5 to 100 times. In addition, in the case of using a developer containing such an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after development.

After image development, additional exposure treatment and heat treatment (post-baking) can be performed after drying. Additional exposure treatment and post-baking are treatments after development for completely curing the film. In the case of performing additional exposure processing, g-rays, h-rays, i-rays, etc. are preferable as light used for exposure, and i-rays are more preferable. Moreover, it may be light obtained by combining a plurality of these types. As a light source, an ultra-high pressure mercury lamp, a metal halide lamp, a laser light source, etc. are mentioned. The illuminance is preferably 500 to 100,000 W/m ^{2 .} The exposure amount is preferably 500 to 10000 mJ/cm ^{2 ,} for example. In addition, in the case of performing post-baking, the post-baking temperature is preferably 50 to 240° C., for example. From a viewpoint of film hardening, 180-230 degreeC is more preferable.

The film thickness of the pixel to be formed is preferably selected as appropriate according to the application and the type of the filter. For example, 2.0 μm or less is preferable, 1.0 μm or less is more preferable, and 0.3 to 1.0 μm is still more preferable. The upper limit is preferably 0.8 μm or less, more preferably 0.6 μm or less. The lower limit is preferably 0.4 μm or more. Moreover, when it is a coloring pixel, as a film thickness of a pixel, 1.0 micrometers or less is preferable, and 0.3-1.0 micrometers is more preferable. The upper limit is preferably 0.8 μm or less, more preferably 0.6 μm or less. The lower limit is preferably 0.4 μm or more. Moreover, when it is a pixel of an infrared-transmitting layer, as a film thickness of a pixel, 2.0 micrometers or less is preferable, and 0.3-2.0 micrometers is more preferable. The upper limit is preferably 1.0 μm or less, more preferably 0.6 μm or less. The lower limit is preferably 0.4 μm or more. Moreover, when it is a pixel of an infrared cut layer, as a film thickness of a pixel, 2.0 micrometers or less is preferable, and 0.3-2.0 micrometers is more preferable. The upper limit is preferably 1.0 μm or less, more preferably 0.6 μm or less. The lower limit is preferably 0.4 μm or more.

In addition, it is preferable to appropriately select the size (line width) of the pixel to be formed in accordance with the application and the type of the filter. For example, 2.0 μm or less is preferable. The upper limit is preferably 1.0 μm or less, more preferably 0.9 μm or less. The lower limit is preferably 0.4 μm or more. Moreover, when it is a coloring pixel, it is preferable that it is 2.0 micrometers or less as a size (line width) of a pixel. The upper limit is preferably 1.0 μm or less, more preferably 0.9 μm or less. The lower limit is preferably 0.4 μm or more. Moreover, when it is a pixel of an infrared-transmitting layer, it is preferable that it is 2.0 micrometers or less as a size (line width) of a pixel. The upper limit is preferably 1.0 μm or less, more preferably 0.9 μm or less. The lower limit is preferably 0.4 μm or more. Moreover, when it is a pixel of an infrared cut layer, it is preferable that it is 2.0 micrometers or less as a size (line width) of a pixel. The upper limit is preferably 1.0 μm or less, more preferably 0.9 μm or less. The lower limit is preferably 0.4 μm or more.

In the case where the device of the present invention has a plurality of pixels, at least one pixel can be formed by the above steps. For example, after patterning the first type of pixel by dry etching, the second and subsequent pixels can be manufactured by the above-mentioned steps. In addition, about at least one of a plurality of pixels, a light having a wavelength exceeding 300 nm can be irradiated, exposed in a pattern, and developed to form a pixel. In addition, about all the pixels, it is possible to irradiate light with a wavelength exceeding 300 nm, expose in a pattern, and develop the pixels to form the pixels.

As the device manufactured by the present invention, a photosensor such as a solid-state imaging element, an image display device, and the like can be mentioned. As an embodiment of the apparatus, a description will be given using FIG. 3 . In this device, an infrared cut filter 111 and an infrared transmission filter 114 are formed in the imaging region of the light receiving element 110 . In addition, a color filter 112 is laminated on the infrared cut filter 111 . A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114 . In addition, a planarization layer 116 is formed so as to cover the microlenses 115 .

The infrared cut filter 111 is a filter for pixels having an infrared cut layer. The infrared cut-off layer has a spectral characteristic of transmitting visible light and shielding at least a part of infrared rays. The spectral characteristics of the infrared cutoff layer can be appropriately selected according to the spectral characteristics of the infrared transmission filter 114 . The infrared cut filter 111 is preferably a filter that shields at least a part of light in the wavelength range of 700 to 1300 nm. Further, the average transmittance of the infrared cut filter 111 in the wavelength range of 400 to 700 nm is preferably 60 to 100%, more preferably 70 to 100%, and particularly preferably 80 to 100%. It is preferable that the average transmittance in this wavelength region is high.

The color filter 112 is a filter with colored pixels. Examples of coloring pixels include red pixels, blue pixels, green pixels, cyan pixels, magenta pixels, yellow pixels, and the like.

The infrared transmission filter 114 is a filter of pixels having an infrared transmission layer. As a preferable example of an infrared-transmitting filter layer, the filter layer which has any one of the spectral characteristics in the following (1)-(4) is mentioned, for example. (1): The maximum value of the transmittance of light in the thickness direction in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the thickness direction The minimum transmittance of the filter layer in the wavelength range of 800-1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this filter layer, light in the wavelength range of 400 to 640 nm can be blocked, and infrared rays having a wavelength of 720 nm can be transmitted. (2): The maximum value of the transmittance of light in the thickness direction in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the thickness direction The minimum transmittance of the filter layer in the wavelength range of 900-1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this filter layer, light in the wavelength range of 400 to 750 nm can be blocked, and infrared rays having a wavelength of 850 nm can be transmitted. (3): The maximum value of the transmittance of light in the thickness direction in the wavelength range of 400 to 850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the thickness direction The minimum transmittance of the filter layer in the wavelength range of 1000-1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this filter layer, light in the wavelength range of 400 to 850 nm can be blocked, and infrared rays having a wavelength of 940 nm can be transmitted. (4): The maximum value of the transmittance of light in the thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the thickness direction The minimum transmittance of the filter layer in the wavelength range of 1100-1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this filter layer, light in the wavelength range of 400 to 950 nm can be blocked, and infrared rays having a wavelength of 1040 nm can be transmitted.

In addition, the device shown in FIG. 3 has the infrared transmission filter 114, the color filter 112, and the infrared cut filter 111, but it can also be set to a state in which the infrared cut filter 111 is not provided, and the color filter is not provided. 112 and the infrared cut filter 111, and the infrared transmission filter 114 is not provided.

It is preferable that the material (including various materials such as cover glass) used for the production of the light sensor of the solid-state imaging element and the like does not generate alpha rays. In order to suppress the generation of alpha rays from the material, it is preferable to use a high-purity material in which radioactive elements such as uranium and thorium contained in the material are reduced. The content of uranium and thorium is preferably 5 mass ppb or less, and preferably 1 mass ppb or less. Although it is preferable that uranium and thorium are not substantially contained, they may be contained within a range where no soft error occurs, considering the balance between high purity and cost. In addition, it is also preferable to use a material that shields the α-ray by covering the material that generates the α-ray.

<Resist composition> Next, the resist composition used for the manufacturing method of the apparatus of this invention is demonstrated. The resist composition used in the method for producing the device of the present invention may be either a positive-type photosensitive composition or a negative-type photosensitive composition, but the positive-type photosensitive composition is easy to form a fine pattern. A photosensitive composition is preferable. Moreover, as a resist composition, it is preferable to decompose|disassemble by the action of an acid, and the composition containing the resin and the photoacid generator whose solubility with respect to a developing solution changes. Such a resist composition can be preferably used as a positive-type photosensitive composition.

The solid content concentration of the resist composition is preferably 25% by mass or more, more preferably 30% by mass or more, more preferably 31% by mass or more, and particularly preferably 32% by mass or more. When the solid content concentration of the resist composition is 25 mass % or more, a resist film having a thickness of 5 μm or more can be easily formed by one coating. In particular, when the solid content concentration of the resist composition is 30 mass % or more, it is easy to form a resist pattern with a favorable pattern shape. The upper limit of the solid content concentration of the resist composition is preferably 45% by mass or less, more preferably 42.5% by mass or less, and even more preferably 40% by mass or less.

From the viewpoint of coatability, the viscosity of the resist composition at 25°C is preferably 30 to 1000 mPa･s, more preferably 100 to 1000 mPa･s. The upper limit is preferably 800 mPa･s or less, more preferably 700 mPa･s or less, and even more preferably 600 mPa･s or less. The lower limit is preferably 150 mPa･s or more, more preferably 200 mPa･s or more, and still more preferably 300 mPa･s or more.

The resist composition contains a resin having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a photoacid generator, and the solid content concentration is preferably 30% by mass or more. Hereinafter, each component used in the resist composition will be described.

<<Resin>> It is preferable that the resist composition contains resin. With respect to the total solid content of the resist composition, the content of the resin in the solid content of the resist composition is preferably 95.0 to 99.9 mass %, more preferably 96.0 to 99.9 mass %, and 97.0 to 99.9 mass % Further preferred.

The Onishi parameter of the resin contained in the resist composition is preferably 3.0 or less, more preferably 2.9 or less, further preferably 2.8 or less, and particularly preferably 2.7 or less. When the Onishi parameter of the resin contained in the resist composition is 3.0 or less, it becomes easy to manufacture an infrared light receiving element with a high S/N ratio with respect to infrared rays. The reason why such an effect can be obtained is presumed to be that a resist film that can more effectively shield ions implanted at the time of ion implantation can be formed.

In the case where the resist composition contains two or more kinds of resins, the resin whose Onishi parameter is 3.0 or less in the total resin amount (preferably a resin whose Onishi parameter is 2.8 or less, more preferably a resin whose Onishi parameter is 2.7 or less) ) is preferably 50 to 100 mass %, more preferably 60 to 100 mass %, and even more preferably 75 to 100 mass %.

The resin contained in the resist composition preferably contains a resin having a repeating unit (hereinafter, also referred to as an acid-decomposable resin) having a group that is decomposed by the action of an acid and generates a polar group ( Hereinafter, also referred to as "acid-decomposable group").

The acid-decomposable group of the acid-decomposable resin includes a group having a structure in which a polar group is protected by a group (hereinafter, also referred to as a leaving group) from which a polar group is removed by the action of an acid. As the polar group, a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamido group, a sulfonimide group, a (alkylsulfonyl group) (alkylcarbonyl)methylene group, an (alkanesulfonyl group) can be mentioned. sulfonamido)(alkycarbonyl)imino, bis(alkcarbonyl)methylene, bis(alkcarbonyl)imido, bis(alkylsulfonamido)methylene, bis(alkylsulfonyl) Acid groups such as acyl)imide group, tris(alkylcarbonyl)methylene, tris(alkylsulfonyl)methylene (2.38 mass % tetramethyl group in the developer used as resist in the past) The dissociated group in ammonium hydroxide aqueous solution) or alcoholic hydroxyl group, etc. Preferable polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

As a leaving group, the group represented by any one of following formula (Y11) - (Y14) is mentioned, for example. Formula (Y11): -C(Rx ₁₁ )(Rx ₁₂ )(Rx ₁₃ ) Formula (Y12): -C(=O)OC(Rx ₁₁ )(Rx ₁₂ )(Rx ₁₃ ) Formula (Y13): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y14): -C(Rn)(H)(Ar)

In formulae (Y11) and (Y12), Rx ₁₁ to Rx ₁₃ each independently represent an alkyl group (straight chain or branched chain) or a cycloalkyl group (monocyclic or polycyclic). The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. When Rx ₁₁ to Rx ₁₃ are all alkyl groups (linear or branched), at least two of _{Rx 11} to Rx _{13 are preferably methyl groups.} More preferably, Rx ₁₁ to Rx ₁₃ are each independently a linear or branched alkyl group, and further preferably, Rx ₁₁ to Rx ₁₃ are each independently a linear alkyl group. Two of Rx ₁₁ to Rx ₁₃ may be bonded to form a ring. Monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl groups, tetracyclodecyl groups, tetracyclododecyl groups, and adamantyl groups as rings formed by two bonds of _{Rx 11} to Rx ₁₃ Isopolycyclic cycloalkyl groups are preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable. In addition, regarding the above-mentioned cycloalkyl group, for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom (eg, a carbonyl group and the like). For the groups represented by the formulae (Y11) and (Y12), for example, Rx ₁₁ is a methyl group or an ethyl group, and Rx ₁₂ and Rx _{13 are} bonded to form the above-mentioned cycloalkyl group.

In formula (Y13), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R ₃₆ is also preferably a hydrogen atom.

As the formula (Y13), the structure represented by the following formula (Y3-1) is more preferable.

L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group obtained by combining an alkylene group and an aryl group.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amine group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.

At least one of L ₁ and L ₂ is a hydrogen atom, and at least one of them is an alkyl group, a cycloalkyl group, an aryl group, or a group obtained by combining an alkylene group and an aryl group.

At least two of Q, M and L ₁ may be bonded to form a ring (preferably a 5-membered or 6-membered ring).

From the viewpoint of the stability of the pattern shape, L ₂ is preferably a second-order alkyl group or a third-order alkyl group, and more preferably a third-order alkyl group. As the secondary alkyl group, isopropyl group, cyclohexyl group, and norbornyl group can be mentioned, and as the tertiary alkyl group, tertiary butyl group and adamantyl group can be mentioned.

In formula (Y14), Ar represents an aromatic ring group. Rn represents alkyl, cycloalkyl or aryl. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

As the repeating unit having an acid-decomposable group, a repeating unit represented by the following general formula (AIa) or (AII) is preferable. [hua 2]

In formula (AIa), Xa ₁ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Ya represents a group released by the action of an acid. Ya is preferably a group represented by any one of the aforementioned formulae (Y11) to (Y14). However, in the case where Ya is a group represented by the formula (Y11), and two of Rx ₁₁ , Rx ₁₂ and Rx ₁₃ are bonded to form a ring, the sum of the carbon numbers of _{Rx 11} , Rx ₁₂ and Rx ₁₃ 11 or more.

Examples of the alkyl group represented by Xa ₁ include a methyl group or a group represented by -CH ₂ -R ₁₁ . R ₁₁ represents a halogen atom (a fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms. , and more preferably methyl. In one aspect, Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.

Examples of the divalent linking group represented by T include an alkylene group, -COO-Rt-, -O-Rt-, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group. T series single bond or -COO-Rt- is preferable. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably -CH ₂ -, -(CH ₂ ) ₂ -, and -(CH ₂ ) ₃ -.

In formula (AII), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may bond with Ar ₆ to form a ring, and R _{62 in this case} represents a single bond or an alkylene group. X ₆ represents a single bond, -COO- or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group. L ₆ represents a single bond or an alkylene group, and a single bond is preferred. Ar ₆ represents an (n+1)-valent aromatic ring group, and when it is _{bonded to R 62} to form a ring, it represents an (n+2)-valent aromatic ring group. The aromatic ring group represented by Ar ₆ is preferably a phenyl ring group or a naphthyl ring group, more preferably a phenyl ring group. In the case of n≧2, Y ₂ each independently represents a group or a hydrogen atom detached by the action of an acid. However, at least one of Y ₂ represents a group that is detached by the action of an acid. The group to be _{removed by the action of the acid as Y 2} is preferably a group represented by any one of the aforementioned formulae (Y11) to (Y14). However, in the case where Y ₂ is a group represented by formula (Y12), and two of Rx ₁₁ , Rx ₁₂ and Rx ₁₃ are bonded to form a ring, the number of carbon atoms of _{Rx 11} , Rx ₁₂ and Rx ₁₃ The total is 11 or more. n represents an integer of 1-4.

Each of the above-mentioned groups in formula (AIa) and formula (AII) may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (2 to 6 carbon atoms). Wait.

The repeating unit represented by the formula (AIa) is preferably an acid-decomposable tertiary alkyl (meth)acrylate-based repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T represents a repeating unit of a single bond).

Regarding the repeating unit having an acid-decomposable group, reference can be made to Paragraph Nos. 0150 to 0159 and 0210 to 0224 of International Publication WO2016/104565, Paragraph Nos. 0227 to 0233, 0270 to 0272, The descriptions in paragraphs 0123 to 0131 of Japanese Patent Laid-Open No. 2012-208447 are incorporated into the present specification.

The acid-decomposable resin may contain only one type of repeating unit having an acid-decomposable group, or may contain two or more types. The content of the repeating unit having an acid-decomposable group in the acid-decomposable resin is preferably 5 to 90 mol % with respect to all the repeating units in the acid-decomposable resin. The lower limit is preferably 10 mol % or more, more preferably 15 mol % or more, and still more preferably 20 mol % or more. The upper limit is more preferably 85 mol % or less, and further more preferably 80 mol % or less.

The acid-decomposable resin may contain a repeating unit having an acid group as a repeating unit other than the repeating unit having an acid-decomposable group. Examples of the acid group include a carboxyl group, a sulfonimidyl group, a sulfonimide group, a bissulfonimide group, a phenolic hydroxyl group, and the like. A phenolic hydroxyl group is a group formed by substituting a hydroxyl group for a hydrogen atom of an aromatic ring group. The aromatic ring is a monocyclic or polycyclic aromatic ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a perylene ring, a phenanthrene ring, etc., an aromatic hydrocarbon ring which may have a substituent of 6 to 18 carbon atoms, or an aromatic hydrocarbon ring containing, for example, a thiophene. ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazole ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring and other heterocycles Aromatic heterocycle. Among them, from the viewpoint of resolution, a benzene ring and a naphthalene ring are preferable, and a benzene ring is the most preferable.

As the repeating unit having an acid group, a repeating unit having a phenolic hydroxyl group is preferable. As a repeating unit which has a phenolic hydroxyl group, the repeating unit represented by following formula (30) is preferable.

In formula (30), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₃₃ may be _{bonded to Ar 3} to form a ring, and R _{33 in this case} represents an alkylene group. X ₃ represents a single bond or a divalent linking group. When Ar ₃ represents an (n3+1)-valent aromatic ring group and is _{bound to R 33} to form a ring, it represents an (n3+2)-valent aromatic ring group. n3 represents an integer from 1 to 4.

環基、咪唑環基、苯并咪唑環基、三唑環基、噻二唑環基、噻唑環基等包含雜環之芳香環基。Ar₃係苯環基為較佳。Ar₃所表示之(n3+1)價的芳香環基還可以具有取代基。作為取代基，可舉出烷基、烷氧基等。 Examples _{of the (n3+1)-valent aromatic ring group represented by Ar 3} include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl ring group, a naphthalene ring group, and an anthracycline group, a thiophene ring group, and a furan ring group. , pyrrole ring group, benzothiophene ring group, benzofuran ring group, benzopyrrole ring group, three

A ring group, an imidazole ring group, a benzimidazole ring group, a triazole ring group, a thiadiazole ring group, a thiazole ring group and the like are aromatic ring groups including heterocycles. Ar _3- series phenyl ring group is preferable. The (n3+1)-valent aromatic ring group represented by Ar _{3 may have a substituent.} As a substituent, an alkyl group, an alkoxy group, etc. are mentioned.

The divalent linking group represented by _{X 3 includes -COO- or -CONR 64} -. R ₆₄ represents a hydrogen atom or an alkyl group. As X ₃ , a single bond, -COO-, and -CONH- are preferable, and a single bond and -COO- are more preferable.

n3 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

Regarding the repeating unit having a phenolic hydroxyl group, reference can be made to the descriptions in paragraphs 0131 to 0147 of International Publication WO2016/104565 and paragraphs 0177 to 0178 of JP 2014-232309 A, which are incorporated into the present specification. .

The acid-decomposable resin may contain only one type of repeating unit having an acid group, or may contain two or more types. The content of the repeating unit having an acid group in the acid-decomposable resin is preferably 5 to 90 mol % with respect to all the repeating units in the acid-decomposable resin. The lower limit is preferably 10 mol % or more, more preferably 15 mol % or more, and still more preferably 20 mol % or more. The upper limit is more preferably 85 mol % or less, and further more preferably 80 mol % or less.

The acid-decomposable resin may further contain a repeating unit having a lactone structure or a sultone (cyclic sulfonate) structure as a repeating unit other than the repeating unit having an acid-decomposable group. Regarding the repeating unit of the lactone structure or the sultone (cyclic sulfonate) structure, the descriptions of paragraph numbers 0161 to 0170 of International Publication WO2016/104565 can be referred to, and the contents are incorporated in the present specification.

The acid-decomposable resin can contain a repeating unit having an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group, as a repeating unit other than the repeating unit having an acid-decomposable group. When the acid-decomposable resin contains such repeating units, the adhesion to the support and the affinity for the developer are improved. As the polar group, a hydroxyl group and a cyano group are preferable. As the alicyclic hydrocarbon structure, an adamantyl group, a diadamantyl group, and a norbornyl group are preferable. Regarding the repeating unit containing an organic group having a polar group, reference can be made to the description of paragraph No. 0172 of International Publication WO2016/104565, the content of which is incorporated in the present specification.

The acid-decomposable resin can have, as a repeating unit other than the repeating unit having an acid-decomposable group, a repeating unit which has a cyclic hydrocarbon structure without a polar group and does not exhibit acid-decomposability. As such a repeating unit, the repeating unit represented by formula (IV) is mentioned.

[hua 4]

In the above formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and no polar group. Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra ₂ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferable.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, cycloalkenyl groups having 3 to 12 carbon atoms such as cyclohexenyl, Phenyl etc. As the polycyclic hydrocarbon group, a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group can be mentioned. As an example of a ring-assembled hydrocarbon group, a bicyclohexyl group, a perhydronaphthyl group, a biphenyl group, a 4-cyclohexylphenyl group, etc. are mentioned. Examples of the cross-linked cyclic hydrocarbon group include bicyclic hydrocarbon ring groups such as pinane ring group, campane ring group, norbornane ring group, norbornane ring group, bicyclooctane ring group, homobreane ( homobledane) ring group, adamantane ring group, tricyclic hydrocarbon ring group such as tricyclo[5.2.1.0 ^2,6 ]decane ring group, tricyclo[4.3.1.1 ^2,5 ]undecanyl ring group, tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] Dodecane ring group, tetracyclic hydrocarbon ring group such as perhydro-1,4-methylene-5,8-methylenenaphthalene ring group, and the like. Moreover, as an example of a bridge|crosslinked cyclic hydrocarbon group, the condensed ring group etc. which condensed a plurality of 5- to 8-membered cycloalkyl rings are mentioned.

These cyclic hydrocarbon structures may have substituents. As a substituent, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, etc. are mentioned.

When the acid-decomposable resin contains a repeating unit having a cyclic hydrocarbon structure without a polar group and showing no acid-decomposability, the content thereof is 1 to 40 mol with respect to all the repeating units in the acid-decomposable resin % is better, more preferably 2-20 mol%.

As a specific example of an acid-decomposable resin, the resin etc. of the following structure are mentioned, for example. Values labeled for each repeating unit are molar ratios. [hua 5]

The weight average molecular weight of the acid-decomposable resin is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and particularly preferably 3,000 to 11,000. When the weight average molecular weight is 1,000 to 200,000, it is excellent in film formability and developability.

The degree of dispersion (molecular weight distribution) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, and even more preferably 1.0 to 2.0. The smaller the molecular weight distribution, the better the resolution, the better the resist shape, and the smoother the sidewall of the resist pattern.

The Onishi parameter of the acid-decomposable resin is preferably 3.0 or less, more preferably 2.9 or less, more preferably 2.8 or less, and particularly preferably 2.7 or less. The lower limit is preferably 2.5 or more, for example.

It is preferable that content of an acid-decomposable resin is 30-99.9 mass % with respect to the total solid content of a resist composition. The lower limit is preferably 50 mass % or more, more preferably 70 mass % or more, more preferably 90 mass % or more, even more preferably 95 mass % or more, further more preferably 96 mass % or more, particularly 97 mass % or more good. Only one type of acid-decomposable resin may be used, or two or more types may be used simultaneously.

Moreover, the content of the acid-decomposable resin in the total amount of the resin contained in the resist composition is preferably 50 to 100 mass %, more preferably 60 to 100 mass %, and still more preferably 70 to 100 mass % Preferably, 80 to 100 mass % is particularly preferable.

The resist composition may contain a hydrophobic resin as the resin. The hydrophobic resin is preferably designed in a way that is biased towards the interface, but unlike surfactants, it is not necessary to have a hydrophilic group in the molecule, and it does not work for uniformly mixing polar/nonpolar substances. As the effect of adding a hydrophobic resin, suppression of outgassing, etc. can be mentioned. As the hydrophobic resin, reference can be made to the descriptions of paragraph numbers 0336 to 0374 of International Publication WO2016/104565, the contents of which are incorporated in the present specification.

<<Photoacid generator>> It is preferable that the resist composition contains a photoacid generator. The photoacid generator may be in the form of a low molecular weight compound or may be in a form embedded in a part of the polymer, but the form of a low molecular weight compound is preferable. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

The photoacid generator is not particularly limited, but an organic acid such as sulfonic acid, bis(alkylsulfonyl)imide or A compound of at least any one of the tri(alkylsulfonyl)methylates is preferred. More preferably, the compounds represented by the following formulae (ZI), (ZII) and (ZIII) can be mentioned, and the compound represented by the formula (ZI) is more preferable.

[hua 6]

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. An aryl group, an alkyl group, a cycloalkyl group etc. are mentioned as an organic group represented by _{R 201} , R ₂₀₂ and R _{203 .} As the aryl group, an aryl group having 6 to 14 carbon atoms can be mentioned. As the alkyl group and the cycloalkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms can be preferably used. The above-mentioned aryl group, alkyl group, and cycloalkyl group may also have a substituent. Examples of the substituent include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably with 1 to 15 carbon atoms), and a cycloalkyl group (with a carbon number of 3 to 15). preferably), aryl (preferably carbon number 6-14), alkoxycarbonyl (preferably carbon number 2-7), acyl group (preferably carbon number 2-12), alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), etc., but not limited to these.

In formula (ZI), two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the formed ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group in the ring. As a _{group formed by two of R 201} to R ₂₀₃ being bonded, an alkylene group (for example, a butylene group and a pentylene group) can be mentioned.

In formula (ZI), the number of aromatic rings contained in the ^{cationic moiety (S +} (R ₂₀₁ )(R ₂₀₂ )(R _{203 )) is} Two or less is preferable, one or less is more preferable, and it is more preferable not to contain an aromatic ring.

In formula (ZI), Z ^- represents a non-nucleophilic anion (an anion having a significantly low ability to cause a nucleophilic reaction). Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkylcarboxylate anion, etc.), sulfonimide anion, bis(alkylsulfonyl)imide anion, tris(alkylsulfonyl)methide anion, etc.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon 3-30 cycloalkyl groups.

As the aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylate anion, an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group, and the like can be preferably used.

The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples of this include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably with 1 to 15 carbon atoms), and a cycloalkyl group (with 3 to 15 carbon atoms). is preferred), aryl (preferably carbon number 6-14), alkoxycarbonyl (preferably carbon number 2-7), acyl group (preferably carbon number 2-12), alkoxycarbonyl Oxy group (preferably with carbon number 2-7), alkylthio group (preferably with carbon number 1-15), alkylsulfonyl group (preferably with carbon number 1-15), alkyliminosulfonyl group group (preferably with carbon number 1-15), aryloxysulfonyl group (preferably with carbon number 6-20), alkylaryloxysulfonyl group (preferably with carbon number 7-20), cycloalkane aryloxysulfonyl (carbon number 10-20), alkoxyalkoxy (carbon number 5-20), cycloalkylalkoxyalkoxy (carbon number 8-20) and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably carbon number 1-15) can also be mentioned as a substituent.

Preferable examples of the aralkyl group in the aralkylcarboxylate anion include aralkyl groups having 7 to 12 carbon atoms, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl groups.

As a sulfonimide anion, a saccharin anion can be mentioned, for example.

In the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms in the alkyl group is preferred. Examples of the substituents of these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxy groups. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred, such as a sulfonyl group. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

As another non-nucleophilic anion, phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), antimony fluoride (for example, SbF ₆ ^- ), etc. are mentioned, for example.

As a non-nucleophilic anion, an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted by a fluorine atom, an aromatic sulfonic acid anion in which an alkyl group is substituted by a fluorine atom, an aromatic sulfonic acid anion in which an alkyl group is substituted by a fluorine atom The (alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methide anion in which the alkyl group is substituted by a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion (more preferably with 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, and more preferably a nonafluorobutanesulfonic acid anion, Perfluorooctanesulfonic acid anion, pentafluorobenzenesulfonic acid anion, 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

From the viewpoint of acid strength, in order to improve the sensitivity, it is preferable that the acid-generating pKa is -1 or less.

Moreover, as a non-nucleophilic anion, the anion represented by following formula (AN1) can also be mentioned as a preferable aspect.

[hua 7]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are plural R ¹ and R ^{2 , they} may be the same or different from each other. L represents a divalent linking group, and when there are plural L, the same or different L may be sufficient. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

As the alkyl group in the alkyl group substituted by the fluorine atom of Xf, the number of carbon atoms is preferably 1 to 10, and the number of carbon atoms is more preferably 1 to 4. As Xf, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferable. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH 2 ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , among which fluorine atom and CF ₃ are preferable . Both Xf-based fluorine atoms are particularly preferred.

The alkyl groups of R ¹ and R ² may have a substituent (preferably a fluorine atom), and those having 1 to 4 carbon atoms are preferred. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. As R ¹ and R ² , a fluorine atom or CF _{3 is} preferable.

x is preferably 1-10, more preferably 1-5. y is preferably 0 to 4, more preferably 0. The z series is preferably 0 to 5, more preferably 0 to 3.

The divalent linking group of L is not particularly limited, and examples include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, and alkylene groups. , a cyclo-extended alkyl group, an alkenylene group, or a linking group obtained by connecting a plurality of these groups, etc., a linking group with a total carbon number of 12 or less is preferred. Among them, -COO-, -OCO-, -CO-, and -O- are preferable, and -COO- and -OCO- are more preferable.

The cyclic organic group of A is not particularly limited as long as it is a group having a cyclic structure, and examples include aliphatic rings, aromatic hydrocarbon rings, and heterocycles (including not only those having aromatic properties, but Groups such as rings without aromaticity are also included. The aliphatic ring may be a monocyclic ring or a polycyclic ring, a monocyclic cycloalkyl ring such as a cyclopentyl ring, a cyclohexyl ring, a cyclooctyl ring, a norbornyl ring, a tricyclodecyl ring, a tetracyclic ring, and the like. Polycyclic cycloalkyl rings such as cyclodecyl ring, tetracyclododecyl ring, and adamantyl ring are preferable. As an aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, etc. are mentioned. Examples of the heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, a decahydroisoquinoline ring, an endocyclic ring. Ester rings, etc.

The above-mentioned cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be any of straight chain, branched chain, and cyclic, preferably having 1 to 12 carbon atoms), cycloalkyl group (can be any one of monocyclic, polycyclic and spirocyclic rings, preferably with 3 to 20 carbon atoms), aryl group (preferably with 6 to 14 carbon atoms), hydroxyl, alkoxy, ester, amide group, urethane group, urea group, thioether group, sulfonamido group, sulfonate group, etc. In addition, the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon.

For details of the formula (AN1), reference can be made to the description of paragraph No. 0259 of International Publication WO2016/104565, which is incorporated in the present specification.

In formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R _{207 are the same} as the aryl group described as the aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the aforementioned compound (ZI). The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R _{207 may have a substituent.} As this substituent, those which may have an aryl group, an alkyl group, or a cycloalkyl group _{of R 201} to R _{203 in the compound (ZI) may also be mentioned.}

In formula (ZII) and (ZIII), Z ^- represents a non-nucleophilic anion, and the same as the non-nucleophilic anion ^{of Z - in formula (ZI) can be mentioned.}

From the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution, the photoacid generator generates an acid with a volume of 130 Å ³ or more (more best sulfonic acid) is the preferred compound, to produce a volume of 190 Å ³ or more size acids (more preferably a sulfonic acid) is more preferably the compound, to produce a volume of 270 Å ³ or more acid size (more preferably A compound of sulfonic acid) is further preferred, and a compound that generates an acid (more preferably a sulfonic acid) having ^{a volume of 400 Å 3 or more is particularly preferred.} However, from the viewpoints of sensitivity and coating solvent solubility, the above-mentioned volume ^{is preferably 2000 Å 3} or less, and ^{more preferably 1500 Å 3} or less. The value of the said volume was calculated|required using "WinMOPAC" made by FUJITSULIMITED. That is, first, the chemical structure of the acid of each example is input, then, the structure is used as the initial structure and the most stable stereo configuration of each acid is determined by molecular force field calculation using the MM3 method. The most stable steric configuration is calculated by molecular orbital calculation using the PM3 method, whereby the "accessible volume" of each acid can be calculated. 1 Å is 1 × ^10-10 m.

As the photoacid generator, paragraphs 0368 to 0377 of JP 2014-41328 A and paragraphs 0240 to 0262 of JP 2013-228681 A (corresponding U.S. Patent Application Publication No. 2015/004533) can be cited. paragraph number 0339 of the specification), which are incorporated into this specification. Moreover, as a preferable specific example, the following compounds are mentioned, but it is not limited to these.

[hua 8]

A photoacid generator can be used individually by 1 type, or can be used in combination of 2 or more types. The content of the photoacid generator is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, still more preferably 3 to 20% by mass, and particularly preferably 0.1 to 30% by mass relative to the total solid content of the resist composition. 3 to 15 mass %.

<<solvent>> It is preferable that the resist composition contains a solvent. As a solvent, it is preferable to contain a solvent (also referred to as "solvent (S)") satisfying the following conditions (a) to (c).

(a) A>-0.026*B+5 (b) 0.9<A<2.5 (c) 120<B<160

The above-mentioned A represents the viscosity (mPa·s) of the above-mentioned solvent (S), and the above-mentioned B represents the boiling point (°C) of the above-mentioned solvent (S). When the above-mentioned solvent (S) contains only one solvent, the above-mentioned A represents the viscosity (mPa·s) of the above-mentioned solvent, and the above-mentioned B represents the boiling point (° C.) of the above-mentioned solvent. When the above-mentioned solvent (S) is a mixed solvent containing two kinds of solvents, the above-mentioned A is calculated from the following formula (a1), and the above-mentioned B is calculated from the following formula (b1). A=μ1 ^{^} X1*μ2 ^{^} X2 (a1) B=T1*X1+T2*X2 (b1) μ1 represents the viscosity of the first solvent (mPa･s), T1 represents the boiling point (°C) of the first solvent, X1 represents the mass ratio of the first solvent to the total mass of the mixed solvent. μ2 represents the viscosity (mPa･s) of the second solvent, T2 represents the boiling point (°C) of the second solvent, and X2 represents the mass ratio of the second solvent to the total mass of the mixed solvent. When the said solvent (S) is a mixed solvent containing n kinds of solvents, said A is calculated by following formula (a2), and said B is calculated by following formula (b2). A=μ1 ^{^} X1*μ2 ^{^} X2*…μn ^{^} Xn (a2) B=T1*X1+T2*X2+…Tn*Xn (b2) μ1 represents the viscosity of the first solvent (mPa･s), T1 represents the boiling point (° C.) of the first solvent, and X1 represents the mass ratio of the first solvent to the total mass of the mixed solvent. μ2 represents the viscosity (mPa･s) of the second solvent, T2 represents the boiling point (°C) of the second solvent, and X2 represents the mass ratio of the second solvent to the total mass of the mixed solvent. μn represents the viscosity (mPa･s) of the nth solvent, Tn represents the boiling point (°C) of the nth solvent, and Xn represents the mass ratio of the nth solvent to the total mass of the mixed solvent. n represents an integer of 3 or more.

The above-mentioned viscosity A (mPa･s) is a value at normal temperature and normal pressure (25°C/1atm). 1 atm is 1.013×10 ⁵ Pa. In addition, the above-mentioned boiling point B (°C) is a value under normal pressure (1 atm), and in the case of using two or more mixed solvents, the influence of the boiling point fluctuation due to azeotropy is not considered, and only the above-mentioned formula (b1) is followed. or (b2).

In addition, in formulas (a1) and (b1), X1+X2=1. In formulas (a2) and (b2), X1+X2+...Xn=1.

The viscosity A (mPa･s) of the solvent (S) preferably satisfies the following condition (b'), and more preferably satisfies the following condition (b''). (b') 1.0 < A < 2.0 (b''') 1.0 < A < 1.5

The boiling point B (°C) of the solvent (S) preferably satisfies the following condition (c'), and more preferably satisfies the following condition (c''). (c') 136 < B < 160 (c''') 140 < B < 150

The solvent (S) is not particularly limited as long as it satisfies the above-mentioned conditions (a) to (c), and examples thereof include lactone-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, and ether-based solvents. Solvents and aromatic organic solvents. The solvent (S) may be only one solvent or a mixed solvent of two or more solvents.

As a lactone type solvent, γ-butyrolactone (GBL) etc. are mentioned. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, cyclohexanone (CyHx), methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone (MAK), and the like. Examples of the ester-based solvent include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate (nBA), methyl pyruvate, ethyl pyruvate, and methyl methoxypropionate. ester (MMP), ethyl ethoxypropionate (EEP), etc. Monomethyl ethers such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, 3-methoxybutyl acetate, etc., Monoalkyl ethers such as diethyl ether, monopropyl ether, monobutyl ether {eg, propylene glycol monomethyl ether acetate (PGMEA), etc.} or monophenyl ether. Examples of the alcohol-based solvent include monovalent alcohols such as 4-methyl-2-pentanol (MIBC), benzyl alcohol, and 3-methoxybutanol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Polyol. Monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether (eg, propylene glycol monomethyl ether (PGME), etc.) and monophenyl ethers of the above-mentioned polyhydric alcohols may also be mentioned. Examples of the ether-based solvent include cyclic ethers such as dioxane, solvents described in the above-mentioned ester-based solvents, and alcohol-based solvents, which contain ether bonds. Examples of the aromatic organic solvent include anisole, ethylbenzyl ether, methyl cresyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butylphenyl ether, ethylbenzene, and diethylbenzene , pentylbenzene, cumene, toluene, xylene, cumene, mesitylene, etc.

Regarding the solvent (S), among the above-mentioned solvents, it is preferable to include at least one of ether-based solvents, ester-based solvents, and ketone-based solvents, and includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl acetate At least one of ethyl oxypropionate, cyclohexanone and methyl methoxypropionate is more preferred, and at least one of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether is further preferred.

Regarding the mixing ratio of each solvent when two or more solvents are used, A calculated by the above formulae (a1) and (a2) and B calculated by the above formulae (b1) and (b2) satisfy the above conditions ( It is better to adjust in the way of a) to (c).

The content of the solvent in the resist composition is preferably 40 to 70 mass %, more preferably 45 to 70 mass %, and even more preferably 55 to 70 mass % with respect to the total mass of the resist composition.

<<Acid Diffusion Control Agent>> It is preferable that the resist composition contains an acid diffusion control agent. The acid diffusion control agent acts as a quencher that captures the acid generated by an acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion generated by the excess acid generation. As the acid diffusion control agent, a basic compound, a low molecular weight compound having a nitrogen atom and a group detached by the action of an acid, or a basic compound whose basicity decreases or disappears by irradiation with actinic rays or radiation can be used The compound or relative to the acid generator becomes an onium salt of a relatively weak acid.

As a basic compound, the compound which has a structure represented by following formula (A) - (E) can be mentioned preferably.

[Chemical 9]

In formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and represent a hydrogen atom, an alkyl group (preferably with 1 to 20 carbon atoms), a cycloalkyl group (with a carbon number of 1 to 20) 3 to 20 are preferred) or an aryl group (preferably a carbon number of 6 to 20), where R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and represent an alkyl group having 1 to 20 carbon atoms.

As the alkyl group having a substituent, the above-mentioned alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. It is more preferable that the alkyl groups in the general formulae (A) and (E) are unsubstituted.

Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and further preferable compounds include Compounds with imidazole structure, diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, compounds with hydroxyl and/or ether bond are exemplified. Alkylamine derivatives, aniline derivatives with hydroxyl and/or ether bonds, etc. Specific examples of preferable compounds include compounds exemplified in paragraph No. 0379 of US2012/0219913.

In addition, as the basic compound, an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group can be preferably used. For details of these, reference can be made to Paragraph Nos. 0307 to 0311 of International Publication WO2016/104565, the contents of which are incorporated in the present specification.

When the resist composition contains a basic compound, the content of the basic compound is preferably 0.001 to 10 mass %, more preferably 0.01 to 5 mass %, relative to the total solid content of the resist composition. In addition, the ratio of the photoacid generator (in the case of having a plurality of types, the total amount) and the basic compound in the resist composition is in molar ratio: photoacid generator/basic compound=2.5 to 300: better. From the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution due to the time-dependent thickening of the resist pattern after exposure to heat treatment, 300 The following are preferred. The aforementioned molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

A low-molecular-weight compound (hereinafter, also referred to as "compound (D-1)") having a nitrogen atom and a group removed by the action of an acid has a group removed by the action of an acid on the nitrogen atom Amine derivatives of the group are preferred. As a group to be removed by the action of an acid, an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, and a hemiamine acetal ether group are preferable, and a urethane group is preferable. , Hemiamine acetal ether group is particularly preferred. The molecular weight of the compound (D-1) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

The compound (D-1) may have a urethane group having a protective group on the nitrogen atom. The protective group constituting the urethane group can be represented by the following formula (d-1).

[Chemical 10]

In formula (d-1), Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), and an aryl group (preferably having 3 carbon atoms). ~30 is preferred), aralkyl (preferably carbon number 1-10) or alkoxyalkyl (carbon number 1-10 is preferred). Rb may be linked to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Rb can be replaced by functional groups such as hydroxyl, cyano, amino, pyrrolidinyl, piperidinyl, morpholinyl, oxo, alkoxy, halogen atom substitution. The same applies to the alkoxyalkyl group represented by Rb. As Rb, a linear or branched alkyl group, a cycloalkyl group, and an aryl group are preferable. More preferably, a linear or branched alkyl group and a cycloalkyl group are used. As a ring formed by connecting two Rbs to each other, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof, etc. can be mentioned. As a specific structure of the group represented by formula (d-1), the structure disclosed in the paragraph No. 0466 of US2012/0135348 gazette can be mentioned, and the content is incorporated in this specification.

The compound (D-1) is preferably a compound having a structure represented by the following formula (6).

[Chemical 11]

In formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be linked to each other to form a heterocycle together with the nitrogen atom in the formula. A heteroatom other than the nitrogen atom in the formula may be contained in the heterocyclic ring. Rb has the same meaning as Rb in the above formula (d-1), and the preferred examples are also the same. l represents an integer from 0 to 2, and m represents an integer from 1 to 3, satisfying l+m=3. In formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra may be substituted with the same groups as the aforementioned groups as the group which may be substituted for the alkane as Rb group, cycloalkyl group, aryl group and aralkyl group.

Specific examples of the compound (D-1) include the compounds described in paragraph No. 0475 of US2012/0135348, the contents of which are incorporated in the present specification.

The compound represented by the formula (6) can be synthesized in accordance with JP 2007-298569 A, JP 2009-199021 A, and the like.

When the resist composition contains the compound (D-1), the content of the compound (D-1) is preferably 0.001 to 20 mass %, preferably 0.001 to 10, with respect to the total solid content of the resist composition. The mass % is more preferable, and 0.01 to 5 mass % is further preferable.

Examples of basic compounds (hereinafter, also referred to as "compounds (PA)") whose basicity is reduced or disappeared by irradiation with actinic rays or radiation include proton-accepting functional groups and are irradiated by light. A compound whose proton-accepting property decreases or disappears or changes from proton-accepting property to acidity due to decomposition by irradiation with chemical rays or radiation.

The so-called proton acceptor functional group refers to a functional group having a group capable of electrostatically interacting with a proton or an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a The functional group of the nitrogen atom of the non-shared electron pair in which π-conjugation does not work. The nitrogen atom having a non-shared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical 12]

As a preferable partial structure of a proton-accepting functional group, crown ether, azacrown ether, a primary-tertiary amine, a pyridine, an imidazole, a pyrazine structure etc. are mentioned, for example.

The compound (PA) produces a compound whose proton accepting property is decomposed by irradiation with actinic ray or radiation, and disappears or changes from proton accepting property to acidity. Here, the decrease or disappearance of the proton-accepting property or the change from the proton-accepting property to the acidity refers to the change of the proton-accepting property caused by the addition of a proton to the proton-accepting functional group, and specifically, the Refers to the reduction of the equilibrium constant in the chemical equilibrium when a proton adduct is formed from a compound (PA) with a proton acceptor functional group and a proton. The proton acceptor property can be confirmed by performing pH measurement. Regarding the compound (PA), reference can be made to the descriptions of paragraphs 0312 to 0320 of International Publication WO2016/104565, the contents of which are incorporated in the present specification.

When the resist composition contains the compound (PA), the content of the compound (PA) is preferably 0.1 to 10 mass %, more preferably 1 to 8 mass % with respect to the total solid content of the resist composition. good. The compound (PA) may be used alone or in combination of two or more.

In the resist composition, an onium salt which is a relatively weak acid relative to the photoacid generator can be used as the acid diffusion control agent. In the case where a photoacid generator is used in combination with an onium salt that generates an acid that is relatively weak (preferably a weak acid with a pKa exceeding -1) relative to the acid generated by the photoacid generator, if the acid is generated by actinic radiation or When the acid generated by the photoacid generator collides with an onium salt having an unreacted weak acid anion upon irradiation with radiation, the weak acid is released by salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with lower catalytic performance, so the acid is deactivated in appearance and can control acid diffusion. Regarding these compounds, reference can be made to paragraphs 0191 to 0210 of JP 2012-242799 A, paragraphs 0037 to 0039 of JP 2013-6827 A, and paragraphs 0027 to 0027 to JP 2013-8020 A 0029, paragraphs 0012 to 0013 of JP 2012-189977 A, and paragraphs 0029 to 0031 of JP 2012-252124 A, these contents are incorporated into this specification.

When the resist composition contains an onium salt which is relatively weak acid relative to the photoacid generator, the content of the resist composition is preferably 0.5 to 10.0% by mass, preferably 0.5 to 8.0% by mass relative to the total solid content of the resist composition. The mass % is more preferable, and 1.0 to 8.0 mass % is further preferable.

<<surfactant>> The resist composition may further contain a surfactant. As the surfactant, any one or both of fluorine-based and/or silicon-based surfactants (fluorine-based surfactants, silicon-based surfactants, and surfactants having both fluorine atoms and silicon atoms) are contained The above is better.

As fluorine-based and/or silicon-based surfactants, surfactants described in <0276> of US Patent Application Publication No. 2008/0248425, for example, EFTOP EF301, EF303 (Shin-Akita Kasei Co. Ltd.), Fluorad FC430, 431, 4430 (manufactured by Sumitomo 3M Limited), Magaface F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC CORPORATION), Surflon S-382, SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by ASAHI GLASS CO., LTD.), TroySol S-366 (manufactured by Troy Chemical Industries Inc.), GF-300, GF-150 (manufactured by TOAGOSEI CO., LTD. .), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD.), EFTOP EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656 , PF6320, PF6520 (manufactured by OMNOVA SOLUTIONS INC.), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos Corporation), etc. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

Further, as the surfactant, in addition to the known surfactants as described above, it is also possible to use the following surfactants, which are prepared by a short-chain polymerization method (also referred to as a short-chain polymer). A fluoroaliphatic group derived from a fluoroaliphatic compound produced by the oligomerization method (also known as the oligomer method). The fluoroaliphatic compound can be synthesized by the method described in JP-A No. 2002-90991. Surfactants suitable for the above include Magaface F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC CORPORATION), and acrylates _{having a C 6} F _{13 group.} (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) with C ₃ F ₇ group, (poly( Oxyethylidene)) acrylate (or methacrylate) and (poly(oxyethylidene)) acrylate (or methacrylate) copolymer and the like.

Furthermore, in the present invention, other surfactants other than the fluorine-based and/or silicon-based surfactants described in paragraph No. 0280 of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.

When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass %, relative to the solid content of the resist composition.

<<Other additives>> As needed, the resist composition can further contain carboxylate onium salts, acid multiplying agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and accelerators relative to development. Liquid-soluble compounds (for example, phenolic compounds with a molecular weight of 1,000 or less, alicyclic or aliphatic compounds having a carboxyl group), and the like.

<The composition for pixel formation> Next, the composition for pixel formation is demonstrated. The composition for forming a pixel is a composition for forming a pixel of an optical filter used in an apparatus. Examples of the type of the composition for forming a pixel include a composition for forming a coloring pixel, a composition for forming a pixel for an infrared transmissive layer, a composition for forming a pixel for an infrared cut layer, and the like, which are selected from the group consisting of coloring pixel forming It is preferable to use at least one of the composition and the composition for forming a pixel of the infrared-transmitting layer. Hereinafter, the composition for forming a color pixel is also referred to as a composition for a color filter. Moreover, the composition for pixel formation of an infrared-transmitting layer is also called the composition for infrared-transmitting filters. Moreover, the composition for pixel formation of an infrared cut layer is also called the composition for infrared cut filters.

As the composition for an infrared cut filter, having an absorbance maximum absorption wavelength in a wavelength range having 400 ~ 600 nm in a wavelength range of 700 ~ 1300 nm of the maximum absorbance A ₁ A ₂ of the maximum absorption wavelength at the A composition having a spectral characteristic with a ratio of A ₁ /A _{2 of 0.3 or less is preferable.} By using the composition which has such a spectral characteristic, the pixel which is excellent in visible transparency and excellent in infrared shielding property can be formed.

As a composition for a color filter, for example, a composition for forming a coloring pixel selected from a red pixel, a blue pixel, a green pixel, a cyan pixel, a magenta pixel, and a yellow pixel is: better.

The composition for an infrared transmission filter has a ratio of the minimum value Amin of the absorbance in the wavelength range of 400 to 640 nm and the maximum value Bmax of the absorbance in the wavelength range of 1100 to 1300 nm, that is, Amin/Bmax is 5 or more The composition of the spectroscopic properties is preferred. Amin/Bmax is more preferably 7.5 or more, more preferably 15 or more, and particularly preferably 30 or more.

The absorbance Aλ at a certain wavelength λ is defined by the following formula (1). Aλ=-log(Tλ/100)...(1) Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ. In this invention, the value of absorbance may be the value measured in the state of a solution, and the value measured in the state of the film produced using the composition for infrared transmission filters may be sufficient as it. In the case of measuring the absorbance in the state of a film, it is preferable to use a film prepared by applying the composition for an infrared transmission filter on a glass substrate by a method such as spin coating, so that the dried The thickness of the film was a predetermined thickness, and it was dried at 100° C. for 120 seconds using a hot plate. The thickness of the film can be measured using a stylus-type surface profiler (DEKTAK150 manufactured by ULVAC INC.) on the substrate having the film.

In addition, the absorbance can be measured using a conventionally known spectrophotometer. The measurement conditions of the absorbance are not particularly limited, but the maximum value B of the absorbance in the wavelength range of 1100 to 1300 nm is measured under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 640 nm is adjusted to 0.1 to 3.0 is better. By measuring the absorbance under such conditions, the measurement error can be further reduced. It does not specifically limit as a method of adjusting the minimum value A of the absorbance in the wavelength range of 400-640 nm to 0.1-3.0. For example, when measuring the absorbance in the state of a solution, the method of adjusting the optical path length of a sample cell is mentioned. Moreover, when measuring absorbance in the state of a film, the method of adjusting a film thickness, etc. are mentioned.

It is more preferable that the composition for infrared transmissive filters satisfies any one of the following spectral characteristics (1) to (4). (1): The ratio of the minimum value Amin1 of the absorbance in the wavelength range of 400 to 640 nm and the maximum value Bmax1 of the absorbance in the wavelength range of 800 to 1300 nm, that is, Amin1/Bmax1 is 5 or more, and 7.5 or more is relatively high. Preferably, 15 or more is more preferable, and 30 or more is further preferable. According to this aspect, it is possible to form a film that shields light in a wavelength range of 400 to 640 nm and transmits infrared rays with a wavelength of 720 nm. (2): The ratio of the minimum value Amin2 of the absorbance in the wavelength range of 400 to 750 nm and the maximum value Bmax2 of the absorbance in the wavelength range of 900 to 1300 nm, that is, Amin2/Bmax2 is 5 or more, and 7.5 or more is relatively high. Preferably, 15 or more is more preferable, and 30 or more is further preferable. According to this aspect, it is possible to form a film that shields light in a wavelength range of 400 to 750 nm and transmits infrared rays with a wavelength of 850 nm. (3): The ratio of the minimum value of absorbance Amin3 in the wavelength range of 400 to 850 nm to the maximum value of absorbance Bmax3 in the wavelength range of 1000 to 1300 nm, that is, Amin3/Bmax3 is 5 or more, and 7.5 or more is relatively high. Preferably, 15 or more is more preferable, and 30 or more is further preferable. According to this aspect, it is possible to form a film that shields light in a wavelength range of 400 to 830 nm and transmits infrared rays with a wavelength of 940 nm. (4): The ratio of the minimum value of absorbance Amin4 in the wavelength range of 400 to 950 nm to the maximum value of absorbance Bmax4 in the wavelength range of 1100 to 1300 nm, that is, Amin4/Bmax4 is 5 or more, and 7.5 or more is relatively high. Preferably, 15 or more is more preferable, and 30 or more is further preferable. According to this aspect, it is possible to form a film that shields light in a wavelength range of 400 to 950 nm and transmits infrared rays with a wavelength of 1040 nm.

When a film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm is formed using the composition for an infrared transmission filter, the light transmittance in the thickness direction of the film is satisfied in the wavelength range of 400 to 640 nm. It is preferable that the maximum value is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film is 70% or more in the wavelength range of 1100 to 1300 nm. The maximum value in the wavelength range of 400 to 640 nm is preferably 15% or less, more preferably 10% or less. The minimum value in the wavelength range of 1100 to 1300 nm is preferably 75% or more, and more preferably 80% or more.

More preferably, the composition for an infrared transmission filter satisfies any one of the following spectral characteristics (11) to (14). (11): When a film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm is formed using the composition for an infrared transmission filter, the transmittance of light in the thickness direction of the film is at a wavelength of 400 to 640 nm The maximum value in the range is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 800 to 1300 nm is 70 % or more (preferably 75% or more, more preferably 80% or more). (12): When a film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm is formed using the composition for an infrared transmission filter, the transmittance of light in the thickness direction of the film is at a wavelength of 400 to 750 nm The maximum value in the range is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 900 to 1300 nm is 70 % or more (preferably 75% or more, more preferably 80% or more). (13): When a film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm is formed using the composition for an infrared transmission filter, the transmittance of light in the thickness direction of the film is at a wavelength of 400 to 830 nm The maximum value in the range is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1000 to 1300 nm is 70 % or more (preferably 75% or more, more preferably 80% or more). (14): When a film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm is formed using the composition for an infrared transmission filter, the transmittance of light in the thickness direction of the film is at a wavelength of 400 to 950 nm The maximum value in the range is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1100 to 1300 nm is 70 % or more (preferably 75% or more, more preferably 80% or more).

The composition for forming a pixel used in the present invention preferably contains a polymerizable compound and a photopolymerization initiator.

<<Photopolymerization initiator>> The photopolymerization initiator is preferably a photoradical polymerization initiator. As the photopolymerization initiator, it is preferable to include at least one compound selected from the group consisting of alkyl phenone compounds, acylphosphine compounds, benzophenone compounds, thioxanthone compounds, trioxanthine compounds and oxime compounds, including oxime compounds. for better.

As an alkyl phenone compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, etc. are mentioned.

As a benzyl dimethyl ketal compound, 2, 2- dimethoxy- 2- phenyl acetophenone etc. are mentioned. As a commercial item, IRGACURE-651 (made by BASF Corporation) etc. are mentioned.

式中，Rv¹ 表示取代基，Rv² 及Rv³ 分別獨立地表示氫原子或取代基，Rv² 與Rv³ 可以彼此鍵結而形成環，m表示0～4的整數。As an α-hydroxyalkylphenone compound, the compound represented by following formula (V-1) is mentioned. Formula (V-1) [Chemical 13]

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, Rv ² and Rv ³ may be bonded to each other to form a ring, and m represents an integer of 0-4.

The substituent represented by Rv ¹ includes an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. The alkyl group and the alkoxy group are preferably linear or branched, more preferably linear. The alkyl group, alkoxy group and aralkyl group represented by Rv ^{1 may be unsubstituted or may have a substituent.} As a substituent, a hydroxyl group etc. are mentioned.

Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable. In addition, Rv ² and Rv ³ may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably straight chain or branched chain, more preferably straight chain.

Specific examples of the α-hydroxyalkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy- 2-methyl-propanyl)-benzyl]phenyl}-2-methyl-propan-1-one and the like. Commercially available products of the α-hydroxyalkylphenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (the above, manufactured by BASF Corporation).

As an α-aminoalkylphenone compound, the compound represented by following formula (V-2) is mentioned. [Chemical 14]

In the formula, Ar represents a phenyl group substituted with ^{-SR 13} or -N(R ^7E )(R ^{8E ), and R 13} represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

R ^1D and R ^2D each independently represent an alkyl group having 1 to 8 carbon atoms. R ^1D and R ^2D may be bonded to each other to form a ring. The alkyl group represented by R ^1D and R ^2D may be any of straight chain, branched chain and cyclic chain, and straight chain or branched chain is preferred. The alkyl group represented by R ^1D and R ^2D may be unsubstituted or substituted. Examples of the substituent include an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^Y1 , -SR ^Y1 , -COR ^Y1 , -COOR ^Y1 , -OCOR ^Y1 , -NR ^Y1 R ^Y2 , - NHCOR ^Y1 , -CONR ^Y1 R ^Y2 , -NHCONR ^Y1 R ^Y2 , -NHCOOR ^Y1 , -SO ₂ R ^Y1 , -SO ₂ OR ^Y1 , -NHSO ₂ R ^Y1 and the like. R ^Y1 and R ^Y2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. The alkyl group represented by R ^Y1 and R ^Y2 preferably has a carbon number of 1 to 20. The alkyl group may be any of straight chain, branched chain and cyclic chain, but straight chain or branched chain is preferred. The aryl group as a substituent and the aryl group ^{represented by R Y1} and R ^Y2 preferably have a carbon number of 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring. Preferably, the heterocyclic group represented by R ^Y1 and R ^Y2 is a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The number system of the heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

R ^3D and R ^4D each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ^3D and R ^4D may be bonded to each other to form a ring. In ^{the case where R 3D} and R ^{4D are} bonded to form a ring, the two can be directly bonded to form a ring, or they can be bonded by -CO-, -O- or -NH- to form a ring. For example, a morpholine ring etc. are mentioned as a ring formed by ^{R 3D} and R ^{4D via -O-.}

R ^7E and R ^8E each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ^7E and R ^8E may be bonded to each other to form a ring. In ^{the case where R 7E} and R ^{8E are} bonded to form a ring, the two may be directly bonded to form a ring, or a ring may be formed by -CO-, -O- or -NH- bonding. For example, a morpholine ring etc. are mentioned as a ring formed by ^{R 7E} and R ^{8E via -O-.}

Specific examples of the α-aminoalkylphenone compound include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]-1-butanone, etc. As a commercial item of an (alpha)-amino alkyl phenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (the above, the BASF company make) etc. are mentioned.

Examples of the acylphosphine compound include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenyl oxide Phosphine etc. As a commercial item of an acylphosphine compound, IRGACURE-819, IRGACURE-TPO (the above, the BASF company make) etc. are mentioned.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide Ether, 3,3',4,4'-tetra(tert-butylperoxyhydroxy)benzophenone, 2,4,6-trimethylbenzophenone, etc.

As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

Examples of the tris(trichloromethyl) compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris(trichloromethyl), 2,4-bis(trichloromethyl) base)-6-(4-methoxynaphthyl)-1,3,5-tris-tris, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triss, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris𠯤, 2,4-bis(trichloromethyl)-6-[2- (5-Methylfuran-2-yl)ethenyl]-1,3,5-tris-2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl ]-1,3,5-Tris𠯤, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3 , 5-Tris 𠯤, 2,4-bis (trichloromethyl)-6-[2-(3,4-dimethoxyphenyl) vinyl]-1,3,5-tris 𠯤, etc.

As the oxime compound, reference can be made to the descriptions of paragraph numbers 0212 to 0236 of International Publication WO2016/190162, the contents of which are incorporated in the present specification. In addition, as the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-80068 A, the compound described in JP 2006-342166 A can be used, Compounds and the like described in Japanese Patent Laid-Open No. 2016-21012. Examples of the oxime compound that can be preferably used in the present invention include 3-benzyloxyiminobutan-2-one and 3-acetoxyiminobutan-2-one. , 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1 -ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one, etc. Also, JCSPerkin II (1979, pp. 1653-1660), JCS Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (Journal of Photopolymer Science and Technology) ( 1995, pp. 202-232), JP-A No. 2000-66385, JP-A No. 2000-80068, JP-A No. 2004-534797, JP-A No. 2006-342166 Wait. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (the above, manufactured by BASF Corporation), TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADECA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese Patent Laid-Open No. 2012-14052). Moreover, as an oxime compound, it is also preferable to use a compound which has no colorability, a compound which is high in transparency and does not easily discolor other components. As a commercial item, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (the above, the product of ADEKA CORPORATION) etc. are mentioned.

In the present invention, as the photopolymerization initiator, an oxime compound having a perylene ring can also be used. As a specific example of the oxime compound which has a perylene ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 is mentioned. This content is incorporated into this specification.

In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in JP 2014-500852 A, and JP 24, 36 to 40. Compound (C-3) and the like described in Kokai Publication No. 2013-164471. This content is incorporated into this specification.

In the present invention, as the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable to use the oxime compound having a nitro group as a dimer. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249 A and paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A The compound described in Japanese Patent No. 4223071, Paragraph Nos. 0007 to 0025, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

In the present invention, as the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication WO2015/036910.

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited to these.

[化16]

[Chemical 15]

[Chemical 16]

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass relative to the total solid content of the composition for forming a pixel. As for the lower limit, for example, 0.5 mass % or more is more preferable, and 1 mass % or more is more preferable. Regarding the upper limit, for example, 25 mass % or less is more preferable, and 20 mass % or less is further preferable. A photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together. In the case where two or more photopolymerization initiators are used simultaneously, it is preferable that the total amount is in the above-mentioned range.

<<Polymerizable compound>> As the polymerizable compound, a compound containing a group having an ethylenically unsaturated bond, etc. are mentioned, and a compound containing two or more groups having an ethylenically unsaturated bond is preferable, and 3 Compounds having more than one group having an ethylenically unsaturated bond are more preferable. The upper limit of the number of groups having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less. As a group which has an ethylenically unsaturated bond, a vinyl group, a styryl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned, (meth)acryloyl group is preferable. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound. Furthermore, the polymerizable compound is preferably a radically polymerizable compound.

The polymerizable compound may be in either form of a monomer or a polymer, but a monomer is preferred. The molecular weight of the monomeric polymerizable compound is preferably 200 to 3000. The upper limit of the molecular weight is preferably 2500 or less, and more preferably 2000 or less. The lower limit of the molecular weight is preferably 250 or more, and more preferably 300 or more.

As an example of a polymerizable compound, the description of the paragraph numbers 0033-0034 of Unexamined-Japanese-Patent No. 2013-253224 can be referred, and the content is incorporated in this specification. As the polymerizable compound, ethoxy-modified pentaerythritol tetraacrylate (as a commercial item, NK ESTER ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (as a commercial item) , KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylic acid Esters (as a commercial item, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial item, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A -DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and compounds having a structure in which these (meth)acryloyl groups are bonded via ethylene glycol residues and/or propylene glycol residues are preferred. In addition, these oligomer types can also be used. In addition, reference can be made to the descriptions of paragraph numbers 0034 to 0038 of JP 2013-253224 A, the contents of which are incorporated in the present specification. In addition, the polymerizable monomers and the like described in paragraph No. 0477 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to paragraph No. 0585 of the specification of US Patent Application Publication No. 2012/0235099 ) can be cited, and these contents are incorporated into this manual. Also, diglycerol EO (ethylene oxide) modified (meth)acrylate (as a commercial item, M-460; manufactured by TOAGOSEI CO., LTD.), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferred. These oligomeric forms can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned. Moreover, ARONIX M-350 and TO-2349 (made by TOAGOSEI CO., LTD.) can also be used as a radically polymerizable compound.

The polymerizable compound may be a compound having an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. As a polymerizable compound which has an acid group, an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid, etc. are mentioned. A polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound is preferred, and among the esters, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is particularly preferred . As a commercial item, ARONIX M-305, M-510, M-520 (above, TOAGOSEI CO., LTD. make) etc. are mentioned, for example. The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g. The lower limit is preferably 5 mgKOH/g or more. The upper limit is preferably 30 mgKOH/g or less.

The polymerizable compound is also a preferred aspect of a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. Alkane, trimethylolpropane, bis-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylol melamine and other polyols with (meth)acrylic acid and ε-caprolactone ε-caprolactone modified polyfunctional (meth)acrylate obtained by esterification. As the polymerizable compound having a caprolactone structure, the descriptions of paragraph numbers 0042 to 0045 of JP 2013-253224 A can be referred to, and the contents are incorporated in the present specification. Examples of compounds having a polycaprolactone structure include: DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.; SARTOMER Company, Inc. . The 4-functional acrylate with 4 ethylene oxide chains, namely SR-494, and the 3-functional acrylate with 3 isobutylene oxide chains, namely TPA-330, etc.

As the polymerizable compound, urethane acrylic acid described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 Esters, those described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 having an ethylene oxide skeleton Urethane compounds are also preferred. In addition, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 1-105238 can be used which have an amine group structure and a sulfide (sulfide) structure in the molecule. of addition polymerizable compounds. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by SANYO-KOKUSAKU PULP CO., LTD.), and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. . Moreover, it is also preferable to use 8UH-1006 and 8UH-1012 (made by TAISEI FINE CHEMICAL CO., LTD.) as a radically polymerizable compound.

The content of the polymerizable compound is preferably 0.1 to 40 mass % with respect to the total solid content of the composition for pixel formation. As for the lower limit, for example, 0.5 mass % or more is more preferable, and 1 mass % or more is more preferable. Regarding the upper limit, for example, 30 mass % or less is more preferable, and 20 mass % or less is further preferable. A polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When using two or more types of polymerizable compounds at the same time, it is preferable that the total amount of these be within the above-mentioned range.

<<Color material>> It is preferable that the composition for pixel formation used by this invention contains a color material. With respect to the total solid content of the composition for pixel formation, the content of the color material is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more Preferably, 50 mass % or more is especially preferable. When content of a color material is 40 mass % or more, it becomes easy to form a pixel with favorable spectral characteristics from a thin film. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. As the color material, a color colorant, a black colorant, a color material (light-shielding material) that shields visible light to be described later, an infrared absorbing dye, and the like are exemplified.

Moreover, when the composition for pixel formation is a composition for color filters, it is preferable to use a color coloring agent as a color material. In the color filter composition, the content of the color colorant is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more with respect to the total solid content of the pixel-forming composition. It is more preferable, 40 mass % or more is even more preferable, and 50 mass % or more is especially preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. In addition, in this invention, a coloring agent is a coloring agent other than a white coloring agent and a black coloring agent.

Moreover, when the composition for pixel formation is a composition for infrared transmission filters, it is preferable to use a light-shielding material as a color material. Moreover, as a color material, it is also preferable to use a light-shielding material and an infrared absorbing dye together. In the composition for an infrared transmissive filter, the infrared absorbing dye has a function of limiting the transmitted light (infrared rays) to the longer wavelength side. In the composition for an infrared transmissive filter, the content of the light-shielding material is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to the total solid content of the composition for infrared rays transmissive filter. It is preferable, 40 mass % or more is more preferable, and 50 mass % or more is especially preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. In addition, in the case where the composition for an infrared transmission filter contains an infrared absorption dye, the total amount of the infrared absorption dye and the light-shielding material is preferably 10% by mass or more relative to the total solid content of the composition for an infrared transmission filter, and 20 mass % or more is preferred. % or more is more preferable, 30 mass % or more is further preferable, 40 mass % or more is still more preferable, and 50 mass % or more is particularly preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. Moreover, it is preferable that content of the infrared absorbing dye in the total amount of an infrared absorbing dye and a light-shielding material is 5-40 mass %. The upper limit is preferably 30 mass % or less, and more preferably 25 mass % or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

Moreover, when the composition for pixel formation is a composition for infrared cut filters, it is preferable to use an infrared absorption dye as a color material. The content of the infrared absorbing dye is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more with respect to the total solid content of the composition for forming a pixel. . The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

(Colour Coloring Agent) As the coloring coloring agent, a red coloring agent, a green coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, an orange coloring agent, etc. are mentioned. The colorant may be a pigment or a dye. Pigments are preferred. The average particle size (r) of the pigment is preferably 20 nm≤r≤300 nm, more preferably 25 nm≤r≤250 nm, and further preferably 30 nm≤r≤200 nm. The "average particle size" as used herein refers to the average particle size of secondary particles formed by aggregating primary particles of the pigment. In addition, the particle size distribution (hereinafter, also simply referred to as "particle size distribution") of the secondary particles of the pigment that can be used is 70% by mass or more of the entire secondary particle system contained within the range of the average particle size ±100 nm More preferably, 80 mass % or more is more preferable. In addition, the particle size distribution of the secondary particles can be measured using the scattering intensity distribution.

Pigments are preferably organic pigments. As an organic pigment, the following are mentioned. Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (above, yellow pigment), CI Pigment Orange (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) , CI Pigment Red (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, etc. (above, red pigment), CI Pigment Green (Pigment Green) 7, 10, 36, 37, 58, 59, etc. (above, green pigment), CI Pigment Violet (Pigment Violet) 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment), CI Pigment Blue (Pigment Blue) 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigments), these organic pigments can be used alone or Use a combination of multiple types.

There is no restriction|limiting in particular as a dye, A well-known dye can be used. As the chemical structure, pyrazoleazo-based, anilino-based azo-based, triarylmethane-based, anthraquinone-based, anthrapyridone-based, benzylidene-based, oxocyanine-based, and pyrazolotriazole-based azo can be used series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole methine azo series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrrole Methylene series and other dyes. In addition, polymers of these dyes can also be used. In addition, dyes described in Japanese Patent Laid-Open No. 2015-028144 and Japanese Patent Laid-Open No. 2015-34966 can also be used.

式中，R¹ 及R² 分別獨立地表示氫原子或取代基，R³ 及R⁴ 分別獨立地表示取代基，a及b分別獨立地表示0～4的整數，在a為2以上之情形下，複數個R³ 可以相同，亦可以不同，複數個R³ 可以鍵結而形成環，在b為2以上之情形下，複數個R⁴ 可以相同，亦可以不同，複數個R⁴ 可以鍵結而形成環。(Black Colorant) Examples of the black colorant include inorganic black colorants such as carbon black, metal oxynitrides (titanium black, etc.), metal nitrides (titanium nitride, etc.), dibenzofuranone compounds, and methylidene. Organic black colorants such as amine compounds, perylene compounds, and azo compounds. As the organic black colorant, a dibenzofuranone compound and a perylene compound are preferable. Examples of the dibenzofuranone compound include compounds described in JP 2010-534726 A, JP 2012-515233 A, JP 2012-515234 A, and the like. For example, BASF can be used. Obtained by making "Irgaphor Black". As a perylene compound, CI Pigment Black 31, 32, etc. are mentioned. Examples of the methylimine compound include those described in Japanese Patent Laid-Open No. 1-170601, Japanese Patent Laid-Open No. 2-34664, and the like. For example, "Chromofine" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. black A1103". The dibenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof. [Chemical 17]

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent, R ³ and R ⁴ each independently represent a substituent, a and b each independently represent an integer of 0 to 4, and when a is 2 or more In this case, a plurality of R ³ can be the same or different, a plurality of R ³ can be bonded to form a ring, and when b is 2 or more, a plurality of R ⁴ can be the same or different, and a plurality of R ⁴ can be bonded knot to form a ring.

The substituents represented by R ¹ to R ⁴ represent halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, aryl groups, heteroaryl groups, -OR ³⁰¹ , -COR ³⁰² , -COOR ³⁰³ , -OCOR ³⁰⁴ , -NR ³⁰⁵ R ³⁰⁶ , -NHCOR ³⁰⁷ , -CONR ³⁰⁸ R ³⁰⁹ , -NHCONR ³¹⁰ R ³¹¹ , -NHCOOR ³¹² , -SR ³¹³ , -SO ₂ R ³¹⁴ , -SO ₂ OR ³¹⁵ , -NHSO ₂ R ³¹⁶ or -SO ₂ NR ³¹⁷ R ³¹⁸ , and R ³⁰¹ to R ³¹⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

For details of the dibenzofuranone compound, reference can be made to the descriptions of paragraph numbers 0014 to 0037 of JP 2010-534726 A, which are incorporated in the present specification.

(Color material for blocking visible light) The color material for blocking visible light (hereinafter, also referred to as a light-shielding material) is preferably a color material that absorbs light in the wavelength region from violet to red. Moreover, in this invention, it is preferable that a light-shielding material is a color material which shields the light of the wavelength region of a wavelength of 400-640 nm. In addition, the light-shielding material is preferably a color material that transmits light having a wavelength of 1100 to 1300 nm. It is preferable that the light-shielding material satisfies at least one of the following requirements (1) and (2). (1): Two or more kinds of color colorants are contained, and two or more kinds of color colorants are combined to form black. (2): Contains an organic black colorant. In the aspect of (2), it is also preferable to further contain a chromatic colorant. The organic black colorant is preferably a colorant having a maximum absorption wavelength in the wavelength range of 400 nm or more and 700 nm or less.

Regarding the light-shielding material, for example, the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 640 nm and the minimum value B of the absorbance in the wavelength range of 1100 to 1300 nm, that is, A/B is preferably 4.5 or more. . The above-mentioned properties may be satisfied with one kind of raw material, or may be satisfied with a combination of plural kinds of raw materials. For example, in the case of the aspect of the above (1), it is preferable to combine a plurality of chromatic colorants so as to satisfy the above-mentioned spectral characteristics. Moreover, in the case of the aspect of said (2), an organic type black coloring agent can satisfy the said spectral characteristic. In addition, the above-mentioned spectral characteristics may be satisfied by a combination of an organic black colorant and a color colorant.

The light-shielding material preferably contains two or more selected from the group consisting of red colorants, blue colorants, yellow colorants, purple colorants, and green colorants. That is, it is preferable that the light-shielding material forms black by a combination of two or more colorants selected from the group consisting of red colorants, blue colorants, yellow colorants, purple colorants, and green colorants. As a preferable combination, the following are mentioned, for example. (1) Containing red colorant and blue colorant. (2) Containing red colorant, blue colorant and yellow colorant. (3) Containing red colorant, blue colorant, yellow colorant and purple colorant. (4) Containing red colorant, blue colorant, yellow colorant, purple colorant and green colorant. (5) Containing red colorant, blue colorant, yellow colorant and green colorant. (6) Containing red colorant, blue colorant and green colorant. (7) Containing yellow colorant and purple colorant.

In the aspect of the above (1), the mass ratio of the red colorant to the blue colorant is preferably red colorant:blue colorant=20-80:20-80, and 20-60:40-80 is More preferably, 20-50:50-80 is more preferable. In the aspect of the above (2), the mass ratio of the red colorant, the blue colorant, and the yellow colorant is red colorant: blue colorant: yellow colorant = 10 to 80: 20 to 80: 10 to 40 More preferably, 10-60:30-80:10-30 is more preferable, and 10-40:40-80:10-20 is more preferable. In the aspect of the above (3), the mass ratio of red colorant, blue colorant, yellow colorant, and purple colorant is red colorant: blue colorant: yellow colorant: purple colorant = 10 to 80 :20～80:5～40:5～40 is better, 10～60:30～80:5～30:5～30 is better, 10～40:40～80:5～20:5～20 for further better. In the aspect of the above (4), the mass ratio of red colorant, blue colorant, yellow colorant, purple colorant, and green colorant is red colorant: blue colorant: yellow colorant: purple colorant : Green colorant=10～80:20～80:5～40:5～40:5～40 is better, 10～60:30～80:5～30:5～30:5～30 is better , 10～40:40～80:5～20:5～20:5～20 is further preferable. In the aspect of the above (5), the mass ratio of red colorant, blue colorant, yellow colorant, and green colorant is red colorant: blue colorant: yellow colorant: green colorant = 10 to 80 :20～80:5～40:5～40 is better, 10～60:30～80:5～30:5～30 is better, 10～40:40～80:5～20:5～20 for further better. In the aspect of the above (6), the mass ratio of the red colorant, the blue colorant, and the green colorant is red colorant: blue colorant: green colorant = 10 to 80: 20 to 80: 10 to 40 More preferably, 10-60:30-80:10-30 is more preferable, and 10-40:40-80:10-20 is more preferable. In the aspect of the above (7), the mass ratio of the yellow colorant to the purple colorant is preferably yellow colorant:purple colorant=10-50:40-80, more preferably 20-40:50-70 , 30～40:60～70 is further preferable.

As the yellow colorant, C.I. Pigment Yellow 139, 150, and 185 are preferable, C.I. Pigment Yellow 139 and 150 are more preferable, and C.I. Pigment Yellow 139 is further preferable. As the blue colorant, C.I. Pigment Blue 15:6 is preferred. As the purple colorant, C.I. Pigment Violet 23 is preferred. As the red colorant, Pigment Red 122, 177, 224, and 254 are preferable, Pigment Red 122, 177, and 254 are more preferable, and Pigment Red 254 is further preferable. As the green colorant, C.I. Pigment Green 7, 36, 58, 59 is preferable.

When an organic black colorant is used as a light-shielding material, it is preferable to use it in combination with a color colorant. By using an organic black colorant and a color colorant at the same time, it is easy to obtain excellent spectral characteristics. As a color coloring agent used in combination with an organic type black coloring agent, a red coloring agent, a blue coloring agent, a purple coloring agent, etc. are mentioned, for example, a red coloring agent and a blue coloring agent are preferable. These may be used alone, or two or more of them may be used simultaneously. Moreover, regarding the mixing ratio of a color colorant and an organic black colorant, 10-200 mass parts of color colorants are preferable with respect to 100 mass parts of organic black colorants, and 15-150 mass parts are more preferable.

The content of the pigment in the light-shielding material is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 99% by mass or more, relative to the total amount of the light-shielding material.

(infrared absorbing pigment)

As the infrared absorbing dye, a compound having a maximum absorption wavelength in the near-infrared region (preferably a wavelength range of 700 to 1300 nm) is preferred. The infrared absorbing pigment may be a pigment or a dye.

In the present invention, as the infrared absorbing dye, an infrared absorbing compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring can be preferably used. The number of atoms other than hydrogen constituting the π-conjugated plane of the infrared absorbing compound is preferably 14 or more, more preferably 20 or more, further preferably 25 or more, and particularly preferably 30 or more. Regarding the upper limit, for example, 80 or less are preferable, and 50 or less are more preferable.

Preferably, the π-conjugated plane of the infrared absorbing compound contains two or more monocyclic or condensed aromatic rings, more preferably three or more of the aforementioned aromatic rings, more preferably four or more of the aforementioned aromatic rings , it is particularly preferable to contain 5 or more of the aforementioned aromatic rings. The upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. As said aromatic ring, a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, Condensed pentaphenyl ring, quaterrylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl (naphthacene) ring, triphenylene ring, triphenylene ring, perylene ring , pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzox azole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazole ring, pyridazine ring, triazole ring, pyrrole ring, indole ring, isoindole ring, carbazole ring and the like Ring condensed ring.

The infrared absorbing compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 700-1000 nm. In addition, in this specification, "having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm" means that the absorption spectrum in the solution of the infrared absorbing compound has the maximum absorption wavelength in the wavelength range of 700 to 1000 nm. Absorbance wavelength. Chloroform, methanol, dimethyl methylene, ethyl acetate, and tetrahydrofuran are mentioned as the measurement solvent used for the measurement of the absorption spectrum of the infrared absorbing compound in the solution. In the case where it was a compound dissolved in chloroform, chloroform was used as the measurement solvent. In the case where it is a compound insoluble in chloroform, methanol is used. In addition, when neither was dissolved in chloroform or methanol, dimethylsulfite was used.

In the present invention, the infrared absorbing compound is selected from the group consisting of pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds, quartane compounds, merocyanine compounds, ketonium compounds, At least one of an oxonol compound, a diimonium compound, a dithiol compound, a triarylmethane compound, a pyrromethene compound, a methanimine compound, an anthraquinone compound and a dibenzofuranone compound One is preferably at least one selected from pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds and diimine compounds, preferably selected from pyrrolopyrrole compounds, At least one of a cyanine compound and a squaraine compound is more preferable, and a pyrrolopyrrole compound is especially preferable. As a diimine compound, the compound described in Unexamined-Japanese-Patent No. 2008-528706 is mentioned, for example, and the content is incorporated in this specification. Examples of the phthalocyanine compound include the compound described in paragraph No. 0093 of JP 2012-77153 A, the oxyphthalocyanine described in JP 2006-343631 A, and JP 2013-195480 The compounds described in paragraphs 0013 to 0029 of Gazette No. 1 are incorporated into the present specification. As a naphthalocyanine compound, the compound described in the paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-77153 is mentioned, for example, and the content is incorporated in this specification. In addition, as the cyanine compound, phthalocyanine compound, naphthalocyanine compound, diimine compound, and squaraine compound, the compounds described in paragraphs 0010 to 0081 of JP 2010-111750 A can be used, the contents of which are incorporated in in this manual. In addition, regarding the cyanine compound, for example, reference can be made to "Functional Pigment, Nobu Ogawara / Ken Matsuoka / Tejiro Kitao / Hirashima Hiroyuki, Kodansha Scientific", the contents of which are incorporated in this specification. Moreover, as an infrared absorbing compound, the compound described in Unexamined-Japanese-Patent No. 2016-146619 can also be used, and the content is incorporated in this specification.

式中，R^1a 及R^1b 各自獨立地表示烷基、芳基或雜芳基，R² 及R³ 各自獨立地表示氫原子或取代基，R² 及R³ 可以彼此鍵結而形成環，R⁴ 各自獨立地表示氫原子、烷基、芳基、雜芳基、-BR^4A R^4B 或金屬原子，R⁴ 可以與選自R^1a 、R^1b 及R³ 中之至少一個進行共價鍵結或者配位鍵結，R^4A 及R^4B 各自獨立地表示取代基。關於式（PP）的詳細內容，能夠參閱日本特開2009-263614號公報的段落號0017～0047、日本特開2011-68731號公報的段落號0011～0036、國際公開WO2015/166873號公報的段落號0010～0024的記載，該等內容被編入本說明書中。As the pyrrolopyrrole compound, a compound represented by the formula (PP) is preferable. [Chemical 18]

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ may be bonded to each other to form a ring, R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B or a metal atom, and R ⁴ may be covalently bonded to at least one selected from R ^1a , R ^1b and R ³ A bond or a coordinate bond, R ^4A and R ^4B each independently represent a substituent. For details of formula (PP), refer to paragraphs 0017 to 0047 of JP 2009-263614 A, paragraphs 0011 to 0036 of JP 2011-68731 A, and paragraphs of International Publication WO2015/166873 The descriptions of Nos. 0010 to 0024 are incorporated into this specification.

Preferably, R ^1a and R ^1b are each independently an aryl group or a heteroaryl group, more preferably an aryl group. In addition, the alkyl group, aryl group and heteroaryl group represented by ^{R 1a} and R ^{1b may have a substituent or may be unsubstituted.} Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, -OCOR ¹¹ , -SOR ¹² , -SO ₂ R ¹³ and the like. R ¹¹ to R ¹³ each independently represent a hydrocarbon group or a heteroaryl group. Moreover, as a substituent, the substituent described in the paragraph numbers 0020-0022 of Unexamined-Japanese-Patent No. 2009-263614 is mentioned. Among them, as the substituent, an alkoxy group, a hydroxyl group, a cyano group, a nitro group, -OCOR ¹¹ , -SOR ¹² , and -SO ₂ R ¹³ are preferable. As the group represented by R ^1a and R ^1b , an aryl group having an alkoxy group containing a branched alkyl group as a substituent, an aryl group having a hydroxyl group as a substituent group, or a group having a group represented ^{by -OCOR 11} An aryl group as a substituent is preferred. The carbon number of the branched alkyl group is preferably 3-30, more preferably 3-20.

At least one of R ² and R ³ is preferably an electron attracting group, R ² represents an electron attracting group (preferably a cyano group), and more preferably R ³ represents a heteroaryl group. The heteroaryl group is preferably a 5-membered or 6-membered ring. Further, the heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring of a condensation number of 2 to 8, and more preferably a monocyclic ring or a condensed ring of a condensation number of 2 to 4. The number system of the heteroatom constituting the heteroaryl group is preferably 1-3, more preferably 1-2. As the hetero atom, for example, a nitrogen atom, an oxygen atom, and a sulfur atom are exemplified. The heteroaryl group preferably has one or more nitrogen atoms. ^{The two R 2} in the formula (PP) may be the same or different from each other. In addition, the two R ³ in formula (PP) may be the same or different from each other.

R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by -BR ^4A R ^{4B , and a hydrogen atom, an alkyl group, an aryl group or a group represented by -BR 4A} R ^4B is More preferably, ^{the group represented by -BR 4A} R ^4B is further preferred. As ^{the substituent represented by R 4A} and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group is preferable, an alkyl group, an aryl group or a heteroaryl group is more preferable, and an aryl group is particularly preferable. These groups may also have substituents. ^{The two R 4} in the formula (PP) may be the same or different from each other.

Specific examples of the compound represented by the formula (PP) include the following compounds. In the following structural formula, Me represents a methyl group, and Ph represents a phenyl group. In addition, as the pyrrolopyrrole compound, the compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, and the compounds described in paragraphs 0037 to 0052 of JP 2011-68731 A , the compounds and the like described in Paragraph Nos. 0010 to 0033 of International Publication WO2015/166873, the contents of which are incorporated in the present specification. [Chemical 19]

式（SQ）中，A¹ 及A² 分別獨立地表示芳基、雜芳基或由式（A-1）表示之基團； [化21]

式（A-1）中，Z¹ 表示形成含氮雜環之非金屬原子團，R² 表示烷基、烯基或芳烷基，d表示0或1，波線表示連結鍵。關於式（SQ）的詳細內容，能夠參閱日本特開2011-208101號公報的段落號0020～0049、日本專利第6065169號公報的段落號0043～0062、國際公開WO2016/181987號公報的段落號0024～0040的記載，該等內容被編入本說明書中。As the squaraine compound, a compound represented by the following formula (SQ) is preferable. [hua 20]

In the formula (SQ), A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the formula (A-1);

In formula (A-1), Z ¹ represents a non-metallic atomic group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a bond. For details of formula (SQ), refer to paragraphs 0020 to 0049 of Japanese Patent Laid-Open No. 2011-208101, paragraphs 0043 to 0062 of Japanese Patent No. 6065169, and paragraph 0024 of International Publication WO2016/181987 ~0040, and these contents are incorporated into this specification.

In addition, in the formula (SQ), the cations are present in a delocalized manner as follows. [Chemical 22]

The squaraine compound is preferably a compound represented by the following formula (SQ-1).

Ring A and Ring B each independently represent an aromatic ring, X ^A and X ^B each independently represent a substituent, G ^A and G ^B each independently represent a substituent, kA represents _{an integer of 0 to n A} and kB represents 0 to n Integer of _{B , n A} and n _B respectively represent the largest integer that can be substituted on ring A or ring B, X ^A and G ^A , X ^B and G ^B , X ^A and X ^B can be bonded to each other to form a ring, When each of G ^A and G ^B exists in plural, they may be bonded to each other to form a ring structure.

As ^{the substituent represented by G A} and G ^B , the substituent T described in the above formula (PP) is exemplified.

The substituents represented by X ^A and X ^B are preferably groups having active hydrogen, -OH, -SH, -COOH, -SO ₃ H, -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -NHSO ₂ R ^X1 , -B(OH) ₂ and -PO(OH) ₂ are more preferred, -OH, -SH and -NR ^X1 R ^X2 are further preferred . R ^X1 and R ^X2 each independently represent a hydrogen atom or a substituent. As a ^{substituent represented by X A} and X ^B , an alkyl group, an aryl group, or a heteroaryl group can be mentioned, and an alkyl group is preferable.

Ring A and ring B each independently represent an aromatic ring. The aromatic ring may be a monocyclic ring or a condensed ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a cyclopentadiene ring, an indene ring, an azulene ring, a heptavine ring, an indane ring, a perylene ring, a condensed pentabenzene ring, and ethane. Naphthalene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, biextended triphenyl ring, perylene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine Ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolezine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalocyanine ring oxazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acridine ring, phenanthrene ring, thien ring, chromene ring, Xanthene ring, phenothiazine ring, phenothiazine ring and phenothiazine ring, preferably benzene ring or naphthalene ring. The aromatic ring may be unsubstituted or may have a substituent. As a substituent, the substituent T demonstrated in the said formula (PP) is mentioned.

X ^A and G ^A , X ^B and G ^B , and X ^A and X ^B may be bonded to each other to form a ring, and when ^{a plurality of G A} and G ^B are present, they may be bonded to each other to form a ring. As the ring, a 5-membered ring or a 6-membered ring is preferable. The ring may be a single ring or a condensed ring. In the case where X ^A and G ^A , X ^B and G ^B , X ^A and X ^B , G ^A and G ^B are bonded to each other to form a ring, they may be directly bonded to form a ring, or they may be formed by including extension An alkyl group, -CO-, -O-, -NH-, -BR-, and a divalent linking group of a combination thereof are bonded to form a ring. R represents a hydrogen atom or a substituent. As the substituent, the substituent T described in the above formula (PP) can be mentioned, and an alkyl group or an aryl group is preferable.

kA represents an integer of 0 ~ nA, kB represents an integer of 0 ~ nB, n _A represents the ring A can be substituted by the maximum integer, n _B represents the substituent on the ring B can be a maximum integer. Preferably, kA and kB independently represent 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.

式（SQ-11） [化25]

式（SQ-12） [化26]

The squaraine compound is also preferably a compound represented by the following formula (SQ-10), formula (SQ-11) or formula (SQ-12). Formula (SQ-10) [Chemical 24]

Formula (SQ-11) [Chemical 25]

Formula (SQ-12) [Chemical 26]

In the formulae (SQ-10) to (SQ-12), X is independently a formula (1) or a formula ( 2) represents a divalent organic group. -(CH ₂ ) _{n1 -...} (1) In formula (1), n1 is 2 or 3. -(CH ₂ ) _n2 -O-(CH ₂ ) _{n3 -...} (2) In formula (2), n2 and n3 each independently represent an integer of 0 to 2, and n2+n3 is 1 or 2. R ¹ and R ² each independently represent an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent or may be unsubstituted. As a substituent, the substituent T demonstrated in the said formula (PP) is mentioned. R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. n is 2 or 3.

As a squaraine compound, the compound of the following structure is mentioned. In the following structural formula, EH represents ethylhexyl. In addition, the compounds described in paragraphs 0044 to 0049 of JP 2011-208101 A, the compounds described in paragraphs 0060 to 0061 of JP 6065169, and International Publication WO2016/181987 The compounds described in paragraph No. 0040 of , the compounds described in JP-A No. 2015-176046, and the like, are incorporated into the present specification. [Chemical 27]

式中，Z¹ 及Z² 分別獨立地為形成可以縮合之5員或6員的含氮雜環之非金屬原子團， R¹⁰¹ 及R¹⁰² 分別獨立地表示烷基、烯基、炔基、芳烷基或芳基， L¹ 表示具有奇數個甲基之次甲基鏈， a及b分別獨立地表示0或1， 在a為0之情形下，碳原子和氮原子以雙鍵鍵結，在b為0之情形下，碳原子和氮原子以單鍵鍵結， 在式中的由Cy表示之部位為陽離子部之情形下，X¹ 表示陰離子，c表示使電荷平衡時所需之數，在式中的由Cy表示之部位為陰離子部之情形下，X¹ 表示陽離子，c表示使電荷平衡時所需之數，式中的由Cy表示之部位的電荷在分子內中和之情形下，c為0。The cyanine compound is preferably a compound represented by the formula (C). Formula (C) [Chemical 28]

In the formula, Z ¹ and Z ² are each independently a non-metallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that can be condensed, and R ¹⁰¹ and R ¹⁰² are respectively independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group an alkyl group or an aryl group, L ¹ represents a methine chain having an odd number of methyl groups, a and b independently represent 0 or 1, and when a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, When b is 0, a carbon atom and a nitrogen atom are bonded by a single bond, and when the site represented by Cy in the formula is a cationic part, X ¹ represents an anion, and c represents a number required for charge balance , in the case where the part represented by Cy in the formula is an anion part, X ¹ represents a cation, c represents the number required to balance the charges, and the charge of the part represented by Cy in the formula is neutralized in the molecule Below, c is 0.

As a specific example of a cyanine compound, the compound shown below is mentioned. In the following structural formula, Me represents a methyl group. In addition, examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of JP 2009-108267 A, compounds described in paragraphs 0026 to 0030 of JP 2002-194040 A, The compounds described in JP 2015-172004 A, the compounds described in JP 2015-172102 A, the compounds described in JP 2008-88426 A, and the like are incorporated in the present specification. [Chemical 29]

In the present invention, a commercially available product can also be used as the infrared absorbing dye. For example, SDO-C33 (manufactured by Arimoto Chemical Co. Ltd.), EX Color IR-14, EX Color IR-10A, EX Color TX-EX-801B, EX Color TX-EX-805K (Nippon Shokubai Co. , manufactured by HAKKO Chemical Co., Ltd.), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (manufactured by HAKKO Chemical Co., Ltd.), EpoliteV-63, Epolight3801, Epolight3036 (manufactured by EPOLIN), PRO - JET825LDI (manufactured by Fujifilm Corporation), NK-3027, NK-5060 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), and the like.

<<The compound which has a cyclic ether group>> It is also preferable that the composition for pixel formation contains the compound which has a cyclic ether group. As a cyclic ether group, an epoxy group, an oxetanyl group, etc. are mentioned. The compound having a cyclic ether group is preferably a compound having an epoxy group. As a compound which has an epoxy group, the compound which has one or more epoxy groups in 1 molecule is mentioned, and the compound which has two or more epoxy groups is preferable. It is preferable that there are 1-100 epoxy groups in 1 molecule. The upper limit of the epoxy group can be, for example, 10 or less, or 5 or less. About the minimum of an epoxy group, 2 or more are preferable. As the compound having an epoxy group, paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, and JP 2014-089408 A can also be used. The compounds described in paragraphs 0085 to 0092. These contents are incorporated into this manual.

The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, and furthermore, a molecular weight of less than 1000), a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more) any of the. The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

When the compound which has an epoxy group is a low molecular compound, the compound represented by following formula (EP1) is mentioned, for example.

[Chemical 30]

In formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom, and an alkyl group, and the alkyl group may have a cyclic structure and may have a substituent. In addition, R ^EP1 and R ^EP2 , and R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Q ^EP represents a single bond or an organic group of ^{n EP valence.} R ^EP1 to R ^EP3 may be ^{bonded to Q EP} to form a ring structure. n ^EP represents an integer of 2 or more, preferably 2-10, more preferably 2-6. Wherein, when Q ^EP is a single bond, n ^EP is 2. For details of R ^EP1 to R ^EP3 and Q ^EP , reference can be made to the descriptions of paragraph numbers 0087 to 0088 of JP 2014-089408 A, which are incorporated in the present specification. Specific examples of the compound represented by the formula (EP1) include the compound described in paragraph 0090 of JP-A-2014-089408 and the compound described in paragraph 0151 of JP-A-2010-054632 , which is incorporated into this manual.

As a commercial item, ADEKA Glycyrol series (for example, ADEKA Glycyrol ED-505 etc.) by ADEKA CORPORATION, EPOLEAD series (for example, EPOLEAD GT401 etc.) by Daicel Corporation, etc. are mentioned.

As a compound which has an epoxy group, an epoxy resin can be used suitably. Examples of epoxy resins include epoxy resins which are glycidyl ether compounds of phenolic compounds, epoxy resins which are glycidyl ether compounds of various novolak resins, alicyclic epoxy resins, and aliphatic epoxy resins. Resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, silicon compounds having epoxy groups, and others Condensates of other silicon compounds, copolymers of polymerizable unsaturated compounds having epoxy groups, and other polymerizable unsaturated compounds, and the like.

The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g/eq, more preferably 310 to 1700 g/eq, and even more preferably 310 to 1000 g/eq.

As an epoxy resin, a commercial item can also be used. For example, 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 (above, manufactured by NOF CORPORATION, epoxy group-containing polymer), etc.

When the composition for forming a pixel contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group is preferably 0.1 to 40% by mass relative to the total solid content of the composition for forming a pixel. . As for the lower limit, for example, 0.5 mass % or more is more preferable, and 1 mass % or more is more preferable. Regarding the upper limit, for example, 30 mass % or less is more preferable, and 20 mass % or less is further preferable. The compound which has a cyclic ether group may be used individually by 1 type, and may use 2 or more types together. In the case of using two or more compounds having a cyclic ether group at the same time, it is preferable that the total amount falls within the above range. Moreover, when the composition for pixel formation contains a polymerizable compound and a compound having a cyclic ether group, the mass ratio of the two is polymerizable compound: compound having a cyclic ether group=100:1 to 100:400 More preferably, 100:1～100:100 is more preferable.

<<Resin>> It is preferable that the composition for pixel formation contains resin. The resin is blended for the purpose of dispersing pigments and the like in the composition, and for the purpose of a binder, for example. In addition, the resin mainly used for dispersing a pigment etc. is also called a dispersing agent. However, this type of use of the resin is an example, and the resin can be used for purposes other than this type of use.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

As resins, (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysilicon resins, polyether resins, polyphenylene resins, Polyaryletherphosphine oxide resin, polyimide resin, polyimide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. One kind of these resins may be used alone, or two or more kinds may be mixed and used. As the cyclic olefin resin, norbornene resin can be preferably used from the viewpoint of improving heat resistance. As a commercial item of norbornene resin, the ARTON series (for example, ARTON F4520) by JSR CORPORATION etc. are mentioned, for example. In addition, the resin described in the Example of International Publication WO2016/088645 can also be used as a resin. Moreover, as resin, it is also preferable to use the resin provided with the repeating unit containing the group which has an ethylenically unsaturated bond in a side chain. As a group which has an ethylenically unsaturated bond, a (meth)acryloyl group etc. are mentioned. In addition, it is preferable that the main chain of the repeating unit and the group having an ethylenically unsaturated bond are bonded via a divalent linking group having an alicyclic structure.

In the present invention, it is preferable to use a resin having an acid group as the resin. According to this aspect, it becomes easy to form a pattern excellent in rectangularity. As an acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. are mentioned, A carboxyl group is preferable. A resin having an acid group can be used as the alkali-soluble resin, for example.

As the resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins Such as alkali-soluble phenolic resins, acid cellulose derivatives having carboxyl groups on the side chains, and resins obtained by adding acid anhydrides to polymers having hydroxyl groups. In particular, copolymers of (meth)acrylic acid and other monomers which can be copolymerized therewith are suitable as the alkali-soluble resin. As another monomer which can be copolymerized with (meth)acrylic acid, an alkyl (meth)acrylate, an aryl (meth)acrylate, a vinyl compound, etc. are mentioned. Examples of alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, cresyl (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. Examples of vinyl compounds include styrene, α-methylstyrene, vinyltoluene , glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. . In addition, as for other monomers, the N-substituted maleimide monomers described in Japanese Patent Laid-Open No. 10-300922, such as N-phenylmaleimide, N-cyclohexylmaleimide, can also be used imine, etc. Moreover, the other monomer which can be copolymerized with these (meth)acrylic acid may be only one type, and may be two or more types.

The resin having an acid group may also have a polymerizable group. As a polymerizable group, an allyl group, a methallyl group, a (meth)acryloyl group, etc. are mentioned. Commercially available products include DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer 6173 (carboxy group-containing urethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R-264, KS RESIST106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (eg, ACA230AA), PLACCEL CF200 series (all manufactured by Daicel Corporation.), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), etc.

Resins having an acid group can preferably use benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth) Ethyl acrylate copolymer, multi-component copolymer of benzyl (meth)acrylate/(meth)acrylic acid/other monomers. In addition, 2-hydroxypropyl (meth)acrylate/polyester described in Japanese Patent Laid-Open No. 7-140654 can also be preferably used by copolymerizing 2-hydroxyethyl(meth)acrylate. Styrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/ Methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer Molecular monomer/benzyl methacrylate/methacrylic acid copolymer, etc.

It is also preferable that the resin having an acid group is a polymer comprising a compound derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, sometimes the Such compounds are called "ether dimers".) The repeating unit of the monomer component.

[Chemical 31]

式（ED2）中，R表示氫原子或碳數1～30的有機基團。作為式（ED2）的具體例，能夠參閱日本特開2010-168539號公報的記載。In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical 32]

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of Formula (ED2), the description of Unexamined-Japanese-Patent No. 2010-168539 can be referred to.

As a specific example of the ether dimer, for example, paragraph No. 0317 of JP 2013-29760 A can be referred to, the content of which is incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.

式（X）中，R₁ 表示氫原子或甲基，R₂ 表示碳數2～10的伸烷基，R₃ 表示氫原子或可以包含苯環之碳數1～20的烷基。n表示1～15的整數。The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X). [Chemical 33]

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

For resins having an acid group, reference can be made to the descriptions of paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to paragraphs 0685 to 0700 of U.S. Patent Application Publication No. 2012/0235099 ), Japanese Patent Laid-Open Publication No. 0685 to 0700 The descriptions of paragraph numbers 0076 to 0099 of Gazette No. 2012-198408 are incorporated into the present specification. Moreover, a commercial item can also be used for resin which has an acid group. For example, AcrybaseFF-426 (made by FUJIKURA KASEI CO., LTD.) etc. are mentioned.

The acid value of the resin having an acid group is preferably 30 to 200 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 150 mgKOH/g or less, and more preferably 120 mgKOH/g or less.

As resin which has an acid group, the resin etc. of the following structure are mentioned, for example. In the following structural formula, Me represents a methyl group. [Chemical 34]

The composition for infrared transmission filters can further contain resin as a dispersant. The dispersing agent includes an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin). Here, the term "acidic dispersant (acidic resin)" refers to a resin in which the amount of acid groups is larger than the amount of basic groups. Regarding the acidic dispersant (acidic resin), when the total amount of the acid group and the basic group is 100 mol%, the resin in which the acid group accounts for 70 mol% or more is preferable, and substantially only Resins containing acid groups are more preferred. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH/g, more preferably 50 to 105 mgKOH/g, and further preferably 60 to 105 mgKOH/g. In addition, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is larger than the amount of acid groups. Regarding the basic dispersant (basic resin), when the total amount of the amount of the acid group and the amount of the basic group is 100 mol %, a resin in which the amount of the basic group exceeds 50 mol % is preferable. The basic group of the basic dispersant is preferably an amine group.

It is preferable that the resin used as a dispersant contains a repeating unit having an acid group. Since the resin used as the dispersing agent contains repeating units having an acid group, it is possible to further reduce the residues generated on the substrate of the pixel when the pattern is formed by the photolithography method.

Resin-based graft copolymers used as dispersants are also preferred. Since the graft copolymer has an affinity with the solvent due to the graft chain, it is excellent in the dispersibility of the pigment and the dispersion stability over time. For details of the graft copolymer, reference can be made to the descriptions of paragraphs 0025 to 0094 of JP 2012-255128 A, which are incorporated in the present specification. Moreover, the following resin is mentioned as a specific example of a graft copolymer. The following resins may be resins having acid groups (alkali-soluble resins). Moreover, as a graft copolymer, the resin described in the paragraph numbers 0072-0094 of Unexamined-Japanese-Patent No. 2012-255128 is mentioned, and the content is incorporated in this specification. [Chemical 35]

Moreover, in this invention, it is also preferable to use the oligoimide type dispersing agent which contains a nitrogen atom in at least one of a main chain and a side chain as a resin (dispersing agent). As the oligoimine-based dispersant, a resin having the following structural unit and side chain, and having a basic nitrogen atom in at least one of the main chain and the side chain is preferable, and the structural unit has a functional group having a pKa of 14 or less In the partial structure X, the side chain includes a side chain Y with 40 to 10,000 atoms. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the oligoimine-based dispersant, reference can be made to the descriptions of paragraph numbers 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated in the present specification. As the oligoimine-based dispersing agent, resins having the following structures, and resins described in paragraphs 0168 to 0174 of JP 2012-255128 A can be used. [Chemical 36]

The dispersing agent can also be obtained as a commercial item, and Disperbyk-111, 161 (manufactured by BYK Chemie GmbH) etc. are mentioned as such a specific example. In addition, the pigment dispersants described in paragraphs 0041 to 0130 of Japanese Patent Laid-Open No. 2014-130338 can also be used, the contents of which are incorporated in this specification. Moreover, resin etc. which have the said acid group can also be used as a dispersing agent.

When the composition for pixel formation contains a resin, the content of the resin is preferably 1 to 60 mass % with respect to the total solid content of the composition for pixel formation. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 50 mass % or less, more preferably 40 mass % or less, and even more preferably 30 mass % or less. When the composition for pixel formation contains a resin having an acid group, the content of the resin having an acid group is preferably 1 to 60 mass % with respect to the total solid content of the composition for pixel formation. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 50 mass % or less, more preferably 40 mass % or less, and even more preferably 30 mass % or less.

When the composition for pixel formation contains a polymerizable compound and a resin, the mass ratio of the polymerizable compound and the resin is preferably polymerizable compound/resin=0.3 to 1.5. The lower limit of the mass ratio is preferably 0.4 or more, and more preferably 0.5 or more. The upper limit of the mass ratio is preferably 1.4 or less, and more preferably 1.3 or less. When the above-mentioned mass ratio is within the above-mentioned range, a pixel with more excellent rectangularity can be formed. Moreover, it is preferable that the mass ratio of the polymerizable compound and the resin having an acid group is the polymerizable compound/resin having an acid group=0.4 to 1.4. The lower limit of the mass ratio is preferably 0.5 or more, and more preferably 0.6 or more. The upper limit of the mass ratio is preferably 1.3 or less, and more preferably 1.2 or less. When the above-mentioned mass ratio is within the above-mentioned range, a pixel with more excellent rectangularity can be formed.

<<Pigment Derivatives>> The composition for forming a pixel may further contain a pigment derivative. Examples of the pigment derivatives include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group, a group having a salt structure, or a phthalimide methyl group. As the pigment derivative, a compound represented by the formula (B1) is preferable.

式（B1）中，P表示色素結構，L表示單鍵或連接基團，X表示酸基、鹼性基、具有鹽結構之基團或酞醯亞胺甲基，m表示1以上的整數，n表示1以上的整數，在m為2以上之情形下，複數個L及X可以彼此不同，在n為2以上之情形下，複數個X可以彼此不同。[Chemical 37]

In formula (B1), P represents a pigment structure, L represents a single bond or a linking group, X represents an acid group, a basic group, a group having a salt structure or a phthalimidomethyl group, and m represents an integer of 1 or more, n represents an integer of 1 or more, and when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of Xs may be different from each other.

The dye structure represented by P is selected from the group consisting of pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, dianthraquinone dye structure, benzisoindole dye structure, Thiazine indigo pigment structure, azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, two 㗁𠯤 pigment structure, perylene pigment structure, perylene pigment structure, benzimidazolone pigment structure , at least one of benzothiazole pigment structure, benzimidazole pigment structure and benzoxazole pigment structure is preferably selected from pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure and At least one of the benzimidazolone pigment structures is more preferable, and the pyrrolopyrrole pigment structure is particularly preferable.

The linking group represented by L includes a hydrocarbon group, a heterocyclic group, -NR-, -SO ₂ -, -S-, -O-, -CO-, or a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.

As an acid group represented by X, a carboxyl group, a sulfonic acid group, a carboxylic acid amido group, a sulfonic acid amido group, an imino acid group, etc. are mentioned. As the carboxyamide group, a group ^{represented by -NHCOR X1} is preferable. As the sulfonamido group, a group represented by -NHSO ₂ R ^X2 is preferable. As the imidic acid group, a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ NHCOR ^X6 is preferable. R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group represented by R ^X1 to R ^{X6 may further have a substituent.} As another substituent, the substituent T described in the above formula (PP) can be mentioned, a halogen atom is preferable, and a fluorine atom is more preferable. An amino group is mentioned as a basic group represented by X. As a salt structure represented by X, the salt of the above-mentioned acid group or basic group is mentioned.

As a pigment derivative, the compound of the following structure is mentioned. In addition, Japanese Patent Laid-Open No. 56-118462, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. 1-217077, Japanese Patent Laid-Open No. 3-9961, and Japanese Patent Laid-Open No. Hei 3-26767 can also be used. Japanese Patent Application Laid-Open No. 3-153780, Japanese Patent Application Laid-Open No. 3-45662, Japanese Patent Application Laid-Open No. 4-285669, Japanese Patent Application Laid-Open No. 6-145546, Japanese Patent Application Laid-Open No. 6-212088, Japanese Patent Application Laid-Open No. 6-212088 6-240158 A, JP 10-30063 A, JP 10-195326 A, Paragraph Nos. 0086 to 0098 of International Publication No. WO2011/024896, Paragraph Nos. 0063 to International Publication No. WO2012/102399 0094, the compound described in Paragraph No. 0082 of International Publication No. WO2017/038252, etc., the content of which is incorporated in the present specification. In the following structural formula, Et is ethyl. [Chemical 38]

When the composition for forming a pixel contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be improved and the aggregation of the pigment can be efficiently suppressed. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above-mentioned range.

<<solvent>> The composition for pixel formation can contain a solvent. As a solvent, an organic solvent is mentioned. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of the organic solvent include esters, ethers, ketones, aromatic hydrocarbons, and the like. For details of these, reference can be made to Paragraph No. 0223 of International Publication WO2015/166779, which is incorporated in the present specification. In addition, an ester-based solvent substituted with a cyclic alkyl group and a ketone-based solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Glycol, Butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol Alcohol acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, etc. In the present invention, one type of organic solvent may be used alone, or two or more types may be used in combination. Moreover, from the viewpoint of improving solubility, 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide are also preferred. However, in some cases, it is preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as a solvent (for example, 50% by mass relative to the total amount of the organic solvent) in some cases. ppm (parts per million: parts per million) or less, can also be set to 10 mass ppm or less, and can also be set to 1 mass ppm or less).

In the present invention, it is preferable to use a solvent with a small metal content, and the metal content of the solvent is preferably 10 parts per billion (parts per billion) or less. As needed, a quality ppt (parts per trillion: parts per trillion) grade solvent, such as a high-purity solvent provided by TOYO Gosei Co., Ltd., for example (Chemical Industry Daily, November 13, 2015), can be used.

As a method for removing impurities such as metals from the solvent, for example, distillation (molecular distillation, thin-film distillation, etc.) or filtration using a filter can be cited. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

Solvents may contain isomers (compounds with the same number of atoms but different structures). In addition, only one type of isomers may be contained, or a plurality of types may be contained.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol/L or less, and more preferably does not substantially contain a peroxide.

The content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass relative to the total amount of the composition for forming a pixel. Moreover, it may be preferable that the composition for pixel formation does not contain aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent from the viewpoint of the environment and the like.

<<Polymerization inhibitor>> The composition for pixel formation can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, tert-butylcatechol, benzoquinone, 4,4'- Sulfur bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine Salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. It is preferable that content of a polymerization inhibitor is 0.001-5 mass % with respect to the total solid content of the composition for pixel formation.

<<Silane coupling agent>> The composition for forming a pixel may contain a silane coupling agent. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than that. In addition, the hydrolyzable group refers to a substituent directly linked to a silicon atom and capable of generating a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, etc. are mentioned, for example, An alkoxy group is preferable. That is, it is preferable that the silane coupling agent is a compound having an alkoxy group. Moreover, as a functional group other than a hydrolyzable group, vinyl group, styryl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, urea group, A thioether group, an isocyanate group, a phenyl group, etc., a (meth)acryloyl group and an epoxy group are preferable. The silane coupling agent includes the compounds described in paragraphs 0018 to 0036 of JP 2009-288703 A, the compounds described in paragraphs 0056 to 0066 of JP 2009-242604 A, and the like. The contents are incorporated into this manual.

The content of the silane coupling agent is preferably 0.01 to 15.0 mass %, more preferably 0.05 to 10.0 mass %, with respect to the total solid content of the pixel forming composition. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<surfactant>> The composition for forming a pixel may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Regarding the surfactant, reference can be made to Paragraph Nos. 0238 to 0245 of International Publication WO2015/166779, the contents of which are incorporated in the present specification.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By including the fluorine-based surfactant in the composition for forming a pixel, the liquid properties (especially, the fluidity) are further improved, and the liquid saving property can be further improved. In addition, a film with a small thickness variation can also be formed.

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

Specific examples of the fluorine-based surfactant include those described in paragraphs 0060 to 0064 of JP 2014-41318 A (corresponding to paragraphs 0060 to 0064 of WO 2014/17669 A) and the like and the surfactants described in paragraph numbers 0117 to 0132 of JP-A No. 2011-132503, and these contents are incorporated in this specification. Commercially available fluorine-based surfactants include, for example, Magaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (the above, DIC CORPORATION), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA SOLUTIONS INC.), etc.

In addition, as the fluorine-based surfactant, an acrylic-based compound can also be preferably used. In the molecular structure of the acrylic-based compound having a functional group containing a fluorine atom, when heat is applied, a part of the functional group containing a fluorine atom is cleaved. The fluorine atom volatilizes. Examples of such fluorine-based surfactants include Magaface DS series manufactured by DIC CORPORATION (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Magaface DS-21.

In addition, as the fluorine-based surfactant, it is also preferable to use a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a polymer of a hydrophilic vinyl ether compound. Regarding such a fluorine-based surfactant, the description of JP-A No. 2016-216602 can be referred to, and the contents are incorporated in the present specification.

上述化合物的重量平均分子量較佳為3,000～50,000，例如為14,000。上述化合物中，表示重複單元的比例之%為莫耳%。As the fluorine-based surfactant, a block polymer can also be used. For example, the compound described in Japanese Patent Laid-Open No. 2011-89090 can be mentioned. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which includes: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; and a repeating unit derived from a (meth)acrylate compound having two or more fluorine atoms. (Preferably 5 or more) repeating units of a (meth)acrylate compound of an alkeneoxy group (preferably an ethene group and a propoxy group). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention. [Chemical 39]

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, for example, 14,000. In the above-mentioned compounds, the % indicating the ratio of repeating units is mol%.

In addition, as the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Magaface RS-101, RS-102, RS-718K, manufactured by DIC CORPORATION, Inc. RS-72-K, etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A can also be used.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) base, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diethyl ether Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901 , 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112- W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

Examples of silicon-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co. , Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, made by Momentive Performance Materials Inc.), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Chemical Co., LTD.), BYK307, BYK323, BYK330 (above, manufactured by BYK-Chemie Corporation), and the like.

The content of the surfactant is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass, with respect to the total solid content of the composition for forming a pixel. Only one type of surfactant may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<Ultraviolet absorber>> The composition for forming a pixel can contain an ultraviolet absorber. As the ultraviolet absorber, conjugated diene compounds, aminobutadiene compounds, methyldibenzyl compounds, coumarin compounds, salicylic acid compounds, benzophenone compounds, and benzotriazole compounds can be used , acrylonitrile compounds, hydroxyphenyl tris 𠯤 compounds, etc. For details of these, reference can be made to the descriptions of paragraphs 0052 to 0072 of JP 2012-208374 A and paragraphs 0317 to 0334 of JP 2013-68814 A, which are incorporated in the present specification. As a commercial item of a conjugated diene compound, UV-503 (made by DAITO CHEMICAL CO., LTD.) etc. are mentioned, for example. In addition, as a benzotriazole compound, the MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. can be used. As the ultraviolet absorber, compounds represented by formula (UV-1) to formula (UV-3) are preferable, and compounds represented by formula (UV-1) or formula (UV-3) are more preferable. Compounds represented by UV-1) are further preferred. [Chemical 40]

In formula (UV-1), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0 to 4. In formula (UV-2), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or an alkyl group, and R ²⁰³ and R ²⁰⁴ each independently represent a substituent. In formula (UV-3), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or an alkyl group, and R ³⁰⁴ and R ³⁰⁵ each independently represent a substituent.

As a specific example of the compound represented by Formula (UV-1) - Formula (UV-3), the following compounds are mentioned. [Chemical 41]

The content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, with respect to the total solid content of the composition for forming a pixel. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above-mentioned range.

<<Antioxidant>> The composition for pixel formation can contain an antioxidant. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, as an antioxidant, a phosphorus-based antioxidant can also be preferably used. Examples of phosphorus-based antioxidants include tris[2-[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]bis Oxaphosphocycloheptan-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetratert-butyldibenzo[d,f][1,3, 2] Dioxaphosphocycloheptan-2-yl)oxy]ethyl]amine, phosphite ethylbis(2,4-di-tert-butyl-6-methylphenyl) and the like. Examples of commercially available antioxidants include ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO- 80. ADKSTAB AO-330 (above, made by ADEKA CORPORATION), etc.

The content of the antioxidant is preferably 0.01 to 20 mass %, more preferably 0.3 to 15 mass %, with respect to the total solid content of the composition for pixel formation. As for the antioxidant, only one type may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above-mentioned range.

<<Other Components>> As needed, the composition for pixel formation may contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliaries (for example, conductive particles, fillers, foaming agents, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately containing these components, properties such as film properties can be adjusted. For these components, for example, refer to the descriptions in paragraph No. 0183 of JP-A No. 2012-003225 (corresponding to paragraph No. 0237 in the specification of US Patent Application Laid-Open No. 2013/0034812 ), JP-A No. 2008-250074 The descriptions of paragraph numbers 0101 to 0104, and 0107 to 0109 of the gazette are incorporated into this specification.

For example, in the case of forming a film by coating, the viscosity (23° C.) of the composition for pixel formation is preferably 1 to 100 mPa·s. The lower limit is more preferably 2 mPa･s or more, and more preferably 3 mPa･s or more. The upper limit is preferably 50 mPa･s or less, more preferably 30 mPa･s or less, and particularly preferably 15 mPa･s or less.

<Storage container> It does not specifically limit as a storage container of the composition for pixel formation, A well-known storage container can be used. In addition, as the container, in order to suppress the contamination of impurities into the raw material or the composition, it is also preferable to use a multilayer bottle having the inner wall of the container composed of 6 kinds of 6-layer resin, or a bottle having 7-layer structure of 6 kinds of resin. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<The preparation method of the composition for pixel formation> The composition for pixel formation can be prepared by mixing the above-mentioned components. When preparing the composition for pixel formation, the composition for pixel formation may be prepared by dissolving or dispersing all components in a solvent at the same time, or two or more solutions obtained by appropriately blending each component may be prepared in advance as required. or dispersion liquid, and these are mixed at the time of use (at the time of coating) to prepare a composition for pixel formation.

Moreover, when the composition for pixel formation contains particles such as pigments, it is preferable to include a process for dispersing the particles. In the process of dispersing particles, compression, pressing, impact, shearing, cavitation, etc. are mentioned as mechanical force for dispersing the particles. Specific examples of these processes include bead milling, sand milling, roll milling, ball milling, paint stirrer, microjet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. In addition, in the grinding of particles in a sand mill (bead mill), it is preferable to treat with the following conditions: by using microbeads with a small diameter and increasing the filling rate of the microbeads, the grinding efficiency is improved. In addition, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, as for the process and dispersing machine for dispersing particles, "Dispersion Technology Encyclopedia, Issued by Information Agency Co., Ltd., July 15, 2005" or "Dispersion Technology Around Suspension (Solid/Liquid Dispersion System)" can be preferably used. The process and dispersing machine described in the "Comprehensive Document Collection on Industrial Applications, Published by the Publishing Department of the Management Development Center, October 10, 1978", Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893. In addition, in the process of dispersing the particles, it is possible to refine the particles in the salt milling step. Regarding the raw materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions of Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629 can be referred to.

When preparing the composition for pixel formation, it is preferable to filter the composition for pixel formation with a filter in order to remove foreign matter, reduce defects, and the like. As a filter, as long as it is a filter conventionally used for filtration applications, etc., it can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) are used. (Containing high-density, ultra-high molecular weight polyolefin resin) and other raw materials filters. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore size of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. When the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. Moreover, it is also preferable to use a fibrous filter material. As a fibrous filter material, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example. Specifically, ROKI TECHNO CO., LTD. SBP type series (SBP008 etc.), TPR type series (TPR002, TPR005 etc.), SHPX type series (SHPX003 etc.) filter element is mentioned.

When using filters, different filters can be combined (eg, 1st filter and 2nd filter, etc.). At this time, the filtration by each filter may be performed only once, or may be performed twice or more. In addition, filters having different pore sizes within the above range may be combined. The pore size here can refer to the filter manufacturer's nominal value. As commercially available filters, for example, it is possible to select from various filters provided by NIHON PALLLTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, LTD., Nihon Entegris K.K. (former Nippon Mykrolis Corporation), KITZ MICRO FILTER Corporation, and the like. The second filter can be formed from the same material or the like as the first filter. In addition, the filtration with the 1st filter is performed only with respect to a dispersion liquid, and after mixing other components, filtration with a 2nd filter may be performed. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are based on mass.

<Method for measuring the viscosity of the resist composition> 1.2 ml of the resist composition adjusted to a temperature of 25° C. was put into RE-85L (manufactured by Toki Sangyo Co., Ltd.), and a high-viscosity rotor was used. The viscosity of the resist composition was measured.

酸擴散控制劑（下述結構的化合物）：0.016質量份 [化43]

界面活性劑（Magaface R-41，DIC CORPORATION製）：0.045質量份 PGMEA：剩餘部分 丙二醇單甲醚：15.000質量份<Preparation of resist composition> (Resist composition 1-8) The following raw material was mixed, and the resist composition 1-8 was prepared. In addition, the solid content concentration of the resist composition was adjusted by the content of propylene glycol monomethyl ether acetate (PGMEA). The resin used for preparing the resist composition, the solid content concentration of the resist composition, and the viscosity of the resist composition at 25° C. are collectively described in the following table. Resins A to E described in the following table: 29.581 parts by mass Photoacid generator (compound of the following structure): 0.358 parts by mass

Acid diffusion control agent (compound of the following structure): 0.016 parts by mass [Chem. 43]

Surfactant (Magaface R-41, manufactured by DIC CORPORATION): 0.045 parts by mass PGMEA: remainder propylene glycol monomethyl ether: 15.000 parts by mass

[Table 1]

Resin A: Resin of the following structure. Values marked in repeating units are molar ratios. Mw=22,000, Onishi parameter=2.87) Resin B: Resin of the following structure. Values marked in repeating units are molar ratios. Mw=21,000, Onishi parameter=2.84) Resin C: Resin of the following structure. Values marked in repeating units are molar ratios. Mw=18,000, Onishi parameter=2.74) Resin D: Resin of the following structure. Values marked in repeating units are molar ratios. Mw=20,000, Onishi parameter=2.73) Resin E: Resin of the following structure. Values marked in repeating units are molar ratios. Mw=19,000, Onishi parameter=2.54) In addition, the composition ratio of resin (molar ratio of repeating unit) ^{was calculated by 1} H-NMR (nuclear magnetic resonance) or ¹³ C-NMR measurement. The weight average molecular weight (Mw: polystyrene conversion) of resin was calculated by GPC (solvent: THF) measurement. The Onishi parameter of the resin was calculated by the following formula. Onishi parameter = the sum of the atomic numbers of C, H and O / (the number of C atoms - the number of O atoms)

[Chemical 44]

<Preparation of the composition for color filters (green (Green) composition, red (Red) composition, blue (Blue) composition)> <<Green composition>> After stirring the following components, use a pore size of It filtered with a 0.45 μm nylon filter (manufactured by NIHON PALL LTD.) to prepare a green composition having a color material concentration of 49% by mass in the solid content. Green pigment dispersion liquid...81.3 g Polymerizable compound 1...3.89 g Resin 1...3.44 g Photopolymerization initiator 1...0.51 g Photopolymerization initiator 2...0.36 g Additive 1...0.38 g Interfacial activity Agent 1…0.01 g Polymerization Inhibitor 1…0.001 g Solvent 1…9.7 g

<<Red composition>> After stirring the following components, it was filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45 μm to prepare a red composition having a color material concentration of 50% by mass in the solid content . Red pigment dispersion liquid...59.5 g Polymerizable compound 2...1.15 g Resin 1...1.39 g Photopolymerization initiator 1...0.40 g Surfactant 2...0.04 g Polymerization inhibitor 1...0.0004 g Solvent 1 ...8.1 g Solvent 2...29.4 g

<<Blue composition>> After stirring the following components, it was filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45 μm to prepare blue with a color material concentration of 36% by mass in the solid content composition. Blue pigment dispersion liquid... 29.6 g Polymerizable compound 1... 4.74 g Resin 1... 3.36 g Photopolymerization initiator 1... 1.13 g Surfactant 2... 0.03 g Polymerization inhibitor 1... 0.001 g Solvent 1…26.7 g Solvent 2…34.4 g

分散劑1：下述結構的樹脂（Mw=26000，在主鏈上標記之數值為莫耳比，在側鏈上標記之數值為重複單元的數量。） [化46]

(Green Pigment Dispersion) 9.2 parts by mass of CI Pigment Green 58, 2.3 parts by mass of CI Pigment Yellow 185, 1.7 parts by mass of Pigment Derivative 1, 4.0 parts by mass of Dispersant 1, and 82.8 parts by mass of propylene glycol monomethyl ether were mixed To the mixed solution of acetate (PGMEA), 230 parts by mass of zirconia microbeads with a diameter of 0.3 mm were added, and a dispersion treatment was performed for 3 hours using a paint stirrer, and the microbeads were separated by filtration to prepare a green pigment dispersion. . About this green pigment dispersion liquid, solid content content was 17.2 mass %, and a pigment content was 11.5 mass %. Pigment Derivative 1: A compound of the following structure. In the following structural formula, Et is an ethyl group. [Chemical 45]

Dispersant 1: Resin of the following structure (Mw=26000, the value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units.) [Chem. 46]

(Red Pigment Dispersion Liquid) 8.76 parts by mass of CI Pigment Red 254, 3.24 parts by mass of CI Pigment Yellow 139, 9.0 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie GmbH), and 79.0 parts by mass of PGMEA were mixed. To the mixed liquid, 230 parts by mass of zirconia microbeads having a diameter of 0.3 mm was added, and dispersion treatment was performed for 3 hours using a paint stirrer, and the microbeads were separated by filtration to prepare a red pigment dispersion liquid. About this red pigment dispersion liquid, the solid content content was 21.0 mass %, and the pigment content was 12.0 mass %.

(Blue Pigment Dispersion) 10.1 parts by mass of CI Pigment Blue 15:6, 2.7 parts by mass of CI Pigment Violet 23, 5.0 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie GmbH) and 82.2 parts by mass were mixed 230 parts by mass of zirconia microbeads with a diameter of 0.3 mm were added to the mixed solution of PGMEA of 2000 , and a dispersion treatment was performed for 3 hours using a paint stirrer, and the beads were separated by filtration to prepare a blue pigment dispersion. About this blue pigment dispersion liquid, solid content content was 17.8 mass %, and a pigment content was 12.8 mass %.

(Polymerizable compound) Polymerizable compound 1: NK ESTER A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound 2: NK ESTER A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd. )

(Resin) Resin 1: ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)

(Photopolymerization initiator) Photopolymerization initiator 1: IRGACURE OXE01 (manufactured by BASF) Photopolymerization initiator 2: IRGACURE OXE03 (manufactured by BASF)

(Surfactant) Surfactant 1: KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.) Surfactant 2: The following mixture (Mw=14000). In the following formula, the % representing the ratio of the repeating unit is mol%. [Chemical 47]

Polymerization inhibitor 1: 4-Methoxyphenol Additive 1: EHPE3150 (manufactured by Daicel Corporation) Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA) Solvent 2: Butyl acetate

聚合性化合物（NK ESTER A-TMMT，Shin-Nakamura Chemical Co.,Ltd.製）……3.2 g 聚合性化合物（KAYARAD DPHA，Nippon Kayaku Co.,Ltd.製）……3.2 g 光聚合起始劑（IRGACURE OXE01，BASF製）……1.0 g 紫外線吸收劑（下述結構的化合物）……1.6 g [化49]

･界面活性劑（上述界面活性劑2）……0.025 g ･聚合抑制劑（4-甲氧基苯酚）……0.003 g ･抗氧化劑（ADKSTABAO-80，ADEKA CORPORATION製）……0.2 g ･PGMEA……41.5 g<Preparation of composition for infrared cut filter> After stirring the following components, it was filtered with a nylon filter (manufactured by NIHON PALL LTD.) having a pore diameter of 0.45 μm to prepare a composition for infrared cut filter. Infrared absorption pigment dispersion liquid...43.8 g Resin of the following structure (The value marked on the main chain is molar ratio. Mw=10,000, acid value=70 mgKOH/g)...5.5 g [Chem. 48]

Polymerizable compound (NK ESTER A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) ...... 3.2 g Polymerizable compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) ...... 3.2 g Photopolymerization initiator (IRGACURE OXE01, manufactured by BASF) ...... 1.0 g UV absorber (compound of the following structure) ...... 1.6 g [Chem. 49]

･Surfactant (Surfactant 2 above)...0.025 g ･Polymerization inhibitor (4-methoxyphenol)...0.003 g ･Antioxidant (ADKSTABAO-80, manufactured by ADEKA CORPORATION)...0.2 g ･PGMEA... …41.5 g

顏料衍生物2：下述結構的化合物。下述結構式中，Ph為苯基。 [化51]

分散劑2：下述結構的樹脂（在主鏈上標記之數值為莫耳比，在側鏈上標記之數值為重複單元的數量。Mw=21000） [化52]

(Preparation of Infrared Absorbing Pigment Dispersion Liquid) In a mixed liquid of 2.5 parts by mass of infrared absorbing dye 1, 0.5 parts by mass of pigment derivative 2, 1.8 parts by mass of dispersant 2, and 39.0 parts by mass of PGMEA, a diameter of 230 parts by mass of 0.3 mm zirconia microbeads were dispersed with a paint stirrer for 3 hours, and the beads were separated by filtration to prepare an infrared-absorbing pigment dispersion liquid. Infrared absorbing dye 1: a compound of the following structure. In the following structural formula, Ph is a phenyl group. [Chemical 50]

Pigment Derivative 2: A compound of the following structure. In the following structural formula, Ph is a phenyl group. [Chemical 51]

Dispersant 2: Resin of the following structure (The value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. Mw=21000) [Chem. 52]

紫外線吸收劑（UV-503，DAITO CHEMICAL CO.,LTD製）……0.4 g 界面活性劑（上述界面活性劑2）……0.008 g 聚合抑制劑（4-甲氧基苯酚）……0.002 g PGMEA……29.2 g<Preparation of Composition for Infrared Transmitting Filter> After stirring the following components, it was filtered with a nylon filter (manufactured by NIHON PALL LTD.) having a pore diameter of 0.45 μm to prepare a composition for an infrared transmissive filter. Pigment dispersion Y-1...23.8 g Pigment dispersion V-1...41.4 g Polymerizable compound (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.)...0.9 g Polymerizable compound (ARONIX TO-2349 , manufactured by TOAGOSEI CO., LTD.) ...... 2.1 g Photopolymerization initiator (IRGACURE OXE02, manufactured by BASF) ...... 0.74 g Resin of the following structure (The value marked on the main chain is molar ratio. Mw=10,000 , acid value = 70 mgKOH/g) ...... 1.4 g [Chem. 53]

Ultraviolet absorber (UV-503, manufactured by DAITO CHEMICAL CO., LTD)...0.4 g Surfactant (Surface Active Agent 2 above)...0.008 g Polymerization inhibitor (4-methoxyphenol)...0.002 g PGMEA ...29.2 g

(Preparation of Pigment Dispersion Liquid Y-1) To a mixed liquid of 2.5 parts by mass of CI Pigment Yellow 139, 1.6 parts by mass of Pigment Derivative 1, 4.4 parts by mass of Dispersant 1, and 83.0 parts by mass of PGMEA, added 230 parts by mass of zirconia microbeads having a diameter of 0.3 mm were dispersed for 3 hours using a paint stirrer, and the microbeads were separated by filtration to prepare a pigment dispersion liquid Y-1.

分散劑4：Disperbyk-111，BYK Chemie GmbH製(Preparation of Pigment Dispersion Liquid V-1) In a mixed liquid of 14.2 parts by mass of CI Pigment Violet 23, 2.0 parts by mass of Dispersant 3, 3.8 parts by mass of Dispersant 4, and 83.0 parts by mass of PGMEA, the addition diameter of 230 parts by mass of 0.3 mm zirconia microbeads were dispersed with a paint stirrer for 3 hours, and the microbeads were separated by filtration to produce Pigment Dispersion V-1. Dispersant 3: Resin of the following structure (The values marked on the main chain are molar ratios. Mw=10,000, acid value=70 mgKOH/g) [Chemical 54]

Dispersant 4: Disperbyk-111, manufactured by BYK Chemie GmbH

<Manufacture of device> Manufacturing Example 1 (Example 1 to Example 8, Comparative Example 2) A p-type silicon substrate was used as a support. Boron was introduced into the p-type silicon substrate by ion implantation, and heat treatment was performed, thereby forming an n-type well ^{with a surface concentration of about 2×10 16} cm ^{−3 .} On the surface of the p-type silicon substrate on the side where the n-type wells are formed, the resist composition described in the following table is applied and patterned, whereby a film having the film thickness described in the following table is formed. resist pattern. Moreover, a resist pattern was formed so that one side of the photodiode part formed by ion implantation might become 1.75 micrometers. Next, using the resist pattern as a mask, by ion implantation, phosphorus was implanted into the support under the conditions of ^{doping amount of 2×10 13} cm ^{-2 and energy of 80 KeV to form p} the photodiode portion of the layer. _{Next, after forming a SiO 2} film as a gate oxide film on the support and the resist pattern, the resist pattern was removed by lift-off. By this operation, the gate oxide film is formed only on the photodiode portion. Next, by ion implantation, boron was implanted into the support obtained by stripping the resist pattern under the conditions of ^{doping amount of 2×10 12} cm ^{-2 and energy of 35 KeV, forming a p-type first} 1 channel doped region. Next, a resist pattern covering the photodiode portion and the first channel doping region is formed on the support, and the resist pattern is used as a mask, and the doping amount is 6× by an ion implantation method. Phosphorus was implanted under the conditions of 10 ¹² cm ^-2 and energy of 50 KeV to form the n-type second channel doped region. Next, after peeling off the resist pattern, a polysilicon control electrode doped with phosphorus is formed on the support and patterning is performed to form the control electrode. Next, according to a known method, a MOS (metal-oxide-semiconductor: metal-oxide-semiconductor) transistor is formed. Next, according to a known method, a first interlayer insulating film, a contact point, a first metal wiring, a second interlayer insulating film, a through hole connecting the first metal wiring and the second metal wiring, a second metal wiring and passivation are sequentially formed. membrane. In this way, the light-receiving element was manufactured.

The above-mentioned composition for an infrared cut filter was applied to the light-receiving element produced in the above-mentioned steps by spin coating so that the film thickness after film formation was 1.0 μm. Next, it heated at 100 degreeC for 2 minutes using a hotplate. Next, using a KrF exposure machine (manufactured by Canon Inc., FPA-6000ES6a), a mask having a Bayer pattern of 1 μm square was interposed, and the exposure was carried out by KrF line (wavelength: 248 nm) at an exposure amount of ^{500 mJ/cm 2 .} exposure. Next, spin-over immersion development was performed at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with a rotary shower, and also rinsed with pure water. Next, by heating at 200° C. for 5 minutes using a hot plate, a 1 μm square Bayer pattern (pixels of the infrared cut layer) was formed and an infrared cut filter was formed. Next, the green composition was applied on the pixels of the infrared cut layer by spin coating so that the film thickness after film formation was 0.5 μm. Next, it heated at 100 degreeC for 2 minutes using a hotplate. Next, using a KrF exposure machine (manufactured by Canon Inc., FPA-6000ES6a), through a mask having a Bayer pattern with a pixel size of 1 μm square, exposure was performed with KrF line at an exposure amount of ^{200 mJ/cm 2 .} . Next, spin-over immersion development was performed at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with a rotary shower, and also rinsed with pure water. Next, green pixels were formed on the pixels of the infrared cut layer by heating at 200° C. for 5 minutes using a hot plate. The red composition and the blue composition were coated in the same manner as above so that the film thickness was 0.5 μm, using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), with a pixel The mask of Bayer pattern with a size of 1 μm square is ^{exposed and developed by i-ray at an exposure amount of 200 mJ/cm 2} , and patterning is performed in sequence, and red pixels and blue pixels are respectively formed on the pixels of the infrared cut-off layer. color pixels to form a color filter. Next, the composition for forming an infrared transmissive filter layer was applied on the light-receiving element on which the color filter was formed by spin coating so that the film thickness after film formation was 0.5 μm. Next, it heated at 100 degreeC for 2 minutes using a hotplate. Next, using a KrF exposure machine (manufactured by Canon Inc., FPA-6000ES6a), through a mask having a Bayer pattern with a pixel size of 1 μm square, ^{the exposure amount was 300 mJ/cm 2} with KrF line. exposure. Next, spin-over immersion development was performed at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with a rotary shower, and also rinsed with pure water. Next, by heating at 200° C. for 5 minutes using a hot plate, pixels of the infrared transmissive layer were formed in the missing portions of the pixels of the infrared cut layer, thereby forming an infrared transmissive filter. The device was fabricated by embedding it in a solid-state imaging element according to a known method.

(Comparative Example 1, Comparative Example 3) Production Example 2 When forming each pixel, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used as an exposure machine, and the pixel of the infrared cut layer was 1000. The exposure amount of mJ/cm ² was exposed with i-rays, and the green pixels, red pixels, and blue pixels were exposed to i-rays at the exposure amount of ^{200 mJ/cm 2 respectively.} The devices of Comparative Example 1 and Comparative Example 3 were produced by forming each pixel by the same method as in Production Example 1, except that the i-ray was exposed at an exposure amount of 300 mJ/cm ^{2 .}

<Evaluation of S/N ratio with respect to infrared rays> The obtained solid-state imaging element was irradiated with infrared rays, and the S/N ratio with respect to infrared rays was evaluated by comparing the signal intensity ratios when irradiated and not irradiated with infrared rays. In addition, as an infrared light source, an infrared power LED (850 nm) OSI3XNE3E1E (manufactured by OPTOSUPPLY) was used.

<Evaluation with respect to visible light noise (SNR10)> Regarding the 24 colors of the Macbert diagram, the illumination light source was determined, and the spectral reflectance in the wavelength range of 400 to 700 nm was obtained. Next, the infrared cut filter characteristics of the solid-state imaging element and the spectral sensitivity of the solid-state imaging element are determined, and the exposure amounts of red, green, and blue received by the solid-state imaging element are calculated. Next, the charge amount of each color of red, green, and blue is calculated from the exposure amount. Then, the output signals r, g, and b and noise (shot noise, dark noise, and stereotype noise) of each color of red, green, and blue are calculated from the charge amounts. The luminance signal noise (S/N) was calculated from these noises, the illuminance value (called SNR10) at which the S/N was 10 was calculated, and the noise with respect to visible light was evaluated according to the following criteria. It means that the smaller the value of SNR10, the lower the noise. The calculation procedure of the SNR10 is based on the method described in paragraphs 0405 to 0426 of Japanese Patent Laid-Open No. 2013-15817. 5: SNR10 is less than 1 lux 4: SNR10 is more than 1 lux and less than 3 lux 3: SNR10 is more than 3 lux and less than 10 lux 2: SNR10 is more than 10 lux and less than 30 lux 1: SNR10 is more than 30 lux and less than 100 lux 0: SNR10 is 100 lux or more

[Table 2]

As shown in the above-mentioned table, the S/N ratio with respect to infrared rays was high in the apparatus of the Example. Also, significant optimization was observed in noise relative to visible light.

In each of the examples, even when a light-receiving element is manufactured using an InGaAs substrate instead of a silicon substrate, the same excellent effects as in each of the examples can be obtained. In each example, even if the photopolymerization initiator in the composition for color filters was changed to the same amount of IRGACURE OXE02 (manufactured by BASF), the same effect was obtained.

1‧‧‧Support body 2‧‧‧Pattern of resist film (resist pattern) 3‧‧‧Photodiode part 110‧‧‧Light receiving element 111‧‧‧Infrared cut filter 112‧‧‧Color filter Optical sheet 114‧‧‧Infrared transmission filter 115‧‧‧Micro lens 116‧‧‧Planarization layer

FIG. 1 is an explanatory diagram of a manufacturing method of a light-receiving element, and is a diagram showing formation of a resist pattern. FIG. 2 is an explanatory diagram of a method of manufacturing a light-receiving element, and is a diagram showing ion implantation. Fig. 3 is a diagram showing an embodiment of the apparatus of the present invention.

1‧‧‧Support

2‧‧‧Pattern of resist film (resist pattern)

Claims (16)

A method for manufacturing a device, comprising: using a resist composition to form a pattern of a resist film having a thickness of 5 μm or more on a support, then using the pattern of the resist film as a mask to apply the pattern to the support A step of manufacturing a light-receiving element by performing ion implantation; a step of forming a layer of a pixel-forming composition of an optical filter on at least a part of the region of the light-receiving element where the ion implantation has been performed; A step of irradiating a layer of the composition with light having a wavelength of 300 nm or less and exposing in a pattern; and a step of developing the exposed layer of the composition for forming a pixel to form a pixel, and the resist is composed of The solid content concentration of the material is 31% by mass or more. The method for manufacturing a device according to claim 1, wherein the step of exposing the layer of the composition for forming a pixel is irradiated with a KrF line and exposed in a pattern. The method for manufacturing a device according to claim 1 or claim 2, wherein the composition for pixel formation is selected from the group consisting of a composition for coloring pixel formation and a composition for pixel formation of an infrared-transmitting layer at least one. The method for manufacturing a device according to the claim 1 or 2 of the claimed scope, wherein the composition for forming a pixel comprises a polymerizable compound and a photopolymerization initiator, and the photopolymerization initiator comprises an alkyl phenone selected from the group consisting of Compounds, Acylphosphine Compounds, Benzophenone Compounds, Thioxanthone Compounds, Tris

At least one of a compound and an oxime compound. The method for manufacturing a device as described in claim 1 or claim 2, wherein the composition for forming a pixel includes a color material. The method for producing a device according to claim 5, wherein the color material is contained in an amount of 40% by mass or more with respect to the total solid content of the composition for forming a pixel. The manufacturing method of the device according to the claim 1 or 2 of the claimed scope, wherein the size of the pixel is 2.0 μm or less. The method for manufacturing the device according to the claim 1 or 2 of the claimed scope, wherein the film thickness of the pixel is 1.0 μm or less. The method for manufacturing a device according to claim 1 or claim 2, wherein the resist film has a thickness of 7 μm or more. The manufacturing method of the device as described in item 1 or item 2 of the scope of the application, wherein the viscosity of the resist composition at 25°C is 30~1000mPa. s. The method for manufacturing a device according to claim 1 or claim 2, wherein the resist composition contains a resin, and the content of the resin in the solid content of the resist composition is 95.0 to 99.9 mass %. The method for manufacturing a device according to claim 11, wherein the Onishi parameter of the resin is 3.0 or less. The method for manufacturing a device according to claim 11, wherein the Onishi parameter of the resin is 2.8 or less. The method for manufacturing a device according to the first or second claim of the claimed scope, wherein the resist composition is a positive-type photosensitive composition. The method for manufacturing a device as described in item 1 or 2 of the claimed scope, wherein the resist composition contains a resin having a repeating unit and a photoacid generator, and the repeating unit is decomposed and generated by the action of an acid polar groups. The method for manufacturing a device according to claim 1 or claim 2, wherein the composition for forming a pixel is a composition for forming a pixel of an infrared-transmitting layer.

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