KR102323060B1 - Device manufacturing method - Google Patents

Abstract

A method of manufacturing a device capable of detecting light with reduced noise while increasing sensitivity to target light is provided. The device manufacturing method comprises the steps of forming a resist film pattern with a thickness of 5 µm or more on a support body using a resist composition, then performing ion implantation into the support body using the resist film pattern as a mask to manufacture a light receiving element; A step of forming a layer of a composition for forming a pixel of an optical filter in at least a part of the region on which ion implantation of the device has been performed, a step of irradiating the layer of the composition for forming a pixel with light having a wavelength of 300 nm or less and exposing it in a pattern; and developing the layer of the composition for forming a pixel after exposure to form a pixel.

Description

Device manufacturing method

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

Solid-state imaging elements, such as CCD (charge coupling element) and CMOS (complementary metal oxide film semiconductor), are used for a video camera, a digital still camera, and a camera function-equipped mobile phone. In these solid-state imaging device manufacturing processes, a resist pattern is formed on a support body, and ion implantation is performed with respect to a support body using this resist pattern as a mask, and manufacturing a light receiving element is performed.

Moreover, optical filters, such as a color filter and an infrared transmission filter, are used for a solid-state image sensor. These optical filters are formed using various compositions for optical filter formation.

For example, in patent document 1, the invention regarding the coloring photosensitive resin composition for color filter manufacture of the solid-state image sensor using the ultra-short wavelength exposure machine of 300 nm or less is described.

Patent Document 1: Japanese Patent Publication No. 2012-532334

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

On the other hand, conventionally, in the manufacture of a light-receiving element, after forming a pattern of a resist film having a thickness of 4 µm or less on a support, ion implantation is performed into the support using the pattern of the resist film as a mask. However, according to the study of the present inventor, it was found that the device using the light-receiving element manufactured in this way tends to have large noise.

Further, according to the invention described in Patent Document 1, by using a photoinitiator containing a compound that reacts with light of 300 nm or less as a photoinitiator, curing to an ultrashort wavelength of 300 nm or less is described, but noise is reduced There is no description or suggestion about what to do.

Accordingly, it is an object of the present invention to provide a method of manufacturing a device capable of detecting light with reduced noise while increasing the sensitivity to the target light.

According to examination of this inventor, it discovered that the said objective can be achieved by setting it as the following structure, and came to complete this invention. Accordingly, the present invention provides the following.

<1> a step of forming a resist film pattern with a thickness of 5 μm or more on a support body using a resist composition, and then performing ion implantation into the support body using the resist film pattern as a mask to manufacture a light receiving element;

A step of forming a layer of a composition for forming pixels of an optical filter on at least a part of a region in which the light-receiving element has been ion-implanted;

A step of irradiating a layer of the composition for forming a pixel with light having a wavelength of 300 nm or less and exposing it in a pattern;

A method for manufacturing a device, comprising the step of developing a layer of the composition for forming a pixel after exposure to form a pixel.

<2> The manufacturing method of the device as described in <1> in which the process of exposing exposes in pattern shape by irradiating KrF line|wire with respect to the layer of the composition for pixel formation.

<3> The manufacturing method of the device as described in <1> or <2> whose composition for pixel formation is at least 1 sort(s) chosen from the composition for color pixel formation, and the composition for pixel formation of an infrared ray transmissive layer.

<4> The composition for pixel formation includes a polymerizable compound and a photoinitiator, and the photoinitiator is selected from an alkylphenone compound, an acylphosphine compound, a benzophenone compound, a thioxanthone compound, a triazine compound, and an oxime compound The manufacturing method of the device in any one of <1>-<3> containing the at least 1 sort(s) of compound used.

<5> The manufacturing method of the device in any one of <1>-<4> in which the composition for pixel formation contains a color material.

<6> The manufacturing method of the device as described in <5> which contains 40 mass % or more of color materials with respect to the total solid of the composition for pixel formation.

<7> The manufacturing method of the device in any one of <1>-<6> whose size of a pixel is 2.0 micrometers or less.

<8> The manufacturing method of the device in any one of <1>-<7> whose film thickness of a pixel is 1.0 micrometer or less.

<9> The method for manufacturing the device according to any one of <1> to <8>, wherein the resist composition has a solid content concentration of 25% by mass or more.

<10> The method for manufacturing the device according to any one of <1> to <9>, wherein the resist composition has a viscosity at 25°C of 30 to 1000 mPa·s.

<11> The method for manufacturing the 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 manufacturing the device according to <11>, wherein the resin has an ounce parameter of 3.0 or less.

<13> The method for manufacturing the device according to <11>, wherein the resin has an ounce parameter of 2.8 or less.

<14> The method for manufacturing the device according to any one of <1> to <13>, wherein the resist composition is a positive photosensitive composition.

<15> The method for manufacturing the device according to any one of <1> to <10>, wherein the resist composition contains a resin having a repeating unit having a group that generates a polar group by being decomposed by the action of an acid, and a photoacid generator. .

<16> The device according to any one of <11> to <14>, wherein the resist composition further contains a photo-acid generator and is a resin having a repeating unit having a group in which the resin is decomposed by the action of an acid to generate a polar group. manufacturing method.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the device which can detect light with reduced noise while increasing the sensitivity with respect to target light can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the manufacturing method of a light receiving element, Comprising: It is a figure which shows resist pattern formation.
Fig. 2 is an explanatory view of a method for manufacturing a light-receiving element, showing ion implantation;
Fig. 3 is a diagram showing one embodiment of the device of the present invention.

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 that as a lower limit and an upper limit.

In the description of the group (atomic group) in the present specification, the description not describing substitution and unsubstitution includes a group having a substituent (atomic group) together with a group having no substituent (atomic group). For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams in exposure unless otherwise specified. Moreover, as light used for exposure, actinic rays or radiations, such as a bright-line spectrum of a mercury vapor lamp, and a deep ultraviolet-ray represented by an excimer laser, extreme ultraviolet (EUV light), X-ray, an electron beam, are mentioned.

In this specification, the (meth)allyl group represents both, or either of allyl and metharyl, "(meth)acrylate" represents both, or either of acrylate and methacrylate, "( "Meth)acryl" represents both or either of acryl and methacryl, and "(meth)acryloyl" represents both, or either of acryloyl and methacryloyl.

In this specification, a weight average molecular weight and a number average molecular weight are polystyrene conversion values measured by the GPC (gel permeation chromatography) method. For GPC, HLC-8120 (manufactured by Tosoh Corporation) was used, TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mmID (inner diameter) x 30.0 cm) was used as a column, and THF (tetrahydrofuran) was used as the eluent. ) can be followed.

In this specification, infrared rays mean light with a wavelength of 700-2500 nm.

In this specification, total solid means the total mass of the component except the solvent from all the components of a composition.

In the present specification, the term "process" is included in this term as long as the desired action of the process is achieved even if it is not clearly distinguished from other processes as well as independent processes.

<Device manufacturing method>

The manufacturing method of the device of the present invention comprises a step of forming a resist film pattern with a thickness of 5 μm or more on a support by using a resist composition, and then performing ion implantation into the support using the resist film pattern as a mask to manufacture a light-receiving element class,

A step of forming a layer of a composition for forming pixels of an optical filter on at least a part of a region in which the light-receiving element has been ion-implanted;

A step of irradiating a layer of the composition for forming a pixel with light having a wavelength of 300 nm or less and exposing it in a pattern;

It characterized by including the process of developing the layer of the composition for pixel formation after exposure to form a pixel.

In the manufacturing process of the light receiving element in the manufacturing method of the device of this invention, the pattern of the resist film of thickness 5 micrometers or more is formed on a support body, and ion implantation is performed with respect to the support body. It is thought that the resist film effectively shields the ions implanted during ion implantation by the resist film in the portion of the support body covered with the resist film, and can effectively suppress the implantation of ions into the portion where ion implantation is unnecessary. For this reason, it is considered that ions can be more selectively implanted into the portion exposed from the resist film of the support. It is assumed that it can be done

In the present invention, after the light-receiving element is formed in this way, a layer of the composition for forming a pixel of an optical filter is formed on at least a part of the region where the ion implantation of the light-receiving element has been performed, and then the composition for forming a pixel The layer 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 having good rectangular properties on the light receiving element. In particular, even if the size of the pixel is further miniaturized, a pixel having good rectangular properties can be formed. By forming a pixel in this way, it is estimated that it is based on the following as a reason that the rectangular property of the pixel obtained can be improved. That is, the layer of the composition for forming a pixel tends to have high absorption for light having a wavelength of 300 nm or less, and when the layer of the composition for forming a pixel is exposed to light with a wavelength of 300 nm or less, the layer of the composition for forming a pixel It is assumed that the surface layer of the resin tends to harden more easily than the inner layer. For this reason, 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 forming a pixel rapidly hardens, and when the surface layer cures quickly, scattering or bouncing back of the exposure light is It is suppressed, and as a result, rectangularity is favorable, and it is estimated that the pixel of a fine pattern size was able to be formed.

By forming the pixel as described above, since the rectangularity of the obtained pixel can be improved, stray light due to irregular reflection of the received light when the device is set can be suppressed, while increasing the sensitivity to the target light. , it is thought that the sensitivity to noise may be lowered.

For the above reasons, according to the present invention, it is possible to manufacture a device capable of detecting light with reduced noise.

Moreover, according to this invention, the pixel excellent in chemical-resistance and scratch resistance can also be formed. As the reason that such an effect is acquired, it is estimated that it is because the surface layer of the layer of the composition for pixel formation can be hardened more effectively by irradiating and exposing light with a wavelength of 300 nm or less with respect to the layer of the composition for pixel formation.

Moreover, according to this invention, generation|occurrence|production of the residue at the time of formation of a pixel can also be suppressed. As mentioned above, in the case of exposure, since the surface layer of the layer of the composition for pixel formation can be hardened rapidly, it is estimated that it is because it can suppress that scattering and bouncing back of exposure light can be carried out.

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

(Process of manufacturing the light receiving element)

[Pattern formation of resist film]

First, the process of manufacturing a light receiving element is demonstrated.

In the step of manufacturing the light-receiving element, first, a resist film pattern (hereinafter also referred to as a resist pattern) 2 having a thickness of 5 μm or more is formed on the 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 .

There is no limitation in particular as a kind of support body. For example, well-known semiconductor substrates, such as a silicon substrate and a ZnO substrate, can be used. Moreover, it is also preferable to use an InGaAs substrate as a support body. Since the InGaAs substrate has good sensitivity to light exceeding a wavelength of 1000 nm, it is possible to manufacture a light receiving element excellent in sensitivity to light exceeding a wavelength of 1000 nm by using the InGaAs substrate. These substrates may be doped with impurities such as boron, aluminum, phosphorus, and arsenic.

The thickness of the resist pattern 2 is 5 µm or more, preferably 6 µm or more, more preferably 7 µm or more, and still more preferably 8 µm or more. Although an upper limit does not have limitation in particular, It is preferable that it is 15 micrometers or less from a viewpoint of a pattern shape, and it is more preferable that it is 10 micrometers or less. 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 good pattern shape can be maintained, and as a result, ions can be efficiently implanted into the targeted range during ion implantation, and The S/N ratio can be further increased. Although the resist pattern 2 of the said thickness may be formed by coating the resist composition twice or more, it is preferable to form by one application|coating from a viewpoint of manufacturing cost. That is, it is preferable to form a resist film having a thickness of 5 µm or more by one application of the resist composition, and then pattern forming the resist film to form a resist pattern 2 having a thickness of 5 µm or more.

The resist composition may be either a positive photosensitive composition or a negative photosensitive composition, but is preferably a positive photosensitive composition from the viewpoint of easy formation of a fine pattern.

The solid content concentration of the resist composition is preferably 25 mass % or more, more preferably 30 mass % or more, still more preferably 31 mass % or more, and particularly preferably 32 mass % or more. When the solid content concentration of the resist composition is 25 mass % or more, it is easy to form a resist film having a thickness of 5 µm or more by one application. 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 good pattern shape. It is preferable that it is 45 mass % or less, and, as for the upper limit of the solid content concentration of a resist composition, it is more preferable that it is 42.5 mass % or less, It is more preferable that it is 40 mass % or less.

From a viewpoint of applicability|paintability, it is preferable that it is 30-1000 mPa*s, and, as for the viscosity in 25 degreeC of a resist composition, it is more preferable that it is 100-1000 mPa*s. It is preferable that it is 800 mPa*s or less, and, as for an upper limit, it is more preferable that it is 700 mPa*s or less, It is more preferable that it is 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 a 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% It is more preferable that

Moreover, it is preferable that it is 3.0 or less, and, as for the sludge parameter of resin contained in a resist composition, it is more preferable that it is 2.9 or less, It is more preferable that it is 2.8 or less, It is especially preferable that it is 2.7 or less. It is preferable that a lower limit is 2.5 or more, for example. If the resin contained in the resist composition has an onisy parameter of 3.0 or less, it is easy to manufacture a device with a high S/N ratio to the target light. The reason such an effect is obtained is presumed to be that a resist film which can more effectively shield the implanted ions at the time of ion implantation can be formed. In addition, an onish parameter is a value defined by the following formula.

Onishi parameter = sum of the number of atoms of C, H and O/(number of C atoms - number of O atoms)

In the present invention, the case where the resin contained in the resist composition has an ounce parameter of 3.0 or less means the following. That is, when there is only one type of resin contained in the resist composition, it means that the resin itself has a sludge parameter of 3.0 or less. Moreover, when two or more types of resin are contained in a resist composition, it means the value computed from the sum of the product of the content of each resin and the nish parameter. In addition, the value calculated by the above-mentioned calculation formula is used for the nish parameter of each resin.

When the resist composition used in the present invention contains two or more kinds of resins, a resin having an onisi parameter of 3.0 or less in the total amount of the resin (preferably a resin having an onisi parameter of 2.8 or less, more preferably a resin having It is preferable that content of 2.7 or less resin) is 50-100 mass %, It is more preferable that it is 60-100 mass %, It is more preferable that it is 75-100 mass %.

The details of the resist composition will be described later.

There is no limitation in particular as a coating method of a resist composition, A well-known coating method can be used. For example, the drip method (drop cast); slit coat method; spray method; roll coat method; spin coat method; flexible application method; slit and spin method; free wet method (for example, the method described in Unexamined-Japanese-Patent No. 2009-145395); Various printing methods, such as discharge system printing, such as inkjet (For example, an on-demand method, a piezo method, a thermal method), a nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and the metal mask printing method; The transfer method etc. using a metal mold|die etc. are mentioned, The spin coating method is preferable. Moreover, it is preferable to perform application|coating by the spin coating method at the rotation speed of 1000-2000 rpm. In addition, as described in JP-A-10-142603, JP-A-H11-302413, JP-A-2000-157922, the application by the spin coating method is applied to spread as a thin film; In order to dry by shaking off, you may raise the rotation speed during application|coating. In addition, the spin coat process described in the "State-of-the-Art Color Filter Process Technology and Chemicals" January 31, 2006, CMC shoot edition can also be suitably used.

After apply|coating a resist composition on a support body, you may dry-process. Drying conditions can be suitably adjusted according to the kind of resist composition. For example, 80-150 degreeC is preferable, as for a drying temperature, 80-140 degreeC is more preferable, 80-130 degreeC is still more preferable. 30-1000 second is preferable, as for heating time, 60-800 second is more preferable, and its 60-600 second is still more preferable.

Next, the pattern formation method is demonstrated. There is no limitation in particular as a pattern formation method, It is preferable to carry out using a conventionally well-known photolithography method. The pattern forming method using the photolithography method includes a step of exposing a resist film formed on a support to actinic ray or radiation (exposure step), and a step of developing the exposed resist film using a developer (development step). desirable.

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 ray or radiation through a predetermined mask. In addition, in electron beam irradiation, drawing (direct drawing) not through a mask is common. Although it does not specifically limit as an actinic light or a radiation, For example, KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV, Extreme Ultra Violet), an electron beam (EB, Electron Beam) etc., Extreme ultraviolet or an electron beam is especially preferable. The exposure may be liquid immersion exposure.

When a resist film is formed using a positive photosensitive composition, it is preferable to bake (heat) after exposure and before developing. Reaction of an exposure part is accelerated|stimulated by baking, and a sensitivity and a pattern shape become more favorable. 80-150 degreeC is preferable, as for heating temperature, 80-140 degreeC is more preferable, 80-130 degreeC is still more preferable. 30-1000 second is preferable, as for heating time, 60-800 second is more preferable, and its 60-600 second is still more preferable.

The developing step is a step of developing the exposed resist film with a developer. In addition, when a resist film is formed using a positive photosensitive composition, the exposed part of a resist film is developed and removed. On the other hand, in the case where the resist film is formed using the negative photosensitive composition, the unexposed portion of the resist film is developed and removed.

As a developing solution, the developing solution containing an organic solvent (organic type developing solution), the aqueous solution containing an alkali agent (alkali developing solution), etc. are mentioned. It can select suitably according to the kind of resist film.

As the organic solvent used for the organic developer, various organic solvents are widely used. For example, solvents such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents can be used. can As the organic solvent, at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, and organic solvents containing at least one of a fluorine atom and a silicon atom. It is preferable that it is an organic solvent of a kind, a hydrocarbon-based solvent, an ester-based or ketone-based solvent is preferable, an ester-based or ketone-based solvent is more preferable, and from the viewpoint of suppressing penetration into the resist film, a hydrocarbon having 5 or more carbon atoms A sub-solvent or a ketone-based solvent having 5 or more carbon atoms is more preferable, and a hydrocarbon-based solvent having 7 or more carbon atoms or a ketone-based solvent having 7 or more carbon atoms is particularly preferable. In the present invention, the ester solvent is a solvent having an ester bond in the molecule, the ketone solvent is a solvent having a ketone group in the molecule, the alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule, and the amide solvent is a molecule It is a solvent which has an amide group in it, and an ether type solvent is a solvent which has an ether bond in a molecule|numerator. Among these, there are also solvents having a plurality of types of the above-mentioned functional groups in one molecule. For example, diethylene glycol monomethyl ether shall correspond to any of the alcohol solvent and ether solvent in the said classification|category. In addition, a hydrocarbon-type solvent is a hydrocarbon-type solvent which does not have a substituent. As specific examples of ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents, reference can be made to the description of paragraphs Nos. 0021 to 0026 of International Publication No. WO2016/104565, this content is incorporated herein by reference.

Two or more said organic solvents may be mixed, and it may mix with solvents and water other than the above, and may use it. However, in order to fully exhibit the effect of this invention, it is preferable that the moisture content as a whole developing solution is less than 10 mass %, and it is more preferable that it contains substantially no water|moisture content. The concentration of the organic solvent (total in the case of multiple mixing) in the developing solution is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably is 90-100 mass %, Especially preferably, it is 95-100 mass %. Most preferably, it is the case where it consists substantially only of an organic solvent. In addition, the case where it consists only of an organic solvent substantially shall include the case where a trace amount surfactant, antioxidant, a stabilizer, an antifoamer, etc. are contained.

It is also preferable that an organic-type developing solution contains antioxidant, a basic compound, and surfactant. As an antioxidant and a basic compound, Paragraph No. 0047 of International Publication WO2016/104565 - description of 0078 can be considered into consideration, and this content is integrated in this specification. As the surfactant, the same surfactant as the surfactant that can be contained in the resist composition described later can be used.

Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n-butylamine secondary amines such as tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyl Tetraalkylammonium hydroxide such as triamylammonium hydroxide and dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, and trimethylbenzylammonium hydroxide An aqueous solution (alkaline aqueous solution) containing an alkali agent such as quaternary ammonium salts such as hydroxide and triethylbenzylammonium hydroxide and cyclic amines such as pyrrole and piperidine can be used. The alkaline developer can also be used by adding an appropriate amount of alcohol and a surfactant to the alkaline aqueous solution. It is preferable that the alkali agent density|concentration of an alkali developing solution is 0.1-20 mass %. It is preferable that pH of an alkaline developing solution is 10.0-15.0. As an alkali developing solution, the alkali developing solution of Paragraph No. 0460 of Unexamined-Japanese-Patent No. 2014-048500 can also be used, and this content is integrated in this specification.

As the developing method, for example, a method of immersing the support in a tank filled with a developer for a certain period of time (dip method), a method of developing by raising the developer on the surface of the support by surface tension and stopping for a certain period of time (paddle method); A method of spraying a developer on the surface of a support (spray method), a method of continuously discharging a developer while scanning a developer discharge nozzle at a constant speed on a support rotating at a constant speed (dynamic dosing method), etc. can be applied. Moreover, you may implement the process of stopping image development, replacing with another solvent after image development. There is no restriction|limiting in particular for image development time, Usually, it is 10-300 second, Preferably it is 20-120 second. 0-50 degreeC is preferable and, as for the temperature of a developing solution, 15-35 degreeC is more preferable.

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

When developing is performed using a developing solution, it is also preferable to perform a rinse process. When developing using an alkaline developing solution, pure water may be used as a rinse liquid in a rinse process, and surfactant may be added and used in an appropriate amount. When development is performed using an organic developer, it is preferable to use a rinse liquid containing an organic solvent as the rinse liquid in the rinse treatment. As the organic solvent used for the rinse liquid, at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is preferable. For the detail of the organic solvent used for a rinse liquid, Paragraph No. 0081 of International Publication No. WO2016/104565 - description of 0084 can be considered into consideration, and this content is integrated in this specification.

Although the method of the rinse treatment is not particularly limited, for example, a method of continuously discharging a rinse liquid onto a support rotating at a constant speed (rotary discharge method), a method of immersing the support in a tank filled with a rinse liquid for a certain period of time (dip method), the method of spraying a rinse liquid on the surface of a support body (spray method), etc. are applicable. Although there is no restriction|limiting in particular in rinsing time, Preferably it is 10 second - 300 second, More preferably, it is 10 second - 180 second, Most preferably, it is 20 second - 120 second. 0-50 degreeC is preferable and, as for the temperature of a rinse liquid, 15-35 degreeC is more preferable.

In addition, after the developing treatment or the rinsing treatment, a treatment for removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be performed. Further, after the developing treatment or the rinsing treatment or the treatment with the supercritical fluid, heat treatment may be performed to remove the solvent remaining in the pattern. Heating temperature is not specifically limited as long as a favorable resist pattern is obtained, Usually, it is 40-160 degreeC. As for heating temperature, 50-150 degreeC is preferable, and 50-110 degreeC is the most preferable. Although it does not specifically limit regarding a heating time as long as a favorable resist pattern is obtained, Usually, it is 15 to 300 second, Preferably it is 15 to 180 second.

[Ion implantation]

Next, ion implantation is performed into the support 1 using the resist pattern 2 formed as described above as a mask (FIG. 2). By doing in this way, an impurity is introduce|transduced into the exposed part from the resist pattern of the support body surface, and the photodiode part 3 is formed in the support body 1 .

Here, 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 appropriately select them according to the purpose. For example, when an n-type semiconductor substrate or a substrate on which an n-type well is formed is used as a support and ion implantation is performed on the support, p-type impurities such as boron and aluminum are preferably selected, and boron is more preferably. Further, when using a p-type semiconductor substrate or a substrate with a p-type well as a support and performing ion implantation on the support, it is preferable to select an n-type impurity such as phosphorus or arsenic.

There is no limitation in particular as ion implantation conditions. For example, as an energy amount, 100-5000 KeV is preferable. It is preferable that it is 400 KeV or less, and, as for an upper limit, it is more preferable that it is 300 KeV or less, It is more preferable that it is 200 KeV or less. It is preferable that it is 150 KeV or more, and, as for a lower limit, it is more preferable that it is 200 KeV or more, and it is still more preferable that it is 300 KeV or more. The dose 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 still 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 still more preferably 5×10 ¹² cm ^-2 or more.

In addition, ion implantation may be performed by reducing the amount of energy in steps, or may be performed by increasing the amount of energy in steps. In the case where the amount of energy is reduced in stages, the effect that noise resulting from damage to the resist pattern can be reduced can be expected. In the case of increasing the amount of energy step by step, since ions can be implanted to a greater depth, the effect of increasing the extracted signal intensity can be expected.

Through such a process, a light receiving element is manufactured. In the present invention, it is preferable to peel the resist pattern from the support after ion implantation. There is no limitation in particular as a peeling method of a resist pattern, A well-known method can be used. For example, it is preferable to peel using a resist removal liquid. As a resist removal liquid, Paragraph No. 0011-0043 of Unexamined-Japanese-Patent No. 2014-142635 can be considered into consideration, and this content is integrated in this specification. Moreover, it is also preferable to form an insulating film on the surface of a support body before or after peeling a resist pattern from a support body. As the material of the insulating film, there may be mentioned SiO _2, ZrO ₂ or the like. Moreover, after peeling a resist pattern from a support body, you may further have the process of forming an insulating film, a control electrode, a metal wiring layer, a source electrode, a drain electrode, etc.

(pixel formation)

[Step of forming a layer of the composition for forming a pixel]

Next, the process until a pixel is formed is demonstrated. First, a layer of the composition for forming a pixel of an optical filter is formed on at least a part of the region where the ion implantation of the light-receiving element manufactured as described above has been performed.

In addition, in this invention, an optical filter means the filter which transmits light. There is no limitation in particular as light which an optical filter permeate|transmits, An ultraviolet-ray, visible light, infrared rays, etc. are mentioned. The optical filter in the present invention may transmit light having at least a part of the wavelength of the incident light. That is, the optical filter of the present invention may selectively transmit or block light of a specific wavelength among incident light, or may transmit almost all of the incident light.

The layer of the composition for pixel formation can be formed by applying the composition for pixel formation to a light receiving element. As a composition for pixel formation, the composition for pixel formation of a colored pixel, the composition for pixel formation of an infrared transmission layer, the composition for pixel formation of an infrared ray blocking layer, etc. are mentioned, From the composition for color pixel formation and the composition for pixel formation of an infrared transmission layer It is preferable that it is at least 1 sort(s) chosen. The detail of the composition for pixel formation is mentioned later.

Although the layer of the composition for pixel formation may be formed directly on the light receiving element, 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, using a method other than the method specified in the present invention on the light-receiving element (for example, a method of forming a pattern by dry etching to form a pixel, or using light having a wavelength exceeding 300 nm (eg, i-line, etc.) A pixel may be formed in advance by the method of exposing, developing, and forming a pixel), and you may form the layer of the composition for pixel formation on this pixel.

A well-known method can be used as an application method of the composition for pixel formation. For example, the drip method (drop cast); slit coat method; spray method; roll coat method; spin coating (spin coating); flexible application method; slit and spin method; free wet method (for example, the method described in Unexamined-Japanese-Patent No. 2009-145395); Various printing methods, such as discharge system printing, such as inkjet (For example, an on-demand method, a piezo method, a thermal method), a nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and the metal mask printing method; a transfer method using a mold or the like; The nanoimprint method etc. are mentioned. The application method using inkjet is not particularly limited, and for example, the method shown in "Diffused and usable inkjet-infinite possibilities viewed as a patent-, published in February 2005, Sumibe Techno Research" (particularly page 115) ~ 133 pages), Japanese Patent Application Laid-Open No. 2003-262716, Japanese Patent Application Laid-Open No. 2003-185831, Japanese Patent Application Laid-Open No. 2003-261827, Japanese Patent Application Laid-Open No. 2012-126830, and Japanese Patent Application Laid-Open No. 2006-169325 The method described in etc. is mentioned.

The layer (henceforth a composition layer) of the composition for pixel formation which applied and formed the composition for pixel formation may be dried (prebaked). When prebaking, 150 degrees C or less is preferable, as for the prebaking temperature, 120 degrees C or less is more preferable, and 110 degrees C or less is still more preferable. The lower limit can be, for example, 50°C or higher, or 80°C or higher. 10 second - 3000 second are preferable, as for prebaking time, 40-2500 second is more preferable, 80-220 second is still more preferable. Pre-baking can be performed using a hot plate, an oven, etc.

[Exposure process]

Next, the composition layer formed as described above is exposed in a pattern by irradiating light with a wavelength of 300 nm or less. For example, the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposure part can be hardened.

As light which can be used at the time of exposure, what is necessary is just light with a wavelength of 300 nm or less, Preferably it is light with a wavelength of 180-300 nm. Specifically, KrF line (wavelength 248 nm), ArF (wavelength 193 nm), etc. are mentioned, and KrF line (wavelength 248 nm) is preferable for the reason that the bond of resin etc. contained in the composition for pixel formation is hard to be cut|disconnected. .

The exposure amount is preferably 1 to 2000 mJ/cm ^{2 , for example.} 1000 mJ/cm ² or less is preferable and, as for an ^{upper limit, 500 mJ/cm 2} or less is more preferable from a viewpoint of productivity. The lower limit is, 5mJ / cm ² or more is preferable, and 10mJ / cm ² or more is more preferred, and more preferred is 20mJ / cm ² or more in view of adhesion to the pixel-forming or not.

The oxygen concentration at the time of exposure can be appropriately selected, and in addition to carrying out under the atmosphere, for example, in a low-oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic) ) or in a high oxygen atmosphere (eg, 22% by volume, 30% by volume, 50% by volume) in which the oxygen concentration exceeds 21% by volume. Moreover, exposure illuminance can be set suitably, and can select from the range of ^1000W/m<2> -100000W/m<^2> (for example, 5000W/m<^2> , 15000W/m<^2> , 35000W/m<^{2> normally).} Oxygen concentration and exposure illuminance may be combined as appropriate, and the conditions, for example, roughness on the oxygen concentration of 10 volume% 10000W / m ^2, 20000W roughness in oxygen concentration 35 vol% / m ² and the like.

[Process of forming pixels (development)]

Next, the composition layer after exposure is developed. More specifically, the composition layer of the unexposed part in the composition layer after exposure is developed and removed, and a pixel (pattern) is formed. Development of the composition layer can be performed using a developing solution. Thereby, the composition layer of the unexposed part in an exposure process elutes to a developing solution, and only the photocured part remains on the light receiving element. As the developer, an alkaline developer that does not cause damage to the light-receiving element or the like on the underlying substrate is preferable. As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. As for image development time, 20 to 180 second is preferable. Moreover, in order to improve residue removability, you may shake off a developing solution every 60 second, and you may repeat the process of newly supplying a developing solution several times.

Examples of the alkali agent used in the developing solution include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethyl. Ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, Organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, metasilicic acid Inorganic alkaline compounds, such as sodium, are mentioned. The alkali agent is preferably a compound having a large molecular weight from the viewpoint of environment and safety. As the developer, an alkaline aqueous solution obtained by diluting these alkali agents with pure water is preferably used. 0.001-10 mass % is preferable and, as for the density|concentration of the alkali agent of alkaline aqueous solution, 0.01-1 mass % is more preferable. Moreover, you may use surfactant for a developing solution. The developer may be once prepared as a concentrate from the viewpoints of transport and storage convenience, and then diluted to a concentration required at the time of use. Although the dilution ratio is not specifically limited, For example, it can set in the range of 1.5-100 times. Moreover, when using the developing solution which consists of such an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after development.

After drying, after image development, an additional exposure process and a heat process (post-baking) can also be performed. An additional exposure process and a post-baking are processes after image development for making hardening of a film|membrane complete. When performing additional exposure processing, as light used for exposure, g line|wire, h line|wire, i line|wire, etc. are preferable, and i line|wire is more preferable. Moreover, the light which combined these two or more may be sufficient. Examples of the light source include an ultra-high pressure mercury lamp, a metal halide lamp, and a laser light source. The illuminance is preferably 500 to 100000 W/m ^{2 .} The exposure amount is, for example, preferably ^{500 to 10000 mJ/cm 2 .} Moreover, when performing a post-baking, 50-240 degreeC of post-baking temperature is preferable, for example. From a viewpoint of film hardening, 180-230 degreeC is more preferable.

As a film thickness of the pixel to be formed, it is preferable to select suitably according to a use and the kind of optical filter. For example, 2.0 micrometers or less are preferable, 1.0 micrometer or less is more preferable, 0.3-1.0 micrometers is still more preferable. 0.8 micrometer or less is preferable and, as for an upper limit, 0.6 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

Moreover, in the case of a colored pixel, as a film thickness of a pixel, 1.0 micrometer or less is preferable and 0.3-1.0 micrometer is more preferable. 0.8 micrometer or less is preferable and, as for an upper limit, 0.6 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

Moreover, in the case of the pixel of an infrared transmission layer, as a film thickness of a pixel, 2.0 micrometers or less are preferable and 0.3-2.0 micrometers is more preferable. 1.0 micrometer or less is preferable and, as for an upper limit, 0.6 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

Moreover, in the case of the pixel of an infrared blocking layer, as a film thickness of a pixel, 2.0 micrometers or less are preferable and 0.3-2.0 micrometers is more preferable. 1.0 micrometer or less is preferable and, as for an upper limit, 0.6 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

Moreover, as a size (line|wire width) of the pixel to be formed, it is preferable to select suitably according to a use and the kind of optical filter. For example, 2.0 µm or less is preferable. 1.0 micrometer or less is preferable and, as for an upper limit, 0.9 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

Moreover, in the case of a colored pixel, as a size (line|wire width) of a pixel, 2.0 micrometers or less are preferable. 1.0 micrometer or less is preferable and, as for an upper limit, 0.9 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

Moreover, in the case of a pixel of an infrared transmission layer, as a pixel size (line|wire width), 2.0 micrometers or less are preferable. 1.0 micrometer or less is preferable and, as for an upper limit, 0.9 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

Moreover, in the case of a pixel of an infrared blocking layer, 2.0 micrometers or less are preferable as a size (line|wire width) of a pixel. 1.0 micrometer or less is preferable and, as for an upper limit, 0.9 micrometer or less is more preferable. As for a lower limit, 0.4 micrometer or more is preferable.

When the device of the present invention has a plurality of types of pixels, at least one type of pixels may be formed through the above-described process. For example, after pattern-forming the 1st pixel by the dry etching method, you may manufacture the 2nd and subsequent pixels through the process mentioned above. Further, at least one of the plurality of types of pixels may be irradiated with light having a wavelength exceeding 300 nm, exposed in a pattern, and developed to form a pixel. Moreover, with respect to all the pixels, you may irradiate light exceeding 300 nm in wavelength, expose in pattern shape, and may develop and form a pixel.

As a device manufactured by this invention, optical sensors, such as a solid-state image sensor, an image display apparatus, etc. are mentioned. An embodiment of the device will be described with reference to 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 . Moreover, on the infrared cut filter 111, the color filter 112 is laminated|stacked. A microlens 115 is disposed 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 to cover the microlens 115 .

The infrared cut filter 111 is a filter having pixels of an infrared cut layer. This infrared blocking layer transmits visible light and has the spectral characteristic of blocking at least a part of infrared rays. The spectral characteristics of the infrared blocking layer are appropriately selected according to the spectral characteristics of the infrared transmitting filter 114 . It is preferable that the infrared cut filter 111 is a filter which light-shields at least a part of light in the range of wavelength 700-1300 nm. Moreover, it is preferable that the average transmittance|permeability of the light of the range of wavelength 400-700 nm of the infrared cut filter 111 is 60-100%, It is more preferable that it is 70-100%, It is especially preferable that it is 80-100%. It is preferable that the average transmittance|permeability in this wavelength range is high.

The color filter 112 is a filter having colored pixels. As a color pixel, a red pixel, a blue pixel, a green pixel, a cyan pixel, a magenta pixel, a yellow pixel, etc. are mentioned.

The infrared transmission filter 114 is a filter having pixels of an infrared transmission layer. As a preferable example of an infrared transmission filter layer, the filter layer which has the spectral characteristic in any one of the following (1)-(4) is mentioned, for example.

(1): the maximum value in the range of 400-640 nm wavelength of the transmittance|permeability of the light in the thickness direction is 20 % or less (preferably 15 % or less, More preferably, 10 % or less) in the thickness direction The filter layer whose minimum value in the range of wavelength 800-1300 nm of the transmittance|permeability of light is 70 % or more (preferably 75 % or more, More preferably, 80 % or more). According to this filter layer, light in the range of wavelength 400-640 nm can be light-shielded, and the infrared rays of wavelength 720 nm can be transmitted.

(2): the maximum value in the range of 400-750 nm wavelength of the transmittance|permeability of the light in the thickness direction is 20 % or less (preferably 15 % or less, More preferably, 10 % or less) in the thickness direction The filter layer whose minimum value in the range of wavelength 900-1300 nm of the transmittance|permeability of light is 70 % or more (preferably 75 % or more, More preferably, 80 % or more). According to this filter layer, light in the range of wavelength 400-750 nm can be light-shielded, and the infrared rays of wavelength 850 nm can be transmitted.

(3): The maximum value in the range of 400-850 nm wavelength of the transmittance|permeability of light in the thickness direction is 20% or less (preferably 15% or less, More preferably, 10% or less) in the thickness direction The filter layer whose minimum value in the range of the wavelength of 1000-1300 nm of the light transmittance is 70% or more (preferably 75% or more, More preferably, 80% or more). According to this filter layer, light in the range of wavelength 400-850 nm can be light-shielded, and the infrared rays of wavelength 940 nm can be transmitted.

(4): the maximum value in the range of 400-950 nm wavelength of the transmittance|permeability of the light in the thickness direction is 20 % or less (preferably 15 % or less, More preferably, 10 % or less) in the thickness direction The filter layer whose minimum value in the range of wavelength 1100-1300 nm of the light transmittance is 70 % or more (preferably 75 % or more, More preferably, 80 % or more). According to this filter layer, light in the range of wavelength 400-950 nm can be light-shielded, and the infrared rays of wavelength 1040 nm can be transmitted.

Moreover, although the device shown in FIG. 3 has the infrared transmission filter 114, the color filter 112, and the infrared cut filter 111, the aspect which does not provide the infrared cut filter 111, and the color filter 112 It can also be set as the aspect which does not provide and the infrared cut filter 111, and the aspect which does not provide the infrared transmission filter 114.

It is preferable that the material (various materials including a cover glass etc.) for producing optical sensors, such as a solid-state image sensor, is a material which does not generate|occur|produce an alpha ray. In order to suppress the generation of α-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. It is preferable that it is 5 mass ppb or less, and, as for content of uranium and thorium, it is preferable that it is 1 mass ppb or less. Although it is preferable that uranium and thorium are not contained substantially, you may contain it in the range which a soft error does not generate|occur|produce from the balance of high purity and cost. Moreover, it is also preferable to coat|cover and use the material which generates an alpha ray with the material which shields the alpha ray.

<Resist composition>

Next, the resist composition used in the manufacturing method of the device of this invention is demonstrated. The resist composition used in the device manufacturing method of the present invention may be either a positive photosensitive composition or a negative photosensitive composition, but it is preferably a positive photosensitive composition from the viewpoint of easy formation of a fine pattern. Moreover, as a resist composition, it is preferable that it is a composition containing the resin which is decomposed|disassembled by the action of an acid and the solubility with respect to a developing solution changes, and a photo-acid generator. Such a resist composition can be suitably used as a positive photosensitive composition.

The solid content concentration of the resist composition is preferably 25 mass % or more, more preferably 30 mass % or more, still more preferably 31 mass % or more, and particularly preferably 32 mass % or more. When the solid content concentration of the resist composition is 25 mass % or more, it is easy to form a resist film having a thickness of 5 µm or more by one application. 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 good pattern shape. It is preferable that it is 45 mass % or less, and, as for the upper limit of the solid content concentration of a resist composition, it is more preferable that it is 42.5 mass % or less, It is more preferable that it is 40 mass % or less.

From a viewpoint of applicability|paintability, it is preferable that it is 30-1000 mPa*s, and, as for the viscosity in 25 degreeC of a resist composition, it is more preferable that it is 100-1000 mPa*s. It is preferable that it is 800 mPa*s or less, and, as for an upper limit, it is more preferable that it is 700 mPa*s or less, It is more preferable that it is 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 preferably contains a resin having a repeating unit having a group that generates a polar group by being decomposed by the action of an acid, and a photoacid generator, and has a solid content concentration of 30% by mass or more. Hereinafter, each component used for a resist composition is demonstrated.

<<Resin>>

The resist composition preferably contains a resin. 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 still more preferably 97.0 to 99.9 mass%, based on the total solid content of the resist composition. .

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

When the resist composition contains two or more types of resins, the resin having an onisi parameter of 3.0 or less in the total amount of the resin (preferably a resin having an ounce parameter of 2.8 or less, and more preferably a resin having an ounce parameter of 2.7 or less) It is preferable that content is 50-100 mass %, It is more preferable that it is 60-100 mass %, It is more preferable that it is 75-100 mass %.

The resin included in the resist composition includes a resin (hereinafter also referred to as acid-decomposable resin) having a repeating unit having a group that generates a polar group by being decomposed by the action of an acid (hereinafter also referred to as “acid-decomposable group”). it is preferable

Examples of the acid-decomposable group included in the acid-decomposable resin include a group having a structure protected by a group from which a polar group is released by the action of an acid (hereinafter, also referred to as a leaving group). As the polar group, phenolic hydroxyl group, carboxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl) imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, tris( an acidic group such as an alkylsulfonyl)methylene group (a group that dissociates in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, which is conventionally used as a developer solution for a resist), an alcoholic hydroxyl group, and the like. A carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), and a sulfonic acid group are mentioned as a preferable polar group.

Examples of the leaving group include groups represented by any of the following formulas (Y11) to (Y14).

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 formulas (Y11) and (Y12), Rx ₁₁ to Rx ₁₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). It is preferable that carbon number of an alkyl group is 1-12, It is more preferable that it is 1-6, It is more preferable that it is 1-4. When all of Rx ₁₁ to Rx ₁₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 11} to Rx _{13 are methyl groups.} More preferably, Rx ₁₁ to Rx ₁₃ are each independently a linear or branched alkyl group, and more preferably, Rx ₁₁ to Rx ₁₃ are each independently a linear alkyl group. Two of Rx ₁₁ to Rx _{13 may} combine to form a ring. Examples of _{the ring formed by bonding two of Rx 11} to Rx ₁₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a polycyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Cycloalkyl groups are preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable. In the 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).

Formula (Y11), groups represented by (Y12), for the Rx ₁₁ is a methyl group or an ethyl group g., To the Rx ₁₂ and Rx ₁₃ bond are preferred embodiments that form a cycloalkyl group of the above.

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 combine with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. It _{is also preferable that R 36} is a hydrogen atom.

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

[Formula 1]

L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino 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 is preferably an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.

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

From the viewpoint of stability of the pattern shape, L ₂ is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group or norbornyl group, and a tert-butyl group and adamantane as the tertiary alkyl group.

In formula (Y14), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may combine with 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.

[Formula 2]

In the 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 which leaves by the action of an acid. It is preferable that Ya is group represented by any one of above-mentioned formula (Y11)-(Y14). However, when Ya is a group represented by the formula (Y11), and two of Rx ₁₁ , Rx ₁₂ and Rx ₁₃ combine to form a ring, the total number of carbon atoms in _{Rx 11} , Rx ₁₂ and Rx _{13 is 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 (such as a fluorine atom), a hydroxy 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 a methyl group. In _{one aspect, Xa 1} is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Examples of the divalent linking group represented by T include an alkylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or -COO-Rt-. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(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 _{combine with Ar 6} to form a ring, in which case R ₆₂ 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 preferable.

Ar ₆ represents a (n+1) valent aromatic _{ring group, and when combined with R 62} to form a ring, represents a (n+2) valent aromatic ring group. The _{aromatic ring group represented by Ar 6} is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

Y ₂ represents a group or a hydrogen atom which is each independently released by the action of an acid in the case of n≧2. Provided that at least one of Y ₂ represents a group eliminated by the action of an acid. Group to elimination by the action of an acid as Y _2, it is preferred that appears due to either formula (Y11) ~ (Y14) described above. However, when Y ₂ is a group represented by the formula (Y12), and when two of Rx ₁₁ , Rx ₁₂ and Rx ₁₃ combine to form a ring, the total number of carbon atoms in _{Rx 11} , Rx ₁₂ and Rx _{13 is 11 or more.}

n represents the integer of 1-4.

Said each group in a formula (AIa) and a formula (AII) may have a substituent. As a substituent, an alkyl group (C1-C4), a halogen atom, a hydroxyl group, an alkoxy group (C1-C4), a carboxyl group, an alkoxycarbonyl group (C2-6) etc. are mentioned, for example.

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

Regarding the repeating unit having an acid-decomposable group, Paragraph Nos. 0150 to 0159, 0210 to 0224 of International Publication No. WO2016/104565, Paragraph Nos. 0227 to 0233, 0270 to 0272 of Japanese Unexamined Patent Application Publication No. 2014-232309, Japanese Patent Application Laid-Open No. 2012- Reference may be made to the description of Paragraph Nos. 0123 to 0131 of 208447, the contents of which are incorporated herein by reference.

The acid-decomposable resin may contain only 1 type of repeating unit which has an acid-decomposable group, and may contain it 2 or more types. It is preferable that content of the repeating unit which has an acid-decomposable group in acid-decomposable resin is 5-90 mol% with respect to all the repeating units in 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. It is more preferable that it is 85 mol% or less, and, as for an upper limit, it is more preferable that it is 80 mol% or less.

The acid-decomposable resin may include 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 sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and a phenolic hydroxyl group. The phenolic hydroxyl group is a group formed by substituting a hydroxyl group for a hydrogen atom in an aromatic ring group. The aromatic ring is a monocyclic or polycyclic aromatic ring, for example, an aromatic hydrocarbon ring which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring, or, for example, Thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiazole ring, thiazole ring, etc. and aromatic heterocycles including heterocycles. Especially, a benzene ring and a naphthalene ring are preferable from a viewpoint of resolution, and a benzene ring is the most preferable.

As a repeating unit which has an acidic radical, it is preferable that it is a repeating unit which has a phenolic hydroxyl group. As a repeating unit which has a phenolic hydroxyl group, the repeating unit represented by following formula (30) is preferable.

Equation (30)

[Formula 3]

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 _{combine with Ar 3} to form a ring, and R ₃₃ in that case represents an alkylene group. X ₃ represents a single bond or a divalent linking group. Ar ₃ represents a (n3+1) valent aromatic _{ring group, and when combined with R 33} to form a ring, represents a (n3+2) valent aromatic ring group. n3 represents the integer of 1-4.

Examples of the (n3+1) valent aromatic ring group represented by Ar ₃ include an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring group and an anthracene ring group, a thiophene ring group, a furan ring group, a pyrrole ring group, and a benzothiophene group. and aromatic ring groups including heterocyclic groups such as ventilation, benzofuran ring group, benzopyrrole ring group, triazine ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiazole ring group, and thiazole ring group. Ar ₃ is preferably a benzene ring group. The (n3+1) valent aromatic ring group represented by _{Ar 3 may further have a substituent.} As a substituent, an alkyl group, an alkoxy group, etc. are mentioned.

Examples of the divalent linking group represented by X _{3 include -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 the integer of 1-4, it is preferable to represent 1 or 2, and it is more preferable to represent 1.

Regarding the repeating unit having a phenolic hydroxyl group, Paragraph Nos. 0131 to 0147 of International Publication No. WO2016/104565 and Paragraph Nos. 0177 to 0178 of Japanese Patent Application Laid-Open No. 2014-232309 can be referred to, the contents of which are incorporated herein by reference. is used

The acid-decomposable resin may contain only 1 type of repeating unit which has an acidic radical, and may contain it 2 or more types. It is preferable that content of the repeating unit which has an acidic radical in acid-decomposable resin is 5-90 mol% with respect to all the repeating units in 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. It is more preferable that it is 85 mol% or less, and, as for an upper limit, it is more preferable that it is 80 mol% or less.

The acid-decomposable resin may contain, as a repeating unit other than the repeating unit having an acid-decomposable group, a repeating unit further having a lactone structure or a sultone (cyclic sulfonic acid ester) structure. For a repeating unit having a lactone structure or a sultone (cyclic sulfonic acid ester) structure, reference may be made to the description of paragraphs 0161 to 0170 of International Publication No. WO2016/104565, the contents of which are incorporated herein by reference.

The acid-decomposable resin may include, as repeating units other than the repeating unit having an acid-decomposable group, a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. When the acid-decomposable resin includes such a repeating unit, the adhesion to the support and the affinity for the developer are improved. As a polar group, a hydroxyl group and a cyano group are preferable. As an alicyclic hydrocarbon structure, an adamantyl group, a diamantyl group, and a norbornein group are preferable. For a repeating unit containing an organic group having a polar group, reference may be made to the description in Paragraph No. 0172 of International Publication No. WO2016/104565, the content of which is incorporated herein by reference.

The acid-decomposable resin may have, as repeating units other than the repeating unit having an acid-decomposable group, a repeating unit having a cyclic hydrocarbon structure not having a polar group and not exhibiting acid-decomposability. As such a repeating unit, the repeating unit represented by Formula (IV) is mentioned.

[Formula 4]

In the formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and not having a 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 is _2, is a hydrogen atom, a methyl group, hydroxy group, trifluoromethyl are preferred, and is preferably a hydrogen atom, a methyl group in particular.

The _{cyclic structure of R 5} includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, a cycloalkenyl group having 3 to 12 carbon atoms, such as a cyclohexenyl group, and a phenyl group. and the like. Examples of the polycyclic hydrocarbon group include a ring aggregated hydrocarbon group and a crosslinked hydrocarbon group. Examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. As the cross-linked hydrocarbon group, for example, a bicyclic hydrocarbon ring group such as a pinane ring group, a bonein ring group, a nopinein ring group, a norbornein ring group, a bicyclooctane ring group, a homobledane ring group, an adamantane ring group , tricyclic hydrocarbon ring groups such as tricyclo[5.2.1.0 ^2,6 ]decane ring group, tricyclo[4.3.1.1 ^2,5 ]undecane ring group, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] tetracyclic hydrocarbon ring groups, such as a dodecane ring group and a perhydro-1,4-methano-5,8-methanonaphthalene ring group, etc. are mentioned. Further, examples of the cross-linked hydrocarbon group include a condensed cyclic group in which a plurality of 5- to 8-membered cycloalkane rings are condensed.

These cyclic hydrocarbon structures may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an acyl group, and an alkoxycarbonyl group.

When the acid-decomposable resin has a cyclic hydrocarbon structure having no polar group and contains repeating units that do not exhibit acid-decomposability, the content thereof is preferably 1 to 40 mol% with respect to all repeating units in the acid-decomposable resin. and more preferably 2 to 20 mol%.

As a specific example of acid-decomposable resin, resin etc. of the following structure are mentioned, for example. The numerical value added to each repeating unit is a molar ratio.

[Formula 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, particularly preferably 3,000 to 11,000. It is excellent in film formability and developability as weight average molecular weights are 1,000-200,000.

It is preferable that it is 1.0-3.0, as for the dispersion degree (molecular weight distribution) of acid-decomposable resin, it is more preferable that it is 1.0-2.6, It is more preferable that it is 1.0-2.0. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the sidewall of the resist pattern.

The sludge parameter of the acid-decomposable resin is preferably 3.0 or less, more preferably 2.9 or less, still more preferably 2.8 or less, and particularly preferably 2.7 or less. It is preferable that a lower limit is 2.5 or more, for example.

The content of the acid-decomposable resin is preferably 30 to 99.9 mass% with respect to the total solid content of the resist composition. The lower limit is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 96% by mass or more, and still more preferably 97% by mass or more. % or more is particularly preferred. Acid-decomposable resin may use only 1 type, and may use 2 or more types together.

Further, the content of the acid-decomposable resin in the total amount of the resin contained in the resist composition is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and more preferably 70 to 100% by mass. It is preferable, and it is especially preferable that it is 80-100 mass %.

The resist composition may contain a hydrophobic resin as resin. The hydrophobic resin is preferably designed to be ubiquitous at the interface, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and does not need to contribute to uniformly mixing polar/non-polar substances. As an effect of adding hydrophobic resin, suppression of an outgas, etc. are mentioned. As hydrophobic resin, Paragraph No. 0336 of International Publication WO2016/104565 - description of 0374 can be considered into consideration, and this content is integrated in this specification.

<<Mine Generator>>

The resist composition preferably contains a photoacid generator. Although the form of a low molecular compound may be sufficient as a photo-acid generator, and the form contained in a part of a polymer may be sufficient, it is preferable that it is the form of a low molecular compound. When a photo-acid generator is in the form of a low molecular weight compound, it is preferable that molecular weight is 3000 or less, It is more preferable that it is 2000 or less, It is more preferable that it is 1000 or less.

Although it does not specifically limit as a photo-acid generator, An organic acid, for example, sulfonic acid, bis(alkylsulfonyl)imide, or tris(alkylsulfonyl ) compounds generating at least any one of methides are preferred. More preferably, the compound represented by a following formula (ZI), (ZII), (ZIII) is mentioned, It is more preferable that it is a compound represented by a formula (ZI).

[Formula 6]

In the formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. _Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R 203 include an aryl group, an alkyl group, and a cycloalkyl group. Examples of the aryl group include an aryl group having 6 to 14 carbon atoms. As an alkyl group and a cycloalkyl group, Preferably, a C1-C10 linear or branched alkyl group and a C3-C10 cycloalkyl group are mentioned. The above-mentioned aryl group, alkyl group, and cycloalkyl group may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms) etc. are mentioned, but it is not limited to these.

In the formula (ZI), _{two of R 201} to R _{203 may} combine to form a ring structure, and the formed ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group in the ring. do. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, a butylene group and a pentylene group).

In the formula (ZI), the ^{number of aromatic rings contained in the cation moiety (S +} (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ )) is preferably two or less from the viewpoint of improving the pattern shape by improving the light transmittance. And, it is more preferable that it is 1 or less, and it is more preferable that it does not contain an aromatic ring.

In the formula (ZI), Z ⁻ represents a non-nucleophilic anion (anion having a remarkably low ability to cause a nucleophilic reaction). Examples of the non-nucleophilic anion include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonyl and a mide anion, a bis(alkylsulfonyl)imide anion, and a tris(alkylsulfonyl)methide anion.

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

As an aromatic group in an aromatic sulfonic acid anion and an aromatic carboxylate anion, Preferably, a C6-C14 aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.

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 having 1 to 15 carbon atoms), and a cycloalkyl group (preferably having 3 to 15 carbon atoms). , an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms). ), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably preferably C6-20), an alkylaryloxysulfonyl group (preferably C7-20), a cycloalkylaryloxysulfonyl group (preferably C10-20), an alkyloxyalkyloxy group (preferably C5-20), a cycloalkylalkyloxyalkyloxy group (preferably C8-20) etc. are mentioned. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) is mentioned further as a substituent.

The aralkyl group in the aralkyl carboxylate anion preferably includes an aralkyl group having 7 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

Examples of the sulfonylimide anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group, and the like, and a fluorine atom Or an alkyl group substituted with a fluorine atom is preferable. Moreover, the alkyl group in the bis(alkylsulfonyl)imide anion may mutually couple|bond and may form ring structure. Thereby, the acid strength increases.

Examples of other non-nucleophilic anions include phosphorus fluoride (eg PF ₆ ⁻ ), boron fluoride (eg BF ₄ ⁻ ), antimony fluoride (eg SbF ₆ ⁻ ), and the like. have.

Examples of the non-nucleophilic anion include an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and bis(alkylsulfonyl)imide in which an alkyl group is substituted with a fluorine atom. An anion and tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom are preferable. As the non-nucleophilic anion, more preferably a perfluoroaliphatic sulfonic acid anion (more preferably 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, even more preferably a nonafluorobutanesulfonic acid anion, perfluorooctanesulfonic acid anion, pentafluorobenzenesulfonic acid anion, and 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

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

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

[Formula 7]

In the formula, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ , R ² each independently represents a hydrogen atom, a fluorine atom, or an alkyl group, and R ¹ and R ^{2 in the case of two or more} may be the same or different, respectively. L represents a divalent linking group, and L in the case of two or more may be the same or different. A represents a cyclic organic group. x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

As an alkyl group in the alkyl group substituted by the fluorine atom of Xf, Preferably it is C1-C10, More preferably, it is C1-C4. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a 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 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 , and among these, a fluorine atom and CF ₃ are preferable. . In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R<^1> , R<^2> may have a substituent (preferably a fluorine atom), and a C1-C4 thing is preferable. More preferably, it is a C1-C4 perfluoroalkyl group. R ¹ , R ² is preferably a fluorine atom or CF ₃ .

1-10 are preferable and, as for x, 1-5 are more preferable. 0-4 are preferable and, as for y, 0 is more preferable. 0-5 are preferable and, as for z, 0-3 are more preferable.

It does not specifically limit as a divalent linking group of L, -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group, an alkenylene group or a linking group in which a plurality of these are linked, and a linking group having a total carbon number of 12 or less is preferable. Among these, -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 includes an aliphatic ring, an aromatic hydrocarbon ring, and a heterocyclic ring (not only having aromaticity but also rings having no aromaticity), etc. can be heard The aliphatic ring may be monocyclic or polycyclic, and monocyclic cycloalkyl rings such as cyclopentyl ring, cyclohexyl ring and cyclooctyl ring, norbornyl ring, tricyclodecanyl ring, tetracyclodecanyl ring, tetracyclododecanyl ring, a Polycyclic cycloalkyl rings, such as a danantyl ring, are preferable. As an aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, a phenanthrene ring, 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, and a lactone ring. have.

The cyclic organic group may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), or a cycloalkyl group (monocyclic, polycyclic, or spiro ring) and preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group , and a sulfonic acid ester group. In addition, carbonyl carbon may be sufficient as the carbon (carbon contributing to cyclicity) constituting the cyclic organic group.

For details of formula (AN1), reference may be made to the description of paragraph No. 0259 of International Publication No. WO2016/104565, the content of which is incorporated herein by reference.

In formulas (ZII), (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 above-mentioned compound (ZI).}

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R _{207 may have a substituent.} Also as a substituent, an aryl group, an alkyl group, a cycloalkyl group of R ₂₀₁ ~ R ₂₀₃ in the above-mentioned compound (ZI) include those which may optionally have.

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

The photo-acid generator suppresses diffusion of the acid generated by exposure to the non-exposed part and improves resolution, by irradiation with an electron beam or extreme ultraviolet rays, ^{an acid having a volume of 130 Å 3} or more (more preferably It is preferably a compound that generates phonic acid), more preferably a compound that generates an ^{acid (more preferably sulfonic acid) having a volume of 190 Å 3} or more, and an acid (more preferably sulfonic acid) with a volume of 270 Å ³ or more. ), and particularly preferably a compound that generates an acid (more preferably sulfonic acid) having a size of ^{400 Angstroms 3 or more in volume.} However, it is preferable that it is ^{2000 Angstrom 3} or less, and, as for the said volume, it is more preferable that it is ^{1500 Angstrom 3} or less from a viewpoint of a sensitivity or coating-solvent solubility. The value of the said volume was calculated|required using "WinMOPAC" manufactured by Fujitsu Corporation. That is, first, the chemical structure of the acid for each example is input, and then, the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method using this structure as the initial structure, and then By performing molecular orbital calculation using the PM3 method with respect to the most stable conformation, the "accessible volume" of each acid can be calculated. 1 Å is 1×10 ^-10 m.

As a photo-acid generator, Paragraph Nos. 0368 to 0377 of Japanese Patent Application Laid-Open No. 2014-041328, Paragraph Nos. 0240 to 0262 of Japanese Unexamined Patent Application Publication No. 2013-228681 (paragraph No. 0339 of U.S. Patent Application Laid-Open No. 2015/004533) may be cited, the contents of which are incorporated herein by reference. Moreover, although the following compound is mentioned as a preferable specific example, it is not limited to these.

[Formula 8]

A photo-acid generator can be used individually by 1 type or 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, further preferably 3 to 20% by mass, particularly preferably based on the total solid content of the resist composition. It is 3-15 mass %.

<<Solvent>>

The resist composition preferably contains a solvent. It is preferable that the solvent (also called "solvent (S)") which satisfies the following conditions (a)-(c) is included as a solvent.

(a) A>-0.026*B+5

(b) 0.9<A<2.5

(c) 120<B<160

Said A shows the viscosity (mPa*s) of the said solvent (S), and said B shows the boiling point (degreeC) of the said solvent (S).

When the solvent (S) consists of only one solvent, A represents the viscosity (mPa·s) of the solvent, and B represents the boiling point (°C) of the solvent.

When the solvent (S) is a mixed solvent composed of two solvents, the A is calculated by the following formula (a1), and the B is calculated by the following formula (b1).

A=μ1^X1*μ2^X2 (a1)

B=T1*X1+T2*X2 (b1)

μ1 represents the viscosity (mPa·s) of the first solvent, 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.

When the solvent (S) is a mixed solvent composed of n types of solvents, the A is calculated by the following formula (a2), and the B is calculated by the following formula (b2).

A=μ1^X1*μ2^X2*… μn^Xn (a2)

B=T1*X1+T2*X2+… Tn*Xn (b2)

μ1 represents the viscosity (mPa·s) of the first solvent, 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 viscosity A (mPa·s) is a value at room temperature and normal pressure (25° C./1 atm). 1 atm is 1.013×10 ⁵ Pa. In addition, the said boiling point B (degrees C) is a value at normal pressure (1 atm), and when two or more types of mixed solvents are used, the influence of boiling point fluctuations due to azeotrope is not considered, and the above formula (b1) or ( Only b2) shall be followed.

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'), more preferably 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 conditions (a) to (c). For example, a lactone solvent, a ketone solvent, an ester solvent, an alcohol solvent, an ether solvent, and an aromatic solvent. and organic solvents. Only 1 type of solvent may be sufficient as a solvent (S), and the mixed solvent of 2 or more types of solvents may be sufficient as it.

Examples of the lactone-based solvent include γ-butyrolactone (GBL).

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone (CyHx), methyl-n-amyl ketone, methyl isoamyl ketone, and 2-heptanone (MAK).

Examples of the ester solvent include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate (nBA), methyl pyruvate, ethyl pyruvate, methyl methoxypropionate (MMP), and ethyl ethoxypropionate (EEP). can In addition, monomethyl ether, monoethyl ether, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, 3-methoxybutyl acetate , monoalkyl ethers such as monopropyl ether and monobutyl ether (eg, propylene glycol monomethyl ether acetate (PGMEA) etc.), or monophenyl ether.

Examples of the alcohol-based solvent include monohydric alcohols such as 4-methyl-2-pentanol (MIBC), benzyl alcohol and 3-methoxybutanol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene. Polyhydric alcohols, such as glycol, are mentioned. In addition, monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the polyhydric alcohol {e.g., propylene glycol monomethyl ether (PGME), etc.}; or monophenyl ether.

Examples of the ether solvent include cyclic ethers such as dioxane, and solvents containing an ether bond among the solvents described in the above ester solvents and alcohol solvents.

Examples of the aromatic organic solvent include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropyl Benzene, toluene, xylene, cymene, mesitylene, etc. are mentioned.

It is preferable that the solvent (S) contains at least 1 sort(s) of an ether type solvent, an ester type solvent, and a ketone type solvent among the said solvent, and it is propylene glycol monomethyl ether acetate and propylene glycol monomethyl. ter, ethyl lactate, ethyl ethoxypropionate, cyclohexanone, and methyl methoxypropionate are more preferably included, and at least one of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether. It is more preferable to include one type.

The mixing ratio of each solvent in the case of using two or more solvents, A calculated by the above formulas (a1) and (a2) and B calculated by the above formulas (b1) and (b2) are It is preferable to adjust so that conditions (a)-(c) may be satisfied.

The content of the solvent in the resist composition is preferably 40 to 70 mass%, more preferably 45 to 70 mass%, still more preferably 55 to 70 mass%, based on the total mass of the resist composition.

<<Acid diffusion control agent>>

The resist composition preferably contains an acid diffusion controlling agent. The acid diffusion controlling agent acts as a secondary agent to trap acid generated from the acid generator or the like during exposure and suppress the reaction of the acid-decomposable resin in the unexposed portion by the excess generated acid. As the acid diffusion control agent, a basic compound, a low molecular weight compound having a group that is detached by the action of an acid having a nitrogen atom, a basic compound whose basicity is lowered or lost by irradiation with actinic ray or radiation, or relatively to an acid generator Onium salts, which are weak acids, can be used.

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

[Formula 9]

In formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), or a cycloalkyl group (preferably having 3 to 20 carbon atoms). ) or an aryl group (having 6 to 20 carbon atoms), wherein 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 an alkyl group which has a substituent with respect to the said alkyl group, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.

It is more preferable that the alkyl group in these general formulas (A) and (E) is unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and the like, and more preferred compounds include imidazole structure, diazabicyclo A compound having a structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether linkage, an aniline derivative having a hydroxyl group and/or an ether linkage, etc. can be heard As a specific example of a preferable compound, the compound illustrated in Paragraph No. 0379 of US2012/0219913 is mentioned.

Moreover, as a basic compound, the amine compound which has a phenoxy group, the ammonium salt compound which has a phenoxy group, the amine compound which has a sulfonic acid ester group, and the ammonium salt compound which has a sulfonic acid ester group can be used preferably. For these details, Paragraph Nos. 0307-0311 of International Publication No. WO2016/104565 can be referred to, and this content is integrated in this 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%, based on the total solid content of the resist composition. Moreover, it is preferable that the ratio of a photo-acid generator (the sum total when it has multiple types) and a basic compound in a resist composition is a molar ratio, and photo-acid generator/basic compound =2.5-300. From the viewpoint of sensitivity and resolution, the above molar ratio is preferably 2.5 or more, and preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to the thickening of the resist pattern with the passage of time from exposure to heat treatment. More preferably, the molar ratio mentioned above is 5.0-200, More preferably, it is 7.0-150.

It is preferable that the low molecular weight compound (hereinafter also referred to as "compound (D-1)") having a group that is released by the action of an acid having a nitrogen atom is an amine derivative having a group that is released by the action of an acid on the nitrogen atom. . As the group which is released by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminoether group are preferable, and a carbamate group and a hemiaminoether group are particularly preferable. do. 100-1000 are preferable, as for the molecular weight of a compound (D-1), 100-700 are more preferable, and 100-500 are especially preferable.

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

[Formula 10]

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

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, and a halogen atom. It may be substituted. The same applies to the alkoxyalkyl group represented by Rb. Rb is preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group. More preferably, they are a linear or branched alkyl group and a cycloalkyl group. Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof. As a specific structure of group represented by Formula (d-1), the structure disclosed by Paragraph No. 0466 of US2012/0135348 publication is mentioned, This content is integrated in this specification.

It is preferable that the compound (D-1) is a compound which has a structure represented by following formula (6).

[Formula 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, two Ra may be the same or different, and two Ra may be mutually connected and may form a heterocycle with the nitrogen atom in a formula. The heterocycle may contain hetero atoms other than the nitrogen atom in the formula.

Rb is synonymous with Rb in the said Formula (d-1), and a preferable example is also the same.

l represents an integer from 0 to 2, m represents an integer from 1 to 3, satisfying l+m=3.

In the formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R a may be substituted with the same groups as the above-mentioned groups as the alkyl group, cycloalkyl group, aryl group, or aralkyl group as R b .

As a specific example of a compound (D-1), the compound described in Paragraph No. 0475 of US2012/0135348 is mentioned, This content is integrated in this specification.

The compound represented by Formula (6) can be synthesize|combined based on Unexamined-Japanese-Patent No. 2007-298569, Unexamined-Japanese-Patent No. 2009-199021, etc.

When the resist composition contains the compound (D-1), the content of the compound (D-1) is preferably 0.001 to 20 mass%, more preferably 0.001 to 10 mass%, based on the total solid content of the resist composition. And, it is more preferable that it is 0.01-5 mass %.

As a basic compound (hereinafter also referred to as "compound (PA)") whose basicity is reduced or lost upon irradiation with actinic ray or radiation, it has a proton-accepting functional group and is decomposed by irradiation with actinic ray or radiation, and a compound in which the proton-accepting property decreases or disappears, or the compound changes from the proton-accepting property to an acidic one.

A proton-accepting functional group is a functional group which has a group or electron which can interact electrostatically with a proton, For example, it contributes to the functional group which has macrocyclic structures, such as cyclic polyether, and π-conjugation. refers to a functional group having a nitrogen atom with a lone pair of electrons that does not The nitrogen atom which has a lone pair of electrons which does not contribute to (pi) conjugation is a nitrogen atom which has a partial structure shown, for example by a following formula.

[Formula 12]

Preferred partial structures of the proton-accepting functional group include, for example, crown ethers, azacrown ethers, primary to tertiary amines, pyridines, imidazoles, and pyrazine structures.

The compound (PA) is decomposed by irradiation with actinic ray or radiation to generate a compound whose proton-accepting properties are reduced or lost, or whose proton-accepting properties are changed from proton-accepting properties to acid. Here, the decrease or loss of proton-accepting properties, or a change from proton-accepting properties to acidity means changes in proton-accepting properties resulting from the addition of protons to proton-accepting functional groups, specifically, proton-accepting properties. When a proton adduct is produced from a compound (PA) having a functional group and a proton, it means that the equilibrium constant decreases in its chemical equilibrium. Proton acceptor properties can be confirmed by measuring pH. For the compound (PA), reference can be made to description of Paragraph Nos. 0312 to 0320 of International Publication No. WO2016/104565, the content of which is incorporated herein by reference.

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%, based on the total solid content of the resist composition. A compound (PA) may be used individually by 1 type, and may be used in combination of 2 or more type.

In the resist composition, an onium salt, which is a relatively weak acid with respect to the photo-acid generator, can be used as the acid diffusion controlling agent. When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid (preferably a weak acid having a pKa of more than -1) with respect to the acid generated from the photoacid generator is mixed and used, the photoacid generator is irradiated with actinic ray property or radiation. When an acid generated from the generator collides with an unreacted onium salt having a weak acid anion, the weak acid is released by salt exchange to generate an onium salt having a strong acid anion. In this process, since the strong acid is exchanged for a weak acid with a lower catalytic ability, apparently the acid is deactivated and acid diffusion can be controlled. About these compounds, Paragraph Nos. 0191 to 0210 of Unexamined-Japanese-Patent No. 2012-242799, Paragraph Nos. 0037 to 0039 of Unexamined-Japanese-Patent No. 2013-006827, Paragraph Nos. 0027-0029 of Unexamined-Japanese-Patent No. 2013-008020, Unexamined-Japanese-Patent No. Paragraph Nos. 0012 to 0013 of Publication No. 2012-189977, Paragraph Nos. 0029 to 0031 of Unexamined-Japanese-Patent No. 2012-252124 can be considered into consideration, and these content is integrated in this specification.

When the resist composition contains an onium salt that is relatively weak acid to the photo-acid generator, its content is preferably 0.5 to 10.0 mass%, more preferably 0.5 to 8.0 mass%, based on the total solid content of the resist composition. It is preferable, and it is more preferable that it is 1.0-8.0 mass %.

<<Surfactant>>

The resist composition may further contain a surfactant. As surfactant, it is more preferable to contain any one, or two or more types of a fluorine type and/or silicone type surfactant (a fluorine type surfactant, silicone type surfactant, surfactant which has both a fluorine atom and a silicon atom).

Examples of the fluorine-based and/or silicone-based surfactant include surfactants described in <0276> of U.S. Patent Application Laid-Open No. 2008/0248425, for example, EFTOP EF301, EF303 (manufactured by Shin-Akita Chemical Co., Ltd.), fluoro Rod FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megapac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Sufflon S-382, SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemicals), 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), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos Corporation), and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone-based surfactant.

Further, as the surfactant, in addition to the well-known ones as shown above, fluorine derived from a fluoroaliphatic compound produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having an aliphatic group may be used. A fluoroaliphatic compound can be synthesize|combined according to the method described in Unexamined-Japanese-Patent No. 2002-090991.

As the surfactant corresponding to the above, Megapac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), an acrylate having a _{C 6} F _{13 group (or meta} copolymers of acrylates) and (poly(oxyalkylene))acrylates (or methacrylates), acrylates (or methacrylates) with C ₃ F ₇ groups and (poly(oxyethylene))acrylates (or and a copolymer of methacrylate) and (poly(oxypropylene))acrylate (or methacrylate).

In the present invention, other surfactants other than the fluorine-based and/or silicone-based surfactants described in Paragraph No. 0280 of U.S. Patent Application Laid-Open No. 2008/0248425 may be used.

These surfactants may be used independently and may be used in combination of 2 or more type.

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

<<Other additives>>

The resist composition, if necessary, further comprises an onium carboxylate salt, an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer (for example, A phenol compound having a molecular weight of 1000 or less, an alicyclic or aliphatic compound having a carboxyl group), and the like can be contained.

<Composition for pixel formation>

Next, the composition for pixel formation is demonstrated. This composition for pixel formation is a composition for forming the pixel of the optical filter used for a device. Examples of the composition for forming a pixel include a composition for forming a colored pixel, a composition for forming a pixel of an infrared transmitting layer, a composition for forming a pixel of an infrared blocking layer, and the like. It is preferable that it is at least 1 sort(s) chosen from a composition. Hereinafter, the composition for color pixel formation is also called the composition for color filters. Moreover, the composition for pixel formation of an infrared transmission layer is also called the composition for infrared transmission 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 infrared cut filters, it has a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and A is the ratio _{of the maximum value A 1 of the absorbance in the wavelength range of 400 to 600 nm and the absorbance A 2} in the above-mentioned maximum absorption wavelength _{It is preferred that 1} /A ₂ be a composition having spectral properties of 0.3 or less. By using the composition having such spectral characteristics, it is possible to form a pixel excellent in visible transparency and excellent in infrared shielding properties.

As a composition for color filters, it is preferable that it is a composition for formation of the color pixel chosen from a red pixel, a blue pixel, a green pixel, a cyan pixel, a magenta pixel, and a yellow pixel, for example.

As a composition for an infrared transmission filter, Amin/Bmax, which is the 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, is a composition having a spectral characteristic of 5 or more desirable. As for Amin/Bmax, it is more preferable that it is 7.5 or more, It is more preferable that it is 15 or more, It is especially preferable that it is 30 or more.

The absorbance Aλ at a predetermined wavelength λ is defined by the following formula (1).

Aλ=-log(Tλ/100)… (One)

Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.

In this invention, the value measured in the solution state may be sufficient as the value of the absorbance, and the value in the film|membrane formed into a film using the composition for infrared transmission filters may be sufficient as it. When measuring the absorbance in a film state, by a method such as spin coating on a glass substrate, the composition for an infrared transmission filter is applied so that the thickness of the film after drying becomes a predetermined thickness, and using a hot plate at 100° C., 120 It is preferable to measure using the membrane prepared by drying for a second. The thickness of a film|membrane can be measured with respect to the board|substrate which has a film|membrane using the stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC).

In addition, absorbance can be measured using a conventionally well-known spectrophotometer. The absorbance measurement conditions are not particularly limited, but the maximum value B of the absorbance in the wavelength range of 1100-1300 nm is measured under the conditions adjusted so that the minimum value A of the absorbance in the wavelength range of 400 to 640 nm is 0.1 to 3.0. It is preferable to do By measuring the absorbance under such conditions, the measurement error can be made smaller. There is no limitation in particular as a method of adjusting so that the minimum value A of the absorbance in the range of wavelength 400-640 nm may become 0.1-3.0. For example, when measuring absorbance in a solution state, the method of adjusting the optical path length of a sample cell is mentioned. Moreover, when measuring absorbance in a film|membrane state, the method of adjusting a film thickness, etc. are mentioned.

As for the composition for infrared transmission filters, it is more preferable that the spectral characteristic in any one of the following (1)-(4) is satisfy|filled.

(1): ratio Amin1/Bmax1 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 is 5 or more, preferably 7.5 or more, 15 It is more preferable that it is more than 30, and it is still more preferable that it is 30 or more. According to this aspect, the film|membrane which can block light in the range of wavelength 400-640 nm and can transmit infrared rays with a wavelength of 720 nm can be formed.

(2): ratio Amin2/Bmax2 of the minimum value of absorbance Amin2 in the range of wavelength 400-750nm and the maximum value Bmax2 of absorbance in the range of wavelength 900-1300nm is 5 or more, It is preferable that it is 7.5 or more, and it is 15 or more It is more preferable, and it is still more preferable that it is 30 or more. According to this aspect, the film|membrane which can block light in the range of wavelength 400-750 nm and can transmit infrared rays with a wavelength of 850 nm can be formed.

(3): ratio Amin3/Bmax3 of the minimum value Amin3 of the absorbance in the wavelength range of 400 to 850 nm and the maximum value Bmax3 of the absorbance in the wavelength range of 1000 to 1300 nm is 5 or more, preferably 7.5 or more, 15 It is more preferable that it is more than 30, and it is still more preferable that it is 30 or more. According to this aspect, the film|membrane which can block light in the range of wavelength 400-830 nm, and can transmit infrared rays with a wavelength of 940 nm can be formed.

(4): ratio Amin4/Bmax4 of the minimum value Amin4 of the absorbance in the wavelength range of 400 to 950 nm and the maximum value Bmax4 of the absorbance in the wavelength range of 1100 to 1300 nm is 5 or more, preferably 7.5 or more, and 15 or more It is more preferable, and it is still more preferable that it is 30 or more. According to this aspect, the film|membrane which can block light in the range of wavelength 400-950 nm and can transmit infrared rays with a wavelength of 1040 nm can be formed.

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 maximum value in the wavelength range of 400 to 640 nm of the transmittance of light in the thickness direction of the film is 20% or less It is preferable that the minimum value in the range of wavelength 1100-1300 nm of the transmittance|permeability of the light in the thickness direction of a film|membrane satisfy|fills the spectral characteristic of 70 % or more. 15% or less is preferable and, as for the maximum in the range of wavelength 400-640 nm, 10 % or less is more preferable. 75 % or more is preferable and, as for the minimum in the range of wavelength 1100-1300 nm, 80 % or more is more preferable.

As for the composition for infrared transmission filters, it is more preferable that the spectral characteristic in any one of the following (11)-(14) is satisfy|filled.

(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 maximum value in the wavelength range of 400 to 640 nm of the transmittance of light in the thickness direction of the film 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 maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20 % or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance of light in the film thickness direction 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 maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20 % or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance of light in the film thickness direction 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 maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20 % or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance of light in the film thickness direction in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75%) or more, more preferably 80% or more).

It is preferable that the composition for pixel formation used by this invention contains a polymeric compound and a photoinitiator.

<<Photoinitiator>>

It is preferable that a photoinitiator is a photoradical polymerization initiator. As a photoinitiator, it is preferable to contain at least 1 sort(s) of compound chosen from an alkylphenone compound, an acylphosphine compound, a benzophenone compound, a thioxanthone compound, a triazine compound, and an oxime compound, It is more preferable to contain an oxime compound desirable.

Examples of the alkylphenone compound include a benzyldimethyl ketal compound, an α-hydroxyketone compound, and an α-aminoketone compound.

Examples of the benzyldimethyl ketal compound include 2,2-dimethoxy-2-phenylacetophenone. As a commercial item, IRGACURE-651 (made by BASF) etc. are mentioned.

Examples of the α-hydroxyalkylphenone compound include compounds represented by the following formula (V-1).

Formula (V-1)

[Formula 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 is 0 to 4 represents an integer.

Examples of the substituent represented by Rv ¹ include 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. A straight chain or a branch is preferable and, as for an alkyl group and an alkoxy group, a straight chain is more preferable. The alkyl group, alkoxy group, and aralkyl group represented by ^{Rv 1 may be unsubstituted or may have a substituent.} A hydroxyl group etc. are mentioned as a substituent.

Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent. As a substituent, a C1-C10 alkyl group and a C6-C20 aryl group are preferable. Further, 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). A straight chain or branch is preferable and, as for an alkyl group, a straight chain is more preferable.

Specific examples of the α-hydroxyalkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 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-propane) onyl)-benzyl]phenyl}-2-methyl-propan-1-one; and the like. As a commercial item of (alpha)-hydroxyalkylphenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, BASF company make), etc. are mentioned.

Examples of the α-aminoalkylphenone compound include compounds represented by the following formula (V-2).

[Formula 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 combine with each other to form a ring.

The ^{alkyl group represented by R 1D} and R ^2D may be linear, branched or cyclic, and linear or branched is preferable.

The ^{alkyl group represented by R 1D} and R ^2D may be unsubstituted or may have a substituent. 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.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As for carbon number of the alkyl group which ^{R Y1} and R ^{Y2 represent, 1-20 are preferable.} The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched.

6-20 are preferable, as for carbon number of the aryl group which the aryl group and R ^Y1 and R ^Y2 represent as a substituent, 6-15 are more preferable, and 6-10 are still more preferable. A monocyclic ring may be sufficient as an aryl group, and a condensed ring may be sufficient as it.

The ^{heterocyclic group represented by R Y1} and R ^Y2 is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be monocyclic or a condensed ring may be sufficient as it. 3-30 are preferable, as for the number of carbon atoms which comprise a heterocyclic group, 3-18 are more preferable, 3-12 are still more preferable. The number of hetero atoms constituting the heterocyclic group is preferably 1-3. 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. When R ^3D and R ^4D are bonded to form a ring, they may be directly bonded to form a ring, or may be bonded to each other via -CO-, -O- or -NH- to form a ring. For example, ^{as a ring in which R 3D} and R ^4D are formed via -O-, a morpholine ring etc. are mentioned.

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. When R ^7E and R ^8E are bonded to form a ring, they may be directly bonded to form a ring, or may be bonded to each other through -CO-, -O- or -NH- to form a ring. For example, ^{as a ring in which R 7E} and R ^8E are formed via -O-, a morpholine ring etc. are mentioned.

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. can be heard As a commercial item of (alpha)- aminoalkylphenone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379 (above, BASF company make), etc. are mentioned.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbo). nyl) benzophenone and 2,4,6-trimethylbenzophenone.

As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy thioxanthones and the like.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4). -Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloro) To methyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) tenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

As an oxime compound, Paragraph No. 0212 of International Publication No. WO2016/190162 - description of 0236 can be considered into consideration, and this content is integrated in this specification. Moreover, as an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, the compound of Unexamined-Japanese-Patent No. 2006-342166, Unexamined-Japanese-Patent No. 2016-021012 The compounds described in , etc. can be used. Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminopentan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) ) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like. In addition, JCS Perkin II (1979, pp. 1653-1660), JCS Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Patent Laid-Open Patent Publication The compound of Unexamined-Japanese-Patent No. 2000-066385, Unexamined-Japanese-Patent No. 2000-080068, Unexamined-Japanese-Patent No. 2004-534797, Unexamined-Japanese-Patent No. 2006-342166, etc. are mentioned. As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd. ) agent),), Adeka Optomer N-1919 (made by ADEKA Co., Ltd., the photoinitiator 2 of Unexamined-Japanese-Patent No. 2012-014052) are mentioned. Moreover, as an oxime compound, it is also preferable to use the compound which does not have colorability, or the compound which transparency is high and is hard to discolor other components. As a commercial item, ADEKA ARCL's NCI-730, NCI-831, NCI-930 (above, ADEKA Co., Ltd. product) etc. are mentioned.

In this invention, as a photoinitiator, the oxime compound which has a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 is mentioned. This content is incorporated herein by reference.

In this invention, as a photoinitiator, the oxime compound which has a fluorine atom can also be used. As a specific example of the oxime compound which has a fluorine atom, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24, 36-40 of Unexamined-Japanese-Patent No. 2014-500852, and the compound of Unexamined-Japanese-Patent No. 2013-164471. (C-3) etc. are mentioned. This content is incorporated herein by reference.

In this invention, the oxime compound which has a nitro group can be used as a photoinitiator. It is also preferable to use the oxime compound which has a nitro group as a dimer. As a specific example of the oxime compound which has a nitro group, Paragraph Nos. 0031 to 0047 of Unexamined-Japanese-Patent No. 2013-114249, Paragraph Nos. 0008 to 0012, 0070 to 0079 of Unexamined-Japanese-Patent No. 2014-137466, Japanese Patent Publication The compound described in Paragraph No. 0007-0025 of 4223071, Adeka Arcles NCI-831 (made by ADEKA Corporation) is mentioned.

In this invention, as a photoinitiator, the oxime compound which has a benzofuran frame|skeleton can also be used. As a specific example, OE-01 - OE-75 described in International Publication WO2015/036910 are mentioned.

Although the specific example of the oxime compound preferably used in this invention is shown below, this invention is not limited to these.

[Formula 15]

[Formula 16]

As for content of a photoinitiator, 0.1-30 mass % is preferable with respect to the total solid of the composition for pixel formation. The lower limit is, for example, more preferably 0.5 mass % or more, and still more preferably 1 mass % or more. The upper limit is, for example, more preferably 25 mass % or less, and still more preferably 20 mass % or less. A photoinitiator may exist individually by 1 type, and may use 2 or more types together. When using 2 or more types of photoinitiators together, it is preferable that a total amount becomes the said range.

<<Polymerizable compound>>

Examples of the polymerizable compound include compounds having a group having an ethylenically unsaturated bond, and the like, preferably a compound having two or more groups having an ethylenically unsaturated bond, and a compound having three or more groups having an ethylenically unsaturated bond more preferably. 15 or less are preferable, for example, and, as for the upper limit of the number of objects of group which has an ethylenically unsaturated bond, 6 or less are more preferable. As group which has an ethylenically unsaturated bond, a vinyl group, a styryl group, (meth)allyl group, (meth)acryloyl group, etc. are mentioned, A (meth)acryloyl group is preferable. It is preferable that it is a 3-15 functional (meth)acrylate compound, and, as for a polymeric compound, it is more preferable that it is a 3-6 functional (meth)acrylate compound. Moreover, it is preferable that a polymeric compound is a radically polymerizable compound.

Although any form of a monomer and a polymer may be sufficient as a polymeric compound, a monomer is preferable. It is preferable that the molecular weight of the polymeric compound of a monomer type is 200-3000. 2500 or less are preferable and, as for the upper limit of molecular weight, 2000 or less are more preferable. 250 or more are preferable and, as for the minimum of molecular weight, 300 or more are more preferable.

As an example of a polymeric compound, Paragraph No. 0033 of Unexamined-Japanese-Patent No. 2013-253224 - description of 0034 can be considered into consideration, and this content is integrated in this specification. Examples of the polymerizable compound include ethylene oxy-modified pentaerythritol tetraacrylate (commercially available, NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available, KAYARAD D-330) ; Nippon Kayaku Co., Ltd. product), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd. product), dipentaerythritol penta (meth) acrylate (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; Shin-Nakamura Chemical Co., Ltd.) ) agent), and a compound having a structure in which (meth)acryloyl groups are bonded via an ethylene glycol residue and/or a propylene glycol residue are preferable. Moreover, these oligomer types can also be used. Moreover, Paragraph No. 0034 of Unexamined-Japanese-Patent No. 2013-253224 - description of 0038 can be considered into consideration, and this content is integrated in this specification. Moreover, the polymerizable monomer etc. of Paragraph No. 0477 of Unexamined-Japanese-Patent No. 2012-208494 (paragraph No. 0585 of the corresponding U.S. Patent Application Publication No. 2012/0235099) are mentioned, These content is integrated in this specification. Moreover, diglycerol EO (ethylene oxide) modified (meth)acrylate (as a commercial item, M-460; Toagosei make), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd. product, A-TMMT), 1 ,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd. product, KAYARAD HDDA) is also preferable. These oligomeric types 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) can also be used as a radically polymerizable compound.

The compound which has acidic groups, such as a carboxyl group, a sulfo group, and a phosphoric acid group, may be sufficient as a polymeric compound. Examples of the polymerizable compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A polymerizable compound in which an acid group is given by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaeryth ritol and/or dipentaerythritol. As a commercial item, Aronix M-305, M-510, M-520 (above, Toagosei Co., Ltd. product) etc. are mentioned, for example. As for the acid value of the polymeric compound which has an acidic radical, 0.1-40 mgKOH/g is preferable. The lower limit is preferably 5 mgKOH/g or more. As for an upper limit, 30 mgKOH/g or less is preferable.

It is also a preferable aspect that a polymeric compound is a compound which has a caprolactone structure. Although it does not specifically limit as a polymeric compound which has a caprolactone structure as long as it has a caprolactone structure in a molecule|numerator, For example, trimethylolethane, ditrimethylolethane, trimethylol propane, ditrimethylol propane , pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, polyhydric alcohols such as trimethylolmelamine, (meth)acrylic acid and ε-caprolactone obtained by esterifying, ε-caprolactone modified polyfunctional (meth)acrylates are mentioned. As a polymeric compound which has a caprolactone structure, Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2013-253224 - description of 0045 can be considered into consideration, and this content is integrated in this specification. The compound having a caprolactone structure is, for example, an ethyleneoxy chain manufactured by Sartomer, such as DPCA-20, DPCA-30, DPCA-60, DPCA-120, commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. SR-494 which is a tetrafunctional acrylate which has 4, TPA-330 which is a trifunctional acrylate which has 3 isobutyleneoxy chain|strands, etc. are mentioned.

As the polymerizable compound, urethe described in Japanese Patent Application Laid-Open No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 2-032293, and Japanese Unexamined Patent Publication No. 2-016765. Phosphorus acrylates and ethylene oxide described in Japanese Patent Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, and Japanese Publication No. 62-039418 Urethane compounds having a system skeleton are also suitable. In addition, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 1-105238 are disclosed. Available. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), 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 (made by Kyoeisha Chemical Co., Ltd.) etc. are mentioned. Moreover, it is also preferable to use 8UH-1006, 8UH-1012 (made by Daisei Fine Chemicals Co., Ltd.) as a radically polymerizable compound.

As for content of a polymeric compound, 0.1-40 mass % is preferable with respect to the total solid of the composition for pixel formation. The lower limit is, for example, more preferably 0.5 mass % or more, and still more preferably 1 mass % or more. The upper limit is, for example, more preferably 30 mass % or less, and still more preferably 20 mass % or less. A polymeric compound may exist individually by 1 type, and may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that those total amounts become the said range.

<<Color material>>

It is preferable that the composition for pixel formation used by this invention contains a color material. The content of the color material is preferably 10% by mass or more with respect to the total solid content of the composition for pixel formation, more preferably 20% by mass or more, still more preferably 30% by mass or more, and still more preferably 40% by mass or more, It is especially preferable that it is 50 mass % or more. When content of a color material is 40 mass % or more, it is easy to form a pixel with favorable spectral characteristics in a thin film. 80 mass % or less is preferable, as for an upper limit, 75 mass % or less is more preferable, and its 70 mass % or less is more preferable. Examples of the color material include a chromatic colorant, a black colorant, a colorant (light-shielding material) that blocks visible light, which will be described later, and an infrared-absorbing dye.

Moreover, when the composition for pixel formation is a composition for color filters, it is preferable to use a chromatic coloring agent as a color material. The composition for color filters WHEREIN: It is preferable that content of a chromatic coloring agent is 10 mass % or more with respect to the total solid of the composition for pixel formation, It is more preferable that it is 20 mass % or more, It is more preferable that it is 30 mass % or more, It is 40 mass % % or more is more preferable, and 50 mass % or more is particularly preferable. 80 mass % or less is preferable, as for an upper limit, 75 mass % or less is more preferable, and its 70 mass % or less is more preferable. In addition, in this invention, a chromatic coloring agent means coloring agents 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, it is also preferable to use together a light shielding material and an infrared ray absorbing dye as a color material. In the composition for infrared transmission filters, the infrared absorption dye has a role of limiting the transmitted light (infrared rays) to the longer wavelength side.

In the composition for an infrared transmission filter, the content of the light-shielding material is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the composition for an infrared transmission filter, 40 It is still more preferable that it is mass % or more, and it is especially preferable that it is 50 mass % or more. 80 mass % or less is preferable, as for an upper limit, 75 mass % or less is more preferable, and its 70 mass % or less is more preferable.

Moreover, when the composition for infrared transmission filters contains an infrared absorption dye, it is preferable that the total amount of an infrared absorption dye and a light shielding material is 10 mass % or more with respect to the total solid of the composition for infrared transmission filters, It is 20 mass % or more More preferably, it is more preferable that it is 30 mass % or more, It is still more preferable that it is 40 mass % or more, It is especially preferable that it is 50 mass % or more. 80 mass % or less is preferable, as for an upper limit, 75 mass % or less is more preferable, and its 70 mass % or less is more preferable. 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 %. 30 mass % or less is preferable and, as for an upper limit, 25 mass % or less is more preferable. 10 mass % or more is preferable and, as for a minimum, 15 mass % or more is more preferable.

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

(chromatic colorant)

As a chromatic colorant, a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, an orange colorant, etc. are mentioned. A pigment may be sufficient as a chromatic coloring agent, and dye may be sufficient as it. Preferably it is a pigment. The average particle diameter (r) of the pigment is preferably 20 nm ≤ r ≤ 300 nm, more preferably 25 nm ≤ r ≤ 250 nm, and still more preferably 30 nm ≤ r ≤ 200 nm. "Average particle diameter" as used herein means the average particle diameter with respect to the secondary particle|grains which the primary particle of a pigment aggregated. In addition, as for the particle size distribution (hereinafter, simply referred to as "particle size distribution") of the secondary particles of the pigment that can be used, it is preferable that the secondary particles included in the average particle size range of ±100 nm are 70 mass% or more of the total, 80 It is more preferable that it is mass % or more. In addition, the particle size distribution of a secondary particle can be measured using scattering intensity distribution.

It is preferable that a pigment is an organic pigment. Examples of the organic pigment include the following.

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 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. (over, orange pigment),

CI 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. red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (over, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),

C. I. 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 pigment);

These organic pigments can be used individually or in various combinations.

There is no restriction|limiting in particular as dye, A well-known dye can be used. As a chemical structure, it is a pyrazolazo type, an anilinoazo type, a triarylmethane type, an anthraquinone type, an anthrapyridone type, a benzylidene type, an oxonol type, a pyrazolotriazolazo type, a pyridonazo type, a cyanine type, and a phenothiazine type. Dyes, such as a pyrrolopyrazole azomethine type, a xanthene type, a phthalocyanine type, a benzopyran type, an indigo type, a pyromethene type, can be used. Moreover, you may use the multimer of these dyes. Moreover, the dye of Unexamined-Japanese-Patent No. 2015-028144 and Unexamined-Japanese-Patent No. 2015-034966 can also be used.

(black colorant)

Examples of the black colorant include inorganic black colorants such as carbon black, metal acid nitride (titanium black, etc.), metal nitride (titanium nitride, etc.), bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, and the like. of organic black colorants. As an organic black coloring agent, a bisbenzofuranone compound and a perylene compound are preferable. As a bisbenzofuranone compound, the compound of Unexamined-Japanese-Patent No. 2010-534726, Unexamined-Japanese-Patent No. 2012-515233, Unexamined-Japanese-Patent No. 2012-515234 etc. are mentioned, For example, "Irgaphor by BASF Corporation" Black". Examples of the perylene compound include C. I. Pigment Black 31 and 32. As an azomethine compound, the thing of Unexamined-Japanese-Patent No. 1-170601, Unexamined-Japanese-Patent No. 2-034664, etc. are mentioned, For example, it obtained as "chromofine black A1103" by Dainichi Seika Co., Ltd. can do. The bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.

[Formula 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 from 0 to 4, and a is 2 In the case of or more, a plurality of R ³ may be the same or different, a plurality of R ³ may be bonded to form a ring, and when b is 2 or more, a plurality of R ⁴ may be the same or different, and a plurality R ^{4 of} may be bonded to form a ring.

The ^{substituents represented by R 1} to R ⁴ are halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, -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 is represented, and R301 to R318 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

About the detail of a bisbenzofuranone compound, Paragraph No. 0014 of Unexamined-Japanese-Patent No. 2010-534726 - description of 0037 can be considered into consideration, and this content is integrated in this specification.

(Color material that blocks visible light)

It is preferable that the color material which blocks visible light (henceforth a light-shielding material) is a color material which absorbs light in the wavelength range of purple to red. Moreover, in this invention, it is preferable that the light-shielding material is a color material which light-shields the light of the wavelength range of wavelength 400-640 nm. Moreover, it is preferable that the light-shielding material is a color material which transmits the light of wavelength 1100-1300 nm. It is preferable that the light-shielding material satisfy|fills the requirement of at least one of the following (1) and (2).

(1): Two or more kinds of chromatic colorants are included, and black is formed by a combination of two or more kinds of chromatic colorants.

(2): An organic black colorant is included. Aspect of (2) WHEREIN: It is also preferable to contain a chromatic coloring agent further. As for the organic type black coloring agent, the coloring agent which has a maximum absorption wavelength in the wavelength range of 400 nm or more and 700 nm or less is preferable.

The light-shielding material preferably has an A/B ratio of, for example, 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 of 4.5 or more. The above characteristics may be satisfied by one type of material, or may be satisfied by a combination of a plurality of materials. For example, in the case of the aspect (1), it is preferable to combine a plurality of chromatic colorants to satisfy the above spectral properties. Moreover, in the case of the aspect of said (2), the organic type black coloring agent may satisfy|fill the said spectral characteristic. Moreover, the said spectral characteristic may be satisfy|filled by the combination of an organic type black colorant and a chromatic colorant.

It is preferable that a light-shielding material contains 2 or more types chosen from a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, and a green coloring agent. That is, it is preferable that the light-shielding material forms black with the combination of 2 or more types of coloring agents chosen from a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, and a green coloring agent. As a preferable combination, the following are mentioned, for example.

(1) An aspect containing a red colorant and a blue colorant.

(2) An aspect containing a red colorant, a blue colorant, and a yellow colorant.

(3) An aspect containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.

(4) Aspects containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.

(5) An aspect containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.

(6) An aspect containing a red colorant, a blue colorant, and a green colorant.

(7) An aspect containing a yellow colorant and a purple colorant.

In the aspect of the above (1), the mass ratio of the red colorant and the blue colorant is preferably red colorant:blue colorant=20 to 80:20 to 80, more preferably 20 to 60:40 to 80, It is more preferable that it is 20-50:50-80.

In the aspect of the above (2), the mass ratio of the red colorant, the blue colorant, and the yellow colorant is preferably a red colorant: a blue colorant: a yellow colorant=10 to 80:20 to 80:10 to 40, and 10 to 60: It is more preferable that it is 30-80:10-30, and it is more preferable that it is 10-40:40-80:10-20.

In the aspect of said (3), the mass ratio of a red colorant, a blue colorant, a yellow colorant, and a purple colorant is red colorant:blue colorant:yellow colorant:purple colorant=10-80:20-80:5-40:5 It is preferable that it is -40, It is more preferable that it is 10-60:30-80:5-30:5-30, It is more preferable that it is 10-40:40-80:5-20:5-20.

In the aspect of the above (4), the mass ratio of the red colorant, the blue colorant, the yellow colorant, the purple colorant, and the green colorant is: red colorant:blue colorant:yellow colorant:purple colorant:green colorant=10 to 80:20 to 80: It is preferable that it is 5-40:5-40:5-40, It is more preferable that it is 10-60:30-80:5-30:5-30:5-30, It is 10-40:40-80:5 It is more preferable that it is -20:5-20:5-20.

In the aspect of the above (5), the mass ratio of the red colorant, the blue colorant, the yellow colorant, and the green colorant is: red colorant:blue colorant:yellow colorant:green colorant=10 to 80:20 to 80:5 to 40:5 to It is preferable that it is 40, It is more preferable that it is 10-60:30-80:5-30:5-30, It is more preferable that it is 10-40:40-80:5-20:5-20.

In the aspect of the above (6), the mass ratio of the red colorant, the blue colorant, and the green colorant is preferably a red colorant: a blue colorant: a green colorant=10 to 80:20 to 80:10 to 40, and 10 to 60: It is more preferable that it is 30-80:10-30, and it is more preferable that it is 10-40:40-80:10-20.

In the aspect of the above (7), the mass ratio of the yellow colorant and the purple colorant is preferably yellow colorant:purple colorant=10-50:40-80, more preferably 20-40:50-70, 30 It is more preferable that it is -40:60-70.

As the yellow colorant, C. I. Pigment Yellow 139, 150, and 185 are preferable, C. I. Pigment Yellow 139, 150 are more preferable, and C. I. Pigment Yellow 139 is more 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 a red colorant, Pigment Red 122, 177, 224, 254 is preferable, Pigment Red 122, 177, 254 is more preferable, and Pigment Red 254 is more preferable. As the green colorant, C. I. Pigment Green 7, 36, 58, 59 are preferable.

When using an organic black colorant as a light-shielding material, it is preferable to use it in combination with a chromatic colorant. By using together an organic type black coloring agent and a chromatic coloring agent, the outstanding optical characteristic is easy to be obtained. As a chromatic colorant used in combination with an organic type black colorant, a red colorant, a blue colorant, a purple colorant etc. are mentioned, for example, A red colorant and a blue colorant are preferable. These may be used independently and may use 2 or more types together. Moreover, 10-200 mass parts of a chromatic coloring agent is preferable with respect to 100 mass parts of organic type black coloring agents, and, as for the mixing ratio of a chromatic coloring agent and an organic type black coloring agent, 15-150 mass parts is more preferable.

It is preferable that it is 95 mass % or more with respect to the whole quantity of a light-shielding material, as for content of the pigment in a light-shielding material, it is more preferable that it is 97 mass % or more, It is more preferable that it is 99 mass % or more.

(Infrared absorbing dye)

As the infrared absorbing dye, a compound having a maximum absorption wavelength in the near-infrared region (preferably in the wavelength range of 700 to 1300 nm) is preferable. A pigment may be sufficient as an infrared ray absorbing dye, and dye may be sufficient as it.

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 ?-conjugated plane of the infrared absorbing compound is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, and particularly preferably 30 or more. It is preferable that it is 80 or less, and, as for an upper limit, it is more preferable that it is 50 or less, for example.

The π-conjugated plane of the infrared absorbing compound preferably contains two or more monocyclic or condensed aromatic rings, more preferably three or more aromatic rings, and includes four or more aromatic rings. It is more preferable to do this, and it is especially preferable to contain 5 or more of the above-mentioned aromatic rings. 100 or less are preferable, as for an upper limit, 50 or less are more preferable, and 30 or less are still more preferable. Examples of the aforementioned aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indecene ring, a perylene ring, a pentacene ring, a quaterrylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, Chrysene ring, triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring , oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, isoindole ring, carbazole ring, and Condensed rings which have these rings are mentioned.

It is preferable that an infrared ray absorbing compound is a compound which has a maximum absorption wavelength in the range of wavelength 700-1000 nm. In addition, in the present specification, "having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm" means having a wavelength showing the maximum absorbance in a wavelength range of 700 to 1000 nm in an absorption spectrum in a solution of an infrared absorbing compound. means that Chloroform, methanol, dimethyl sulfoxide, ethyl acetate, and tetrahydrofuran are mentioned as a measurement solvent used for the measurement of the absorption spectrum in the solution of an infrared-absorbing compound. In the case of a compound soluble in chloroform, chloroform is used as the measurement solvent. For compounds that do not dissolve in chloroform, methanol is used. Moreover, when it does not dissolve in either chloroform or methanol, dimethyl sulfoxide is used.

In the present invention, the infrared absorbing compound is a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterrylene compound, a merocyanine compound, a croconium compound, oxo At least one selected from a nol compound, a diimmonium compound, a dithiol compound, a triarylmethane compound, a pyromethene compound, an azomethine compound, an anthraquinone compound, and a dibenzofuranone compound is preferable, and a pyrrolopyrrole compound , at least one selected from a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, and a diimmonium compound is more preferable, from a pyrrolopyrrole compound, a cyanine compound and a squarylium compound At least 1 type selected is more preferable, and a pyrrolopyrrole compound is especially preferable. As a diimmonium compound, the compound of Unexamined-Japanese-Patent No. 2008-528706 is mentioned, for example, This content is integrated in this specification. As a phthalocyanine compound, For example, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153, the oxytitanium phthalocyanine of Unexamined-Japanese-Patent No. 2006-343631, Unexamined-Japanese-Patent No. 2013-195480 Paragraph Nos. 0013 - the compound of 0029 is mentioned, These content is integrated in this specification. As a naphthalocyanine compound, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned, for example, This content is integrated in this specification. In addition, the cyanine compound, the phthalocyanine compound, the naphthalocyanine compound, the diimmonium compound, and the squarylium compound may use the compound described in Paragraph No. 0010-0081 of Unexamined-Japanese-Patent No. 2010-111750, This content is incorporated herein by reference. In addition, for a cyanine compound, "functional pigment, Makoto Ogawara / Masaru Matsuoka / Daiiro Kitao / Tsuneaki Hirashima, by Kodansha Scientific" can be referred to, for example, the content of which is incorporated herein by reference, for example. do. Moreover, as an infrared-absorbing compound, the compound of Unexamined-Japanese-Patent No. 2016-146619 can also be used, and this content is integrated in this specification.

As a pyrrolopyrrole compound, it is preferable that it is a compound represented by Formula (PP).

[Formula 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, R ² and R ³ are bonded to each other A ring may be formed, and 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 is from R ^1a , R ^1b and R ³ . At least one selected may be covalently bonded or coordinated, and R ^4A and R ^4B each independently represent a substituent. About the detail of Formula (PP), Paragraph Nos. 0017-0047 of Unexamined-Japanese-Patent No. 2009-263614, Paragraph Nos. 0011-0036 of Unexamined-Japanese-Patent No. 2011-068731, Paragraph Nos. 0010-0024 of International Publication WO2015/166873 Reference may be made to the description, the contents of which are incorporated herein by reference.

R ^1a and R ^1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. Moreover, the alkyl group, the aryl group, and the heteroaryl group which ^R<1a> and R< ^{1b represent may have a substituent, and 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 , and -SO ₂ R ¹³ . R ¹¹ to R ¹³ each independently represent a hydrocarbon group or a heteroaryl group. Moreover, as a substituent, Paragraph No. 0020 of Unexamined-Japanese-Patent No. 2009-263614 - the substituent of 0022 is mentioned. Especially, as a substituent, an alkoxy group, a hydroxyl group, a cyano group, a nitro group, -OCOR ¹¹ , -SOR ¹² , and -SO ₂ R ¹³ are preferable. The ^{group represented by R 1a} and R ^1b is preferably an aryl group having an alkoxy group having a branched alkyl group as a substituent, an aryl group having a hydroxyl group as a substituent, or an aryl group having a group represented by ^{-OCOR 11 as a substituent.} 3-30 are preferable and, as for carbon number of a branched alkyl group, 3-20 are more preferable.

At least one of R ² and R ³ preferably represents an electron withdrawing group, R ² represents an electron withdrawing group (preferably a cyano group), and R ³ more preferably represents a heteroaryl group. As for the heteroaryl group, a 5-membered ring or a 6-membered ring is preferable. Moreover, monocyclic or condensed ring is preferable, as for heteroaryl group, monocyclic or condensed ring of 2-8 condensed ring is preferable, and monocyclic or condensed ring of 2-4 condensed ring is more preferable. 1-3 are preferable and, as for the number of the hetero atoms which comprise a heteroaryl group, 1-2 are more preferable. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example. The heteroaryl group preferably has one or more nitrogen atoms. ^{Two R<2>} in Formula (PP) may be same or different. ^{Moreover, two R<3>} in Formula (PP) may be same or different.

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 , more preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by ^{-BR 4A} R ^{4B, -} It is more preferably a group represented by BR ^4A R ^4B. 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 further have a substituent. ^{Two R<4>} in Formula (PP) may be same or different.

The following compound is mentioned as a specific example of the compound represented by Formula (PP). In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. Moreover, as a pyrrolopyrrole compound, the compound described in Paragraph Nos. 0016 to 0058 of Unexamined-Japanese-Patent No. 2009-263614, the compound of Paragraph No. 0037-0052 of Unexamined-Japanese-Patent No. 2011-068731, Paragraph of International Publication No. WO2015/166873 The compounds of numbers 0010 - 0033 etc. are mentioned, These content is integrated in this specification.

[Formula 19]

As a squarylium compound, the compound represented by a following formula (SQ) is preferable.

[Formula 20]

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

[Formula 21]

In the formula (A-1), Z ¹ represents a non-metal atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a broken line ) indicates a connecting hand. For the details of the formula (SQ), Paragraph Nos. 0020 to 0049 of Unexamined Patent Publication No. 2011-208101, Paragraph Nos. 0043 to 0062 of Unexamined Japanese Patent No. 6065169, Paragraph Nos. 0024 to 0040 of International Publication No. WO2016/181987. reference, the contents of which are incorporated herein by reference.

In addition, in Formula (SQ), a cation delocalizes and exists as follows.

[Formula 22]

As for a squarylium compound, the compound represented by a following formula (SQ-1) is preferable.

[Formula 23]

Ring A and ring B each independently represent an aromatic ring,

X ^A and X ^B each independently represents a substituent,

G ^A and G ^B each independently represent a substituent,

kA represents an integer from 0 to n _A , kB represents an integer from 0 to n _B ,

n _A and n _B each represent the largest integer substitutable for ring A or ring B,

When X ^A and G ^A, X ^B and G ^B, X ^A and X ^B is being bonded to form a ring, G ^A and G ^B are multiple presence each are, may form a ring structure by bonding with each other do.

Examples ^{of the substituent represented by G A} and G ^B include the substituent T described in the above formula (PP).

The ^{substituent represented by X A} and X ^B is preferably a group having an 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, and -OH, -SH and -NR ^X1 R ^X2 are more preferred. R ^X1 and R ^X1 each independently represent a hydrogen atom or a substituent. As ^{a substituent which X A} and X ^B represent, an alkyl group, an aryl group, or a heteroaryl group is mentioned, An alkyl group is preferable.

Ring A and ring B each independently represent an aromatic ring. A monocyclic ring may be sufficient as an aromatic ring, and a condensed ring may be sufficient as it. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indecene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenyl Lene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring Ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring , an acridine ring, a phenanthroline ring, a cyanthrene ring, a chromene ring, a xanthene ring, a phenoxacyin ring, a phenothiazine ring, and a phenazine ring are mentioned, A benzene ring or a naphthalene ring is preferable. Unsubstituted may be sufficient as an aromatic ring, and may have a substituent. As a substituent, the substituent T demonstrated by Formula (PP) mentioned above is mentioned.

X ^A with G ^A, X ^B and G ^B, X ^A and X ^B is being bonded to form a ring, if there is a G ^A and G ^B multiple presence each are bonded to each other may form a ring . As a ring, a 5-membered ring or a 6-membered ring is preferable. A monocyclic ring may be sufficient as a ring, and a condensed ring may be sufficient as it. When X in the ^A and G ^A, G ^B and X ^B, X ^A and X ^B, G ^A or G ^B bonded together with each other to form a ring, and also they are attached directly to form a ring, an alkylene group, -CO- , -O-, -NH-, -BR-, and a divalent linking group comprising a combination thereof may be bonded to each other to form a ring. R represents a hydrogen atom or a substituent. As a substituent, the substituent T demonstrated by Formula (PP) mentioned above is mentioned, An alkyl group or an aryl group is preferable.

kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, n _A represents the maximum integer substitutable for ring A, and n _B represents the maximum integer substitutable for ring B. 0-4 are preferable, respectively independently, 0-2 are more preferable, 0-1 are especially preferable, as for kA and kB.

It is also preferable that a squarylium compound is a compound represented by a following formula (SQ-10), a formula (SQ-11), or a formula (SQ-12).

Formula (SQ-10)

[Formula 24]

Formula (SQ-11)

[Formula 25]

Formula (SQ-12)

[Formula 26]

In Formulas (SQ-10) to (SQ-12), X is independently Formula (1) or Formula (2) in which one or more hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group ) is a divalent organic group represented by

-(CH ₂ ) _n1 -... (One)

In formula (1), n1 is 2 or 3.

-(CH ₂ ) _n2 -O-(CH ₂ ) _n3 -... (2)

In formula (2), n2 and n3 are each independently an integer of 0-2, 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 and may be unsubstituted. As a substituent, the substituent T demonstrated by Formula (PP) mentioned above 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 squarylium compound, the compound of the following structure is mentioned. In the following structural formulas, EH represents an ethylhexyl group. Moreover, the compound of Paragraph No. 0044 of Unexamined-Japanese-Patent No. 2011-208101 - 0049, the compound of Paragraph No. 0060 - 0061 of Unexamined-Japanese-Patent No. 6065169, The compound of Paragraph No. 0040 of International Publication WO2016/181987, JP-A The compound described in Patent Publication No. 2015-176046, etc. are mentioned, These content is integrated in this specification.

[Formula 27]

As for a cyanine compound, the compound represented by Formula (C) is preferable.

Formula (C)

[Formula 28]

In the formula, Z ¹ and Z ² are each independently a non-metal atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle which may be condensed,

R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,

L ¹ represents a metaprint with an odd number of metapopularities,

a and b are each independently 0 or 1,

When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,

When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a number necessary to balance charges, and when the moiety represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c represents the number necessary to balance the charges, and c is 0 when the charge at the site represented by Cy in the formula is neutralized in the molecule.

As a specific example of a cyanine compound, the compound shown below is mentioned. In the following structural formulas, Me represents a methyl group. Moreover, as a cyanine compound, the compound of Paragraph Nos. 0044 - 0045 of Unexamined-Japanese-Patent No. 2009-108267, the compound of Paragraph No. 0026 - 0030 of Unexamined-Japanese-Patent No. 2002-194040, Unexamined-Japanese-Patent No. 2015-172004 The compound of the description, the compound of Unexamined-Japanese-Patent No. 2015-172102, the compound of Unexamined-Japanese-Patent No. 2008-088426, etc. are mentioned, These content is integrated in this specification.

[Formula 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 (manufactured by Nippon Shokubai), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (manufactured by Hakko Chemical), EpoliteV-63, Epolight3801, Epolight3036 (manufactured by EPOLIN), PRO-JET825LDI (manufactured by Fujifilm Co., Ltd.), NK-3027, NK-5060 (manufactured by Hayashibara Corporation), YKR-3070 (manufactured by Mitsui Chemicals Co., Ltd.), and the like.

<<Compound having 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, oxetanyl group, etc. are mentioned. It is preferable that the compound which has a cyclic ether group is a compound which has 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, The compound which has two or more epoxy groups is preferable. It is preferable to have 1-100 epoxy groups in 1 molecule. The upper limit of the epoxy group may be, for example, 10 or less, or 5 or less. As for the minimum of an epoxy group, two or more are preferable. As a compound which has an epoxy group, Paragraph Nos. 0034 to 0036 of Unexamined-Japanese-Patent No. 2013-011869, Paragraph Nos. 0147 to 0156 of Unexamined-Japanese-Patent No. 2014-043556, Paragraph Nos. 0085 to 0092 of Unexamined-Japanese-Patent No. 2014-089408 Compounds can also be used. These contents are incorporated herein by reference.

The compound having an epoxy group may be a low molecular weight compound (for example, molecular weight less than 2000, and molecular weight less than 1000), or a high molecular weight compound (macromolecule) (for example, molecular weight 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 or more ) may be 200-100000 are preferable and, as for the weight average molecular weight of the compound which has an epoxy group, 500-50000 are more preferable. 10000 or less are preferable, as for the upper limit of a weight average molecular weight, 5000 or less are more preferable, 3000 or less are still more preferable.

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

[Formula 30]

In formula (EP1) ^{, each of R EP1} to R ^EP3 represents a hydrogen atom, a halogen atom, and an alkyl group, and the alkyl group may have a cyclic structure or may have a substituent. Moreover, R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Q ^EP represents a single bond or an n ^EP valent organic group. R ^EP1 to R ^EP3 may ^{also be bonded to Q EP} to form a ring structure. n ^EP represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. provided that when Q ^EP is a single bond, n ^EP is 2.

About ^{the detail of R EP1} -R ^EP3 , Q ^EP , Paragraph No. 0087 of Unexamined-Japanese-Patent No. 2014-089408 - description of 0088 can be considered into consideration, and this content is integrated in this specification. As a specific example of the compound represented by Formula (EP1), the compound of Paragraph 0090 of Unexamined-Japanese-Patent No. 2014-089408, Paragraph No. 0151 of Unexamined-Japanese-Patent No. 2010-054632 The compound of Paragraph No. 0151 is mentioned, This content is included in this specification is used

As a commercial item, ADEKA glycyrol series manufactured by ADEKA Co., Ltd. (for example, ADECA glycyrol ED-505 etc.), Daicel Corporation EPOLID series (eg EPOLID GT401) etc.) and the like.

As a compound which has an epoxy group, an epoxy resin can be used preferably. Examples of the epoxy resin include an epoxy resin that is a glycidyl ether of a phenol compound, an epoxy resin that is a glycidyl ether of various novolac resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, A glycidyl ester-based epoxy resin, a glycidylamine-based epoxy resin, an epoxy resin obtained by glycidylating halogenated phenols, a condensate of a silicon compound having an epoxy group and another silicon compound, and a polymerizable unsaturated having an epoxy group A copolymer of a compound and another polymerizable unsaturated compound other than that, etc. are mentioned.

It is preferable that it is 310-3300 g/eq, as for the epoxy equivalent of an epoxy resin, it is more preferable that it is 310-1700 g/eq, It is more preferable that it is 310-1000 g/eq.

A commercial item can also be used for an epoxy resin. For example, EHPE 3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Mapproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G- 1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, Nichiyu Co., Ltd. product, epoxy group containing polymer) etc. are mentioned.

When the composition for pixel formation contains the compound which has a cyclic ether group, as for content of the compound which has a cyclic ether group, 0.1-40 mass % is preferable with respect to the total solid of the composition for pixel formation. The lower limit is, for example, more preferably 0.5 mass % or more, and still more preferably 1 mass % or more. The upper limit is, for example, more preferably 30 mass % or less, and still more preferably 20 mass % or less. The compound which has a cyclic ether group may exist individually by 1 type, and may use 2 or more types together. When using together 2 or more types of compounds which have a cyclic ether group, it is preferable that a total amount becomes the said range.

Moreover, when the composition for pixel formation contains a polymeric compound and the compound which has a cyclic ether group, the mass ratio of both is polymeric compound: compound which has a cyclic ether group = 100:1-100:400 is preferable, 100:1 to 100:100 are more preferable.

<<Resin>>

It is preferable that the composition for pixel formation contains resin. The resin is blended for, for example, a use of dispersing a pigment or the like in a composition, or a use of a binder. In addition, a resin mainly used for dispersing a pigment or the like is also called a dispersing agent. However, such a use of resin is an example, and resin can also be used for purposes other than such a use.

As for the weight average molecular weight (Mw) of resin, 2,000-2,000,000 are preferable. 1,000,000 or less are preferable and, as for an upper limit, 500,000 or less are more preferable. 3,000 or more are preferable and, as for a minimum, 5,000 or more are more preferable.

As the resin, (meth)acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene Etherphosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. are mentioned. From these resins, 1 type may be used individually, and 2 or more types may be mixed and used for them. As cyclic olefin resin, norbornene resin can be used preferably from a viewpoint of a heat resistance improvement. As a commercial item of norbornene resin, the JSR Co., Ltd. product ARTON series (for example, ARTON F4520) etc. are mentioned, for example. Moreover, as resin, the resin described in the Example of international publication WO2016/088645 can also be used. Moreover, as resin, it is also preferable to use resin which has a repeating unit which has group which has an ethylenically unsaturated bond in a side chain. As group which has an ethylenically unsaturated bond, a (meth)acryloyl group etc. are mentioned. Moreover, it is preferable that the principal chain of a repeating unit and the group which has an ethylenically unsaturated bond are couple|bonded via the divalent coupling group which has an alicyclic structure.

In this invention, it is preferable to use resin which has an acidic radical as resin. According to this aspect, it is easy to form the pattern excellent in rectangular property. As an acidic radical, a carboxyl group, a phosphoric acid group, a sulfo group, phenolic hydroxyl group, etc. are mentioned, A carboxyl group is preferable. Resin which has an acidic radical can be used as alkali-soluble resin, for example.

As resin which has an acidic radical, the polymer which has a carboxyl group in a side chain is preferable. Specific examples include alkali-soluble phenol resins such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, novolac resins, and carboxyl groups in the side chain Resin which added the acid anhydride to the polymer which has an acidic cellulose derivative which has, and a hydroxyl group is mentioned. In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is suitable as alkali-soluble resin. As another monomer copolymerizable with (meth)acrylic acid, an alkyl (meth)acrylate, an aryl (meth)acrylate, a vinyl compound, etc. are mentioned. As alkyl (meth)acrylate and aryl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate , pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate , cyclohexyl (meth) acrylate, etc., as the vinyl compound, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydro Fufuryl methacrylate, a polystyrene macromonomer, a polymethyl methacrylate macromonomer, etc. are mentioned. As another monomer, the N-position substituted maleimide monomer described in Japanese Patent Application Laid-Open No. 10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide, and the like may be used. In addition, the number of other monomers copolymerizable with these (meth)acrylic acid may be one, and 2 or more types may be sufficient as them.

Resin which has an acidic radical may further have a polymeric group. As a polymeric group, an allyl group, a metharyl group, a (meth)acryloyl group, etc. are mentioned. As commercially available products, Diana NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscot R-264, KS resist 106 (all of them) Osaka Yuki Chemical Co., Ltd.), Cyclomer P series (eg, ACA230AA), Flaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (made by Daicel Yushibi Corporation), Acrycure RD- F8 (made by Nippon Shokubai Co., Ltd.) etc. are mentioned.

Resin which has an acidic radical is a benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer, benzyl (meth)acryl A multi-component copolymer composed of rate/(meth)acrylic acid/other monomers can be preferably used. Moreover, what copolymerized 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate / polystyrene macromonomer / benzyl methacrylate / meth, described in Unexamined-Japanese-Patent No. 7-140654. Acrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / A methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, etc. can also be used preferably.

The resin having an acid group is a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, such a compound may be referred to as an "ether dimer"). It is also preferable that it is a polymer containing a unit.

[Formula 31]

In formula (ED1), R<^1> and R<^2> respectively independently represent a C1-C25 hydrocarbon group which may have a hydrogen atom or a substituent.

[Formula 32]

In formula (ED2), R represents a hydrogen atom or a C1-C30 organic group. As a specific example of Formula (ED2), description of Unexamined-Japanese-Patent No. 2010-168539 can be referred.

As a specific example of an ether dimer, Paragraph No. 0317 of Unexamined-Japanese-Patent No. 2013-029760 can be considered into consideration, for example, This content is integrated in this specification. One type may be sufficient as an ether dimer, and 2 or more types may be sufficient as it.

Resin which has an acidic radical may contain the repeating unit derived from the compound represented by following formula (X).

[Formula 33]

In Formula (X), R<_1> represents a hydrogen atom or a methyl group, R<_2> represents a C2-C10 alkylene group, R<_3> is a C1-C20 alkyl group which may also contain a hydrogen atom or a benzene ring. indicates n represents the integer of 1-15.

About resin which has an acidic radical, Paragraph No. 0558 of Unexamined-Japanese-Patent No. 2012-208494 - Paragraph No. 0571 of (corresponding U.S. Patent Application Laid-Open No. 2012/0235099 Paragraph No. 0685 - 0700 of Unexamined-Japanese-Patent No. 2012-198408) Reference may be made to the description of Paragraph Nos. 0076 to 0099, the contents of which are incorporated herein by reference. Moreover, a commercial item can also be used for resin which has an acidic radical. For example, Acrybase FF-426 (made by Fujikura Kasei Co., Ltd.) etc. is mentioned.

As for the acid value of resin which has an acidic radical, 30-200 mgKOH/g is preferable. 50 mgKOH/g or more is preferable and, as for a minimum, 70 mgKOH/g or more is more preferable. 150 mgKOH/g or less is preferable and, as for an upper limit, 120 mgKOH/g or less is more preferable.

As resin which has an acidic radical, resin etc. of the following structure are mentioned, for example. In the following structural formulas, Me represents a methyl group.

[Formula 34]

The composition for infrared transmission filters may contain resin as a dispersing agent. As a dispersing agent, an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin) are mentioned. Here, an acidic dispersing agent (acidic resin) shows resin with more quantity of an acidic radical than the quantity of a basic group. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acidic groups accounts for 70 mol% or more when the total amount of the acidic group and the basic group is 100 mol%, and a resin substantially composed of only acidic groups is more preferable. . As for the acidic radical which an acidic dispersing agent (acidic resin) has, a carboxyl group is preferable. 40-105 mgKOH/g is preferable, as for the acid value of an acidic dispersing agent (acidic resin), 50-105 mgKOH/g is more preferable, 60-105 mgKOH/g is still more preferable. Moreover, a basic dispersing agent (basic resin) shows resin with more quantity of a basic group than the quantity of an acidic radical. When a basic dispersing agent (basic resin) makes the total amount of the quantity of an acidic radical and the quantity of a basic group 100 mol%, resin in which the quantity of a basic group exceeds 50 mol% is preferable. It is preferable that the basic group which a basic dispersing agent has is an amino group.

It is preferable that resin used as a dispersing agent contains the repeating unit which has an acidic radical. When resin used as a dispersing agent contains the repeating unit which has an acidic radical, when pattern-forming by the photolithographic method, the residue which generate|occur|produces on the base of a pixel can be reduced more.

It is also preferable that resin used as a dispersing agent is a graft copolymer. Since a graft copolymer has affinity with a solvent by a graft chain, it is excellent in the dispersibility of a pigment, and dispersion stability after aging. For the detail of a graft copolymer, Paragraph No. 0025 of Unexamined-Japanese-Patent No. 2012-255128 - description of 0094 can be considered into consideration, and this content is integrated in this specification. Moreover, the following resin is mentioned as a specific example of a graft copolymer. The following resin is also resin (alkali-soluble resin) which has an acidic radical. Moreover, as a graft copolymer, Paragraph No. 0072 of Unexamined-Japanese-Patent No. 2012-255128 - resin of 0094 is mentioned, This content is integrated in this specification.

[Formula 35]

Moreover, in this invention, it is also preferable to use the oligoimine type|system|group dispersing agent which contains a nitrogen atom in at least one of a main chain and a side chain as resin (dispersing agent). As the oligoimine dispersant, a resin having a side chain including a structural unit having a partial structure X having a functional group of pKa of 14 or less and a side chain Y having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain is preferable There is no restriction|limiting in particular as long as a basic nitrogen atom is a nitrogen atom which shows basicity. About the oligoimine type dispersing agent, Paragraph No. 0102 of Unexamined-Japanese-Patent No. 2012-255128 - description of 0166 can be considered into consideration, and this content is integrated in this specification. As an oligoimine type dispersing agent, resin of the following structure and the resin of Paragraph No. 0168 - 0174 of Unexamined-Japanese-Patent No. 2012-255128 can be used.

[Formula 36]

A dispersing agent is also available as a commercial item, Disperbyk-111, 161 (made by BYKChemie) etc. are mentioned as such a specific example. Moreover, Paragraph No. 0041 of Unexamined-Japanese-Patent No. 2014-130338 - the pigment dispersant of 0130 can also be used, This content is integrated in this specification. Moreover, resin etc. which have the above-mentioned acidic radical can also be used as a dispersing agent.

When the composition for pixel formation contains resin, as for content of resin, 1-60 mass % is preferable with respect to the total solid of the composition for pixel formation. 5 mass % or more is preferable and, as for a minimum, 10 mass % or more is more preferable. 50 mass % or less is preferable, as for an upper limit, 40 mass % or less is more preferable, and its 30 mass % or less is still more preferable.

When the composition for pixel formation contains resin which has an acidic radical, as for content of resin which has an acidic radical, 1-60 mass % is preferable with respect to the total solid of the composition for pixel formation. 5 mass % or more is preferable and, as for a minimum, 10 mass % or more is more preferable. 50 mass % or less is preferable, as for an upper limit, 40 mass % or less is more preferable, and its 30 mass % or less is still more preferable.

When the composition for pixel formation contains a polymeric compound and resin, it is preferable that mass ratio of a polymeric compound and resin is polymeric compound/resin =0.3-1.5. 0.4 or more are preferable and, as for the minimum of the said mass ratio, 0.5 or more are more preferable. 1.4 or less are preferable and, as for the upper limit of the said mass ratio, 1.3 or less are more preferable. If the said mass ratio is the said range, the pixel which is more excellent in rectangular property can be formed.

Moreover, it is preferable that mass ratio of a polymeric compound and resin which has an acidic radical is resin =0.4-1.4 which has a polymeric compound/acid group. 0.5 or more are preferable and, as for the minimum of the said mass ratio, 0.6 or more are more preferable. 1.3 or less are preferable and, as for the upper limit of the said mass ratio, 1.2 or less are more preferable. If the said mass ratio is the said range, the pixel which is more excellent in rectangular property can be formed.

<<Pigment Derivatives>>

The composition for pixel formation may further contain a pigment derivative. As the pigment derivative, a compound 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 phthalimidemethyl group is exemplified. As a pigment derivative, the compound represented by Formula (B1) is preferable.

[Formula 37]

In formula (B1), P represents a dye 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 phthalimidemethyl group, m represents an integer of 1 or more, n represents an integer of 1 or more, a plurality of L and X may be different from each other when m is 2 or more, and a plurality of Xs may be different from each other when n is 2 or more.

As a dye structure represented by P, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a quinacridone dye structure, an anthraquinone dye structure, a dianthraquinone dye structure, a benzisoindole dye structure, a thiazine indigo dye structure, Azo dye structure, quinophthalone dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, benzothiazole dye At least one selected from a structure, a benzimidazole pigment structure, and a benzoxazole pigment structure is preferable, and selected from a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, and a benzimidazolone pigment structure At least 1 sort(s) used are more preferable, and a pyrrolopyrrole pigment|dye structure is especially preferable.

Examples of the linking group represented by L include groups comprising 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.

Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imide acid group. As a carboxylic acid amide group, the group represented by ^{-NHCOR X1 is preferable.} As the sulfonic acid amide group, a group represented by _{-NHSO 2} R ^{X 2 is preferable.} As the imide group is preferably represented by the group ^{_{-SO 2 NHSO 2 R X3, -CONHSO}} 2 R X4, -CONHCOR X5 or -SO ₂ NHCOR ^X6. R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and heterocyclic group represented by ^{R X1} to R ^{X6 may further have a substituent.} As an additional substituent, the substituent T demonstrated by Formula (PP) mentioned above is mentioned, It is preferable that it is a halogen atom, and it is more preferable that it is a fluorine atom. An amino group is mentioned as a basic group which X represents. As a salt structure represented by X, the salt of the above-mentioned acidic group or basic group is mentioned.

As a pigment derivative, the compound of the following structure is mentioned. In addition, Japanese Patent Application Laid-Open No. 56-118462, Japanese Unexamined Patent Publication No. 63-264674, Japanese Unexamined Patent Publication No. Hei 1-217077, Japanese Unexamined Patent Publication No. 3-009961, and Japanese Unexamined Patent Publication No. 3-026767. No., Japanese Unexamined Patent Publication No. Hei 3-153780, Japanese Unexamined Patent Publication No. Hei 3-045662, Japanese Unexamined Patent Publication No. Hei 4-285669, Japanese Unexamined Patent Publication No. 6-145546, Japanese Unexamined Patent Publication No. Hei 6-212088 No., Japanese Unexamined Patent Publication No. 6-240158, Japanese Patent Application Laid-Open No. Hei 10-030063, Japanese Unexamined Patent Publication No. Hei 10-195326, International Publication No. WO2011/024896 Paragraph Nos. 0086 to 0098, International Publication No. WO2012/ Paragraph Nos. 0063 to 0094 of 102399, Paragraph Nos. 0082 of International Publication No. WO2017/038252, etc. can also be used for the compound, The content is integrated in this specification. In the following structural formulas, Et is an ethyl group.

[Formula 38]

When the composition for pixel formation contains a pigment derivative, as for content of a pigment derivative, 1-50 mass parts is preferable with respect to 100 mass parts of pigments. 3 mass parts or more are preferable and, as for a lower limit, 5 mass parts or more are more preferable. 40 mass parts or less are preferable and, as for an upper limit, 30 mass parts or less are more preferable. When content of a pigment derivative is the said range, the dispersibility of a pigment can be improved and aggregation of a pigment can be suppressed efficiently. Only 1 type may be used for a pigment derivative, and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<Solvent>>

The composition for pixel formation can contain a solvent. As a solvent, an organic solvent is mentioned. There is no restriction|limiting in particular in particular as long as a solvent satisfy|fills the solubility of each component and the applicability|paintability of a composition. Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. For details of these, reference may be made to Paragraph No. 0223 of International Publication No. WO2015/166779, the content of which is incorporated herein by reference. Moreover, the ester solvent substituted by the cyclic alkyl group and the ketone system solvent which the cyclic alkyl group substituted can also be used preferably. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Methyl oxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate and the like. In this invention, an organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, 3-methoxy-N,N- dimethylpropaneamide and 3-butoxy-N,N- dimethylpropaneamide are also preferable from a viewpoint of a solubility improvement. However, there are cases where it is better to reduce the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for reasons such as environmental reasons (for example, 50 mass ppm with respect to the total amount of the organic solvent) (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In this invention, it is preferable to use the solvent with little metal content, and it is preferable that the metal content of a solvent is 10 mass ppb (parts per billion) or less, for example. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided by, for example, Toyo Kosei Corporation (Kagaku Kogyo Nippo, November 13, 2015).

As a method of removing impurities, such as a metal, from a solvent, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter is mentioned, for example. As a filter pore diameter of the filter used for filtration, 10 micrometers or less are preferable, 5 micrometers or less are more preferable, and 3 micrometers or less are still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be contained and multiple types of isomers may be contained.

In this invention, it is preferable that the content rate of a peroxide is 0.8 mmol/L or less, and, as for the organic solvent, it is more preferable that a peroxide is not included substantially.

It is preferable that content of a solvent is 10-90 mass % with respect to the whole quantity of the composition for pixel formation, It is more preferable that it is 20-80 mass %, It is more preferable that it is 25-75 mass %. Moreover, it may be preferable that the composition for pixel formation does not contain aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for reasons, such as an environmental aspect.

<<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, pyrogallol, tert-butylcatechol, benzoquinone, and 4,4'-thiobis(3-methyl-6). -tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salt (ammonium salt, cerium salt, etc.) are mentioned. . Especially, p-methoxyphenol is preferable. As for content of a polymerization inhibitor, 0.001-5 mass % is preferable with respect to the total solid of the composition for pixel formation.

<<Silane Coupling Agent>>

The composition for pixel formation can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. Moreover, a hydrolysable group refers to the substituent which directly connects to a silicon atom and can generate|occur|produce a siloxane bond by at least any one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, as for a silane coupling agent, the compound which has an alkoxysilyl group is preferable. Moreover, as a functional group other than a hydrolysable group, For example, a vinyl group, a styryl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group etc. are mentioned, A (meth)acryloyl group and an epoxy group are preferable. As a silane coupling agent, the compound of Paragraph No. 0018 of Unexamined-Japanese-Patent No. 2009-288703 - 0036, The compound of Paragraph No. 0056 - 0066 of Unexamined-Japanese-Patent No. 2009-242604 are mentioned, These content is included in this specification is used

0.01-15.0 mass % is preferable with respect to the total solid of the composition for pixel formation, and, as for content of a silane coupling agent, 0.05-10.0 mass % is more preferable. One type may be sufficient as a silane coupling agent, and two or more types may be sufficient as it. In the case of two or more types, it is preferable that a total amount becomes the said range.

<<Surfactant>>

The composition for pixel formation may contain surfactant. As surfactant, various surfactants, such as a fluorochemical surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone type surfactant, can be used. For surfactant, reference may be made to Paragraph Nos. 0238 to 0245 of International Publication No. WO2015/166779, the contents of which are incorporated herein by reference.

In this invention, it is preferable that surfactant is a fluorochemical surfactant. By containing a fluorine-type surfactant in the composition for pixel formation, liquid characteristic (especially fluidity|liquidity) improves more, and liquid property can be improved more. Moreover, a film|membrane with a small thickness dispersion|variation can also be formed.

As for the fluorine content rate in a fluorine-type surfactant, 3-40 mass % is suitable, More preferably, it is 5-30 mass %, Especially preferably, it is 7-25 mass %. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid-forming properties, and the solubility in the composition is also good.

Specifically as a fluorochemical surfactant, Paragraph Nos. 0060 to 0064 of Unexamined-Japanese-Patent No. 2014-041318 (paragraph Nos. 0060-0064 of International Publication No. 2014/017669 corresponding to), etc., Surfactants, Unexamined-Japanese-Patent No. 2011-132503 The surfactant described in Paragraph Nos. 0117 to 0132 is mentioned, These content is integrated in this specification. As a commercially available product of fluorine-based surfactant, for example, Megapac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above, DIC Corporation) ), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Sufflon 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).

In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved when heat is applied and the fluorine atom is volatilized can also be suitably used. As such a fluorine-based surfactant, Megapac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo, February 22, 2016) (Nikkei Sangyo Shinbun, February 23, 2016), for example, Megapac DS- 21 can be mentioned.

Moreover, it is also preferable to use the polymer of the fluorine atom containing vinyl ether compound which has a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound as a fluorine-type surfactant. For such a fluorine-based surfactant, the description of Unexamined-Japanese-Patent No. 2016-216602 can be considered into consideration, and this content is integrated in this specification.

A block polymer can also be used for a fluorochemical surfactant. For example, the compound of Unexamined-Japanese-Patent No. 2011-089090 is mentioned. The fluorine-based surfactant has two or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meth) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 39]

The weight average molecular weight of said compound becomes like this. Preferably it is 3,000-50,000, for example, is 14,000. Among the above compounds, % indicating the proportion of the repeating unit is mol%.

Moreover, as a fluorine-type surfactant, the fluorine-containing polymer which has an ethylenically unsaturated group in a side chain can also be used. As a specific example, Paragraph Nos. 0050 - 0090 and Paragraph Nos. 0289 - 0295 of Unexamined-Japanese-Patent No. 2010-164965, For example, DIC Corporation Megapac RS-101, RS-102, RS-718K, RS -72-K etc. are mentioned. As the fluorine-based surfactant, the compounds described in Paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Japan) Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Junyaku Kogyo Co., Ltd. product), Pionein D-6112, D-6112-W, D-6315 (Takemoto Yushi) Co., Ltd.), Olfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.), and the like.

As a silicone type surfactant, For example, 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, Toray Corporation Dow) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, new) S-Silicone Co., Ltd. make), BYK307, BYK323, BYK330 (above, Big Chemi company make) etc. are mentioned.

0.001 mass % - 5.0 mass % are preferable with respect to the total solid of the composition for pixel formation, and, as for content of surfactant, 0.005-3.0 mass % is more preferable. One type may be sufficient as surfactant, and two or more types may be sufficient as it. In the case of two or more types, it is preferable that a total amount becomes the said range.

<<Ultraviolet Absorbent>>

The composition for pixel formation can contain a ultraviolet absorber. Examples of the ultraviolet absorber include a conjugated diene compound, an aminobutadiene compound, a methyldibenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, and the like. is available. About these details, Paragraph Nos. 0052 to 0072 of Unexamined-Japanese-Patent No. 2012-208374, Paragraph Nos. 0317 to 0334 of Unexamined-Japanese-Patent No. 2013-068814 can be considered into consideration, and these content is integrated in this specification. As a commercial item of a conjugated diene compound, UV-503 (made by Daito Chemical Co., Ltd.) etc. is mentioned, for example. Moreover, as a benzotriazole compound, you may use the MYUA series (Kagaku Kogyo Nippo, February 1, 2016) manufactured by Miyoshi Yushi. As a ultraviolet absorber, the compound represented by Formula (UV-1) - Formula (UV-3) is preferable, the compound represented by Formula (UV-1) or Formula (UV-3) is more preferable, Formula (UV-1) ) is more preferable.

[Formula 40]

In formula (UV-1), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0-4. In the 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 the 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.

The following compounds are mentioned as a specific example of the compound represented by Formula (UV-1) - Formula (UV-3).

[Formula 41]

0.01-10 mass % is preferable with respect to the total solid of the composition for pixel formation, and, as for content of a ultraviolet absorber, 0.01-5 mass % is more preferable. In this invention, only 1 type may be used for a ultraviolet absorber, and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<Antioxidant >>

The composition for pixel formation can contain antioxidant. As antioxidant, a phenol compound, a phosphorous acid ester compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. The compound which has a substituent in the site|part (orthosite) adjacent to a phenolic hydroxyl group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, as for antioxidant, the compound which has a phenol group and a phosphorous acid ester group in the same molecule is also preferable. Moreover, as antioxidant, phosphorus antioxidant can also be used suitably. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphospepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl) oxy]ethyl]amine, ethyl bisphosphite (2,4-di-tert-butyl-6-methylphenyl), and the like. As a commercial item of antioxidant, adekastave AO-20, adekastave AO-30, adekastave AO-40, adekastave AO-50, adekastave AO-50F, adekastave AO-60 is, for example, for example. , ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (above, ADEKA Co., Ltd.) etc. are mentioned.

It is preferable that it is 0.01-20 mass % with respect to the total solid of the composition for pixel formation, and, as for content of antioxidant, it is more preferable that it is 0.3-15 mass %. An antioxidant may use only 1 type and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<Other ingredients>>

The composition for pixel formation is a sensitizer, hardening accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (for example, electroconductive particle, a filler, an antifoamer, a flame retardant, a leveling agent, a peeling accelerator, a fragrance|flavor, A surface tension modifier, a chain transfer agent, etc.) may be contained. By containing these components appropriately, properties such as film properties can be adjusted. These components are, for example, Paragraph No. 0183 of Unexamined-Japanese-Patent No. 2012-003225 (paragraph No. 0237 of U.S. Patent Application Laid-Open No. 2013/0034812), Paragraph No. of Unexamined-Japanese-Patent No. 2008-250074, for example. Reference can be made to descriptions, such as 0101-0104, 0107-0109, and these content is integrated in this specification.

It is preferable that the viscosity (23 degreeC) of the composition for pixel formation is 1-100 mPa*s, when forming a film|membrane by application|coating, for example. The lower limit is more preferably 2 mPa·s or more, and still more preferably 3 mPa·s or more. The upper limit is more preferably 50 mPa·s or less, still more preferably 30 mPa·s or less, and particularly preferably 15 mPa·s or less.

<Receiving container>

There is no limitation in particular as a container for the composition for pixel formation, A well-known container can be used. In addition, for the purpose of suppressing the mixing of impurities into raw materials and compositions as a container for storage, a multi-layer bottle in which the inner wall of the container is composed of 6 types of 6 layers of resin or a bottle with 6 types of resins in a 7-layer structure is also used. desirable. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Method for preparing the composition for forming a pixel>

The composition for pixel formation can be prepared by mixing the above-mentioned components. When preparing the composition for forming a pixel, the composition for forming a pixel may be prepared by dissolving or dispersing all the components in a solvent at the same time, and if necessary, preparing in advance two or more solutions or dispersions in which each component is appropriately blended, You may mix these at the time of use (at the time of application|coating) and prepare it as a composition for pixel formation.

Moreover, when the composition for pixel formation contains particle|grains, such as a pigment, it is preferable to include the process of disperse|distributing particle|grains. In the process of dispersing particles, examples of the mechanical force used to disperse the particles include compression, compression, impact, shear, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like. Moreover, in the grinding|pulverization of the particle|grains in a sand mill (bead mill), it is preferable to process under the conditions which improved the grinding|pulverization efficiency by using small diameter beads, increasing the filling rate of the beads, etc. After the pulverization treatment, it is preferable to remove the coarse particles by filtration, centrifugation, or the like. In addition, the process and disperser for dispersing particles are "Dispersion Technology Exhibition, Published by Johokiko Co., Ltd., July 15, 2005" and "Suspension (solid/liquid dispersion system) centered on dispersion technology and practical synthesis of industrial applications" The process and disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. Moreover, in the process of disperse|distributing particle|grains, you may perform the refinement|miniaturization process of particle|grains by a salt milling process. As for the raw material used in the salt milling process, the apparatus, the processing conditions, etc., description of Unexamined-Japanese-Patent No. 2015-194521 and Unexamined-Japanese-Patent No. 2012-046629 can be referred, for example.

Preparation of the composition for pixel formation WHEREIN: It is preferable to filter the composition for pixel formation with a filter for the purpose of removal of a foreign material, reduction of a defect, etc. As a filter, if it is a filter conventionally used for a filtration use etc., it can use without being specifically limited. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) A filter using a material such as (including a high-density and ultra-high molecular weight polyolefin resin) is mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

As for the pore diameter of a filter, about 0.01-7.0 micrometers is suitable, Preferably it is about 0.01-3.0 micrometers, More preferably, it is about 0.05-0.5 micrometers. If 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 medium. As a fibrous filter medium, a polypropylene fiber, a nylon fiber, a glass fiber, etc. are mentioned, for example. Specifically, the filter cartridges of the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), SHPX type series (SHPX003 etc.) made by Rocky Techno are mentioned.

When using a filter, you may combine other filters (for example, a 1st filter, a 2nd filter, etc.). In that case, the filtration to each filter may be performed only once, and may be performed twice or more.

Moreover, you may combine filters of different pore diameters within the above-mentioned range. The hole diameter here can refer to the nominal value of a filter manufacturer. As a commercially available filter, for example, Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microliss Co., Ltd.), or Kits Microfilter Co., Ltd. can select from various filters provided.

The second filter may be formed of the same material as the first filter or the like.

Moreover, after performing filtration with a 1st filter only with respect to a dispersion liquid and mixing another component, you may filter with a 2nd filter.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. Materials, usage amounts, ratios, treatment contents, treatment procedures, and the like 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 Viscosity of Resist Composition>

1.2 ml of the resist composition adjusted to the temperature of 25 degreeC was thrown into RE-85L (made by Toki Sangyo Co., Ltd.), and the viscosity of the resist composition was measured using the rotor for high viscosity.

<Preparation of resist composition>

(resist compositions 1 to 8)

The following raw materials were mixed to prepare resist compositions 1 to 8. In addition, the solid content concentration of the resist composition was adjusted by content of propylene glycol monomethyl ether acetate (PGMEA). The resin used for the preparation of the resist composition, the solid content concentration of the resist composition, and the viscosity of the resist composition at 25°C are described in the table below.

Resins A to E described in the table below: 29.581 parts by mass

Photoacid generator (compound of the following structure): 0.358 mass part

[Formula 42]

Acid diffusion controlling agent (compound of the following structure): 0.016 parts by mass

[Formula 43]

Surfactant (EGAFAC R-41, manufactured by DIC Corporation): 0.045 parts by mass

PGMEA: Balance

Propylene glycol monomethyl ether: 15.000 parts by mass

[Table 1]

Resin A: Resin of the following structure. The numerical value added to the repeating unit is a molar ratio. Mw=22,000, Onish parameter=2.87)

Resin B: Resin of the following structure. The numerical value added to the repeating unit is a molar ratio. Mw=21,000, Onish parameter=2.84)

Resin C: Resin of the following structure. The numerical value added to the repeating unit is a molar ratio. Mw=18,000, Onishi parameter=2.74)

Resin D: Resin of the following structure. The numerical value added to the repeating unit is a molar ratio. Mw=20,000, Onish parameter=2.73)

Resin E: Resin of the following structure. The numerical value added to the repeating unit is a molar ratio. Mw=19,000, Onish parameter=2.54)

In addition, the composition ratio of resin (molar ratio of a repeating unit) was ^{computed by 1} H-NMR (nuclear magnetic resonance) or ¹³ C-NMR measurement. The weight average molecular weight (Mw: polystyrene conversion) of resin was computed by GPC (solvent: THF) measurement. The nish parameter of resin was computed from the following formula.

Onishi parameter = sum of the number of atoms of C, H and O/(number of C atoms - number of O atoms)

[Formula 44]

<Preparation of composition for color filter (Green composition, Red composition, Blue composition)>

<<Green composition>>

After stirring the following components, it filtered with a nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometer, and the color material density|concentration in solid content prepared the Green composition whose 49 mass %.

Green pigment dispersion... 81.3g

Polymeric compound 1... 3.89g

Resin 1… 3.44g

Photoinitiator 1... 0.51g

Photoinitiator 2... 0.36g

Additive 1… 0.38g

Surfactant 1... 0.01g

Polymerization inhibitor 1... 0.001g

Solvent 1… 9.7g

<<Red composition>>

After stirring the following components, it filtered with the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometer, and the color material density|concentration in solid content prepared the Red composition whose 50 mass %.

Red pigment dispersion... 59.5g

Polymeric compound 2... 1.15g

Resin 1… 1.39g

Photoinitiator 1... 0.40g

Surfactant 2... 0.04g

Polymerization inhibitor 1... 0.0004g

Solvent 1… 8.1g

Solvent 2… 29.4g

<<Blue composition>>

After stirring the following components, it filtered with a nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometer, and the color material density|concentration in solid content prepared the Blue composition whose 36 mass %.

Blue pigment dispersion... 29.6g

Polymeric compound 1... 4.74g

Resin 1… 3.36g

Photoinitiator 1... 1.13g

Surfactant 2... 0.03g

Polymerization inhibitor 1... 0.001g

Solvent 1… 26.7g

Solvent 2… 34.4g

(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 acetate (PGMEA) To the mixed liquid, 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added, dispersion treatment was performed for 3 hours using a paint shaker, and the beads were separated by filtration to prepare a green pigment dispersion. Solid content content of this green pigment dispersion liquid was 17.2 mass %, and 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.

[Formula 45]

Dispersant 1: Resin of the following structure (Mw=26000, the numerical value indicated in the main chain is the molar ratio, and the numerical value indicated in the side chain is the number of repeating units.)

[Formula 46]

(Red Pigment Dispersion)

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 dispersing agent (Disperbyk-161, manufactured by BYKChemie), and 79.0 parts by mass of PGMEA to a mixed solution mixed with zirconia beads 230 having a diameter of 0.3 mm A mass part was added, the dispersion process was performed using the paint shaker for 3 hours, the beads were isolate|separated by filtration, and the red pigment dispersion liquid was prepared. Solid content content of this red pigment dispersion liquid was 21.0 mass %, and 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 dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 82.2 parts by mass of PGMEA were mixed with zirconia having a diameter of 0.3 mm. 230 mass parts of beads were added, the dispersion process was performed using the paint shaker for 3 hours, the beads were isolate|separated by filtration, and the blue pigment dispersion liquid was prepared. Solid content content of this blue pigment dispersion liquid was 17.8 mass %, and pigment content was 12.8 mass %.

(Polymerizable compound)

Polymerizable compound 1: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymeric compound 2: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)

(profit)

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

(Photoinitiator)

Photoinitiator 1: IRGACURE OXE01 (manufactured by BASF)

Photoinitiator 2: IRGACURE OXE03 (manufactured by BASF)

(Surfactants)

Surfactant 1: KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.)

Surfactant 2: the following mixture (Mw=14000). In the following formula, % indicating the proportion of the repeating unit is mol%.

[Formula 47]

Polymerization inhibitor 1: 4-methoxyphenol

Additive 1: EHPE 3150 (made by Daicel)

Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA)

Solvent 2: Butyl acetate

<Preparation of composition for infrared cut filter>

After stirring the following components, it filtered with the nylon filter (Nippon Pole Co., Ltd. product) with a pore diameter of 0.45 micrometers, and the composition for infrared cut filters was prepared.

Infrared absorbing dye dispersion... 43.8g

Resin of the following structure (the numerical value added to the main chain is the molar ratio. Mw = 10,000, acid value = 70 mgKOH/g)... 5.5g

[Formula 48]

Polymerizable compound (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.)... 3.2g

Polymeric compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)... 3.2g

Photoinitiator (IRGACURE OXE01, manufactured by BASF)... 1.0g

Ultraviolet absorber (compound of the following structure)... 1.6g

[Formula 49]

- Surfactant (Surfactant 2 mentioned above)... 0.025g

- Polymerization inhibitor (4-methoxyphenol)... 0.003g

・Antioxidant (Adekastave AO-80, manufactured by ADEKA Co., Ltd.)... 0.2g

・PGMEA… 41.5g

(Preparation of infrared absorbing dye dispersion)

2.5 mass parts of infrared absorbing dye 1, 0.5 mass part of pigment derivative 2, 1.8 mass part of dispersing agent 2, and 39.0 mass parts of PGMEA are mixed, 230 mass parts of zirconia beads of diameter 0.3mm are added to the mixed solution, and a paint shaker is used Then, dispersion treatment was performed for 3 hours, the beads were separated by filtration to prepare an infrared absorbing dye dispersion.

Infrared absorbing dye 1: A compound of the following structure. In the following structural formula, Ph is a phenyl group.

[Formula 50]

Pigment derivative 2: a compound of the following structure. In the following structural formula, Ph is a phenyl group.

[Formula 51]

Dispersant 2: Resin of the following structure (the numerical value indicated in the main chain is the molar ratio, and the numerical value indicated in the side chain is the number of repeating units. Mw=21000)

[Formula 52]

<Preparation of composition for infrared transmission filter>

After stirring the following components, it filtered with the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometers, and the composition for infrared transmission filters was prepared.

Pigment dispersion Y-1... 23.8g

Pigment dispersion V-1... 41.4g

Polymeric compound (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.)... 0.9g

Polymeric compound (Aronix TO-2349, manufactured by Toagosei Co., Ltd.)... 2.1g

Photoinitiator (IRGACURE OXE02, manufactured by BASF)... 0.74g

Resin of the following structure (the numerical value added to the main chain is the molar ratio. Mw = 10,000, acid value = 70 mgKOH/g)... 1.4g

[Formula 53]

Ultraviolet absorber (UV-503, manufactured by Daito Chemical Co., Ltd.)… 0.4g

Surfactant (Surfactant 2 mentioned above)... 0.008g

Polymerization inhibitor (4-methoxyphenol)... 0.002g

PGMEA… 29.2g

(Preparation of pigment dispersion Y-1)

2.5 parts by mass of CI Pigment Yellow 139, 1.6 parts by mass of the pigment derivative 1, 4.4 parts by mass of the dispersant 1, and 230 parts by mass of zirconia beads having a diameter of 0.3 mm are added to the mixed solution mixed with 83.0 parts by mass of PGMEA, and a paint shaker The dispersion treatment was performed for 3 hours, the beads were separated by filtration, and the pigment dispersion Y-1 was prepared.

(Preparation of pigment dispersion V-1)

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 230 parts by mass of zirconia beads having a diameter of 0.3 mm are added to the mixed solution mixed with 83.0 parts by mass of PGMEA, using a paint shaker Then, the dispersion treatment was performed for 3 hours, the beads were separated by filtration to prepare a pigment dispersion V-1.

Dispersant 3: Resin of the following structure (Numbers appended to the main chain are molar ratios. Mw = 10,000, acid value = 70 mgKOH/g)

[Formula 54]

Dispersant 4: Disperbyk-111, manufactured by BYK Chemie

<Production of Device> Preparation Example 1

(Examples 1 to 8, Comparative Example 2)

A p-type silicon substrate was used as the support. With respect to the p-type silicon substrate, boron was introduced by ion implantation and heat treatment was performed to form an n-type well having a ^{surface concentration of about 2×10 16} cm ^{−3 .} On the surface of the p-type silicon substrate on the side on which the n-type well was formed, the resist composition described in the following table was applied, pattern formation was performed, and a resist pattern having the film thickness described in the table below was formed. In addition, the 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, phosphorus was implanted into the support by an ion implantation method ^{under conditions of a dose of 2×10 13} cm ⁻² and an energy of 80 KeV to form a p-layer photodiode portion. Then, SiO ₂ film as a gate oxide film, after forming on a substrate and the resist pattern was peeled off the resist pattern. By this operation, a gate oxide film is formed only on the photodiode portion.

Next, a p-type first channel doped region was formed by implanting boron into the support from which the resist pattern was peeled by an ion implantation method ^{under conditions of a dose of 2×10 12} cm ^{−2 and an energy of 35 KeV.} Next, a resist pattern covering the photodiode portion and the first channel doped region is formed on the support, and phosphorus is applied by ion implantation using the resist pattern as a mask at a dose of 6×10 ¹² cm ⁻² and an energy of 50 KeV. By implanting under the conditions, an n-type second channel doped region was formed.

Next, after peeling off the resist pattern, a polysilicon control electrode doped with phosphorus was formed on the support and patterned to form a control electrode. Then, according to a known method, a MOS (metal-oxide-semiconductor) transistor was formed. Next, according to a known method, a first interlayer insulating film, a contact, a first metal wiring, a second interlayer insulating film, a via connecting the first metal wiring and the second metal wiring, a second metal wiring, and a passivation film were sequentially formed. . In this way, a light-receiving element was manufactured.

With respect to the light receiving element produced by the said process, the said composition for infrared cut filters was apply|coated by the spin coating method so that the film thickness after film formation might be set to 1.0 micrometer. Then, it heated at 100 degreeC for 2 minute(s) using the hotplate. Next, using a KrF exposure machine (manufactured by Canon, FPA-6000ES6a), it was exposed with a KrF line (wavelength 248 nm) ^{through a mask having a Bayer pattern of 1 µm square at an exposure dose of 500 mJ/cm 2 .}

Then, puddle development was performed at 23 degreeC for 60 second using the tetramethylammonium hydroxide (TMAH) 0.3 mass % aqueous solution. Thereafter, it was rinsed with a spin shower and further washed with pure water. Next, by heating at 200°C for 5 minutes using a hot plate, a Bayer pattern (pixels in the infrared blocking layer) of 1 µm square was formed to form an infrared cut filter.

Next, on the pixel of the infrared blocking layer, the green composition was applied by spin coating so that the film thickness after forming the film was 0.5 µm. Then, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using a KrF exposure machine (manufactured by Canon, FPA-6000 ES6a), the KrF line was exposed at an exposure amount of ^{200 mJ/cm 2 through a mask having a Bayer pattern having a pixel size of 1 µm square.} Then, puddle image development was performed at 23 degreeC for 60 second using the tetramethylammonium hydroxide (TMAH) 0.3 mass % aqueous solution. Then, it rinsed by spin shower and further washed with pure water. Then, a green pixel was formed on the pixel of the infrared blocking layer by heating at 200° C. for 5 minutes using a hot plate.

The Red composition and the Blue composition were also coated to have a film thickness of 0.5 µm in the same manner as above, and using an i-line stepper exposure apparatus FPA-3000 i5+ (manufactured by Canon Co., Ltd.), a Bayer pattern having a pixel size of 1 µm square Exposed to i-line at an exposure amount of 200 mJ/cm ^{2 through a mask having}

Next, on the light receiving element in which the said color filter was formed, the composition for infrared transmission filter layer formation was apply|coated by the spin coating method so that the film thickness after film-forming might be set to 0.5 micrometer. Then, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using a KrF exposure machine (manufactured by Canon, FPA-6000 ES6a), the KrF line was exposed at an exposure amount of ^{300 mJ/cm 2 through a mask having a Bayer pattern having a pixel size of 1 µm square.} Then, puddle development was performed at 23 degreeC for 60 second using the tetramethylammonium hydroxide (TMAH) 0.3 mass % aqueous solution. Then, it rinsed by spin shower and further washed with pure water. Next, by heating at 200°C for 5 minutes using a hot plate, pixels of the infrared transmission layer were formed in the unformed portion of the pixels of the infrared blocking layer, and an infrared transmission filter was formed. This was introduced into a solid-state image sensor according to a known method to manufacture a device.

(Comparative Examples 1 and 3) Preparation Example 2

In the formation of each pixel, an i-line stepper exposure apparatus FPA-3000 i5+ (manufactured by Canon Co., Ltd.) is used as an exposure machine, and the pixels of the infrared blocking layer are exposed with an i-line at an exposure amount of ^{1000 mJ/cm 2 ,} For the green pixel, the red pixel, and the blue pixel, exposure to i-line at an exposure amount of ^{200 mJ/cm 2} , respectively, and for the pixel of the infrared transmission layer, exposure to the i-line at an exposure amount of ^{300 mJ/cm 2 Production Example 1} Each pixel was formed in the same manner as described above, and devices of Comparative Examples 1 and 3 were manufactured.

<Evaluation of S/N ratio for infrared rays>

The obtained solid-state imaging element was irradiated with infrared rays, and the signal intensity ratio at the time of irradiation and non-irradiation of infrared rays was compared, and the S/N ratio with respect to infrared rays was evaluated. In addition, as an infrared light source, an infrared power LED (850 nm) OSI3XNE3E1E (manufactured by OPTOSUPPLY) was used.

<Evaluation of noise for visible light (SNR10)>

For 24 colors of the Markubes chart, the illumination light source was prescribed|regulated, and the spectral reflectance in the range of wavelength 400-700 nm was calculated|required. Next, the infrared cut filter characteristics of the solid-state imaging device and the spectral sensitivity of the solid-state imaging device were prescribed, and the exposure amounts of red, green, and blue received by the solid-state imaging device were calculated. Next, the electric charge amount of each color of red, green, and blue was calculated from this exposure amount. Next, the output signals r, g, and b and noise (short noise, dark noise, and fixed pattern noise) of each color of red, green, and blue were calculated from these charges. The luminance signal noise (S/N) was calculated from these noises, the illuminance value (referred to as SNR10) at which this S/N is 10 was calculated, and the noise with respect to visible light was evaluated according to the following criteria. The smaller the value of SNR10, the lower the noise. About the calculation procedure of SNR10, it was based on the method of Paragraph No. 0405-0426 of Unexamined-Japanese-Patent No. 2013-015817.

5: SNR10 less than 1lux

4: SNR10 is greater than or equal to 1 lux and less than 3 lux

3: SNR10 is 3 lux or more and less than 10 lux

2: SNR10 is 10 lux or more and less than 30 lux

1: SNR10 is 30 lux or more and less than 100 lux

0: SNR10 is 100 lux or more

[Table 2]

As shown in the table above, the devices of Examples had a high S/N ratio to infrared rays. Moreover, a remarkable improvement was seen also in the noise with respect to visible light.

In each embodiment, even when the light receiving element is manufactured using an InGaAs substrate instead of a silicon substrate, the same excellent effect as in each embodiment is obtained.

In each Example, even if it changes the photoinitiator in the composition for color filters with the same amount of IRGACURE OXE02 (made by BASF), the same effect is acquired.

1: support
2: Pattern of resist film (resist pattern)
3: Photodiode part
110: light receiving element
111: infrared cut filter
112: color filter
114: infrared transmission filter
115: micro lens
116: planarization layer

Claims (20)

forming a pattern of a resist film having a thickness of 5 μm or more on a support using a resist composition, and then performing ion implantation into the support using the pattern of the resist film as a mask to manufacture a light-receiving element;
forming a layer of a composition for forming a pixel of an optical filter on at least a part of the light-receiving element on the ion-implanted region;
A step of exposing the layer of the composition for forming a pixel by irradiating light having a wavelength of 300 nm or less and exposing it in a pattern;
A method of manufacturing a device comprising the step of forming a pixel by developing the layer of the composition for forming a pixel after exposure,
The method for manufacturing a device, wherein the resist composition includes a resin, and the resin has an onisy parameter of 3.0 or less. The method according to claim 1,
The said exposing process is a manufacturing method of a device, wherein the layer of the composition for forming a pixel is exposed in a pattern by irradiating a KrF line. The method according to claim 1 or 2,
The said composition for pixel formation is at least 1 sort(s) chosen from the composition for color pixel formation, and the composition for pixel formation of an infrared transmission layer, The manufacturing method of a device. The method according to claim 1 or 2,
The composition for forming a pixel includes a polymerizable compound and a photoinitiator, wherein the photoinitiator is selected from an alkylphenone compound, an acylphosphine compound, a benzophenone compound, a thioxanthone compound, a triazine compound, and an oxime compound A method of making a device comprising at least one compound. The method according to claim 1 or 2,
The said composition for pixel formation contains a color material, The manufacturing method of a device. 6. The method of claim 5,
The manufacturing method of the device which contains the said color material 40 mass % or more with respect to the total solid of the said composition for pixel formation. The method according to claim 1 or 2,
The method of manufacturing a device, wherein the size of the pixel is 2.0 μm or less. The method according to claim 1 or 2,
The manufacturing method of the device whose film thickness of the said pixel is 1.0 micrometer or less. The method according to claim 1 or 2,
The method for manufacturing a device, wherein the resist composition has a solid content concentration of 25% by mass or more. The method according to claim 1 or 2,
The manufacturing method of the device whose viscosity at 25 degreeC of the said resist composition is 30-1000 mPa*s. The method according to claim 1 or 2,
The method for manufacturing a device, wherein the content of the resin in the solid content of the resist composition is 95.0 to 99.9 mass%. delete The method according to claim 1 or 2,
The method for manufacturing a device, wherein the resin has an onisy parameter of 2.8 or less. The method according to claim 1 or 2,
The said resist composition is a positive photosensitive composition, The manufacturing method of a device. The method according to claim 1 or 2,
The method for manufacturing a device, wherein the resist composition contains a resin having a repeating unit having a group that generates a polar group by being decomposed by the action of an acid, and a photoacid generator. 12. The method of claim 11,
The method for manufacturing a device, wherein the resist composition further contains a photoacid generator, and the resin is a resin having a repeating unit having a group that generates a polar group by decomposing the resin by the action of an acid. The method according to claim 1 or 2,
The thickness of the said resist film is 7 micrometers or more, and the solid content concentration of the said resist composition is 30 mass % or more, The manufacturing method of the device. The method according to claim 1 or 2,
The said composition for pixel formation is a composition for pixel formation of an infrared transmission layer, The manufacturing method of a device. The method according to claim 1 or 2,
The method for manufacturing a device, wherein the resin has an ounce parameter of 2.5 or more and 2.8 or less. The method according to claim 1 or 2,
The method for manufacturing a device, wherein the content of the resin having an onisy parameter of 3.0 or less in the total amount of the resin in the resist composition is 75 to 100% by mass.

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