JP7337189B2 - composition, film, microlens, solid-state imaging device and display device - Google Patents

Description

The present invention relates to compositions for forming high refractive index members such as microlenses. The present invention also relates to films, microlenses, solid-state imaging devices, and display devices.

2. Description of the Related Art Conventionally, in solid-state imaging devices such as charge-coupled device (CCD) image sensors, attempts have been made to colorize images using color filters. Also, a microlens is provided on the optical path of the color filter to increase the sensitivity of the pixels in each color filter.

Patent Document 1 describes an invention relating to a microlens-forming resin composition containing a copolymer having a predetermined structural unit and a solvent.

WO2015/115155

Generally, it is known that a substance that absorbs light of a certain wavelength tends to have anomalous dispersion of the refractive index in the vicinity of the maximum absorption wavelength of the substance. Here, the refractive index of a substance generally tends to decrease as the wavelength of light increases. Such a phenomenon is called normal dispersion of the refractive index. On the other hand, a phenomenon in which the refractive index abruptly increases or decreases as the wavelength becomes longer, deviating greatly from the normal dispersion, is called anomalous dispersion of the refractive index.

In microlenses, it was believed that the anomalous dispersion of the refractive index would reduce the light-gathering efficiency of visible light. was used. Also, no attempt has been made to incorporate a near-infrared absorbing dye into the microlens.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide novel compositions, films, microlenses, solid-state imaging devices, and display devices.

The inventor provides the following.
<1> an organic compound A having a refractive index of 1.58 or more for light with a wavelength of 633 nm;
a near-infrared absorbing dye;
A composition comprising a solvent,
The organic compound A is at least one selected from polymerizable compounds and resins,
When a film having a thickness of 0.35 μm is formed using the above composition, the refractive index of the film for light with a wavelength of 633 nm is 1.58 or more, and the transmittance of the film for light with a wavelength of 400 to 600 nm is A composition having a minimum value of 85% or more.
<2> The composition according to <1>, wherein the film has an average transmittance of 80% or less for light having a wavelength of 800 to 870 nm when a film having a thickness of 0.35 μm is formed using the composition. .
<3> The composition according to <1> or <2>, wherein the organic compound A is a compound having at least one structure selected from a fluorene structure, a triazine structure and a carbazole structure.
<4> The composition according to any one of <1> to <3>, containing two or more kinds of the organic compound A.
<5> The content of the organic compound having a refractive index of 1.63 or more for light with a wavelength of 633 nm in the total amount of the organic compound A contained in the composition is 5 to 100% by mass, <1> to <4 The composition according to any one of .
<6> The composition according to any one of <1> to <5>, wherein the content of the organic compound A in the total solid content of the composition is 50% by mass or more.
<7> The composition according to any one of <1> to <6>, wherein the content of the near-infrared absorbing dye in the total solid content of the composition is 1 to 20% by mass.
<8> The composition according to any one of <1> to <7>, wherein the near-infrared absorbing dye is a compound having a maximum absorption wavelength in the wavelength range of 750 to 1000 nm.
<9> The composition according to any one of <1> to <8>, wherein the near-infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, and polymethine compounds. .
<10> The composition according to any one of <1> to <9>, which is used for microlenses.
<11> A film obtained using the composition according to any one of <1> to <10>.
<12> A microlens having the film according to <11>.
<13> A solid-state imaging device having the microlens according to <12>.
<14> A display device comprising the microlens according to <12>.

ADVANTAGE OF THE INVENTION According to this invention, the novel composition which can form films|membranes, such as a microlens, with a near-infrared shielding property and high condensing performance of visible light can be provided. Also, a film, a microlens, a solid-state imaging device, and a display device using the composition can be provided.

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

<Composition>
The compositions of the present invention are
an organic compound A having a refractive index of 1.58 or more for light with a wavelength of 633 nm;
a near-infrared absorbing dye;
A composition comprising a solvent,
The organic compound A is at least one selected from polymerizable compounds and resins,
When a film with a thickness of 0.35 μm is formed using the above composition, the film has a refractive index of 1.58 or more for light with a wavelength of 633 nm, and the film transmits light with a wavelength of 400 to 600 nm. The minimum ratio is 85% or more.

INDUSTRIAL APPLICABILITY The composition of the present invention can provide a novel composition capable of forming a film such as a microlens having a near-infrared shielding property and a high ability to collect visible light. That is, since the composition of the present invention contains a near-infrared absorbing dye, it can form a film having near-infrared shielding properties. The composition of the present invention further contains an organic compound A having a refractive index of 1.58 or more for light with a wavelength of 633 nm, and when forming a film with a thickness of 0.35 μm, the wavelength of the film The refractive index for light of 633 nm is 1.58 or more, and the minimum transmittance of the above-mentioned film for light with a wavelength of 400 to 600 nm is 85% or more, so it has near-infrared shielding properties. In addition, it is possible to form a film such as a microlens with high visible light condensing performance.

Therefore, for example, by setting a film such as a microlens obtained using the composition of the present invention on the light incident side of the pixel of the solid-state imaging device, the light collection performance of the visible light incident on the pixel is enhanced. Visible light sensitivity of the pixels can be increased, near-infrared rays can be suppressed from entering the pixels, and a clear image or the like can be detected. Therefore, the composition of the present invention can be preferably used as a composition for microlenses. More preferably, it can be used for microlenses of solid-state imaging devices. More preferably, it can be used as a microlens arranged on the light path of a solid-state imaging device having a color filter on the light incident side to the color filter.

In the composition of the present invention, when a film having a thickness of 0.35 μm is formed, the refractive index of the film for light having a wavelength of 633 nm is 1.58 or more, preferably 1.60 or more. 0.62 or more is more preferable. Further, the average refractive index of the above-mentioned film for light with a wavelength of 400 to 600 nm is preferably 1.60 or more, more preferably 1.62 or more, and even more preferably 1.64 or more. Although the upper limit is not particularly limited, it can be 1.75 or less. Such refractive index characteristics can be achieved by adjusting the types and contents of the organic compound A and the near-infrared absorbing dye. For example, it can be achieved by increasing the content of the organic compound A in the total solid content of the composition, using an organic compound A having a higher refractive index, or the like.

When the composition of the present invention is used to form a film having a thickness of 0.35 μm, the minimum transmittance of light having a wavelength of 400 to 600 nm of the film is 85% or more, and is 90% or more. Preferably, it is 95% or more. In addition, the average transmittance of the above-described film for light with a wavelength of 400 to 600 nm is preferably 90% or more, more preferably 93% or more, and even more preferably 96% or more. In order to achieve such transmittance characteristics, it is necessary to reduce the content of materials that absorb in the visible region, such as chromatic colorants and black colorants, in the total solid content of the composition. This can be achieved by methods such as using highly near-infrared absorbing dyes.

When the composition of the present invention forms a film having a thickness of 0.35 μm, the average transmittance of the above-mentioned film for light with a wavelength of 800 to 870 nm is preferably 80% or less, and preferably 75% or less. is more preferable, and 70% or less is even more preferable. In addition, the minimum transmittance of the above-described film for light with a wavelength of 800 to 870 nm is preferably 70% or less, more preferably 65% or less, and even more preferably 60% or less. Further, the maximum transmittance of the above-mentioned film for light with a wavelength of 800 to 870 nm is preferably 85% or less, more preferably 82% or less, and even more preferably 80% or less. Such transmittance characteristics can be achieved by adjusting the type and content of the near-infrared absorbing dye. For example, it can be achieved by increasing the content of the near-infrared absorbing dye or using a near-infrared absorbing dye with a high absorption coefficient at the maximum absorption wavelength.

The compositions of the present invention are preferably substantially free of chromatic colorants and black colorants. When the composition of the present invention does not substantially contain a chromatic colorant and a black colorant, the total content of the chromatic colorant and the black colorant is 0.1% by mass based on the total solid content of the composition. It is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and particularly preferably not contained.

The viscosity of the composition of the present invention at 25° C. is preferably 3 to 20 mPa·s from the viewpoint of coating properties. The lower limit is preferably 4 mPa·s or more, more preferably 5 mPa·s or more. The upper limit is preferably 15 mPa·s or less, more preferably 13 mPa·s or less.

The solid content concentration of the composition of the present invention is preferably 10 to 30% by mass from the viewpoint of coating properties. The lower limit is preferably 13% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 27% by mass or less, more preferably 25% by mass or less.

The composition of the present invention will be described in detail below.

<<Organic compound A>>
The composition of the present invention contains an organic compound A having a refractive index of 1.58 or higher for light with a wavelength of 633 nm. The refractive index of the organic compound A for light with a wavelength of 633 nm is preferably 1.63 or more. Although the upper limit of the refractive index is not specified, it can be 1.80 or less.
Further, the content of the organic compound having a refractive index of 1.63 or more for light with a wavelength of 633 nm in the total amount of the organic compound A contained in the composition is preferably 5 to 100% by mass, more preferably 20 to 100% by mass. % is more preferred, and 40 to 100% by mass is even more preferred.
The refractive index of the organic compound A was measured by coating it on a support such as a silicon wafer so that the film thickness after coating was 0.3 μm, heating it at 100° C. for 2 minutes and then heating it at 200° C. for 5 minutes, and measuring it with an ellipsometer. It is a value measured using

Organic compound A is at least one selected from polymerizable compounds and resins.

Examples of the polymerizable compound used as the organic compound A include a compound having an ethylenically unsaturated bond-containing group, a compound having a cyclic ether group, a compound having a hydroxy group, a compound having a carboxy group, and a compound having a _—NH2 group. mentioned. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Cyclic ether groups include epoxy groups and oxetanyl groups. The polymerizable compound used as the organic compound A may contain two or more polymerizable compounds. The polymerizable compound used as the organic compound A preferably contains at least either a compound having an ethylenically unsaturated bond-containing group or a compound having a cyclic ether group.

When the organic compound A is a polymerizable compound, the organic compound A is preferably a monomer. Further, the molecular weight of the organic compound A is preferably 200-1000. The upper limit is preferably 900 or less, more preferably 800 or less. The lower limit is preferably 250 or more, more preferably 300 or more.

When the organic compound A is a resin, the weight average molecular weight of the organic compound A is preferably 2,000 to 100,000. The upper limit is preferably 90,000 or less, more preferably 80,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more. Incidentally, the resin may have a polymerizable group such as an ethylenically unsaturated bond-containing group, a cyclic ether group, a hydroxy group, a carboxyl group, or a --NH ₂ group.

The composition of the present invention preferably contains two or more organic compounds A. Among them, it is preferable to contain at least one resin-type organic compound A and at least one polymerizable compound-type organic compound A, respectively. According to such an aspect, it is possible to form a film with small film shrinkage after film formation and high strength. Further, when the resin type organic compound A and the polymerizable compound type organic compound A are used in combination, the composition of the present invention contains a polymerizable compound type organic compound with respect to 100 parts by mass of the resin type organic compound A. It preferably contains 10 to 800 parts by mass of compound A, more preferably 50 to 700 parts by mass. According to this aspect, the effects described above can be obtained more remarkably.

Organic compound A is preferably a compound having at least one structure selected from a fluorene structure, a triazine structure and a carbazole structure. A film having a high refractive index can be formed by using a compound having such a structure. The aforementioned compounds may be monomer type compounds or resin type compounds.

Compounds having a fluorene structure include compounds having a partial structure represented by the following formula (Fr).
(Fr)

In the formula, a wavy line represents a bond, R ^f1 and R ^f2 each represent a substituent, and m and n each independently represent an integer of 0 to 5. when m is 2 or more, m R ^f1 may be the same or different, and two R ^f1 out of m R ^f1 are bonded to form a ring; good too. When n is 2 or more, n R ^f2 may be the same or different, and two R ^f2 out of n R ^f2 are bonded to form a ring; good too. Substituents represented by R ^f1 and R ^f2 include the substituent T described later.

Compounds having a triazine structure include compounds having a partial structure represented by the following formula (Ta). A wavy line in the formula represents a bond.
(Ta)

The compound having a triazine structure is also preferably a compound having a group represented by the following formula (Ta-1).
(Ta-1)

A wavy line in the formula represents a bond.
Each of C ¹ to C ³ independently represents -NR _N -, -O-, or -S-. R _N represents a hydrogen atom, an alkyl group (preferably having 1 to 7 carbon atoms), or an aryl group. C ¹ to C ³ are each independently preferably -NH-, -N(CH ₃ )-, -O- or -S-, more preferably -NH-.
Ar ¹ and Ar ² each independently represent an aryl group or a heterocyclic group. A phenyl group is preferred as the aryl group. The heterocyclic group may or may not exhibit aromaticity, but preferably exhibits aromaticity. The number of hetero atoms constituting the hetero ring is preferably 1-3. A heteroatom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The aryl group and heterocyclic group may have a substituent. Examples of the substituent include a substituent T described later and a polymerizable group. Examples of polymerizable groups include ethylenically unsaturated bond-containing groups such as vinyl groups, (meth)allyl groups and (meth)acryloyl groups; cyclic ether groups such as epoxy groups and oxetanyl groups; hydroxy groups; carboxy groups _; and the like.
Ar ³ represents an arylene group or a divalent heterocyclic group. A phenylene group is preferred as the arylene group.
_LA represents a single bond or a divalent linking group. The divalent linking group includes -NH-, -O-, -CO-, -CO-O-, an alkylene group (preferably having 1 to 3 carbon atoms), or a combination thereof (e.g., -O-alkylene Groups -, etc.) are preferred.

Preferred examples of compounds having a triazine structure include compounds represented by the following formula (I).
(A) _m -X-(B) _n (I)
In formula (I), m represents an integer of 2 or more. n represents an integer of 0 or more.
A represents a group represented by formula (Ta-1).
X represents an m+n-valent linking group.
B represents a polymer chain or substituent.
In addition, multiple A's may be the same or different. When there are multiple B's, the multiple B's may be the same or different.

The m+n-valent linking group represented by X is not particularly limited, but the following structural units or groups composed of two or more of the following structural units in combination (which may form a ring structure) may be mentioned. can.

The polymer chain represented by B is a chain having a plurality of predetermined repeating units. The structure of the polymer chain is not particularly limited and can be selected depending on the purpose. Among them, the polymer chain is a polymer selected from the group consisting of vinyl monomer polymers or copolymers, ester-based polymers, ether-based polymers, urethane-based polymers, amide-based polymers, epoxy-based polymers, and silicone-based polymers. A polymer chain composed of a (meth)acrylic compound is preferable, and a polymer chain composed of a polymer or copolymer of a (meth)acrylic compound is more preferable. A polymer chain may have a substituent. In addition, when multiple substituents are present, the multiple substituents may be the same or different. The weight average molecular weight of the polymer chain represented by B is preferably 200-10,000, more preferably 300-5,000. Further, examples of the substituent represented by B include the substituent T described later.

A compound represented by the following formula (Ta-10) is also preferable as the compound having a triazine structure.
(Ta-10)

Each of C ¹ to C ³ independently represents -NR _N -, -O-, or -S-. R _N represents a hydrogen atom, an alkyl group (preferably having 1 to 7 carbon atoms), or an aryl group. C ¹ to C ³ are each independently preferably -NH-, -N(CH ₃ )-, -O- or -S-, more preferably -NH-.
Rt ¹ to Rt ¹⁵ each independently represent a hydrogen atom or a substituent, and at least one of Rt ¹ to Rt ¹⁵ represents a polymerizable group. Examples of the substituent include a substituent T described later and a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups such as a vinyl group, (meth)allyl group, and (meth)acryloyl group, epoxy groups, cyclic ether groups such as an oxetanyl group, hydroxy groups, carboxy groups, and -NH. ₂ groups and the like.
At least one of Rt ¹ to Rt ⁵ and at least one of Rt ⁶ to Rt ¹⁰ each preferably represent a polymerizable group, and any one of Rt ¹ to Rt ⁵ and any one of Rt ⁶ to Rt ¹⁰ More preferably, each represents a polymerizable group.

Compounds having a carbazole structure include compounds having a partial structure represented by the following formula (Cz).
(Cz)

In the formula, a wavy line represents a bond, R ^c1 and R ^c2 each represent a substituent, and m2 and n2 each independently represent an integer of 0 to 5. when m2 is 2 or more, m2 R ^c1 may be the same or different, and two R ^c1 among m2 R ^c1 are bonded to form a ring; good too. When n2 is 2 or more, n2 R ^c2 may be the same or different, and two R ^c2 out of n2 R ^c2 are bonded to form a ring; good too. Substituents represented by R ^c1 and R ^c1 include the substituent T described later.

Specific examples of the organic compound A as the polymerizable compound include compounds having the structures shown below, Ogusol PG-100 (manufactured by Osaka Gas Chemicals Co., Ltd., an epoxy compound having a fluorene structure), Ogusol EG-200 (Osaka Gas Chemical Co., Ltd., epoxy compound having a fluorene structure) and the like.

Specific examples of the organic compound A as the resin include compounds having the structures shown below, the resin described in Synthesis Example 1 of JP-A-2013-139588, and the resin described in Example 1 of JP-A-2017-031311. etc.

The content of the organic compound A in the total solid content of the composition is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more. The upper limit is preferably 98% by mass or less, more preferably 95% by mass or less.
Further, when the organic compound A is a polymerizable compound or a resin, the content of the organic compound A in the total amount of the resin and the polymerizable compound contained in the composition is preferably 50 to 100% by mass, and 60 to 100% by mass. % by mass is more preferred, and 70 to 100% by mass is even more preferred.

<<Near-infrared absorption dye>>
The composition of the present invention contains a near-infrared absorbing dye. The near-infrared absorbing dye used in the present invention is preferably a compound having a maximum absorption wavelength in the wavelength range of 750 to 1000 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 770 to 950 nm. A compound having a maximum absorption wavelength in the wavelength range of 800 to 900 nm is more preferable. In addition, the ratio A ¹ /A ² between the absorbance A ¹ at a wavelength of 500 nm and the absorbance A ² at the maximum absorption wavelength of the near-infrared absorbing dye is preferably 0.08 or less, more preferably 0.04 or less. preferable.

The near-infrared absorbing dye may be a pigment or a dye. When a pigment is used, a film having excellent heat resistance and light resistance can be formed. When a dye is used, a film with a small haze can be formed.

Near-infrared absorbing dyes include pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, polymethine compounds, iminium compounds, quaterrylene compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds and dithiolene metals. It is preferably at least one selected from pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds and polymethine compounds, more preferably pyrrolopyrrole compounds. Examples of polymethine compounds include cyanine compounds, squarylium compounds, and croconium compounds.

The pyrrolopyrrole compound is preferably a compound represented by formula (PP).
In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ are Each R ⁴ 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 R It may be covalently or coordinately bonded to at least one selected from ^1a , ^R1b and ^R3 , and ^R4A and ^R4B each independently represent a substituent. For details of the formula (PP), paragraph numbers 0017 to 0047 of JP 2009-263614, paragraph numbers 0011 to 0036 of JP 2011-068731, paragraph numbers 0010 to 0024 of WO 2015/166873 can be referred to, and the contents thereof are incorporated herein.

In formula (PP), R ^1a and R ^1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. In addition, the alkyl group, aryl group and heteroaryl group represented by R ^1a and R ^1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614 and the following substituent T. In addition, when the alkyl group, aryl group and heteroaryl group represented by R ^1a and R ^1b have two or more substituents, the substituents may combine to form a ring.

(substituent T)
Alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl group having 6 to 30 carbon atoms), amino group (preferably amino group having 0 to 30 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 30 carbon atoms), aryloxy group (preferably 6 to 30 aryloxy group), heteroaryloxy group, acyl group (preferably an acyl group having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably is an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 6 to 30 carbon atoms), heteroarylsulfonyl group (preferably 1 to 30 carbon atoms), alkylsulfinyl group (preferably 1 to 30 carbon atoms), arylsulfinyl group (preferably 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxyl group , a carboxyl group, a sulfo group, a phosphoric acid group, a carboxylic acid amide group (preferably a group represented by —NHCOR ^A1 , where R ^A1 represents a hydrocarbon group or a heterocyclic group. A hydrocarbon group and a heterocyclic group may further have a substituent, which is preferably a halogen atom, more preferably a fluorine atom), a sulfonic acid amide group (preferably represented by —NHSO ₂ R ^A2 R ^A2 represents a hydrocarbon group or a heterocyclic group, which may further have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom. ), an imidic acid group (preferably a group represented by —SO ₂ NHSO ₂ R ^A3 , —CONHSO ₂ R ^A4 , —CONHCOR ^A5 or —SO ₂ NHCOR ^A6 . R ^A3 to R ^A6 are each independently represents a hydrocarbon group or a heterocyclic group.The hydrocarbon group and heterocyclic group may further have a substituent.), mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group , hydrazino group, imino group, heteroaryl group (preferably having 1 to 30 carbon atoms).
These groups may further have substituents if they are substitutable groups. Examples of the substituent include the groups described for the substituent T described above.

Specific examples of the groups represented by R ^1a and R ^1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxyl group as a substituent, and an aryl group having an acyloxy group as a substituent.

In formula (PP), ^R2 and ^R3 each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituent T described above. At least one of R ² and R ³ is preferably an electron-withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-withdrawing group. Here, there are a σp value and a σm value as substituent constants determined by Hammett's rule. These values can be found in many popular books. In the present invention, a substituent having a Hammett's substituent constant σ value of 0.20 or more can be exemplified as an electron-withdrawing group. The σ value is preferably 0.25 or more, more preferably 0.30 or more, and even more preferably 0.35 or more. Although the upper limit is not particularly limited, it is preferably 0.80 or less. Specific examples of the electron-withdrawing group include a cyano group (σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), an alkoxycarbonyl group (eg, -COOMe: σp value = 0.45). 45), aryloxycarbonyl groups (eg, —COOPh: σp value = 0.44), carbamoyl groups (eg, —CONH ₂ : σp value = 0.36), alkylcarbonyl groups (eg, —COMe: σp value = 0.50), arylcarbonyl groups (eg —COPh: σp value = 0.43), alkylsulfonyl groups (eg —SO ₂ Me: σp value = 0.72), arylsulfonyl groups (eg —SO ₂ Ph: σp value = 0.68), etc., and a cyano group is preferred. Here, Me represents a methyl group and Ph represents a phenyl group. Regarding Hammett's substituent constant σ value, for example, paragraphs 0017 to 0018 of JP-A-2011-068731 can be referred to, and the contents thereof are incorporated herein.

In formula (PP), ^R2 preferably represents an electron-withdrawing group (preferably a cyano group) and ^R3 preferably represents a heteroaryl group. A heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring with 2 to 8 condensed numbers, more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. Heteroaryl groups preferably have one or more nitrogen atoms. Two R ² groups in formula (PP) may be the same or different. Two R ³ groups in formula (PP) may be the same or different.

In formula (PP), R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by -BR ^4A R ^4B , and is preferably a hydrogen atom, an alkyl group, an aryl group or -BR A group represented by ^4A R ^4B is more preferable, and a group represented by -BR ^4A R ^4B is even more preferable. The substituent represented by R ^4A and R ^4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and an aryl group. Especially preferred. These groups may further have a substituent. Two ^R4 's in formula (PP) may be the same or different. ^R4A and ^R4B may combine with each other to form a ring.

Specific examples of the compound represented by the formula (PP) include the compounds described in Examples below. Further, as the pyrrolopyrrole compound, compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, International Publication No. 2015/166873 and the compounds described in paragraph numbers 0010 to 0033 of No.

Examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987. Compounds described in, compounds described in JP-A-2015-176046, compounds described in paragraph No. 0072 of WO 2016/190162, compounds described in paragraph Nos. 0196 to 0228 of JP-A-2016-074649 , the compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in Patent 6197940, Examples include compounds described in International Publication No. 2016/120166. As the cyanine compound, compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004. The compound, the compound described in JP-A-2015-172102, the compound described in JP-A-2008-088426, the compound described in paragraph number 0090 of WO 2016/190162, JP-A-2017-031394 and the like compounds described in. Examples of croconium compounds include compounds described in JP-A-2017-082029. As the iminium compound, for example, compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, International Publication No. 2018/043564 and the compounds described in paragraphs 0048 to 0063 of. Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. and vanadium phthalocyanine compounds described in Japanese Patent No. 6081771. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-077153. Dithiolene metal complexes include compounds described in Japanese Patent No. 5733804.

Further, as the near-infrared absorbing dye, the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in International Publication No. 2016/154782, the patent No. squarylium compounds described in Japanese Patent No. 6036689; squarylium compounds described in Japanese Patent No. 5810604; Pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of JP-A-2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078 to 0082 of JP-A-2018-040955, JP-A-2018-002773 Pyrrole ring-containing compounds described in paragraph numbers 0043 to 0069, squarylium compounds having an aromatic ring at the amide α-position described in paragraph numbers 0024 to 0086 of JP-A-2018-041047, and those described in JP-A-2017-179131 Amide-linked squarylium compounds, compounds having a pyrrole-bis-type squarylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole-bis-type squarylium compounds described in JP-A-2017-082029, JP-A-2017- Asymmetric compounds described in paragraph numbers 0027 to 0114 of 068120, pyrrole ring-containing compounds (carbazole type) described in JP-A-2017-067963, phthalocyanine compounds described in Japanese Patent No. 6251530, etc. can also be used.

The content of the near-infrared absorbing dye in the total solid content of the composition is preferably 1 to 20% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 17% by mass or less, more preferably 15% by mass or less.

Further, the total content of the above-mentioned organic compound A and the near-infrared absorbing dye in the total solid content of the composition is preferably 70% by mass or more, more preferably 75% by mass or more, and 80% by mass. % or more is more preferable. The upper limit can be 100% by mass or less, and can also be 98% by mass or less.

The composition preferably contains 1 to 30 parts by mass of the near-infrared absorbing dye per 100 parts by mass of the organic compound A described above. The lower limit is preferably 2 parts by mass or more, more preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less. According to this aspect, it is possible to achieve both high near-infrared absorption performance and high refractive index.

In the composition of the present invention, only one type of near-infrared absorbing dye may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

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

In the present invention, it is preferable to use a solvent with a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a ppt (parts per trillion) level solvent may be used, and such a high-purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

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

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.

In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.

The solvent content in the composition is preferably 70 to 90% by mass. The lower limit is preferably 73% by mass or more, more preferably 75% by mass or more. The upper limit is preferably 87% by mass or less, more preferably 85% by mass or less.

<<Other polymerizable compounds>>
The composition of the present invention can contain a polymerizable compound (hereinafter also referred to as another polymerizable compound) other than the organic compound A described above. Other polymerizable compounds include compounds having an ethylenically unsaturated bond-containing group, compounds having a cyclic ether group, and the like, and compounds having an ethylenically unsaturated bond-containing group are preferred. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Cyclic ether groups include epoxy groups and oxetanyl groups.

A compound having an ethylenically unsaturated bond-containing group may be in any chemical form such as a monomer, a prepolymer, an oligomer, etc., but a monomer is preferred. The molecular weight of the compound having an ethylenically unsaturated bond-containing group is preferably 100-3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, even more preferably 250 or more.

The compound having an ethylenically unsaturated bond-containing group is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups. More preferably, it is a compound containing 3 to 6 ethylenically unsaturated bond-containing groups. The compound having an ethylenically unsaturated bond-containing group is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of the compound having an ethylenically unsaturated bond-containing group, paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph of JP-A-2008-292970 Numbers 0254 to 0257, paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807 , and compounds described in JP-A-2017-194662, the contents of which are incorporated herein.

Further, as the compound having an ethylenically unsaturated bond-containing group, dipentaerythritol triacrylate (as a commercial product KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth)acryloyl groups are ethylene glycol and/or propylene glycol residues. (for example, SR454 and SR499 commercially available from Sartomer) and the like. Examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, and isocyanuric acid. Trifunctional (meth)acrylate compounds such as ethyleneoxy-modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate can also be used. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) etc.

A compound having an acid group can also be used as the compound having an ethylenically unsaturated bond-containing group. The acid group includes a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferred. Commercially available products include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).

The compound having an ethylenically unsaturated bond-containing group is also preferably a compound having a caprolactone structure. Compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60 and DPCA-120.

Compounds having an ethylenically unsaturated bond-containing group are compounds described in JP-A-2017-048367, JP-A-6057891, JP-A-6031807, JP-A-2017-194662. Compounds, 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. are also preferably used.

The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of epoxy groups is preferably two or more. Examples of epoxy compounds include compounds described in paragraph numbers 0034 to 0036 of JP-A-2013-011869, compounds described in paragraph numbers 0147-0156 of JP-A-2014-043556, and JP-A-2014-089408. It is also possible to use the compounds described in paragraph numbers 0085 to 0092 of and the compounds described in JP-A-2017-179172.

Epoxy compounds may be low molecular weight compounds (e.g. molecular weight less than 2000, further molecular weight less than 1000) or macromolecules (e.g. molecular weight 1000 or more, weight average molecular weight 1000 or more in the case of polymers). Either The weight average molecular weight of the epoxy compound is preferably 200-100,000, more preferably 500-50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

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

The content of other polymerizable compounds in the total solid content of the composition is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
It is also preferred that the composition of the present invention does not substantially contain other polymerizable compounds. According to this aspect, a film having a higher refractive index can be formed. In addition, when the composition of the present invention does not substantially contain other polymerizable compounds, it means that the content of other polymerizable compounds is 0.1% by mass or less in the total solid content of the composition. However, it is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and particularly preferably not contained.

<<other resins>>
The composition of the present invention can contain a resin other than the organic compound A (hereinafter also referred to as another resin). The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the purpose of binder. A resin mainly used for dispersing particles and the like in a composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

The weight average molecular weight (Mw) of other resins is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

Other resins include, for example, (meth)acrylic resins, (meth)acrylamide resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, Examples include polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins.

Other resins may have acid groups. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used. A resin having an acid group can also be used as an alkali-soluble resin or a dispersant.

When the other resin has an acid group, the acid value of the acid group of the other resin is preferably 30-500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

Other resins include repeating units derived from compounds represented by the following formula (ED1) and/or compounds represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that the resin contains

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), the description in JP-A-2010-168539 can be referred to.

Specific examples of the ether dimer can be referred to paragraph number 0317 of JP-A-2013-029760, the content of which is incorporated herein.

Other resins may have ethylenically unsaturated bond-containing groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Commercially available resins having an ethylenically unsaturated bond-containing group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), and Viscoat R. -264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cychromer P series (for example, ACA230AA), Praxel CF200 series (both manufactured by Daicel Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.) ), Acrylic RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), DP-1305 (manufactured by Fuji Film Fine Chemicals Co., Ltd.), and the like.

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

It is also preferable that the resin used as the dispersant is a graft copolymer. The graft copolymer has affinity with the solvent due to the graft chain, and is therefore excellent in pigment dispersibility and dispersion stability over time. Details of the graft copolymer can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein. Further, specific examples of the graft copolymer include the following resins. Further, examples of graft copolymers include resins described in paragraphs 0072 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

It is also preferable to use an oligoimine-based resin containing a nitrogen atom in at least one of the main chain and the side chain as the dispersant. The oligoimine resin has a structural unit having a partial structure X having a functional group with a pKa of 14 or less, and a side chain containing a side chain Y having 40 to 10,000 atoms, and at least the main chain and the side chain A resin having a basic nitrogen atom on one side is preferred. Regarding the oligoimine resin, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein. As the oligoimine-based resin, resins having the following structure and resins described in paragraphs 0168 to 0174 of JP-A-2012-255128 can be used.

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by BYK Chemie (e.g., Disperbyk-111, 2001, etc.), Solsperse series manufactured by Nippon Lubrizol Co., Ltd. ( For example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine-Techno Co., Inc., and the like can be mentioned. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.

The content of other resins in the total solid content of the composition is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
It is also preferred that the composition of the present invention is substantially free of other resins. According to this aspect, a film having a higher refractive index can be formed. In addition, when the composition of the present invention does not substantially contain other resins, it means that the content of other resins is 0.1% by mass or less based on the total solid content of the composition. It is preferably 05% by mass or less, more preferably 0.01% by mass or less, and particularly preferably not contained.

<<Pigment derivative>>
The composition of the invention can contain pigment derivatives. When a pigment-type near-infrared absorbing dye is used, the composition preferably contains a pigment derivative. Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. Dye skeletons constituting pigment derivatives include quinoline dye skeletons, benzimidazolone dye skeletons, benzoisoindole dye skeletons, benzothiazole dye skeletons, inimium dye skeletons, squarylium dye skeletons, croconium dye skeletons, oxonol dye skeletons, and pyrrolopyrrole dye skeletons. skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, An isoindoline dye skeleton, an isoindolinone dye skeleton, a quinophthalone dye skeleton, an iminium dye skeleton, a dithiol dye skeleton, a triarylmethane dye skeleton, a pyrromethene dye skeleton, and the like are included. Acid groups include sulfo groups, carboxyl groups, phosphoric acid groups and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ etc.), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like. Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups. Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

Specific examples of pigment derivatives include the compounds described in the examples described later, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, and JP-A-03-009961. , JP-A-03-026767, JP-A-03-153780, JP-A-03-045662, JP-A-04-285669, JP-A-06-145546, JP-A-06-212088, Patent JP-A-06-240158, JP-A-10-030063, JP-A-10-195326, paragraph numbers 0086 to 0098 of WO 2011/024896, paragraph numbers 0063 to 0094 of WO 2012/102399 , International Publication No. 2017/038252, paragraph number 0082, International Publication No. 2017/146092, paragraph number 0052, JP 2015-151530, paragraph number 0171, JP 2011-252065, paragraph numbers 0162 to 0183 , JP 2003-081972, JP 5299151, JP 2015-172732, JP 2014-199308, JP 2014-085562, JP 2014-035351, JP 2008 -081565 and the compounds described therein.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination. When two or more are used in combination, the total amount thereof is preferably within the above range.

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

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazoles. dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, α-hydroxyketone compounds , α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Further, as the photopolymerization initiator, JP 2014-130173, paragraphs 0065 to 0111, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3, the peroxide photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 JP 2019-044030 A includes photopolymerization initiators described in JP 2019-044030 A, the contents of which are incorporated herein.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure. 127 (above, BASF company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 3. 79EG (above, BASF made), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No. 2015 / 152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, Examples include compounds described in International Publication No. 2013/167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by Co., Ltd. Photopolymerization initiator 2) described in JP-A-2012-014052 manufactured by ADEKA. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA Corporation).

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

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

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

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

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

As a photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.

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

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

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the composition can be improved. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 and oxime ester photoinitiators.

The content of the photopolymerization initiator in the total solid content of the composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. In the composition of the present invention, one type of photopolymerization initiator may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<<white or colorless pigment (white pigment)>>
The composition of the present invention can contain a white or colorless pigment (hereinafter also referred to as white pigment). At least one element selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S is used as the white pigment. Oxide particles containing at least one element selected from Ti, Zr, Sn, Al and Si are preferred. As the oxide, titanium oxide and zirconium oxide are preferred, and titanium oxide is more preferred. Examples of titanium oxide include rutile-type titanium oxide, anatase-type titanium oxide, and amorphous-type titanium oxide, with rutile-type titanium oxide being preferred. Moreover, it is also preferable that the above oxide is surface-treated with a surface-treating agent. Examples of surface treatment agents include inorganic compounds and organic compounds. An inorganic compound and an organic compound may be used in combination. Specific examples of surface treatment agents include polyol, aluminum oxide, aluminum hydroxide, amorphous silica, hydrated silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agent, and titanate coupling agent. etc.

The shape of the white pigment is not particularly limited. Examples thereof include isotropic shapes (eg, spherical, polyhedral, etc.), anisotropic shapes (eg, needle-like, rod-like, plate-like, etc.), irregular shapes, and the like.

The weight average particle size of the primary particles of the white pigment is preferably 150 nm or less, more preferably 100 nm or less, and even more preferably 80 nm or less. Although there is no particular lower limit, it is preferably 1 nm or more. Regarding the weight average particle diameter of the white pigment, unless otherwise specified, the mixture or dispersion containing the white pigment is diluted 80 times with propylene glycol monomethyl ether acetate, and the resulting diluted solution is dynamically It is obtained by measuring using a light scattering method. The measured value in this case is the weight-average particle diameter obtained by using Microtrac (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.

The specific surface area of the white pigment is preferably 10 to 400 m ² /g, more preferably 20 to 200 m ² /g, even more preferably 30 to 150 m ² /g.

The refractive index of the white pigment is preferably 1.6 to 3.0. The lower limit is preferably 1.7 or more, more preferably 1.8 or more. The upper limit is preferably 2.9 or less, more preferably 2.8 or less. The method for measuring the refractive index of white pigments conforms to Japanese Industrial Standards (JIS K 0062:1992).

A commercially available white pigment may be used. For example, titanium oxide includes TTO series (TTO-51(A), TTO-51(C), TTO-55(C), etc.), TTO-S, V series (TTO-S-1, TTO-S- 2, TTO-V-3, etc.) (all trade names, manufactured by Ishihara Sangyo Co., Ltd.), MT series (MT-01, MT-05, etc.) (manufactured by Tayca Co., Ltd., trade names), and the like.

<<Curing accelerator>>
The composition of the invention may contain a curing accelerator. Curing accelerators include thiol compounds, methylol compounds, amine compounds (aliphatic amines, aromatic amines, heterocyclic amines, etc.), phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilanes. compounds, onium salt compounds, phosphorus compounds, and the like. Specific examples of the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraphs 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraphs 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200559, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, carboxyl group-containing epoxy curing agents described in JP-A-2017-036379, and the like.

The content of the curing accelerator in the total solid content of the composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass. In the composition of the present invention, only one curing accelerator may be used, or two or more curing accelerators may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<<Silane coupling agent>>
The composition of the invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two functional groups with different reactivity in one molecule is preferable. The silane coupling agent contains at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. is preferred. Specific examples of silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-602), N-2-(aminoethyl)-3 -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. manufactured by KBM-403). For details of the silane coupling agent, the description in paragraphs 0155 to 0158 of JP-A-2013-254047 can be referred to, the contents of which are incorporated herein.

The content of the silane coupling agent in the total solid content of the composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1% to 5% by mass. . The composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types thereof. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.

<<polymerization inhibitor>>
The composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-t-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.) and the like.

The content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5% by mass. The composition of the present invention may contain only one polymerization inhibitor, or may contain two or more polymerization inhibitors. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.

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

The content of the ultraviolet absorber in the total solid content of the composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. The composition of the present invention may contain only one ultraviolet absorber, or may contain two or more ultraviolet absorbers. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.

<<Antioxidant>>
The compositions of the invention may contain antioxidants. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, antioxidants include compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, and compounds described in WO 2017/164024. can also be used.

The content of the antioxidant in the total solid content of the composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. The composition of the present invention may contain only one antioxidant, or may contain two or more antioxidants. When two or more kinds are included, it is preferable that the total amount thereof is within the above range.

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

In the present invention, the surfactant is preferably a fluorosurfactant. By including a fluorosurfactant in the composition, the liquid properties (particularly fluidity) can be further improved, and the liquid saving property can be further improved. In addition, it is also possible to form a film with less unevenness in thickness.

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

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

Fluorine-based surfactants also include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. Such fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.

A block polymer can also be used as the fluorosurfactant. The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. In addition, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol %.

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

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) etc.

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

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

<<Other Additives>>
Various additives such as fillers, adhesion promoters, antioxidants, anti-aggregation agents and the like can be added to the composition of the present invention, if necessary. Examples of these additives include additives described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein.

The compositions of the present invention may also contain latent antioxidants. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Specific examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available products include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.). In addition, the composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph number 0078 of JP-A-2004-295116, and a thermal polymerization inhibitor described in paragraph number 0081 of the same publication. .

<Container>
The storage container for the composition of the present invention is not particularly limited, and known storage containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used in order to suppress the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.

<Method for producing composition>
The compositions of the present invention can be prepared by admixing the aforementioned ingredients. In producing the composition, the composition may be produced by dissolving and/or dispersing all the components in a solvent at the same time, or if necessary, each component may be appropriately prepared as two or more solutions or dispersions. A composition may be produced by mixing these at the time of use (at the time of application).

Moreover, a process of dispersing particles such as pigments may be included in the production of the composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, 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. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. In addition, it is preferable to remove coarse particles, beads, impurities mixed by abrasion of beads, impurities mixed by abrasion of a dispersing machine, and the like by filtration, centrifugation, or the like after the pulverization treatment. Impurities mixed from beads or a dispersing machine are preferably 2000 ppm or less with respect to the entire composition. In addition, the process and dispersing machine for dispersing pigments are described in ``Dispersion Technology Encyclopedia, Information Organization Co., Ltd., July 15, 2005'' and ``Dispersion Technology Centered on Suspension (Solid/Liquid Dispersion System) and Industrial Applications'' The process and disperser described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the pigment, the particles may be made finer in the salt milling process. Materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.

In manufacturing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene, polypropylene (PP) (high density, ultra high molecular weight (including polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like can be used as filters.

It is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.

<Membrane>
The membrane of the invention is obtained using the composition of the invention described above. The film of the present invention can be preferably used for microlenses and the like.

<Micro lens>
The microlens of the invention has the film of the invention as described above.

The refractive index of the microlens of the present invention for light with a wavelength of 633 nm is preferably 1.58 or more, more preferably 1.60 or more, and even more preferably 1.62 or more. The average refractive index of the microlens of the present invention for light with a wavelength of 400 to 600 nm is preferably 1.60 or more, more preferably 1.62 or more, and even more preferably 1.64 or more. . Although the upper limit is not particularly limited, it can be 1.75 or less.

In the microlens of the present invention, the minimum transmittance of light with a wavelength of 400 to 600 nm is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. The microlens of the present invention preferably has an average transmittance of 90% or more, more preferably 93% or more, and even more preferably 96% or more for light with a wavelength of 400 to 600 nm.

For the microlens of the present invention, the average transmittance of light with a wavelength of 800 to 870 nm is preferably 80% or less, more preferably 75% or less, and even more preferably 70% or less. In the microlens of the present invention, the minimum transmittance of light with a wavelength of 800 to 870 nm is preferably 70% or less, more preferably 65% or less, and further preferably 60% or less. preferable. Further, in the microlens of the present invention, the maximum transmittance of light having a wavelength of 800 to 870 nm is preferably 85% or less, more preferably 82% or less, and further preferably 80% or less. preferable.

The lens shape of the microlens is not particularly limited, and can take various shapes derived from the design of the optical system. For example, convex shape, concave shape, etc. are mentioned. Moreover, the radius of curvature of the lens is not particularly limited, and is preferably set appropriately within a range in which the desired effect is achieved.

The thickness of the microlens is preferably 0.1 to 1.0 μm. The upper limit is preferably 0.9 μm or less, more preferably 0.8 μm or less. The lower limit is preferably 0.15 μm or more, more preferably 0.2 μm or more. Here, the thickness of the microlens means the thickness of the thickest portion of the microlens. For example, in the case of a biconvex lens, it is the distance from the vertex of one convex surface to the vertex of the other convex surface.

<Microlens manufacturing method>
Next, a method for manufacturing a microlens will be described. The method for producing a microlens preferably includes the steps of applying the above composition of the present invention onto a support to form a composition layer, and processing the composition layer into a lens shape. Each step will be described below.

(Step of forming composition layer)
In the step of forming a composition layer, the composition of the present invention is used to form a composition layer on a support. Examples of the support include glass substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamideimide substrates, polyimide substrates, and the like. An organic light-emitting layer may be formed on these substrates. Further, a color filter may be formed on the organic light emitting layer. In addition, the substrate and the color filter may be provided with an undercoat layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface.

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

The composition layer formed on the support may be dried (pre-baked). When prebaking is performed, the prebaking temperature is preferably 100° C. or lower, more preferably 90° C. or lower, still more preferably 80° C. or lower, and particularly preferably 70° C. or lower. The lower limit can be, for example, 40° C. or higher. The prebake time is preferably 10 to 3600 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

(Step of processing into lens shape)
As a method for processing the composition layer into a lens shape, a conventionally known processing method can be used. For example, it can be manufactured using a transfer method, an imprint method, a thermal drip method, or the like. Among them, the transfer method is preferable because the lens shape can be easily controlled.

In the transfer method, a composition layer formed on a support is cured to form a cured product layer, a resist layer is formed on this cured product layer, this resist layer is patterned into a lens shape, and this pattern is formed. The cured product layer is dry-etched using the formed resist layer as a mask, and the lens shape can be transferred to the cured product layer. In addition, the method of manufacturing a lens using the transfer method is described in JP-A-2006-073605, JP-A-2006-190903, JP-A-2008-281414, JP-A-2014-029524, etc. Methods can also be used, the contents of which are incorporated herein.

In the imprinting method, a mold having a pattern is pressed onto a composition layer formed on a support to sandwich the composition layer between the mold and the support, and the composition layer is exposed while being sandwiched. It can be produced by curing with a pressure and then peeling off the mold from the support.

In the heat dripping method, a composition layer formed on a support is cured to form a cured layer, the cured layer is heated, and the surface of the cured layer is thermally dripped to form a cured layer. It can be processed into a lens shape.

The step of processing into a lens shape may include a step of exposing the composition layer. Exposure is used as a curing treatment for the composition layer. The exposure is preferably carried out by irradiating the composition layer with radiation. Radiation includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferred. A long-wave light source of 300 nm or more can also be used.

Further, the exposure may be performed by continuously irradiating the light, or by pulsing the light (pulse exposure). Note that the pulse exposure is an exposure method in which light irradiation and pause are repeated in a cycle of short time (for example, less than millisecond level).

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

<Solid-state image sensor>
A solid-state imaging device of the present invention has the above-described microlens of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it has the microlens of the present invention and functions as a solid-state imaging device.

A plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. , a color filter on the device protective film, and a microlens on the color filter. The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure are described in JP-A-2012-227478, JP-A-2014-179577, International Publication No. 2018/043654, and US Patent Application Publication No. 2018/0040656. device. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.

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

The organic electroluminescence display device may have a light source composed of a white organic electroluminescence element. A tandem structure is preferable for the white organic electroluminescence element. Regarding the tandem structure of the organic electroluminescence element, see Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Forefront of Organic EL Technology Development - High Brightness, High Precision, Long Life, Collection of Know-how -", Technical Information Institute. , pp. 326-328, 2008. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430 nm-485 nm), green region (530 nm-580 nm) and yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferred.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the structural formulas shown below, Me represents a methyl group and Ph represents a phenyl group.

<Preparation of dispersion>
The raw materials shown in the table below were mixed, 230 parts by mass of zirconia beads with a diameter of 0.3 mm were added, dispersion treatment was performed using a paint shaker for 5 hours, and the beads were separated by filtration to produce a dispersion liquid. .

The raw materials listed in the above table are as follows.
(Near-infrared absorbing dye)
P-1 to P-4: compounds having the following structures
P-5: Near-infrared absorbing compound A-43 (croconium compound) described in International Publication No. 2018/043185
P-6: Cyanine compound e described in JP-A-2015-172004
P-1 to P-6 are compounds having maximum absorption wavelengths in the wavelength range of 800 to 900 nm.

(pigment derivative)
Sy-1 to Sy-4: compounds having the following structures

(dispersant)
D-1: Resin having the following structure. The numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 20,000.
D-2: Resin having the following structure. The numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 24,000.
D-3: Resin having the following structure. The numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. r/s/t/u=15/59/7/19, Mw=18300.

(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)

<Preparation of composition>
Compositions of Examples and Comparative Examples were prepared by mixing raw materials shown in the table below. The numerical values in the table below are parts by mass.

The raw materials listed in the above table are as follows.

(dispersion liquid)
Dispersions 1-12: Dispersions 1-12 described above

(Near-infrared absorbing dye)
Dye-1: a compound having the following structure (iC ₈ H ₁₇ and iC ₁₀ H ₂₁ are isomer mixtures with different carbon numbers and branching positions).

(Polymerizable compound)
M-1: Compound with the following structure (refractive index for light with a wavelength of 633 nm is 1.63 or more)
M-2: Compound with the following structure (refractive index for light with a wavelength of 633 nm is 1.63 or more)
M-3: compound with the following structure (refractive index for light with a wavelength of 633 nm is 1.58 or more and less than 1.63)
M-4: Ogsol PG-100 (manufactured by Osaka Gas Chemicals Co., Ltd., epoxy compound having a fluorene structure. Refractive index for light with a wavelength of 633 nm is 1.63 or more)
M-5: Ogsol EG-200 (manufactured by Osaka Gas Chemicals Co., Ltd., an epoxy compound having a fluorene structure. The refractive index for light with a wavelength of 633 nm is 1.58 or more and less than 1.63)
M-6: EHPE3150 (manufactured by Daicel Co., Ltd., epoxy compound. Refractive index for light with a wavelength of 633 nm is less than 1.58)

(resin)
B-1: Resin having the following structure (Mw = 5000, refractive index for light with a wavelength of 633 nm is 1.58 or more and less than 1.63)
B-2: Resin having a fluorene structure produced by the method described in Synthesis Example 1 of paragraphs 0122 to 0126 of JP-A-2013-139588 (Mw = 4300, refractive index for light with a wavelength of 633 nm is 1.63 or more )
B-3: Resin having a fluorene structure produced by the method described in Example 1 of paragraphs 0085 to 0086 of JP-A-2017-031311 (Mw = 28800, refractive index for light with a wavelength of 633 nm is 1.63 or more )
B-4: Resin with the following structure (Mw = 10000, refractive index for light with a wavelength of 633 nm is 1.63 or more)
B-5: Resin with the following structure (Mw = 8000, refractive index for light with a wavelength of 633 nm is 1.63 or more)
B-6: Resin with the following structure (Mw = 13000, refractive index for light with a wavelength of 633 nm is 1.63 or more)
B-7: Resin having the following structure (numerical values attached to the main chain are molar ratios, Mw = 10000, refractive index for light with a wavelength of 633 nm is less than 1.58)
B-8: Resin with the following structure (Mw = 3100, refractive index for light with a wavelength of 633 nm is 1.63 or more)
B-9: Resin having the following structure (numerical values attached to chains are molar ratios, Mw = 20000, refractive index for light with a wavelength of 633 nm is 1.63 or more)
B-10: Resin having the following structure (numerical values attached to the main chain are molar ratios, Mw = 40000, refractive index for light with a wavelength of 633 nm is 1.58 or more and less than 1.63)

(Additive)
A-1: Adekastab AO-80 (manufactured by ADEKA Co., Ltd.)
A-2: 2-ethyl-4-methylimidazole A-3: triphenylphosphine A-4: compound having the following structure
A-5: tris (4-methylphenyl) phosphine

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

(Polymerization inhibitor)
In-1: p-methoxyphenol

(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: Propylene glycol monomethyl ether (PGME)
S-3: Cyclohexanone

<Measurement of refractive index and transmittance>
Each composition was coated on a quartz glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) so that the film thickness after post-baking was 0.35 μm to form a coating film. Next, using a hot plate, heating was performed at 100 ° C. for 120 seconds (pre-baking), and then using the hot plate again, heating was performed at 200 ° C. for 300 seconds (post-baking) to obtain a film with a thickness of 0.35 μm. got For the obtained film, the refractive index (refractive index 1) for light with a wavelength of 633 nm was measured using Ellipsometry VUV-VASE (manufactured by JA Woollam Japan). In addition, the obtained film was measured for light transmittance with a wavelength of 400 to 1100 nm using a multichannel spectrometer MCPD-9800 (manufactured by Otsuka Electronics Co., Ltd.). The average transmittance for light with wavelengths of 800 to 870 nm was measured. When measuring the refractive index, the back surface of the glass was polished so that there would be no reflection from the back surface of the glass, and the glass was processed into a frosted glass.

In Examples 1 to 25, the minimum value of transmittance for light with a wavelength of 400 to 600 nm was 85% or more. Moreover, in Examples 1 to 25, the average transmittance of light with a wavelength of 800 to 870 nm was 80% or less.

<Production of microlenses>
On an 8-inch (20.32 cm) silicon wafer, the coloring composition for forming a green pixel was applied by a spin coating method so that the film thickness after forming the film would be 0.5 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ/cm ² through a mask having a 0.8 μm square Bayer pattern. Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, a hot plate was used to heat the wafer at 200° C. for 5 minutes to form green pixels (pattern size: 0.8 μm, thickness: 0.5 μm) on the silicon wafer. Next, the red pixel-forming coloring composition and the blue pixel-forming coloring composition are sequentially patterned, and in the missing part of the green pixel, the red pixel (pattern size 0.8 μm, thickness 0.5 μm), the blue pixel (pattern size 0.8 μm and 0.5 μm in thickness) to form color filters.
Next, on the color filter, the compositions of Examples 1 to 25 and Comparative Example 1 were applied by spin coating, then heated at 100 ° C. for 2 minutes using a hot plate, and then using a hot plate. A lens material composition layer having a thickness of 1.2 μm was formed by heating at 200° C. for 5 minutes.
After that, using a well-known etch-back transfer method, the lens material composition layer was processed so that the height from the lens top to the lens bottom was 400 nm, thereby manufacturing a microlens.

The microlenses produced using the compositions of Examples 1 to 25 had high transmittance and refractive index for light in the visible region, and were also excellent in near-infrared shielding properties. Therefore, the solid-state imaging device in which the microlens is manufactured using the composition of the example improves the light collection performance of visible light to each pixel of the color filter while suppressing the incidence of near-infrared rays to each pixel of the color filter. could be suppressed. Therefore, a clear image can be detected, and the image recognition accuracy is excellent. Similar results are obtained when the surfactant is omitted from Example 1. Similar results are obtained when the polymerization inhibitor is omitted from Example 1. Similar results can also be obtained by replacing P-5 with P-7, P-8, P-9 or P-10 below as the near-infrared absorbing dye.
P-7 to P-10 are compounds having maximum absorption wavelengths in the wavelength range of 800 to 900 nm.
P-7: Compound No. described in JP-A-2012-224593. 1
P-8: Near-infrared absorbing compound A-44 (croconium compound) described in International Publication No. 2018/043185
P-9: a compound having the following structure
P-10: a compound having the following structure

On the other hand, the microlens manufactured using the composition of Comparative Example 1 had a low refractive index for light in the visible region, and thus was inferior to the Examples in the performance of condensing visible light to each pixel of the color filter. Therefore, the image recognition accuracy of the solid-state imaging device in which the microlens was manufactured using the composition of the comparative example was inferior to that of the example.

(Coloring composition for forming green pixels)
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a coloring composition for forming green pixels.
Green pigment dispersion liquid...88.74 parts by mass Resin 1...0.40 parts by mass Polymerizable compound 1...1.62 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF)...1. 09 parts by mass Polymerization inhibitor (p-methoxyphenol) ... 0.0008 parts by mass Surfactant 1 ... 4.17 parts by mass Ultraviolet absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ... 0.3 parts by mass PGMEA ... 3.68 parts by mass

(Coloring composition for forming red pixels)
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a coloring composition for red pixel formation.
Red pigment dispersion...51.7 parts by mass Resin 1...0.6 parts by mass Polymerizable compound 4...0.6 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF)...0.4 Parts by mass Surfactant 1: 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.): 0.3 parts by mass PGMEA: 42.6 parts by mass

(Coloring composition for blue pixel formation)
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a blue pixel-forming coloring composition.
Blue pigment dispersion...44.9 parts by mass Resin 1...2.1 parts by mass Polymerizable compound 1...1.5 parts by mass Polymerizable compound 4...0.7 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ... 0.8 parts by mass Surfactant 1 ... 4.2 parts by mass Ultraviolet absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ... 0.3 parts by mass PGMEA ... 45.8 parts by mass

Raw materials used to prepare the green pixel-forming coloring composition, the red pixel-forming coloring composition, and the blue pixel-forming coloring composition are as follows.

- Green pigment dispersion C.I. I. Pigment Green 36, 8.15 parts by weight, C.I. I. 3.33 parts by weight of Pigment Yellow 150, 0.97 parts by weight of dispersant 1 shown below, 2.50 parts by weight of dispersant 2 shown below, 66.01 parts by weight of PGMEA, and PGME A mixture of 1.09 parts by mass and 5.09 parts by mass of cyclohexanone was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.3 mm) to prepare a pigment dispersion. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under a pressure of 2000 kg/cm 3 and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.

Dispersant 1: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 10,000, acid value = 44 mgKOH/g)

Dispersant 2: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 20,000, acid value = 36 mgKOH/g)

- Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. Pigment Yellow 139 of 4.3 parts by mass, a dispersing agent (Disperbyk-161, manufactured by BYK Chemie) of 6.8 parts by mass, and PGMEA of 79.3 parts by mass. A pigment dispersion was prepared by mixing and dispersing with a 3 mm diameter) for 3 hours. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under a pressure of 2000 kg/cm 3 and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

- Blue pigment dispersion C.I. I. Pigment Blue 15:6 with 9.7 parts by weight of C.I. I. Pigment Violet 23 of 2.4 parts by mass, a dispersing agent (Disperbyk-161, manufactured by BYK Chemie) of 5.5 parts by mass, and PGMEA of 82.4 parts by mass. A pigment dispersion was prepared by mixing and dispersing with a 3 mm diameter) for 3 hours. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under a pressure of 2000 kg/cm 3 and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion.

- Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- Polymerizable compound 4: a compound having the following structure

- Resin 1: Resin having the following structure. (The numerical values attached to the main chain are molar ratios. Mw = 10,000, acid value = 70 mgKOH/g, glass transition temperature = 46°C)

- Surfactant 1: 1 wt% PGMEA solution of the following mixture (Mw = 14000). In the following formula, % indicating the ratio of repeating units is % by mass.

Claims (11)

an organic compound A having a refractive index of 1.58 or more for light with a wavelength of 633 nm;
a near-infrared absorbing dye;
A microlens obtained by processing a composition containing a solvent into a lens shape ,
Containing 3 to 30 parts by mass of the near-infrared absorbing dye with respect to 100 parts by mass of the organic compound A,
The organic compound A is a polymerizable compound having at least one structure selected from a fluorene structure, a triazine structure and a carbazole structure and having a molecular weight of 200 to 1000, and a polymerizable compound selected from a fluorene structure, a triazine structure and a carbazole structure. and a resin having a weight average molecular weight of 2000 to 100000, and containing 10 to 800 parts by mass of the polymerizable compound with respect to 100 parts by mass of the resin,
When a film having a thickness of 0.35 μm is formed using the composition, the refractive index of the film for light with a wavelength of 633 nm is 1.58 or more, and the transmittance of the film for light with a wavelength of 400 to 600 nm is a minimum value of 85% or more,
micro lens . 2. The microlens according to claim 1, wherein when the composition is used to form a film having a thickness of 0.35 μm, the film has an average transmittance of 80% or less for light having a wavelength of 800 to 870 nm. 3. The micrometer according to claim 1, wherein the content of the organic compound having a refractive index of 1.63 or more for light with a wavelength of 633 nm is 5 to 100% by mass in the total amount of the organic compound A contained in the composition. lens . 4. The microlens according to any one of claims 1 to 3, wherein the content of the organic compound A in the total solid content of the composition is 50% by mass or more. 5. The microlens according to any one of claims 1 to 4, wherein the content of said near-infrared absorbing dye in the total solid content of said composition is 1 to 20% by mass. The microlens according to any one of claims 1 to 5, wherein the near-infrared absorbing dye is a compound having a maximum absorption wavelength in the wavelength range of 750 to 1000 nm. The microlens according to any one of claims 1 to 5, wherein the near-infrared absorbing dye is a compound having a maximum absorption wavelength in the wavelength range of 800 to 900 nm. The microlens according to any one of claims 1 to 7, wherein the near-infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, and polymethine compounds. The microlens according to any one of claims 1 to 7, wherein the near-infrared absorbing dye is a pyrrolopyrrole compound. A solid-state imaging device comprising the microlens according to any one of claims 1 to 9 . A display device comprising the microlens according to any one of claims 1 to 9 .