KR20220061167A - Compositions, Films, Micro Lenses, Solid State Imaging Devices and Display Devices - Google Patents

Abstract

A novel composition, film, microlens, solid-state image sensor, and display device are provided. A composition comprising an organic compound A having a refractive index with respect to light having a wavelength of 633 nm of 1.58 or more, a near-infrared absorbing dye, and a solvent, wherein the organic compound A is at least one selected from a polymerizable compound and a resin, and the above-described composition is used When a film having a thickness of 0.35 μm is formed, the refractive index of the above-mentioned film with respect to light having a wavelength of 633 nm is 1.58 or more, and the minimum value of the transmittance of light having a wavelength of 400 to 600 nm of the above-mentioned film is 85% or more.

Description

Compositions, Films, Micro Lenses, Solid State Imaging Devices and Display Devices

The present invention relates to a composition for forming a member having a high refractive index, such as a microlens. Moreover, this invention relates to a film|membrane, a microlens, a solid-state image sensor, and a display device.

BACKGROUND ART In a solid-state imaging device such as a charge-coupled device (CCD) image sensor, attempts have been made conventionally for colorization of an image using a color filter. Moreover, providing a microlens on the optical path of a color filter, and raising the sensitivity of the pixel in each color filter is also performed.

Patent Document 1 describes an invention relating to a resin composition for forming microlenses comprising a copolymer having a predetermined structural unit and a solvent.

Patent Document 1: International Publication No. 2015/115155

In general, it is known that, in a substance having absorption to light of a certain wavelength, abnormal dispersion of refractive index tends to occur in the vicinity of the maximum absorption wavelength of the substance. Here, in general, the refractive index of a material tends to decrease as the wavelength of light becomes longer. This phenomenon is called normal dispersion of the refractive index. On the other hand, a phenomenon in which the refractive index sharply increases or decreases as the wavelength becomes longer while deviating greatly from the normal dispersion is referred to as an abnormal dispersion of the refractive index.

In a microlens, it was thought that the light collection index of visible light would fall when abnormal dispersion|distribution of a refractive index generate|occur|produced. Therefore, a microlens with high transmittance|permeability with respect to visible light and near infrared rays was used conventionally. Moreover, the trial which makes a microlens contain a near-infrared absorbing dye has not been considered until now.

Accordingly, an object of the present invention is to provide a novel composition, a film, a microlens, a solid-state image sensor, and a display device.

The present inventors provide the following.

<1> an organic compound A having a refractive index of 1.58 or more with respect to light having a wavelength of 633 nm;

a near-infrared absorbing dye;

As a composition comprising a solvent,

The organic compound A is at least one selected from a polymerizable compound and a resin,

When a film having a thickness of 0.35 μm is formed using the composition, the refractive index of the film with respect to light having a wavelength of 633 nm is 1.58 or more, and the minimum value of the transmittance of light having a wavelength of 400 to 600 nm of the film is 85% or more.

<2> The composition according to <1>, wherein when a film having a thickness of 0.35 µm is formed using the composition, the film has an average transmittance of light having a wavelength of 800 to 870 nm of 80% or less.

<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>, comprising two or more kinds of the organic compound A.

<5> In any one of <1> to <4>, wherein the content of the organic compound having a refractive index of 1.63 or more with respect to light having a wavelength of 633 nm in the total amount of the organic compound A contained in the composition is 5 to 100% by mass described composition.

<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 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 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 a wavelength range of 750 nm to 1000 nm.

<9> The near-infrared absorbing dye is at least one selected from a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound, as described in any one of <1> to <8>. composition.

<10> The composition according to any one of <1> to <9>, which is for microlenses.

<11> A film obtained by using the composition according to any one of <1> to <10>.

<12> The microlens having the film according to <11>.

<13> The solid-state imaging element which has a microlens as described in <12>.

<14> The display device having the microlens according to <12>.

ADVANTAGE OF THE INVENTION According to this invention, it has near-infrared shielding property and can provide the novel composition which can form film|membrane, such as a microlens with high visible light condensing performance. Moreover, a film|membrane, a microlens, a solid-state image sensor, and a display device using the composition can be provided.

Hereinafter, the content of the present invention will be described in detail.

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

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

In this specification, the numerical range indicated using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

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

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

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

In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Composition>

The composition of the present invention is

An organic compound A having a refractive index of 1.58 or more with respect to light having a wavelength of 633 nm;

a near-infrared absorbing dye;

As a composition comprising a solvent,

The organic compound A is at least one selected from a polymerizable compound and a resin,

When a film having a thickness of 0.35 μm is formed using the composition, the refractive index of the film with respect to light having a wavelength of 633 nm is 1.58 or more, and the minimum value of transmittance of light having a wavelength of 400 to 600 nm of the film is 85% or more.

The composition of this invention has near-infrared shielding property, and can provide the novel composition which can form films|membrane, such as a microlens with high visible light condensing performance. That is, since the composition of this invention contains a near-infrared absorbing dye, it can form the film|membrane which has near-infrared shielding property. And, the composition of the present invention further contains the organic compound A having a refractive index of 1.58 or more with respect to light having a wavelength of 633 nm, and when a film having a thickness of 0.35 μm is formed, the refractive index of the above-mentioned film with respect to light having a wavelength of 633 nm is 1.58 Above, since the minimum value of transmittance of light having a wavelength of 400 to 600 nm of the above-described film has a characteristic of 85% or more, it is possible to form a film such as a microlens having a high visible light condensing performance while having near-infrared shielding properties.

Therefore, for example, by setting a film such as a microlens obtained by using the composition of the present invention on the light incident side with respect to the pixel of the solid-state imaging device, the condensing performance of visible light incident on the pixel is increased to increase the visible light sensitivity of the pixel. In addition, it is possible to suppress the near-infrared rays from entering the pixel, so that a clear image or the like can be detected. For this reason, the composition of this invention can be used suitably as a composition for microlenses. More preferably, it can use as objects for microlenses of a solid-state image sensor. More preferably, it can be used for a microlens arrange|positioned on the optical path of the light-incident side with respect to a color filter of the solid-state image sensor provided with a 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 with respect to light having a wavelength of 633 nm is 1.58 or more, preferably 1.60 or more, and more preferably 1.62 or more. Moreover, it is preferable that the average refractive index with respect to the light of wavelength 400-600 nm of the above-mentioned film|membrane is 1.60 or more, It is more preferable that it is 1.62 or more, It is still more preferable that it is 1.64 or more. Although the upper limit is not specifically limited, It can be made into 1.75 or less. Such a characteristic of a refractive index can be achieved by adjusting the kind and content of the organic compound A and a near-infrared absorbing dye. For example, it can achieve by methods, such as increasing content of the organic compound A in the total solid in a composition, or using the organic compound A with a higher refractive index.

In the composition of the present invention, when a film having a thickness of 0.35 µm is formed, the minimum value of the transmittance of light having a wavelength of 400 to 600 nm of the above-mentioned film is 85% or more, preferably 90% or more, and more preferably 95% or more. Moreover, it is preferable that the average transmittance|permeability of the light of wavelength 400-600 nm of the above-mentioned film|membrane is 90 % or more, It is more preferable that it is 93 % or more, It is more preferable that it is 96 % or more. In order to achieve such a transmittance characteristic, the content of a material having absorption in the visible region, such as a chromatic colorant or a black colorant, in the total solid content of the composition is reduced, or a near-infrared absorbing dye with high visible transparency is used. Methods such as can be achieved with

In the composition of the present invention, when a film having a thickness of 0.35 μm is formed, the average transmittance of light having a wavelength of 800 to 870 nm of the above-mentioned film is preferably 80% or less, more preferably 75% or less, and still more preferably 70% or less. Moreover, it is preferable that it is 70 % or less, and, as for the minimum value of the transmittance|permeability of the light of wavelength 800-870 nm of the above-mentioned film|membrane, it is more preferable that it is 65 % or less, It is more preferable that it is 60 % or less. Moreover, it is preferable that it is 85 % or less, and, as for the maximum value of the transmittance|permeability of the light of wavelength 800-870 nm of the above-mentioned film|membrane, it is more preferable that it is 82 % or less, It is more preferable that it is 80 % or less. Such a characteristic of the transmittance|permeability can be achieved by methods, such as adjusting the kind and content of a near-infrared absorbing dye. For example, it can be achieved by a method, such as increasing content of a near-infrared absorbing dye, or using a near-infrared absorbing dye with a high extinction coefficient in a maximal absorption wavelength.

It is preferable that the composition of this invention does not contain a chromatic coloring agent and a black coloring agent substantially. When the composition of the present invention contains substantially no chromatic colorant and black colorant, it means that the total content of the chromatic colorant and black colorant is 0.1% by mass or less in the total solid content of the composition, preferably 0.05% by mass or less, It is more preferable that it is 0.01 mass % or less, and it is especially preferable not to contain it.

It is preferable that the viscosity in 25 degreeC of the composition of this invention is 3-20 mPa*s from a viewpoint of applicability|paintability. 4 mPa*s or more is preferable and, as for a minimum, 5 mPa*s or more is more preferable. 15 mPa*s or less is preferable and, as for an upper limit, 13 mPa*s or less is more preferable.

It is preferable that solid content concentration of the composition of this invention is 10-30 mass % from a viewpoint of applicability|paintability. 13 mass % or more is preferable and, as for a minimum, 15 mass % or more is more preferable. 27 mass % or less is preferable and, as for an upper limit, 25 mass % or less is more preferable.

Hereinafter, the composition of the present invention will be described in detail.

<<Organic Compound A>>

The composition of this invention contains the organic compound A whose refractive index with respect to the light of wavelength 633nm is 1.58 or more. It is preferable that the refractive index with respect to the light of wavelength 633nm of organic compound A is 1.63 or more. The upper limit of the refractive index is not particularly limited, but may be 1.80 or less.

In addition, the content of the organic compound having a refractive index of 1.63 or more with respect to light having 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, , 40-100 mass % is more preferable.

In addition, the value of the refractive index of the organic compound A is measured using an ellipsometer by applying on a support such as a silicon wafer so that the film thickness after application becomes 0.3 μm, heating at 100°C for 2 minutes, and heating at 200°C for 5 minutes. is the value

The organic compound A is at least 1 sort(s) chosen from a polymeric compound and resin.

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 hydroxyl group, a compound having a carboxy group, and a compound having a —NH ₂ group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group. As a cyclic ether group, an epoxy group, oxetanyl group, etc. are mentioned. The polymeric compound used as the organic compound A may also contain 2 or more types of polymeric compounds. It is preferable that the polymeric compound used as organic compound A contains at least either the compound which has an ethylenically unsaturated bond containing group, and the compound which has a cyclic ether group.

When the organic compound A is a polymerizable compound, it is preferable that the organic compound A is a monomer. Moreover, as molecular weight of organic compound A, it is preferable that it is 200-1000. It is preferable that it is 900 or less, and, as for an upper limit, it is more preferable that it is 800 or less. It is preferable that it is 250 or more, and, as for a minimum, it is more preferable that it is 300 or more.

When the organic compound A is resin, it is preferable that it is 2000-100000 as a weight average molecular weight of the organic compound A. It is preferable that it is 90000 or less, and, as for an upper limit, it is more preferable that it is 80000 or less. It is preferable that it is 3000 or more, and, as for a minimum, it is more preferable that it is 4000 or more. Moreover, resin may have polymeric groups, such as an ethylenically unsaturated bond containing group, a cyclic ether group, a hydroxyl group, _a carboxy group, and -NH2 group.

It is preferable that the composition of this invention contains 2 or more types of organic compounds A. Especially, it is preferable to contain 1 or more types of organic compound A of a resin type, and organic compound A of a polymerizable compound type, respectively. According to such an aspect, the film|membrane contraction|shrinkage after film formation is small, and a film|membrane with high intensity|strength can be formed. In addition, when the resin type organic compound A and the polymerizable compound type organic compound A are used together, the composition of the present invention contains the polymerizable compound type organic compound A with respect to 100 parts by mass of the resin type organic compound A. It is preferable to contain 10-800 mass parts, and it is more preferable to contain 50-700 mass parts. According to this aspect, the effect mentioned above is acquired more notably.

It is preferable that the organic compound A is a compound which has at least 1 sort(s) of structure chosen 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 compound mentioned above may be a compound of a monomer type, and a compound of a resin type may be sufficient as it.

As a compound which has a fluorene structure, the compound which has a partial structure represented by a following formula (Fr) is mentioned.

(Fr)

[Formula 1]

In the formula, a broken 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 pieces of R ^f1 may be the same or different, respectively, and two R ^f1 of m pieces of R ^f1 may be bonded to each other to form a ring. When n is 2 or more, n pieces of R ^f2 may be the same or different, respectively, and two R ^f2 of n pieces of R ^f2 may be bonded to each other to form a ring. Examples of the substituent represented by R ^f1 and R ^f2 include a substituent T described later.

As a compound which has a triazine structure, the compound which has a partial structure represented by a following formula (Ta) is mentioned. In the formula, a broken line indicates a bond.

(Ta)

[Formula 2]

It is also preferable that the compound which has a triazine structure is a compound which has group represented by a following formula (Ta-1).

(Ta-1)

[Formula 3]

In the formula, a broken line indicates a bond.

C ¹ to C ³ each independently represent -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-, and more preferably -NH-.

Ar ¹ and Ar ² each independently represent an aryl group or a heterocyclic group. As the aryl group, a phenyl group is preferable. Although the heterocyclic group may or may not show aromaticity, it is preferable to show aromaticity. As for the number of hetero atoms which comprise a heterocyclic ring, 1-3 are preferable. The hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aryl group and the heterocyclic group may have a substituent. As a substituent, the substituent T mentioned later and a polymeric group are mentioned. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups such as vinyl group, (meth)allyl group and (meth)acryloyl group, cyclic ether groups such as epoxy group and oxetanyl group, hydroxyl group, carboxy group, -NH ₂ group and the like.

Ar ³ represents an arylene group or a divalent heterocyclic group. As the arylene group, a phenylene group is preferable.

L _A represents a single bond or a divalent linking group. Examples of the divalent linking group include -NH-, -O-, -CO-, -CO-O-, an alkylene group (preferably having 1 to 3 carbon atoms), or a combination thereof (eg, -O-alkylene group). - etc.) is preferable.

As a preferable example of the compound which has a triazine structure, the compound represented by following formula (I) is mentioned.

(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 group represented by Formula (Ta-1).

X represents an m+n valent linking group.

B represents a polymer chain or a substituent.

In addition, two or more A's may be same or different, respectively. When two or more Bs exist, two or more Bs may be same or different, respectively.

Although it does not specifically limit as a linking group of m+n valence represented by X, Group (which may form a ring structure) is mentioned by the following structural unit or the following structural unit combining 2 or more.

[Formula 4]

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 may be selected depending on the purpose and the like. Among them, the polymer chain is a vinyl monomer polymer or copolymer, an ester-based polymer, an ether-based polymer, a urethane-based polymer, an amide-based polymer, an epoxy-based polymer, and a polymer composed of a polymer selected from the group consisting of a silicone-based polymer A chain|strand is preferable and the polymer chain comprised from the polymer or copolymer of a (meth)acrylic compound is more preferable. The polymer chain may have a substituent. In addition, when two or more substituents exist, the substituent which exists two or more may be same or different. 200-10000 are preferable and, as for the weight average molecular weight of the polymer chain represented by B, 300-5000 are more preferable. Moreover, as a substituent which B represents, the substituent T mentioned later is mentioned.

As a compound which has a triazine structure, it is also preferable that it is a compound represented by a following formula (Ta-10).

(Ta-10)

[Formula 5]

C ¹ to C ³ each independently represent -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-, and more preferably -NH-.

Rt ¹ to Rt ¹⁵ each independently represents a hydrogen atom or a substituent, and at least one of Rt ¹ to Rt ¹⁵ represents a polymerizable group. As a substituent, the substituent T mentioned later and a polymeric group are mentioned. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups such as vinyl group, (meth)allyl group and (meth)acryloyl group, cyclic ether groups such as epoxy group and oxetanyl group, hydroxyl group, carboxy group, -NH ₂ group and the like.

It is preferable that at least one of Rt ¹ to Rt ⁵ and at least one of Rt ⁶ to Rt ¹⁰ each represent a polymerizable group, and any one of Rt ¹ to Rt ⁵ and any one of Rt ⁶ to Rt ¹⁰ each represents a polymerizable group It is more preferable to represent

As a compound which has a carbazole structure, the compound which has a partial structure represented by a following formula (Cz) is mentioned.

(Cz)

[Formula 6]

In the formula, a broken 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 pieces of R ^c1 may be the same or different, respectively, and two R ^c1s among m2 pieces of R ^c1 may be bonded to each other to form a ring. When n2 is 2 or more, n2 pieces of R ^c2 may be the same or different, respectively, and two R ^c2 of n2 pieces of R ^c2 may be bonded to each other to form a ring. Examples of the substituent represented by R ^c1 and R ^c1 include a substituent T described later.

As a specific example of the organic compound A as a polymeric compound, the compound of the structure shown below, Ogsol PG-100 (Osaka Gas Chemical Co., Ltd. product, the epoxy compound which has a fluorene structure), Ogsol EG-200 (Osaka Gas) Chemical Co., Ltd. product, the epoxy compound which has a fluorene structure) etc. are mentioned.

[Formula 7]

As a specific example of the organic compound A as resin, the compound of the structure shown below, the resin described in Synthesis Example 1 of Unexamined-Japanese-Patent No. 2013-139588, the resin of Example 1 of Unexamined-Japanese-Patent No. 2017-031311, etc. are mentioned. .

[Formula 8]

[Formula 9]

[Formula 10]

50 mass % or more is preferable, as for content of the organic compound A in the total solid of a composition, 55 mass % or more is more preferable, and its 60 mass % or more is still more preferable. 98 mass % or less is preferable and, as for an upper limit, 95 mass % or less is more preferable.

Moreover, when organic compound A is a polymeric compound or resin, 50-100 mass % is preferable, and, as for content of organic compound A in the total amount of resin and polymeric compound contained in a composition, 50-100 mass % is It is more preferable, and 70-100 mass % is still more preferable.

<<Near-infrared absorbing dye>>

The composition of this 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 a wavelength range of 750 to 1000 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 770 to 950 nm, with a wavelength of 800 to More preferably, it is a compound having a maximum absorption wavelength in the range of 900 nm. Moreover, it is preferable that it is 0.08 or less, and, as for ratio ^A1 /A2 ^{of the} absorbance A1 in wavelength 500nm of a near-infrared absorbing dye, and the absorbance A2 in ^a maximal absorption wavelength, it is more preferable that it is 0.04 or less.

A pigment may be sufficient as a near-infrared absorption dye, and dye may be sufficient as it. When a pigment is used, a film excellent in heat resistance, light resistance, etc. can be formed. When a dye is used, a film|membrane with a small haze can be formed.

Examples of the near-infrared absorbing dye include a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, a polymethine compound, an iminium compound, a quaterrylene compound, a dithiol compound, a triarylmethane compound, a pyromethene compound, an azomethine compound, an anthraquinone compound, a dibenzofuranone compound, and a dithiorene metal complex, and a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound It is preferable that it is at least 1 type, and it is more preferable that it is a pyrrolopyrrole compound. As a polymethine compound, a cyanine compound, a squarylium compound, a croconium compound, etc. are mentioned.

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

[Formula 11]

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, R ² and R ³ are bonded to each other A ring may be formed, and R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, and R ⁴ is R ^1a , R ^1b and R ³ It may be covalently bonded or coordinated with at least one selected from, and R ^4A and R ^4B each independently represent a substituent. About the detail of Formula (PP), Paragraph No. 0017 of Unexamined-Japanese-Patent No. 2009-263614, Paragraph No. 0011-0036 of Unexamined-Japanese-Patent No. 2011-068731, Paragraph No. 0010-0024 of International Publication No. 2015/166873 Reference may be made to the description, the contents of which are incorporated herein by reference.

In formula (PP), R ^1a and R ^1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. Moreover, the alkyl group, aryl group, and heteroaryl group which R<^1a> and R ^<1b represent may have a substituent, and may be unsubstituted. As a substituent, Paragraph No. 0020 of Unexamined-Japanese-Patent No. 2009-263614 - the substituent of 0022, and the following substituent T are mentioned. Moreover, when the alkyl group, aryl group, and heteroaryl group represented by R ^1a and R ^1b have two or more substituents, the substituents may couple|bond together and may form the ring.

(substituent T)

An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an alkynyl group having 2 to 30 carbon atoms) is an aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an alkoxy group having 6 to 30 carbon atoms) aryloxy group), heteroaryloxy group, acyl group (preferably an acyl group having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably an acyl group having 2 to 30 carbon atoms). 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 an acyloxy group having 2 to 30 carbon atoms) is an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), A 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 having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably having 1 to 30 carbon atoms), an arylsulfonyl group (preferably having 6 to 30 carbon atoms), a heteroarylsulfonyl group (preferably having 6 to 30 carbon atoms). 1 to 30), an alkylsulfinyl group (preferably 1 to 30 carbon atoms), an arylsulfinyl group (preferably 6 to 30 carbon atoms), a heteroarylsulfinyl group (preferably 1 to 30 carbon atoms), a ureido group (preferably is C1-30), a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, a carboxylic acid amide group (preferably a group represented by -NHCOR ^A1 , and R ^A1 represents a hydrocarbon group or a heterocyclic group. Hydrocarbon group and heterocyclic group The ventilation may further have a substituent.As a substituent, it is preferable that it is a halogen atom, and it is more preferable that it is a fluorine atom.), a sulfonic acid amide group (preferably represented by -NHSO ₂ R ^A2 ) i'm gi R ^A2 represents a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group may further have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.), an imidic acid group (preferably -SO ₂ NHSO ₂ R ^A3 , -CONHSO ₂ R ^A4 , -CONHCOR ^A5 or -SO ₂ ) It is a group represented by NHCOR ^A6 . Each of R ^A3 to R ^A6 independently represents a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group may further have a substituent), a mercapto group, a halogen atom; A cyano group, an alkylsulfino group, an arylsulfino group, a hydrazino group, an imino group, a heteroaryl group (preferably having 1 to 30 carbon atoms).

When these groups are substitutable groups, they may further have a substituent. As a substituent, the group demonstrated by the above-mentioned substituent T is mentioned.

Specific examples of the group 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 the formula (PP), R ² and R ³ each independently represent a hydrogen atom or a substituent. As a substituent, the above-mentioned substituent T is mentioned. At least one of R ² and R ³ has a preferable electron withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron withdrawing group. Here, the substituent constants obtained by Hammett's law include σp values and σm values. These values can be found in most general books. In this invention, the substituent whose Hammett's substituent constant (sigma) value is 0.20 or more can be illustrated as an electron withdrawing group. 0.25 or more are preferable, as for sigma value, 0.30 or more are more preferable, and 0.35 or more are still more preferable. Although there is no restriction|limiting in particular as an upper limit, Preferably it is 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), and an aryloxycarbonyl group (eg -COOPh: σp value = 0.44), carbamoyl group (eg, -CONH ₂ : σp value = 0.36), alkylcarbonyl group (eg, -COMe: σp value = 0.50), aryl A carbonyl group (eg, -COPh: σp value = 0.43), an alkylsulfonyl group (eg, -SO ₂ Me: σp value = 0.72), an arylsulfonyl group (eg, -SO ₂ Ph: σp value) =0.68), and a cyano group is preferable. Here, Me represents a methyl group and Ph represents a phenyl group. In addition, about the substituent constant (sigma) value of Hammett, Paragraph No. 0017 of Unexamined-Japanese-Patent No. 2011-068731 - 0018 can be considered into consideration, for example, This content is integrated in this specification.

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

In the 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 a hydrogen atom, an alkyl group, an aryl group or a group represented by -BR ^4A R ^4B It is more preferable that it is a group, and it is more preferable that it is a group represented by -BR ^4A R ^4B . As the substituent represented by R ^4A and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, an alkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is particularly preferable. These groups may further have a substituent. Two R< ⁴ > in Formula (PP) may be same or different. R ^4A and R ^4B may be bonded to each other to form a ring.

As a specific example of the compound represented by Formula (PP), the compound described in the Example mentioned later is mentioned. Moreover, as a pyrrolopyrrole compound, the compound of Paragraph Nos. 0016 to 0058 of Unexamined-Japanese-Patent No. 2009-263614, the compound of Paragraph No. 0037-0052 of Unexamined-Japanese-Patent No. 2011-068731, International Publication No. 2015/166873 Paragraph numbers 0010 - the compound of 0033, etc. are mentioned.

As a squarylium compound, Paragraph No. 0044 of Unexamined-Japanese-Patent No. 2011-208101 - Paragraph No. 0049, The compound of Paragraph No. 0060 - 0061 of Unexamined-Japanese-Patent No. 6065169 Paragraph No. 0040 of International Publication No. 2016/181987 The compound described, the compound described in Japanese Unexamined Patent Publication No. 2015-176046, the compound described in Paragraph No. 0072 of International Publication No. 2016/190162, the compound described in Paragraph No. 0196 to 0228 of Japanese Unexamined Patent Publication No. 2016-074649, Japanese Patent Application Laid-Open No. The compound described in Paragraph No. 0124 of Publication No. 2017-067963, the compound described in International Publication No. 2017/135359, the compound described in Japanese Patent Application Laid-Open No. 2017-114956, the compound described in Japanese Patent Publication No. 6197940, International Publication No. 2016 The compound of /120166, etc. are mentioned. As a cyanine compound, the compound of Paragraph Nos. 0044 - 0045 of Unexamined-Japanese-Patent No. 2009-108267, Paragraph No. 0026 - 0030 of Unexamined-Japanese-Patent No. 2002-194040, The compound of Unexamined-Japanese-Patent No. 2015-172004. , the compound described in JP-A-2015-172102, the compound described in JP-A 2008-088426, the compound described in Paragraph No. 0090 of International Publication No. 2016/190162, the compound described in JP-A 2017-031394 A compound etc. are mentioned. As a croconium compound, the compound of Unexamined-Japanese-Patent No. 2017-082029 is mentioned. As an iminium compound, For example, the compound of Unexamined-Japanese-Patent No. 2008-528706, the compound of Unexamined-Japanese-Patent No. 2012-012399, the compound of Unexamined-Japanese-Patent No. 2007-092060, International Publication No. 2018 Paragraph Nos. 0048 to 0063 of /043564 can be mentioned. As a phthalocyanine compound, Paragraph No. 0013 of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153, oxytitanium phthalocyanine of Unexamined-Japanese-Patent No. 2006-343631, Paragraph No. 0013 of Unexamined-Japanese-Patent No. 2013-195480. The compound described in ~0029 and the vanadium phthalocyanine compound described in Japanese Patent Application Laid-Open No. 6081771 are mentioned. As a naphthalocyanine compound, the compound of Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned. As a dithiorene metal complex, the compound of Unexamined-Japanese-Patent No. 5733804 is mentioned.

Moreover, as a near-infrared absorbing dye, the squarylium compound described in Unexamined-Japanese-Patent No. 2017-197437, the squarylium compound described in Unexamined-Japanese-Patent No. 2017-025311, and the squarylium described in International Publication No. 2016/154782. The compound, the squarylium compound described in Japanese Patent Publication No. 5884953, the squarylium compound described in Japanese Patent Publication No. 6036689, the squarylium compound described in Japanese Patent Publication No. 5810604, Paragraph of International Publication No. 2017/213047 The squarylium compound described in Nos. 0090 to 0107, the pyrrole ring-containing compound described in Paragraph Nos. 0019 to 0075 of Japanese Patent Application Laid-Open No. 2018-054760, and the pyrrole ring-containing compound described in Paragraph Nos. , a pyrrole ring-containing compound described in Paragraph Nos. 0043 to 0069 of Japanese Patent Application Laid-Open No. 2018-002773, a squarylium compound having an aromatic ring on the amide α described in Paragraph Nos. 0024 to 0086 of Japanese Patent Application Laid-Open No. 2018-041047, JP Amide-linked squarylium compound described in Patent Publication No. 2017-179131, a compound having a pyrrolebis-type squarylium skeleton or croconium skeleton described in Japanese Patent Application Laid-Open No. 2017-141215, described in Japanese Patent Application Laid-Open No. 2017-082029 Dihydrocarbazole bis-type squarylium compound, the asymmetric compound described in Paragraph Nos. 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017-068120, and a pyrrole ring-containing compound described in Japanese Patent Application Laid-Open No. 2017-067963 (carbazole type) , the phthalocyanine compound described in Japanese Patent Application Laid-Open No. 6251530 or the like can also be used.

As for content of the near-infrared absorbing dye in the total solid of a composition, 1-20 mass % is preferable. 2 mass % or more is preferable and, as for a minimum, 3 mass % or more is more preferable. 17 mass % or less is preferable and, as for an upper limit, 15 mass % or less is more preferable.

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

It is preferable that a composition contains 1-30 mass parts of near-infrared absorbing dyes with respect to 100 mass parts of organic compound A mentioned above. 2 mass parts or more are preferable and, as for a minimum, 3 mass parts or more are more preferable. 25 mass parts or less are preferable and, as for an upper limit, 20 mass parts or less are more preferable. According to this aspect, coexistence of high near-infrared absorption performance and high refractive index can be aimed at.

The composition of this invention WHEREIN: Only 1 type may be used for a near-infrared absorbing dye, and 2 or more types may be used for it. When using 2 or more types, it is preferable that those total amounts become the said range.

<<Solvent>>

The composition of this invention contains a solvent. There is no restriction|limiting in particular in particular as long as a solvent satisfy|fills the solubility of each component and the applicability|paintability of a composition. It is preferable that a solvent is an organic solvent. Examples of the organic solvent include an ester solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. For details of these, reference may be made to paragraph No. 0223 of International Publication No. 2015/166779, the content of which is incorporated herein by reference.

Moreover, the ester type solvent by which the cyclic alkyl group was substituted, and the ketone type solvent by which the cyclic alkyl group was substituted can also be used preferably. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl Ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, etc. are mentioned. However, there are cases where it is better to reduce the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the organic solvent for reasons such as environmental reasons (for example, 50 mass ppm based on the total amount of the organic solvent) (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

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

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

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

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

It is preferable that content of the solvent in a composition is 70-90 mass %. It is preferable that it is 73 mass % or more, and, as for a minimum, it is more preferable that it is 75 mass % or more. It is preferable that it is 87 mass % or less, and, as for an upper limit, it is more preferable that it is 85 mass % or less.

<<Other Polymerizable Compounds>>

The composition of the present invention may contain a polymerizable compound (hereinafter also referred to as another polymerizable compound) other than the organic compound A described above. As another polymerizable compound, the compound which has an ethylenically unsaturated bond containing group, the compound which has a cyclic ether group, etc. are mentioned, It is preferable that it is a compound which has an ethylenically unsaturated bond containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group. As a cyclic ether group, an epoxy group, oxetanyl group, etc. are mentioned.

As the compound having an ethylenically unsaturated bond-containing group, any of chemical forms such as a monomer, a prepolymer, and an oligomer may be used, but a monomer is preferable. As for the molecular weight of the compound which has an ethylenically unsaturated bond containing group, 100-3000 are preferable. 2000 or less are more preferable and, as for an upper limit, 1500 or less are still more preferable. 150 or more are more preferable, and, as for a minimum, 250 or more are still more preferable.

The compound having an ethylenically unsaturated bond-containing group is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and an ethylenically unsaturated bond-containing group It is more preferable that it is a compound containing 3-6 containing groups. Moreover, it is preferable that it is a 3-15 functional (meth)acrylate compound, and, as for the compound which has an ethylenically unsaturated bond containing group, it is more preferable that it is a 3-6 functional (meth)acrylate compound. As a specific example of the compound which has an ethylenically unsaturated bond containing group, Paragraph No. 0095 of Unexamined-Japanese-Patent No. 2009-288705, Paragraph 0227 of Unexamined-Japanese-Patent No. 2013-029760, Paragraph No. 0254 of Unexamined-Japanese-Patent No. 2008-292970 Paragraph 0254-0257 , Paragraph Nos. 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, Paragraph Nos. 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048367, Japanese Patent Publication No. 6057891, Japanese Patent Publication No. 6031807, The compound described in Unexamined-Japanese-Patent No. 2017-194662 is mentioned, These content is integrated in this specification.

Moreover, as a compound which has an ethylenically unsaturated bond containing group, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial item; Nippon Kayaku Co., Ltd. product), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial item) ; Nippon Kayaku Co., Ltd. product), dipentaerythritol penta (meth) acrylate (as a commercial item, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa (meth) acrylate (as a commercial item) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are ethylene glycol and/or propylene glycol and compounds having a structure bonded through a residue (eg, SR454 and SR499 commercially available from Sartomer) and the like. Moreover, as a compound which has an ethylenically unsaturated bond containing group, trimethylol propane tri(meth)acrylate, trimethylol propane propyleneoxy modified|denatured tri(meth)acrylate, trimethylol propane ethyleneoxy modified|denatured tri(meth) ) acrylate, trifunctional (meth)acrylate compounds such as isocyanuric acid ethyleneoxy-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate can be used. As a commercial item of a trifunctional (meth)acrylate compound, Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305 , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) ) and the like.

As the compound having an ethylenically unsaturated bond-containing group, a compound having an acid group can also be used. As an acidic radical, a carboxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned, A carboxyl group is preferable. As a commercial item, Aronix M-510, M-520, Aronix TO-2349 (made by Toagosei Co., Ltd.), etc. are mentioned.

It is also preferable that the compound which has an ethylenically unsaturated bond containing group is a compound which has a caprolactone structure. The compound which has a caprolactone structure is marketed, for example as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., DPCA-20, DPCA-30, DPCA-60, DPCA-120 etc. are mentioned.

The compound having an ethylenically unsaturated bond-containing group is a compound described in Japanese Patent Application Laid-Open No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent Application Laid-Open No. 2017-194662. It is also preferable to use a compound, 8UH-1006, 8UH-1012 (above, Daisei Fine Chemicals Co., Ltd. product), light acrylate POB-A0 (Kyoeisha Chemical Co., Ltd. product) etc. are used.

As a compound which has a cyclic ether group, it is preferable that it is a compound (henceforth an epoxy compound) which has an epoxy group. As an epoxy compound, the compound which has one or more epoxy groups in 1 molecule is mentioned, The compound which has two or more epoxy groups is preferable. As for an epoxy compound, the compound which has 1-100 epoxy groups in 1 molecule is preferable. The upper limit of the epoxy group may be, for example, 10 or less and may be 5 or less. As for the minimum of an epoxy group, two or more are preferable. As an epoxy compound, Paragraph No. 0085 of Unexamined-Japanese-Patent No. 2013-011869 Paragraph No. 0034 - 0036, Paragraph No. 0085 of Unexamined-Japanese-Patent No. 2014-089408 The compound of Paragraph No. 0147 - 0156 of Unexamined-Japanese-Patent No. 2014-043556 The compound described in 0092 and the compound described in Japanese Patent Application Laid-Open No. 2017-179172 can also be used.

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

As a commercial item of the compound which has a cyclic ether group, For example, EHPE3150 (made by Daicel Corporation), EPICLON N-695 (made by DIC Corporation), Mapproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, Nichiyu Co., Ltd. product, epoxy group containing polymer) etc. are mentioned.

It is preferable that content of the other polymeric compound in the total solid of a composition is 30 mass % or less, 25 mass % or less is more preferable, and its 20 mass % or less is more preferable.

Moreover, it is also preferable that the composition of this invention does not contain another polymeric compound substantially. According to this aspect, the film|membrane with a higher refractive index can be formed. In addition, when the composition of this invention does not contain another polymeric compound substantially, it means that content of another polymeric compound is 0.1 mass % or less in the total solid of a composition, It is preferable that it is 0.05 mass % or less, and 0.01 mass % or less is more preferable, and it is particularly preferable not to contain it.

<<Other resins>>

The composition of the present invention may contain a resin (hereinafter also referred to as other resin) other than the organic compound A described above. Resin is mix|blended for the use of disperse|distributing particle|grains, such as a pigment, in a composition, and the use of a binder, for example. In addition, a resin mainly used for dispersing particles or the like in the composition is also referred to as a dispersing agent. However, such a use of resin is an example, and resin can also be used for the purpose other than such a use.

As for the weight average molecular weight (Mw) of other resin, 2000-200000 are preferable. 1000000 or less are preferable and, as for an upper limit, 500000 or less are more preferable. 3000 or more are preferable, as for a minimum, 4000 or more are more preferable, and 5000 or more are still more preferable.

As other resin, for example, (meth)acrylic resin, (meth)acrylamide resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether Tersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, etc. are mentioned. .

Other resin may have an acidic radical. As an acidic radical, a carboxyl group, a phosphoric acid group, a sulfo group, phenolic hydroxyl group etc. are mentioned, for example. The number of these acidic radicals may be one, and 2 or more types may be sufficient as them. Resin which has an acidic radical can also be used as alkali-soluble resin and a dispersing agent.

When other resin has an acidic radical, as for the acid value of the acidic radical of another resin, 30-500 mgKOH/g is preferable. As for a minimum, 50 mgKOH/g or more is more preferable, and 70 mgKOH/g or more is still more preferable. The upper limit is more preferably 400 mgKOH/g or less, still more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

Another resin is a resin containing a repeating unit derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). desirable.

[Formula 12]

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.

[Formula 13]

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

About the specific example of an ether dimer, Paragraph No. 0317 of Unexamined-Japanese-Patent No. 2013-029760 can be considered into consideration, and this content is integrated in this specification.

Other resin may have an ethylenically unsaturated bond containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group. Examples of commercially available resins having an ethylenically unsaturated bond-containing group include DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), and Viscot. R-264, KS resist 106 (all manufactured by Osaka Yuki Chemical Co., Ltd.), Cyclomer P series (eg, ACA230AA), Flaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (Daisel Corporation) Civi Corporation make), Acrycure RD-F8 (made by Nippon Shokubai Co., Ltd.), DP-1305 (Fujifilm Fine Chemicals Co., Ltd. product), etc. are mentioned.

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

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

[Formula 14]

Moreover, it is also preferable to use the oligoimine-type resin which contains a nitrogen atom in at least one of a main chain and a side chain as a dispersing agent. The oligoimine-based resin has a structural unit having a partial structure X having a functional group with a pKa of 14 or less, a side chain including a side chain Y having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain It is preferable that it is resin. About oligoimine-type resin, Paragraph No. 0102 of Unexamined-Japanese-Patent No. 2012-255128 - description of 0166 can be considered into consideration, and this content is integrated in this specification. As oligoimine-type resin, resin of the following structure and the resin of Paragraph No. 0168 - 0174 of Unexamined-Japanese-Patent No. 2012-255128 can be used.

[Formula 15]

A dispersing agent is also available as a commercial item, As such a specific example, the Disperbyk series (for example, Disperbyk-111, 2001 etc.) manufactured by Bikchemi, and Solsperse series made by Nippon Lubrizol Co., Ltd. (for example, , Solsperse 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd. Ajisper series, etc. are mentioned. Moreover, the product of Paragraph No. 0129 of Unexamined-Japanese-Patent No. 2012-137564, and the product of Paragraph No. 0235 of Unexamined-Japanese-Patent No. 2017-194662 can also be used as a dispersing agent.

It is preferable that content of other resin in the total solid of a composition is 30 mass % or less, 25 mass % or less is more preferable, and its 20 mass % or less is still more preferable.

Moreover, it is also preferable that the composition of this invention does not contain another resin substantially. According to this aspect, the film|membrane with 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 in the total solid content of the composition, preferably 0.05% by mass or less, and more preferably 0.01% by mass or less It is preferable, and it is especially preferable not to contain it.

<<Pigment Derivatives>>

The composition of the present invention may contain a pigment derivative. When a pigment-type near-infrared absorbing dye is used, it is preferable that the composition contains a pigment derivative. As a pigment derivative, the compound which has the structure in which the acidic radical or the basic group couple|bonded with the pigment skeleton is mentioned. As the dye skeleton constituting the pigment derivative, quinoline dye skeleton, benzimidazolone dye skeleton, benzisoindole dye skeleton, benzothiazole dye skeleton, iminium dye skeleton, squarylium dye skeleton, croconium dye skeleton, oxonol Pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, azo pigment skeleton, azomethine pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, anthraquinone pigment skeleton, quinacridone pigment Skeleton, dioxazine pigment skeleton, perinone pigment skeleton, perylene pigment skeleton, thioindigo pigment skeleton, isoindoline pigment skeleton, isoindolinone pigment skeleton, quinophthalone pigment skeleton, iminium pigment skeleton, dithiol Dye skeleton, triarylmethane dye skeleton, pyromethene dye skeleton, etc. are mentioned. Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group, and salts thereof. Examples of the atom or group constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , etc.), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ , etc.), ammonium ions, imidazolium ions, and pyridinium ions. , phosphonium ions, and the like. Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, an ammonium group salt, and a phthalimidemethyl group. A hydroxide ion, a halogen ion, a carboxylate ion, a sulfonic acid ion, a phenoxide ion, etc. are mentioned as an atom or atomic group which comprises a salt.

As a specific example of a pigment derivative, the compound described in the Example mentioned later, Unexamined-Japanese-Patent No. 56-118462, Unexamined-Japanese-Patent No. 63-264674, Unexamined-Japanese-Patent No. Hei 01-217077, Unexamined-Japanese-Patent No. Hei 03. -009961, Japanese Unexamined Patent Publication No. Hei03-026767, Japanese Unexamined Patent Publication No. Hei03-153780, Japanese Unexamined Patent Publication No. Hei03-045662, Japanese Unexamined Patent Publication No. Hei04-285669, Japanese Unexamined Patent Publication No. Hei06 -145546, Japanese Unexamined Patent Publication No. Hei 06-212088, Japanese Unexamined Patent Publication No. Hei 06-240158, Japanese Unexamined Patent Publication No. Hei 10-030063, Japanese Unexamined Patent Publication No. Hei 10-195326, International Publication No. 2011/ Paragraph Nos. 0086 to 0098 of 024896, Paragraph Nos. 0063 to 0094 of International Publication No. 2012/102399, Paragraph No. 0082 of International Publication No. 2017/038252, Paragraph No. 0052 of International Publication No. 2017/146092, Japanese Patent Application Laid-Open No. Paragraph No. 0171 of 2015-151530, Paragraph No. 0162 to 0183 of Unexamined-Japanese-Patent No. 2011-252065, Unexamined-Japanese-Patent No. 2003-081972, Unexamined-Japanese-Patent No. 5299151, Unexamined-Japanese-Patent No. 2015-172732, Unexamined-Japanese-Patent No. The compound of Unexamined-Japanese-Patent No. 2014-199308, Unexamined-Japanese-Patent No. 2014-085562, Unexamined-Japanese-Patent No. 2014-035351, and Unexamined-Japanese-Patent No. 2008-081565 is mentioned.

1-30 mass parts is preferable with respect to 100 mass parts of pigments, and, as for content of a pigment derivative, 3-20 mass parts is more preferable. A pigment derivative may use only 1 type and may use 2 or more types together. When using 2 or more types together, it is preferable that those total amounts are the said range.

<<Photoinitiator>>

The composition of this invention may contain the photoinitiator. There is no restriction|limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, a compound having photosensitivity to light in the visible region from the ultraviolet region is preferable. It is preferable that a photoinitiator is a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (eg, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound, hexaarylbiimidazole, an oxime compound, an organic peroxide, thi five compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. A photoinitiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, α-hydroxyketone compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, and a metallocene from a viewpoint of exposure sensitivity. compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl substituted coumarin It is preferable that it is a compound, It is more preferable that it is a compound chosen from an oxime compound, (alpha)-hydroxyketone compound, (alpha)-amino ketone compound, and an acylphosphine compound, It is more preferable that it is an oxime compound. Moreover, as a photoinitiator, Paragraph 0065 of Unexamined-Japanese-Patent No. 2014-130173 - 0111, the compound of Unexamined-Japanese-Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide-based 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, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-043864, The photoinitiator of Unexamined-Japanese-Patent No. 2019-044030 is mentioned, These content is integrated in this specification.

Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above, manufactured by BASF). can As commercially available products of the α-aminoketone compound, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (above, manufactured by BASF), etc. there is. As a commercial item of an acylphosphine compound, Omnirad 819, Omnirad TPO (above, IGM Resins B.V. company make), Irgacure 819, Irgacure TPO (above, BASF company make) etc. are mentioned.

As an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, the compound of Unexamined-Japanese-Patent No. 2006-342166, J.C.S. Perkin II (1979, pp. 1653) -1660), the compound described in J. C. S. Perkin II (1979, pp. 156-162), the compound described in the Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A 2000- The compound described in 066385, the compound described in JP 2004-534797 A, the compound described in JP 2006-342166 , the compound described in JP 2017-019766 , the compound described in JP 6065596 A Compound, the compound described in International Publication No. 2015/152153, the compound described in International Publication No. 2017/051680, the compound described in Japanese Patent Application Laid-Open No. 2017-198865, Paragraph No. 0025 of International Publication No. 2017/164127 The compound of 0038, the compound of International Publication No. 2013/167515, etc. are mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one , 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.); Adeka optomer N-1919 (made by ADEKA Corporation, the photoinitiator 2 of Unexamined-Japanese-Patent No. 2012-014052) is mentioned. Moreover, as an oxime compound, it is also preferable to use the compound without coloring property, and the compound which transparency is high and is hard to change color. As a commercial item, ADEKA ARCL's NCI-730, NCI-831, NCI-930 (above, ADEKA Co., Ltd. make) etc. are mentioned.

As a photoinitiator, the oxime compound which has a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 is mentioned.

As a photoinitiator, the oxime compound which has frame|skeleton in which the at least 1 benzene ring of a carbazole ring became a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound of international publication 2013/083505 is mentioned.

As a photoinitiator, the oxime compound which has a fluorine atom can also be used. As a specific example of the oxime compound which has a fluorine atom, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24 of Unexamined-Japanese-Patent No. 2014-500852, 36-40, and the compound of Unexamined-Japanese-Patent No. 2013-164471. (C-3) etc. are mentioned.

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

As a photoinitiator, the oxime compound which has benzofuran frame|skeleton can also be used. As a specific example, OE-01 - OE-75 described in International Publication No. 2015/036910 are mentioned.

As a photoinitiator, the oxime compound which the substituent which has the hydroxyl group couple|bonded with the carbazole skeleton can also be used. As such a photoinitiator, the compound of International Publication No. 2019/088055, etc. are mentioned.

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

[Formula 16]

[Formula 17]

The compound which has a maximum absorption wavelength in the range of wavelength 350-500 nm is preferable, and, as for an oxime compound, the compound which has a maximum absorption wavelength in the range of wavelength 360-480 nm is more preferable. Moreover, it is preferable from a viewpoint of a sensitivity that the molar extinction coefficient in wavelength 365nm or wavelength 405nm of an oxime compound is high, It is more preferable that it is 1000-30000, It is more preferable that it is 2000-30000, It is 5000-20000 It is particularly preferred. The molar extinction coefficient of a compound can be measured using a well-known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g/L using an ethyl acetate solvent.

As a photoinitiator, you may use the photoradical polymerization initiator more than bifunctional or trifunctional. By using such a photo-radical polymerization initiator, since two or more radicals generate|occur|produce from 1 molecule of a photo-radical polymerization initiator, favorable sensitivity is acquired. Moreover, when the compound of an asymmetric structure is used, crystallinity falls and solubility with respect to a solvent etc. improves, it becomes difficult to precipitate over time, and it can improve the aging stability of a composition. As a specific example of a bifunctional or trifunctional or more than trifunctional photoradical polymerization initiator, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, Paragraph of Japanese Unexamined Patent Publication No. 2016-532675 No. 0407 to 0412, the dimer of the oxime compound described in Paragraph No. 0039 to 0055 of International Publication No. 2017/033680, the compound (E) and the compound (G) described in Japanese Unexamined Patent Publication No. 2013-522445, Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in Paragraph No. 0007 of Japanese Patent Application Laid-Open No. 2017-523465, Paragraph Nos. 0020 to 0033 of Japanese Unexamined Patent Publication No. 2017-167399 The photoinitiator described in , the photoinitiator (A) described in Paragraph Nos. 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, and the oxime ester photoinitiator described in Japanese Patent Publication No. 6469669, etc. are mentioned.

As for content of the photoinitiator in the total solid of a composition, 0.1-30 mass % is preferable. 0.5 mass % or more is preferable and, as for a minimum, 1 mass % or more is more preferable. 20 mass % or less is preferable and, as for an upper limit, 15 mass % or less is more preferable. The composition of this invention WHEREIN: Only 1 type may be used for a photoinitiator, and 2 or more types may be used for it. When using 2 or more types, it is preferable that those total amounts become the said range.

<<White or colorless pigment (white pigment)>>

The composition of the present invention may contain a white or colorless pigment (hereinafter also referred to as a white pigment). The white pigment contains 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. oxide particles are mentioned, and it is preferable that the oxide particles contain at least one element selected from Ti, Zr, Sn, Al, and Si. As the oxide, titanium oxide and zirconium oxide are preferable, and titanium oxide is more preferable. Moreover, as a titanium oxide, a rutile type titanium oxide, anatase type titanium oxide, and amorphous type titanium oxide are mentioned, A rutile type titanium oxide is preferable. Moreover, it is also preferable that the said oxide is surface-treated with a surface treating agent. An inorganic compound and an organic compound are mentioned as a surface treatment agent. You may use an inorganic compound and an organic compound together. Specific examples of the surface treatment agent include polyol, aluminum oxide, aluminum hydroxide, amorphous silica, hydrous silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogendimethicone, silane coupling agent, titanate coupling agent and the like.

The shape of the white pigment is not particularly limited. For example, shapes, such as an isotropic shape (For example, spherical shape, polyhedral shape, etc.), anisotropic shape (For example, needle shape, rod shape, plate shape, etc.), are mentioned.

It is preferable that it is 150 nm or less, and, as for the weight average particle diameter of the primary particle of a white pigment, it is more preferable that it is 100 nm or less, It is more preferable that it is 80 nm or less. Although there is no particular lower limit, it is preferable that it is 1 nm or more. In addition, as for 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 dynamic light scattering with respect to the obtained diluted solution It is obtained by measuring using the method. The measured value in this case is the weight average particle diameter obtained by carrying out using the Nikkiso Corporation Microtrac (brand name) UPA-EX150.

As a specific surface area of a white pigment, it is preferable that it is 10-400 m2/g, It is ^more preferable that it is 20-200 m2/g, It is ^more preferable that it is ^30-150 m2/g.

It is preferable that the refractive index of a white pigment is 1.6-3.0. It is preferable that it is 1.7 or more, and, as for a minimum, it is more preferable that it is 1.8 or more. It is preferable that it is 2.9 or less, and, as for an upper limit, it is more preferable that it is 2.8 or less. In addition, the measuring method of the refractive index of a white pigment follows Japanese Industrial Standards (JIS K 0062:1992).

A commercial item may be used for a white type pigment. For example, as titanium oxide, 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.) (above, a brand name, manufactured by Ishihara Sangyo Co., Ltd.), MT series (MT-01, MT-05, etc.) (made by Teika Co., Ltd., brand name), etc. are mentioned. .

<<curing accelerator>>

The composition of the present invention may contain a curing accelerator. Examples of the curing accelerator 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, alkoxy A silane compound, an onium salt compound, a phosphorus compound, etc. are mentioned. As a specific example of a hardening accelerator, Paragraph No. 0094 - 0097 of International Publication No. 2018/056189, the compound of Paragraph No. 0246 - 0253 of Unexamined-Japanese-Patent No. 2015-034963 Paragraph number of Unexamined-Japanese-Patent No. 2013-041165. The compound of 0186-0251, the ionic compound of Unexamined-Japanese-Patent No. 2014-055114, the compound of Paragraph No. 0071 of Unexamined-Japanese-Patent No. 2012-150180 - the compound of 0080, The epoxy group of Unexamined-Japanese-Patent No. 2011-253054 The alkoxysilane compound which has, the compound of Paragraph Nos. 0085 - 0092 of Unexamined-Japanese-Patent No. 5765059, the carboxyl group containing epoxy curing agent of Unexamined-Japanese-Patent No. 2017-036379, etc. are mentioned.

0.3-8.9 mass % is preferable and, as for content of the hardening accelerator in total solid of a composition, 0.8-6.4 mass % is more preferable. The composition of this invention WHEREIN: Only 1 type may be used for a hardening accelerator, and 2 or more types may be used for it. When using 2 or more types, it is preferable that those total amounts become the said range.

<<Silane Coupling Agent>>

The composition of the present invention may contain a silane coupling agent. As a silane coupling agent, the silane compound which has a functional group from which at least 2 types of reactivity differ in 1 molecule is preferable. The silane coupling agent is at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, an ureido group, a mercapto group, a sulfide group, and an isocyanate group; , a silane compound having an alkoxy group is preferable. As a specific example of a silane coupling agent, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (Shinetsu Chemical Co., Ltd. product, KBM-602), N-2-(aminoethyl) )-3-Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) ), 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM) -503) and 3-glycidoxypropyl trimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.). About the detail of a silane coupling agent, Paragraph No. 0155 of Unexamined-Japanese-Patent No. 2013-254047 - description of 0158 can be considered into consideration, and this content is integrated in this specification.

0.001-20 mass % is preferable, as for content of the silane coupling agent in the total solid of a composition, 0.01-10 mass % is more preferable, 0.1 mass % - 5 mass % are especially preferable. The composition of this invention may contain 1 type, and may contain 2 or more types of silane coupling agents. When 2 or more types are included, it is preferable that those total amounts become the said range.

<<Polymerization inhibitor>>

The composition of this invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, and 4,4'-thiobis(3-methyl-6). -t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, cerium salt, etc.), etc. are mentioned. there is.

As for content of the polymerization inhibitor in the total solid of a composition, 0.0001-5 mass % is preferable. The composition of this invention may contain 1 type, and may contain 2 or more types of polymerization inhibitors. When 2 or more types are included, it is preferable that those total amounts become the said range.

<<Ultraviolet absorbent>>

The composition of this invention can contain a ultraviolet absorber. Examples of the ultraviolet absorber include a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, and a triazine compound. can As such a compound, Paragraph No. 0038 of Unexamined-Japanese-Patent No. 2009-217221 - Paragraph No. 0052 of Unexamined-Japanese-Patent No. 2012-208374 Paragraph No. 0052 - 0072 of Unexamined-Japanese-Patent No. 2013-068814 Paragraph No. 0317-0334 of Unexamined-Japanese-Patent No. Paragraph Nos. 0061 to 0080 of Publication No. 2016-162946 can be mentioned, These content is integrated in this specification. Moreover, as a benzotriazole compound, the MYUA series (Kagaku Kogyo Nippo, February 1, 2016) manufactured by Miyoshi Yushi is mentioned. Moreover, the compound of Paragraph No. 0049 - 0059 of Unexamined-Japanese-Patent No. 6268967 can also be used for a ultraviolet absorber.

0.1-10 mass % is preferable, as for content of the ultraviolet absorber in the total solid of a composition, 0.1-5 mass % is more preferable, 0.1-3 mass % is especially preferable. The composition of this invention may contain only 1 type and may contain 2 or more types of ultraviolet absorbers. When 2 or more types are included, it is preferable that those total amounts become the said range.

<<Antioxidant >>

The composition of this invention can contain antioxidant. As antioxidant, a phenol compound, a phosphorous acid ester compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. The compound which has a substituent in the site|part (orthosite) adjacent to a phenolic hydroxyl group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, as for antioxidant, the compound which has a phenol group and a phosphite group in the same molecule is also preferable. Moreover, as antioxidant, phosphorus antioxidant can also be used suitably. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphospepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl) oxy]ethyl]amine, ethyl bisphosphite (2,4-di-tert-butyl-6-methylphenyl), and the like. As a commercial item of antioxidant, For example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (above, made by ADEKA) etc. are mentioned. Moreover, as antioxidant, the compound of Paragraph No. 0023 - 0048 of Unexamined-Japanese-Patent No. 6268967, the compound of International Publication No. 2017/006600, and the compound of International Publication No. 2017/164024 can also be used.

It is preferable that it is 0.01-20 mass %, and, as for content of the antioxidant in the total solid of a composition, it is more preferable that it is 0.3-15 mass %. The composition of this invention may contain only 1 type, and may contain it 2 or more types. When 2 or more types are included, it is preferable that those total amounts become the said range.

<<Surfactant>>

The composition of the present invention may contain a surfactant. As surfactant, various surfactants, such as a fluorochemical surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone type surfactant, can be used. About surfactant, Paragraph No. 0238 of International Publication No. 2015/166779 - the surfactant of 0245 is mentioned, This content is integrated in this specification.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-type surfactant in a composition, liquid characteristic (especially fluidity|liquidity) improves more and liquid saving property can be improved more. Moreover, a film|membrane with a small thickness nonuniformity can also be formed.

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

As a fluorochemical surfactant, Paragraph No. 0060-0064 of Unexamined-Japanese-Patent No. 2014-041318 (paragraph No. 0060-0064 of Corresponding International Publication No. 2014/017669) etc., Paragraph number of Unexamined-Japanese-Patent No. 2011-132503 The surfactants described in 0117-0132 are mentioned, These content is integrated in this specification. Examples of commercially available fluorine-based surfactants include Megapac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Corporation), Sufflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Corporation), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), etc. are mentioned. .

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

Moreover, it is also preferable to use the polymer of the fluorine atom containing vinyl ether compound which has a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound as a fluorine-type surfactant. As for such a fluorine-type surfactant, the fluorine-type surfactant of Unexamined-Japanese-Patent No. 2016-216602 is mentioned, This content is integrated in this specification.

A block polymer can also be used for a fluorochemical surfactant. The fluorine-based surfactant has two or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meth) ) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used. Moreover, the fluorine-containing surfactant of Paragraph No. 0016 - 0037 of Unexamined-Japanese-Patent No. 2010-032698, and the following compound are also illustrated as a fluorochemical surfactant used by this invention.

[Formula 18]

The weight average molecular weight of said compound becomes like this. Preferably it is 3000-50000, for example, it is 14000. Among the above compounds, % indicating the proportion of the repeating unit is mol%.

Further, as the fluorine-containing surfactant, a fluorinated polymer having an ethylenically unsaturated bond-containing group in a side chain may be used. As a specific example, the compound of Paragraph Nos. 0050 to 0090 and Paragraph Nos. 0289 to 0295 of Unexamined-Japanese-Patent No. 2010-164965, DIC Corporation Megapac RS-101, RS-102, RS-718K, RS-72- K etc. are mentioned. Moreover, Paragraph No. 0015 of Unexamined-Japanese-Patent No. 2015-117327 - the compound of 0158 can also be used for a fluorine-type surfactant.

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

As a silicone type surfactant, For example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, new S-Silicone Co., Ltd. make), BYK307, BYK323, BYK330 (above, the product made by Big Chemi), etc. are mentioned.

0.001-5.0 mass % is preferable and, as for content of surfactant in the total solid of a composition, 0.005-3.0 mass % is more preferable. One type may be sufficient as surfactant, and 2 or more types may be sufficient as it. In the case of 2 or more types, it is preferable that those total amounts become the said range.

<<Other additives>>

Various additives, for example, a filler, an adhesion promoter, antioxidant, aggregation inhibitor, etc. can be mix|blended with the composition of this invention as needed. Paragraph No. 0155 of Unexamined-Japanese-Patent No. 2004-295116 - the additive of 0156 are mentioned as these additives, This content is integrated in this specification.

Moreover, the composition of this invention may contain a latent antioxidant. As a latent antioxidant, the site functioning as an antioxidant is a compound protected by a protecting group, and the protecting group is detached by heating at 100 to 250 ° C. or by heating at 80 to 200 ° C. in the presence of an acid/base catalyst to function as an antioxidant. compounds can be mentioned. As a specific example of a latent antioxidant, the compound of International Publication No. 2014/021023, International Publication No. 2017/030005, and Unexamined-Japanese-Patent No. 2017-008219 is mentioned. As a commercial item, Adeka Arcles GPA-5001 (made by ADEKA Corporation) etc. are mentioned. Moreover, the composition of this invention can contain the sensitizer and light stabilizer of Paragraph No. 0078 of Unexamined-Japanese-Patent No. 2004-295116, and the thermal polymerization inhibitor of Paragraph No. 0081 of the same publication.

<Receiving container>

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

<Method for producing composition>

The composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, the composition may be prepared by simultaneously dissolving and/or dispersing all the components in a solvent, and if necessary, each component is appropriately prepared as two or more solutions or dispersions, You may manufacture a composition by mixing.

Moreover, at the time of manufacture of a composition, you may include the process of disperse|distributing particle|grains, such as a pigment. In the process of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, compression, impact, shear, and cavitation. 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, and ultrasonic dispersion. Moreover, in the grinding|pulverization of the pigment in a sand mill (bead mill), it is preferable to process under the conditions which improved grinding|pulverization efficiency by using small diameter beads, increasing the filling rate of beads, etc. In addition, it is preferable to remove coarse particles, beads, impurities mixed with abrasion of beads, impurities mixed with abrasion of the disperser, etc. by filtration or centrifugation after the pulverization treatment. It is preferable that the impurities mixed from the beads or the disperser be 2000 ppm or less based on the total composition. In addition, the process and dispersing machine for dispersing pigments are "Dispersion Technology Exhibition, Published by Johokiko Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid/liquid dispersion system) and practical synthesis of industrial applications" The process and disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. Moreover, in the process of dispersing a pigment, you may perform the refinement|miniaturization process of particle|grains by a salt milling process. As for the material, apparatus, processing conditions, etc. used in the salt milling process, description of Unexamined-Japanese-Patent No. 2015-194521 and Unexamined-Japanese-Patent No. 2012-046629 can be referred, for example.

In the production of the composition, the composition is preferably filtered through a filter for the purpose of removing foreign matter or reducing defects. As a filter, if it is a filter conventionally used for a filtration use, etc., it will not specifically limit, It can be used. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) ( and a filter using a material such as high-density and ultra-high molecular weight polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

0.01-7.0 micrometers is preferable, as for the pore diameter of a filter, 0.01-3.0 micrometers is more preferable, 0.05-0.5 micrometers is still more preferable. If the hole diameter of a filter is the said range, a fine foreign material can be removed more reliably. For the pore diameter value of the filter, the nominal value of the filter maker can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microliss Co., Ltd.) and Kits Microfilter Co., Ltd. can be used.

Moreover, it is also preferable to use a fiber-form filter medium as a filter. As a fibrous filter medium, a polypropylene fiber, a nylon fiber, a glass fiber, etc. are mentioned, for example. As a commercial item, the SBP type series (SBP008 etc.), the TPR type series (TPR002, TPR005 etc.) made by a Rocky Techno company, and the SHPX type series (SHPX003 etc.) are mentioned.

When using a filter, you may combine different filters (for example, a 1st filter, a 2nd filter, etc.). In that case, the filtration using each filter may be performed only once, and may be performed 2 times or more. Moreover, you may combine filters of different pore diameters within the above-mentioned range. Moreover, after performing filtration using a 1st filter only with respect to a dispersion liquid, and mixing another component, you may filter with a 2nd filter.

<act>

The film of the present invention is obtained by using the above-described composition of the present invention. The film|membrane of this invention can be used suitably for a microlens etc.

<Micro Lens>

The microlens of this invention has the film|membrane of this invention mentioned above.

It is preferable that the refractive index of the microlens of this invention with respect to the light of wavelength 633nm is 1.58 or more, It is more preferable that it is 1.60 or more, It is more preferable that it is 1.62 or more. Moreover, it is preferable that it is 1.60 or more, as for the average refractive index with respect to the light of wavelength 400-600 nm of the microlens of this invention, it is more preferable that it is 1.62 or more, It is more preferable that it is 1.64 or more. Although the upper limit is not specifically limited, It can be made into 1.75 or less.

About the microlens of this invention, it is preferable that the minimum value of the transmittance|permeability of the light of wavelength 400-600 nm is 85 % or more, It is more preferable that it is 90 % or more, It is still more preferable that it is 95 % or more. About the microlens of this invention, it is preferable that the average transmittance of the light of wavelength 400-600 nm is 90 % or more, It is more preferable that it is 93 % or more, It is more preferable that it is 96 % or more.

About the microlens of this invention, it is preferable that the average transmittance|permeability of the light of wavelength 800-870 nm is 80 % or less, It is more preferable that it is 75 % or less, It is more preferable that it is 70 % or less. Moreover, about the microlens of this invention, it is preferable that it is 70 % or less, and, as for the minimum value of the transmittance|permeability of the light of wavelength 800-870 nm, it is more preferable that it is 65 % or less, It is more preferable that it is 60 % or less. Moreover, about the microlens of this invention, it is preferable that the maximum value of the transmittance|permeability of the light of wavelength 800-870 nm is 85 % or less, It is more preferable that it is 82 % or less, It is more preferable that it is 80 % or less.

It does not specifically limit as a lens shape of a microlens, It can take various shapes derived|led out by optical system design. For example, a convex shape, a concave shape, etc. are mentioned. Moreover, the radius of curvature of a lens is not specifically limited, It is preferable to set suitably within the range which shows a desired effect.

It is preferable that the thickness of a microlens is 0.1-1.0 micrometer. It is preferable that it is 0.9 micrometer or less, and, as for an upper limit, it is more preferable that it is 0.8 micrometer or less. It is preferable that it is 0.15 micrometer or more, and, as for a minimum, it is more preferable that it is 0.2 micrometer or more. Here, the thickness of the microlens means the thickness of the thickest part 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.

<Method for manufacturing micro lens>

Next, the manufacturing method of a microlens is demonstrated. It is preferable that the manufacturing method of a microlens includes the process of apply|coating the composition of this invention mentioned above on a support body to form a composition layer, and processing the composition layer into a lens shape. Hereinafter, each process is demonstrated.

(Step of forming a composition layer)

In the process of forming a composition layer, a composition layer is formed on a support body using the composition of this invention. Examples of the support include a glass substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light emitting layer may be formed on these substrates. Moreover, a color filter may be further formed on the organic light emitting layer. Moreover, the undercoat layer may be provided in a board|substrate or a color filter in order to improve adhesiveness with an upper layer, to prevent diffusion of a substance, or to planarize a surface.

As a coating method of a composition, a well-known method can be used. For example, the drip method (drop cast); slit coat method; spray method; roll coat method; spin coating (spin coating); soft coating method; slit and spin method; free-wet method (for example, the method described in Unexamined-Japanese-Patent No. 2009-145395); Various printing methods, such as discharge system printing, such as inkjet (For example, an on-demand method, a piezo method, a thermal method), a nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and the metal mask printing method; a transfer method using a mold or the like; The nanoimprint method etc. are mentioned. The method of application in inkjet is not particularly limited, and for example, the method shown in "Diffuse and usable inkjet -infinite possibilities viewed as a patent -, published in February 2005, Sumibe Techno Research" (particularly page 115) ~ 133 pages), Japanese Unexamined Patent Publication No. 2003-262716, Japanese Unexamined Patent Publication No. 2003-185831, Japanese Unexamined Patent Publication No. 2003-261827, Japanese Unexamined Patent Publication No. 2012-126830, Japanese Unexamined Patent Publication No. 2006-169325 The method described in etc. is mentioned. In addition, about the application|coating method of a composition, International Publication No. 2017/030174 and description of International Publication No. 2017/018419 can be referred to, and these content is integrated in this specification.

The composition layer formed on the support body may be dried (pre-baked). When prebaking, 100 degrees C or less is preferable, as for prebaking temperature, 90 degrees C or less is more preferable, 80 degrees C or less is still more preferable, and 70 degrees C or less is especially preferable. The lower limit can be, for example, 40°C or higher. As for prebaking time, 10 to 3600 second is preferable. Pre-baking can be performed with a hot plate, an oven, etc.

(Process of processing into lens shape)

As a method of processing a composition layer into a lens shape, a conventionally well-known processing method can be used. For example, it can be manufactured using a transfer method, an imprint method, a thermal deformation method, and the like. Among them, the transfer method is preferable because it is easy to control the lens shape.

In the transfer method, the composition layer formed on the support is cured to form a cured material layer, a resist layer is formed on the cured material layer, the resist layer is patterned in a lens shape, and the patterned resist layer is formed. It can be manufactured by dry etching the cured material layer using as a mask, and transferring the lens shape to the cured material layer. Moreover, about the manufacturing method of the lens using the transfer method, Unexamined-Japanese-Patent No. 2006-073605, Unexamined-Japanese-Patent No. 2006-190903, Unexamined-Japanese-Patent No. 2008-281414, Unexamined-Japanese-Patent No. 2014-029524, etc. Methods may also be used, the contents of which are incorporated herein by reference.

In the imprint method, the composition layer is sandwiched between the mold and the support by pressing a mold having a pattern on the composition layer formed on the support, and the composition layer is exposed and cured in the sandwiched state, and then the mold is removed from the support. It can be manufactured by peeling.

In the thermal deformation method, the cured material layer is processed into a lens shape by curing the composition layer formed on the support to form a cured material layer, and heating the cured material layer to thermally deform the surface of the cured material layer. can

The process of processing into a lens shape may include the process of exposing a composition layer. Exposure is used as a curing treatment of the composition layer. It is preferable to perform exposure by irradiating a radiation with respect to a composition layer. Examples of the radiation include g-line, i-line, and the like. Moreover, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180-300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. In addition, a light source having a long wavelength of 300 nm or more can also be used.

Moreover, in the case of exposure, you may expose by irradiating light continuously, and you may irradiate and expose by pulse (pulse exposure). In addition, pulse exposure is an exposure method of the system of repeating exposure of light irradiation and pause in a cycle of a short time (for example, a millisecond level or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , and more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to carrying out under the atmosphere, for example, in a low-oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially anoxic), or exposure in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. In addition, the exposure illuminance can be set appropriately, and can be selected from the range of usually 1000 W/m ² to 100000 W/m ² (eg, 5000 W/m ² , 15000 W/m ² , or 35000 W/m ² ). . The oxygen concentration and exposure illuminance may appropriately combine conditions, for example, an illuminance of 10000 W/m ^{2 with an oxygen concentration of 10 vol%, an illuminance of 20,000 W/m 2 with} an oxygen concentration of 35 vol% or the like.

<Solid-state imaging device>

The solid-state imaging element of this invention has the microlens of this invention mentioned above. Although there will be no limitation in particular as a structure of a solid-state imaging element, if it is a structure provided with the microlens of this invention and functioning as a solid-state image sensor, For example, the following structures are mentioned.

Transmission consisting of a plurality of photodiodes constituting a light receiving area of a solid-state image sensor (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on a substrate, polysilicon, etc. It has an electrode, has a light-shielding film on the photodiode and the transfer electrode in which only the light-receiving portion of the photodiode is opened, and has a device protective film made of silicon nitride or the like formed on the light-shielding film to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, and on the device protective film It has a color filter and the structure which has a microlens on a color filter is mentioned. The color filter may have a structure in which each color pixel is embedded in a space partitioned, for example, in a grid shape by a partition wall. It is preferable that the partition in this case has a lower refractive index than each color pixel. As an example of the imaging device which has such a structure, Unexamined-Japanese-Patent No. 2012-227478, Unexamined-Japanese-Patent No. 2014-179577, International Unexamined-Japanese-Patent No. 2018/043654, The apparatus described in U.S. Patent Application Laid-Open No. 2018/0040656 can be heard The imaging device provided with the solid-state imaging element of the present invention can be used not only for a digital camera and an electronic device having an imaging function (such as a cellular phone), but also as an object for an on-board camera or a surveillance camera.

<Display device>

The display device of this invention has the microlens of this invention mentioned above. As a display device, a liquid crystal display device, an organic electroluminescent display device, etc. are mentioned. For the definition of a display device and the details of each display device, see, for example, "Electronic Display Device (author Akio Sasaki, Kokocho Chosakai, published in 1990)", "Display device (author Sumiaki Ibuki, Tosho Sangyo) Note) published in the first year of the Heisei year)", etc. Moreover, about a liquid crystal display device, it describes, for example in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Kokocho Chosakai, published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in "Next-generation liquid crystal display technology".

The organic electroluminescent display device may have a light source which consists of a white organic electroluminescent element. As a white organic electroluminescent element, it is preferable that it is a tandem structure. Regarding the tandem structure of organic electroluminescent devices, Japanese Patent Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Forefront of organic EL technology development - high luminance, high precision, long life, know-how-", Kijutsu Joho Kyo Kai, pp. 326-328, 2008 et al. The spectrum of white light emitted by the organic EL device preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, it is more preferable to further have a maximum emission peak in the red region (650 nm to 700 nm).

Example

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 without departing from the gist thereof. In addition, in the structural formula shown below, Me represents a methyl group, Ph represents a phenyl group.

<Preparation of dispersion>

The raw materials described in the table below were mixed, and 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added, followed by dispersion treatment for 5 hours using a paint shaker, and the beads were separated by filtration to prepare a dispersion.

[Table 1]

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

(Near-infrared absorbing dye)

P-1 to P-4: a compound of the following structure

[Formula 19]

P-5: Near-infrared absorption compound A-43 (croconium compound) described in International Publication No. 2018/043185

P-6: cyanine compound e described in Japanese Patent Application Laid-Open No. 2015-172004

P-1 to P-6 are compounds having a maximum absorption wavelength in a wavelength range of 800 to 900 nm.

(pigment derivative)

Sy-1 to Sy-4: a compound of the following structure

[Formula 20]

(dispersant)

D-1: Resin of the following structure. The numerical value indicated in the main chain is the molar ratio, and the numerical value indicated in the side chain is the number of repeating units. Mw=20,000.

[Formula 21]

D-2: Resin of the following structure. The numerical value indicated for the main chain is the molar ratio, and the number indicated for the side chain is the number of repeating units. Mw=24,000.

[Formula 22]

D-3: Resin of the following structure. The numerical value indicated for the main chain is the molar ratio, and the number indicated for the side chain is the number of repeating units. r/s/t/u=15/59/7/19, Mw=18300.

[Formula 23]

(solvent)

S-1: propylene glycol monomethyl ether acetate (PGMEA)

<Preparation of composition>

The raw materials described in the table below were mixed to prepare compositions of Examples and Comparative Examples. The numerical values shown in the table below are parts by mass.

[Table 2]

[Table 3]

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

(dispersion)

Dispersions 1 to 12: Dispersions 1 to 12 described above

(Near-infrared absorbing dye)

Dye-1: A compound of the following structure (iC ₈ H ₁₇ and iC ₁₀ H ₂₁ moieties are isomer mixtures having different carbon numbers and branching positions.)

[Formula 24]

(Polymerizable compound)

M-1: a compound of the following structure (refractive index with respect to light having a wavelength of 633 nm is 1.63 or more)

M-2: a compound of the following structure (refractive index with respect to light having a wavelength of 633 nm is 1.63 or more)

M-3: a compound of the following structure (with a refractive index of 1.58 or more and less than 1.63 for light having a wavelength of 633 nm)

M-4: Ogsol PG-100 (manufactured by Osaka Gas Chemical Co., Ltd., an epoxy compound having a fluorene structure. The refractive index with respect to light having a wavelength of 633 nm is 1.63 or more)

M-5: Ogsol EG-200 (manufactured by Osaka Gas Chemical Co., Ltd., an epoxy compound having a fluorene structure. The refractive index with respect to light having 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 to light with a wavelength of 633 nm is less than 1.58)

[Formula 25]

(profit)

B-1: Resin of the following structure (Mw=5000, refractive index with respect to light having 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 Paragraph Nos. 0122 to 0126 of Japanese Patent Application Laid-Open No. 2013-139588 (Mw = 4300, refractive index with respect to light of wavelength 633 nm is 1.63 or more)

B-3: Resin having a fluorene structure prepared by the method described in Example 1 of Paragraph Nos. 0085 to 0086 of Japanese Patent Application Laid-Open No. 2017-031311 (Mw = 28800, refractive index with respect to light at a wavelength of 633 nm is 1.63 or more)

B-4: Resin of the following structure (Mw=10000, refractive index with respect to light having a wavelength of 633 nm is 1.63 or more)

B-5: Resin of the following structure (Mw=8000, refractive index with respect to light of wavelength 633 nm is 1.63 or more)

B-6: Resin of the following structure (Mw=13000, refractive index with respect to light having a wavelength of 633 nm is 1.63 or more)

B-7: a resin having the following structure (the numerical value given to the main chain is the molar ratio. Mw=10000, the refractive index with respect to light having a wavelength of 633 nm is less than 1.58)

B-8: Resin of the following structure (Mw=3100, refractive index with respect to light having a wavelength of 633 nm is 1.63 or more)

B-9: a resin having the following structure (the numerical value added to the main chain is the molar ratio. Mw = 20000, the refractive index with respect to light having a wavelength of 633 nm is 1.63 or more)

B-10: Resin of the following structure (the numerical value added to the main chain is the molar ratio. Mw=40000, refractive index with respect to light having a wavelength of 633 nm is 1.58 or more and less than 1.63)

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

(additive)

A-1: ADEKA STAB AO-80 (made by ADEKA)

A-2: 2-ethyl-4-methylimidazole

A-3: triphenylphosphine

A-4: a compound of the following structure

[Formula 30]

A-5: tris (4-methylphenyl) phosphine

(Surfactants)

Su-1: a compound of the following structure (Mw = 14000, the numerical value of % representing the proportion of repeating units is mole %, fluorine-based surfactant)

[Formula 31]

(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 applied onto a quartz glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) so as to have a film thickness of 0.35 µm after post-baking to form a coating film. Subsequently, using a hot plate, after heating (pre-baking) for 100 ° C. for 120 seconds, heating (post-baking) for 200 ° C. for 300 seconds was performed again using a hot plate, and a 0.35 µm-thick film was obtained. About the obtained film|membrane, the refractive index (refractive index 1) with respect to the light of wavelength 633nm was measured using Ellipsometry VUV-VASE (made by J.A. Woolam Japan). In addition, with respect to the obtained film, the transmittance of light having a wavelength of 400 to 1100 nm is measured using a multi-channel spectrometer MCPD-9800 (manufactured by Otsuka Denshi Corporation), and the minimum value of transmittance for light having a wavelength of 400 to 600 nm, a wavelength of 800 to 870 nm The average transmittance with respect to light was measured respectively. At the time of measuring the refractive index, the back surface was polished so that there was no reflection from the glass back surface, and the measurement was carried out by processing into an opaque glass form.

[Table 4]

In Examples 1-25, the minimum value of the transmittance|permeability of the light of wavelength 400-600 nm was 85 % or more in all. Moreover, in Examples 1-25, the average transmittance|permeability of the light of wavelength 800-870 nm was 80 % or less in all.

<Manufacture of micro lens>

On an 8-inch (20.32 cm) silicon wafer, the coloring composition for green pixel formation was apply|coated by the spin coating method so that the film thickness after film formation might be set to 0.5 micrometer. Then, it heated at 100 degreeC for 2 minute(s) using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.), exposure was performed at an exposure amount of 1000 mJ/cm ² through a mask having a square Bayer pattern with one side of 0.8 µm. Then, puddle image development was performed at 23 degreeC for 60 second using the tetramethylammonium hydroxide (TMAH) 0.3 mass % aqueous solution. Thereafter, it was rinsed with a spin shower and further washed with pure water. Then, a green pixel (pattern size 0.8 µm, thickness 0.5 µm) was formed on the silicon wafer by heating at 200°C for 5 minutes using a hot plate. Next, the coloring composition for red pixel formation and the coloring composition for blue pixel formation are sequentially patterned, and in the unformed part of a green pixel, a red pixel (pattern size 0.8 micrometer, thickness 0.5 micrometer), a blue pixel (pattern size 0.8 micrometer, thickness 0.5) μm) to form a color filter.

Next, on the color filter, the compositions of Examples 1 to 25 and Comparative Example 1 were applied by spin coating, followed by heating at 100° C. for 2 minutes using a hot plate, and then 200 using a hot plate. It was heated at °C for 5 minutes to form a lens material composition layer having a film thickness of 1.2 µm.

Then, using the transfer method by the etch-back which is a well-known technique, the lens material composition layer was processed so that the height from a lens top to a lens bottom might become 400 nm, and the microlens was manufactured.

The microlens manufactured using the composition of Examples 1-25 had the high transmittance|permeability and refractive index of the light of a visible region, Furthermore, it was excellent also in near-infrared shielding property. For this reason, the solid-state image sensor in which the microlens was manufactured using the composition of an Example was able to suppress the incident of near-infrared to each pixel of a color filter, while improving the condensing performance of visible light with respect to each pixel of a color filter. For this reason, a clear image could be detected and it was excellent in image recognition precision. In addition, the same result is obtained also when the surfactant is removed from Example 1. The same result is obtained also when the polymerization inhibitor is removed from Example 1. Moreover, even if it substitutes with the following P-7, P-8, P-9, or P-10 instead of P-5 as a near-infrared absorbing dye, the same result is obtained.

P-7 to P-10 are compounds having a maximum absorption wavelength in a wavelength range of 800 to 900 nm.

P-7: Compound No. described in Japanese Patent Application Laid-Open No. 2012-224593. One

P-8: Near-infrared absorbing compound A-44 (croconium compound) described in International Publication No. 2018/043185

P-9: a compound of the following structure

[Formula 32]

P-10: a compound of the structure

[Formula 33]

On the other hand, since the microlens manufactured using the composition of Comparative Example 1 had a low refractive index of light in the visible region, the visible light condensing performance for each pixel of the color filter was inferior to that of the Example. For this reason, the solid-state image sensor which manufactured the microlens using the composition of the comparative example was inferior to the image recognition precision of an Example.

(Coloring composition for green pixel formation)

After mixing and stirring the following components, it filtered with the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometers, and the coloring composition for green pixel formation was prepared.

Green Pigment Dispersion … 88.74 parts by mass

Resin 1 … 0.40 parts by mass

Polymeric compound 1 ... 1.62 parts by mass

Photoinitiator (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 Chemical Co., Ltd.) … 0.3 parts by mass

PGMEA… 3.68 parts by mass

(Coloring composition for red pixel formation)

After mixing and stirring the following components, it filtered with the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometers, and the coloring composition for red pixel formation was prepared.

Red pigment dispersion … 51.7 parts by mass

Resin 1 … 0.6 parts by mass

Polymeric compound 4 ... 0.6 parts by mass

Photoinitiator (Irgacure OXE01, manufactured by BASF) ... 0.4 parts by mass

Surfactant 1 ... 4.2 parts by mass

Ultraviolet absorber (UV-503, manufactured by Daito Chemical 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, it filtered with the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometers, and the coloring composition for blue pixel formation was prepared.

Blue pigment dispersion … 44.9 parts by mass

Resin 1 … 2.1 parts by mass

Polymeric compound 1 ... 1.5 parts by mass

Polymeric compound 4 ... 0.7 parts by mass

Photoinitiator (Irgacure OXE01, manufactured by BASF) ... 0.8 parts by mass

Surfactant 1 ... 4.2 parts by mass

Ultraviolet absorber (UV-503, manufactured by Daito Chemical Co., Ltd.) … 0.3 parts by mass

PGMEA… 45.8 parts by mass

The raw materials used for preparation of the coloring composition for green pixel formation, the coloring composition for red pixel formation, and the coloring composition for blue pixel formation are as follows.

・Green pigment dispersion

8.15 parts by mass of C. I. Pigment Green 36, 3.33 parts by mass of C. I. Pigment Yellow 150, 0.97 parts by mass of dispersant 1 shown below, 2.50 parts by mass of dispersant 2 shown below, 66.01 parts by mass of PGMEA, and PGME 1.09 mass parts of and the mixed liquid which consists of 5.09 mass parts of cyclohexanone was mixed and disperse|distributed for 3 hours with the bead mill (zirconia beads 0.3 mm diameter), and the pigment dispersion liquid was prepared. Thereafter, dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm 3 using a high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon Biei Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.

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

[Formula 34]

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

[Formula 35]

・Red pigment dispersion

A mixed solution consisting of 9.6 parts by mass of C. I. Pigment Red 254, 4.3 parts by mass of C. I. Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie) and 79.3 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter), mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm 3 using a high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon Biei Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

・Blue pigment dispersion

A mixture consisting of 9.7 parts by mass of C. I. Pigment Blue 15:6, 2.4 parts by mass of C. I. Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia). Beads 0.3 mm in diameter) were mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm 3 using a high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon Biei Co., Ltd.). 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 of the following structure

[Formula 36]

-Resin 1: Resin of the following structure. (The numerical value added to the main chain is the molar ratio. Mw=10,000, acid value=70mgKOH/g, glass transition temperature=46℃)

[Formula 37]

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

[Formula 38]

Claims (14)

An organic compound A having a refractive index of 1.58 or more with respect to light having a wavelength of 633 nm;
a near-infrared absorbing dye;
As a composition comprising a solvent,
The organic compound A is at least one selected from a polymerizable compound and a resin,
When a film having a thickness of 0.35 μm is formed using the composition, the refractive index of the film with respect to light having a wavelength of 633 nm is 1.58 or more, and the minimum value of the transmittance of light having a wavelength of 400 to 600 nm of the film is 85% or more. The method according to claim 1,
When a film having a thickness of 0.35 μm is formed using the composition, the average transmittance of light having a wavelength of 800 to 870 nm of the film is 80% or less. The method according to claim 1 or 2,
The said organic compound A is a compound which has at least 1 sort(s) of structure selected from a fluorene structure, a triazine structure, and a carbazole structure, The composition. 4. The method according to any one of claims 1 to 3,
A composition comprising two or more kinds of the organic compound A. 5. The method according to any one of claims 1 to 4,
The composition whose content of the organic compound whose refractive index with respect to the light of wavelength 633nm in the whole quantity of the organic compound A contained in the said composition is 1.63 or more is 5-100 mass %. 6. The method according to any one of claims 1 to 5,
The composition in which content of the said organic compound A in the total solid of the said composition is 50 mass % or more. 7. The method according to any one of claims 1 to 6,
The composition whose content of the said near-infrared absorbing dye in the total solid of the said composition is 1-20 mass %. 8. The method according to any one of claims 1 to 7,
The said near-infrared absorbing dye is a compound which has a maximum absorption wavelength in the wavelength range of 750-1000 nm, The composition. 9. The method according to any one of claims 1 to 8,
The said near-infrared absorbing dye is at least 1 sort(s) chosen from a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymetain compound, The composition. 10. The method according to any one of claims 1 to 9,
A composition for micro lenses. A film obtained by using the composition according to any one of claims 1 to 10. A microlens having the film according to claim 11 . The solid-state image sensor which has the microlens of Claim 12. A display device having the microlens according to claim 12 .