JP2022068962A - Near-infrared ray-absorbing composition, near-infrared ray transmission composition, and optical filter - Google Patents

Abstract

To provide a near-infrared ray-absorbing composition which has a high capability of blocking a near-infrared ray ranging from 700nm to 900 nm, transmits a 940 nm near-infrared ray, and has excellent coating property, a near-infrared ray transmission composition, and an optical filter formed by using the same.SOLUTION: A near-infrared ray-absorbing composition includes two kinds or more of squarylium dye (A) that has maximum absorption wavelength between 800 and 900 nm within a range of 400 to 1000 nm. When the maximum absorption wavelength of a first squarylium dye (A-1) is λ1max and the maximum absorption wavelength of a second squarylium dye (A-2) is λ2max, the following formula (1) is satisfied: formula (1) 0 nm<λ2max-λ1max≤100 nm.SELECTED DRAWING: None

Description

The present invention relates to a near-infrared absorbing composition, a near-infrared transmitting composition, and an optical filter formed using the same.

In recent years, mainly mobile terminals such as smartphones and tablet terminals have been equipped with a user authentication function using biometric information such as fingerprints, faces, irises, and voices. In particular, fingerprint authentication has the excellent convenience of being able to unlock by simply placing a finger on it, and because it is compact and inexpensive, the use of fingerprint authentication sensors is expanding in smartphones.

In addition, in smartphones, in order to increase the size of the display due to size restrictions, it has been proposed to use the entire body as a display and incorporate a fingerprint authentication sensor into the screen (in-screen fingerprint authentication). In particular, in an organic electroluminescence (organic EL) display device, fingerprint authentication can be performed using light emitted from blue or green pixels, and an in-screen fingerprint authentication method is spreading.

On the other hand, in liquid crystal display devices that require a backlight, the in-screen fingerprint authentication method has not been adopted so far. However, in recent years, an infrared transmitter has been installed at the bottom of the display to irradiate infrared rays, and the sensor receives and reads the light reflected by the fingerprints, which enables in-screen fingerprint authentication even for liquid crystal displays. Has been done.

A 940 nm near-infrared LED light source may be used as the infrared light source used for in-screen fingerprint authentication in this liquid crystal display device. This is because 940 nm is a wavelength at which sunlight, which is external light noise, is absorbed by water vapor, so that it can be sensed with lower noise than other wavelengths. Further, by cutting near infrared rays of 700 nm to 900 nm with an optical filter or the like, external light noise can be further reduced and the sensing accuracy of the fingerprint authentication sensor can be improved.

The near-infrared cut filter is manufactured by using a composition containing a near-infrared absorber as in Patent Document 1, for example. However, the ability to cut near infrared rays of 700 nm to 900 nm was not always satisfactory. Furthermore, it cannot be said that the coatability required for manufacturing a near-infrared cut filter is sufficient.

WO2017-130825

The present invention is a near-infrared absorbing composition, a near-infrared transmitting composition, and a near-infrared transmitting composition having a high ability to cut near-infrared rays of 700 nm to 900 nm, transmitting near-infrared light of 940 nm, and having good coatability, and formed by using the same. It is an object of the present invention to provide an optical filter.

As a result of diligent research to solve the above problems, the present inventors have conducted near-infrared rays containing two or more types of squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 800 and 900 nm. In the absorption composition, when the maximum absorption wavelength of the first squarylium dye (A-1) is λ1 _max and the maximum absorption wavelength of the second squarylium dye (A-2) is λ2 _max , the following equation (1) ), The near-infrared absorbing composition characterized by satisfying the relationship of) has a high near-infrared cut ability from around 700 nm to 900 nm and good coatability, and the present invention was made based on this finding. It is a thing.
Equation (1) 0 nm <λ2 _max -λ1 _max ≤ 100 nm

That is, the present invention is a near-infrared absorbing composition containing two or more kinds of squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 800 and 900 nm, and is the first squarylium dye (A-1). ), When the _{maximum absorption wavelength of the second squarylium dye (A-2) is λ2 max ,} the near-infrared absorption composition is characterized by satisfying the relationship of the following formula (1). ..
Equation (1) 0 nm <λ2 _max -λ1 _max ≤ 100 nm

The present invention also relates to the near-infrared absorbing composition, wherein the λ1 _max and the λ2 _max satisfy the relationship of the following formula (2).
Equation (2) 10 nm ≤ λ2 _max -λ1 _max ≤ 100 nm

（一般式（１）中、Ｒ^１～Ｒ^４はそれぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アラルキル基、－ＯＲ^１０、－ＣＯＲ^１１、－ＣＯＯＲ^１２、－ＣＯＯＭ^１、－ＯＣＯＲ^１３、－ＮＲ^１４Ｒ^１５、－ＮＨＣＯＲ^１６、－ＣＯＮＲ^１７Ｒ^１８、－ＮＨＣＯＮＲ^１９Ｒ^２０、－ＮＨＣＯＯＲ^２１、－ＳＲ^２２、－ＳＯ_２Ｒ^２３、－ＳＯ_２ＯＲ^２４、－ＳＯ_３Ｍ^２、－ＮＨＳＯ_２Ｒ^２５、－ＳＯ_２ＮＲ^２６Ｒ^２７、－Ｂ（ＯＲ^２８）_２、または－ＮＨＢＲ^２９Ｒ^３０を表す。Ｒ^１０～Ｒ^３０は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、およびアラルキル基を表す。なお、－ＣＯＯＲ^１２のＲ^１２が水素の場合は、水素原子が解離してもよい。－ＣＯＯＭ^１は、カルボキシル基の金属塩またはアルキルアンモニウム塩を表す。また、－ＳＯ_２ＯＲ^２４のＲ^２４が水素原子の場合は、水素原子が解離してもよい。－ＳＯ_３Ｍ^２は、スルホ基の金属塩またはアルキルアンモニウム塩を表す。また、Ｒ^１とＲ^２、Ｒ^３とＲ^４はお互いに結合して環を形成しても良い。） The present invention also relates to the near-infrared absorbing composition, wherein the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (1).

General formula (1)

(In the general formula (1), R ¹ to R ⁴ are independently each of a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR ¹⁰ , -COR ¹¹ , -COOR ¹² , -COOM ¹ , -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , -NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ¹⁹ R ²⁰ , -NHCOOR ²¹ , -SR ²² , -SO ₂ R ²³ , -SO ₂ OR ²⁴ , -SO ₃ M ² , -NHSO ₂ R ²⁵ , -SO ₂ NR ²⁶ R ²⁷ , -B ⁽ OR ²⁸ ) ₂ , or ^{-NHBR 29} R ³⁰ . Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, R ¹² of −COOR ¹² is hydrogen. In some cases, the hydrogen atom may be dissociated.-COMM ¹ represents a metal salt or an alkylammonium salt of a carboxyl group. Further, when R ²⁴ of -SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom is dissociated. -SO ₃ M ² may represent a metal salt or an alkylammonium salt of a sulfo group, and R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring. .)

（一般式（２）中、Ｒ^５～Ｒ^８はそれぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アラルキル基、－ＯＲ^５０、－ＣＯＲ^５１、－ＣＯＯＲ^５２、－ＣＯＯＭ^３、－ＯＣＯＲ^５３、－ＮＲ^５４Ｒ^５５、－ＮＨＣＯＲ^５６、－ＣＯＮＲ^５７Ｒ^５８、－ＮＨＣＯＮＲ^５９Ｒ^６０、－ＮＨＣＯＯＲ^６１、－ＳＲ^６２、－ＳＯ_２Ｒ^６３、－ＳＯ_２ＯＲ^６４、－ＳＯ_３Ｍ^４、－ＮＨＳＯ_２Ｒ^６５、－ＳＯ_２ＮＲ^６６Ｒ^６７、－Ｂ（ＯＲ^６８）_２、または－ＮＨＢＲ^６９Ｒ^７０を表す。Ｒ^５０～Ｒ^７０は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、およびアラルキル基を表す。なお、－ＣＯＯＲ^５２のＲ^５２が水素の場合は、水素原子が解離してもよい。－ＣＯＯＭ^３は、カルボキシル基の金属塩またはアルキルアンモニウム塩を表す。また、－ＳＯ_２ＯＲ^６４のＲ^６４が水素原子の場合は、水素原子が解離してもよい。－ＳＯ_３Ｍ^４は、スルホ基の金属塩またはアルキルアンモニウム塩を表す。また、Ｒ^５とＲ^６、Ｒ^７とＲ^８はお互いに結合して環を形成しても良い。） The present invention also relates to the near-infrared absorbing composition, wherein the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (2).

General formula (2)

(In the general formula (2), R ⁵ to R ⁸ are independently each of a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, −OR ⁵⁰ , -COR ⁵¹ , -COOR ⁵² , -COOM ³ , -OCOR ⁵³ , -NR ⁵⁴ R ⁵⁵ , -NHCOR ⁵⁶ , -CONR ⁵⁷ R ⁵⁸ , -NHCONR ⁵⁹ R ⁶⁰ , -NHCOOR ⁶¹ , -SR ⁶² , -SO ₂ R ⁶³ , -SO ₂ OR ⁶⁴ , -SO ₃ M ⁴ , -NHSO ₂ R ⁶⁵ , -SO ₂ NR ⁶⁶ R ⁶⁷ , -B (OR ⁶⁸ ) ₂ , or ^{-NHBR 69} R ^{70 .} Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, R ⁵² of -COOR ⁵² is hydrogen. In some cases, the hydrogen atom may be dissociated.-COM ³ represents a metal salt or an alkylammonium salt of a carboxyl group. Further, when R ⁶⁴ of -SO ₂ OR ⁶⁴ is a hydrogen atom, the hydrogen atom is dissociated. -SO ₃ M ⁴ may represent a metal salt or an alkylammonium salt of a sulfo group, and R ⁵ and R ⁶ and R ⁷ and R ⁸ may be bonded to each other to form a ring. .)

The present invention also relates to the near-infrared absorbing composition, which is characterized in that the transmittance at 940 nm is 50% or more when the coating film is formed so that the transmittance at 800 nm is 1%.

The present invention also relates to the near-infrared absorbing composition, which further comprises a basic resin-type dispersant.

The present invention also relates to the near-infrared absorbing composition, which further comprises a photopolymerization initiator.

The present invention also relates to a near-infrared ray transmitting composition comprising the near-infrared absorbing composition and a coloring composition exhibiting black color.

The present invention also relates to an optical filter formed by using the near-infrared absorbing composition.

The present invention also relates to an optical filter formed by using the near-infrared ray transmitting composition.

INDUSTRIAL APPLICABILITY According to the present invention, a near-infrared absorbing composition having a high ability to cut near-infrared rays of 700 nm to 900 nm, transmitting near-infrared light of 940 nm, and having good coatability, a near-infrared ray transmitting composition, and a near-infrared ray transmitting composition formed by using the same. An optical filter can be provided.

Hereinafter, each component of the coloring composition of the present invention will be described.
In the present application, the term "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" is particularly described. Unless there is an acryloyl and / or methacrylic acid, acrylic and / or methacrylic acid, acrylic acid and / or methacrylic acid, acrylate and / or methacrylate, or acrylamide and / or methacrylic acid, respectively. It shall be represented.
Further, "CI" mentioned in the present specification means a color index (CI).

<Squarylium pigment>
The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing two or more kinds of squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 800 and 900 nm, and is the first squarylium. When the maximum absorption wavelength of the dye (A-1) is λ1 _max and the maximum absorption wavelength of the second squarylium dye (A-2) is λ2 _max , the relationship of the following formula (1) is satisfied.
Equation (1) 0 nm <λ2 _max -λ1 _max ≤ 100 nm

It is preferable that the λ1 _max and the λ2 _max satisfy the relationship of the following formula (2).
Equation (2) 10 nm ≤ λ2 _max -λ1 _max ≤ 100 nm

The value of the maximum absorption wavelength of the squarylium dye is a value measured by the method described in Examples described later.

By containing two types of squarylium dyes with different maximum absorption wavelengths, the absorption wavelength range is widened, and by having the maximum absorption wavelength in the range of 400 to 1000 nm between 800 and 900 nm, near infrared rays from 700 nm to 900 nm are widely cut. can do. In addition, the applicability is improved by using different dyes in combination.

（一般式（１）中、Ｒ^１～Ｒ^４はそれぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アラルキル基、－ＯＲ^１０、－ＣＯＲ^１１、－ＣＯＯＲ^１２、－ＣＯＯＭ^１、－ＯＣＯＲ^１３、－ＮＲ^１４Ｒ^１５、－ＮＨＣＯＲ^１６、－ＣＯＮＲ^１７Ｒ^１８、－ＮＨＣＯＮＲ^１９Ｒ^２０、－ＮＨＣＯＯＲ^２１、－ＳＲ^２２、－ＳＯ_２Ｒ^２３、－ＳＯ_２ＯＲ^２４、－ＳＯ_３Ｍ^２、－ＮＨＳＯ_２Ｒ^２５、－ＳＯ_２ＮＲ^２６Ｒ^２７、－Ｂ（ＯＲ^２８）_２、または－ＮＨＢＲ^２９Ｒ^３０を表す。Ｒ^１０～Ｒ^３０は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、およびアラルキル基を表す。なお、－ＣＯＯＲ^１２のＲ^１２が水素の場合は、水素原子が解離してもよい。－ＣＯＯＭ^１は、カルボキシル基の金属塩またはアルキルアンモニウム塩を表す。また、－ＳＯ_２ＯＲ^２４のＲ^２４が水素原子の場合は、水素原子が解離してもよい。－ＳＯ_３Ｍ^２は、スルホ基の金属塩またはアルキルアンモニウム塩を表す。また、Ｒ^１とＲ^２、Ｒ^３とＲ^４はお互いに結合して環を形成しても良い。） The squarylium dyes (A-1) and (A-2) are preferably compounds represented by the following general formula (1). Since the naphthalene ring is bonded to the compound represented by the following general formula (1) so that the π-conjugated system spreads from the cyclobutene ring, the maximum absorption wavelength is lengthened and light of 800 nm to 900 nm is well absorbed. This improves the near-infrared ray cutting ability up to around 900 nm. In addition, the naphthalene ring portions are easily associated with each other, and the absorption wavelength region is widened by the absorption derived from the association, and near infrared rays of 700 nm to 900 nm can be widely cut. Furthermore, since the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (1), they act as dye derivatives and improve the fluidity. A near-infrared absorbing composition having good coatability. It is considered that an appropriate association state due to the inclusion of two types of squarylium dyes having partially the same structure makes it possible to achieve both the expansion of the absorption wavelength region and the coatability.

General formula (1)

(In the general formula (1), R ¹ to R ⁴ are independently each of a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR ¹⁰ , -COR ¹¹ , -COOR ¹² , -COOM ¹ , -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , -NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ¹⁹ R ²⁰ , -NHCOOR ²¹ , -SR ²² , -SO ₂ R ²³ , -SO ₂ OR ²⁴ , -SO ₃ M ² , -NHSO ₂ R ²⁵ , -SO ₂ NR ²⁶ R ²⁷ , -B ⁽ OR ²⁸ ) ₂ , or ^{-NHBR 29} R ³⁰ . Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, R ¹² of −COOR ¹² is hydrogen. In some cases, the hydrogen atom may be dissociated.-COMM ¹ represents a metal salt or an alkylammonium salt of a carboxyl group. Further, when R ²⁴ of -SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom is dissociated. -SO ₃ M ² may represent a metal salt or an alkylammonium salt of a sulfo group, and R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring. .)

In -COOM ¹ and -SO ₃ M ² , M ¹ and M ² represent a metal forming a metal salt with a carboxyl group or a sulfo group, or an amine forming an alkylammonium salt with a carboxyl group or a sulfo group.
Examples of the metal forming a metal salt with a carboxyl group or a sulfo group include, but are limited to, sodium, potassium, magnesium, calcium, manganese, iron, cobalt, nickel, copper, zinc, silver, and aluminum. is not.

Examples of the amine that forms an alkylammonium salt with a carboxyl group or sulfo group include dimethylamine, trimethylamine, diethylamine, triethylamine, hydroxyethylamine, dihydroxyethylamine, 2-ethylhexylamine, N, N-dimethylaminopropylamine, N, N-diethylamino. Lower amines such as propylamine, N, N-dibutylaminopropylamine, long-chain alkylamines having an alkyl group having 2 or more carbon atoms such as laurylamine, oleylamine, palmitylamine, stearylamine, and dimethyllaurylamine, laurylammonium, Examples thereof include long-chain alkyl quaternary ammonium ions having an alkyl group having 12 or more carbon atoms such as stearylammonium, lauryltrimethylammonium, dilauryldimethylammonium, stearyltrimethylammonium, and distearyldimethylammonium, but are not limited thereto. not.

Examples of the "substituted group" include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group.
-OR ¹⁰⁰ , -COR ¹⁰¹ , -COOR ¹⁰² , -OCOR ¹⁰³ , -NR ¹⁰⁴ R ¹⁰⁵ , -NHCOR ¹⁰⁶ , -CONR ¹⁰⁷ R ¹⁰⁸ , -NHCONR ¹⁰⁹ R ¹¹⁰ , -NHCOOR ¹¹¹ , -SR ¹¹² , -SO ₂ R ¹¹³ , -SO ₂ OR ¹¹⁴ , -NHSO ₂ R ¹¹⁵ or -SO ₂ NR ¹¹⁶ R ¹¹⁷ can be mentioned.
R ¹⁰⁰ to R ¹¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ¹⁰² of -COOR ¹⁰² is hydrogen (that is, a carboxyl group), the hydrogen atom may be dissociated (that is, a carbonate group), or it may be in a salt state. Further, when R ¹¹⁴ of -SO ₂ OR ¹¹⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated (that is, a sulfonate group) or may be in a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched or cyclic.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic.
The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkynyl group may be linear, branched or cyclic.
The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms.
The alkyl moiety of the aralkyl group is the same as the above alkyl group. The aryl moiety of the aralkyl group is the same as the above aryl group. The carbon number of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and particularly preferably 7 to 25.
The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and particularly preferably a monocyclic ring or a condensed ring having a condensed number of condensed rings of 2 to 4. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12.
The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, and aralkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned "substituent".

It is more preferable that the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (2).

（一般式（２）中、Ｒ^５～Ｒ^８はそれぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アラルキル基、－ＯＲ^５０、－ＣＯＲ^５１、－ＣＯＯＲ^５２、－ＣＯＯＭ^３、－ＯＣＯＲ^５３、－ＮＲ^５４Ｒ^５５、－ＮＨＣＯＲ^５６、－ＣＯＮＲ^５７Ｒ^５８、－ＮＨＣＯＮＲ^５９Ｒ^６０、－ＮＨＣＯＯＲ^６１、－ＳＲ^６２、－ＳＯ_２Ｒ^６３、－ＳＯ_２ＯＲ^６４、－ＳＯ_３Ｍ^４、－ＮＨＳＯ_２Ｒ^６５、－ＳＯ_２ＮＲ^６６Ｒ^６７、－Ｂ（ＯＲ^６８）_２、または－ＮＨＢＲ^６９Ｒ^７０を表す。Ｒ^５０～Ｒ^７０は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、およびアラルキル基を表す。なお、－ＣＯＯＲ^５２のＲ^５２が水素の場合は、水素原子が解離してもよい。－ＣＯＯＭ^３は、カルボキシル基の金属塩またはアルキルアンモニウム塩を表す。また、－ＳＯ_２ＯＲ^６４のＲ^６４が水素原子の場合は、水素原子が解離してもよい。－ＳＯ_３Ｍ^４は、スルホ基の金属塩またはアルキルアンモニウム塩を表す。また、Ｒ^５とＲ^６、Ｒ^７とＲ^８はお互いに結合して環を形成しても良い。） Since the squarylium dyes (A-1) and (A-2) are compounds having a perimidine skeleton represented by the general formula (2), a near-infrared absorbing composition having high light resistance is obtained.

General formula (2)

(In the general formula (2), R ⁵ to R ⁸ are independently each of a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, −OR ⁵⁰ , -COR ⁵¹ , -COOR ⁵² , -COOM ³ , -OCOR ⁵³ , -NR ⁵⁴ R ⁵⁵ , -NHCOR ⁵⁶ , -CONR ⁵⁷ R ⁵⁸ , -NHCONR ⁵⁹ R ⁶⁰ , -NHCOOR ⁶¹ , -SR ⁶² , -SO ₂ R ⁶³ , -SO ₂ OR ⁶⁴ , -SO ₃ M ⁴ , -NHSO ₂ R ⁶⁵ , -SO ₂ NR ⁶⁶ R ⁶⁷ , -B (OR ⁶⁸ ) ₂ , or ^{-NHBR 69} R ^{70 .} Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, R ⁵² of -COOR ⁵² is hydrogen. In some cases, the hydrogen atom may be dissociated.-COM ³ represents a metal salt or an alkylammonium salt of a carboxyl group. Further, when R ⁶⁴ of -SO ₂ OR ⁶⁴ is a hydrogen atom, the hydrogen atom is dissociated. -SO ₃ M ⁴ may represent a metal salt or an alkylammonium salt of a sulfo group, and R ⁵ and R ⁶ and R ⁷ and R ⁸ may be bonded to each other to form a ring. .)

-COMM ³ and -SO ₃ M ⁴ are synonymous with -COOM ¹ and -SO ₃ M ² described above.

The "substituent" has the same meaning as the above-mentioned "substituent".

Specific examples of the squarylium dyes (A-1) and (A-2) include, but are not limited to, the compounds shown below. Further, the compounds described in paragraph numbers [0044] to [0049] of JP-A-2011-208101 and the compounds described in paragraph number [0072] of Japanese Patent No. 6453456 can be mentioned.

The maximum absorption wavelength λ1 _max in the range of 400 to 1000 nm of the squarylium dye (A-1) is preferably 800 nm to 850 nm, and more preferably 800 nm to 830 nm.

The maximum absorption wavelength λ2 _max in the range of 400 to 1000 nm of the squarylium dye (A-2) is preferably 820 nm to 900 nm, and more preferably 830 to 900 nm.

The total amount of the squarylium dye (A-1) and the squarylium dye (A-2) in the total solid content in the near-infrared absorbing composition is preferably 2 to 80% by mass, preferably 4 to 70% by mass. Is more preferable.

The content ratio of the squarylium dye (A-1) and the squarylium dye (A-2) in the near-infrared absorbing composition is preferably 95/5 to 30/70, more preferably 90/10 to 40/60.

<Other near-infrared absorbing dyes>
The near-infrared absorbing composition of the present invention may contain other near-infrared absorbing dyes, if necessary, as long as the spectral characteristics of the squarylium dye (A-1) and the squarylium dye (A-2) are not impaired. .. Examples of other near-infrared absorbing dyes include cyanine compounds, squarylium compounds (excluding squarylium dyes (A-1) and squarylium dyes (A-2)), phthalocyanine compounds, naphthalocyanine compounds, aminium compounds, diimmonium compounds, and croconium. Examples thereof include compounds, azo compounds, quinoid type complex compounds, dithiol metal complex compounds and the like.

<Other dyes (excluding near-infrared absorbing dyes)>
The near-infrared absorbing composition of the present invention may contain other dyes (excluding near-infrared absorbing dyes) depending on its use.

The near-infrared absorbing composition of the present invention preferably has a transmittance of 50% or more at 940 nm when the coating film is formed so that the transmittance at 800 nm is 1%. This facilitates sensing using a light source of 940 nm while reducing external light noise, so that sensing accuracy can be improved.

<Coloring composition exhibiting black color>
The near-infrared absorbing composition of the present invention can be used as a near-infrared transmitting composition by containing a coloring composition exhibiting black color. The coloring composition exhibiting black color is not particularly limited as long as it exhibits black color, and may contain a black dye, a dye composition exhibiting black color by combining a plurality of dyes, and the like.

<Dye derivative>
A dye derivative can be used in the near-infrared absorbing composition of the present invention, if necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group and the like in the organic dye residue. The dye derivative has, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and a basic substituent such as an amine salt, a sulfonamide group, or a tertiary amino group at the terminal thereof. Examples thereof include compounds and compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.

Specifically, the diketopyrrolopyrrole dye derivative is JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine-based. For dye derivatives, JP-A-2007-226161, WO2016 / 163351 pamphlet, JP-A-2017-165820, JP-A-5753266, and for anthraquinone-based dye derivatives, JP-A-63-246674, JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet, quinacridone-based dye derivatives are JP-A-48-54128, JP-A-48-54128. JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 for dioxazine-based dye derivatives, JP-A-2007-314785 for thiazine indigo-based dye derivatives, Triazine-based dye derivatives. Is JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681. , Benzoisoindole-based dye derivatives are JP-A-2009-57478, and quinophthalone-based dye derivatives are JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012. -226110, naphthol-based dye derivatives are JP-A-2012-208329, JP-A-2014-5439, and azo-based dye derivatives are JP-A-2001-172520, JP-A-2012-1722092, acidic. Substituents are referred to in JP-A-2004-307854, and basic substituents are referred to in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. Examples include the described dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

These dye derivatives can be used alone or in combination of two or more.

The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the dye.

When the dye is a pigment, the dye derivative is adsorbed on the pigment surface by adding a pigment derivative and performing pigmentation treatment such as acid pacing, acid slurry, dry milling, salt milling, and solvent salt milling. , The primary particles of the pigment can be made finer as compared with the case where the dye derivative is not added.

By adding a dye derivative to the pigment and performing dispersion treatment such as wet dispersion using two rolls, three rolls, and beads, the dye derivative is adsorbed on the pigment surface and the pigment surface has polarity, and the resin type dispersant is adsorbed. Is promoted, compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and temporal viscosity stability of the near-infrared absorbing composition are improved. In addition, due to the improved compatibility, the coating film has excellent stability over time when the near-infrared absorbing composition is applied to a glass substrate or the like, and the waiting time from application to exposure of the near-infrared absorbing composition (PCD: Post Coating). Stability and characteristic dependence such as pattern shape with respect to Delay) and waiting time from exposure to heat treatment (PED: Post Exposure Delay), and line width sensitivity stability are improved. Further, by adsorbing and coating the pigment surface with the pigment derivative and the resin type dispersant, it is possible to suppress the aggregation of the pigment and the crystal precipitation due to sublimation when the coating film is heated and fired. Furthermore, variations in development time and development residues are suppressed.

<Resin type dispersant>
The near-infrared absorbing composition of the present invention can contain a resin-type dispersant. The resin-type dispersant has a pigment-affinity moiety having a property of adsorbing to the pigment and a relaxation moiety having a high affinity with components other than the pigment and causing steric repulsion between the dispersed particles. As the resin type dispersant, a structurally controlled resin such as a graft type (comb type) or a block type is preferably used.

The resin-type dispersant may be, for example, a urethane-based dispersant such as polyurethane, a polycarbonic acid ester such as polyacrylate, unsaturated polyamide, polycarbonic acid, polycarbonic acid (partial) amine salt, or polycarbonate ammonium salt. Polycarbonic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarbonic acid esters and their modifications; formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Amid and its salts; (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc .; polyester, modification Examples thereof include polyacrylate, ethylene oxide / propylene oxide addition compound, and phosphoric acid ester type.

In terms of ionicity, examples of the resin-type dispersant include an acidic resin-type dispersant and a basic resin-type dispersant.

The basic resin-type dispersant has a nitrogen atom-containing graft copolymer and a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain, and has a nitrogen atom-containing acrylic block co-weight. Examples thereof include coalescing and urethane-based polymer dispersants.
The basic resin type dispersant can be used by neutralizing the basic group with phosphoric acid or sulfonic acid.

The near-infrared absorbing composition of the present invention preferably contains a basic resin-type dispersant, and more preferably a resin-type dispersant having a tertiary amino group or a quaternary ammonium salt as a dye adsorbing group.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti- SOLPERSE-3000, 9000, 13000, 13240, 13650, manufactured by Japan Lubrizol, such as Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykuman, etc. 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, etc. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Examples thereof include Ajispar PA111, PB711, PB821, PB822, PB824 manufactured by Fine Techno.

The resin-type dispersant can be used alone or in combination of two or more.

The content of the resin type dispersant is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to the total amount of the dye. When an appropriate amount is contained, a film is easily formed.

<Binder resin>
The near-infrared absorbing composition of the present invention may contain a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, the binder resin includes, for example, a thermoplastic resin, a thermosetting resin, an active energy ray curable resin, and the like. The active energy ray-curable resin may have an active energy ray-reactive functional group in the thermoplastic resin or the thermosetting resin. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. The alkali solubility is for imparting development solubility in the alkali development step at the time of producing an optical filter, and an acidic group is required.

The binder resin can be used alone or in combination of two or more.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the dye. When an appropriate amount is contained, a film can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, a polyurethane resin, and the like. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group and a sulfone group. The alkali-soluble thermoplastic resin is, for example, an acrylic resin having an acidic group, an α-olefin / (maleic) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, or an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (maleic anhydride) maleic anhydride copolymer and the like. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable in terms of improving developability, heat resistance, and transparency.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the methods (i) and (ii) shown below. Due to the effect of the active energy rays, the resin is three-dimensionally crosslinked to increase the crosslink density and improve the chemical resistance.

[Method (i)]
In method (i), for example, an ethylenically unsaturated monomer is added to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. The carboxyl group of the unsaturated monobasic acid having a heavy bond is subjected to an addition reaction. Next, it is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by reacting the generated hydroxyl group with a polybasic acid anhydride.

Ethylene unsaturated monomers having an epoxy group include, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and the like. And 3,4-epoxycyclohexyl (meth) acrylates. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity with unsaturated monobasic acid.

Unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, cyano substituents and the like. Examples include carboxylic acid.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic acid anhydride was used, or a tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride was used to remain. Anhydrous groups can also be hydrolyzed.

Examples of other monomers include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) (Meta) acrylates such as acrylates, phenoxyethyl (meth) acrylates, phenoxydiethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates, or ethoxypolyethylene glycol (meth) acrylates,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides Styrene, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate. And so on.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Hexanoart, N-substituted maleimides such as N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimideacridin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethyleneoxide (EO) -modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, PO-modified (meth) acrylate of nonylphenol, etc. Can be mentioned.

As a method similar to the method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and another monomer are copolymerized with a part of the side chain carboxyl group of the copolymer obtained. This is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction.

[Method (ii)]
In the method (ii), the ethylenically unsaturated monomer having an isocyanate group is added to the side chain hydroxyl group of the copolymer obtained by copolymerizing the ethylenically unsaturated monomer having a hydroxyl group with another monomer. This is a method of reacting a monomeric isocyanate group.

The ethylenically unsaturated monomer having a hydroxyl group is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and the like. Examples thereof include hydroxyalkyl methacrylates such as glycerol mono (meth) acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by superpolymerizing hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Polyester mono (meth) acrylate to which 12-hydroxystearic acid or the like is added can also be mentioned. 2-Hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. Therefore, glycerol mono (meth) acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate. Will be.

Other monomers that can constitute the alkali-soluble resin include N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphate ester group-containing ethylenically unsaturated monomers in addition to the other ethylenically unsaturated monomers described above. Examples thereof include monomers and carboxyl group-containing ethylenically unsaturated monomers.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-. 4-Methyl-3-maleimidecoumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedi maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitro) Phenyl) Maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, Examples thereof include N-succinimidyl-6-maleimidehexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenylacrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, and paracumylphenol. Examples thereof include EO or propylene oxide (PO) modified (meth) acrylate, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomer described above can be used.

The phosphoric acid ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. be.

<Alkali-soluble resin without ethylenically unsaturated double bond>
The near-infrared absorbing composition of the present invention may contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 30,000 or less, preferably 4,000, in order to impart alkali development solubility. More preferably 20,000 or less. Further, the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg / g) in order to impart alkali development solubility, preferably 70 or more and 180 or less, and more preferably 90 or more and 170 or less. Is. When the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.

Each raw material used for synthesizing the binder resin can be used alone or in combination of two or more.

<Thermosetting compound>
In the present invention, the binder resin can be used in combination with a thermoplastic resin to further contain a thermosetting compound. When an optical filter is produced using the near-infrared absorbing composition of the present invention, the inclusion of a thermosetting compound causes a reaction during firing of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment. However, the effect of suppressing pigment aggregation during firing of the filter segment and improving the contrast ratio can be obtained.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound include, but are limited to, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. It is not something that is done. Epoxy compounds and oxetane compounds are preferably used in the near-infrared absorbing composition of the present invention.

<Polymerizable compound>
A photosensitive near-infrared absorbing composition can be obtained by containing the near-infrared absorbing composition of the present invention, a polymerizable compound, and a photopolymerization initiator. The polymerizable compound includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin.

The polymerizable compound is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth). Acrylate, Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Triethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Trimethylol propanthry (meth) acrylate, Phenoxytetra Ethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A Diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, methylolation Various acrylic acid esters such as melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Examples thereof include trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Polymerizable compound having an acid group)
The polymerizable compound can contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

The photopolymerizable monomer having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a mono. Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

(Polymerizable compound with urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional isocyanate being reacted with an alcohol and further reacting with a (meth) acrylate having a hydroxyl group. Examples thereof include polyfunctional urethane acrylate obtained by subjecting the mixture.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate , Gloxydimethacrylate, 2-hydroxy-3-acryloylpropylmethacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, a hydroxyl group-containing polyol polyacrylate and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

The polymerizable compound can be used alone or in combination of two or more.

The blending amount of the polymerizable compound is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, based on 100% by mass of the non-volatile content of the near-infrared absorbing composition. When an appropriate amount is blended, curability and developability are further improved.

<Photopolymerization initiator>
The photopolymerization initiator is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (Phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Acetphenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone , 4-Benzoyl-4'-methyldiphenylsulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone. , Isoxanthone compounds such as isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6- Triazine compounds such as triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime)], or oxime esters such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) Compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphinoxide or diphenyl-2,4,6-trimethylbenzoylphosphinoxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone. Kinone-based compounds such as; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanosen-based compounds and the like can be mentioned. Among these, oxime ester compounds are preferable.

The photopolymerization initiator can be used alone or in combination of two or more.

(Oxime ester compound)
The oxime ester compound breaks the NO bond of the oxime by absorbing ultraviolet rays, and produces an iminyl radical and an arcroxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the dye concentration of the near-infrared absorbing composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low, but the oxime ester compound is preferably used because it has high quantum efficiency. ..

The oxime ester compound is described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, and the like. Examples thereof include ester-based photopolymerization initiators.

The content of the photopolymerization initiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the dye. When an appropriate amount is blended, the photocurability and developability are further improved.

<Sensitizer>
Further, the near-infrared absorbing composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Among the above sensitizers, examples of the sensitizer that can be particularly preferably sensitized include a thioxanthone derivative, a Michler ketone derivative, and a carbazole derivative. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis. (Dimethylamino) Benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizer described in "Special Functional Materials" (1986, CMC) can be mentioned, but is not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

The sensitizer can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, curability and developability are further improved.

<Thiol chain transfer agent>
The near-infrared absorbing composition of the present invention preferably contains a thiol-based chain transfer agent as the chain transfer agent. By using thiol together with a photopolymerization initiator, a chil radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so that the obtained near-infrared absorbing composition has high sensitivity. It becomes.

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more thiol groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, Trimethylol Propanitris Thioglycolate, Trimethylol Propanitris Thiopropionate, Trimethylol Propantris (3-Mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Trimercaptopropionic Acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Examples thereof include triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropanetristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the non-volatile content of the near-infrared absorbing composition. When an appropriate amount is contained, the light sensitivity and the tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating film.

<Polymerization inhibitor>
The near-infrared absorbing composition of the present invention may contain a polymerization inhibitor. As a result, the exposure due to the diffracted light of the mask can be suppressed during the exposure of the photolithography method, so that a pattern having a desired shape can be easily obtained.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-. Propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4- Alkyl catechol compounds such as tert-butyl catechol and 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl Alkyl resorcinol compounds such as resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphin compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide and the like. Examples thereof include phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100% by mass of the non-volatile content of the near-infrared absorbing composition. In this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles of the coating film, pattern resolution, and the like are improved.

<UV absorber>
The near-infrared absorbing composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. ..

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the near-infrared absorbing composition. When an appropriate amount is contained, the adhesion between the substrate and the coating film is further improved, and good resolution can be obtained.

Examples of benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and 2- [2-hydroxy-3,5. -Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1-dimethyl)-(1,1-dimethyl) Ethyl) -4-hydroxy, a mixture of C7-9 side chains and linear alkyl esters, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3-( Reaction product of 2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole-2-yl) -4- (1,1) , 3,3-Tetramethylbutyl) Phenol, 2,2'-Methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2 -(2H-benzotriazole-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole-2-yl) -6-t-butyl-4-methylphenol, 2- (3,5) -Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3-tert- Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-) 2H-benzotriazole-2-yl) phenyl] propionate can be mentioned. In addition, oligomer-type and polymer-type compounds having a benzotriazole structure can also be used.

Examples of the triazine compound include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4,6. -Bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4- Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyl) Oxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2-Hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like can be mentioned. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

Examples of the benzophenone compound include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, and the like. 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadesiloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The near-infrared absorbing composition of the present invention can contain an antioxidant. Antioxidants are used to reduce the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the near-infrared absorbing composition from oxidizing and yellowing due to the thermal process during thermal curing or ITO annealing. Can be improved. In particular, when the colorant concentration of the coloring composition is high, the amount of the cross-linking component of the coating film is small, so that the yellowing of the thermal process becomes strong due to the use of a highly sensitive cross-linking component and the increase of the amount of the photopolymerization initiator. Can be seen. Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and obtain a high transmittance of the coating film.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable from the viewpoint of achieving both the transmittance and the sensitivity of the coating film.

The antioxidant can be used alone or in combination of two or more.

Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in the solid content of 100% by mass of the near-infrared absorbing composition because the transmittance, the spectral characteristics and the sensitivity are good.

<Leveling agent>
It is preferable to add a leveling agent to the near-infrared absorbing composition of the present invention for the purpose of improving the coatability of the composition on the transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

When the near-infrared absorbing composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.0% by mass with respect to the total solid content of the composition of the present invention. More preferably, it is 0.005 to 1.0% by mass. Within this range, the balance between the coatability of the near-infrared absorbing composition, the pattern adhesion, and the transmittance is good.
The near-infrared absorbing composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactant. When two or more types are included, it is preferable that the total amount is within the above range.

<Storage stabilizer>
The near-infrared absorbing composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

<Adhesion improver>
The near-infrared absorbing composition of the present invention may contain an adhesion improving agent such as a silane coupling agent in order to enhance the adhesion to the substrate. By improving the adhesion by the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

Examples of the adhesion improver include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-. (Meta) acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-) Aminosilanes such as butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropylmethyldimethoxy Melcaptos such as silane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, and sulfides such as bis (triethoxysilylpropyl) tetrasulfide. , 3-Silane Coupling agents such as isocyanates such as propyltriethoxysilane and the like can be mentioned. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the near-infrared absorbing composition. It is more preferable because the effect is large within this range and the balance between adhesion, resolution and sensitivity is good.

<Manufacturing method of near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention has two kneaders of a dye in a dye carrier such as a dispersant and a binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or surfactant). It can be finely dispersed and produced by using various dispersion means such as a roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (dye dispersion). At this time, two or more kinds of dyes and the like may be dispersed in the dye carrier at the same time, or those dispersed separately in the dye carrier may be mixed. If the dye is highly soluble, such as a dye, specifically, it is highly soluble in the solvent used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to disperse it finely as described above. There is no.

When used as a photosensitive near-infrared absorbing composition (resist material), it can be prepared as a solvent-developed type or alkali-developed near-infrared absorbing composition. The solvent-developed or alkali-developed near-infrared absorbing composition includes the dye dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other dispersion aids, and addition. It can be adjusted by mixing agents and the like. The photopolymerization initiator may be added at the stage of preparing the near-infrared absorbing composition, or may be added later to the prepared near-infrared absorbing composition.

<Solvent>
The near-infrared absorbing composition of the present invention is coated on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm, and contains a solvent in order to facilitate the formation of a dye film. The solvent is selected in consideration of the solubility of each component of the near-infrared absorbing composition and the safety in addition to the good applicability of the near-infrared absorbing composition.

As the solvent, a solvent usually used in the art can be used, and in consideration of performance such as boiling point, SP value, evaporation rate, viscosity, etc., it may be used alone or as appropriate according to the coating conditions (speed, drying conditions, etc.). Used as a mixture.

Examples of the solvent used include an ester solvent (solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (solvent containing -O- in the molecule and not containing -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule but not -COO-), alcohol solvent (OH in the molecule) Included, -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Among the above solvents, it is preferable to include an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm from the viewpoint of coatability and drying property. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferable.

<Removal of coarse particles>
The near-infrared absorbing composition of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 1 μm or more, by means such as centrifugation at a gravitational acceleration of 3000 to 25000 G and filtration by a sintering filter or a membrane filter. It is preferable to remove coarse particles of 0.5 μm or more and mixed dust. As described above, it is preferable that the near-infrared absorbing composition does not substantially contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Manufacturing method of optical filter>
The optical filter of the present invention can be manufactured by a printing method or a photolithography method. Since the formation of the filter segment by the printing method can be patterned by printing and drying the near-infrared absorbing composition, the filter manufacturing method is low cost and excellent in mass productivity. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When forming a filter segment by a photolithography method, a method of applying a near-infrared absorbing composition prepared as a solvent-developed or alkali-developed resist material onto a substrate by spray coating, spin coating, slit coating, roll coating, or the like. Therefore, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or alkaline developer or spraying the developer with a spray to remove the uncured part to form a desired pattern, the same operation is repeated for other colors to manufacture a filter. Can be done. Further, in order to promote the polymerization of the resist material, heating can be applied as needed. According to the photolithography method, a filter having higher accuracy than the above printing method can be manufactured.

The substrate is not particularly limited, but a sheet-shaped, film-shaped, or plate-shaped transparent substrate can be used as the shape. Colors are also colorless and colored, and are not particularly limited. The material of the transparent base material is a highly transparent material, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or triacetyl cellulose (TAC). Examples thereof include acrylic resins such as methyl methacrylate-based copolymers, styrene resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, vinyl chloride resins, polymethacrylicimide resins, and glass plates.

For development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the resist material was applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin was applied and dried to form a film for preventing polymerization inhibition by oxygen. Later, UV exposure can also be performed.

The optical filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an inkjet method, or the like in addition to the above methods.

<Use>
The near-infrared absorbing composition can be used as an optical filter.
For example, a digital camera recognizes colors by decomposing the light received during imaging with red, green, and blue filters and sending it to a photodiode that converts the light into an electrical signal. However, the photodiode also reacts to near-infrared rays and converts it into an electric signal, so a filter that blocks this is required. A coating or a molded product formed from the near-infrared absorbing composition can be used as a filter for blocking the near-infrared rays. It is important that the filter that blocks near infrared rays has little absorption in the visible region. If there is a lot of absorption in the visible region, the received light will be colored, which will adversely affect the color recognition of the photodiode. Since the near-infrared absorbing pigment of the present invention absorbs little in the visible region and has high invisibility, it has little adverse effect on the color recognition of the photodiode.

In addition, for example, smartphones, tablet PCs, etc., bank ATMs, multimedia terminals, etc. are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication for security protection. In particular, the development of fingerprint authentication technology used for smartphones and tablet PCs is rapid, and as the authentication range increases to the screen size (full screen), fingerprint authentication sensors with built-in displays have been developed for organic EL displays, liquid crystal displays, etc. There is.
However, since many fingerprint sensors with a built-in display irradiate the fingerprint with various light sources installed in the display and sense the reflected light, illegal external light (such as sunlight or LED lighting) is used. When a sensor has a wide range of wavelengths and is subject to strong light), there is a problem of noise during imaging, and there remains some concern about accuracy when used outdoors. A coating or molded product formed from a near-infrared absorbing composition can be used as a filter to block this noise.
By containing other dyes according to the wavelength of the light source for sensing, the accuracy of biometric authentication can be further improved.
When a light source of about 570 nm is used for fingerprint authentication, as another dye, for example, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63 and the like may be contained. When a light source of about 940 nm is used, it is preferable to contain a black dye, a dye composition in which a plurality of dyes are combined to exhibit black, and the like. Needless to say, the present invention is not limited to these.

Optical filters using the near-infrared absorbing composition include a near-infrared cut filter and a near-infrared transmissive filter. The near-infrared cut filter is mainly composed of a near-infrared absorbing dye and has a role of blocking near-infrared rays and transmitting visible light. On the other hand, the near-infrared ray transmitting filter is composed of a colored dye that absorbs visible light in addition to the near-infrared absorbing dye, blocks visible light and near-infrared rays in the wavelength range absorbed by the near-infrared absorbing dye, and is longer than that. It has the role of transmitting near infrared rays of wavelength.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, "part" means "part by weight". Further, "PGMAC" means propylene glycol monomethyl ether acetate.

(Method for identifying squarylium pigment)
A MALDI TOF-MS spectrum was used to identify the squarylium dye used in the present invention. For the MALDI TOF-MS spectrum, the obtained compound was identified by matching the molecular ion peak of the obtained mass spectrum with the mass number obtained by calculation using the MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics. rice field.

(Method for identifying other refined dyes (PB-1) to (PB-4))
The identification of the other micronized dyes (PB-1) to (PB-4) used in the present invention was obtained by using a time-of-flight mass spectrometer (autoflexIII (TOF-MS), manufactured by Bruker Daltonics). Matching of the molecular ion peak of the mass spectrum with the mass number obtained by calculation, and the ratio of carbon, hydrogen and nitrogen obtained by using an elemental spectrometer (2400CHN elemental analyzer, manufactured by Perkin-Elmer). It was done by matching with the theoretical value. The number of halogen atom substitutions is determined by the amount of halogen in the liquid obtained by burning the pigment by the oxygen combustion flask method and absorbing the combustible in water by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX). Was quantified and converted into the number of halogen atom substitutions.

(Acid value of other resin type dispersants and binder resin)
The acid value of the resin-type dispersant and the binder resin was determined by a potentiometric titration method using a 0.1 N potassium hydroxide / ethanol solution. The acid value of the resin and the resin type dispersant indicates the acid value of the non-volatile component.

(Weight average molecular weight (Mw) of other resin-type dispersants and binder resins)
The weight average molecular weight (Mw) of the resin-type dispersant and the binder resin is a GPC (Tosoh, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh), and THF is used as a developing solvent. It is a polystyrene-equivalent weight average molecular weight (Mw) measured in the above.

(Weight average molecular weight (Mw) of basic resin type dispersant)
The weight average molecular weight (Mw) of the basic resin type dispersant was measured by gel permeation chromatography (GPC) equipped with an RI detector.
Using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, connecting two separation columns in series, using "TSKgel SUPER-AW3000" as both fillers, an oven temperature of 40 ° C., 3 mM triethylamine as an eluent and A 10 mM LiBr N, N-dimethylformamide solution was used, and the measurement was performed at a flow rate of 0.6 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in 10 microliters. All molecular weights are polystyrene-equivalent values.

(Amine value of resin type dispersant)
The amine value of the resin-type dispersant was determined by a potentiometric titration method using a 0.1 N aqueous hydrochloric acid solution, and then converted to the equivalent of potassium hydroxide. The amine value of the resin type dispersant indicates the amine value of the non-volatile component.

(Quaternary ammonium salt value of resin type dispersant)
The quaternary ammonium salt value of the resin-type dispersant was determined by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to the equivalent of potassium hydroxide. The quaternary ammonium salt value of the resin type dispersant below indicates the quaternary ammonium salt value of the non-volatile component.

<Manufacturing of miniaturized squarylium dye (P)>
(Synthesis of squarylium dye (A-1_1))
400 parts of toluene is mixed with 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture is heated and stirred in an atmosphere of nitrogen gas. It was refluxed for hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation.
After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, and dried under reduced pressure to obtain 61.9 parts (yield: 92%) of squarylium dye (A-1_1). rice field. As a result of mass spectrometry by TOF-MS, it was identified as a squarylium dye (A-1_1).

(Synthesis of squarylium dye (A-1_2))
The same operation as the synthesis of squarylium dye (A-1_1) except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the synthesis of squarylium dye (A-1_1). To obtain 72.6 parts (yield: 98%) of squarylium dye (A-1_2). As a result of mass spectrometry by TOF-MS, it was identified as a squarylium dye (A-1_2).

(Synthesis of squarylium dye (A-1_3))
The same operation as the synthesis of the squarylium dye (A2-1) was performed except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the synthesis of the squarylium dye (A-1_1). , 67.2 parts (yield: 95%) of squarylium dye (A-1_3) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a squarylium dye (A-1_3).

(Synthesis of squarylium dye (A-1_4))
The squarylium compound Q-39 used in the examples of Patent Document WO2017 / 130825 was used as the squarylium dye (A-1_4).

(Synthesis of squarylium dye (A-2-_1))
400 parts of toluene was mixed with 40.0 parts of 1,8-diaminonaphthalene, 46.0 parts of 9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in an atmosphere of nitrogen gas. It was refluxed for 3 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, and dried under reduced pressure to obtain 84.6 parts (yield: 97%) of squarylium dye (A-2-_1). rice field. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium dye (A-2_1).

(Synthesis of squarylium dye (A-2_2))
Squalylium dye (60.7 parts of 2,7-bis (trifluoromethyl) -9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the synthesis of squalylium dye (A-2-1-1). The same operation as for the synthesis of A-2-1) was carried out to obtain 109.8 parts (yield: 91%) of the squarylium dye (A-2_1). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium dye (A-2_2).

(Synthesis of squarylium dye (A-2_3))
With the synthesis of squarylium dye (A-2_1), except that 50.1 parts of 2-hydroxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the synthesis of squarylium dye (A-2-1-1). The same operation was carried out to obtain 83.9 parts (yield: 92%) of squarylium dye (A-2_3). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium dye (A-2_3).

(Synthesis of squarylium dye (A-2_4))
Compound 4 used in the examples of Patent Document WO2017 / 104283 was used as a squarylium dye (A-2_4).

(Solvent treatment and miniaturization of squarylium dye)
[Solvent treatment process]
50 parts of squarylium dye (A-1_1) was mixed with 250 parts of N-methylpyrrolidone, and the mixture was stirred at 23 ° C. for 24 hours. Then, the mixture was filtered, washed with 150 parts of methanol, taken out, and dried at 80 ° C. for 24 hours to obtain 25 parts of powder.
[Miniaturization process]
10 parts of the obtained powder, 100 parts of sodium chloride, and 12.5 parts of ethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 12 hours. Next, the kneaded mixture is put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. for 24 hours and pulverized. As a result, 9.4 parts of a finely divided slurryyl dye (P-1_1) was obtained.
[Average particle size]
The average primary particle size of the pigment was measured by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to a cube having the obtained particle size, and the volume average particle size was taken as the average primary particle size. The electron microscope used was a transmission type (TEM).
As a result of measurement by this method, the average primary particle size was 50 nm.
[Component ratio]
5.0 mg of squarylium dye (P-1_1) was placed in a 100 ml volumetric flask, THF for HPLC was added, and ultrasonic waves were irradiated for 30 minutes to dissolve the mixture, and a 100 ml THF solution was prepared. Using this solution, HPLC measurement of dye compound B was carried out under the above equipment and the above conditions.
The HPLC measurement was analyzed by reverse phase liquid chromatography under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as a mobile phase.
As a result, multiple peaks were shown.
Specifically, a peak with a retention time of 12 ± 1 minute (peak 1), a peak with a retention time of 42 ± 1 minute (peak 2), and a peak with a retention time of 46 ± 2 minutes (peak 3). It is composed of a peak with a retention time of 50 ± 2 minutes (peak 4) and a peak with a retention time of 57 ± 2 minutes (peak 5).
The area of peak 5 was 70% of the total area of peaks 1-5.

The squarylium dyes (A-1_2) and (A-1_3) were subjected to solvent treatment and miniaturization in the same manner as the squarylium dyes (A-1_1) to obtain miniaturized squarylium dyes (P-1_2) and (P-1_3). .. The squarylium dyes (A-1_4) and (A-2_1) to (A-2_4) were not treated with a solvent and were only miniaturized, and the miniaturized squarylium dyes (P-1_4) and (P-) were refined. 2_1) to (P-2_4).

<Manufacturing of other miniaturized squarylium dyes (PX)>
(Manufacturing of other miniaturized squarylium dyes (PX-1))
The squarylium compound SQ-R1 used in the examples of Patent Document 2020/013089 was used as another squarylium dye (X-1). The other squarylium dye (X-1) was miniaturized in the same manner as the squarylium dye (A-1_4) to obtain other squarylium dyes (PX-1).

(Manufacturing of other miniaturized squarylium dyes (PX-2))
The squarylium compound SQ-1 used in the examples of Patent Document 2020/013089 was used as another squarylium dye (X-2). The other squarylium dye (X-2) was refined in the same manner as the squarylium dye (A-1_4) to obtain other refined squarylium dyes (PX-2).

The structures of the squarylium dye and other squarylium dyes produced as described above are as follows.

<Measurement of maximum absorption wavelength of miniaturized squarylium dye (P)>
The micronized squarylium dye (P) is dissolved in NMP (N-methyl-2-pyrrolidone) so that the maximum absorbance is about 1, and 400 to 400 using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). The absorption spectrum in the wavelength range of 1000 nm was measured. The results are shown in Table 1.

<Dye derivative 1>
The compound represented by the following formula (3) was used as the dye derivative 1.

（式（３）中、Ｃｕ－Ｐｃは、銅フタロシアニン構造残基である。） Equation (3)

(In formula (3), Cu-Pc is a copper phthalocyanine structural residue.)

<Manufacturing of dispersant solution>
(Manufacturing of 1 solution of basic resin type dispersant)

41 parts of N, N-dimethylpropanediamine and 120 parts of chloroform were charged in a reaction vessel equipped with a stirrer and a thermometer, stirred at room temperature, and 50 parts of methacrylic acid chloride was added dropwise over 1 hour. After stirring at room temperature for 3 hours and confirming that the reaction is completed by ¹ H-NMR, the reaction solution is sequentially washed with 300 parts of ion-exchanged water and 200 parts of saturated saline, and then 20 g of magnesium sulfate is added to the organic layer. Was added, and after stirring, filtration was performed. The solvent in the obtained solution was distilled off by a rotary evaporator to obtain 58 parts of the compound [b] represented by the following formula (4) as a pale yellow transparent liquid (yield 85%). Identification of the obtained compound was carried out by ¹ H-NMR.

Equation (4)

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and 50 parts were flowed with nitrogen. The mixture was stirred at ° C. for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to make the first block. Polymerization was started. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 25 parts of PGMAc and 30.3 parts of the above compound [b] as a second block monomer were put into this reaction vessel, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. to continue the reaction. Two hours after the addition of the compound [b] represented by the above formula (4), the polymerization solution is sampled and the solid content is measured, and the polymerization conversion rate of the second block is 98% or more in terms of the non-volatile content. It was confirmed.
Further, 6.8 parts of benzyl chloride was added to this reaction device, and the mixture was stirred for 3 hours while maintaining the atmosphere of 110 ° C. and nitrogen, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. In this way, the basic resin type dispersant 1 having an amine value of 70 mgKOH / g per solid content, a quaternary ammonium salt value of 30 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by weight. A solution was obtained.

(Manufacturing of 2 solutions of basic resin type dispersant)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged in a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and nitrogen was flowed at 50 ° C. for 1 hour. The mixture was stirred and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reaction apparatus, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. to continue the reaction. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was brought to room temperature. It was cooled to stop the polymerization.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, two solutions of the basic resin type dispersant having an amine value of 71.4 mgKOH / g per non-volatile component, a weight average molecular weight of 9,900 (Mw) and a non-volatile content of 40% by mass were obtained.

(Manufacturing of 3 solutions of basic resin type dispersant)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged in a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and nitrogen was flowed at 50 ° C. for 1 hour. The mixture was stirred and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 25.6 parts of a methacryloyloxyethyltrimethylammonium chloride aqueous solution (“Acryester DMC78” manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to this reaction device, and the temperature was maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was prepared. The polymerization was stopped by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, three solutions of the basic resin type dispersant having an amine value of 29.4 mgKOH / g per non-volatile content, a weight average molecular weight of 9,800 (Mw) and a non-volatile content of 40% by mass were obtained.

(Manufacturing of other resin type dispersant 4 solutions)
In a reaction vessel equipped with a gas introduction tube, temperature, condenser, and stirrer, 10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate are charged, and nitrogen gas is charged. Replaced with. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by solid content measurement that 95% had reacted.
Add 19 parts of pyromellitic acid anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and react at 100 ° C. for 7 hours. rice field. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the acid so that the solid content was 40% by measuring the solid content. Another resin-type dispersant 4 having a value of 70 mgKOH / g and a mass average molecular weight of 8500 was obtained.

<Manufacturing of binder resin solution>
(Manufacturing of 1 solution of binder resin)
70.0 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then the dropping tube was used. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Ether acetate was added to prepare a binder resin 1 solution.

(Manufacturing of binder resin 2 solution)
370 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C., the inside of the flask was replaced with nitrogen, and then the dropping tube was used. A mixture of 18 parts of cyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. .. After the dropping, the reaction was further carried out at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the solid acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Acetate was added to prepare a binder resin 2 solution. The weight average molecular weight (Mw) was 19000.

(Manufacturing of binder resin 3 solution)
207 parts of propylene glycol monomethyl ether acetate was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. After that, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix (registered trademark) M110” manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate from the dropping tube. A mixture of parts and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd.). A mixture of 6.5 parts of Karenz (registered trademark) MOI, 0.08 part of dibutyltin laurate and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. Ether acetate was added to prepare a binder resin 3 solution. The weight average molecular weight (Mw) was 18,000.

<Manufacturing of near-infrared absorbing composition (D)>
[Example 1: Near-infrared absorbing composition (D-1)]
(Manufacturing of Near Infrared Absorption Composition (D-1))
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to obtain a near-infrared absorbing composition (D-1). ) Was produced.
Miniaturized squarylium dye (P-1_1): 8.4 parts Miniaturized squarylium dye (P-2_1): 3.6 parts Basic resin type dispersant 1 solution: 9.0 parts Binder resin 1 solution: 22.0 parts PGMAC: 57.0 copies

[Examples 2 to 24: Near-infrared absorbing compositions (D-2) to (D-24), Comparative Examples 1 to 3: Near-infrared absorbing compositions (D-25) to (D-27)]
(Manufacturing of Near Infrared Absorption Compositions (D-2) to (D-27))
Hereinafter, the near-infrared absorbing composition is the same as the near-infrared absorbing composition (D-1) except that the finely divided squarylium dye, the dye derivative, the dispersant solution, and the binder resin solution are changed to the compositions and amounts shown in Table 2. (D-2) to (D-27) were produced.

<Evaluation of spectral characteristics of near-infrared absorbing composition (D)>
The obtained near-infrared absorbing composition (D) was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the transmittance at 800 nm was 1%, and dried at 60 ° C. for 5 minutes. Then, it was heated at 230 ° C. for 20 minutes to prepare a substrate. The spectrum of the obtained substrate was measured for absorption spectra in the wavelength range of 400 to 1000 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
The average transmittance (T) of each range was calculated from the measured absorption spectrum and evaluated according to the following criteria. The evaluation results are shown in Table 2.

Spectral characteristics 1: 700 nm to 750 nm
◯: (T) ≤ 5%
Δ: 5% <(T) ≤ 10%
×: 10% <(T)

Spectral characteristics 2: 750 nm to 850 nm
◯: (T) ≤ 5%
Δ: 5% <(T) ≤ 10%
×: 10% <(T)

Spectral characteristics 3: 850 nm-900 nm
◯: (T) ≤ 5%
Δ: 5% <(T) ≤ 10%
×: 10% <(T)

Spectral characteristics 4: 940 nm
〇: 50% ≤ (T)
Δ: 40% ≤ (T) <50%
×: (T) <40%

<Evaluation of coatability of near-infrared absorbing composition (D)>
The obtained near-infrared absorbing composition (D) was spin-coated on a substrate having a plate thickness of 0.7 mm and a size of 360 mm × 465 mm so that the film thickness (referred to as A) at the center was 2.0 μm, and at 60 ° C. After drying for 5 minutes, the average value (referred to as B) of the film thickness of the central portion and the film thickness of the portion 200 mm from the center on the diagonal line was measured, and the coating uniformity of the film thickness was evaluated by the following formula.
(AB) × 100 / {(A + B) / 2} [%]
○: Less than 2% △: 2% or more and less than 5% ×: 5% or more

By containing two or more kinds of squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm of the present invention between 800 and 900 nm, the near infrared ray cutting ability from 700 nm to 900 nm is high (spectral characteristics 1 to 3). ), A colored composition that transmits near-infrared light of 940 nm (spectral characteristic 4) and has good coatability could be obtained.

<Manufacturing of Photosensitive Near Infrared Absorption Composition (R)>
(Example 25: Production of photosensitive near-infrared absorbing composition (R-1))
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 0.5 μm filter to prepare a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorption composition (D-2): 31.3 parts Binder resin 2 solution: 8.5 parts Thermocurable compound (E): 0.8 parts Polymerizable compound (F): 4.5 parts Photopolymerization started Agent (G): 0.7 part Sensitizer (H): 0.1 part Thiol-based chain transfer agent (I): 0.2 part Polymerization inhibitor (J): 0.2 part UV absorber (K) : 0.2 parts Antioxidant (L): 0.2 parts Leveling agent (M): 5.0 parts Storage stabilizer (N): 0.2 parts Adhesion improver (O): 0.2 parts Solvent ( P): 48.4 copies

(Examples 26 to 29: Photosensitive near-infrared absorbing compositions (R-2) to (R-5),
Comparative Examples 4 to 5: Production of photosensitive near-infrared absorbing compositions (R-6) to (R-7))
Hereinafter, the photosensitive near-infrared absorbing composition is the same as that of the photosensitive near-infrared absorbing composition (R-1) except that the near-infrared absorbing composition (D-1) is changed to the near-infrared absorbing composition shown in Table 3. Objects (R-2) to (R-7) were produced.

The details of the material used for producing the photosensitive near-infrared absorbing composition (R) are as follows.

[Thermosetting compound (E)]
(E-1-1) 1,2-Epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2'-bis (hydroxymethyl) -1-butanol
[EHPE-3150 (manufactured by Daicel)]
(E-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)]
(E-1-3) Triglycidyl isocyanurate,
(E-1-4) 3-Ethyl-3-[(3-Ethyloxetane-3-yl) Methoxymethyl] Oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]
As described above, the same amounts of (E-1-1) to (E-1--4) were mixed to obtain a thermosetting compound (E).

[Polymerizable compound (F)]
(F-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(F-2) Dipentaerythritol penta and hexaacrylate (E-2)
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(F-3) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(F-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(F-5) Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) is charged in a reaction vessel having a polyfunctional urethane acrylate content of 1 liter and 5 mouths according to the following, and reacted at 60 ° C. for 8 hours to form a (meth) acryloyl group. A product containing the polyfunctional urethane acrylate (F-5) having the above was obtained. The proportion of the polyfunctional urethane acrylate (F-5) in the product was 70% by mass, and the balance was other photopolymerizable. It is occupied by monomer. It was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(F-6) Bifunctional bisphenol A type (meth) acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(F-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
As described above, (F-1) to (F-7) were mixed in the same amount to obtain a photopolymerizable monomer (F).

[Photopolymerization Initiator (G)]
(G-1) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one
[Omnirad 907 (manufactured by IGM Resins)]]
(G-2) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(G-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
(G-4) 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole
[Viimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
(G-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(G-6) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(G-7) 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
(G-8) Bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)]
As described above, (G-1) to (G-8) were mixed in the same amount to obtain a photopolymerization initiator (G).

[Sensitizer (H)]
(H-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amount to obtain a sensitizer (H).

[Thiol chain transfer agent (I)]
(I-1) Trimethylolethane ethanetris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(I-2) Trimethylolpropane Tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(I-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-4) Trimethylolpropane Tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
As described above, (I-1) to (I-5) were mixed in the same amount to prepare a thiol-based chain transfer agent (I).

[Polymerization inhibitor (J)]
(J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) tert-Butylhydroquinone The above and (J-1) to (J-3) are mixed in the same amount, respectively, and a polymerization inhibitor is used. It was designated as (J).

[Ultraviolet absorber (K)]
(K-1) 2- [4-[(2-Hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine
[TINUVIN400 (manufactured by BASF Japan)]
(K-2) 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan)]
As described above, (K-1) and (K-2) were mixed in the same amount to obtain an ultraviolet absorber (K).

[Antioxidant (L)]
(L-1) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (L-2) 3,3'-dioctadecylthiodipropanoate (L-3) tris [2] , 4-Di- (tert) -Butylphenyl] Phenylphosphite (L-4) Bis (2,2,6,6-Tetramethyl-4-piperidyl) Sevacate (L-5) P-octylphenyl salicylate or higher, ( L-1) to (L-5) were mixed in the same amount to prepare an antioxidant (L).

[Leveling agent (M)]
1 part of "Megafuck F-551: Fluorine-containing lipophilic group-containing oligomer" manufactured by DIC Corporation,
"BYK-330: Polyether-modified Polydimethylsiloxane" manufactured by Big Chemie, 1 part,
A mixed solution in which 1 part of "Emargen 103: Polyoxyethylene lauryl ether" manufactured by Kao Corporation is dissolved in 97 parts of propylene glycol monomethyl ether acetate.

[Storage stabilizer (N)]
(N-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine ("TPP" manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (N-1) and (N-2) were mixed in the same amount to prepare a storage stabilizer (N).

[Adhesion improver (O)]
(O-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3) N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (O-1) to (O-4) were mixed in the same amount to prepare a silane coupling agent (O).

[Solvent (P)]
(P-1) Propylene Glycol Monomethyl Ether Acetate 30 Parts (P-2) Cyclohexanone 30 Parts (P-3) Ethyl 3-ethoxypropionate 10 Parts (P-4) Propylene Glycol Monomethyl Ether 10 Parts (P-5) Cyclo Hexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts or more, (P-1) to (P-6) were mixed by the above mass parts to prepare a solvent (P).

<Evaluation of spectral characteristics of photosensitive near-infrared absorbing composition (R)>
The obtained photosensitive near-infrared absorbing composition (R) was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the transmittance at 800 nm was 1%, and the temperature was 60 ° C. for 5 minutes. After drying, the substrate is irradiated with 100 mJ / cm ² of ultraviolet rays using an ultra-high pressure mercury lamp, spray-developed with an alkaline developer consisting of a 0.2 mass% sodium carbonate aqueous solution, and then heated at 230 ° C. for 20 minutes. Was produced. The spectrum of the obtained substrate was measured for absorption spectra in the wavelength range of 400 to 1000 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
The average transmittance (T) in each range was calculated from the measured absorption spectrum, and evaluated by the same criteria as the spectral characteristic evaluation of the near-infrared absorption composition (D). The evaluation results are shown in Table 3.

<Evaluation of coatability of photosensitive near-infrared absorbing composition (R)>
The obtained photosensitive near-infrared absorbing composition (R) was evaluated in the same manner as in the evaluation of the coatability of the near-infrared absorbing composition (D). The evaluation results are shown in Table 3.

In the case of the photosensitive near-infrared absorbing composition (R), the result is the same as that of the near-infrared absorbing composition (D), and the squarylium dye having a maximum absorption wavelength in the range of 400 to 1000 nm of the present invention between 800 and 900 nm. By containing two or more types of A), the ability to cut near-infrared rays from 700 nm to 900 nm is high (spectral characteristics 1 to 3), near-infrared light of 940 nm is transmitted (spectral characteristics 4), and coloring with good coatability. The composition could be obtained.

<Manufacturing of Photosensitive Near Infrared Absorption Coloring Composition (RG)>
(Manufacturing of other refined dyes (PB-1))
To 1250 parts of n-amyl alcohol in a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water under stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid in the reaction vessel at room temperature. The sulfuric acid solution was injected into 24,000 parts of cold water at 3 ° C. with stirring at 40 ° C. for 3 hours. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (5).

Equation (5)

In a reaction vessel, 100 parts of an aluminum phthalocyanine pigment represented by the above formula (5) and 43.2 parts of diphenylphosphine acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give 112 parts of the other dye (B-1).
Subsequently, 100 parts of the obtained other dye (B-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. bottom. This kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours, and others. (PB-1) was obtained. The average primary particle size was 29.5 nm.

(Manufacturing of other refined dyes (PB-2))
To 1000 parts of methanol in a reaction vessel, 100 parts of an aluminum phthalocyanine pigment represented by the above formula (5) and 49.5 parts of diphenyl phosphate were added, heated to 40 ° C., and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give 114 parts of the other dye (B-2).
The other dye (B-2) obtained was subjected to the same salt milling treatment method as the other dye (B-1) to obtain another refined dye (PB-2). The average primary particle size was 31.2 nm.

(Manufacturing of other refined dyes (PB-3))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (6), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 20 ° C. for 6 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and a sampled residue were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 10.1 bromine atoms were substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added, and 90 parts were added. The mixture was heated to ° C. and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give another micronized dye (PB-3). The average primary particle size was 27 nm.

Equation (6)

(Manufacturing of other refined dyes (PB-4))
250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added to a three-necked flask, and the mixture was stirred at 150 ° C. for 30 minutes. 50 parts of the aluminum phthalocyanine pigment represented by the above formula (5) was added thereto, and the mixture was stirred at 155 ° C. for 30 minutes to dissolve. Further, 58.5 parts of trichloroisocyanuric acid was added, and the mixture was stirred at 190 ° C. for 5 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and a sampled residue were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which an average of 8.1 chlorine atoms were substituted on the phthalocyanine ring.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 8.1 chlorine atoms were substituted on the obtained phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added, and 90 parts were added. It was heated to ° C. and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give another micronized dye (PB-4). The average primary particle size was 29 nm.

(Manufacturing of other refined dyes (PB-5))
C. I. Pigment Blue 15: 3 (PB15: 3) (Toyo Color Co., Ltd. "Rionol Blue FG-7351") 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 80 ° C. for 6 hours. This mixture was put into 2000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours, 95 parts and others. (PB-5) was obtained.

(Manufacturing of other refined dyes (PB-6))
C. I. Pigment Blue 15: 3 (PB15: 3) (“Rionol Blue FG-7351” manufactured by Toyo Color Co., Ltd.), C.I. I. Pigment Green 58 (PG58) (“FASTGEN GREEN A110” manufactured by DIC Corporation), except that the other refined dye (PB-6) was used in the same manner as in the production of the other refined dye (PB-5). Obtained.

The structures of the other refined dyes (PB-1) to (PB-6) produced as described above are as follows.

(Manufacturing of Coloring Composition (BG-1))
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to obtain a colored composition (BG-1). Made.
Other refined dyes (PB-1): 12.0 parts Basic resin type dispersant 1 solution: 9.0 parts Binder resin 1 solution: 22.0 parts PGMAC: 57.0 parts

(Manufacturing of Coloring Compositions (BG-2) to (BG-6))
Hereinafter, the coloring composition (BG-2) is the same as the coloring composition (BG-1) except that the other refined dye (PB-1) is changed to the other refined dye (BG) shown in Table 4. )-(BG-6) were prepared.

(Example 30: Production of photosensitive near-infrared absorbing coloring composition (RG-1))
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 0.5 μm filter to prepare a photosensitive near-infrared absorbing coloring composition (RG-1).
Near-infrared absorption composition (D-5): 15.7 parts Coloring composition (BG-1): 15.7 parts Binder resin 2 solution: 8.5 parts Thermocurable compound (E): 0.8 parts Polymerization Sex compound (F): 4.5 parts Photopolymerization initiator (G): 0.7 parts Sensitizer (H): 0.1 parts Thiol-based chain transfer agent (I): 0.2 parts Polymerization inhibitor ( J): 0.2 parts UV absorber (K): 0.2 parts Antioxidant (L): 0.2 parts Leveling agent (M): 5.0 parts Storage stabilizer (N): 0.2 parts Adhesion improver (O): 0.2 parts Solvent (P): 48.4 parts

(Examples 31 to 37: photosensitive near-infrared absorbing coloring compositions (RG-2) to (RG-8),
Comparative Example 6: Production of Photosensitive Near Infrared Absorbent Coloring Composition (RG-9))
Hereinafter, the same applies to the photosensitive near-infrared absorbing coloring composition (RG-1) except that the near-infrared absorbing composition (D-5) and the coloring composition (BG-1) are changed to the compositions and amounts shown in Table 5. The photosensitive near-infrared absorbing coloring compositions (RG-2) to (RG-9) were prepared.

<Evaluation of spectral characteristics of photosensitive near-infrared absorbing coloring composition (RG)>
The obtained photosensitive near-infrared absorbing coloring composition (RG) was spin-coated on a 1.1 mm-thick glass substrate using a spin coater so that the coating film thickness was 1.5 μm, and at 60 ° C. After drying for 5 minutes, it is irradiated with 100 mJ / cm ² of ultraviolet rays using an ultra-high pressure mercury lamp, spray-developed with an alkaline developer consisting of a 0.2 mass% sodium carbonate aqueous solution, and then heated at 230 ° C. for 20 minutes. , A substrate was prepared. The spectrum of the obtained substrate was measured for absorption spectra in the wavelength range of 400 to 1000 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
The average transmittance (T) in each range was calculated from the measured absorption spectrum, and the spectral characteristics 1 to 3 were evaluated based on the same criteria as the spectral characteristic evaluation of the near-infrared absorption composition (D). The spectral characteristics 5 and 6 were evaluated according to the following criteria.
The evaluation results are shown in Table 5.

Spectral characteristics 5: 450 nm to 550 nm
◯: 70% ≦ (T)
Δ: 60% ≤ (T) <70%
×: (T) <60%

Spectral characteristics 6: 600 nm to 700 nm
◯: (T) ≤ 5%
Δ: 5% <(T) ≤ 10%
×: 10% <(T)

For example, an organic EL display device by containing two or more kinds of squalylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm of the present invention between 800 and 900 nm and also containing a blue or green dye. High transmittance of blue to green light used for detection of in-screen fingerprint authentication (spectroscopic characteristic 5), red light that becomes noise (spectral characteristic 6), and near-infrared cut ability from 700 nm to 900 nm (spectroscopic characteristic). A photosensitive near-infrared absorbing coloring composition having high properties 1 to 3) could be obtained.

<Manufacturing of near infrared cut filter (FC)>
(Example 38: Manufacture of near-infrared cut filter (FC-1))
The photosensitive near-infrared absorbing composition (R-1) was spin-coated on a 1.1 mm thick glass substrate using a spin coater so that the coating film thickness was 1.5 μm, and the temperature was 60 ° C. for 5 minutes. It was dry. Then, using an ultra-high pressure mercury lamp, 100 mJ / cm2 of ultraviolet rays were irradiated through a photomask to form a 100 μm square near-infrared cut filter. The exposed coating film was spray-developed with an alkaline developer consisting of a 0.2 mass% sodium carbonate aqueous solution to form a 100 μm square pattern. Then, it was heated at 230 ° C. for 20 minutes to prepare a near infrared cut filter (FC-1).

(Examples 39 to 42: Near infrared cut filters (FC-2) to (FC-5))
Near-infrared cut filter except that the photosensitive near-infrared absorbing composition (R-1) was changed to the photosensitive near-infrared absorbing composition (R) or the photosensitive near-infrared absorbing coloring composition (RG) shown in Table 6. Near-infrared cut filters (FC-2) to (FC-5) were produced in the same manner as in (FC-1).

The near-infrared cut filter containing two or more types of squarylium dye (A) having a maximum absorption wavelength in the range of 400 to 1000 nm of the present invention between 800 and 900 nm cuts near-infrared rays with high near-infrared cut ability from 700 nm to 900 nm. I was able to get a filter.
Further, by containing two or more kinds of squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm of the present invention between 800 and 900 nm, and by containing a blue or green dye (Example 40). ~ 42) For example, the transmittance of blue to green light used for detection of in-screen fingerprint authentication of an organic EL display device is high, and the ability to cut red light that becomes noise and near infrared rays from 700 nm to 900 nm is high. I was able to get an infrared cut filter.

<Manufacturing of Photosensitive Near Infrared Transmissive Composition (RB)>
(Manufacturing of other refined dyes (PB-7))
Blue organic pigment C.I. I. Pigment Blue 15: 6 (PB15: 6) (Toyo Color Co., Ltd. "Rionol Blue ES") 100 parts, crushed salt 800 parts, and diethylene glycol 100 parts are charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 70 ° C. for 12 hours. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain another finely divided dye (PB-7).

(Manufacturing of other refined dyes (PB-8))
Yellow organic pigment C.I. I. Pigment Yellow 139 (PY139) (Clariant's "Novoperm Yellow P-M3R"), 800 parts of crushed salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and 12 at 70 ° C. Time kneaded. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain another finely divided dye (PB-8).

(Manufacturing of other refined dyes (PB-9))
Purple organic pigment C.I. I. Pigment Violet 23 (PV23) (“LIONOGEN VIOLET FG-6140” manufactured by Toyo Color Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. Kneaded for 12 hours. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain another finely divided dye (PB-9).

(Manufacturing of Coloring Composition (BB-1))
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to obtain the colored composition (BB-1). Made.
Other refined dyes (PB-7): 4.2 parts Other refined dyes (PB-8): 4.2 parts Other refined dyes (PB-9): 3.6 parts Basic resin type dispersion Agent 1 solution: 15.0 parts Binder resin 1 solution: 10.0 parts PGMAC: 63.0 parts

(Example 43: Production of photosensitive near-infrared ray transmissive composition (RB-1))
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 0.5 μm filter to prepare a photosensitive near-infrared ray transmissive composition (RB-1).
Near-infrared absorption composition (D-5): 11.3 parts Coloring composition (BB-1): 45.0 parts Binder resin 2 solution: 0.8 parts Dipentaerythritol penta and hexaacrylate (manufactured by Toagosei Co., Ltd. Aronix M402 "): 3.0 parts ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime) [irgacure OXE02 (manufactured by BASF Japan)]: 0.5 parts Leveling agent (M): 5.0 parts Solvent (P): 34.6 parts

<Manufacturing of near-infrared transmission filter (FT)>
(Manufacturing of near-infrared transmission filter (FT-1))
The photosensitive near-infrared ray transmissive composition (RB-1) was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the coating film thickness was 2.0 μm, and 5 at 60 ° C. It was dried for a minute. Then, using an ultra-high pressure mercury lamp, 100 mJ / cm2 of ultraviolet rays were irradiated through a photomask to form a 100 μm square near-infrared ray transmitting filter. The exposed coating film was spray-developed with an alkaline developer consisting of a 0.2 mass% sodium carbonate aqueous solution to form a 100 μm square pattern. Then, it was heated at 230 ° C. for 20 minutes to prepare a near infrared transmission filter (FT-1).

In addition to containing two or more kinds of squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm of the present invention between 800 and 900 nm, a coloring composition exhibiting black color by combining a plurality of dyes is included. As a result, it was possible to obtain a near-infrared transmission filter that shields visible light of 400 nm to 700 nm and near-infrared rays of 700 nm to 900 nm and transmits near-infrared rays having a wavelength longer than 900 nm.

Claims (10)

A near-infrared absorbing composition containing two or more types of squarylium dye (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 800 and 900 nm, wherein the maximum absorption wavelength of the first squarylium dye (A-1) is present. The near-infrared absorption composition is characterized by satisfying the relationship of the following formula (1), where λ1 _max and the maximum absorption wavelength of the second squarylium dye (A-2) are λ2 _max .
Equation (1) 0 nm <λ2 _max -λ1 _max ≤ 100 nm The near-infrared absorbing composition according to claim 1, wherein the λ1 _max and the λ2 _max satisfy the relationship of the following formula (2).
Equation (2) 10 nm ≤ λ2 _max -λ1 _max ≤ 100 nm The near-infrared absorbing composition according to claim 1 or 2, wherein the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (1).

General formula (1)

(In the general formula (1), R ¹ to R ⁴ are independently each of a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR ¹⁰ , -COR ¹¹ , -COOR ¹² , -COOM ¹ , -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , -NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ¹⁹ R ²⁰ , -NHCOOR ²¹ , -SR ²² , -SO ₂ R ²³ , -SO ₂ OR ²⁴ , -SO ₃ M ² , -NHSO ₂ R ²⁵ , -SO ₂ NR ²⁶ R ²⁷ , -B ⁽ OR ²⁸ ) ₂ , or ^{-NHBR 29} R ³⁰ . Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, R ¹² of −COOR ¹² is hydrogen. In some cases, the hydrogen atom may be dissociated.-COMM ¹ represents a metal salt or an alkylammonium salt of a carboxyl group. Further, when R ²⁴ of -SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom is dissociated. -SO ₃ M ² may represent a metal salt or an alkylammonium salt of a sulfo group, and R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring. .) The near-infrared absorption composition according to any one of claims 1 to 3, wherein the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (2). thing.

General formula (2)

(In the general formula (2), R ⁵ to R ⁸ are independently each of a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, −OR ⁵⁰ , -COR ⁵¹ , -COOR ⁵² , -COOM ³ , -OCOR ⁵³ , -NR ⁵⁴ R ⁵⁵ , -NHCOR ⁵⁶ , -CONR ⁵⁷ R ⁵⁸ , -NHCONR ⁵⁹ R ⁶⁰ , -NHCOOR ⁶¹ , -SR ⁶² , -SO ₂ R ⁶³ , -SO ₂ OR ⁶⁴ , -SO ₃ M ⁴ , -NHSO ₂ R ⁶⁵ , -SO ₂ NR ⁶⁶ R ⁶⁷ , -B (OR ⁶⁸ ) ₂ , or ^{-NHBR 69} R ^{70 .} Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, R ⁵² of -COOR ⁵² is hydrogen. In some cases, the hydrogen atom may be dissociated. ^- COM3 represents a metal salt or an alkylammonium salt of a carboxyl group. Further, when ^R64 of -SO ₂ OR ⁶⁴ is a hydrogen atom, the hydrogen atom is dissociated. -SO ₃ M ⁴ may represent a metal salt or an alkylammonium salt of a sulfo group, and R ⁵ and R ⁶ and R ⁷ and R ⁸ may be bonded to each other to form a ring. .) The near-infrared absorbing composition according to any one of claims 1 to 4, wherein when the coating film is formed so that the transmittance at 800 nm is 1%, the transmittance at 940 nm is 50% or more. thing. The near-infrared absorbing composition according to any one of claims 1 to 5, further comprising a basic resin-type dispersant. The near-infrared absorbing composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator. A near-infrared ray transmitting composition comprising the near-infrared absorbing composition according to any one of claims 1 to 7 and a coloring composition exhibiting black color. An optical filter formed by using the near-infrared absorbing composition according to claims 1 to 7. An optical filter formed by using the near-infrared ray transmitting composition according to claim 8.