JP7537226B2 - Near infrared absorbing composition, near infrared transmitting composition, and optical filter - Google Patents

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, mobile devices such as smartphones and tablet computers have been equipped with user authentication functions that use biometric information such as fingerprints, faces, irises, and voice. Fingerprint authentication in particular offers the convenience of unlocking the device simply by placing your finger on it, and it is small and inexpensive, allowing for enhanced security, so the adoption of fingerprint authentication sensors in smartphones is expanding.

In addition, in order to increase the size of smartphone displays despite their size constraints, it has been proposed to make the entire body a display and incorporate a fingerprint authentication sensor into the screen (in-screen fingerprint authentication). In particular, organic electroluminescence (organic EL) display devices can perform fingerprint authentication using light emitted from blue and green pixels, and in-screen fingerprint authentication methods are becoming more widespread.

Meanwhile, in-screen fingerprint authentication methods have not been adopted for LCD display devices, which require a backlight. In recent years, however, in-screen fingerprint authentication has been realized even on LCD display devices by installing an infrared transmitter at the bottom of the display, emitting infrared light, and receiving and reading the light reflected by the fingerprint with a sensor.

A 940 nm near-infrared LED light source is sometimes used as the infrared light source for on-screen fingerprint authentication in this LCD display device. 940 nm is the wavelength at which sunlight, which causes external light noise, is absorbed by water vapor, making it possible to sense with lower noise than other wavelengths. Furthermore, by cutting near-infrared light in the 700 nm to 900 nm range using an optical filter or the like, external light noise can be further reduced, improving the sensing accuracy of the fingerprint authentication sensor.

Near-infrared cut filters are manufactured using a composition containing a near-infrared absorbent, as in Patent Document 1, for example. However, the ability to cut near-infrared rays in the range of 700 nm to 900 nm is not necessarily satisfactory. Furthermore, the coating properties required for manufacturing near-infrared cut filters are not sufficient.

WO2017-130825 publication

The present invention aims to provide a near-infrared absorbing composition, a near-infrared transmitting composition, and an optical filter formed using the same, which have high near-infrared blocking capability in the 700 nm to 900 nm range, transmit near-infrared light of 940 nm, and have good coatability.

The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result, have found that a near infrared absorbing composition containing two or more squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 800 and 900 nm, wherein the near infrared absorbing composition is characterized in that, 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 near infrared absorbing composition has a high near infrared cutting ability in the range of around 700 nm to 900 nm and good coatability. The present invention is based on this finding.
Formula (1) 0nm < λ2 _max - λ1 _max ≦ 100nm

That is, the present invention relates to a near infrared absorbing composition containing two or more squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1,000 nm, between 800 and 900 nm, wherein the near infrared absorbing composition satisfies the relationship of the following formula (1), where the maximum absorption wavelength of the first squarylium dye (A-1) is _λ1max and the maximum absorption wavelength of the second squarylium dye (A-2) is _λ2max :
Formula (1) 0nm < λ2 _max - λ1 _max ≦ 100nm

The present invention also relates to the near infrared absorbing composition, wherein the _λ1max and _λ2max satisfy the relationship of the following formula (2):
Formula (2) 10nm ≦ λ2 _max - λ1 _max ≦ 100nm

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 general formula (1), R ¹ to R ⁴ each independently represent 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. R ¹⁰ to R ³⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ¹² in -COOR ¹² is a hydrogen atom, the hydrogen atom may be dissociated. -COOM ¹ represents a metal salt or an alkylammonium salt of a carboxyl group. When R ²⁴ in -SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom may be dissociated. -SO ₃ M ² represents a metal salt or an alkylammonium salt of a sulfo group. R ¹ and R ² , and R ³ and R ⁴ may be bonded to each other to form a ring.)

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 each independently represent 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. R ⁵⁰ to R ⁷⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ⁵² in -COOR ⁵² is a hydrogen atom, the hydrogen atom may be dissociated. -COOM ³ represents a metal salt or an alkylammonium salt of a carboxyl group. When R ⁶⁴ in -SO ₂ OR ⁶⁴ is a hydrogen atom, the hydrogen atom may be dissociated. -SO ₃ M ⁴ represents a metal salt or an alkylammonium salt of a sulfo group. 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 when a coating film is formed so that the transmittance at 800 nm is 1%, the transmittance at 940 nm is 50% or more.

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

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

The present invention also relates to a near-infrared transmitting composition that contains the near-infrared absorbing composition and a coloring composition that exhibits a black color.

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

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

The present invention can provide a near-infrared absorbing composition, a near-infrared transmitting composition, and an optical filter formed using the same that have high near-infrared blocking capability in the 700 nm to 900 nm range, transmit near-infrared light of 940 nm, and have good coatability.

Each of the components of the colored composition of the present invention will be described below.
In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide".
In addition, "C.I." in this specification means Color Index (C.I.).

<Squarylium dyes>
The near infrared absorbing composition of the present invention is a near infrared absorbing composition containing two or more squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm, which is between 800 to 900 nm, and is characterized in that, when the maximum absorption wavelength of the first squarylium dye (A-1) is _λ1max and the maximum absorption wavelength of the second squarylium dye (A-2) is _λ2max , the near infrared absorbing composition satisfies the relationship of the following formula (1):
Formula (1) 0nm < λ2 _max - λ1 _max ≦ 100nm

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

The maximum absorption wavelength of the squarylium dye is measured using the method described in the Examples below.

By containing two squarylium dyes with different maximum absorption wavelengths, the absorption wavelength range is expanded, and by having a maximum absorption wavelength between 800 and 900 nm in the 400 to 1000 nm range, it is possible to cut a wide range of near infrared rays from 700 nm to 900 nm. In addition, the use of different dyes in combination improves coatability.

The squarylium dyes (A-1) and (A-2) are preferably compounds represented by the following general formula (1). In the compound represented by the following general formula (1), the naphthalene ring is bonded so that the π-conjugated system spreads from the cyclobutene ring, and therefore the maximum absorption wavelength is longer, and light of 800 nm to 900 nm is well absorbed. This improves the near-infrared blocking ability up to around 900 nm. In addition, the naphthalene ring portion is prone to association, and the absorption wavelength range is broadened by the absorption derived from the association, making it possible to block a wide range of near-infrared rays from 700 nm to 900 nm. Furthermore, since the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (1), they act as dye derivatives with each other, improving the fluidity and resulting in a near-infrared absorbing composition with better coatability. It is believed that the moderate association state achieved by containing two squarylium dyes having partially the same structure makes it possible to achieve both a broader absorption wavelength range and coatability.

General formula (1)

(In general formula (1), R ¹ to R ⁴ each independently represent 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. R ¹⁰ to R ³⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ¹² in -COOR ¹² is a hydrogen atom, the hydrogen atom may be dissociated. -COOM ¹ represents a metal salt or an alkylammonium salt of a carboxyl group. When R ²⁴ in -SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom may be dissociated. -SO ₃ M ² represents a metal salt or an alkylammonium salt of a sulfo group. R ¹ and R ² , and R ³ and R ⁴ may be bonded to each other to form a ring.)

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

Examples of amines that form alkylammonium salts with carboxyl or sulfo groups include, but are not limited to, lower amines such as dimethylamine, trimethylamine, diethylamine, triethylamine, hydroxyethylamine, dihydroxyethylamine, 2-ethylhexylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, and N,N-dibutylaminopropylamine; long-chain alkylamines having an alkyl group with 2 or more carbon atoms such as laurylamine, oleylamine, palmitylamine, stearylamine, and dimethyllaurylamine; and long-chain alkyl quaternary ammonium ions having an alkyl group with 12 or more carbon atoms such as laurylammonium, stearylammonium, lauryltrimethylammonium, dilauryldimethylammonium, stearyltrimethylammonium, and distearyldimethylammonium.

The "substituent" may be 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,
Examples thereof include —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 and —SO ₂ NR ¹¹⁶ R ¹¹⁷ .
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 a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may be dissociated (i.e., a carbonate group) or may be in the form of a salt. When R ¹¹⁴ of -SO ₂ OR ¹¹⁴ is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The number of carbon atoms in the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, and particularly preferably from 1 to 8. The alkyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkenyl group is preferably from 2 to 20, more preferably from 2 to 12, and particularly preferably from 2 to 8. The alkenyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkynyl group is preferably from 2 to 20, more preferably from 2 to 12, and particularly preferably from 2 to 8. 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 portion of the aralkyl group is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the aryl group described above. The number of carbon atoms in 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 2 to 8 condensed rings, and particularly preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered or 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, the alkenyl group, the alkynyl group, the aryl group, the heteroaryl group, and the aralkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned "substituents."

The squarylium dyes (A-1) and (A-2) are more preferably compounds represented by the following general formula (2):

Since the squarylium dyes (A-1) and (A-2) are compounds having a perimidine skeleton represented by general formula (2), the near infrared absorbing composition has high light resistance.

General formula (2)

(In the general formula (2), R ⁵ to R ⁸ each independently represent 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. R ⁵⁰ to R ⁷⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ⁵² in -COOR ⁵² is a hydrogen atom, the hydrogen atom may be dissociated. -COOM ³ represents a metal salt or an alkylammonium salt of a carboxyl group. When R ⁶⁴ in -SO ₂ OR ⁶⁴ is a hydrogen atom, the hydrogen atom may be dissociated. -SO ₃ M ⁴ represents a metal salt or an alkylammonium salt of a sulfo group. R ⁵ and R ⁶ , and R ⁷ and R ⁸ may be bonded to each other to form a ring.)

—COOM ³ and —SO ₃ M ⁴ have the same meanings as —COOM ¹ and —SO ₃ M ² described above.

"Substituent" has the same meaning as "substituent" above.

Specific examples of squarylium dyes (A-1) and (A-2) include the compounds shown below, but the present invention is not limited to these. Other examples include the compounds described in paragraphs [0044] to [0049] of JP2011-208101A and the compounds described in paragraph [0072] of JP6453456A.

The maximum absorption wavelength _λ1max of the squarylium dye (A-1) in the range of 400 to 1000 nm is preferably in the range of 800 to 850 nm, and more preferably in the range of 800 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 in the range of 820 nm to 900 nm, and more preferably in the range of 830 to 900 nm.

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

The content ratio of the squarylium dye (A-1) to the squarylium dye (A-2) in the near infrared absorbing composition is preferably 95/5 to 30/70, and 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, within a range that does not impair the spectral properties of the squarylium dye (A-1) and the squarylium dye (A-2). Examples of other near infrared absorbing dyes include cyanine compounds, squarylium compounds (excluding the squarylium dye (A-1) and the squarylium dye (A-2)), phthalocyanine compounds, naphthalocyanine compounds, aminium compounds, diimmonium compounds, croconium compounds, azo compounds, quinoid-type complex compounds, dithiol metal complex compounds, etc.

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

When the near-infrared absorbing composition of the present invention is formed into a coating film so that the transmittance at 800 nm is 1%, it is preferable that the transmittance at 940 nm is 50% or more. This makes it easier to perform sensing using a 940 nm light source while reducing external light noise, thereby improving sensing accuracy.

<Black coloring composition>
The near infrared absorbing composition of the present invention can be used as a near infrared transmitting composition by containing a coloring composition that exhibits black color. The coloring composition that exhibits black color is not particularly limited as long as it exhibits black color, and may contain a black pigment, a pigment composition that exhibits black color by combining multiple pigments, or the like.

<Dye derivatives>
In the near infrared absorbing composition of the present invention, a dye derivative can be used as necessary.The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue.The dye derivative can be, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, as well as the amine salts thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and a compound having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009/081930 B, WO 2011/052617 B, WO 2012/102399 B, and JP 2017-156397 A; phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016/163351 B, JP 2017-165820 B, and Japanese Patent No. 5753266 A; anthraquinone dye derivatives are described in , JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet; quinacridone dye derivatives are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine dye derivatives are disclosed in JP-A-2011-162662; thiazine indigo dye derivatives are disclosed in JP-A-2007-314 785, triazine-based dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681, benzoisoindole-based dye derivatives are disclosed in JP-A-2009-57478, quinophthalone-based dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2007-314681. Examples of the naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, examples of the azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092, examples of the acidic substituents include those described in JP-A-2004-307854, and examples of the basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In addition, in these documents, the dye derivative may be described as a derivative, pigment derivative, dispersant, pigment dispersant, or simply a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

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

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

When the colorant is a pigment, adding a colorant derivative and carrying out a pigmentation process such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling causes the colorant derivative to be adsorbed onto the pigment surface, making it possible to make the primary particles of the pigment finer than when the colorant derivative is not added.

By adding a dye derivative to the pigment and carrying out a dispersion treatment such as wet dispersion using a two-roll roll, a three-roll roll, or beads, the dye derivative is adsorbed to the pigment surface, the pigment surface becomes polar, and the adsorption of the resin-type dispersant is promoted, and the compatibility with the pigment, the dye derivative, the resin-type dispersant, the solvent, and other additives is improved, and the dispersion stability and viscosity stability over time of the near-infrared absorbing composition are improved. In addition, improved compatibility provides excellent stability over time of the coating film when the near-infrared absorbing composition is applied to a glass substrate, etc., and the stability and characteristic dependency of the pattern shape on the waiting time from application of the near-infrared absorbing composition to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay) and line width sensitivity stability are improved. In addition, by adsorbing and covering the pigment surface with the dye 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 baked. Furthermore, the variation in development time and development residue are also 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 that has a property of being adsorbed to the pigment, and a relaxation moiety that has high affinity with components other than the pigment and causes steric repulsion between dispersed particles. As the resin type dispersant, a resin with a controlled structure, such as a graft type (comb type) or block type, is preferably used.

Resin-type dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphate esters.

In addition, examples of ionic resin-type dispersants include acidic resin-type dispersants and basic resin-type dispersants.

Examples of basic resin-type dispersants include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc., in the side chains.
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 adsorption 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, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, manufactured by BYK Japan Co., Ltd. 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, etc. manufactured by Lubrizol Japan Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 2 4000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 manufactured by BASF , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

Resin-type dispersants can be used alone or in combination of two or more types.

The content of the resin-type dispersant is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on the total amount of pigment. If an appropriate amount is included, it is easy to form a coating.

<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 may be, for example, a thermoplastic resin, a thermosetting resin, an active energy ray curable resin, or 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 during the production of an optical filter, and an acidic group is required.

Binder resins can be used alone or in combination of two or more types.

The content of the binder resin is preferably 20 to 400 parts by weight, and more preferably 50 to 250 parts by weight, per 100 parts by weight of the pigment. If an appropriate amount is included, a coating can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin/maleic acid (anhydride) copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene/styrenesulfonic acid copolymers are preferred 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 following methods (i) and (ii). The resin is three-dimensionally crosslinked by the effect of active energy rays, increasing the crosslink density and improving chemical resistance.

[Method (i)]
In the method (i), for example, an ethylenically unsaturated monomer having an epoxy group is copolymerized with another monomer to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction with the side chain epoxy group of the copolymer.Then, a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. If necessary, for example, to increase the number of carboxyl groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride groups.

Examples of the other monomers include the following: (meth)acrylates such as 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)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate;
Alternatively, examples of the vinyl monomer include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of such compounds include N-substituted maleimides such as imidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

A method similar to method (i) is, for example, a method in which an ethylenically unsaturated monomer having an epoxy group is added to some of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
The method (ii) is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

Examples of ethylenically unsaturated monomers having a hydroxyl group include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and/or poly(12-hydroxystearic acid), etc. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use one having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

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

Examples of other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine and the like. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

The carboxyl group-containing ethylenically unsaturated monomer can be any of the monomers already described.

The phosphate 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 phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The near infrared absorbing composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film.

In the present invention, the weight average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, more preferably 4,000 to 20,000, in order to provide alkali development solubility. The value of Mw/Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate decreases, and the exposed pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility decreases, residues are generated, and the linearity of the pattern deteriorates.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg/g) in order to impart solubility in alkaline development, preferably from 70 to 180, and more preferably from 90 to 170. If the acid value is less than 50, the solubility in alkaline development decreases, residues are generated, and linearity of the pattern deteriorates. If the acid value exceeds 200, adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

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

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

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 epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. In the near infrared absorbing composition of the present invention, epoxy compounds and oxetane compounds are preferably used.

<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 oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

Examples of the polymerizable compound include 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, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene 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, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include 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, methylolated melamine (meth)acrylic acid ester, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

(Polymerizable compound having an acid group)
The polymerizable compound may contain a photopolymerizable monomer having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

Examples of photopolymerizable monomers having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid with monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Polymerizable compound having a urethane bond)
The polymerizable compound may contain a monomer having an ethylenically unsaturated bond and a urethane bond. Examples of the monomer include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(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, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc.

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

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

<Photopolymerization initiator>
Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 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-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine. triazine-based compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, or 1-(O-acetyloxime) or other oxime ester-based compounds; phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, or ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds. Among these, oxime ester-based compounds are preferred.

Photopolymerization initiators can be used alone or in combination of two or more types.

(Oxime ester compounds)
In the oxime ester compound, the N-O bond of the oxime is cleaved by absorbing ultraviolet light, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, so that 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 decrease, and the degree of curing of the coating film may decrease, but the oxime ester compound has high quantum efficiency and is therefore preferably used.

Examples of oxime ester compounds include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc.

The content of the photopolymerization initiator is preferably 2 to 50 parts by weight, and more preferably 2 to 30 parts by weight, per 100 parts by weight of the dye. When an appropriate amount is added, the photocuring property and developability are further improved.

<Sensitizer>
Furthermore, the near infrared ray absorbing composition of the present invention may contain a sensitizer.
Examples of sensitizers include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. 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, and 3,6-dibenzoyl-N-ethylcarbazole are used.

More specifically, examples of sensitizers include those described in "Dye Handbook" edited by Okawara Makoto et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Okawara Makoto et al. (CMC, 1981), "Tokushu No Futon Zairyo" edited by Ikemori Chuzaburo et al., and "Tokushu No Futon Zairyo" (CMC, 1986), but are not limited to these. In addition, sensitizers that absorb light from the ultraviolet to near infrared regions can also be included.

Sensitizers can be used alone or in combination of two or more types.

The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. When an appropriate amount is included, the curing property and developability are further improved.

<Thiol-based chain transfer agent>
The near infrared absorbing composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, the thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates a thiyl radical that is not easily inhibited by oxygen in polymerization, so that the obtained near infrared absorbing composition has high sensitivity.

In addition, polyfunctional aliphatic thiols having two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups are preferred. Polyfunctional aliphatic thiols having four or more thiol groups are more preferred. By increasing the number of functional groups, the polymerization initiation function is improved, and curing can be achieved from the surface of the pattern to near the substrate.

Examples of polyfunctional thiols include hexanedithiol and decanedithiol. , 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. are included, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent is preferably 0.1 to 10 mass %, and more preferably 0.1 to 3 mass %, based on 100 mass % of the nonvolatile content of the near infrared absorbing composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The near infrared ray absorbing composition of the present invention may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern with a desired shape.

Examples of polymerization inhibitors include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butylcatechol. Examples of such compounds include alkyl resorcinol compounds such as ethylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinol.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the nonvolatile content of the near-infrared absorbing composition. In this range, the effect of the polymerization inhibitor becomes greater, and the linearity of the taper, wrinkles in the coating film, pattern resolution, etc. become better.

<Ultraviolet absorbing agent>
The near infrared absorbing composition of the present invention may contain an ultraviolet absorbing agent. The ultraviolet absorbing agent in the present invention is an organic compound having an ultraviolet absorbing function, and examples of the ultraviolet absorbing agent 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 UV absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the UV absorber being 100% by mass. If an appropriate amount is included, the resolution after development will be further improved.

In addition, 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 nonvolatile content of the near-infrared absorbing composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 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-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl ester mixture, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-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-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. Other oligomer and polymer type compounds having a benzotriazole structure can also be used.

Triazine compounds 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, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomer and polymer type compounds having a triazine structure can also be used.

Benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomer and polymer compounds having a benzophenone structure can also be used.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidants>
The near infrared absorbing composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound contained in the near infrared absorbing composition from being oxidized and yellowed by the thermal process during heat curing or ITO annealing, and can improve the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component is reduced, so that a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased, resulting in a phenomenon in which yellowing during the thermal process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

Examples of antioxidants 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, from the viewpoint of achieving both transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Antioxidants can be used alone or in combination of two or more types.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the near-infrared absorbing composition, since this results in good transmittance, spectral characteristics, and sensitivity.

<Leveling Agent>
In order to improve the coating property of the composition on the transparent substrate and the drying property of the colored coating film, it is preferable to add a leveling agent to the near infrared ray absorbing composition of the present invention. As the leveling agent, various surfactants such as silicone surfactants, fluorine 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 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition of the present invention. When the amount is within this range, the near infrared absorbing composition has a good balance among the coatability, pattern adhesion, and transmittance.
The near infrared ray absorbing composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably 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 storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer may 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 improver such as a silane coupling agent in order to improve adhesion to a substrate. The adhesion improver improves the reproducibility of fine lines and improves the resolution.

Adhesion improvers include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Examples of the silane coupling agent include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. 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, relative to 100 parts by mass of the colorant in the near infrared absorbing composition. This range is more effective and provides a good balance of adhesion, resolution, and sensitivity, making it more preferable.

<Method of producing near infrared absorbing composition>
The near infrared absorbing composition of the present invention can be produced by finely dispersing the dye in a dye carrier such as a dispersant or binder resin and/or a solvent, preferably together with a dispersion aid (dye derivative or surfactant), using various dispersing means such as a kneader, a two-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 may be dispersed in the dye carrier at the same time, or they may be dispersed separately in the dye carrier and mixed. When the solubility of the dye, such as a dye, is high, specifically, when it is highly soluble in the solvent used and dissolved by stirring, and no foreign matter is found, it is not necessary to produce it by finely dispersing it as described above.

When used as a photosensitive near-infrared absorbing composition (resist material), it can be prepared as a solvent-developable or alkali-developable near-infrared absorbing composition. The solvent-developable or alkali-developable near-infrared absorbing composition can be prepared by mixing the dye dispersion, the photopolymerizable monomer and/or the photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, additives, etc. 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 contains a solvent in order to easily form a dye film by coating the composition on a substrate such as glass so as to have a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of the good coatability of the near infrared absorbing composition, the solubility of each component of the near infrared absorbing composition, and further the safety.

Solvents that are commonly used in the field can be used, and they can be used alone or in combination as appropriate to suit the application conditions (speed, drying conditions, etc.) taking into account performance such as boiling point, SP value, evaporation rate, and viscosity.

Solvents that can be used include, for example, ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents (solvents that contain -O- in the molecule but do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule but do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule but do not contain -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Among the above solvents, from the viewpoint of coatability and drying property, it is preferable to use an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm. 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, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

<Removal of coarse particles>
From the near infrared absorbing composition of the present invention, it is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and further preferably coarse particles of 0.5 μm or more, and mixed dust, by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the near infrared absorbing composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

<Method of Manufacturing Optical Filter>
The optical filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by a printing method can be patterned by printing and drying a near-infrared absorbing composition, so that the method for manufacturing the filter is low cost and has excellent mass productivity. Furthermore, the development of printing technology allows printing of fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by a dispersant or an extender pigment.

When forming filter segments by photolithography, a near-infrared absorbing composition prepared as a solvent-developable or alkali-developable resist material is applied to a substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern that is in contact with or not in contact with the film. Thereafter, the uncured parts are removed by immersing the film in a solvent or alkali developer or spraying the developer with a spray or the like to form a desired pattern, and the same operation is repeated for other colors to produce filters. Furthermore, heating can be performed as necessary to promote polymerization of the resist material. According to the photolithography method, a filter with higher precision than the above printing method can be produced.

The substrate is not particularly limited, but a transparent substrate in the form of a sheet, film, or plate can be used. The color can be colorless or colored, and is not particularly limited. The material of the transparent substrate is a highly transparent material, for example, polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), triacetyl cellulose (TAC), acrylic resin such as methyl methacrylate copolymer, styrene resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, vinyl chloride resin, polymethacrylimide resin, glass plate, etc.

For development, an aqueous solution of sodium carbonate, sodium hydroxide, etc. is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine, triethanolamine, etc. can also be used. An antifoaming agent or surfactant can also be added to the developer. In order to increase the sensitivity to ultraviolet light exposure, after the resist material is applied and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, can be applied and dried to form a film that prevents polymerization inhibition by oxygen, and then ultraviolet light exposure can be performed.

In addition to the above method, the optical filter of the present invention can also be manufactured by electrochemical deposition, transfer printing, inkjet printing, etc.

<Applications>
The near infrared absorbing composition can be used as an optical filter.
For example, a digital camera recognizes color by splitting the light it receives into red, green, and blue filters when capturing an image and sending it to a photodiode that converts the light into an electrical signal. However, photodiodes also react to near-infrared light and convert it into an electrical signal, so a filter that blocks this is necessary. A coating or molded article formed from a near-infrared absorbing composition can be used as a filter that blocks near-infrared light. It is important that a filter that blocks near-infrared light has low absorption in the visible range. If there is a lot of absorption in the visible range, the light received will be colored, which will have an adverse effect on the color recognition of the photodiode. The near-infrared absorbing pigment of the present invention has low absorption in the visible range and is highly invisible, so there is little adverse effect on the color recognition of the photodiode.

For security reasons, biometric authentication functions such as fingerprint authentication and finger vein authentication are installed in smartphones, tablet PCs, bank ATMs, multimedia terminals, etc. Fingerprint authentication technology used in smartphones and tablet PCs in particular has been developing rapidly, and as the authentication range expands to the screen size (full screen), fingerprint authentication sensors built into displays such as organic electroluminescence displays and liquid crystal displays have been developed.
However, since most of the fingerprint sensors built into a display use an optical system in which a fingerprint is irradiated with various light sources installed in the display and the reflected light is sensed, there is a problem that when external irregular light (strong light having a wide range of wavelengths such as sunlight or LED lighting) is incident on the sensor, it causes noise during imaging, and there are some concerns about accuracy when used outdoors. A coating or molded article formed from the near-infrared absorbing composition can be used as a filter to block this noise.
By incorporating other dyes that match the wavelength of the light source used for sensing, the accuracy of biometric authentication can be further improved.
When a light source of about 570 nm is used for fingerprint authentication, other dyes such as C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:1, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62, C.I. Pigment Green 63, etc. may be contained. When a light source of about 940 nm is used, a black dye, a dye composition that combines multiple dyes to exhibit black color, etc. may be contained. It goes without saying that the present invention is not limited to these.

Optical filters using near-infrared absorbing compositions include near-infrared cut filters and near-infrared transmission filters. Near-infrared cut filters are mainly composed of near-infrared absorbing dyes, and have the role of blocking near-infrared light and transmitting visible light. On the other hand, near-infrared transmission filters are composed of near-infrared absorbing dyes and colored dyes that absorb visible light, and have the role of blocking visible light and near-infrared light in the wavelength range absorbed by the near-infrared absorbing dyes, and also transmitting near-infrared light with longer wavelengths.

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

(Method of Identifying Squarylium Dyes)
The squarylium dyes used in the present invention were identified by MALDI TOF-MS spectroscopy using a Bruker Daltonics MALDI mass spectrometer AutoflexIII, and the compounds were identified based on the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation.

(Method of Identifying Other Microfine Pigments (PB-1) to (PB-4))
The other finely divided dyes (PB-1) to (PB-4) used in the present invention were identified by the agreement between the molecular ion peak of the mass spectrum obtained using a time-of-flight mass spectrometer (AutoflexIII (TOF-MS), manufactured by Bruker Daltonics) and the mass number obtained by calculation, and by the agreement between the ratios of carbon, hydrogen and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin-Elmer) and the theoretical values. The number of substitutions of halogen atoms was obtained by burning the pigment by the oxygen combustion flask method, absorbing the combustion product into water, quantifying the amount of halogen in the liquid using an ion chromatograph (ICS-2000 ion chromatograph, manufactured by DIONEX), and converting it into the number of substitutions of halogen atoms.

(Acid Values of Other Resin-Type Dispersants and Binder Resins)
The acid values of the resin-type dispersant and the binder resin were determined by potentiometric titration using a 0.1 N potassium hydroxide-ethanol solution. The acid values of the resin and the resin-type dispersant indicate the acid value of the non-volatile content.

(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 polystyrene-equivalent weight average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as a developing solvent.

(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.
The apparatus used was an HLC-8320GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, both of which used "TSKgel SUPER-AW3000" as the packing material, and the oven temperature was 40°C, with an N,N-dimethylformamide solution of 3 mM triethylamine and 10 mM LiBr as the eluent, and measurements were 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 10 microliters was injected. All molecular weights are polystyrene equivalent values.

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

(Quaternary Ammonium Salt Value of Resin-Type Dispersant)
The quaternary ammonium salt value of the resin-type dispersant was determined by titration with 0.1 N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and then converted into the potassium hydroxide equivalent. The quaternary ammonium salt value of the resin-type dispersant below indicates the quaternary ammonium salt value of the non-volatile content.

<Production of fine squarylium dye (P)>
(Synthesis of squarylium dye (A-1_1))
400 parts of toluene were 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 was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, 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, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation.
After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added to the resulting reaction mixture while stirring. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain 61.9 parts of squarylium dye (A-1_1) (yield: 92%). As a result of mass analysis by TOF-MS, the squarylium dye (A-1_1) was identified.

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

(Synthesis of squarylium dye (A-1_3))
The same procedure as in the synthesis of squarylium dye (A2-1) was carried out, except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the synthesis of squarylium dye (A-1_1), to obtain 67.2 parts of squarylium dye (A-1_3) (yield: 95%). As a result of mass analysis by TOF-MS, the squarylium dye was identified as 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 were 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 a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, 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, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added while stirring the resulting reaction mixture. The resulting 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 a squarylium dye (A-2_1). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium dye was identified as (A-2_1).

(Synthesis of squarylium dye (A-2_2))
The same procedure as in the synthesis of squarylium dye (A-2_1) was carried out, except that 80.7 parts of 2,7-bis(trifluoromethyl)-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the synthesis of squarylium dye (A-2_1), to obtain 109.8 parts of squarylium dye (A-2_2) (yield: 91%). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium dye was identified as squarylium dye (A-2_2).

(Synthesis of squarylium dye (A-2_3))
The same procedure as in the synthesis of squarylium dye (A-2_1) was carried out, 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), to obtain 83.9 parts of squarylium dye (A-2_3) (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium dye was identified as 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 the squarylium dye (A-2_4).

(Solvent treatment and micronization of squarylium dyes)
[Solvent treatment process]
50 parts of squarylium dye (A-1_1) was mixed with 250 parts of N-methylpyrrolidone and stirred for 24 hours at 23° C. Then, the mixture was filtered, washed with 150 parts of methanol, and then taken out and dried at 80° C. for one day 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 charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 60° C. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 80° C. to form a slurry, which was then filtered and washed with water to remove the salt and diethylene glycol, and then dried overnight at 80° C. and pulverized to obtain 9.4 parts of a finely divided squarylium dye (P-1_1).
[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 microscope photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment were measured, and the average was taken as the particle size of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to a cube of the calculated particle size, and the volume average particle size was taken as the average primary particle size. Note that a transmission electron microscope (TEM) was used.
As a result of measurement by this method, the average primary particle diameter was found to be 50 nm.
[Component ratio]
5.0 mg of squarylium dye (P-1_1) was placed in a 100 ml measuring flask, HPLC grade THF was added, and the dye was dissolved by irradiating with ultrasound for 30 minutes to prepare a 100 ml THF solution. Using this solution, HPLC measurement of dye compound B was carried out using the above-mentioned device and conditions.
The HPLC measurement was performed by reversed-phase liquid chromatography using a mixed solution of acetonitrile and water in a volume ratio of 8:2 as a mobile phase.
The results showed multiple peaks.
Specifically, it is composed of a peak (Peak 1) that appears at a retention time of 12±1 minutes, a peak (Peak 2) that appears at a retention time of 42±1 minutes, a peak (Peak 3) that appears at a retention time of 46±2 minutes, a peak (Peak 4) that appears at a retention time of 50±2 minutes, and a peak (Peak 5) that appears at a retention time of 57±2 minutes.
The area of peak 5 was 70% of the total area of peaks 1 to 5.

Squaryllium dyes (A-1_2) and (A-1_3) were treated with a solvent and refined in the same manner as squarylium dye (A-1_1), to give refined squarylium dyes (P-1_2) and (P-1_3). Note that squarylium dyes (A-1_4), (A-2_1) to (A-2_4) were not treated with a solvent and were only refined, to give refined squarylium dyes (P-1_4), (P-2_1) to (P-2_4).

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

(Production of other fine squarylium dyes (PX-2))
The squarylium compound SQ-1 used in the examples of Patent Document 2020/013089 was used as the other 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 the other refined squarylium dye (PX-2).

The structures of the squarylium dyes produced as above and other squarylium dyes are as follows:

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

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

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

<Preparation of Dispersant Solution>
(Preparation of Basic Resin-Type Dispersant 1 Solution)

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

Equation (4)

A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, 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 initiate polymerization of the first block. 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 based on the non-volatile content.
Next, 25 parts of PGMAc and 30.3 parts of the compound [b] as the second block monomer were added to the reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of the compound [b] represented by the formula (4) above, a sample of the polymerization solution was taken and the solid content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more, calculated from the non-volatile content.
Further, 6.8 parts of benzyl chloride was added to the reaction vessel, and the mixture was stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the block copolymer solution synthesized above so that the nonvolatile content was 40% by weight. In this way, a basic resin-type dispersant 1 solution was obtained, which had an amine value per solid content of 70 mg KOH/g, a quaternary ammonium salt value of 30 mg KOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by weight.

(Preparation of Basic Resin-Type Dispersant 2 Solution)
In a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, 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 initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile 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 reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of dimethylaminoethyl methacrylate, a sample was taken from the polymerization solution and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a basic resin-type dispersant 2 solution was obtained having an amine value per non-volatile content of 71.4 mgKOH/g, a weight average molecular weight of 9,900 (Mw), and a non-volatile content of 40% by mass.

(Preparation of Basic Resin-Type Dispersant 3 Solution)
In a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, 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 initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining 110° C. and a nitrogen atmosphere. Two hours after the addition of methacryloyloxyethyl trimethyl ammonium chloride, the polymerization solution was sampled and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a basic resin-type dispersant 3 solution was obtained having an amine value per non-volatile content of 29.4 mgKOH/g, a weight average molecular weight of 9,800 (Mw), and a non-volatile content of 40% by mass.

(Preparation of 4 other resin-type dispersant solutions)
A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 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, and the atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate was added and reacted for 7 hours. It was confirmed that 95% had reacted by solid content measurement.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted for 7 hours at 100° C. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and propylene glycol monomethyl ether acetate was added to dilute the mixture to a solid content of 40% by measuring the solid content, thereby obtaining other resin-type dispersant 4 having an acid value of 70 mgKOH/g and a mass average molecular weight of 8,500.

<Preparation of binder resin solution>
(Preparation of binder resin 1 solution)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80 ° C. and substituted with nitrogen in the reaction vessel. A mixture of 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 Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20 mass % to prepare binder resin 1 solution.

(Preparation of binder resin 2 solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, heated to 80°C, and the atmosphere in the flask was replaced with nitrogen. A mixture of 18 parts of dicyclopentanyl 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 from the dropping tube. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel, and the reaction was continued for 6 hours at 120° C., and the reaction was terminated when the solid acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120° C., to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass to prepare a binder resin 2 solution. The weight average molecular weight (Mw) was 19,000.

(Preparation of binder resin 3 solution)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts of propylene glycol monomethyl ether acetate was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd.'s "Aronix (registered trademark) M110"), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate 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, the nitrogen gas was stopped and the whole amount of the copolymer solution was stirred while injecting dry air for 1 hour, and then cooled to room temperature. Then, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate ("Karens (registered trademark) MOI" manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70 ° C. for 3 hours. After the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate was added to the resin solution synthesized earlier so that the non-volatile content was 20% by mass to prepare a binder resin 3 solution. The weight average molecular weight (Mw) was 18,000.

<Production of near infrared absorbing composition (D)>
[Example 1: Near infrared absorbing composition (D-1)]
(Production of near infrared absorbing composition (D-1))
A mixture having the following composition was stirred and mixed uniformly, and then dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a 0.5 μm filter to prepare a near infrared absorbing composition (D-1).
Fine squarylium dye (P-1_1): 8.4 parts Fine 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 parts

[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)]
(Production of near infrared absorbing compositions (D-2) to (D-27))
Hereinafter, near infrared absorbing compositions (D-2) to (D-27) were prepared in the same manner as for the near infrared absorbing composition (D-1), except that the fine squarylium dye, the dye derivative, the dispersant solution, and the binder resin solution were changed to the compositions and amounts shown in Table 2.
However, Examples 11 to 13 and 24 are reference examples.

<Spectral Characteristic Evaluation of Near-Infrared Absorbing Composition (D)>
The obtained near infrared absorbing composition (D) was spin-coated onto a 1.1 mm thick glass substrate using a spin coater so that the transmittance at 800 nm was 1%, and the substrate was prepared by drying at 60° C. for 5 minutes and then heating at 230° C. for 20 minutes. The absorption spectrum of the obtained substrate was measured 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 region 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: 700nm to 750nm
○: (T)≦5%
△: 5% < (T) ≦ 10%
×: 10% < (T)

Spectral characteristics 2: 750nm to 850nm
○: (T)≦5%
△: 5% < (T) ≦ 10%
×: 10% < (T)

Spectral characteristics 3: 850nm to 900nm
○: (T)≦5%
△: 5% < (T) ≦ 10%
×: 10% < (T)

Spectral characteristics 4: 940nm
〇: 50% ≦ (T)
△: 40% ≦ (T) < 50%
×: (T) < 40%

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

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

<Production of Photosensitive Near-Infrared Absorbing Composition (R)>
(Example 25: Production of photosensitive near infrared absorbing composition (R-1))
A mixture having the following composition was stirred and mixed uniformly and then filtered through a 0.5 μm filter to prepare a photosensitive near infrared ray absorbing composition (R-1).
Near infrared absorbing composition (D-2): 31.3 parts Binder resin 2 solution: 8.5 parts Thermosetting compound (E): 0.8 parts Polymerizable compound (F): 4.5 parts Photopolymerization initiator (G): 0.7 parts Sensitizer (H): 0.1 parts Thiol chain transfer agent (I): 0.2 parts Polymerization inhibitor (J): 0.2 parts Ultraviolet 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 26 to 29: Photosensitive near infrared absorbing compositions (R-2) to (R-5),
Comparative Examples 4 and 5: Production of Photosensitive Near-Infrared Absorbing Compositions (R-6) to (R-7)
Hereinafter, photosensitive near infrared absorbing compositions (R-2) to (R-7) were prepared in the same manner as for the photosensitive near infrared absorbing composition (R-1), except that the near infrared absorbing composition (D-1) was changed to a near infrared absorbing composition shown in Table 3.
However, Examples 28 and 29 are reference examples.

Details of the materials used in producing the photosensitive near-infrared absorbing composition (R) are as follows:

[Thermosetting compound (E)]
(E-1-1) 1,2-epoxy-4-(2-oxiranyl)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-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]
The above (E-1-1) to (E-1-4) were mixed in equal amounts to prepare 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)]

(F-5) Multifunctional urethane acrylate as described below: Pentaerythritol triacrylate (432 g) and 84 g of hexamethylene diisocyanate were charged into a 1-liter five-necked reaction vessel and reacted at 60°C for 8 hours to obtain a product containing a multifunctional urethane acrylate (F-5) having a (meth)acryloyl group. The proportion of the multifunctional urethane acrylate (F-5) in the product was 70 mass%, with the remainder being other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

(F-6) Difunctional 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.)]
The above (F-1) to (F-7) were mixed in equal amounts to prepare a photopolymerizable monomer (F).

[Photopolymerization initiator (G)]
(G-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Omnirad 907 (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
[Biimidazole (Kurokane Chemicals)]
(G-5) p-Dimethylaminoacetophenone
[DMA (manufactured by Daikifine)]
(G-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-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)]
The above (G-1) to (G-8) were mixed in equal amounts to prepare a photopolymerization initiator (G).

[Sensitizer (H)]
(H-1) 2,4-Diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku)]
(H-2) 4,4'-bis(diethylamino)benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
The above (H-1) and (H-2) were mixed in equal amounts to prepare a sensitizer (H).

[Thiol-based chain transfer agent (I)]
(I-1) Trimethylolethane tris(3-mercaptobutyrate)
[TEMB (Showa Denko)]
(I-2) Trimethylolpropane tris(3-mercaptobutyrate)
[TPMB (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.)]
The above (I-1) to (I-5) were mixed in equal amounts 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 (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (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
[TINUVIN 400 (manufactured by BASF Japan)]
(K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
The above (K-1) and (K-2) were mixed in equal amounts to prepare an ultraviolet absorber (K).

[Antioxidant (L)]
(L-1) pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (L-2) dioctadecyl 3,3'-thiodipropanoate (L-3) tris[2,4-di-(tert)-butylphenyl]phosphite (L-4) bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (L-5) p-octylphenyl salicylate. The above (L-1) to (L-5) were mixed in equal amounts to give antioxidant (L).

[Leveling Agent (M)]
1 part of "MEGAFAC F-551: Fluorine-containing lipophilic group-containing oligomer" manufactured by DIC Corporation,
1 part of BYK-330: polyether-modified polydimethylsiloxane manufactured by BYK,
A mixed solution of 1 part of Kao Corporation's "Emulgen 103: polyoxyethylene lauryl ether" 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 Hokko Chemical Industry Co., Ltd.)
The above (N-1) and (N-2) were mixed in equal amounts 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.)]
The above (O-1) to (O-4) were mixed in equal amounts 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) Cyclohexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above parts by mass to obtain solvent (P).

<Spectral characteristic evaluation of photosensitive near infrared absorbing composition (R)>
The obtained photosensitive near infrared absorbing composition (R) was spin-coated onto a 1.1 mm thick glass substrate using a spin coater so that the transmittance at 800 nm was 1%, and the substrate was dried at 60° C. for 5 minutes, and then irradiated with 100 mJ/cm ² ultraviolet light using an ultra-high pressure mercury lamp, spray-developed with an alkaline developer consisting of a 0.2 mass % aqueous sodium carbonate solution, and then heated at 230° C. for 20 minutes to prepare a substrate. The absorption spectrum of the obtained substrate was measured 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 based on the same criteria as in the evaluation of the spectral characteristics of the near infrared absorbing composition (D). The evaluation results are shown in Table 3.

<Evaluation of Coating Properties of Photosensitive Near-Infrared Absorbing Composition (R)>
The photosensitive near infrared absorbing composition (R) thus obtained was evaluated for coatability in the same manner as in the evaluation 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 results were similar to those of the near-infrared absorbing composition (D). By including two or more squarylium dyes (A) of the present invention having a maximum absorption wavelength between 800 and 900 nm in the range of 400 to 1000 nm, it was possible to obtain a colored composition that has high near-infrared blocking ability from 700 nm to 900 nm (spectral properties 1 to 3), transmits near-infrared light of 940 nm (spectral property 4), and has good coatability.

<Production of Photosensitive Near-Infrared Absorbing Colored Composition (RG)>
(Production of other finely divided dyes (PB-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to 1250 parts of n-amyl alcohol and stirred. 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were added to the mixture, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and 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. Furthermore, 100 parts of chloroaluminum phthalocyanine were slowly added to 1200 parts of concentrated sulfuric acid in a reaction vessel at room temperature. The mixture was stirred at 40°C for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3°C. 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 the aluminum phthalocyanine pigment represented by the above formula (5) and 43.2 parts of diphenylphosphinic acid were added to 1,000 parts of methanol, heated to 40° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of other dye (B-1).
Next, 100 parts of the obtained other dye (B-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded product was added to 3000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain other finely divided dye (PB-1). The average primary particle size was 29.5 nm.

(Production of other finely divided dyes (PB-2))
In a reaction vessel, 100 parts of the aluminum phthalocyanine pigment represented by the above formula (5) and 49.5 parts of diphenyl phosphate were added to 1,000 parts of methanol, heated to 40° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of other dye (B-2).
The obtained other dye (B-2) was subjected to the same salt milling treatment as for the other dye (B-1) to obtain another finely divided dye (PB-2). The average primary particle size was 31.2 nm.

(Production of other finely divided dyes (PB-3))
Into a three-neck 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, and reacted at 20°C for 6 hours. Thereafter, the above reaction mixture was poured into 5,000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. Into a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the collected residue were added, and stirred at 80°C for 1 hour. Thereafter, this mixture was filtered, 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, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-neck flask, heated to 90° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain another finely divided dye (PB-3). The average primary particle size was 27 nm.

Equation (6)

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

(Production of other finely divided dyes (PB-5))
100 parts of C.I. Pigment Blue 15:3 (PB15:3) ("Lionol Blue FG-7351" manufactured by Toyo Color Co., Ltd.), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. This mixture was poured into 2000 parts of hot water, heated to 80° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain 95 parts of other finely divided dyes (PB-5).

(Production of other finely divided dyes (PB-6))
Other finely divided dyes (PB-6) were obtained in the same manner as in the production of other finely divided dyes (PB-5), except that C.I. Pigment Blue 15:3 (PB15:3) ("Lionol Blue FG-7351" manufactured by Toyo Color Co., Ltd.) was changed to C.I. Pigment Green 58 (PG58) ("FASTGEN GREEN A110" manufactured by DIC Corporation).

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

(Production of Colored Composition (BG-1))
The mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a colored composition (BG-1).
Other finely divided 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

(Production of Colored Compositions (BG-2) to (BG-6))
Hereinafter, colored compositions (BG-2) to (BG-6) were prepared in the same manner as colored composition (BG-1), except that the other finely divided dye (PB-1) was replaced with the other finely divided dye (BG) shown in Table 4.

(Example 30: Production of photosensitive near infrared absorbing colored composition (RG-1))
The mixture having the following composition was stirred and mixed uniformly, and then filtered through a 0.5 μm filter to prepare a photosensitive near infrared absorbing colored composition (RG-1).
Near infrared absorbing composition (D-5): 15.7 parts Coloring composition (BG-1): 15.7 parts Binder resin 2 solution: 8.5 parts Thermosetting compound (E): 0.8 parts Polymerizable compound (F): 4.5 parts Photopolymerization initiator (G): 0.7 parts Sensitizer (H): 0.1 parts Thiol chain transfer agent (I): 0.2 parts Polymerization inhibitor (J): 0.2 parts Ultraviolet 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 absorbing coloring composition (RG-9)
Hereinafter, the near infrared absorbing composition (D-5) and the coloring composition (BG-1) were changed to the compositions and amounts shown in Table 5. In the same manner as in the photosensitive near infrared absorbing coloring composition (RG-1), photosensitive near infrared absorbing coloring compositions (RG-2) to (RG-9) were prepared.
However, Example 33 is a reference example.

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

Spectral characteristics 5: 450nm to 550nm
○: 70% ≦ (T)
△: 60% ≦ (T) < 70%
×: (T) < 60%

Spectral characteristics 6: 600nm to 700nm
○: (T)≦5%
△: 5% < (T) ≦ 10%
×: 10% < (T)

In addition to containing two or more squarylium dyes (A) having a maximum absorption wavelength between 800 and 900 nm in the range of 400 to 1000 nm according to the present invention, by containing blue and green dyes, it has become possible to obtain a photosensitive near-infrared absorbing coloring composition that has high transmittance for blue to green light (spectral characteristic 5), which is used for detection such as in-screen fingerprint authentication of an organic EL display device, and has high ability to cut off red light (spectral characteristic 6) that becomes noise and near-infrared rays from 700 nm to 900 nm (spectral characteristics 1 to 3).

<Production of Near-Infrared Cut Filter (FC)>
(Example 38: Production 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 thickness was 1.5 μm, and dried at 60 ° C. for 5 minutes. Then, using an ultra-high pressure mercury lamp, 100 mJ / cm2 of ultraviolet light was irradiated through a photomask to form a near infrared cut filter of 100 μm square. The exposed coating film was spray-developed with an alkaline developer consisting of a 0.2 mass% aqueous sodium carbonate solution to form a pattern of 100 μm square. 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 ray cut filters (FC-2) to (FC-5) were produced in the same manner as the near infrared ray cut filter (FC-1), except that the photosensitive near infrared ray absorbing composition (R-1) was changed to the photosensitive near infrared ray absorbing composition (R) or the photosensitive near infrared ray absorbing colored composition (RG) shown in Table 6.
However, Example 39 is a reference example.

By using the near-infrared cut filter of the present invention containing two or more squarylium dyes (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 800 and 900 nm, a near-infrared cut filter having high near-infrared cut capability from 700 nm to 900 nm can be obtained.
Furthermore, by containing two or more 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 also a blue or green dye (Examples 40 to 42), it was possible to obtain a near-infrared cut filter having high transmittance for blue to green light used, for example, in detection of on-screen fingerprint authentication of an organic EL display device, and high ability to cut red light that becomes noise and near-infrared light from 700 nm to 900 nm.

<Production of Photosensitive Near-Infrared Transmitting Composition (RB)>
(Production of other micronized dyes (PB-7))
100 parts of blue organic pigment C.I. Pigment Blue 15:6 (PB15:6) ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This mixture was added to 3000 parts of hot water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain another finely divided dye (PB-7).

(Production of other micronized dyes (PB-8))
100 parts of yellow organic pigment C.I. Pigment Yellow 139 (PY139) (Clariant "Novoperm Yellow P-M3R"), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70 ° C. This mixture was added to 3000 parts of hot water, heated to about 70 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain other finely divided pigments (PB-8).

(Production of other finely divided dyes (PB-9))
100 parts of a purple organic pigment C.I. Pigment Violet 23 (PV23) ("LIONOGEN VIOLET FG-6140" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70 ° C. This mixture was added to 3000 parts of hot water, heated to about 70 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain another finely divided dye (PB-9).

(Production of Colored Composition (BB-1))
The mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a colored composition (BB-1).
Other finely divided dyes (PB-7): 4.2 parts Other finely divided dyes (PB-8): 4.2 parts Other finely divided dyes (PB-9): 3.6 parts Basic resin type dispersant 1 solution: 15.0 parts Binder resin 1 solution: 10.0 parts PGMAC: 63.0 parts

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

<Production of Near-Infrared Transmitting Filter (FT)>
(Production of near-infrared transmission filter (FT-1))
The photosensitive near-infrared transmitting composition (RB-1) was spin-coated on a 1.1 mm thick glass substrate using a spin coater so that the coating thickness was 2.0 μm, and dried at 60° C. for 5 minutes. Next, an ultra-high pressure mercury lamp was used to irradiate the substrate with ultraviolet light at 100 mJ/cm2 through a photomask to form a near-infrared transmitting filter of 100 μm square. The exposed coating film was spray-developed with an alkaline developer consisting of a 0.2 mass% aqueous sodium carbonate solution to form a pattern of 100 μm square. The substrate was then heated at 230° C. for 20 minutes to produce a near-infrared transmitting filter (FT-1).

In addition to containing two or more squarylium dyes (A) of the present invention that have a maximum absorption wavelength between 800 and 900 nm in the range of 400 to 1000 nm, a coloring composition that combines multiple dyes to exhibit a black color has been obtained, making it possible to obtain a near-infrared transmission filter that blocks visible light of 400 nm to 700 nm and near-infrared light of 700 nm to 900 nm, and transmits near-infrared light with wavelengths longer than 900 nm.

Claims (9)

A near infrared absorbing composition comprising two or more squarylium dyes (A) each having a maximum absorption wavelength in the range of 400 to 1000 nm, the maximum absorption wavelength being between 800 and 900 nm, the composition satisfying the relationship of the following formula (1) 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 near infrared absorbing composition , wherein the squarylium dyes (A-1) and (A-2) are compounds represented by the following general formula (1) :
Formula (1) 0nm < λ2 _max - λ1 _max ≦ 100nm


General formula (1)
(In general formula (1), R ¹ to R ⁴ each independently represent 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. R ¹⁰ to R ³⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R 12 in -COOR 12 is ^{a hydrogen} atom, the hydrogen atom may be dissociated. -COOM ¹ represents a metal salt or an alkylammonium salt of a carboxyl group. When R ²⁴ in -SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom may be dissociated. -SO ₃ M ² represents a metal salt or an alkylammonium salt of a sulfo group. R ¹ and R ² , and R ³ and R ⁴ may be bonded to each other to form a ring.) 2. The near infrared absorbing composition according to claim 1, wherein the _λ1max and _λ2max satisfy the relationship of the following formula (2):
Formula (2) 10nm ≦ λ2 _max - λ1 _max ≦ 100nm 3. The near infrared absorbing composition according to claim 1, wherein the squarylium dyes (A-1) and (A- 2 ) are compounds represented by the following general formula (2):

General formula (2)
(In general formula (2), R ⁵ to R ⁸ each independently represent 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 , -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 , -NHSO ₂ R ⁶⁵ or -SO ₂ NR ⁶⁶ R ⁶⁷ , -B(OR ⁶⁸ ) ₂ , and -NHBR ⁶⁹ R ^70. R R ⁵⁰ to R ⁷⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ⁵² of -COOR ⁵² is a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may be dissociated (i.e., a carbonate group) or may be in the form of a salt. When R ⁶⁴ of -SO ₂ OR ⁶⁴ is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt. R ⁵ and R ⁶ , and R ⁷ and R ⁸ may be bonded to each other to form a ring. 4. The near infrared absorbing composition according to claim 1, wherein when a coating film is formed so as to have a transmittance of 1% at 800 nm, the near infrared absorbing composition has a transmittance of 50% or more at 940 nm. The near infrared absorbing composition according to any one of claims 1 to 4 , further comprising a basic resin-type dispersing agent. The near infrared absorbing composition according to any one of claims 1 to 5 , further comprising a photopolymerization initiator. A near-infrared transmitting composition comprising the near-infrared absorbing composition according to any one of claims 1 to 6 and a coloring composition that exhibits black color. An optical filter formed by using the near infrared absorbing composition according to any one of claims 1 to 6 . An optical filter formed using the near infrared transmitting composition according to claim 7 .