Dye composition, film, optical filter, image display device, infrared sensor, and fingerprint authentication sensor

Abstract

To provide a dye composition capable of forming a near-infrared cut filter which achieves both transparency in the visible region and shielding from near-infrared rays having wavelength of 680-1000 nm.SOLUTION: The dye composition contains a squarylium-based compound (a) having a chemical structure represented by general formula (1) in the figure, and contains a dithiolate complex compound and / or a cyanine compound, where the dithiolate complex compound and the cyanine compound have absorption maxima at wavelength of 900-1200 nm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dye composition, a film, an optical filter, an image display device, an infrared sensor, and a fingerprint authentication method. This relates to sensors for [Background technology]

[0002] Video cameras, digital still cameras, and mobile phones with camera functions are equipped with color image CCD (charge-coupled device) and CMOS (complementary metal-oxide semiconductor) are solid-state imaging devices. These solid-state imaging devices have infrared sensitivity in their light receiving areas. It uses a silicon photodiode. For this reason, in solid-state imaging devices, near-infrared cut filters are used to correct visibility. The near-infrared cut filter may be, for example, a filter that uses a composition containing an infrared absorbing agent. It is manufactured in accordance with the above.

[0003] As infrared absorbing agents, squarylium compounds and the like are known (see, for example, Patent Document (See reference 1). On the other hand, Patent Document 2 describes a method for blocking neon orange light in plasma displays. It is described that a specific squarylium compound is used in the above, and Patent Document 3 describes the photodegradation It is described that squarylium compounds are used in combination with specific solvents to suppress the Moreover, on pages 28 to 32 of Patent Document 4, there is a description of an increase in a photoconductive layer in an electrophotographic recording element. As sensitizers, squarylium compounds (I-98 to I-117) are described. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 104283 [Patent Document 2] JP 2002-363434 A [Patent Document 3] JP 2016-180058 A [Patent Document 4] DE 3740421 Summary of the Invention [Problem to be solved by the invention]

[0005] Near-infrared cut filter used in solid-state imaging devices using CMOS (CMOS sensors) The material has the ability to block near-infrared light (wavelength 650-1100 nm) and transmit visible light. In recent years, the demand for baluns has increased in the entire near infrared region. It is required to provide good shielding against the electromagnetic interference. According to the investigations conducted by the present inventors, the squarylium compound described in Patent Document 1 is It was found that the side absorption was large and the transmittance in the visible region was insufficient.

[0006] The squarylium compound described in Patent Document 2 has an absorption maximum at wavelengths of 550 to 61 It was found that the absorption of the fluorine-containing ... The squarylium-based compound described in Patent Document 4 is a squarylium-based compound. Although it is commercially available as the compound with the longest wavelength absorption, it has a stronger electron donating site. Since the present invention does not have any of the above properties, it is possible to obtain a squarylium-based compound having a longer absorption wavelength. It has been thought to be difficult to achieve.

[0007] In addition, nickel dithiol is a near-infrared dye that has an absorption maximum in the wavelength range of 680 to 900 nm. However, this alone has a low molar absorption coefficient in the near infrared region, so It is necessary to increase the concentration to block ultraviolet radiation, but increasing the concentration reduces the visible range, especially wavelength 4. Since side absorption around 00 nm inhibits the transmittance in the visible region, On the other hand, it has not been possible to sufficiently achieve both the function of ensuring the shielding ability against near-infrared rays.

[0008] Therefore, the present invention is a method for preventing near-infrared rays having a wavelength of 680 to 1000 nm from being transmitted in the visible region. To provide a dye composition capable of forming a near-infrared cut filter having both transparency and transparency. The purpose is to: [Means for solving the problem]

[0009] As a result of intensive research conducted by the present inventors in order to solve the above problems, The present invention relates to a squarylium compound having a dithiolate complex compound and / or a cyanine compound. The present invention has been completed based on the discovery that the above problems can be solved by combining the above problems. That is, the present invention relates to the following.

[0010] [1] A squarylium compound (a) having a chemical structure represented by the following general formula (1): Contains Contains a dithiolate complex compound and / or a cyanine compound, The dithiolate complex compound and the cyanine compound have an absorption wavelength of 900 to 1200 nm. A dye composition having a maximum convergence.

[0011] [ka]

[0012] (In formula (1), R 1 is an aliphatic hydrocarbon group which may have a substituent, or represents an optionally substituted aromatic ring group. The naphthalene ring in formula (1) may have any substituent and may further form a condensed ring. It is okay to do so. A represents an aromatic ring group which may have a substituent.

[0013] [2] The dithiolate complex compound is selected from the group 10 elements, the group 11 elements, and the group 12 elements. It is a dithiolate complex compound containing at least one element selected from the group consisting of [1] A dye composition. [3] The dithiolate complex compound is a nickel dithiolate complex compound. [1] Or a dye composition of [2]. [4] The nickel dithiolate complex compound is represented by the following general formula (2) or the following general formula (3) The dye composition of [3] has a chemical structure represented by the formula:

[0014] [ka]

[0015] [ka]

[0016] (In formulas (2) and (3), X 1 , X 2 , X 3 , X 4 Each independently may have a substituent. It represents an optionally substituted aliphatic hydrocarbon group, or an optionally substituted aromatic ring group. X 1 and X 2 , X 3 and X 4 may each independently form a ring via a linking group. [5] The cyanine compound has a chemical structure represented by the following general formula (4): [4] Any of the dye compositions.

[0017] [ka]

[0018] (In formula (4), R 9 , R 11 each independently represents a hydrogen atom or an aliphatic group which may have a substituent Represents a hydrocarbon group. R 12 , R 13 Each independently represents a hydrogen atom, a halogen atom, or a substituent. an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or represents an optionally substituted amino group. R 8 , R 10 , R 14 each independently represents a hydrogen atom or an aliphatic hydrocarbon which may have a substituent represents an aromatic ring group which may have a substituent.

[0019] R 8 and R 14 , R 13 and R 10 may each independently be bonded to form a nitrogen-containing heterocycle. stomach. X - represents an anion. n is an integer of 3 or greater.)

[0020] [6] A squarylium-based compound (b) other than the squarylium-based compound (a) is contained. A dye composition according to any one of [1] to [5]. [7] The squarylium compound (b) has an absorption maximum at a wavelength of 680 nm to 900 nm. and the molar extinction coefficient at the absorption maximum is 1.0×10 5 The pigment composition of [6] is as above. thing. [8] A dye composition according to any one of [1] to [7], which contains a resin.

[0021] [9] A film formed using any one of the dye compositions [1] to [8].

[10] [9] Optical filter with a film.

[11] An image display device having the film according to [9].

[12] An infrared sensor having the film described in claim 9.

[13] An optical filter

[10] used in combination with a CMOS sensor.

[14]

[10] A fingerprint authentication sensor equipped with the optical filter and a CMOS sensor. Effect of the Invention

[0022] According to the present invention, the near-infrared shielding property of the wavelength of 680 to 1000 nm and the transparency in the visible region are To provide a dye composition capable of forming a near-infrared cut filter having both transparency and transparency. can be done. [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 shows the transmission spectra of the near-infrared cut filters of the examples and the comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments. The present invention is not limited to the above, and can be modified and implemented in various ways within the scope of the present invention. In the present invention, "(meth)acrylic" means "acrylic and / or methacrylic". The same applies to "(meth)acrylate" and "(meth)acryloyl." In the present invention, the term "total solid content" means all components other than the solvent contained in the dye composition. Even if ingredients other than the solvent are liquid at room temperature, they are not included in the solvent and are included in the total solids. include.

[0025] In the present invention, the "weight average molecular weight" refers to a molecular weight determined by gel permeation chromatography (GPC). This refers to the weight average molecular weight (Mw) calculated as polystyrene using a polystyrene standard. In the present invention, the term "near infrared region" refers to a wavelength region of 650 to 1100 nm. "Near infrared" means light with wavelengths in the near infrared region. In the present invention, the term "cyanine compound" refers to a compound having a nitrogen-containing substituent at both ends of a polymethine skeleton. The compound having the formula:

[0026] [1] Dye composition The dye composition of the present invention comprises a squarylium compound (a) represented by the general formula (1). The dithiolate complex compound and / or the cyanine compound are contained, and the dithiolate The complex compound and the cyanine compound have an absorption maximum at a wavelength of 900 to 1200 nm. The dye composition of the present invention comprises the squarylium compound (a) and a dithiolate complex. By containing a compound and / or a cyanine compound, the molar Due to its large absorption coefficient, side absorption in the visible region is suppressed, and near-infrared absorption in the wavelength range of 680 to 1000 nm is suppressed. A near-infrared cut filter is formed that is capable of blocking ultraviolet rays and transmitting visible light. It becomes possible.

[0027] <Squarylium compounds (a)> The dye composition of the present invention comprises a squarylium compound having a chemical structure represented by the following general formula (1): The squarylium compound (a) (hereinafter referred to as "squarylium compound (a)") is contained.

[0028] [ka]

[0029] In formula (1), R 1 is an aliphatic hydrocarbon group which may have a substituent, or represents an optionally substituted aromatic ring group. The naphthalene ring in formula (1) may have any substituent and may further form a condensed ring. It is okay to do so. A represents an aromatic ring group which may have a substituent.

[0030] The squarylium compound (a) has a specific group derived from an indolenyl group. It is believed that the absorption peak shifts to longer wavelengths, improving the shielding properties in the near infrared region. Increasing the conjugated system of the structure also strengthens the H-association, restricting the free rotation within the molecule. This is believed to result in good transmittance in the visible region. In addition, the squarylium compound (a) may contain an aromatic ring as A which may have a substituent. However, it acts as an electron-rich functional group due to the conjugation extension of the aromatic ring. It is considered that the absorption maximum due to A is in the near infrared region. an aromatic ring group having an amino group, an indolenyl group having an amino group which may have a substituent In the case of a non-benzenoid group having seven or more members, which may have a substituent, or a condensed aromatic ring group, These include the electron-donating effect of nitrogen atoms and the electron-rich functionality due to the conjugation expansion of certain aromatic rings. By functioning as a group, the absorption maximum derived from A is in a desired wavelength region in the near infrared region. It is thought that this will be the case.

[0031] The squarylium compound (a) has an absorption maximum derived from the specific group and an absorption maximum derived from the A. By having an absorption maximum at the same wavelength, the absorption band in the near infrared region is broad and For example, in the case of a near-infrared cut filter, this square By using the lylium-based compound (a), the screen required to block the entire near-infrared region is reduced. The number of types of arylium compounds can be reduced, and thus squarylium compounds can be The content of , has also been reduced, making it possible to achieve both near-infrared shielding and visible light transmission. It is believed that a filter can be obtained.

[0032] (R 1 ) In the formula (1), R 1 is an aliphatic hydrocarbon group which may have a substituent, or represents an optionally substituted aromatic ring group. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Any of the above may be used, and from the viewpoint of avoiding steric hindrance with the squaric acid portion, it is preferable that the alkyl group is linear. I wish.

[0033] The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. is preferably 3 or more, more preferably 4 or more, and is preferably 10 or less; It is more preferable that the content is 8 or less, and even more preferable that the content is 6 or less. In addition, by making the content equal to or less than the upper limit, the solubility in organic solvents is good. There is a tendency for this to happen.

[0034] Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. From the viewpoints of stability and solubility, an alkyl group is preferred. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, and the like. 1-butyl, 1-pentyl, 1-hexyl, and 1-octyl groups. From the viewpoint of stability of a specific group derived from an indolenyl group, an alkyl group having 4 to 6 carbon atoms is used. A 1-butyl group, a 1-pentyl group, or a 1-hexyl group is preferred, a 1-butyl group, a 1-pentyl group, or a 1-hexyl group is more preferred, and a 1-butyl group, a 1-pentyl group, or a 1-hexyl group is more preferred. The ethyl group is more preferred.

[0035] Examples of the substituent that the aliphatic hydrocarbon group may have include a hydroxyl group, a dialkyl group, and amino group, alkoxy group, ethylene glycol group, and fluorine atom. From the viewpoint of stability of a specific group derived from the group, it is preferably unsubstituted. On the other hand, examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. From the viewpoint of suppressing side absorption in the region, an aromatic hydrocarbon ring group is preferred.

[0036] The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more, and more preferably 6 or more. Also, it is preferably 10 or less, more preferably 8 or less, and even more preferably 7 or less. By setting the content to the limit or more, the stability of the squarylium compound tends to be improved. By setting the content to the upper limit or less, the maximum absorption wavelength in the near infrared region tends to be a desired one. .

[0037] The ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. From the viewpoint of suppressing this, a monocyclic ring is preferred. The aromatic hydrocarbon ring group may be a benzene ring, a naphtha ring, or a phenyl ring having one free valence. Phthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring , benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring In order to suppress side absorption in the visible region, A benzene ring is preferred.

[0038] The ring in the aromatic heterocyclic group may be a single ring or a condensed ring, and is preferably a ring that suppresses side absorption in the visible region. From the viewpoint of this, a monocyclic ring is preferred. Examples of the aromatic heterocyclic group include a pyrrole ring, a pyrazolo ring, and a pyrazolo ring having one free valence. an isoxazole ring, an imidazole ring, an indole ring, an oxadiazole ring, an oxazole ring, an isoxazole ring, Sazol ring, thiazole ring, isothiazole ring, pyrroloimidazole ring, pyrrolopyrrole ring, thienopyrrole ring, furopyrrole ring, benzimidazole ring, benzisoxazol ring ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridine ... Examples of the ring include a pyrimidine ring, a triazine ring, a quinoline ring, and an isoquinoline ring. From the viewpoint of adjusting the infrared absorption maximum, a pyrrole ring, a thiophene ring, and a thiophene ring having one free valence were used. A cyclic ring is preferred.

[0039] Examples of the substituent that the aromatic ring group may have include a dialkylamino group and a hydroxyl group. , diphenyl ether, an alkoxy group, an alkyl group, and a fluorine atom. From the viewpoint of being able to set the maximum absorption wavelength to a desired value, it is preferably unsubstituted.

[0040] (Optional Substituents That the Naphthalene Ring May Have) The naphthalene ring in the formula (1) may have any substituent, and may further have a condensed ring. It may be formed. Examples of the optional substituent include an alkyl group, a dialkylamino group, a hydroxyl group, an alkoxy group, and an aryl group. The ease of synthesis and stability of squarylium compounds are From this viewpoint, non-substitution is preferred. In addition, when a condensed ring is formed with any substituent, for example, the following general formula (1') is Some examples include:

[0041] [ka]

[0042] (In formula (1'), R 1 and A has the same meaning as in general formula (1').

[0043] (A) In the formula (1), A represents an aromatic ring group which may have a substituent. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. From the viewpoint of the stability of the rubber-based compound, an aromatic hydrocarbon ring group is preferred. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more, and more preferably 6 or more. Also, it is preferably 10 or less, more preferably 8 or less, and even more preferably 7 or less. If the value is set to be equal to or greater than the upper limit, the maximum absorption wavelength tends to become longer. This tends to improve the solubility.

[0044] The ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. From the viewpoint of suppressing this, a monocyclic ring is preferred. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphtha ring, and the like, each of which has one free valence. A thalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, Benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, From the viewpoint of solubility, valence groups with one free atom are A benzene ring or an azulene ring having one free valence is preferred.

[0045] The ring in the aromatic heterocyclic group may be a single ring or a condensed ring, and is preferably a ring that suppresses side absorption in the visible region. From the viewpoint of this, a monocyclic ring is preferred. Examples of the aromatic heterocyclic group include a pyrrole ring, a thiophene ring, and a cyclohexane ring having one free valence. ring, pyrazole ring, imidazole ring, indole ring, oxadiazole ring, oxazo an isoxazole ring, a thiazole ring, an isothiazole ring, a pyrroloimidazole ring, Pyrrolopyrrole ring, thienopyrrole ring, furopyrrole ring, benzimidazole ring, benzo Isoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, a radizine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, From the viewpoint of high electron donating ability, a pyridine ring having one free valence and a A thiophene ring having a free valence of is preferred.

[0046] Examples of the substituent that the aromatic ring group may have include a dialkylamino group, an alkoxy group, and the like. oxy group, hydroxyl group, alkyl group, diphenyl ether ring group, non-benzenoid aromatic ring group, halogen atom Among these, dialkyl groups are used in order to suppress side absorption in the visible region. An amino group, an alkyl group, a diphenyl ether ring group, or a non-benzenoid aromatic ring group is preferred. Among these substituents, dialkylamino groups, diphenyl ether ring groups, non-benzenoid aromatic groups, Substituents with high planarity and rich electrons, such as aromatic ring groups, have good shielding properties in the near infrared region. This is preferable because it tends to have a high effect of suppressing side absorption in the visible region.

[0047] In the formula (1), A is an aromatic ring group which may have a substituent. From the viewpoint of the Hammett constant σ p A value less than zero is preferred. I wish. Hammett constant σ p For example, see Chem. Rev. 91, pp. 165-195 (1 The values ​​published in the literature (1991) were used, regardless of the substitution position. p Data It is defined using:

[0048] The Hammett constant σ of the substituent p Values ​​of -0.40 or less are preferred, and -0.50 More preferably, it is -0.55 or less, and more preferably, it is -0.90 or more. The lower limit of the above range is preferably not less than -0.87, more preferably not less than -0.85. By setting the value to the upper limit or less, it is possible to obtain a desired long wavelength. It tends to be possible to tune the location of absorption in the outer region.

[0049] Examples of the substituent include the following. The numbers in parentheses are Hamme Represents the σp value of the tt constant. Methylamino group (-0.70), ethylamino group (-0.61 ) and other monoalkylamino groups having 1 to 12 carbon atoms; phenylamino groups (-0.56), etc. Monoarylamino groups having 6 to 15 carbon atoms; dimethylamino group (-0.83), diethyl Dialkylamino groups having 2 to 20 carbon atoms, such as amino groups (-0.72); diphenylamino Diarylamino groups having 12 to 30 carbon atoms, such as the (-0.67) group.

[0050] <Squarylium compounds (a1)> Among squarylium compounds (a), there are a few squarylium compounds that are radiative in the near infrared region. From the viewpoint of shielding with a compound, a squaryriu compound having a chemical structure represented by the following general formula (2) is used. Squarylium-based compounds (hereinafter, sometimes referred to as "squarylium-based compounds (a1)") are preferred. It is.

[0051] [ka]

[0052] In formula (1A), R 1 has the same meaning as that in the above general formula (1A). R 2 ~R 5 each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or R represents an aromatic ring group which may have a substituent. 2 ~R 5 At least two of They may be linked to form a ring. R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, or a hydroxyl group.

[0053] (R 2 ~R 5 ) In the formula (1A), R 2 ~R 5 each independently represents an aliphatic hydrocarbon which may have a substituent group, or an aromatic ring group which may have a substituent. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Any of the above may be used, and from the viewpoint of avoiding steric hindrance with the squaric acid portion, it is preferable that the alkyl group is linear. I wish.

[0054] The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. is preferably 3 or more, more preferably 4 or more, and is preferably 10 or less; It is more preferable that the content is 8 or less, and even more preferable that the content is 6 or less. In addition, by making the content equal to or less than the upper limit, the solubility in organic solvents is good. There is a tendency for this to happen.

[0055] Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. From the viewpoint of solubility, an alkyl group is preferred. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, and the like. 1-butyl, 1-pentyl, 1-hexyl, and 1-octyl groups. From the viewpoint of stability of the specific group derived from the indolenyl group, an alkyl group having 3 to 6 carbon atoms is preferred. is preferred, 1-butyl, 1-pentyl and 1-hexyl are more preferred, and 1-butyl The aryl group is more preferred.

[0056] Examples of the substituent that the aliphatic hydrocarbon group may have include a hydroxyl group, a dialkyl group, and Amino groups, alkoxy groups, ethylene glycol groups, and fluorine atoms. It is preferably unsubstituted. On the other hand, examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. From the viewpoint of suppressing side absorption in the region, an aromatic hydrocarbon ring group is preferred.

[0057] The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more, and more preferably 6 or more. Also, it is preferably 10 or less, more preferably 8 or less, and even more preferably 7 or less. By setting the content to the limit or more, the stability of the squarylium compound tends to be improved. By setting the content to the upper limit or less, the maximum absorption wavelength in the near infrared region tends to be a desired one. .

[0058] The ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. From the viewpoint of suppressing this, a monocyclic ring is preferred. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphtha ring, and the like, each of which has one free valence. A thalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, Benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Fluorene rings are one example. In order to suppress side absorption in the visible region, A benzene ring is preferred.

[0059] The ring in the aromatic heterocyclic group may be a single ring or a condensed ring, and is preferably a ring that suppresses side absorption in the visible region. From the viewpoint of this, a monocyclic ring is preferred. Examples of the aromatic heterocyclic group include a pyrrole ring, a pyrazole ring, and the like, each of which has one free valence. ring, imidazole ring, indole ring, oxadiazole ring, oxazole ring, isoxa Zole ring, thiazole ring, isothiazole ring, pyrroloimidazole ring, pyrrolopyrrole ring , thienopyrrole ring, furopyrrole ring, benzimidazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyrida Examples of the ring include a pyrimidine ring, a triazine ring, a quinoline ring, and an isoquinoline ring. Among these, from the viewpoint of adjusting the absorption maximum in the near infrared region, A pyrrole ring or a thiophene ring is preferred.

[0060] Examples of the substituent that the aromatic ring group may have include a dialkylamino group and a hydroxyl group. , diphenyl ether, an alkoxy group, an alkyl group, and a fluorine atom. From the viewpoint of being able to set the maximum absorption wavelength to a desired value, it is preferably unsubstituted. R 2 ~R 5 At least two of the groups may be bonded to form a ring, for example, The following are included:

[0061] [ka]

[0062] (R 6 and R 7 ) In the formula (1A), R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, or a hydroxyl group. represent. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. From the viewpoint of hydrogen bonding with the hydroxyl group on the squaric acid, a fluorine atom is preferred.

[0063] R 6 and R 7 As for the above, the planarity of the formula (1A) is maintained and the absorption region is effectively shifted to longer wavelengths. From this viewpoint, a hydrogen atom or a hydroxyl group is preferred. Specific examples of the squarylium compound (a) are given below. ) can be written as multiple resonance structures as follows, but these are synonymous unless otherwise noted. be.

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] The maximum absorption wavelength of the squarylium compound (a) is not particularly limited, but 680 nm or more is preferable, 700 nm or more is more preferable, and 710 nm or more is even more preferable. It is preferable that the wavelength is 720 nm or more, and more preferable that the wavelength is 950 nm or less. m or less, more preferably 900 nm or less, and even more preferably 880 nm or less. It is preferable that the wavelength is 860 nm or less, and more preferable that the wavelength is 840 nm or less. By setting the value to the lower limit or more, it is possible to block the required long wavelength region of the near infrared region. By setting the content to be equal to or less than the upper limit, it tends to be possible to block the short wavelength region of the near infrared region.

[0068] The molar extinction coefficient at the absorption maximum of the squarylium compound (a) is preferably 8. 0×10 4 More preferably, 8.5×10 4 More preferably, 9.0×10 4 The upper limit is not particularly limited, but is usually 2.0×10 5 The following is the result. When the squarylium compound (a) has two or more absorption maxima, The difference in the wavelength of maximum absorption is preferably 15 nm or more, more preferably 30 nm or more, and more preferably 50 nm or more. more preferably, 200 nm or less, and even more preferably, 180 nm or less; More preferably, the thickness is 150 nm or less, even more preferably, the thickness is 120 nm or less, and still more preferably, the thickness is 100 nm or less. By setting the value to the lower limit or more, a dye blend that utilizes multiple absorption maxima can be obtained. In addition, by setting the value to the upper limit or less, the necessary amount of light for blocking the near infrared region can be reduced. This tends to reduce the number of dyes required.

[0069] When the squarylium compound (a) has two or more absorption maxima, the absorption maximum on the shortest wavelength side The maximum absorption wavelength is not particularly limited, but is preferably 670 nm or more, and more preferably 680 nm or more. More preferably, the wavelength is 700 nm or more, and particularly preferably, the wavelength is 720 nm or more. In addition, 800 nm or less is preferable, 770 nm or less is more preferable, and 750 nm or less is even more preferable. By setting the value to be equal to or more than the lower limit, it is possible to block the near-infrared region on the short wavelength side. Furthermore, by setting the content to be equal to or less than the upper limit, there is a tendency that side absorption in the visible region can be suppressed.

[0070] When a squarylium compound has two or more absorption maxima, the absorption maximum at the longest wavelength is selected. The maximum absorption wavelength is not particularly limited, but is preferably 800 nm or more, and more preferably 850 nm or more. Preferably, 870 nm or more is more preferable, and 950 nm or less is more preferable, and 930 nm or less is more preferable, 920 nm or less is even more preferable, and 900 nm or less is even more preferable. It is particularly preferable that the wavelength is 880 nm or less, and particularly preferable that the wavelength is 880 nm or less. In addition, by setting the value to the upper limit or less, it is possible to block the near-infrared region. These tend to reduce the number of dyes required to produce a uniform color.

[0071] When squarylium compounds have two or more absorption maxima, they block the entire near infrared region. From this viewpoint, it is preferable that the absorption maxima at least partially overlap with each other. . The squarylium compound (a) may be used alone or in combination of two or more. However, from the viewpoint of reducing the transmittance of near infrared rays having a wavelength of 680 to 900 nm, two types of It is preferable to use a combination of more than one type.

[0072] The squarylium compound (a) can be produced by a known method. For example, According to the method described in Heterocycl. Chem. 14, 133-181 (2008), It can be manufactured in accordance with the above.

[0073] <Squarylium compounds (b)> The dye composition of the present invention is a squarylium compound other than the squarylium compound (a). The composition may contain compound (b). From the viewpoint of efficiently shielding the near infrared region, the squarylium compound (b) has a wavelength It has an absorption maximum at 680 to 900 nm and a molar absorption coefficient at the absorption maximum of 1.0×1 0 5 More preferably, it is equal to or greater than this.

[0074] Since the wavelength band of the near infrared region is wide, the squarylium compound (a) and the near infrared light having a wavelength of 680 to 680 nm are preferably used. It has an absorption maximum at 900 nm and a molar absorption coefficient at the absorption maximum of 1.0 × 10 5 End By combining it with a squarylium compound (b), which is While maintaining the same efficiency, it is possible to improve the blocking of near-infrared rays with wavelengths of 680 to 900 nm. This makes it possible.

[0075] Squarylium compounds exhibit sharp color development through intermolecular association (J-association). Therefore, a mixture of squarylium compounds is preferred. From the viewpoint of increasing the transmittance in the visible region, the squarylium compound (b) is used in the wavelength range of 680 to The molar extinction coefficient at the absorption maximum at 900 nm is usually 1.0 × 10 5 That's all. , 1.7×10 5 More than 1.75×10 is preferable. 5 More preferably, 1.8×10 5 The upper limit is not particularly limited, but is usually 4.0×10 5 Below Below.

[0076] The squarylium compound (b) has an absorption maximum at a wavelength of 680 to 900 nm, The molar extinction coefficient at the maximum is 1.0 x 10 5 In order to achieve the above, for example, the squaryli One example is to have a strong electron-donating group consisting of a condensed ring in the skeleton structure of the cation-based compound (b). By adding a strong electron donating group consisting of a condensed ring, squarylium compounds can be synthesized. The intramolecular vibration of the substituent in the skeletal structure of compound (b) is suppressed, and the squarylium compound It becomes possible to increase the molar absorption coefficient of (b).

[0077] Examples of the squarylium-based compound (b) include the following squarylium-based compounds: Can be obtained.

[0078] [ka]

[0079] [ka]

[0080] Examples of the squarylium-based compound (b) include SK01 and SK01 manufactured by Oji Chemical Co., Ltd. C, SI-14, and Tokyo Chemical Industry Co., Ltd.: B4649. The squarylium compound (b) may be used alone or in combination of two or more. However, from the viewpoint of blocking near infrared rays having a wavelength of 680 to 900 nm, two or more types of It is preferable to use a combination of the above.

[0081] When two or more squarylium compounds (b) are used in combination, for example, Squarylium compounds (b1) corresponding to the lylium compounds (b) and squarylium Squarylium-based compounds (b) other than the squarylium-based compound (b1) (hereinafter, squarylium-based compounds (b2)) is preferably used in combination, and the absorption maxima of the wavelength region is different. The squarylium compound (b1) and the squarylium compound (b2) present in It is more preferable to use them in combination. For example, and a squarylium compound (b1) having an absorption maximum in the wavelength range of 680 to 740 nm. It is particularly preferable to use a squarylium compound (b2) having the formula:

[0082] <Squarylium compounds (c)> The dye composition of the present invention comprises the squarylium compound (a) and the squarylium The squarylium compound (c) may be included other than the compound (b), The compound (c) has an absorption maximum at a wavelength of 650 to 680 nm, and the molar ratio at the absorption maximum is The extinction coefficient is 1.5 x 10 5 More preferably, it is equal to or greater than this.

[0083] The dye composition of the present invention contains the squarylium compound (c), and thus has a wavelength of 600 nm. Blocks visible light of wavelengths above 600 nm without compromising transmittance in the visible range below 100 nm. There is a tendency to be able to. The molar absorption coefficient of the squarylium compound (c) at the absorption maximum is In terms of the transmittance of the visible region below 1.0 × 10 5 More than 1.5 x 1 is preferable. 0 5 The upper limit is not particularly limited, but is usually 4.0×10 5 The following is the result.

[0084] The squarylium compound (c) has an absorption maximum at a wavelength of 650 to 680 nm, The molar extinction coefficient at the maximum is 1.5 x 10 5 In order to achieve this, for example, The skeleton of the cyclic compound (c) is a condensation compound having a strong electron-withdrawing group such as a cyano group or a nitro group. Aromatic carbon having an aromatic heterocycle or an amino group which may be substituted It is preferable that the ring has a hydrogen atom.

[0085] Examples of the squarylium-based compound (c) include the following squarylium-based compounds: Can be obtained.

[0086] [ka]

[0087] Examples of the squarylium-based compound (c) include SN08 manufactured by Oji Chemical Co., Ltd. and SN08 manufactured by Tokyo Chemical Industry Co., Ltd. Company: B4342. The squarylium compound (c) may be used alone or in combination of two or more. It may also be used. The content of the squarylium compound (a) in the dye composition of the present invention is not particularly limited. However, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total solid content of the dye composition. More preferably, the content is 0.5 mass% or more, further preferably 0.5 mass% or more, and more preferably 8 mass% or less. It is more preferable that the content is 6 mass % or less, and further preferably 6 mass % or less. The stability of the dye in the dye composition tends to be improved. Therefore, pigment deposition is less likely to occur.

[0088] The content of the squarylium compound (b) in the dye composition of the present invention is not particularly limited. However, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total solid content of the dye composition. More preferably, the content is 0.5 mass% or more, further preferably 0.5 mass% or more, and more preferably 8 mass% or less. It is more preferable that the content is 6 mass % or less, and further preferably 6 mass % or less. The stability of the dye in the dye composition tends to be improved. Therefore, pigment deposition is less likely to occur.

[0089] Squarylium Compound (a) in the Dye Composition of the Present Invention The blending ratio of the compound (b) is not particularly limited, but it is preferable that the squarylium compound (a) is 100%. The amount of the squarylium compound (b) is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. More preferably, the amount is 30 parts by mass or more, even more preferably, 200 parts by mass or less. The lower limit is preferably 180 parts by mass or less, more preferably 170 parts by mass or less. By setting the value to be equal to or higher, the absorption spectrum tends to be well balanced. By setting the wavelength below 100 nm, the required absorption in the near infrared region tends to be obtained.

[0090] When the dye composition of the present invention contains a squarylium compound (b1), The content of the compound (b1) is not particularly limited, but is preferably 0.1 mass % based on the total solid content of the dye composition. % or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. The content is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less. By setting the content to the lower limit or more, the stability of the dye in the dye composition is improved. By setting the content to the upper limit or less, pigment deposition tends to be less likely to occur.

[0091] When the dye composition of the present invention contains a squarylium compound (b2), The content of the compound (b2) is not particularly limited, but is preferably 0.1 mass % based on the total solid content of the dye composition. % or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. The content is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less. By setting the content to the lower limit or more, the stability of the dye in the dye composition is improved. By setting the content to the upper limit or less, pigment deposition tends to be less likely to occur.

[0092] When the dye composition of the present invention contains a squarylium compound (c), The content of compound (c) is not particularly limited, but is preferably 0.1% by mass or more based on the total solid content of the dye composition. Preferably, the content is 0.15% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.15% by mass or more. , 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is more preferable. By setting the content to the lower limit or more, the stability of the dye in the dye composition is improved. By setting the content to the upper limit or less, pigment deposition tends to be less likely to occur.

[0093] <Other squarylium compounds> The dye composition of the present invention comprises a squarylium compound (a), a squarylium compound (b ) and squarylium compounds other than squarylium compounds (c) (hereinafter referred to as "other squarylium compounds"). The quarylium-based compound may further comprise a quarylium-based compound. The maximum absorption wavelength of the other squarylium compounds is not particularly limited, but is preferably 700 nm or more is preferable, 720 nm or more is more preferable, and 730 nm or more is even more preferable. , 870 nm or less is preferable, 850 nm or less is more preferable, and 830 nm or less is It is more preferable that the squarylium compound (a) and the squarylium-based compound (b) are not less than the lower limit. Areas that cannot be adequately shielded by squarylium-based compounds (b) and squarylium-based compounds (c) alone By setting the value to the upper limit or less, the shielding property of the near infrared region tends to be good. These trends tend to reduce the number of dye types required to produce a desired color.

[0094] When the dye composition of the present invention contains other squarylium compounds, the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, based on the total solid content of the dye composition. % by mass or more is more preferable, 0.3% by mass or more is even more preferable, and 10% by mass or less is still more preferable. The lower limit is preferably 8% by mass or less, more preferably 7% by mass or less. By setting the content to be equal to or higher than the upper limit, the stability of the dye in the dye composition tends to be improved. By keeping the value below this value, pigment deposition tends to be less likely to occur.

[0095] <Dithiolate complex compounds> The dye composition of the present invention contains a dithiolate complex compound and / or a cyanine compound. . The dithiolate complex compound has an absorption maximum at wavelengths of 900 to 1200 nm. As long as it is, there is no particular limitation, but from the viewpoint of providing an absorption maximum in this wavelength region, it is preferable to use a group 10 element. At least one element selected from the group consisting of elements from Group 11 and 12 It is preferred.

[0096] Examples of Group 10 elements, Group 11 elements, and Group 12 elements include Ni, Pd, Pt, and C. Examples of suitable metals include u, Ag, Au, and Zn. From the viewpoint of solubility, however, Ni, Cu, Pd, and Zn are preferred. Preferably, Ni or Cu is more preferable, and Ni is further preferable. As the dithiolate complex compound, nickel dithiolate is preferably used from the viewpoint of solubility as described above. The aryloxy group complex compounds are preferred.

[0097] In addition, nickel dithiolate complex compounds have a sufficient absorption maximum at wavelengths of 950 to 1100 nm. From the viewpoint of obtaining a desired yield, the compound has a chemical structure represented by the following general formula (2) or the following general formula (3). It is preferable that

[0098] [ka]

[0099] [ka]

[0100] In formula (2) and formula (3), X 1 , X 2 , X 3 , X 4 Each independently may have a substituent. It represents an optionally substituted aliphatic hydrocarbon group, or an optionally substituted aromatic ring group. X 1 and X 2 , X 3 and X 4 may each independently form a ring via a linking group.

[0101] (X 1 , X 2 , X 3 , X 4 ) X 1 , X 2 , X 3 , X 4 each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. The aliphatic hydrocarbon group may be a straight-chain, branched-chain or cyclic aliphatic hydrocarbon group. Among these, from the viewpoint of solubility, branched aliphatic hydrocarbon groups are preferred.

[0102] The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 4 or more, and It is preferably 0 or less, more preferably 8 or less, and even more preferably 6 or less. For example, 3 to 10 The number of branched chains is preferably 3 to 8, and more preferably 4 to 6. In addition, by making the content equal to or less than the upper limit, thermal stability tends to be ensured. .

[0103] Specific examples of the linear aliphatic hydrocarbon group include a methyl group, an ethyl group, and an n-propyl group. Among these, the most suitable groups are the butyl group, the n-hexyl group, and the n-heptyl group. From the viewpoint of hydrolysis, an n-butyl group is preferred. Specific examples of the branched chain aliphatic hydrocarbon group include the linear aliphatic hydrocarbon groups described above. , and methyl, ethyl, n-propyl, isopropyl, and n-butyl groups as side chains. Examples of the structure include a structure having a butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. do.

[0104] Examples of the ring contained in the cyclic aliphatic hydrocarbon group include a cyclohexane ring, a cyclohepta ring, and the like. Cyclodecane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring Examples of such groups include those in which one hydrogen atom has been removed from a cyclohexane ring or a cyclododecane ring. Examples of the substituent that the aliphatic hydrocarbon group may have include a methoxy group, an ethoxy group, and the like. Examples of the alkoxy group having 1 to 5 carbon atoms include a hydroxyl group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of solubility, an alkoxy group is preferred.

[0105] The aromatic ring group includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pentane ring, A rylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, Examples of the ring include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0106] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrolidinyl ring, Azole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazo pyrrolyl ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoyl ring isoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring azine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, schizoline ring, Nolin ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring quinazoline ring, quinazolinone ring, and azulene ring. From this viewpoint, a monocyclic ring is preferred.

[0107] Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, Propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group , amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of solubility, a substituent at the meta position is preferred, and an alkyl group is particularly preferred. .

[0108] X 1 and X 2 , X 3 and X 4 may each independently form a ring via a linking group. Examples of the bond include the following.

[0109] [ka]

[0110] Specific examples of the dithiolate complex compound are given below. In the following specific examples, the central element of the complex is shown as Ni, but the central element is limited to Ni. It is not something that is done.

[0111] [ka]

[0112] As the dithiolate complex compound, for example, 024-11 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 811, and Tokyo Chemical Industry Co., Ltd.: T1272. The dithiolate complex compound may be used alone or in combination of two or more. This is also fine. When the dye composition of the present invention contains a dithiolate complex compound, the content ratio of the dithiolate complex compound is not particularly limited. Although not limited, the content is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the dye composition. Preferably, the content is 3% by mass or more, more preferably 10% by mass or less, and more preferably 8% by mass or less. It is more preferable that the content is 7 mass % or less, and further more preferable that the content is 7 mass % or less. Infrared light shielding properties tend to be ensured, and by setting the value to the upper limit or less, the binder - Solubility in resin tends to be ensured.

[0113] The dithiolate complex compound contained in the dye composition of the present invention has a wavelength of 900 to 1200 nm. It has an absorption maximum, but from the viewpoint of effectively blocking near infrared rays with wavelengths of 900 to 1100 nm, The absorption maximum wavelength of the dithiolate complex compound is preferably 950 nm or more, and more preferably 1000 nm or more. More preferably, the wavelength is 1150 nm or less. The molecular weight of the dithiolate complex compound is preferably 1,000 or less from the viewpoint of thermal stability. More preferably, it is 800 or less. From the viewpoint of ensuring solubility, it is preferably 400 or more. 500 or more is more preferable.

[0114] <Cyanine compounds> As the cyanine compound, any compound having an absorption maximum at a wavelength of 900 to 1200 nm is acceptable. From the viewpoint of solubility, the compound having a chemical structure represented by the following general formula (4) is preferably used, but is not particularly limited to this. In the chemical structure represented by the following general formula (4), the double bond is preferably a resonance structure. It is also acceptable to take the following.

[0115] [ka]

[0116] In formula (4), R 9 , R 11 each independently represents a hydrogen atom or an aliphatic group which may have a substituent Represents a hydrocarbon group. R 12 , R 13 Each independently represents a hydrogen atom, a halogen atom, or a substituent. an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or represents an optionally substituted amino group. R 8 , R 10 , R14 each independently represents a hydrogen atom or an aliphatic hydrocarbon which may have a substituent represents an aromatic ring group which may have a substituent.

[0117] R 8 and R 14 , R 13 and R 10 may each independently be bonded to form a nitrogen-containing heterocycle. stomach. X - represents an anion. n is an integer of 3 or greater.

[0118] (R 9 , R 11 ) In the above general formula (4), R 9 , R 11 Each independently has a hydrogen atom or a substituent. represents an optionally substituted aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is usually 1 or more, preferably 2 or more, and more preferably 3 or more. It is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. For example, it is 1 to 10, preferably 2 to 8, and more preferably 3 to 6.

[0119] Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n- Among these, from the viewpoint of maintaining the thermal decomposition temperature, Of these, ethyl, n-propyl and n-butyl groups are preferred, and n-butyl is particularly preferred. . Examples of the substituent that the aliphatic hydrocarbon group may have include a methoxy group, an ethoxy group, and the like. Examples of the alkoxy group having 1 to 5 carbon atoms include a hydroxyl group, a nitro group, a cyano group, and a carboxy group. From the viewpoint of solubility, non-substitution is preferred.

[0120] (R 12 , R13 ) R 12 , R 13 each independently represents a hydrogen atom, a halogen atom, or an aliphatic group which may have a substituent A hydrocarbon group, an aromatic ring group which may have a substituent, or an amine group which may have a substituent. Represents the no group. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. From the viewpoint of ease of synthesis, a chlorine atom is preferred.

[0121] The number of carbon atoms in the aliphatic hydrocarbon group is usually 1 or more, preferably 2 or more, and more preferably 3 or more. It is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. For example, it is 1 to 10, preferably 2 to 8, and more preferably 3 to 6. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n- Examples of the alkyl group include a hexyl group and an n-heptyl group.

[0122] Examples of the substituent that the aliphatic hydrocarbon group may have include a methoxy group, an ethoxy group, and the like. Examples of the alkoxy group having 1 to 5 carbon atoms include a hydroxyl group, a nitro group, a cyano group, and a carboxy group. can be done. The aromatic ring group includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pentane ring, A rylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, Suppresses side absorption in the visible region, such as acenaphthene ring, fluoranthene ring, and fluorene ring From the viewpoint of this, a benzene ring is preferred.

[0123] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrolidinyl ring, Azole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazo pyrrolyl ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoyl ring isoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring azine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, schizoline ring, Nolin ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring quinazoline ring, quinazolinone ring, and azulene ring. From this viewpoint, a monocyclic ring is preferred.

[0124] Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, Propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group , amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of solubility, a methoxy group is preferred. The amino group which may have a substituent includes, in addition to the amino group represented by -NH2, the above The aliphatic hydrocarbon group and the amino group having the aromatic ring group as a substituent are exemplified. Specifically, for example, a dimethylamino group, a diethylamino group, a (2-ethylhexyl)amino group, From the viewpoint of setting the absorption maximum wavelength in a preferred range, a diphenylamino group and a diphenylamino group are preferable. Phenylamino groups are preferred.

[0125] Among these, R12 , R 13 Examples of the alkyl group include a hydrogen atom, a halogen atom, a phenyl group, a methoxy group, and the like. Diphenyl and diphenylamino groups are preferred, and hydrogen and methoxyphenyl groups are particularly preferred. It is.

[0126] (R 8 , R 10 , R 14 ) R 8 , R 10 , R 14 each independently represents a hydrogen atom or an aliphatic hydrocarbon which may have a substituent represents an aromatic ring group which may have a substituent. The number of carbon atoms in the aliphatic hydrocarbon group is usually 1 or more, preferably 2 or more, and more preferably 3 or more. It is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. For example, it is 1 to 10, preferably 2 to 8, and more preferably 3 to 6.

[0127] Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n- Examples of the alkyl group include a hexyl group and an n-heptyl group. Examples of the substituent that the aliphatic hydrocarbon group may have include a methoxy group, an ethoxy group, and the like. Examples of the alkoxy group having 1 to 5 carbon atoms include a hydroxyl group, a nitro group, a cyano group, and a carboxy group. can be done.

[0128] The aromatic ring group includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pentane ring, A rylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, Examples of the ring include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0129] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrolidinyl ring, Azole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazo pyrrolyl ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoyl ring isoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring azine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, schizoline ring, Nolin ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring , a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0130] Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, Propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group , amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. Can be obtained. R 8 and R 14 , R 13 and R 10 may each independently be bonded to form a nitrogen-containing heterocycle. stomach.

[0131] There is no particular limitation as long as it is a nitrogen-containing heterocyclic ring, but a 5-membered ring or a 6-membered ring is preferred. . Examples of the nitrogen-containing heterocycle include a pyrrole ring, a pyrazole ring, an imidazole ring, and an o- oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyr azole ring, pyrrolopyrrole ring, benzisoxazole ring, benzisothiazole ring, Benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring Quinoline ring, isoquinoline ring, cinnaline ring, quinoxaline ring, phenanthridine ring , benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, 1-substituted-2 -Methylbenzo[cd]indolium salts are examples of such compounds. Fused rings are preferred, especially 1-substituted 2-methylbenzo[cd]indolium salts. .

[0132] X in general formula (4) - represents an anion, and examples of the anion include chlorine anion, bromine anion, iodine anion, fluorine anion and other halogen anions; perchloric acid anion Acid anion, chlorate anion, thiocyanate anion, phosphorus hexafluoride anion, hexafluoride Inorganic anions such as antimony anion and boron tetrafluoride anion; benzenesulfonic acid Anion, toluenesulfonate anion, trifluoromethanesulfonate anion, difluoromethanesulfonate anion Phenylamine-4-sulfonic acid anion, 2-amino-4-methyl-5-chlorobenzene Organic sulfonates such as sulfonate anion and 2-amino-5-nitrobenzenesulfonate anion phosphate anion;octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate Organic phosphates such as acid anion, phenyl phosphate anion, and nonylphenyl phosphate anion Anion, Bistrifluoromethylsulfonylimide anion, Bisperfluorobutane Sulfonylimide anion, Perfluoro-4-ethylcyclohexanesulfonate anion tetrakis(pentafluorophenyl)borate anion, tris(fluoroalkyls phenyl)carbanion.

[0133] From the viewpoint of versatility, toluenesulfonate anion and boron tetrafluoride anion are preferred. , boron tetrafluoride anion is particularly preferred. In the general formula (4), n is an integer of 3 or more. The upper limit is not particularly limited, but is preferably The upper limit value is preferably 8 or less, and more preferably 6 or less. They tend to have absorption maxima. Specific examples of the cyanine compound are given below.

[0134] [ka]

[0135] Examples of cyanine compounds include S01259 manufactured by SPECTRUM INFO, Examples include S01445, S09427, S01966, and S01446. The cyanine compounds may be used alone or in combination of two or more. . When the dye composition of the present invention contains a cyanine compound, the content ratio thereof is not particularly limited. However, it is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the dye composition. More preferably, the content is 3% by mass or more, and more preferably, 8% by mass or less, and even more preferably, 7% by mass or less. It is preferable that the content is 6 mass % or less, and more preferable that the content is 6 mass % or less. In addition, by making the content equal to or less than the upper limit, the solubility in the binder resin tends to be improved. There is a tendency for the decomposition property to be ensured.

[0136] The cyanine compound contained in the dye composition of the present invention has an absorption maximum at wavelengths of 900 to 1200 nm. However, from the viewpoint of effectively blocking near infrared rays with a wavelength of 900 to 1100 nm, The absorption maximum wavelength of the compound is preferably 950 nm or more, more preferably 1000 nm or more. Also, 1150 nm or less is preferable. The molar absorption coefficient at the maximum absorption wavelength of the cyanine compound is 1.5 × 10 5 More than this is preferred 2.0×10 5 More preferably, the upper limit is not particularly limited, but is usually 4.0×1 0 5 The following is the result.

[0137] From the viewpoint of solubility, the molecular weight of the cyanine compound is preferably 1,500 or less, and more preferably 1,000 or less. From the viewpoint of thermal stability, it is preferably 400 or more, and more preferably 500 or more. This is more preferable. The dye composition of the present invention comprises the squarylium compound, the dithiolate complex compound and / or In addition to the cyanine compound, other components may be contained as necessary. Examples of the components include other dyes, resins, solvents, and the like.

[0138] <Resin> The dye composition of the present invention may contain a resin. The resin is not particularly limited. However, for example, (meth)acrylic resins (PMMA, etc.), polyamide resins, Examples of the dye composition include olefin resins, polyolefin resins, and polycarbonate resins. From the viewpoint of the stability of the dye in the ink, a (meth)acrylic resin is preferred.

[0139] When the dye composition of the present invention contains a resin, the content of the resin is not particularly limited. The solid content is preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 97% by mass or more. More preferably, the content is 99.99% by mass or less, and more preferably, 99.9% by mass or less. By making the content equal to or more than the lower limit, the film-forming property is improved. By setting the content to be equal to or less than the upper limit, the reliability tends to be improved.

[0140] <Solvent> The dye composition of the present invention may contain a solvent. The solvent is not particularly limited. However, for example, alkanes such as butane, pentane, hexane, heptane, and octane Cycloalkane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and other cycloalkanes Cans: ethanol, propanol, butanol, amyl alcohol, hexanol, Butanol, octanol, decanol, undecanol, diacetone alcohol, fulveol Alcohols such as furyl alcohol; methyl cellosolve, ethyl cellosolve, butyl cellosolve Cellosolves such as Cellosolve, Methyl Cellosolve Acetate, and Ethyl Cellosolve Acetate; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monobutyl ether, propylene glycol monomethyl ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Propylene glycol dimethyl ether, such as monobutyl ether acetate and dipropylene glycol dimethyl ether glycols; acetone, methyl amyl ketone, cyclohexanone, acetophenone, etc. ketones; dioxane, tetrahydrofuran and other ethers; butyl acetate, amyl acetate , Ethyl butyrate, Butyl butyrate, Diethyl oxalate, Ethyl pyruvate, Ethyl-2-hydroxybutyrate hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, 3-methoxy Esters such as methyl propionate; chloroform, methylene chloride, tetrachloroethane halogenated hydrocarbons such as benzene, toluene, xylene, and other aromatic hydrocarbons; Examples of highly polar solvents include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Can be obtained.

[0141] When the dye composition of the present invention contains a solvent, the content of the solvent is not particularly limited. It is preferably 0% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more. It is preferably 99% by mass or less, more preferably 95% by mass or less, and more preferably 92% by mass or less. By setting the content to the lower limit or more, the solution stability tends to be good, Furthermore, by making the content equal to or less than the upper limit, the performance of the coating film tends to be improved.

[0142] [2] Membrane Next, the film of the present invention will be described. The film of the present invention is formed by using the dye composition of the present invention described above. This was formed by The film of the present invention has excellent near-infrared shielding properties and visible light transmittance, and therefore is effective in blocking near-infrared rays. The film of the present invention can be preferably used as an infrared transmission filter. The film of the present invention may be used as a patterned film or a heat shielding filter. The film of the present invention may be a film having no pattern (flat film). The film may be laminated on a support or may be peeled off from the support.

[0143] The thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The thickness is preferably 25 μm or less. The lower limit of the film thickness is preferably 1 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. The lower limit is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more. If it is equal to or higher than the upper limit, the reliability tends to be improved, and if it is equal to or lower than the upper limit, the pigment precipitation tends to be prevented. tends to be less likely to occur.

[0144] The film of the present invention can also be used in combination with a color filter. In the present invention, the near-infrared cut filter is a filter that transmits light having a wavelength in the visible region (visible light). and blocks at least a portion of light in the near infrared region (near infrared light). The near-infrared cut filter may transmit all light in the visible wavelength range. It is not a filter that allows light of a specific wavelength range to pass through, but a filter that allows light of a specific wavelength range to pass through. In the present invention, the color filter may be a filter that blocks light in the visible region. A filter that allows light in a specific wavelength range to pass and blocks light in a specific wavelength range. An infrared transmission filter is a filter that blocks light with wavelengths in the visible range and transmits light with wavelengths in the near infrared range. This refers to a filter that transmits at least a portion of light with wavelengths in the near infrared region.

[0145] When the film of the present invention is used as a near-infrared cut filter, the film of the present invention has a wavelength of 650 It is preferable that the maximum absorption wavelength is in the range of 1 to 1500 nm. The preferred range of near-infrared shielding properties of a filter varies depending on the application, but it is generally in the range of 650 to 1500 nm. It is preferable that the transmittance at at least one point in the range of 15 nm is 15% or less. is more preferable, and 10% or less is even more preferable.

[0146] When the film of the present invention is used as a near-infrared cut filter, it is preferable that the film has a wavelength of 380 to 600 nm. The average transmittance is preferably 30% or more, and more preferably 35% or more. It is more preferable that the ratio is 40% or more. The upper limit is not particularly limited, but it is usually 100% or more. Below. When the film of the present invention is used as a near-infrared cut filter, it is preferable that the film has a wavelength of 680 to 900 nm. The average transmittance is preferably 13% or less, and more preferably 12% or less. The lower limit is not particularly limited, but is usually 0% or more.

[0147] When the film of the present invention is used as a near-infrared cut filter, it is preferable to use copper in addition to the film of the present invention. The insulating film may have a layer containing the above-mentioned compound, a dielectric multilayer film, an ultraviolet absorbing layer, or the like. When the film of the present invention is used as a near-infrared cut filter or an infrared transmission filter, A near-infrared cut filter and an infrared transmission filter can also be used in combination. By using a combination of an infrared cut filter and an infrared transmission filter, The filter can be preferably used for an infrared sensor that detects infrared rays of the above two types. When using a combination of near-infrared cut filters and infrared transmission filters, The dye composition of the present invention may be used to form the film. It may also be formed using a composition.

[0148] The film of the present invention can be used in devices such as CCDs (charge-coupled devices) and CMOSs ​​(complementary metal-oxide semiconductors). The present invention can be used in various devices such as solid-state imaging devices, infrared sensors, and image display devices.

[0149] [3] Optical filters Next, the optical filter of the present invention will be described. The optical filter of the present invention has a near-infrared cut filter and an infrared transmission filter. It can be preferably used as at least one type selected from filters. The optical filter of the present invention has the ability to block near-infrared rays with wavelengths of 680 to 1000 nm and the ability to block visible light. The optical transparency can be improved and the optical transparency can be favorably combined with a CMOS sensor.

[0150] [4] Laminate The laminate of the present invention comprises the film of the present invention and a color filter. The film of the invention and the color filter may or may not be adjacent to each other in the thickness direction. When the film of the present invention and the color filter are not adjacent to each other in the thickness direction, The film of the present invention may be formed on a substrate other than the substrate on which the filter is formed. Between the filter and other components constituting the solid-state imaging element (for example, microlenses, flat A layer such as a flattening layer may be interposed.

[0151] [5] Solid-state imaging device The solid-state imaging device of the present invention has the above-mentioned film of the present invention. As the configuration, it is particularly preferable that the configuration has the film of the present invention and functions as a solid-state imaging element. For example, the following configurations are possible. A plurality of photodiodes and polysilicon constituting the light receiving area of ​​the solid-state image sensor are disposed on the support. A transfer electrode made of silicon or the like is provided, and the photodiode is disposed on the transfer electrode. The light-shielding film is made of tungsten or the like and has an opening only in the light-receiving portion of the board. and a device made of silicon nitride or the like formed to cover the light receiving portion of the photodiode. The device has a protective film, and the film of the present invention is disposed on the device protective film. A light collecting means (e.g., a microlens) is provided on the protective film and below the film of the present invention (on the side closer to the support). The same applies below) or a configuration having a light collecting means on the film of the present invention. The color filter is preferably arranged such that each color pixel is arranged in a space partitioned by partitions in a grid pattern, for example. In this case, the partition wall may have a structure in which a cured film that forms the It is preferable that the refractive index of the film is low with respect to the refractive index of the film. For example, the devices described in JP-A-2012-227478 and JP-A-2014-179577 Examples include:

[0152] [6] Image display device The film of the present invention is useful for liquid crystal display devices, organic electroluminescence (organic EL) display devices, etc. For example, the film of the present invention can be used as a backlight for an image display device. To block infrared light contained in lights (e.g. white light emitting diodes (white LEDs)), Used to prevent malfunction of peripheral devices and to form infrared pixels in addition to each color pixel. It is possible.

[0153] For details on image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki) , published by Kogyo Chosakai Co., Ltd. in 1990), "Display Devices (by Junsho Ibuki, For liquid crystal display devices, see the following: For example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., 1994) There is no particular limitation on the liquid crystal display device to which the present invention can be applied. For example, For the various types of liquid crystal display devices described in the above "Next Generation Liquid Crystal Display Technology" Applicable.

[0154] The image display device may include a white organic EL element. The tandem structure of the organic EL element is preferably as follows: Publication No. 2003-45676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - high brightness "High Precision, Long Life, and Know-How Collection," Technical Information Association, pp. 326-328, 2008 The spectrum of white light emitted by organic EL elements is in the blue region (43 0nm-485nm), green region (530nm-580nm) and yellow region (580nm It is preferable that the photodiode has a strong maximum emission peak at 100 nm or less (-620 nm). Furthermore, it is more preferable that the maximum emission peak is in the red region (650 nm to 700 nm). stomach.

[0155] [7] Infrared sensor The infrared sensor of the present invention has the above-mentioned film of the present invention. As the configuration, it is particularly preferable that the configuration has the film of the present invention and functions as an infrared sensor. For example,

[0201] to

[0207] in JP 2018-45011 A The embodiment described above is an example.

[0156] [8] Fingerprint authentication sensor The fingerprint authentication sensor of the present invention has the above-mentioned film of the present invention. The sensor has a structure including the film of the present invention and functions as a fingerprint authentication sensor. There is no particular limitation as long as the composition is the same as described in Chinese Patent Publication No. 111066032 and Japanese Patent Publication No. 202 Described in paragraphs

[0081] to

[0098] and [Figures 7] to [Figures 9] of Publication No. 0-009397 The following embodiments are included.

[0157] The film of the present invention has near-infrared shielding properties in the wavelength range of 680 to 1000 nm and transmittance in the visible range. By combining it with a CMOS sensor, for example, highly sensitive fingerprint authentication is possible. It is possible to obtain a sensor for this purpose. EXAMPLES

[0158] The dye composition of the present invention will be described below with reference to specific examples. As long as the scope of the present invention is not exceeded, the present invention is not limited to the following examples. (Synthesis Example 1: Synthesis of Compound 3)

[0159] [ka]

[0160] Compound 1 (5.0 g) and compound 2 (4.39 g) were added to 500 mL of toluene and incubated for 3 h. The mixture was refluxed at 110°C. After cooling to below 50°C, the mixture was concentrated under reduced pressure. Acetic acid was added to the resulting crude product. 80 mL of the mixture, 80 mL of water, and 4 mL of 12N concentrated hydrochloric acid were added, and the mixture was vigorously stirred at 110° C. for 2 hours. After cooling to room temperature, the mixture was left to stand overnight, and the resulting precipitate was washed with chloroform and then dried under reduced pressure. As a result, 4.6 g of compound 3 was obtained.

[0161] (Synthesis Example 2: Synthesis of Compound 5)

[0162] [ka]

[0163] Compound 5 was synthesized in the same manner as in Synthesis Example 1, except that compound 4 was used instead of compound 1, and the resulting mixture was mixed with 3.8 mL of compound 5. I got g.

[0164] (Synthesis Example 3: Synthesis of squarylium compound (a)-1)

[0165] [ka]

[0166] Compound 3 (200 mg) and compound 18 (250 mg) were dissolved in 20 mL of toluene and n-butanol. The mixture was heated and stirred at 125°C for 3 hours by the Dean-Stark method. During the heating, 20 mL of toluene was added three times. After cooling to room temperature, The solid was washed with ether and dried, and then 195 mg of squarylium compound (a)-1 was added. I got it at.

[0167] (Synthesis Example 4: Synthesis of squarylium compound (a)-2)

[0168] [ka]

[0169] The squarylium-based compound was synthesized in the same manner as in Synthesis Example 3, except that Compound 5 was used instead of Compound 3. 202 mg of compound (a)-2 was obtained.

[0170] <Squarylium compounds (b)> SK01C: Oji Chemical's "SK01C" (absorption maximum at wavelengths of 680 to 900 nm) The molar extinction coefficient of is 1.9 x 10 5 )

[0171] <Squarylium compounds (c)> SN08: Oji Chemical's "SN08" (a model with an absorption maximum at wavelengths of 650 to 680 nm) The absorption coefficient is 3.6 x 10 5 )

[0172] <Dithiolate complex compound 1> Fujifilm Wako Pure Chemical Industries, Ltd.: 024-11811 was used. The chemical structure represented by the following formula The maximum absorption wavelength is 1001 nm.

[0173] [ka]

[0174] <Cyanine compound 1> Spectrum Info: S01445 was used. Chemical structure represented by the following formula: The maximum absorption wavelength is 985 nm.

[0175] [ka]

[0176] <Naphthalocyanine compound 1> Yamada Chemical's FDN-010 was used. The maximum absorption wavelength was 1014 nm.

[0177] <Measurement of molar extinction coefficient> The absorption maximum wavelength and molar absorption coefficient at the absorption maximum of each compound are based on JIS K 0115 (2 004) and an ultraviolet, visible, near-infrared spectrophotometer (JASCO V-770 manufactured by JASCO Corporation) ) was used to measure and calculate the concentration of chloroform at 25°C.

[0178] <Evaluation of the optical properties of squarylium-based compounds (a)-1 and (a)-2> Squarylium compounds (a)-1 and (a)-2, UV-Vis-NIR spectrophotometer (JASCO V-770, manufactured by JASCO Corporation) was used, and the absorbance at the maximum absorption wavelength was set to 1. A tetrahydrofuran solution was prepared so as to obtain the above-mentioned solution, and the absorption spectrum was measured. The number of absorption maxima read from the absorption spectrum and the maximum absorption wavelength of each absorption maximum are shown in Table 1. show.

[0179] [Table 1]

[0180] <Preparation of dye composition and near-infrared cut filter> A solution of toluene and 1-methoxy-2-propanol mixed in a mass ratio of 5:5. 15 g of Dianal BR-80 (manufactured by Mitsubishi Chemical Corporation) was dissolved in 1 g of water, and the compound shown in Table 2 was added. The materials were added and thoroughly stirred to prepare dye compositions of Example 1, Example 2 and Comparative Example 1. Each of the obtained dye compositions was coated on a polyethylene terephthalate film and incubated at 90° C. After drying for 2 minutes, a film having a thickness of 10 μm was formed, and a near-infrared cut filter was prepared.

[0181] [Table 2]

[0182] Next, the near-infrared cut filter was measured using a spectrophotometer (Hitachi High-Tech Science Corporation, The transmittance spectrum was measured in the wavelength range of 400 to 1200 nm using a 300-mm square lens (U4100). The measured spectra of Example 1, Example 2 and Comparative Example 1 are shown in FIG. Next, from the obtained transmittance spectra for Example 1, Example 2, and Comparative Example 1, the following was obtained: Transmittance results for T(680-1000nm) and T(450-600nm) defined below is shown in Table 3.

[0183] T(680-1000nm): Average transmittance in 1nm increments from 680 to 1000nm value. T(450-600nm): The average transmittance in 1 nm increments for wavelengths from 450 to 600 nm.

[0184] [Table 3]

[0185] As is clear from Table 3, the near-infrared shielding ability is as follows based on the T(680-1000nm) value: Examples 1 and 2 are superior to Comparative Example 1, and the values ​​of T(450-600 nm) are In addition, the transmittance in the visible region is also superior in Examples 1 and 2. The near-infrared cut filter in Example 2 has the ability to block near-infrared rays with wavelengths of 680 to 1000 nm and to block visible light. It can be seen that the transmittance in the region is compatible.

[0186] The near infrared cut filters of Examples 1 and 2 each contain a squarylium compound (a) and The present invention relates to a method for producing a cyanine compound, a dithiolate complex compound, or a cyanine compound. The cyanine compound has an absorption maximum in the wavelength range of 900 to 1200 nm. Squarylium-based compounds (a) are aromatic units that exhibit strong absorption in the near infrared region. By having a ring group and a specific group derived from an indolenyl group, It has an absorption maximum in the near infrared region, that is, it has high and wide absorbance in the near infrared region. Since the dye has an absorption band, the type of dye required to block the entire near infrared region is It is believed that the number of classes could be set to three or four. Furthermore, the molar absorption coefficient in the near infrared region is large. This allows the amount of additive to be reduced, and prevents the inclusion of insoluble matter or impurities that affect the light transmittance in the visible range. It is believed that the light transmittance in the visible region was increased because the suppression of the oxidative stress was achieved.

[0187] As shown in FIG. 1, in Examples 1 and 2, the absorption maximum is in the wavelength range of 900 to 1200 nm. By using a dithiolate complex compound or a cyanine compound, the transmittance in the visible region is high, It is now possible to block near-infrared rays with wavelengths of around 1000 nm. On the other hand, when a naphthalocyanine compound is used as in Comparative Example 1, the transmittance in the visible region is The results were also poor in blocking near-infrared rays with wavelengths of about 1000 nm.

Claims

1. The present invention comprises a squarylium compound (a) having a chemical structure represented by the following general formula (1): Contains a dithiolate complex compound and / or a cyanine compound, The dithiolate complex compound and the cyanine compound have an absorption maximum in a wavelength range of 900 to 1200 nm, the content of the squarylium compound (a) is 0.1% by mass or more and 8% by mass or less based on the total solid content of the dye composition, the content of the dithiolate complex compound is 1% by mass or more and 10% by mass or less based on the total solid content of the dye composition, A dye composition, wherein the content of the cyanine compound is 1% by mass or more and 8% by mass or less based on the total solid content of the dye composition. 【Chemistry 1】 (In formula (1), R 1 represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. The naphthalene ring in the formula (1) may have any substituent and may further form a condensed ring. A represents an aromatic ring group which may have a substituent.

2. 2. The dye composition according to claim 1, wherein the dithiolate complex compound contains at least one element selected from the group consisting of Group 10 elements, Group 11 elements, and Group 12 elements.

3. 3. The dye composition according to claim 1, wherein the dithiolate complex compound is a nickel dithiolate complex compound.

4. The dye composition according to claim 3 , wherein the nickel dithiolate complex compound has a chemical structure represented by the following general formula (2) or the following general formula (3): 【Chemistry 2】 【Chemistry 3】 (In formula (2) and formula (3), X １ , X ２ , X ３ , X ４ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. X １ and X ２ , X ３ and X ４ may each independently form a ring via a linking group.

5. 5. The dye composition according to claim 1, wherein the cyanine compound has a chemical structure represented by the following general formula (4): 【Chemistry 4】 (In formula (4), R 9 , R 11 R each independently represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. 12 , R 13 each independently represents a hydrogen atom, a halogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted amino group. R 8 , R 10 , R 14 each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or an optionally substituted aromatic ring group. R 8 and R 14 , R 13 and R 10 may each independently be bonded to form a nitrogen-containing heterocycle. X － represents an anion. n is an integer of 3 or more.

6. 6. The dye composition according to claim 1, further comprising a squarylium compound (b) other than the squarylium compound (a).

7. The squarylium compound (b) has an absorption maximum at a wavelength of 680 nm to 900 nm, and a molar absorption coefficient at the absorption maximum is 1.0×10 ５ The dye composition according to claim 6,

8. The dye composition according to any one of claims 1 to 7, which contains a resin.

9. A film formed by using the dye composition according to any one of claims 1 to 8.

10. An optical filter comprising the film according to claim 9.

11. An image display device comprising the film according to claim 9.

12. An infrared sensor comprising the film according to claim 9.

13. The optical filter of claim 10 used in combination with a CMOS sensor.

14. A fingerprint authentication sensor comprising the optical filter according to claim 10 and a CMOS sensor.

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