Resin composition, method for producing same, application of same, method for producing molded body, and method for producing image sensor

Abstract

The purpose of the present invention is to provide a resin composition that is a molten mixture containing a resin and a near infrared-absorbing colorant, and from which it is possible to produce a molded body having good optical characteristics even when used in melt forming. The present invention is a resin composition characterized by being a molten mixture containing a resin and a cyanine colorant and / or a squarylium colorant. The resin composition is also characterized in that the cyanine colorant is a compound that includes a cation constituted from a cyanine structure and an anion comprising tetrakis(pentafluorophenyl)borate, in that the cation constituted from a cyanine structure has a specific structure or has a specific structure at at least one terminal of a polymethine skeleton, and in that the squarylium colorant has a structure that includes a nitrogen-containing conjugated system in which at least one structure added to a squaric acid moiety is constituted from a 5-membered ring or a 6-membered ring or has a structure that includes a nitrogen-containing conjugated system in which at least one structure added to a squaric acid moiety is constituted from a 5-membered ring or a 6-membered ring via one conjugated carbon.

Description

Resin composition, its manufacturing method, its uses, manufacturing method of molded body, and manufacturing method of imaging element

[0001] The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition that can be melt-molded to give a molded article having good optical properties, a method for producing the same, uses of the same, a method for producing a molded article, and a method for producing an imaging element.

[0002] In recent years, various applications have been proposed for materials that selectively transmit or block light rays in a specific wavelength range, such as near-infrared rays (700 nm to 1150 nm). Examples of such applications include near-infrared cut filters used in solid-state imaging devices, and optical filters for eyeglasses, sunglasses, and semiconductor light-receiving devices.

[0003] As such a material, a resin composition containing a near-infrared absorbing dye and a resin is used, and various studies have been conducted on the resin composition to meet the requirements for various applications (for example, Patent Documents 1 and 2).

[0004] JP 2015-172102 A JP 2021-102756 A

[0005] However, the heat resistance of conventionally used resin compositions is still insufficient, and when a resin composition containing a near-infrared absorbing dye is applied to a substrate and dried to form a coating film, a molded article having good optical properties can be obtained. However, when the resin composition is melt-molded, the near-infrared absorbing dye cannot withstand the melting temperature and deteriorates, resulting in a problem that a molded article having good optical properties cannot be obtained. In particular, there has been a need for a molten mixture of a dye and a resin that does not deteriorate during injection molding such as lens molding or extrusion molding such as film molding or sheet molding, and that can suitably produce a molded article having good optical properties.

[0006] The present invention has been made in view of the above-mentioned current situation, and aims to provide a resin composition that is a molten mixture containing a near-infrared absorbing dye (cyanine dye and / or squarylium dye) and a resin, which can be used to produce a molded article having good optical properties when used in melt molding.

[0007] In order to solve the above-mentioned problems, the present inventors have conducted extensive research into resin compositions containing a near-infrared absorbing dye and a resin, and have found that by containing a specific near-infrared absorbing dye (cyanine dye and / or squarylium dye) and a resin, a resin composition can be obtained that can achieve good optical properties even as a molten mixture, and have thus completed the present invention.

[0008] That is, the present invention includes the following aspects: <1> A molten mixture containing a cyanine dye and / or a squarylium dye and a resin, the cyanine dye being a compound containing a cation having a cyanine structure and an anion having tetrakispentafluorophenylborate, the cation having a cyanine structure being represented by the following formula (1):

[0009]

[0010] (In formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or —CR ａ R ｂ - represents. ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent; R ａ and R ｂ may be bonded to form a ring structure. １ or Y ２ * represents the bonding site with the polymethine skeleton. R １ and R ６ are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group. ２ ~R ５ and R ７ ~R １２ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, or a structure represented by the following formula (2):

[0011]

[0012] (In formula (2), R ２１represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. ２２ ~R ２７ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent. * represents a bonding site with the polymethine skeleton. A resin composition characterized by having a structure represented by the following formula: (I) wherein the squarylium dye is a compound in which at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring, or in which at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring connected via one conjugated carbon. <2> A molded article characterized by using the resin composition described in <1> above. <3> An injection-molded article characterized by using the resin composition described in <1> above. <4> An extrusion-molded article characterized by using the resin composition described in <1> above. <5> An optical lens characterized by using the resin composition described in <1> above. <6> An optical filter characterized by including a sheet formed using the resin composition described in <1> above. <7> An imaging element characterized by comprising the optical lens described in <5> above and / or the optical filter described in <6> above. <8> A method for producing a resin composition, the method comprising the step of melt-mixing a cyanine dye and / or a squarylium dye with a resin, wherein the cyanine dye is a compound containing a cation having a cyanine structure and an anion having tetrakispentafluorophenylborate, and the cation having a cyanine structure is represented by the following formula (1):

[0013]

[0014] (In formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or —CR ａ R ｂ - represents. ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent; R ａ and R ｂ may be bonded to form a ring structure.１ or Y ２ * represents the bonding site with the polymethine skeleton. R １ and R ６ are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group. ２ ~R ５ and R ７ ~R １２ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, or a structure represented by the following formula (2):

[0015]

[0016] (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. ２２ ~R ２７ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent. * represents a bonding site with the polymethine skeleton. A method for producing a resin composition, characterized in that the squarylium dye has a structure represented by the following formula (1):

[0017]

[0018] (In formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or —CR ａ R ｂ - represents.ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent; R ａ and R ｂ may be bonded to form a ring structure. １ or Y ２ * represents the bonding site with the polymethine skeleton. R １ and R ６ are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group. ２ ~R ５ and R ７ ~R １２ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, or a structure represented by the following formula (2):

[0019]

[0020] (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. ２２ ~R ２７are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent. * represents a bonding site to the polymethine skeleton. A method for producing a molded article, characterized in that the squarylium dye has a structure represented by the following formula: (I) wherein at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring, or at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring connected via one conjugated carbon atom. <10> A method for producing a molded article according to <9> above, wherein the melt molding is injection molding or extrusion molding. <11> A method for producing a molded article according to <9> or <10> above, wherein the molded article is in the form of a pellet, a lens, or a sheet. <12> A method for producing a molded article according to <9> or <10> above, wherein the molded article is an optical lens. <13> A method for producing a molded article according to <9> or <10> above, wherein the molded article is an optical filter. <14> A method for manufacturing an image sensor including an optical lens group and a light receiving element, the method comprising: melt-mixing a cyanine dye and / or a squarylium dye with a resin; and melt-molding the molten mixture to manufacture at least one optical lens constituting the optical lens group, wherein the cyanine dye is a compound including a cation having a cyanine structure and an anion having tetrakispentafluorophenylborate, and the cation having the cyanine structure is represented by the following formula (1):

[0021]

[0022] (In formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or —CR ａ R ｂ - represents. ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent; R ａ and R ｂ may be bonded to form a ring structure. １ or Y ２* represents the bonding site with the polymethine skeleton. R １ and R ６ are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group. ２ ~R ５ and R ７ ~R １２ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, or a structure represented by the following formula (2):

[0023]

[0024] (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. ２２ ~R ２７ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent. * represents a bonding site with the polymethine skeleton. ), and the squarylium dye is a compound in which at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring, or in which at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring connected via one conjugated carbon. <15> A method for manufacturing an imaging element comprising an optical lens group, an optical filter, and a light-receiving element, the method comprising the steps of melt-mixing a cyanine dye and / or a squarylium dye with a resin, and melt-molding the molten mixture to manufacture at least one optical lens and / or optical filter constituting the optical lens group, wherein the cyanine dye is a compound containing a cation having a cyanine structure and an anion composed of tetrakispentafluorophenylborate, and the cation having a cyanine structure is represented by the following formula (1):

[0025]

[0026] (In formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or —CRａ R ｂ - represents. ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent; R ａ and R ｂ may be bonded to form a ring structure. １ or Y ２ * represents the bonding site with the polymethine skeleton. R １ and R ６ are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group. ２ ~R ５ and R ７ ~R １２ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, or a structure represented by the following formula (2):

[0027]

[0028] (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. ２２ ~R ２７ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent. * represents a bonding site to the polymethine skeleton.), and the squarylium dye is a compound in which at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring, or at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring connected via one conjugated carbon atom.

[0029] The resin composition of the present invention can also be used in melt molding to give a molded article having good optical properties.

[0030] 1 is a diagram showing an absorbance curve of a molded body of Example 1. FIG. 2 is a diagram showing an absorbance curve of a molded body of Comparative Example 1.

[0031] The present invention will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0032] 1. Resin Composition The present invention relates to a molten mixture comprising a cyanine dye and / or a squarylium dye, and a resin, wherein the cyanine dye is a compound comprising a cation having a cyanine structure and an anion having tetrakispentafluorophenyl borate, the cation having a cyanine structure having a structure represented by formula (1) above, or a structure represented by formula (2) above at at least one end of a polymethine skeleton, and the squarylium dye is a compound in which at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a five-membered ring and a six-membered ring, or at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a five-membered ring and a six-membered ring connected via one conjugated carbon atom.

[0033] As described above, the resin composition of the present invention contains a specific dye and a resin, and thus can produce a molded article having good optical properties even when melt-molded. The reason for this effect is presumably that the main skeleton of the specific dye contained in the resin composition of the present invention is robust and the bonding strength between the cation species and the anion species is strong, making them less likely to be liberated even when heated at high temperatures.

[0034] The resin composition of the present invention is a molten mixture containing a cyanine dye and / or a squarylium dye and a resin. In the present invention, the molten mixture is a mixture of the cyanine dye and / or the squarylium dye and the resin, which is melt-mixed by heating the mixture to a temperature equal to or higher than the melting point of the resin so as to melt and mix the components uniformly.

[0035] The above-mentioned melt mixing means mixing at or above the melting point when the resin contained in the resin composition of the present invention is a thermoplastic resin having a melting point as measured by a differential scanning calorimeter (DSC), and means mixing at a temperature 80°C or higher than the glass transition temperature as measured by DSC when the resin is a thermoplastic resin having no melting point as measured by DSC.

[0036] The DSC measurement is performed according to JIS K 7121:2012.

[0037] From the viewpoint of the application of the resin composition of the present invention, when the resin contained in the resin composition of the present invention is a thermoplastic resin having the above melting point, the melting point is preferably 200° C. or higher and 260° C. or lower, and more preferably 220° C. or higher and 255° C. or lower. When the resin does not have the above melting point, the glass transition temperature is preferably 100° C. or higher and 200° C. or lower, more preferably 110° C. or higher and 180° C. or lower, and even more preferably 120° C. or higher and 160° C. or lower.

[0038] (Cyanine Dye) The cyanine dye used in the present invention is a compound containing a cation having a cyanine structure and an anion having tetrakispentafluorophenylborate.

[0039] The cation having the cyanine structure has the structure represented by the formula (1) (structure A1) or the structure represented by the formula (2) (structure A2) at at least one end of the polymethine skeleton.

[0040] (Structure A1) In the above formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or —CR ａ R ｂ - represents. ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent; R ａ and R ｂ may be bonded to form a ring structure.

[0041] R ａ and R ｂ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among these, a fluorine atom and a chlorine atom are preferred in that dyes are easily available and have little absorption of visible light, and a chlorine atom is more preferred in that it is easy to handle during synthesis.

[0042] R ａ and R ｂThe number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 6, in that the solubility of the dye in a thermoplastic resin can be improved.

[0043] R ａ and R ｂ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and still more preferably a methyl group.

[0044] R ａ and R ｂ Examples of the substituent that the aliphatic hydrocarbon group represented by the formula (R) may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are preferred, and a chlorine atom is more preferred. ａ and R ｂ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0045] R ａ and R ｂ The ring structure formed by bonding may be a monocyclic ring or a polycyclic ring. The ring structure may be an alicyclic ring, an aromatic ring, or a condensed ring thereof. The ring structure is preferably a 5- to 18-membered ring, more preferably a 5- to 12-membered ring, and even more preferably a 5- or 6-membered ring.

[0046] Among them, X １ and X ２ are the same or different and have a higher heat resistance and are each an oxygen atom, a sulfur atom, or -CR ａ R ｂ - (R ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent; R ａ and R ｂ At least one of the above represents an aliphatic hydrocarbon group. ａ R ｂ -In R ａ and R ｂEach of the X's is preferably an aliphatic hydrocarbon group which may have a substituent, and more preferably an aliphatic hydrocarbon group. １ and X ２ It is more preferable that they are the same.

[0047] In the above formula (1), Y represents Y １ or Y ２ Y is a group represented by the formula: １ and Y ２ In the formula, * represents the bonding site to the polymethine skeleton. １ and Y ２ The carbon atom at the position where the line segment with an * at its end is bonded is bonded to the polymethine skeleton. Therefore, the structure represented by the above formula (1) is preferably specifically a structure represented by the following formula (1a) or (1b):

[0048] (In the formula, R １ ~R １２ is the same as equation (1).

[0049] In the above formula (1), X １ and X ２ is an oxygen atom or a sulfur atom, and Y is Y ２ That is, the structure represented by the formula (1) is preferably represented by the formula (1b), and in the formula (1b), X １ and X ２ is preferably an oxygen atom or a sulfur atom.

[0050] In the above formula (1), R １ and R ６ are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group. １ and R ６ The number of carbon atoms in the aliphatic hydrocarbon group represented by R is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 4. １ and R ６The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and even more preferably a methyl group.

[0051] R １ and R ６ Examples of the substituent that the aliphatic hydrocarbon group represented by R may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are preferred, and a chlorine atom is more preferred. １ and R ６ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0052] Among them, R １ and R ６ are preferably the same or different and each is an aliphatic hydrocarbon group which may have a substituent, and more preferably an aliphatic hydrocarbon group. １ and R ６ are preferably the same.

[0053] In the above formula (1), R ２ ~R ５ and R ７ ~R １０ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent.

[0054] R ２ ~R ５ and R ７ ~R １０ The halogen atom represented by the formula ａ Among these, a chlorine atom is preferred because of its higher heat resistance.

[0055] R ２ ~R ５ and R ７ ~R １０ The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0056] Also, R ２~R ５ and R ７ ~R １０ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and even more preferably a methyl group.

[0057] R ２ ~R ５ and R ７ ~R １０ Examples of the substituent that the aliphatic hydrocarbon group represented by R may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are preferred, and a chlorine atom is more preferred. ２ ~R ５ and R ７ ~R １０ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0058] Among them, R ２ ~R ５ and R ７ ~R １０ are the same or different and are preferably a hydrogen atom or an optionally substituted aliphatic hydrocarbon group, more preferably a hydrogen atom or an aliphatic hydrocarbon group.

[0059] R ２ ~R ５ Among R, it is preferred that 0 or 1 is an aliphatic hydrocarbon group which may have a substituent, and the rest are hydrogen atoms. ７ ~R １０ Preferably, 0 or 1 of these is an aliphatic hydrocarbon group which may have a substituent, and the rest are hydrogen atoms.

[0060] In the above formula (1), R ２ and R ７ , R ３ and R ８ , R ４ and R ９ , R ５ and R １０ and are preferably the same.

[0061] In the above formula (1), R １１ and R １２ R may be the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent. １１ and R １２ The halogen atom and the optionally substituted aliphatic hydrocarbon group represented by R ２ Among these, the halogen atom and the aliphatic hydrocarbon group which may have a substituent represented by R １１ and R １２ are the same or different and are preferably a halogen atom, more preferably a chlorine atom. １１ and R １２ are preferably the same.

[0062] (Structure A2) In the above formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. ２１ The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0063] R ２１ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and even more preferably a methyl group.

[0064] R ２１ Preferred examples of the substituent that the aliphatic hydrocarbon group represented by R may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom and a chlorine atom are more preferred, and a chlorine atom is even more preferred. ２１ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0065] Among them, R ２１ is preferably an aliphatic hydrocarbon group which may have a substituent, and more preferably an aliphatic hydrocarbon group.

[0066] In the above formula (2), R ２２~R ２７ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent.

[0067] R ２２ ~R ２７ The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0068] R ２２ ~R ２７ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and even more preferably a methyl group.

[0069] R ２２ ~R ２７ Preferred examples of the substituent that the aliphatic hydrocarbon group represented by R may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are more preferred, and a chlorine atom is even more preferred. ２２ ~R ２７ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0070] Among them, R ２２ ~R ２７ are the same or different and are preferably a hydrogen atom or an optionally substituted aliphatic hydrocarbon group, more preferably a hydrogen atom or an aliphatic hydrocarbon group.

[0071] R ２２ ~R ２７ It is preferred that 0 or 1 of the groups be an aliphatic hydrocarbon group and the remainder be hydrogen atoms.

[0072] In the above formula (2), * represents the bonding site with the polymethine skeleton. That is, the carbon atom at the bonding site of the line segment with * at the end in formula (2) is the carbon atom that is bonded to the polymethine skeleton ([-CH=CH-CH ２The structure A2 has the structure represented by formula (2) at least at one end of the polymethine skeleton, but preferably has the structure represented by formula (2) at both ends of the polymethine skeleton.

[0073] As the cation having the structure A2 represented by the formula (2) at at least one end of the polymethine skeleton, for example, a compound represented by the following formula (2a) is preferably mentioned.

[0074] (In the formula, R ２１ ~R ２７ are the same or different and are the same as above. ａ１ is R ２１ Same as R ａ２ ~R ａ７ are the same or different, and R ２２ ~R ２７ is the same as

[0075] The cyanine dye can be synthesized by a general organic synthesis method such as a conventionally known method for synthesizing cyanine dyes. Preferably, the dye can be purified by column to a purity of 99% or more, and then the molecular structure can be confirmed and obtained by NMR. Alternatively, a commercially available product may be used.

[0076] (Squarylium Dye) The squarylium dye used in the present invention is a compound in which at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring, or at least one of the structures added to the squaric acid moiety has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring connected via one conjugated carbon atom.

[0077] The squarylium dye is a compound represented by the following formula (3), and the squaric acid moiety is the moiety shown in brackets [ ] in the formula (3).

[0078]

[0079] In formula (3), R ３１ and R ３２ are the same or different and represent an organic group, which corresponds to the structural portion added to the squaric acid moiety. ３１ and R３２ At least one of the above is a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring (hereinafter also referred to as "Structure B1"), or a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring via one conjugated carbon (hereinafter also referred to as "Structure B2").

[0080] (Structure B1) In the structure containing a nitrogen-containing conjugated system composed of the above-mentioned 5-membered ring and 6-membered ring, the nitrogen atom may be contained in the 5-membered ring, may be contained in the 6-membered ring, or may be contained in both the 5-membered ring and the 6-membered ring, but is preferably contained in the 5-membered ring.

[0081] The numbers of 5-membered rings and 6-membered rings constituting the nitrogen-containing conjugated system are not particularly limited, but the nitrogen-containing conjugated system preferably consists of one 5-membered ring and one 6-membered ring. Examples of the nitrogen-containing conjugated system include Form 1, in which a 6-membered ring and a 5-membered ring are arranged in this order around the squaric acid moiety, and Form 2, in which a 5-membered ring and a 6-membered ring are arranged in this order.

[0082] Examples of the nitrogen-containing conjugated system composed of the above-mentioned five-membered ring and six-membered ring include structures obtained by removing one hydrogen atom from indole, indoline, indolizine, isoindole, indazole, imidazole, benzimidazole, benzotriazole, and derivatives thereof to make them monovalent.

[0083] Among these, as the nitrogen-containing conjugated system composed of the above-mentioned 5-membered ring and 6-membered ring, a structure represented by the following formula (3a), a structure represented by the following formula (3b), and a structure represented by the following formula (3c) are preferred, and a structure represented by the following formula (3a) is more preferred.

[0084] (In formula (3a), R ａ１ ~R ａ６ are the same or different and each represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or —NH—CO—R ａ７ R represents a group represented by the formula: ａ７ represents an aliphatic hydrocarbon group which may have a substituent. * indicates the bonding site with the squaric acid moiety.

[0085] (In formula (3b), R ｂ１ ~R ｂ６are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group; n represents 0 or 1; * indicates the bonding site with the squaric acid moiety.

[0086]

[0087] (In formula (3c), R ｃ１ ~R ｃ５ are the same or different and each represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or —NR ｃ６ R ｃ７ R represents a group represented by the formula: ｃ６ and R ｃ７ are the same or different and represent an aliphatic hydrocarbon group which may have a substituent. * indicates the bonding site with the squaric acid moiety.

[0088] In the above formula (3a), R ａ１ ~R ａ６ The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0089] R ａ１ ~R ａ６ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and even more preferably a methyl group.

[0090] R ａ１ ~R ａ６ Preferred examples of the substituent that the aliphatic hydrocarbon group represented by R may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are more preferred, and a chlorine atom is even more preferred. ａ１ ~R ａ６ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0091] R ａ７ The number of carbon atoms in the aliphatic hydrocarbon group represented by R is preferably 1 to 18, and more preferably 1 to 8. ａ７ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group.

[0092] R ａ７ The substituents that the aliphatic hydrocarbon group represented by the formula (I) may have include the above-mentioned R ａ１ ~R ａ６ Among these, a fluorine atom and a chlorine atom are more preferred, and a chlorine atom is even more preferred. ａ７ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0093] Among them, R ａ１ ~R ａ６ are the same or different and are preferably a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, more preferably a hydrogen atom or an aliphatic hydrocarbon group, and even more preferably a hydrogen atom or an alkyl group. ａ１ ~R ａ３ are the same or different and are alkyl groups, and R ａ４ and R ａ６ are the same or different and are a hydrogen atom or an alkyl group, and R ａ５ is -NH-CO-R ａ７ A group represented by the following formula is particularly preferred.

[0094] The bonds represented by dashed and solid lines in the formula (3a) above include single and double bonds. When the structure represented by the formula (3a) above is bonded to the squaric acid moiety represented by the formula (3), the positions of the single and double bonds may change due to resonance. The same applies to the bonds represented by dashed and solid lines in the formulas (3b) and (3c) above.

[0095] The structure represented by the above formula (3a) includes a structure in a resonance relationship, and specifically, it preferably includes at least one of a structure represented by the following formula (3a-1) and a structure represented by the following formula (3a-2):

[0096] (R in formula (3a-1) ａ１ ~R ａ６ is R in formula (3a) ａ１ ~R ａ６ (The * indicates the binding site with the squaric acid moiety.) (R in formula (3a-2) ａ１ ~R ａ６ is R in formula (3a) ａ１ ~R ａ６ (The * indicates the binding site with the squaric acid moiety.)

[0097] In the above formula (3b), R ｂ１ ~R ｂ６ The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0098] R ｂ１ ~R ｂ６ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and even more preferably a methyl group.

[0099] R ｂ１ ~R ｂ６ Preferred examples of the substituent that the aliphatic hydrocarbon group represented by R may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are more preferred, and a chlorine atom is even more preferred. ｂ１ ~R ｂ６ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0100] Among them, R ｂ１ ~R ｂ６ are the same or different and are preferably a hydrogen atom or an optionally substituted aliphatic hydrocarbon group, more preferably a hydrogen atom or an aliphatic hydrocarbon group, and even more preferably a hydrogen atom or an alkyl group.

[0101] The structure represented by the above formula (3b) includes a structure in a resonance relationship, and specifically, it preferably includes at least one of a structure represented by the following formula (3b-1) and a structure represented by the following formula (3b-2):

[0102] (R in formula (3b-1) ｂ１ ~R ｂ５ is R in formula (3b) ｂ１~R ｂ５ (The * indicates the binding site with the squaric acid moiety.)

[0103] (R in formula (3b-2) ｂ１ ~R ｂ６ is R in formula (3b) ｂ１ ~R ｂ６ (The * indicates the binding site with the squaric acid moiety.)

[0104] In the above formula (3c), R ｃ１ ~R ｃ５ The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms.

[0105] R ｃ１ ~R ｃ５ The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group, and even more preferably a methyl group.

[0106] R ｃ１ ~R ｃ５ Preferred examples of the substituent that the aliphatic hydrocarbon group represented by R may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are more preferred, and a chlorine atom is even more preferred. ｃ１ ~R ｃ５ The aliphatic hydrocarbon group represented by R preferably has no substituent. ｃ５ is preferably a hydrogen atom.

[0107] R ｃ６ and R ｃ７ R may be the same or different and represent an aliphatic hydrocarbon group which may have a substituent. ｃ６ and R ｃ７ The number of carbon atoms in the aliphatic hydrocarbon group represented by R is preferably 1 to 18, more preferably 1 to 16, and even more preferably 1 to 12. ｃ６ and R ｃ７The aliphatic hydrocarbon group represented by the formula (I) is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a tert-butyl group.

[0108] R ｃ６ and R ｃ７ The substituents that the aliphatic hydrocarbon group represented by the formula (I) may have include the above-mentioned R ｃ１ ~R ｃ５ The substituents may be the same as those that may be contained in the aliphatic hydrocarbon group represented by R ｃ６ and R ｃ７ The aliphatic hydrocarbon group represented by the formula (I) preferably has no substituent.

[0109] The structure represented by the above formula (3c) includes a structure in a resonance relationship, and specifically, it preferably includes at least one of a structure represented by the following formula (3c-1) and a structure represented by the following formula (3c-2):

[0110] (R in formula (3c-1) ｃ１ ~R ｃ５ is R in formula (3c) ｃ１ ~R ｃ５ (The * indicates the binding site with the squaric acid moiety.)

[0111] (R in formula (3c-2) ｃ１ ~R ｃ５ is R in formula (3c) ｃ１ ~R ｃ５ (The * indicates the binding site with the squaric acid moiety.)

[0112] The squarylium dye having the structure B1 is represented by the formula (3) R ３１ and R ３２ and the organic groups represented by the formula (3a), (3b) or (3c) are the same or different and have the structure represented by the formula (3a), (3b) or (3c), respectively. ３１ and R ３２ In the above, the organic group represented by the formula (3a) is more preferred.

[0113] (Structure B2) The above Structure B2 includes a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring via one conjugated carbon, i.e., a structure in which a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring is bonded to a squaric acid moiety via one conjugated carbon.

[0114] "Through one conjugated carbon" means that one conjugated carbon, i.e., -CR= or =CR-, exists between the squaric acid moiety and the nitrogen-containing conjugated system composed of the five-membered ring and the six-membered ring.

[0115] Examples of the nitrogen-containing conjugated system composed of the five-membered ring and the six-membered ring include the same structure as the above-mentioned Structure B1. That is, examples of the nitrogen-containing conjugated system composed of the five-membered ring and the six-membered ring include monovalent structures obtained by removing one hydrogen atom from indole, indoline, indolizine, isoindole, indazole, imidazole, benzimidazole, benzotriazole, and derivatives thereof.

[0116] The nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring via one conjugated carbon atom is preferably a structure represented by the following formula (4a), (4b) or (4c).

[0117] (In formula (4a), R ａ１ ~R ａ６ are the same or different and each represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or —NH—CO—R ａ７ R represents a group represented by the formula: ａ７ represents an aliphatic hydrocarbon group which may have a substituent. ａ８ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. * indicates the bonding site with the squaric acid moiety.

[0118] (In formula (4b), R ｂ１ ~R ｂ６ are the same or different and represent a hydrogen atom or an optionally substituted aliphatic hydrocarbon group. ｂ７ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms. n represents 0 or 1. * indicates the bonding site with the squaric acid moiety.

[0119] (In formula (4c), R ｃ１ ~R ｃ５ are the same or different and each represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or —NR ｃ６ R ｃ７ R represents a group represented by the formula: ｃ６ and R ｃ７ R may be the same or different and represent an aliphatic hydrocarbon group which may have a substituent. ｃ８ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. * indicates the bonding site with the squaric acid moiety.

[0120] R in the above formula (4a) ａ１ ~R ａ６ As the group, R in the above formula (3a) ａ１ ~R ａ６ The R in the above formula (4a) is the same as ａ８ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a hydrogen atom.

[0121] The above formula (4a) contains a structure in a resonance relationship, and specifically, it preferably contains at least one of a structure represented by the following formula (4a-1) and a structure represented by the following formula (4a-2).

[0122] (R in formula (4a-1) ａ１ ~R ａ６ and R ａ８ is R in formula (4a) ａ１ ~R ａ６ and R ａ８ (The * indicates the binding site with the squaric acid moiety.)

[0123] (R in formula (4a-2) ａ１ ~R ａ６ and R ａ８ is R in formula (4a) ａ１ ~R ａ６ and R ａ８ (The * indicates the binding site with the squaric acid moiety.)

[0124] R in the above formula (4b) ｂ１ ~R ｂ６ As the R ｂ１ ~Rｂ６ The R in the above formula (4b) is the same as ｂ７ Examples of the alkyl group include a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms.

[0125] The above formula (4b) contains a structure in a resonance relationship, and specifically, it preferably contains at least one of a structure represented by the following formula (4b-1) and a structure represented by the following formula (4b-2).

[0126] (R in formula (4b-1) ｂ１ ~R ｂ７ is R in formula (4b) ｂ１ ~R ｂ７ (The * indicates the binding site with the squaric acid moiety.)

[0127] (R in formula (4b-2) ｂ１ ~R ｂ５ and R ｂ７ is R in formula (4b) ｂ１ ~R ｂ５ and R ｂ７ (The * indicates the binding site with the squaric acid moiety.)

[0128] R in the above formula (4c) ｃ１ ~R ｃ５ As for R in formula (3c), ｃ１ ~R ｃ５ The R in the above formula (4c) is the same as ｃ８ The group includes a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably a hydrogen atom.

[0129] The above formula (4c) contains a structure in a resonance relationship, and specifically, it preferably contains at least one of a structure represented by the following formula (4c-1) and a structure represented by the following formula (4c-2).

[0130] (R in formula (4c-1) ｃ１ ~R ｃ５ and R ｃ８ is R in formula (4c) ｃ１ ~R ｃ５ and R ｃ８(The * indicates the binding site with the squaric acid moiety.)

[0131] (R in formula (4c-2) ｃ１ ~R ｃ５ and R ｃ８ is R in formula (4c) ｃ１ ~R ｃ５ and R ｃ８ (The * indicates the binding site with the squaric acid moiety.)

[0132] The squarylium dye having the structure B2 is represented by the formula (3) R ３１ and R ３２ and the organic groups represented by the formula (3) are the same or different and are groups having a structure represented by the formula (4a), (4b) or (4c). ３１ and R ３２ In the above, the organic group represented by the formula (4b) is more preferably a group having a structure represented by the formula (4b).

[0133] The squarylium dye can be synthesized by a general organic synthesis method, such as a conventionally known squarylium dye synthesis method. Preferably, the squarylium dye can be obtained by column purification to a purity of 99% or more, followed by confirmation of its molecular structure by NMR. Alternatively, a commercially available product may be used.

[0134] The squarylium dye preferably has a maximum absorption wavelength in the range of 690 to 750 nm, more preferably in the range of 700 to 745 nm, and even more preferably in the range of 705 to 740 nm.

[0135] The cyanine dye preferably has a maximum absorption wavelength in the range of 730 to 1200 nm, more preferably in the range of 740 to 1150 nm, and even more preferably in the range of 750 to 1100 nm.

[0136] In the present invention, the cyanine dye or squarylium dye may be contained alone or in combination of two or more kinds.

[0137] The content of the cyanine dye and / or squarylium dye in the resin composition of the present invention is not particularly limited and may be appropriately selected depending on the thickness of the molded article, etc., but is preferably 0.005 to 3 mass%, more preferably 0.01 to 2 mass%, and even more preferably 0.02 to 1.5 mass%, relative to 100 mass% of the resin composition of the present invention.

[0138] (Resin) The resin contained in the resin composition of the present invention is not particularly limited, but is preferably a thermoplastic resin, since it can be easily melted and mixed with the dye.

[0139] Examples of the thermoplastic resin include polyolefin resins, cycloolefin resins, acrylic resins, styrene resins, vinyl chloride resins, polyvinyl alcohol resins, polyester resins, polyacetal resins, polycarbonate resins, polyamide resins, polyimide resins, polysulfone resins, polyphenylene ether resins, polyphenylene sulfide resins, fluororesins, cellulose derivatives, and polyurethane resins. These may be used alone or in combination of two or more. Among these, cycloolefin resins and polycarbonate resins are preferred, and cycloolefin resins are more preferred, in terms of their good optical properties, heat resistance, and moldability.

[0140] The content of the above resin is preferably 90 to 99.9 mass%, more preferably 92 to 99.7 mass%, and even more preferably 94 to 99.5 mass%, based on 100 mass% of the resin composition of the present invention.

[0141] (Other Components) In addition to the dye and resin described above, the resin composition of the present invention may contain other components such as near-infrared absorbing dyes other than the dyes described above and ultraviolet absorbers, as long as they do not adversely affect the effects of the present invention.

[0142] Examples of the other near-infrared absorbing dyes include cyanine dyes and squarylium dyes other than those mentioned above, croconium dyes, cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, naphthalocyanines, cholines, etc.) which may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as a central metal ion, pyrrolopyrrole dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes, quaterrylene dyes, diimonium dyes, perylene dyes, quinacrylonitrile dyes, oxazine dyes, dipyrromethene dyes, nickel dyes, and the like. Examples of suitable dyes include Kel complex dyes, copper ion dyes (copper phosphonates (copper phosphates), copper phosphate complexes (complexes of phosphoric acid monoesters and copper, complexes of phosphoric acid diesters and copper)), dithiol metal complex dyes, azo dyes, polymethine dyes, phthalide dyes, quinone dyes (naphthoquinone dyes, anthraquinone dyes), indophenol dyes, pyrylium dyes, thiopyrylium dyes, croconium dyes, tetradehydopyocoline dyes, triphenylmethane dyes, aluminum dyes, and pyran dyes (pyrans, benzopyrans, chromones, coumarins, xanthenes).

[0143] Examples of the ultraviolet absorber include organic ones such as triazines, benzotriazoles, benzophenones, benzoxazines, and the ethylene compounds described in JP-A-2019-14707, and inorganic ones (particles) such as titanium oxide, zinc oxide, and cerium oxide. Among these, the ethylene compounds described in JP-A-2019-14707 are preferred because they are capable of correcting blue tones.

[0144] In addition to the above-mentioned components, the resin composition of the present invention may contain known components contained in general molding materials, such as an antioxidant, an antistatic agent, a release agent, a plasticizer, a fluorescent brightening agent, and an adhesive.

[0145] 2. Method for Producing Resin Composition The method for producing the resin composition of the present invention is not particularly limited as long as it is a method that can obtain a molten mixture by melt-mixing the above-mentioned components, but preferably includes a step of melt-mixing the above-mentioned cyanine dye and / or squarylium dye with a resin. A method for producing a resin composition that includes such a step also constitutes one aspect of the present invention.

[0146] The melt mixing is not particularly limited as long as it is a method that can heat and mix the above-mentioned cyanine dye and / or squarylium dye with the resin, and examples thereof include methods of mixing using known mixers, dispersers, kneaders, etc., such as a single-screw or multi-screw extruder, a blender, a mixer, or a kneader. Among these, extrusion melt kneading is preferred because it can uniformly mix the components. Of these, those equipped with a vacuum vent are more preferred. Another preferred method is to directly charge a thermoplastic resin powder or pellets and the dye into an injection molding machine. From the viewpoint of preventing oxidation during melt kneading, it is also preferred to seal the resin supply section with carbon dioxide gas or nitrogen gas.

[0147] The heating temperature during the melt mixing may be appropriately selected depending on the type of resin used, but when the resin contained in the resin composition is a thermoplastic resin having a melting point, a temperature equal to or higher than the melting point of the resin is preferred, for example, preferably 220 to 280°C, more preferably 230 to 270°C. When the resin contained in the resin composition is a thermoplastic resin without a melting point, the heating temperature is preferably 180 to 300°C, more preferably 200 to 280°C, and even more preferably 220 to 270°C. The heating temperature may be changed during heating, or may be changed in multiple stages.

[0148] The method for producing the resin composition may include other steps in addition to the melt-mixing step. For example, after the melt-mixing step, the molten mixture may be cooled and pulverized to obtain the resin composition of the present invention. The pulverization method is not particularly limited, and may be a known pulverization or granulation method.

[0149] Alternatively, after the melt mixing, the mixture may be discharged in the form of a strand (string) from the tip of the extruder, the strand may be cooled in a water tank or the like, and then introduced into a cutting machine (pelletizer) and cut, thereby obtaining a resin composition that is a pelletized molten mixture.

[0150] 3. Molded Article The present invention also includes a molded article obtained using the resin composition of the present invention. Since the molded article of the present invention is obtained using the resin composition described above, the dye does not deteriorate during molding and the molded article has good optical properties.

[0151] The molding method is not particularly limited, and examples thereof include known methods such as injection molding, extrusion molding, blow molding, compression molding, and vacuum molding. Alternatively, molding into a desired shape may be performed by a casting method, coating method, or other method. The molding conditions can be appropriately selected from known methods depending on the type of resin and the shape and dimensions of the molded product.

[0152] Among these, injection molding and extrusion molding are preferred because they provide excellent dimensional accuracy of the molded article. The injection molded article and extrusion molded article obtained using the above resin composition also constitute one aspect of the present invention.

[0153] The shape of the molded product is not particularly limited and may be appropriately selected depending on the purpose and application, and examples thereof include various shapes such as lens, sphere, rod, plate, column, cylinder, tube, fiber, film, sheet, etc. The molded product is preferably a pellet, lens, or sheet.

[0154] Alternatively, the resin composition may be melted to prepare pellets, and then the pellets may be used to form lenses, sheets, etc. The pellets may be prepared by the same method as the method for preparing the pellet-shaped resin composition described above.

[0155] 4. Method for Producing Molded Articles The method for producing the molded article is not particularly limited, but preferably includes a step of melt-mixing the above-described cyanine dye and / or squarylium dye with a resin, and a step of melt-molding the molten mixture. The melt-mixing step and the melt-molding step may be performed continuously, separately, or simultaneously. Such a method for producing a molded article, including a step of melt-mixing the above-described cyanine dye and / or squarylium dye with a resin, and a step of melt-molding the molten mixture, also constitutes one aspect of the present invention.

[0156] The step of melt-mixing the cyanine dye and / or squarylium dye with the resin may be the same as the melt-mixing step in the above-mentioned method for producing a resin composition.

[0157] The step of melt-molding the molten mixture includes the molding methods described above. Among them, the melt-molding is preferably injection molding or extrusion molding. Pellets of the resin composition may be used as the molten mixture.

[0158] The melt molding temperature may be set appropriately depending on the resin and dye used, but in order to obtain the required optical properties, in the case of a thermoplastic resin having a melting point, the temperature is preferably equal to or higher than the melting point, for example, preferably 220 to 280° C., more preferably 230 to 270° C. In the case of a thermoplastic resin without a melting point, the temperature is preferably 200 to 300° C., more preferably 220 to 270° C., and even more preferably 230 to 260° C.

[0159] An example of a case in which the melt-mixing step and the melt-molding step are carried out simultaneously is when the above-mentioned cyanine dye and / or squarylium dye and resin are supplied to a multi-screw extruder, an injection molding machine, or the like, and extrusion molding or injection molding is carried out. In the multi-screw extruder or injection molding machine, the dye and resin are supplied, heated and stirred, melt-mixed, and extrusion-molded or injection-molded to produce a molded article. When the dye and resin are supplied to the multi-screw extruder or injection molding machine, the dye and resin may be supplied separately, a dry blend of the dye and resin may be supplied, or pre-prepared pellets containing the dye and resin may be supplied. This embodiment is also one embodiment of the production method of the present invention.

[0160] The method for producing the molded article may further include a step of producing pellets by the melt-mixing step and the melt-molding step, and then molding the pellets into a lens or a sheet.

[0161] As described above, the resin composition and molded article of the present invention have good optical properties even when melt-molded. Therefore, the resin composition and molded article of the present invention are preferably used particularly for optical applications.

[0162] Preferred examples of the optical applications include optical lenses, optical filters, etc. Preferred embodiments of the molded article of the present invention will be described below.

[0163] (Optical Lens) The shape of the optical lens is not particularly limited, and may be appropriately selected from known shapes such as convex, concave, aspherical, etc. depending on the purpose and use. The thickness of the optical lens may be appropriately selected from known techniques depending on the purpose and use.

[0164] The content of the cyanine dye and / or squarylium dye in the optical lens may be adjusted as appropriate, but is preferably 0.01 to 2 g / m per unit area of ​​the lens surface. ２ , more preferably 0.02 to 1 g / m ２ is.

[0165] The optical lens may have an anti-reflection coating on at least one surface of the lens body molded using the resin composition of the present invention. The anti-reflection coating reflects light in the ultraviolet region and suppresses reflection of light in the visible region.

[0166] The antireflection film is not particularly limited, and examples thereof include known films such as a dielectric multilayer film and a moth-eye structure, among which a dielectric multilayer film is preferred because of its ease of handling. Examples of the dielectric multilayer film include a laminate in which high-refractive index material layers and low-refractive index material layers are alternately stacked.

[0167] Examples of the material for the high refractive index material layer include materials having a refractive index of 1.7 or more, and typically materials having a refractive index of 1.7 to 2.5. Examples of the material for the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; nitrides such as silicon nitride; mixtures of the above oxides or nitrides, and oxides doped with metals such as aluminum and copper or carbon (for example, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO)).

[0168] The low refractive index material layer may be made of a material having a refractive index of 1.6 or less, and typically has a refractive index of 1.2 to 1.6. Examples of the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0169] The lamination of each dielectric film is not particularly limited, and low refractive index dielectric films and high refractive index dielectric films may be alternately laminated directly on at least one surface of the optical lens by a known method such as CVD, sputtering, vacuum deposition, ion plating, or ion beam sputtering.

[0170] From the viewpoint of balancing cost and performance, the total number of the high refractive index material layers and the low refractive index material layers is preferably in the range of 3 to 11 layers, more preferably in the range of 3 to 9 layers, and even more preferably in the range of 5 to 7 layers.

[0171] The thickness of the antireflection film is preferably 0.05 to 1 μm, more preferably 0.08 to 0.7 μm, and even more preferably 0.1 to 0.5 μm.

[0172] An optical lens made using the above-described resin composition also constitutes one aspect of the present invention.

[0173] (Optical filter) Examples of optical filters include a filter in which a near-infrared absorbing layer made of the above-described resin composition is formed on a transparent substrate. Such an optical filter including a sheet made of the above-described resin composition also constitutes one aspect of the present invention.

[0174] The thickness of the near-infrared absorbing layer is not particularly limited, but from the viewpoint of handling and preventing environmental changes such as moisture absorption, it is preferably 30 to 1000 μm, more preferably 50 to 500 μm, and even more preferably 70 to 300 μm.

[0175] The optical filter may have an antireflection film on at least one surface. Examples of the antireflection film include the same antireflection films as those of the optical lenses described above. The thickness of the antireflection film in the optical filter is not particularly limited and can be adjusted as appropriate, but from the viewpoint of productivity, it is preferably 0.08 to 0.7 μm, more preferably 0.1 to 0.5 μm.

[0176] (Imaging element) An imaging element using the above-described optical lens is also one preferred embodiment of the present invention. The imaging element includes an optical lens group and a light receiving element. The optical lens group includes one or more lens elements, and at least one of the lens elements is an optical lens formed using the above-described resin composition of the present invention.

[0177] Examples of light receiving elements include elements that convert received light into an electrical signal, and specific examples include a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor.

[0178] The imaging element may further include an optical filter. By including an optical filter, it is possible to adjust the optical properties by absorbing near-infrared light. The optical filter is not particularly limited, and a known optical filter used in imaging elements can be used, but the optical filter using the resin composition of the present invention described above is preferred. An imaging element including such an optical lens and / or optical filter described above also constitutes one aspect of the present invention.

[0179] The imaging element may contain other components in addition to those described above. Examples of such other components include a cover glass. The imaging element may be assembled by a known method using an optical lens group, a light-receiving element, and, if necessary, any other components, for example, in the order of the cover glass, the optical lens group, and the light-receiving element from the light incident side.

[0180] Furthermore, a method for manufacturing an image sensor including an optical lens group and a light receiving element, the method including the steps of melt-mixing the above-described cyanine dye and / or squarylium dye with a resin, and melt-molding the molten mixture to manufacture an optical lens, is one of the preferred embodiments of the present invention.

[0181] The optical lens produced by melt-molding the molten mixture may be at least one of the optical lenses constituting the optical lens group. The present invention also provides a method for producing an image sensor including the optical lens group and a light-receiving element, the method including the steps of melt-mixing the cyanine dye and / or squarylium dye with a resin, and melt-molding the molten mixture to produce at least one of the optical lenses constituting the optical lens group.

[0182] The step of melt-mixing the dye and resin may be the same as the melt-mixing step in the above-mentioned method for producing a resin composition. The step of melt-molding the molten mixture to produce an optical lens may be the above-mentioned molding method. The method for producing an imaging element may further include other known steps that are performed in the production of a normal imaging element.

[0183] The present invention also provides a method for manufacturing an imaging element including an optical lens group, an optical filter, and a light-receiving element, the method including the steps of melt-mixing the above-described cyanine dye and / or squarylium dye with a resin, and melt-molding the molten mixture to manufacture at least one optical lens and / or optical filter that constitutes the optical lens group.

[0184] The step of melt-mixing the dye and resin and the step of producing the optical lens may each be the same as the steps described above.

[0185] The process of producing an optical filter by melt-molding the molten mixture includes, for example, a method of forming a near-infrared absorbing layer on a transparent substrate using the molten mixture, as described above. The method of forming the near-infrared absorbing layer is not particularly limited, and examples thereof include a method of extruding the molten mixture on a transparent substrate, a casting method, a coating method, etc.

[0186] The optical filter may have an anti-reflection film on at least one surface thereof. Examples of the anti-reflection film include the same anti-reflection films as those of the optical lenses described above.

[0187] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0188] (Example 1) (1) Production of Resin Composition 0.05 g of squarylium dye SQ1 and 500 g of polycarbonate resin were collected in a 10 L polyethylene bag and dry-blended to a uniform consistency. The resulting mixture was fed to a twin-screw extruder (manufactured by Technovel Co., Ltd., KZW15TW-45MG-NH(-700)) at a cylinder temperature setting of C1: 220 ° C, C2: 240 ° C, C3 to C6: 250 ° C, H1 / D1: 240 ° C, screw rotation speed: 150 rpm at a rate of 1.2 kg / hr. After discarding 200 g as a nose cutter, a string-like extrudate was obtained. The resulting string-like extrudate was cut using a pelletizer (manufactured by Isuzu Chemical Engineering Co., Ltd., SCF-100) to obtain cylindrical pellets with a diameter of approximately 2 mm and a length of 3 mm.

[0189] (2) Production of Molded Body The pellets obtained above were used in a compression molding machine (SFA-10, manufactured by Shinto Metal Industries Co., Ltd.) to produce a sheet-like molded body having a length of 60 mm to 100 mmφ and a thickness of approximately 0.20 to 0.50 mm. Specifically, a polyimide film was placed in the molding machine, and approximately 3 g of the resin composition was placed flat. Then, a polyimide film was placed on top, and a 0.25 mm shim plate was placed and pressurized. Pressurization was performed at a molding temperature of 205 ° C., with a primary pressure (1 MPa) of 120 seconds and a secondary pressure (9 MPa) of 60 seconds. The molded body was then removed from the molding machine, and the polyimide film adhering to both sides was removed to obtain a molded body (press sheet).

[0190] (3) Measurement of Absorbance (Weight Absorption Coefficient) The obtained molded body (thickness 0.3 to 1 mm) was cut into a 25 mm x 45 mm rectangle, and the weight absorption coefficient was measured using the following evaluation method. The results are shown in Table 1. FIG. 1 also shows the absorbance curve for the molded body of Example 1. The vertical axis represents absorbance (Abs), and the horizontal axis represents wavelength (nm). <Measurement of Absorbance (Weight Absorption Coefficient)> The absorbance of the obtained molded body was measured at wavelengths of 300 nm to 1100 nm using an ultraviolet-visible-near-infrared spectrophotometer (UV3600, manufactured by Shimadzu Corporation). The weight absorption coefficient was calculated using the following formula using the thickness of the measured object, the concentration of the dye added, and the specific gravity of the resin. A clear resin molded body made of the same resin but without the dye was used as a blank. The thickness was measured to the nearest 0.001 using a microgauge, and the last digit was rounded off. <Calculation formula for weight absorption coefficient> Weight absorption coefficient ε (g) = A / M / (T / 10000) Absorbance at λmax = A Thickness of measured object = T (μm) Concentration of added dye = M (g / L) λmax (maximum absorption wavelength) is the wavelength showing the maximum absorbance in the range of 600 nm to 1100 nm when absorbance measurement is performed using an ultraviolet-visible-near-infrared spectrophotometer.

[0191] Examples 2 to 11 Molded bodies were obtained and weight absorption coefficients were determined in the same manner as in Example 1, except that the dyes shown in Table 1 were used. The results are shown in Table 1.

[0192] Example 12: 0.05 g of squarylium dye SQ1 and 500 g of cycloolefin resin were placed in a 10 L polyethylene bag and dry-blended to achieve uniformity. The resulting mixture was fed into a twin-screw extruder (described above) at a cylinder temperature setting of C1: 200°C, C2: 220°C, C3-C6: 230°C, H1 / D1: 230°C, and a screw rotation speed of 150 rpm at a rate of 1.2 kg / hr. After discarding 200 g as a nose cutter, a string-like extrudate was obtained. The resulting string-like extrudate was cut using a pelletizer (described above) to obtain cylindrical pellets with a diameter of approximately 2 mm and a length of 3 mm. Using the resulting pellets, a sheet-like molded product was obtained in the same manner as in Example 1, and the weight absorption coefficient was determined. The results are shown in Table 1.

[0193] (Examples 13 to 26) Molded bodies were obtained and weight absorption coefficients were determined in the same manner as in Example 12, except that the resins and dyes shown in Table 1 were used. The results are shown in Table 1.

[0194] (Example 27) (1) Production of Resin Composition 0.025 g of squarylium dye SQ1 and 500 g of polycarbonate resin were collected in a 10 L polyethylene bag and dry-blended to a uniform consistency. The resulting mixture was fed into a twin-screw extruder (described above) at a cylinder temperature setting of C1: 220 ° C, C2: 240 ° C, C3 to C6: 250 ° C, H1 and D1: 240 ° C, and a screw rotation speed of 150 rpm at a rate of 1.2 kg / hr. After discarding 200 g as a nose cutter, a string-like extrudate was obtained. The resulting string-like extrudate was cut using a pelletizer (described above) to obtain cylindrical pellets with a diameter of approximately 2 mm and a length of 3 mm.

[0195] (2) Production of Molded Articles Using the pellets obtained above as raw materials, a plate-shaped molded article (injection-molded sheet) measuring 100 mm in length, 100 mm in width, and 1 mm in thickness was produced using an injection molding machine (NS40-5A, manufactured by Nissei Plastic Industrial Co., Ltd.). The conditions for the injection molding machine were as follows: Cylinder temperature C1: 260°C, C2 to C4: 260°C Nozzle temperature: 260°C Mold: 100 mm in length, 100 mm in width, 1 mm in depth, held at 100°C (cooled) for 30 seconds The obtained molded article was cut into a 25 mm x 45 mm rectangle, and the weight absorption coefficient was obtained in the same manner as in Example 1. The results are shown in Table 2.

[0196] (Examples 28 to 48) Molded bodies were obtained and weight absorption coefficients were determined in the same manner as in Example 27, except that the resins and dyes shown in Table 2 were used. The results are shown in Table 2.

[0197] (Comparative Examples 1 to 3) Molded bodies were obtained in the same manner as in Example 1, except that the resins and dyes shown in Table 2 were used, and the weight absorption coefficients were obtained. Note that, since absorption disappears when molded into a molded body, λmax in the comparative examples was determined by measuring the absorbance of an ethanol solution containing only the dye. The results obtained are shown in Table 2. Also, Figure 2 shows the absorbance curve for the molded body of Comparative Example 1. The vertical axis represents absorbance (Abs), and the horizontal axis represents wavelength (nm).

[0198] The resins and dyes in Tables 1 and 2 are shown below: (Resins) Polycarbonate resin (PC): Panlite (registered trademark) L1225WL (manufactured by Teijin Limited) Cycloolefin resin (COC): APEL (registered trademark) 5014CL (manufactured by Mitsui Chemicals, Inc.) Cycloolefin resin (COP): ZEONEX (registered trademark) K26R (Zeon Corporation)

[0199] (Dyes) Some of the dyes were synthesized by a general organic synthesis method, purified using a column to a purity of 99% or more, and then their molecular structures were confirmed by NMR. Squarylium dye SQ1

[0200]

[0201] Squarylium dye SQ2

[0202]

[0203] Squarylium dye SQ3

[0204]

[0205] Squarylium dye SQ4

[0206]

[0207] Cyanine dye CY1

[0208]

[0209] Cyanine dye CY2

[0210]

[0211] Cyanine dye CY3

[0212]

[0213] Cyanine dye CY4

[0214]

[0215] Cyanine dye CY5

[0216]

[0217] Cyanine dye CY6

[0218]

[0219] Cyanine dye CY7

[0220]

[0221] Cyanine dye D4773 (Tokyo Chemical Industry Co., Ltd.)

[0222]

[0223] Cyanine dye D5013 (Tokyo Chemical Industry Co., Ltd.)

[0224]

[0225] Cyanine dye I1026 (Tokyo Chemical Industry Co., Ltd.)

[0226]

[0227]

[0228]

[0229] From Tables 1 and 2, it was found that the resin compositions of the examples exhibited high weight absorption coefficients of 30 or more when melt mixed, had maximum absorption wavelengths (λmax) of approximately 700 to 900 nm, and exhibited desired optical properties, and therefore had excellent heat resistance.

Claims

1. A molten mixture comprising a cyanine dye and / or a squarylium dye and a resin, wherein the cyanine dye is a compound comprising a cation having a cyanine structure and an anion consisting of tetrakispentafluorophenylborate, and the cation having a cyanine structure is represented by the following formula (1): (In formula (1), X １ and X ２ are the same or different and each represents a sulfur atom, an oxygen atom, or -CR ａ R ｂ -. R ａ and R ｂ are the same or different and each represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, and R ａ and R ｂ may combine to form a ring structure. Y represents a group represented by Y １ or Y ２ . * represents the bonding site with the polymethine skeleton. R １ and R ６ are the same or different and each represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２ to R ５ and R ７ to R １２ are the same or different and each represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent.) represented by the structure, or at least one of the ends of the polymethine skeleton has the following formula (2): (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２２ to R ２７ are the same or different and each represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent. * represents the bonding site with the polymethine skeleton.) having the structure represented by, and the squarylium dye has a structure containing a nitrogen-containing conjugated system in which at least one of the structures added to the squaric acid moiety is composed of a 5-membered ring and a 6-membered ring, or a structure containing a nitrogen-containing conjugated system in which at least one of the structures added to the squaric acid moiety is composed of a 5-membered ring and a 6-membered ring via one conjugated carbon atom, A resin composition characterized by being a compound.

2. A molded article characterized by being formed using the resin composition according to claim 1.

3. An injection molded article characterized by being formed using the resin composition according to claim 1.

4. An extrusion molded article characterized by being formed using the resin composition according to claim 1.

5. An optical lens characterized by being formed using the resin composition according to claim 1.

6. An optical filter characterized by including a sheet formed using the resin composition according to claim 1.

7. An imaging device characterized by comprising the optical lens according to claim 5 and / or the optical filter according to claim 6.

8. A method for producing a resin composition, the production method including a step of melt-mixing a cyanine dye and / or a squarylium dye with a resin, the cyanine dye being a compound including a cation having a cyanine structure and an anion consisting of tetrakispentafluorophenylborate, the cation having a cyanine structure being represented by the following formula (1): (In formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or -CR ａ R ｂ -. R ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, and R ａ and R ｂ may combine to form a ring structure. Y represents a group represented by Y １ or Y ２ . * represents a bonding site with the polymethine skeleton. R １ and R ６ are the same or different and represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２ to R ５ and R ７ to R １２ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent.) represented structure, or at at least one end of the polymethine skeleton, the following formula (2): (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２２ to R ２７ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, either the same or different. * represents the bonding site with the polymethine skeleton.) having a structure represented by, and the squarylium dye has a structure containing a nitrogen-containing conjugated system in which at least one of the structures added to the squaric acid site is composed of a 5-membered ring and a 6-membered ring, or at least one of the structures added to the squaric acid site has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring via one conjugated carbon atom. A method for producing a resin composition, characterized in that it is a compound.

9. A method for manufacturing a molded article, the manufacturing method including a step of melt-mixing a cyanine dye and / or a squarylium dye with a resin, and a step of melt-molding the melt mixture, the cyanine dye being a compound including a cation having a cyanine structure and an anion consisting of tetrakispentafluorophenylborate, the cation having a cyanine structure being represented by the following formula (1): (In formula (1), X １ and X ２ are the same or different and represent a sulfur atom, an oxygen atom, or -CR ａ R ｂ -. R ａ and R ｂ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, and R ａ and R ｂ may combine to form a ring structure. Y represents a group represented by Y １ or Y ２ . * represents a bonding site with the polymethine skeleton. R １ and R ６ are the same or different and represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２ to R ５ and R ７ to R １２ are the same or different and represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent.).), or the following formula (2) at at least one end of the polymethine skeleton: (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２２ to R ２７ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, either the same or different. * represents a bonding site to the polymethine skeleton.) having a structure represented by the formula, and the squarylium dye has a structure in which at least one of the structures added to the squaric acid site contains a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring, or at least one of the structures added to the squaric acid site has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring via one conjugated carbon atom. A method for producing a molded article, characterized in that it is a compound.

10. The method for manufacturing a molded article according to claim 9, wherein the melt molding is injection molding or extrusion molding.

11. The method for manufacturing a molded article according to claim 9, wherein the molded article is a pellet, a lens, or a sheet.

12. The method for manufacturing a molded article according to claim 9, wherein the molded article is an optical lens.

13. The method for manufacturing a molded article according to claim 9, wherein the molded article is an optical filter.

14. A method for manufacturing an imaging device including an optical lens group and a light receiving element, the method including a step of melt-mixing a cyanine dye and / or a squarylium dye with a resin, and a step of melt-molding the melt mixture to manufacture at least one optical lens constituting the optical lens group, wherein the cyanine dye is a compound including a cation having a cyanine structure and an anion consisting of tetrakispentafluorophenylborate, and the cation having a cyanine structure is represented by the following formula (1): (In formula (1), X １ and X ２ are the same or different and each represents a sulfur atom, an oxygen atom, or -CR ａ R ｂ -. R ａ and R ｂ are the same or different and each represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, and R ａ and R ｂ may combine to form a ring structure. Y represents a group represented by Y １ or Y ２ . * represents a bonding site with the polymethine skeleton. R １ and R ６ are the same or different and each represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２ to R ５ and R ７ to R １２ are the same or different and each represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent.) or a structure represented by the following formula (2) at at least one end of the polymethine skeleton: (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２２ to R ２７ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, either identical or different. * represents the bonding site to the polymethine skeleton.) having a structure represented by, and the squarylium dye has a structure containing a nitrogen-containing conjugated system in which at least one of the structures added to the squaric acid site is composed of a 5-membered ring and a 6-membered ring, or at least one of the structures added to the squaric acid site has a structure containing a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring via one conjugated carbon atom. A method for manufacturing an imaging device, characterized in that it is a compound.

15. A method for manufacturing an image sensor including an optical lens group, an optical filter, and a light receiving element, the method including a step of melt-mixing a cyanine dye and / or a squarylium dye with a resin, and a step of melt-molding the melt mixture to manufacture at least one optical lens and / or an optical filter constituting the optical lens group, wherein the cyanine dye is a compound including a cation having a cyanine structure and an anion having a tetrakispentafluorophenyl borate, and the cation having a cyanine structure is represented by the following formula (1): (In formula (1), X １ and X ２ are the same or different and each represents a sulfur atom, an oxygen atom, or -CR ａ R ｂ -. R ａ and R ｂ are the same or different and each represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, and R ａ and R ｂ may be bonded to form a ring structure. Y represents a group represented by Y １ or Y ２ . * represents a bonding site with the polymethine skeleton. R １ and R ６ are the same or different and each represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２ to R ５ and R ７ to R １２ are the same or different and each represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent.) or a structure represented by the following formula (2) at at least one end of the polymethine skeleton: (In formula (2), R ２１ represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. R ２２ to R ２７ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group which may have a substituent, either the same or different. * represents the bonding site to the polymethine skeleton.) having a structure represented by, and the squarylium dye has a structure in which at least one of the structures added to the squaric acid site includes a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring, or at least one of the structures added to the squaric acid site has a structure including a nitrogen-containing conjugated system composed of a 5-membered ring and a 6-membered ring via one conjugated carbon atom. A method for manufacturing an imaging device, characterized in that it is a compound.

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