Resin composition, method for producing the same, use thereof, method for producing molded body, and method for producing imaging element

Abstract

The present invention aims to provide a resin composition which is a melt mixture of a near-infrared absorbing dye and a resin, and which can produce a molded body having good optical properties even when melt-molded. The present invention is a resin composition characterized by being a melt mixture of a resin and a cyanine dye and / or a squarylium cyanine dye, the cyanine dye being a compound containing a cation composed of a cyanine structure and an anion composed of tetra(pentafluorophenyl)borate, the cation composed of a cyanine structure having a specific structure or having a specific structure at at least one terminal of a polymethine skeleton, the squarylium cyanine dye being a compound having the following structure: at least one of the structures attached to the squarylium site contains a nitrogen-containing conjugated system composed of a five-membered ring and a six-membered ring; or, at least one of the structures attached to the squarylium site contains a nitrogen-containing conjugated system composed of a five-membered ring and a six-membered ring via one conjugated carbon.

Description

Technical Field

[0001] This invention relates to resin compositions. More specifically, it relates to resin compositions that can produce molded articles with good optical properties even when melt-molded, methods for manufacturing the same, uses thereof, methods for manufacturing molded articles, and methods for manufacturing imaging elements. Background Technology

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

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

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2015-172102

[0007] Patent Document 2: Japanese Patent Application Publication No. 2021-102756 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, the heat resistance of conventionally used resin compositions is insufficient. While it is possible to obtain molded articles with good optical properties by coating a resin composition containing near-infrared absorbing dyes onto a substrate and drying it to form a film, a problem arises when the resin composition is melt-molded: the near-infrared absorbing dyes cannot withstand the melting temperature and deteriorate, resulting in molded articles with good optical properties. In particular, there is a need for a molten mixture of dye and resin that does not deteriorate during injection molding (such as lens molding), extrusion molding (such as film molding), or sheet molding, thus ideally producing molded articles with good optical properties.

[0010] The present invention was made in view of the above-mentioned situation, and its object is to provide a resin composition comprising a near-infrared absorbing dye (cyanine dye and / or squaric acid cyanine dye) and a resin, which can produce molded articles with good optical properties even when used for melt molding.

[0011] Methods for solving problems

[0012] In order to solve the above-mentioned problems, the inventors conducted various studies on resin compositions containing near-infrared absorbing dyes and resins, and found that by including specific near-infrared absorbing dyes (cyanine dyes and / or squaric acid cyanine dyes) and resins, a resin composition that can achieve good optical properties even as a melt mixture was obtained, thus completing the present invention.

[0013] That is, the present invention includes the following methods.

[0014] <1> A resin composition characterized in that it comprises a molten mixture of a resin and a cyanine dye and / or a squaric acid cyanine dye, the cyanine dye being a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, the cyanine cation having a structure represented by formula (1) or having a structure represented by formula (2) at at least one end of a polymethyl skeleton.

[0015] [Chemical Formula 1]

[0016] (In formula (1), X) 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -. R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can bond together to form a ring structure. Y represents Y 1 Or Y 2 The group indicated. Indicates the site where it is bonded to the polymethyl backbone. R 1 and R 6 Same or different, representing a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 2 ~R 5 and R 7 ~R 12 "Same or different" indicates hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0017] [Chemical Formula 2]

[0018] (In equation (2), R) 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 22 ~R 27Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. This indicates the site where the compound is bonded to the polymethyl backbone.

[0019] The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

[0020] <2> A molded body, characterized in that it uses the above-mentioned <1> It is formed from the resin composition described above.

[0021] <3> An injection-molded article, characterized in that it uses the above-mentioned <1> It is formed from the resin composition described above.

[0022] <4> An extruded molded article, characterized in that it uses the above-mentioned <1> It is formed from the resin composition described above.

[0023] <5> An optical lens, characterized in that it uses the above-mentioned <1> It is formed from the resin composition described above.

[0024] <6> An optical filter, characterized in that it comprises using the above-mentioned... <1> The sheet is formed from the resin composition described above.

[0025] <7> A camera element, characterized in that it comprises the above-mentioned <5> The optical lens and / or the above-mentioned <6> The aforementioned optical filter.

[0026] <8> A method for manufacturing a resin composition, characterized in that the method includes a step of melt mixing the resin with a cyanine dye and / or a squaric acid cyanine dye, the cyanine dye being a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, the cyanine cation having a structure represented by formula (1) below, or having a structure represented by formula (2) below at at least one end of a polymethyl skeleton.

[0027] [Chemical Formula 3]

[0028] (In formula (1), X) 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -. R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, Ra With R b They can bond together to form a ring structure. Y represents Y 1 Or Y 2 The group indicated. Indicates the site where it is bonded to the polymethyl backbone. R 1 and R 6 Same or different, representing a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 2 ~R 5 and R 7 ~R 12 "Same or different" indicates hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0029] [Chemical Formula 4]

[0030] (In equation (2), R) 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. This indicates the site where the compound is bonded to the polymethyl backbone.

[0031] The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

[0032] <9> A method for manufacturing a molded article, characterized in that the method comprises: a step of melt mixing a resin with a cyanine dye and / or a squaric acid cyanine dye, and a step of melt molding the molten mixture, wherein the cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has a structure represented by the following formula (1) or has a structure represented by the following formula (2) at at least one end of a polymethyl skeleton.

[0033] [Chemical Formula 5]

[0034] (In formula (1), X) 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -. R a and R bSame or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can bond together to form a ring structure. Y represents Y 1 Or Y 2 The group indicated. Indicates the site where it is bonded to the polymethyl backbone. R 1 and R 6 Same or different, representing a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 2 ~R 5 and R 7 ~R 12 "Same or different" indicates hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0035] [Chemical Formula 6]

[0036] (In equation (2), R) 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. This indicates the site where the compound is bonded to the polymethyl backbone.

[0037] The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

[0038] <10> As mentioned above <9> The method for manufacturing the molded body is characterized in that the melt molding is injection molding or extrusion molding.

[0039] <11> As mentioned above <9> or <10> The method for manufacturing the molded body is characterized in that the molded body is a particle, a lens, or a sheet.

[0040] <12> As mentioned above <9> or <10> The method for manufacturing the molded body is characterized in that the molded body is an optical lens.

[0041] <13> As mentioned above <9> or <10> The method for manufacturing the molded body is characterized in that the molded body is an optical filter.

[0042] <14> A method for manufacturing an imaging element comprising an optical lens group and a light receiving element, characterized in that the manufacturing method includes: a step of moltenly mixing a resin with a cyanine dye and / or a squaric acid cyanine dye; and a step of melting and molding the molten mixture to manufacture at least one optical lens constituting the optical lens group, wherein the cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has a structure represented by formula (1) below or has a structure represented by formula (2) below at at least one end of a polymethyl skeleton.

[0043] [Chemical Formula 7]

[0044] (In formula (1), X) 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -. R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can bond together to form a ring structure. Y represents Y 1 Or Y 2 The group indicated. Indicates the site where it is bonded to the polymethyl backbone. R 1 and R 6 Same or different, representing a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 2 ~R 5 and R 7 ~R 12 "Same or different" indicates hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0045] [Chemical Formula 8]

[0046] (In equation (2), R) 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. This indicates the site where the compound is bonded to the polymethyl backbone.

[0047] The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

[0048] <15> A method for manufacturing an imaging element comprising an optical lens group, an optical filter, and a light receiving element, characterized in that the manufacturing method includes: a step of moltenly mixing a resin with a cyanine dye and / or a squaric acid cyanine dye; and a step of melting and 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 comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has a structure represented by formula (1) below or has a structure represented by formula (2) below at at least one end of a polymethyl skeleton.

[0049] [Chemical Formula 9]

[0050] (In formula (1), X) 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -. R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can bond together to form a ring structure. Y represents Y 1 Or Y 2 The group indicated. Indicates the site where it is bonded to the polymethyl backbone. R 1 and R 6 Same or different, representing a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 2 ~R 5 and R 7 ~R 12 "Same or different" indicates hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0051] [Chemical Formula 10]

[0052] (In equation (2), R) 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R 22 ~R27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. This indicates the site where the compound is bonded to the polymethyl backbone.

[0053] The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

[0054] Invention Effects

[0055] The resin composition of the present invention can produce molded articles with good optical properties even when used for melt molding. Attached Figure Description

[0056] Figure 1 This is a graph showing the absorbance curve of the molded body of Example 1.

[0057] Figure 2 This is a graph showing the absorbance curve of the molded body of Comparative Example 1. Detailed Implementation

[0058] The present invention will be described in detail below.

[0059] It should be noted that combining two or more of the preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0060] 1. Resin composition

[0061] The present invention is a resin composition comprising a resin and a cyanine dye and / or a squaric acid cyanine dye, characterized in that the cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has a structure represented by formula (1) above or has a structure represented by formula (2) above at at least one end of a polymethyl skeleton, and the squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

[0062] As described above, the resin composition of the present invention, by comprising specific dyes and resins, can produce molded articles with good optical properties even during melt molding. The reason for this effect is presumably that the specific dyes contained in the resin composition of the present invention have a robust backbone and strong binding force between cationic and anionic species, making them less prone to dissociation even when heated at high temperatures.

[0063] The resin composition of the present invention comprises a molten mixture of resin and cyanine dye and / or squaric acid cyanine dye. In the present invention, a molten mixture refers to a substance formed by heating the mixture of resin and cyanine dye and / or squaric acid cyanine dye to a temperature above the melting point of the resin, thereby uniformly melting and mixing the components.

[0064] Regarding the above-mentioned melt mixing, when the resin contained in the resin composition of the present invention is a thermoplastic resin having a melting point as determined by differential scanning calorimetry (DSC), it means mixing at a temperature above its melting point; when the resin is a thermoplastic resin not having a melting point as determined by DSC, it means mixing at a temperature 80°C or higher than the glass transition temperature determined by DSC.

[0065] It should be noted that the DSC determination was performed according to the method specified in JIS K 7121:2012.

[0066] From the viewpoint of the use 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-mentioned melting point, the melting point is preferably 200°C or higher and 260°C or lower, more preferably 220°C or higher and 255°C or lower. When the resin is a thermoplastic resin not having the above-mentioned melting point, its 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.

[0067] (Cyan dye)

[0068] The cyanine dyes used in this invention are compounds comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion.

[0069] The cations composed of cyanine structures described above have the structure represented by formula (1) (structure A1) or have the structure represented by formula (2) (structure A2) at at least one end of the polymethyl skeleton.

[0070] (Structure A1)

[0071] In the above formula (1), X 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -. Ra and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can bond together to form a ring structure.

[0072] As a result of R a and R b Examples of halogen atoms that can be represented include fluorine, chlorine, bromine, and iodine atoms. Among these, fluorine and chlorine atoms are preferred from the perspective of easy availability of dyes and low absorption of visible light, and chlorine atoms are further preferred from the perspective of ease of handling during synthesis.

[0073] From the perspective of improving the solubility of dyes in thermoplastic resins, R a and R b The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6.

[0074] As a result of R a and R b The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0075] As a result of R a and R b The aliphatic hydrocarbon group may have substituents, such as halogen atoms such as fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being preferred, and chlorine atoms being even more preferred.

[0076] By R a and R b The aliphatic hydrocarbon group represented preferably does not have substituents.

[0077] R a With R b The bonded ring structure can be a single ring or a multi-ring structure. The ring structure can be an alicyclic ring, an aromatic ring, or a fused ring of these. Preferably, the ring structure is a five- to eighteen-membered ring, more preferably a five- to twelve-membered ring, and even more preferably a five- to six-membered ring.

[0078] Among them, considering higher heat resistance, X is preferred. 1 and X 2 The same or different, consisting of oxygen atoms, sulfur atoms, or -CR a R b -(R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, Ra and R b At least one of them represents an aliphatic hydrocarbon group.

[0079] The above-mentioned -CR a R b -in, R a and R b All are preferably aliphatic hydrocarbon groups with or without substituents, and more preferably aliphatic hydrocarbon groups.

[0080] The above X 1 and X 2 More preferably the same.

[0081] In the above formula (1), Y is the product of Y 1 Or Y 2 The group represented by Y. 1 and Y 2 The expression in Indicates the site where it is bonded to the polymethyl backbone. Y 1 and Y 2 front end of The carbon atoms at the sites where the line segments are bonded are bonded to the polymethyl skeleton. Therefore, the structure represented by the above formula (1) is preferably the structure represented by the following formula (1a) or (1b).

[0082] [Chemical Formula 11]

[0083] (where R is in the formula) 1 ~R 12 Same as equation (1).

[0084] In the above formula (1), considering the high heat resistance, X is preferred. 1 and X 2 It is an oxygen atom or a sulfur atom, and Y is Y 2 That is, preferably, the structure represented by the above formula (1) is represented by the above formula (1b), in which X 1 and X 2 It consists of oxygen or sulfur atoms.

[0085] In equation (1) above, R 1 and R 6 Same or different, indicating hydrogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0086] By R 1 and R 6 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 4.

[0087] As a result of R1 and R 6 The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0088] As a result of R 1 and R 6 The aliphatic hydrocarbon group may have substituents, such as halogen atoms such as fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being preferred, and chlorine atoms being more preferred.

[0089] By R 1 and R 6 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0090] Among them, R is preferred. 1 and R 6 Whether the groups are the same or different, they are all aliphatic hydrocarbon groups with or without substituents, and more preferably aliphatic hydrocarbon groups.

[0091] R 1 and R 6 The same is preferred.

[0092] In equation (1) above, R 2 ~R 5 and R 7 ~R 10 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0093] By R 2 ~R 5 and R 7 ~R 10 The halogen atoms represented can be exemplified by R mentioned above. a The halogen atom represented is the same halogen atom. Among them, chlorine atom is preferred from the perspective of higher heat resistance.

[0094] By R 2 ~R 5 and R 7 ~R 10 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 4.

[0095] Additionally, by R 2 ~R 5 and R 7 ~R 10 The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0096] As a result of R2 ~R 5 and R 7 ~R 10 The aliphatic hydrocarbon group may have substituents, such as halogen atoms such as fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being preferred, and chlorine atoms being more preferred.

[0097] By R 2 ~R 5 and R 7 ~R 10 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0098] Among them, R is preferred. 2 ~R 5 and R 7 ~R 10 Whether the atoms are the same or different, they are hydrogen atoms or aliphatic hydrocarbon groups with or without substituents, more preferably hydrogen atoms or aliphatic hydrocarbon groups.

[0099] R 2 ~R 5 In the presence of hydrogen atoms, preferably 0 or 1 aliphatic hydrocarbon groups with or without substituents.

[0100] R 7 ~R 10 In the presence of hydrogen atoms, preferably 0 or 1 aliphatic hydrocarbon groups with or without substituents.

[0101] In the above formula (1), R is preferred. 2 With R 7 R 3 With R 8 R 4 With R 9 R 5 With R 10 They are the same.

[0102] In equation (1) above, R 11 and R 12 "Same" or "different" indicates the presence or absence of substituents in hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups, whether or not they have substituents. As a group composed of R... 11 and R 12 The halogen atom represented, and the aliphatic hydrocarbon group with or without substituents, can be exemplified by R. 2 The same group represents a halogen atom, an aliphatic hydrocarbon group with or without substituents. Preferably, R... 11 and R 12 Whether the atoms are the same or different, they are halogen atoms, more preferably chlorine atoms. Additionally, R... 11 and R 12 The same is preferred.

[0103] (Structure A2)

[0104] In equation (2) above, R 21 It represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents.

[0105] By R 21 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6.

[0106] By R 21 The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0107] As a result of R 21 The aliphatic hydrocarbon group may have substituents, preferably halogen atoms such as fluorine, chlorine, bromine, and iodine. Among these, fluorine and chlorine atoms are more preferred, and chlorine atoms are even more preferred.

[0108] By R 21 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0109] Among them, R 21 Preferably, it is an aliphatic hydrocarbon group with or without substituents, and more preferably an aliphatic hydrocarbon group.

[0110] In equation (2) above, R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents.

[0111] By R 22 ~R 27 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 4.

[0112] By R 22 ~R 27 The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0113] As a result of R 22 ~R 27 The aliphatic hydrocarbon group may have substituents, preferably halogen atoms such as fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being more preferred, and chlorine atoms being even more preferred.

[0114] By R 22 ~R 27 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0115] Among them, R is preferred. 22 ~R 27 Whether the atoms are the same or different, they are hydrogen atoms or aliphatic hydrocarbon groups with or without substituents, more preferably hydrogen atoms or aliphatic hydrocarbon groups.

[0116] R 22 ~R 27 In this configuration, preferably 0 or 1 aliphatic hydrocarbon groups, with the remainder being hydrogen atoms.

[0117] In the above formula (2), This indicates the site where the compound is bonded to the polymethyl backbone. That is, the leading edge band in formula (2) The carbon atoms at the sites where the line segments are bonded are bonded to the polymethyl skeleton ([-CH=CH-CH2-]n). The above structure A2 only needs to have the above formula (2) at at least one end of the polymethyl skeleton, and preferably has the structure represented by the above formula (2) at both ends of the polymethyl skeleton.

[0118] As a cation having the structure A2 represented by the above formula (2) at at least one end of the above polymethyl skeleton, the cation represented by the following formula (2a) is preferably exemplified.

[0119] [Chemical Formula 12]

[0120] (where R is in the formula) 21 ~R 27 Same or different, same as above; R a1 With R 21 Same, R a2 ~R a7 Same or different, with R 22 ~R 27 same.)

[0121] The aforementioned cyanine dyes can be synthesized using conventional organic synthesis methods, such as those known for the synthesis of cyanine dyes. Preferably, they can be identified and obtained by confirming their molecular structure using NMR after column purification to a purity of 99% or higher. Alternatively, commercially available products can also be used.

[0122] (Square cyanine dye)

[0123] The squaric acid cyanine dye used in this invention is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

[0124] Squamousine dye is a compound represented by the following formula (3), where the squamous acid site is the site indicated in [] of the formula (3).

[0125] [Chemical Formula 13]

[0126] In equation (3), R 31 With R 32 The same or different indicates an organic group, equivalent to the structural part attached to the aforementioned squaric acid site. R 31 and R 32 At least one of them is a structure comprising a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring (hereinafter also referred to as "structure B1"), or represents a structure comprising a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon (hereinafter also referred to as "structure B2").

[0127] (Structure B1)

[0128] In the above-mentioned structure comprising a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring, the nitrogen atom may be contained in the five-membered ring, or in the six-membered ring, or in both the five-membered ring and the six-membered ring, preferably in the five-membered ring.

[0129] The number of five-membered and six-membered rings constituting the above-mentioned nitrogen-containing conjugated system is not particularly limited, but the above-mentioned nitrogen-containing conjugated system is preferably composed of one five-membered ring and one six-membered ring. As examples of the above-mentioned nitrogen-containing conjugated system, there is configuration 1 in which the six-membered ring and the five-membered ring are arranged relative to the squaric acid site, and configuration 2 in which the five-membered ring and the six-membered ring are arranged relative to the squaric acid site.

[0130] Examples of nitrogen-containing conjugated systems composed of five-membered and six-membered rings include structures that are monovalent by removing one hydrogen atom from indole, indoline, indoleazine, isoindole, indazole, imidazole, benzimidazole, benzotriazole and their derivatives.

[0131] Among them, the structure represented by formula (3a), the structure represented by formula (3b), and the structure represented by formula (3c) are preferred as the nitrogen-containing conjugated system composed of five-membered rings and six-membered rings, and the structure represented by formula (3a) is more preferred.

[0132] [Chemical Formula 14]

[0133] (In equation (3a), R) a1 ~R a6 Same or different, representing hydrogen atoms, aliphatic hydrocarbon groups with or without substituents, or -NH-CO-R a7 The group indicated by R.a7 This indicates an aliphatic hydrocarbon group with or without substituents. This indicates the site where the squaric acid is bonded.

[0134] [Chemical Formula 15]

[0135] (In equation (3b), R) b1 ~R b6 Same or different, representing hydrogen atoms, or aliphatic hydrocarbon groups with or without substituents. n represents 0 or 1. This indicates the site where the squaric acid is bonded.

[0136] [Chemical Formula 16]

[0137] (In equation (3c), R) c1 ~R c5 Same or different, representing hydrogen atoms, aliphatic hydrocarbon groups with or without substituents, or -NR c6 R c7 The group indicated by R. c6 and R c7 Same or different indicates whether the aliphatic hydrocarbon group has or does not have substituents. This indicates the site where the squaric acid is bonded.

[0138] In the above equation (3a), R a1 ~R a6 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 4.

[0139] By R a1 ~R a6 The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0140] As R a1 ~R a6 The aliphatic hydrocarbon group may have substituents, preferably halogen atoms such as fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being more preferred, and chlorine atoms being even more preferred.

[0141] By R a1 ~R a6 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0142] By R a7 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 8.

[0143] By R a7 The aliphatic hydrocarbon group represented is preferably an alkyl group.

[0144] As a result of R a7 The aliphatic hydrocarbon group represented may have substituents, and examples of substituents related to the R group mentioned above can be given. a1 ~R a6 The aliphatic hydrocarbon group represented may have the same substituents. Among these, fluorine atoms and chlorine atoms are more preferred, and chlorine atoms are even more preferred. (From R) a7 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0145] Among them, R is preferred. a1 ~R a6 The same or different, is a hydrogen atom or an aliphatic hydrocarbon group with or without substituents, more preferably a hydrogen atom or an aliphatic hydrocarbon group, and even more preferably a hydrogen atom or an alkyl group.

[0146] In addition, R is particularly preferred. a1 ~R a3 Same or different, alkyl, R a4 and R a6 Same or different, hydrogen atom or alkyl group, R a5 -NH-CO-R a7 The group to be represented.

[0147] The bonds represented by the dashed and solid lines in equation (3a) above include both single and double bonds. When the structure represented by equation (3a) is bonded to the squaric acid site represented by equation (3), the positions of the single and double bonds may sometimes change due to resonance.

[0148] The keys represented by the dashed lines and solid lines in equations (3b) and (3c) above are the same.

[0149] The structure represented by the above formula (3a) includes structures in a resonance relationship. Specifically, it preferably includes at least one of the structures represented by formula (3a-1) and formula (3a-2).

[0150] [Chemical Formula 17]

[0151] (R in equation (3a-1)) a1 ~R a6 R in equation (3a) respectively a1 ~R a6 same. This indicates the site where the squaric acid is bonded.

[0152] [Chemical Formula 18]

[0153] (R in equation (3a-2)) a1 ~R a6 R in equation (3a) respectively a1 ~R a6 same. This indicates the site where the squaric acid is bonded.

[0154] In equation (3b) above, R b1 ~R b6 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 4.

[0155] By R b1 ~R b6 The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0156] As R b1 ~R b6 The aliphatic hydrocarbon group may have substituents, preferably halogen atoms such as fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being more preferred, and chlorine atoms being even more preferred.

[0157] By R b1 ~R b6 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0158] Among them, R is preferred. b1 ~R b6 The same or different, is a hydrogen atom or an aliphatic hydrocarbon group with or without substituents, more preferably a hydrogen atom or an aliphatic hydrocarbon group, and even more preferably a hydrogen atom or an alkyl group.

[0159] The structure represented by the above formula (3b) includes structures in a resonance relationship. Specifically, it preferably includes at least one of the structures represented by formula (3b-1) and formula (3b-2).

[0160] [Chemical Formula 19]

[0161] (R in equation (3b-1)) b1 ~R b5 R in equation (3b) respectively b1 ~R b5 same. This indicates the site where the squaric acid is bonded.

[0162] [Chemical Formula 20]

[0163] (R in equation (3b-2)) b1 ~R b6 R in equation (3b) respectively b1 ~R b6 same. This indicates the site where the squaric acid is bonded.

[0164] In the above equation (3c), R c1 ~R c5 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 8.

[0165] By R c1 ~R c5 The aliphatic hydrocarbon group represented is preferably alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and even more preferably methyl.

[0166] As R c1 ~R c5 The aliphatic hydrocarbon group may have substituents, preferably halogen atoms such as fluorine, chlorine, bromine, and iodine, with fluorine and chlorine atoms being more preferred, and chlorine atoms being even more preferred.

[0167] By R c1 ~R c5 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0168] R c5 Hydrogen atoms are preferred.

[0169] R c6 and R c7 Same or different indicates whether the aliphatic hydrocarbon group has or does not have substituents.

[0170] By R c6 and R c7 The aliphatic hydrocarbon group represented preferably has 1 to 18 carbon atoms, more preferably 1 to 16, and even more preferably 1 to 12.

[0171] By R c6 and R c7 The aliphatic hydrocarbon group represented is preferably alkyl, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.

[0172] As R c6 and R c7 The aliphatic hydrocarbon group represented may have substituents, and examples of substituents related to the R group mentioned above can be given. c1 ~R c5 The aliphatic hydrocarbon group can have the same substituents as the group.

[0173] By R c6 and R c7 The aliphatic hydrocarbon group represented preferably does not have substituents.

[0174] The structure represented by the above formula (3c) includes a structure in a resonance relationship. Specifically, it preferably includes at least one of the structures represented by formula (3c-1) and formula (3c-2).

[0175] [Chemical Formula 21]

[0176] (R in equation (3c-1)) c1 ~R c5 R in equation (3c) respectively c1 ~R c5 same. This indicates the site where the squaric acid is bonded.

[0177] [Chemical Formula 22]

[0178] (R in equation (3c-2)) c1 ~R c5 R in equation (3c) respectively c1 ~R c5 same. This indicates the site where the squaric acid is bonded.

[0179] As a squaric acid cyanine dye having the above-described structure B1, R in formula (3) above is preferred. 31 and R 32 The organic groups represented may be the same or different, and are compounds having the structures represented by formulas (3a), (3b) or (3c) above; more preferably, R in formula (3) above. 31 and R 32 The organic group represented is a compound having the structure represented by formula (3a) above.

[0180] (Structure B2)

[0181] The aforementioned structure B2 comprises a nitrogen-containing conjugated system consisting of five-membered and six-membered rings via a conjugated carbon atom. That is, it is a structure in which a nitrogen-containing conjugated system consisting of five-membered and six-membered rings is bonded to a conjugated carbon atom at the squaric acid site.

[0182] The term "via a conjugated carbon" refers to the presence of a conjugated carbon, i.e., -CR= or =CR-, between the squaric acid site and the nitrogen-containing conjugated system composed of five-membered and six-membered rings.

[0183] As a nitrogen-containing conjugated system composed of five-membered and six-membered rings, a structure identical to structure B1 described above can be cited. That is, as a nitrogen-containing conjugated system composed of five-membered and six-membered rings, for example, a structure that becomes monovalent by removing one hydrogen atom from indole, indoline, indoleazine, isoindole, indazole, imidazole, benzimidazole, benzotriazole and their derivatives can be cited.

[0184] As the nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon, the structure represented by the following formulas (4a), (4b) or (4c) is preferably exemplified.

[0185] [Chemical Formula 23]

[0186] (In equation (4a), R) a1 ~R a6 Same or different, representing hydrogen atoms, aliphatic hydrocarbon groups with or without substituents, or -NH-CO-R a7 The group indicated by R. a7 Indicates an aliphatic hydrocarbon group with or without substituents. R a8 It represents an alkyl group having 1 to 12 hydrogen atoms or carbon atoms. This indicates the site where the squaric acid is bonded.

[0187] [Chemical Formula 24]

[0188] (In equation (4b), R) b1 ~R b6 Same or different, representing a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents. R b7 This indicates an alkyl group with 1 to 16 hydrogen atoms or carbon atoms. n represents 0 or 1. This indicates the site where the squaric acid is bonded.

[0189] [Chemical Formula 25]

[0190] (In equation (4c), R) c1 ~R c5 Same or different, representing hydrogen atoms, aliphatic hydrocarbon groups with or without substituents, or -NR c6 R c7 The group indicated by R. c6 and R c7 Same or different indicates whether an aliphatic hydrocarbon group has or does not have substituents. R c8 It represents an alkyl group having 1 to 12 hydrogen atoms or carbon atoms. This indicates the site where the squaric acid is bonded.

[0191] R in the above equation (4a) a1 ~R a6 Examples of R that correspond to R in equation (3a) above can be given. a1 ~R a6 Same group.

[0192] R in equation (4a) above a8 Preferably, it is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom.

[0193] Equation (4a) above includes structures in a resonance relationship, and more preferably includes at least one of the structures represented by equation (4a-1) and equation (4a-2).

[0194] [Chemical Formula 26]

[0195] (R in equation (4a-1)) a1 ~R a6 and R a8 R in equation (4a) respectively a1 ~R a6 and R a8 same. This indicates the site where the squaric acid is bonded.

[0196] [Chemical Formula 27]

[0197] (R in equation (4a-2)) a1 ~R a6 and R a8 R in equation (4a) respectively a1 ~R a6 and R a8 same. This indicates the site where the squaric acid is bonded.

[0198] R in the above equation (4b) b1 ~R b6 Examples of R related to equation (3b) can be given. b1 ~R b6 Same group.

[0199] R in the above equation (4b) b7 Examples of alkyl groups with 1 to 16 carbon atoms include hydrogen atoms, with alkyl groups with 1 to 12 carbon atoms being more preferred.

[0200] Equation (4b) above includes structures in a resonance relationship, and more preferably includes at least one of the structures represented by equation (4b-1) and equation (4b-2).

[0201] [Chemical Formula 28]

[0202] (R in equation (4b-1)) b1 ~R b7 R in equation (4b) respectively b1 ~R b7 same. This indicates the site where the squaric acid is bonded.

[0203] [Chemical Formula 29]

[0204] R in equation (4b-2) b1 ~R b5 and R b7 R in equation (4b) respectively b1 ~R b5 and R b7 same. This indicates the site where the squaric acid is bonded.

[0205] R in the above equation (4c) c1 ~R c5 Examples of R related to equation (3c) can be given. c1 ~R c5 Same group.

[0206] R in the above equation (4c) c8 Examples of such examples include alkyl groups having 1 to 12 carbon atoms or hydrogen atoms, with hydrogen atoms being a preferred example.

[0207] The above formula (4c) includes structures in a resonance relationship. Specifically, it preferably includes at least one of the structures represented by formula (4c-1) and formula (4c-2).

[0208] [Chemical Formula 30]

[0209] (R in equation (4c-1)) c1 ~R c5 and R c8 R in equation (4c) respectively c1 ~R c5 and R c8 same. This indicates the site where the squaric acid is bonded.

[0210] [Chemical Formula 31]

[0211] R in equation (4c-2) c1 ~R c5 and R c8 R in equation (4c) respectively c1 ~R c5 and R c8 same. This indicates the site where the squaric acid is bonded.

[0212] As a squaric acid cyanine dye having the above-described structure B2, R in formula (3) above is preferred. 31 and R 32 The organic groups represented may be the same or different, and are compounds having the structures represented by formulas (4a), (4b) or (4c) above; more preferably, R in formula (3) above. 31 and R 32 The organic group represented is a compound having the structure represented by formula (4b) above.

[0213] The aforementioned squaricine dyes can be synthesized using conventional organic synthesis methods, such as those known for the synthesis of squaricine dyes. Preferably, they can be identified and obtained by confirming their molecular structure using NMR after column purification to a purity of 99% or higher. Alternatively, commercially available products can also be used.

[0214] The maximum absorption wavelength of the above-mentioned squaric acid cyanine dye is preferably in the range of 690-750 nm, more preferably in the range of 700-745 nm, and even more preferably in the range of 705-740 nm.

[0215] The maximum absorption wavelength of the above-mentioned cyanine dye is preferably 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.

[0216] In this invention, the above-mentioned cyanine dyes and squaric acid cyanine dyes may contain only one type or two or more types.

[0217] The content of the above-mentioned cyanine dye and / or squaric acid cyanine dye in the resin composition of the present invention is not particularly limited, and can be appropriately selected according to the thickness of the molded article, etc. In 100% by mass of the resin composition of the present invention, it is preferably 0.005 to 3% by mass, more preferably 0.01 to 2% by mass, and even more preferably 0.02 to 1.5% by mass.

[0218] (resin)

[0219] The resin contained in the resin composition of the present invention is not particularly limited, but a thermoplastic resin is preferred from the viewpoint that it can easily form a melt mixture with the above-mentioned dyes.

[0220] Examples of the aforementioned thermoplastic resins 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, fluoropolymers, cellulose derivatives, and polyurethane resins. Only one type may be used, or two or more may be used in combination. Among these, considering good optical properties, heat resistance, and processability, cycloolefin resins and polycarbonate resins are preferred, with cycloolefin resins being more preferred.

[0221] In the resin composition of the present invention, the content of the above-mentioned resin is preferably 90 to 99.9% by mass, more preferably 92 to 99.7% by mass, and even more preferably 94 to 99.5% by mass in 100% by mass.

[0222] (Other ingredients)

[0223] In addition to the dyes and resins described above, the resin composition of the present invention may contain other components such as near-infrared absorbing dyes and ultraviolet absorbers, to a extent that does not adversely affect the effects of the present invention.

[0224] Other near-infrared absorbing dyes mentioned above include, in addition to cyanine dyes and squaric acid cyanine dyes, ketone acid dyes, cyclic tetrapyrrole dyes (porphyrins, dihydroporphyrins, phthalocyanines, naphthalene phthalocyanines, choline dyes, etc.) that may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as central metal ions, pyrrolopyrrole dyes, azo dyes, quinone dyes, xanthine dyes, indoline dyes, arylmethane dyes, tetranaphthalene-triphenyl dyes, diimide dyes, perylene dyes, quinacridone dyes, oxazine dyes, dipyrrole-methylene dyes, and nickel dyes. Complex dyes, copper ion dyes (copper phosphonate (copper phosphate), copper phosphate ester complexes (complexes of monophosphate esters and copper, complexes of diesters and copper)), dithiol metal complex dyes, azo dyes, polymethyl dyes, phthaloyl dyes, quinone dyes (naphthoquinone dyes, anthraquinone dyes), indophenol dyes, pyranonium dyes, thiopyranonium dyes, ketone acid dyes, tetrahydromethylpyridine dyes, triphenylmethane dyes, aluminum dyes, pyranium dyes (pyrans, benzopyrans, chromogens, coumarins, xanthannes), etc.

[0225] Examples of UV absorbers include organic UV absorbers such as triazine-based, benzotriazole-based, benzophenone-based, benzoxazine-based, and ethylene compounds as described in Japanese Patent Application Publication No. 2019-14707, as well as inorganic UV absorbers (particles) such as titanium dioxide, zinc oxide, and cerium oxide. Among these, ethylene compounds as described in Japanese Patent Application Publication No. 2019-14707 are preferred from the perspective of enabling blue hue correction.

[0226] In addition to the above-mentioned components, the resin composition of the present invention may also contain known components commonly found in molding materials, such as antioxidants, antistatic agents, release agents, plasticizers, fluorescent whitening agents, and adhesives.

[0227] 2. Method for manufacturing the resin composition

[0228] The method for manufacturing the resin composition of the present invention is not particularly limited as long as it is a method that can obtain a melt mixture of the above-mentioned components, but preferably includes a step of melt mixing the resin with the above-mentioned cyanine dye and / or squaric acid cyanine dye. A method for manufacturing a resin composition including such a step is also one aspect of the present invention.

[0229] As for melt mixing, there is no particular limitation on the method that can heat and mix the resin with the aforementioned cyanine dyes and / or squaric acid cyanine dyes. Examples include mixing using known mixers, dispersers, and compounding machines such as short-screw or multi-screw extruders, mixers, agitators, and kneaders. Extrusion melt mixing is preferred from the perspective of uniformly mixing the components. A method with a vacuum vent is more preferred. Furthermore, it is also preferable to directly feed the thermoplastic resin powder, granules, and dye into the injection molding machine. From the viewpoint of preventing oxidation during melt mixing, it is also preferable to seal the resin supply section using carbon dioxide or nitrogen.

[0230] The heating temperature during the melt mixing process can be appropriately selected according to the type of resin used. When the resin in the resin composition is a thermoplastic resin with a melting point, a temperature above the melting point of the resin is preferred, for example, 220–280°C, more preferably 230–270°C. When the resin in the resin composition is a thermoplastic resin without a melting point, a temperature of 180–300°C is preferred, more preferably 200–280°C, and even more preferably 220–270°C. The heating temperature can be varied during heating or varied in multiple stages.

[0231] The method for manufacturing the above-described resin composition may include steps other than the melt-mixing step described above. For example, after the melt-mixing, the mixture may be cooled and pulverized to obtain the resin composition of the present invention. The pulverizing method is not particularly limited and may be carried out by known pulverizing or granulation methods.

[0232] Alternatively, after the above-mentioned melt mixing, the material can be discharged from the front end of the extruder in the form of a filament (rope), cooled in a water tank or the like, and then fed into a cutting machine (granulator) for cutting, thereby obtaining a resin composition as a granular melt mixture.

[0233] 3. Molded body

[0234] The molded articles formed using the resin composition of the present invention are also part of the present invention. The molded articles of the present invention are obtained using the above-described resin composition, therefore the dye does not deteriorate during molding and they possess excellent optical properties.

[0235] The above-mentioned molding process is not particularly limited, and known methods such as injection molding, extrusion molding, blow molding, compression molding, and vacuum molding can be cited as examples. Alternatively, methods such as casting and coating can also be used to mold the desired shape. Molding conditions can be appropriately selected from known methods based on the type of resin, the shape of the molded body, and its dimensions.

[0236] From the perspective of excellent dimensional accuracy of the molded article, injection molding and extrusion molding are preferred. Injection-molded articles and extruded articles formed using the above-described resin composition are also part of the present invention.

[0237] The shape of the molded body described above is not particularly limited, and can be appropriately selected according to the purpose and use. Examples of possible shapes include lens shape, spherical shape, rod shape, plate shape, cylindrical shape, tubular shape, fibrous shape, film shape, or sheet shape. The molded body described above is preferably a particle, lens, or sheet.

[0238] Alternatively, after temporarily preparing granules by melting the above-described resin composition, the granules can be used to form lenses, sheets, etc. The granules can be prepared by the same method as the method for preparing the above-described granular resin composition.

[0239] 4. Manufacturing method of molded body

[0240] The method for manufacturing the molded article is not particularly limited, but preferably includes: a step of melt-mixing the resin with the aforementioned cyanine dye and / or squaric acid cyanine dye, and a step of melt-molding the molten mixture. The melt-mixing step and the melt-molding step can be performed continuously, separately, or simultaneously. Such a method for manufacturing a molded article, including the step of melt-mixing the resin with the aforementioned cyanine dye and / or squaric acid cyanine dye, and the step of melt-molding the molten mixture, is also one aspect of the present invention.

[0241] As a step of melt-mixing the resin with the aforementioned cyanine dye and / or squaric acid cyanine dye, examples can be given of steps that are the same as the melt-mixing step in the method for manufacturing the aforementioned resin composition.

[0242] The above-described molding method can be cited as a process for melting and molding the above-described molten mixture. Among these, injection molding or extrusion molding is preferred. As the above-described molten mixture, granules of a resin composition can be used.

[0243] The melt molding temperature can be appropriately set according to the resin and dye used. From the perspective of obtaining the desired optical properties, in the case of thermoplastic resins with a melting point, a temperature above the melting point is preferred, for example, preferably 220-280°C, more preferably 230-270°C. In the case of thermoplastic resins without a melting point, a temperature of 200-300°C is preferred, more preferably 220-270°C, and even more preferably 230-260°C.

[0244] As an example of simultaneously performing the above-described melt mixing and melt molding processes, one could feed the resin and the aforementioned cyanine dye and / or squaric acid cyanine dye into a multi-screw extruder or injection molding machine for extrusion molding or injection molding. In the multi-screw extruder or injection molding machine, when the dye and resin are supplied, they are heated and stirred, melt-mixed, and then extruded or injected 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 can be supplied separately, or a dry mixture of dye and resin can be supplied, or pre-prepared granules containing dye and resin can be supplied. This is also one embodiment of the manufacturing method of the present invention.

[0245] Furthermore, the above-described method for manufacturing molded articles may, after producing granules through the above-described melt mixing process and melt molding process, further include a process of using the granules to form lenses or sheets.

[0246] 5. Applications

[0247] As described above, the resin composition and molded articles of the present invention exhibit good optical properties even when melt-molded. Therefore, the resin composition and molded articles of the present invention are particularly preferred for optical applications.

[0248] Examples of optical applications described above include optical lenses and optical filters. Hereinafter, a preferred form of the molded body of the present invention will be described.

[0249] (Optical lens)

[0250] There are no particular limitations on the shape of optical lenses; they can be appropriately selected from known shapes such as convex, concave, and aspherical, depending on the purpose and application. The thickness of optical lenses can also be appropriately selected from known technologies, depending on the purpose and application.

[0251] The content of the aforementioned cyanine dyes and / or squaric acid cyanine dyes in the optical lens can be adjusted appropriately, preferably 0.01–2 g / m² based on the unit area of ​​the lens surface. 2 More preferably, it is 0.02–1 g / m 2 .

[0252] The optical lens may have an anti-reflective film on at least one surface of the lens body molded using the resin composition of the present invention described above. The anti-reflective film reflects light in the ultraviolet region and suppresses the reflection of light in the visible light region.

[0253] There are no particular limitations on the anti-reflective film; known anti-reflective films such as dielectric multilayer films and moth-eye structures can be cited. Among these, dielectric multilayer films are preferred from the perspective of ease of processing. As the aforementioned dielectric multilayer film, a laminate formed by alternately stacking high-refractive-index material layers and low-refractive-index material layers can be cited.

[0254] Materials with a refractive index of 1.7 or higher can be used as the high refractive index material layer, and materials with a refractive index of 1.7 to 2.5 are commonly used. Examples of materials used as 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 materials doped with metals such as aluminum and copper, or carbon (e.g., indium tin oxide (ITO) or tin oxide (ATO)).

[0255] Materials used as the aforementioned low-refractive-index material layer include those with a refractive index of 1.6 or less, with materials typically used having a refractive index of 1.2 to 1.6. Examples of materials used as the aforementioned low-refractive-index material layer include silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0256] There are no particular limitations on the stacking of the dielectric films. Low-refractive-index dielectric films and high-refractive-index dielectric films can be alternately stacked directly on at least one surface of the optical lens using known methods such as CVD, sputtering, vacuum evaporation, ion plating, and ion beam sputtering.

[0257] From the perspective of balancing cost and performance, the total number of layers of the above-mentioned high refractive index material layer and low refractive index material layer 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.

[0258] The thickness of the antireflective film is preferably 0.05-1 μm, more preferably 0.08-0.7 μm, and even more preferably 0.1-0.5 μm.

[0259] Such an optical lens formed using the above-described resin composition is also one aspect of the present invention.

[0260] (Optical filters)

[0261] As an optical filter, an example is a filter in which a near-infrared absorption layer composed of the above-described resin composition is formed on a transparent substrate. Such an optical filter comprising a sheet formed using the above-described resin composition is also one aspect of the present invention.

[0262] The thickness of the aforementioned near-infrared absorption layer is not particularly limited. Considering the aspects of processing 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.

[0263] The aforementioned optical filter may have an anti-reflective film on at least one surface. Examples of such anti-reflective films include those similar to those used in the aforementioned optical lens.

[0264] The thickness of the anti-reflective coating in the optical filter is not particularly limited and can be adjusted appropriately. From a productivity point of view, it is preferably 0.08 to 0.7 μm, and more preferably 0.1 to 0.5 μm.

[0265] (Camera element)

[0266] In addition, using the above-mentioned optical lens as a camera element is also one of the preferred embodiments of the present invention.

[0267] The imaging element includes an optical lens group and a light receiving element. The optical lens group consists of one or more lens elements, at least one of which is an optical lens formed using the resin composition of the present invention described above.

[0268] As light receiving elements, examples include elements that convert received light into electrical signals, such as CCD (charge-coupled device) image sensors and CMOS (complementary metal-oxide-semiconductor) image sensors.

[0269] In addition, the imaging element may also include an optical filter. By including an optical filter, near-infrared light can be absorbed to adjust optical properties. There are no particular limitations on the optical filter; known optical filters used in imaging elements can be used, but the optical filter of the resin composition of the present invention described above is preferred. Such an imaging element equipped with the above-described optical lens and / or optical filter is also part of the present invention.

[0270] The imaging element described above may also have other components besides those mentioned above. Examples of other components include protective glass. The imaging element may use an optical lens group, a light-receiving element, and any other components as needed, and may be assembled, for example, from the light incident side in the order of protective glass, optical lens group, and light-receiving element, using known methods.

[0271] Furthermore, the following method for manufacturing the imaging element is one of the preferred embodiments of the present invention. It is a method for manufacturing an imaging element having an optical lens group and a light receiving element, which includes: a step of melting and mixing resin with the above-mentioned cyanine dye and / or squaric acid cyanine dye; and a step of melting and molding the molten mixture to manufacture an optical lens.

[0272] An optical lens manufactured by melting and molding the above-mentioned molten mixture is any one optical lens constituting the above-mentioned optical lens group. The following method for manufacturing an imaging element is also one aspect of the present invention. It is a method for manufacturing an imaging element comprising the above-mentioned optical lens group and a light-receiving element, comprising: a step of melting and mixing resin with the above-mentioned cyanine dye and / or squaric acid cyanine dye; and a step of melting and molding the molten mixture to manufacture at least one optical lens constituting the above-mentioned optical lens group.

[0273] As a step of melting and mixing the dye and resin, an example is the same as the melt mixing step in the method for manufacturing the resin composition.

[0274] The molding method described above can be cited as a process for manufacturing an optical lens by melting and molding the above-mentioned molten mixture.

[0275] The above-mentioned method for manufacturing camera elements may also include other known processes that are typically performed in the manufacturing of camera elements.

[0276] In addition, the present invention also relates to a method for manufacturing an imaging element, which is a method for manufacturing an imaging element comprising an optical lens group, an optical filter and a light receiving element, comprising: a step of melting and mixing a resin with the above-mentioned cyanine dye and / or squaric acid cyanine dye; and a step of melting and molding the molten mixture to manufacture at least one optical lens and / or optical filter constituting the optical lens group.

[0277] As for the process of melting and mixing the dye with the resin and the process of manufacturing the optical lens, there are processes that are the same as those described above.

[0278] As a process for manufacturing an optical filter by melting and molding the aforementioned molten mixture, an example is the method described above for forming a near-infrared absorption layer on a transparent substrate using the aforementioned molten mixture. The formation of the near-infrared absorption layer is not particularly limited, and methods such as extruding the aforementioned molten mixture onto a transparent substrate, casting, or coating can be used.

[0279] The aforementioned optical filter may have an anti-reflective film on at least one surface. Examples of such anti-reflective films include those similar to those used in the aforementioned optical lens.

[0280] Example

[0281] The present invention is illustrated in more detail by the following embodiments, but the present invention is not limited to these embodiments.

[0282] (Example 1)

[0283] (1) Manufacturing of resin composition

[0284] 0.05g of squaricine dye SQ1 and 500g of polycarbonate resin were collected in a 10L polyethylene bag and dry-mixed until homogeneous. The resulting mixture was fed into a twin-screw extruder (TECHNOVEL Corporation, KZW15TW-45MG-NH(-700)) at a rate of 1.2kg / hr under the following conditions: barrel temperature set to C1: 220℃, C2: 240℃, C3~C6: 250℃, H1·D1: 240℃, screw speed: 150rpm. After discarding 200g as initial waste, a rope-like extrudate was obtained. The rope-like extrudate was cut into cylindrical granules (Isuzu Chemical Machinery Co., Ltd., SCF-100) using a granulator to obtain granules with a diameter of approximately 2mm and a length of 3mm.

[0285] (2) Manufacturing of molded parts

[0286] The granules obtained above were then processed into lengths of 60mm to 100mm using a compression molding machine (SFA-10 manufactured by Shinto Metal Industries, Ltd.). A sheet-like molded body with a thickness of approximately 0.20–0.50 mm is produced. Specifically, a polyimide film is placed inside the molding machine, and approximately 3 g of resin composition is laid flat. Then, the polyimide film is placed on top, a 0.25 mm pad is placed, and pressure is applied. The pressure is applied at a molding temperature of 205°C, with a first pressure application (1 MPa) for 120 seconds and a second pressure application (9 MPa) for 60 seconds. The body is then removed from the molding machine, and the polyimide film adhering to both sides is removed to obtain the molded body (pressed sheet).

[0287] (3) Determination of absorbance (gravimetric absorptivity)

[0288] The resulting molded body (thickness 0.3–1 mm) was cut into rectangles of 25 mm × 45 mm, and the weight-based absorbance coefficient was obtained using the evaluation method described below. The results are shown in Table 1. Additionally, Figure 1 The absorbance curve of the molded article of Example 1 is shown. The vertical axis represents absorbance (Abs), and the horizontal axis represents wavelength (nm).

[0289] <Determination of Absorbance (Gross Absorbance)>

[0290] For the obtained molded body, the absorbance at wavelengths of 300 nm to 1100 nm was measured using a UV-Vis-NIR spectrophotometer (UV3600, manufactured by Shimadzu Corporation). The weight absorbance coefficient was calculated using the following formula based on the thickness of the sample, the concentration of dye added, and the specific gravity of the resin.

[0291] It should be noted that, as a blank, a transparent resin molded body made of the same resin and without dye was used. Additionally, the thickness was measured using a MicroGauge micrometer to the nearest 0.001, rounding off the last digit.

[0292] <Formula for calculating gravimetric absorptivity>

[0293] The weight-based absorptivity ε(g) = A / M / (T / 10000)

[0294] The absorbance of λmax = A

[0295] Thickness of the measured object = T (μm)

[0296] The concentration of dye added = M (g / L)

[0297] λmax (maximum absorption wavelength) is the wavelength at which the maximum absorbance is measured in the range of 600 nm to 1100 nm using a UV-Vis-NIR spectrophotometer.

[0298] (Examples 2-11)

[0299] Except for the dyes shown in Table 1, the molded articles were obtained by the same method as in Example 1, and the weight absorbance coefficients were obtained. The results are shown in Table 1.

[0300] (Example 12)

[0301] 0.05 g of squaric acid cyanine dye SQ1 and 500 g of cyclic olefin resin were collected in a 10 L polyethylene bag and dry-mixed until homogeneous. The resulting mixture was fed into a twin-screw extruder (described above) at a rate of 1.2 kg / h under the following conditions: barrel temperature set to C1: 200 °C, C2: 220 °C, C3~C6: 230 °C, H1·D1: 230 °C, and screw speed: 150 rpm. After discarding 200 g as initial waste, a rope-like extrudate was obtained. The rope-like extrudate was cut using a granulator (described above) to obtain cylindrical granules with a diameter of approximately 2 mm and a length of 3 mm. Using the obtained granules, sheet-like molded bodies were obtained using the same method as in Example 1, and the weight absorbance was measured. The results are shown in Table 1.

[0302] (Examples 13-26)

[0303] Except for the resins and dyes shown in Table 1, the molded articles were obtained by the same method as in Example 12, and the weight absorbance coefficients were obtained. The results are shown in Table 1.

[0304] (Example 27)

[0305] (1) Manufacturing of resin composition

[0306] 0.025g of squaricine dye SQ1 and 500g of polycarbonate resin were collected in a 10L polyethylene bag and dry-mixed until homogeneous. The resulting mixture was fed into a twin-screw extruder (as described above) at a rate of 1.2kg / hour under the following conditions: barrel temperature set to C1: 220℃, C2: 240℃, C3~C6: 250℃, H1·D1: 240℃, and screw speed: 150rpm. After discarding 200g as initial waste, a rope-like extrudate was obtained. The rope-like extrudate was cut using a granulator (as described above) to obtain cylindrical granules with a diameter of approximately 2mm and a length of 3mm.

[0307] (2) Manufacturing of molded parts

[0308] Using the granules obtained above as raw material, an injection molding machine (manufactured by Nissei Resin Kogyo Co., Ltd., NS40-5A) was used to manufacture a sheet-shaped molded body (injection molded sheet) with a length of 100 mm, a width of 100 mm, and a thickness of 1 mm. The conditions in the injection molding machine are as follows.

[0309] • Barrel temperature C1: 260℃, C2~C4: 260℃

[0310] Nozzle temperature: 260℃

[0311] • Mold: 100mm long, 100mm wide, 1mm deep, held at 100℃ for 30 seconds (cooling).

[0312] The resulting molded body was cut into rectangles of 25mm × 45mm, and the weight absorption coefficient was obtained using the same method as in Example 1. The results are shown in Table 2.

[0313] (Examples 28-48)

[0314] Except for the resins and dyes shown in Table 2, the molded articles were obtained by the same method as in Example 27, and the weight absorbance coefficients were obtained. The results are shown in Table 2.

[0315] (Comparative Examples 1-3)

[0316] Except for the resins and dyes shown in Table 2, the molded articles were obtained by the same method as in Example 1, and the weight absorbance coefficients were obtained. It should be noted that, regarding the comparative example, λmax no longer had absorption when the molded article was formed, so it was determined by measuring the absorbance of the ethanol solution containing only the dye.

[0317] The results are shown in Table 2. Additionally, Figure 2 The absorbance curve of the molded body of Comparative Example 1 is shown. The vertical axis represents absorbance (Abs), and the horizontal axis represents wavelength (nm).

[0318] In addition, the resins and dyes in Tables 1 and 2 are shown below.

[0319] (resin)

[0320] • Polycarbonate resin (PC): PANLITE (registered trademark) L1225WL (manufactured by Teijin Corporation)

[0321] • Cycloolefin resin (COC): APEL (registered trademark) 5014CL (manufactured by Mitsui Chemicals Co., Ltd.)

[0322] • Cycloolefin resin (COP): ZEONEX (registered trademark) K26R (Zeon Corporation, Japan)

[0323] (dye)

[0324] A portion of the dye was synthesized using conventional organic synthesis methods. After column purification, the molecular structure was confirmed by NMR once the purity reached over 99%.

[0325] Squamous acid dye SQ1

[0326] [Chemical Formula 32]

[0327] Squamous acid dye SQ2

[0328] [Chemical Formula 33]

[0329] SQ3 squaric acid cyanine dye

[0330] [Chemical Formula 34]

[0331] SQ4 Squamarine Dye

[0332] [Chemical Formula 35]

[0333] Cyanide CY1

[0334] [Chemical Formula 36]

[0335] Cyanide CY2

[0336] [Chemical Formula 37]

[0337] cyanine dye CY3

[0338] [Chemical Formula 38]

[0339] cyanine dye CY4

[0340] [Chemical Formula 39]

[0341] Cyanide CY5

[0342] [Chemical Formula 40]

[0343] cyanine dye CY6

[0344] [Chemical Formula 41]

[0345] Cyanide dye CY7

[0346] [Chemical Formula 42]

[0347] Cyanide dye D4773 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0348] [Chemical Formula 43]

[0349] Cyanide dye D5013 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0350] [Chemical Formula 44]

[0351] Cyanide dye I1026 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0352] [Chemical Formula 45] [Table 1]

[0353] [Table 2]

[0354] As can be seen from Tables 1 and 2, the resin compositions of the examples, when melt-mixed, exhibit a high value of more than 30 in weight absorptivity and a maximum absorption wavelength (λmax) of about 700 to 900 nm, showing the desired optical properties and thus excellent heat resistance.

Claims

1. A resin composition, characterized in that, It is a molten mixture containing resin and cyanine dyes and / or squaric acid cyanine dyes. The cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has the structure represented by formula (1) below, or has the structure represented by formula (2) below at at least one end of a polymethyl skeleton: [Chemical Formula 1] In equation (1), X 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -;R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can bond together to form a ring structure; Y represents Y 1 Or Y 2 The group to be represented; Indicates the site where the polymethyl skeleton is bonded; R 1 and R 6 Same or different, representing hydrogen atoms, or aliphatic hydrocarbon groups with or without substituents; R 2 ~R 5 and R 7 ~R 12 "Same" or "different" refers to hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. [Chemical Formula 2] In equation (2), R 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents; R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents; Indicates the site where the polymethyl skeleton is bonded; The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; Alternatively, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of five-membered and six-membered rings via a conjugated carbon.

2. A molded body, characterized in that, It is formed using the resin composition of claim 1.

3. An injection-molded article, characterized in that, It is formed using the resin composition of claim 1.

4. An extruded molded article, characterized in that, It is formed using the resin composition of claim 1.

5. An optical lens, characterized in that, It is formed using the resin composition of claim 1.

6. An optical filter, characterized in that, It comprises a sheet formed using the resin composition of claim 1.

7. A camera element, characterized in that, It comprises the optical lens of claim 5 and / or the optical filter of claim 6.

8. A method for manufacturing a resin composition, characterized in that, The manufacturing method includes a step of melt-mixing resin with cyanine dye and / or squaric acid cyanine dye. The cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has the structure represented by formula (1) below, or has the structure represented by formula (2) below at at least one end of a polymethyl skeleton: [Chemical Formula 3] In equation (1), X 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -;R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can be bonded to form a ring structure; Y represents Y 1 Or Y 2 The group to be represented; Indicates the site where it is bonded to the polymethyl backbone; R 1 and R 6 Same or different, representing hydrogen atoms, or aliphatic hydrocarbon groups with or without substituents; R 2 ~R 5 and R 7 ~R 12 "Same" or "different" refers to hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. [Chemical Formula 4] In equation (2), R 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents; R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents; Indicates the site where the polymethyl skeleton is bonded; The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; Alternatively, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of five-membered and six-membered rings via a conjugated carbon.

9. A method for manufacturing a molded article, characterized in that, The manufacturing method includes: a step of melt-mixing resin with cyanine dye and / or squaric acid cyanine dye, and a step of melting and molding the molten mixture. The cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has the structure represented by formula (1) below, or has the structure represented by formula (2) below at at least one end of a polymethyl skeleton: [Chemical Formula 5] In equation (1), X 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -;R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can be bonded to form a ring structure; Y represents Y 1 Or Y 2 The group to be represented; Indicates the site where it is bonded to the polymethyl backbone; R 1 and R 6 Same or different, representing hydrogen atoms, or aliphatic hydrocarbon groups with or without substituents; R 2 ~R 5 and R 7 ~R 12 "Same" or "different" refers to hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. [Chemical Formula 6] In equation (2), R 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents; R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents; Indicates the site where it is bonded to the polymethyl backbone. The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

10. The method for manufacturing a molded article according to claim 9, characterized in that, The melt molding is either injection molding or extrusion molding.

11. The method for manufacturing a molded article according to claim 9, characterized in that, The molded body is a particle, lens, or sheet.

12. The method for manufacturing a molded article according to claim 9, characterized in that, The molded body is an optical lens.

13. The method for manufacturing a molded article according to claim 9, characterized in that, The molded body is an optical filter.

14. A method for manufacturing an imaging element, comprising an imaging element having an optical lens group and a light receiving element, characterized in that, The manufacturing method includes: a step of melt-mixing resin with cyanine dye and / or squaric acid cyanine dye; and a step of melting and molding the molten mixture to manufacture at least one optical lens constituting the optical lens assembly. The cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has the structure represented by formula (1) below, or has the structure represented by formula (2) below at at least one end of a polymethyl skeleton: [Chemical Formula 7] In equation (1), X 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -;R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can be bonded to form a ring structure; Y represents Y 1 Or Y 2 The group to be represented; Indicates the site where it is bonded to the polymethyl backbone; R 1 and R 6 Same or different, representing hydrogen atoms, or aliphatic hydrocarbon groups with or without substituents; R 2 ~R 5 and R 7 ~R 12 "Same" or "different" refers to hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. [Chemical Formula 8] In equation (2), R 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents; R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents; Indicates the site where it is bonded to the polymethyl backbone. The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

15. A method for manufacturing an imaging element, comprising an optical lens group, an optical filter, and a light receiving element, characterized in that, The manufacturing method includes: a step of melt-mixing resin with cyanine dye and / or squaric acid cyanine dye; and a step of melting and molding the molten mixture to manufacture at least one optical lens and / or optical filter constituting the optical lens assembly. The cyanine dye is a compound comprising a cation consisting of a cyanine structure and an anion consisting of a tetra(pentafluorophenyl)borate ion, wherein the cyanine cation has the structure represented by formula (1) below, or has the structure represented by formula (2) below at at least one end of a polymethyl skeleton: [Chemical Formula 9] In equation (1), X 1 and X 2 Same or different, indicating sulfur atom, oxygen atom or -CR a R b -;R a and R b Same or different, representing hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents, R a With R b They can be bonded to form a ring structure; Y represents Y 1 Or Y 2 The group to be represented; Indicates the site where it is bonded to the polymethyl backbone; R 1 and R 6 Same or different, representing hydrogen atoms, or aliphatic hydrocarbon groups with or without substituents; R 2 ~R 5 and R 7 ~R 12 "Same" or "different" refers to hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents. [Chemical Formula 10] In equation (2), R 21 Represents a hydrogen atom, or an aliphatic hydrocarbon group with or without substituents; R 22 ~R 27 Same or different, indicating hydrogen atoms, halogen atoms, or aliphatic hydrocarbon groups with or without substituents; Indicates the site where it is bonded to the polymethyl backbone. The squaric acid cyanine dye is a compound having the following structure: at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring; or, at least one structure in the structure attached to the squaric acid site comprises a nitrogen-containing conjugated system consisting of a five-membered ring and a six-membered ring via a conjugated carbon.

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