Resin composition, lens, light-transmitting filter, optical member, and imaging camera

Abstract

This resin composition comprises a resin (A) and a dye (B), wherein a 1 mm-thick flat plate made from the resin composition and measured in accordance with JIS Z 8781-4:2013 gives values for L*, a*, and b* in the L*a*b* color system in the following ranges, respectively: L* : 80 to 95; a* : -5 to 5; and b* : -20 to -5. The resin composition has a water absorption rate of not more than 0.15% when the aforementioned flat plate is measured, in accordance with ASTM D570, after immersion for 24 hours in distilled water at a temperature of 23°C.

Description

Resin composition, lens, light-transmitting filter, optical member, and imaging camera

[0001] The present invention relates to a resin composition, a lens, a light-transmitting filter, an optical member, and an imaging camera.

[0002] In imaging cameras, a phenomenon known as color noise occurs, where colors appear different from their actual colors. Color noise can be caused by a variety of factors, such as diffraction and aberration in the optical system or noise during digital processing, but because it reduces image contrast, it is desirable to avoid it as much as possible.

[0003] Patent Document 1 discloses an imaging device that has an optical lens and an imaging element with a light-receiving surface that forms an image of a subject through the optical lens, and generates and records image data from an image signal output from the imaging element, and that has a contrast data calculation means that calculates contrast data based on the image data, a color data calculation means that calculates color data based on the image data, a first lens position determination means that determines a first lens position of the optical lens that focuses the image of the subject on the light-receiving surface based on the contrast data, a second lens position determination means that determines a second lens position of the optical lens where the color data peaks, and a determination means that calculates a difference between the first lens position and the second lens position and compares the difference with a predetermined threshold value, and the determination means determines that color moiré will occur when the difference is smaller than the threshold value.

[0004] Patent Document 2 discloses an image processing device that includes an estimation means for estimating moiré components contained in an image based on optical characteristic information, a determination means for determining a correction amount based on the estimated moiré components, and a correction means for correcting the image based on the correction amount so as to reduce the moiré components contained in the image.

[0005] JP 2014-053883 A JP 2017-028594 A

[0006] The present invention provides a resin composition that can be used to obtain an imaging camera with improved reliability under high-humidity conditions and reduced color noise. The present invention also provides a lens that can be used to obtain an imaging camera with improved reliability under high-humidity conditions and reduced color noise.

[0007] That is, according to the present invention, there are provided a resin composition, a lens, a light-transmitting filter, an optical member, and an imaging camera as shown below. 1. A resin composition comprising: a resin (A); and a dye (B), wherein the L ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ The values ​​of are within the following ranges, ＊ :80 or more and 95 or less a ＊ : -5 or more and 5 or less b ＊ : -20 or more and -5 or less A resin composition having a water absorption of 0.15% or less, as measured by immersing the flat plate in distilled water at a temperature of 23°C for 24 hours in accordance with ASTM D570. 2. The resin composition according to 1., wherein the resin (A) comprises a thermoplastic resin. 3. The resin composition according to 1. or 2., wherein the resin (A) comprises at least one selected from the group consisting of a copolymer of an α-olefin and a cyclic olefin, and a ring-opening polymer of a cyclic olefin. 4. The resin composition according to any of 1. to 3., wherein the resin (A) has a structural unit (a) derived from a cyclic olefin represented by the following general formula [I]: (In the general formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R ａ and R ｂ are each independently the following atoms or hydrocarbon groups, and when q is 0, the respective bonds are bonded to form a 5-membered ring. １ ~R １８ and R ａ and R ｂare each independently a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) 5. The resin (A) is a copolymer of ethylene and tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 6. The resin composition according to any one of 1. to 5., wherein the dye (B) comprises a compound represented by the following general formula (1): (In the general formula (1), R １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ Each of R represents a hydrogen atom or a linear, branched, or cyclic alkyl group. １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ are not the same. M represents Cu or VO. 7. In the general formula (1), R １ , R ３ , R ５ and R ７ is a tert-butyl group, and R ２ , R ４ , R ６ and R ８is a hydrogen atom, and M is Cu. 8. The resin composition according to any one of 1. to 7., wherein the content of the dye (B) relative to 100 parts by mass of the resin (A) is 0.0003 parts by mass or more and 0.03 parts by mass or less. 9. A lens comprising a molded article of the resin composition according to any one of 1. to 8.. 10. A light-transmitting filter comprising a molded article of the resin composition according to any one of 1. to 8.. 11. An optical member comprising the lens according to 9. or the light-transmitting filter according to 10.. 12. An imaging camera comprising the optical member according to 11.. 13. A lens comprising a molded article of a resin composition comprising resin (A) and dye (B), wherein L ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ Lenses whose values ​​are within the following ranges: ＊ :80 or more and 95 or less a ＊ : -5 or more and 5 or less b ＊ 14. The lens according to 13., wherein the resin (A) contains a thermoplastic resin. 15. The lens according to 13. or 14., wherein the dye (B) contains a compound represented by the following general formula (1): (In the general formula (1), R １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ Each of R represents a hydrogen atom or a linear, branched, or cyclic alkyl group. １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ are not the same. M represents Cu or VO. 16. In the general formula (1), R １ , R３ , R ５ and R ７ is a tert-butyl group, and R ２ , R ４ , R ６ and R ８ is a hydrogen atom and M is Cu. 17. The lens according to any one of 13. to 16., wherein the content of the dye (B) relative to 100 parts by mass of the resin (A) is 0.0003 parts by mass or more and 0.03 parts by mass or less.

[0008] According to the present invention, it is possible to provide a resin composition that can be used to obtain an imaging camera with improved reliability under high-humidity conditions and reduced color noise generation. Also, according to the present invention, it is possible to provide a lens that can be used to obtain an imaging camera with improved reliability under high-humidity conditions and reduced color noise generation.

[0009] The present invention will be described below based on embodiments. In this disclosure, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, each monomer constituting the cyclic olefin copolymer of the present invention may be a monomer obtained from a fossil raw material, or a monomer obtained from an animal or plant raw material.

[0010] [Resin Composition] The resin composition of this embodiment will be described in detail below.

[0011] The resin composition of the present embodiment is a resin composition containing a resin (A) and a dye (B), wherein the L ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ The values ​​of are within the following ranges, ＊ :80 or more and 95 or less a ＊: -5 or more and 5 or less b ＊ : -20 or more and -5 or less The water absorption rate measured in accordance with ASTM D570 by immersing the flat plate in distilled water at 23°C for 24 hours is 0.15% or less.

[0012] Although the mechanism by which the resin composition of the present embodiment solves the above-mentioned problems is not clear, it is presumed that the above-mentioned problems are solved by the following mechanism. ＊ , a ＊ and b ＊ It is presumed that adjusting the value of within a certain range will suppress excessive incidence of yellow light on the RGB color sensor. Generally, yellow light exhibits strong sensitivity to both the R sensor and the G sensor of an RGB color sensor, and is therefore likely to cause color noise. Therefore, it is presumed that suppressing excessive incidence of yellow light will correct color noise. Furthermore, it is presumed that adjusting the water absorption rate of the resin composition of this embodiment within a certain range will improve the reliability of lenses obtained from the resin composition in high-humidity environments.

[0013] Here, the methods described in Patent Documents 1 and 2, etc., require the addition of a drive system or the like to correct color noise, which can result in an increase in the size of the imaging device, or in increased power consumption of the device due to complex image processing. On the other hand, the resin composition of this embodiment makes it possible to obtain an imaging camera in which the generation of color noise is suppressed. Therefore, the resin composition of this embodiment makes it possible to address color noise without the use of an additional drive system or image processing technology.

[0014] Hereinafter, each component contained in the resin composition of the present embodiment will be described in detail.

[0015] <Resin (A)> The resin composition of this embodiment contains a resin (A). There are no particular limitations on the resin (A), and it may be a thermosetting resin or a thermoplastic resin. Specific examples include epoxy resins, polyester resins, polyolefin resins (including copolymers of α-olefins and cyclic olefins), polycarbonate resins, polyvinyl chloride resins, styrene resins, acrylic resins, polyamide resins, cellulose resins, urethane resins, and silicone resins. The resin (A) may be used alone or in combination of two or more.

[0016] Among these, from the viewpoints of achieving dimensional stability, moldability, and optical properties of the lens, as well as reducing the water absorption rate described below, it is preferable for the resin (A) to contain a thermoplastic resin, and it is more preferable for it to contain at least one type selected from a copolymer of an α-olefin and a cyclic olefin, and a ring-opening polymer of a cyclic olefin (hereinafter, these will also be collectively referred to as a "cyclic olefin polymer").

[0017] The cyclic olefin polymer will be described in detail below.

[0018] From the viewpoints of achieving dimensional stability, moldability, and optical properties of the lens, as well as reducing the water absorption rate described below, the resin (A) preferably contains a cyclic olefin polymer having a structural unit (a) derived from a cyclic olefin represented by the following general formula [I]. Specific examples of such cyclic olefin polymers include the polymer (A) described in JP-A-2009-120794.

[0019]

[0020] In the above general formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R ａ and R ｂ are each independently the following atoms or hydrocarbon groups, and when q is 0, the respective bonds are bonded to form a 5-membered ring. １ ~R １８ and R ａ and R ｂare each independently a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom, wherein the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0021] Furthermore, examples of the hydrocarbon groups include, independently, alkyl groups typically having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, examples of the alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups, examples of the cycloalkyl groups include cyclohexyl groups, and examples of the aromatic hydrocarbon groups include phenyl and naphthyl groups. These hydrocarbon groups may be substituted with a halogen atom.

[0022] Furthermore, in the above general formula [I], R １５ ~R １８ may be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed may have a double bond. Specific examples of the monocyclic or polycyclic ring formed here are shown below.

[0023]

[0024] In the above examples, the carbon atoms numbered 1 and 2 are R １５ (R １６ ) or R １７ (R １８ ) indicates the carbon atom to which it is bonded. １５ and R １６ With or R １７ and R １８ and may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group.

[0025] More specific examples of the cyclic olefin represented by the general formula [I] are given below.

[0026]

[0027] Examples of suitable bicyclo[2.2.1]-2-heptenes include bicyclo[2.2.1]-2-heptenes represented by the above formula (where the numbers 1 to 7 indicate the carbon position numbers), and derivatives of bicyclo[2.2.1]-2-heptene substituted with, for example, halogen atoms or hydrocarbon groups optionally substituted with halogen atoms. Examples of suitable halogen atoms include the same halogen atoms as those in the general formula [I]. Examples of suitable hydrocarbon groups include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5-phenyl, 5-benzyl, 5-tolyl, 5-(ethylphenyl), 5-(isopropylphenyl), 5-(biphenyl), 5-(beta-naphthyl), 5-(alpha-naphthyl), 5-(anthracenyl), and 5,6-diphenyl. These hydrocarbon groups may be substituted with fluorine, chlorine, bromine, or iodine atoms.

[0028] Further examples of the derivatives include cyclopentadiene-benzyne adducts, cyclopentadiene-acenaphthylene adducts, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, and 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracenadonobicyclo[2.2.1]-2-heptene derivatives.

[0029] Still other derivatives include tricyclo[4.3.0.1 ２，５ ]-3-decene, 2-methyltricyclo[4.3.0.1 ２，５ ]-3-decene, 5-methyltricyclo[4.3.0.1 ２，５ ]-3-decene, and the like ２，５ ]-3-decene derivatives, tricyclo[4.4.0.1 ２，５ ]-3-undecene, 10-methyltricyclo[4.4.0.1 ２，５ ]-3-undecene, and the like ２，５ ]-3-undecene derivatives and the like.

[0030]

[0031] Tetracyclo[4.4.0.1] represented by the above formula ２，５ .1 ７，１０ ]-3-dodecene (where the numbers 1 to 12 indicate the carbon position numbers) and derivatives thereof substituted with hydrocarbon groups. Examples of this hydrocarbon group include 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10-dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8 8-n-propylidene-9-methyl, 8-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8-(ethylphenyl), 8-(isopropylphenyl), 8,9-diphenyl, 8-(biphenyl), 8-(beta-naphthyl), 8-(alpha-naphthyl), 8-(anthracenyl), 5,6-diphenyl, and the like.

[0032] Specific examples of the cyclic olefin represented by general formula [I] are given above, but more specific structural examples of these compounds include the structural examples of cyclic olefins shown in paragraphs

[0038] to

[0058] of the original specification of JP-A-6-228380 and the structural examples of cyclic olefins shown in paragraphs

[0027] to

[0029] of the original specification of JP-A-2005-330465. The cyclic olefin polymer according to this embodiment may contain two or more types of units derived from the above cyclic olefins.

[0033] The cyclic olefins represented by the general formula [I] described above can be produced by subjecting cyclopentadiene to a Diels-Alder reaction with an olefin having a corresponding structure. The cyclic monomer obtained by such a Diels-Alder reaction is usually obtained as an isomeric mixture of endo and exo isomers, with the endo isomer being predominant. However, the concentration of the exo isomer in the isomeric mixture can be increased by a method known in the art, such as that described in Japanese Patent Application Laid-Open No. 5-86131. ​​Accordingly, the endo / exo isomer ratio of the cyclic monomers can be adjusted within a range that does not impair the objectives of the present invention.

[0034] Among the above, the cyclic olefin polymer according to the present embodiment is preferably a norbornene polymer obtained by polymerizing a norbornene monomer containing a structural unit derived from a monomer having a norbornene skeleton. Specific examples of the norbornene monomer are described below.

[0035] (Copolymer of Ethylene or α-olefin and Cyclic Olefin) As described above, the cyclic olefin polymer according to this embodiment includes at least one selected from a copolymer of ethylene or α-olefin and a cyclic olefin, and a ring-opening polymer of a cyclic olefin, and preferably includes a copolymer of ethylene or α-olefin and a cyclic olefin. Examples of the copolymer of ethylene or α-olefin and a cyclic olefin that can be used include the polymers described in paragraphs 0030 to 0123 of WO 2008 / 047468 and the cyclic olefin polymers described in JP 2016-8236 A.

[0036] The copolymer of ethylene or an α-olefin with a cyclic olefin is, for example, a polymer having an alicyclic structure in at least a part of its repeating structural units (hereinafter, also simply referred to as a "polymer having an alicyclic structure"), as long as at least a part of the repeating units of the polymer has an alicyclic structure, and specifically, it preferably includes a polymer having one or more structures represented by the following formula (1):

[0037] In formula (1), x and y represent copolymerization ratios and are real numbers satisfying 0 / 100≦y / x≦95 / 5. x and y are based on moles. n represents the number of substituents Q and is a real number satisfying 0≦n≦2. R １ R is one or more (2+n) valent groups selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. ２ R is one or more monovalent groups selected from the group consisting of a hydrogen atom and hydrocarbon groups having 1 to 10 carbon atoms. ３ is one or more tetravalent groups selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms. ｄ (R ｄ is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms. １ , R ２ , R ３ and Q may each be one type, or may have two or more types in any ratio.

[0038] For each symbol in the above formula (1), the following preferable conditions can be mentioned, and these conditions can be used in combination as necessary. [1] R １ is a group having at least one ring structure in the structure. [2] R ３ However, when n=0, the following exemplary structures (a), (b), and (c) are given.

[0039] In the above formulas (a) to (c), R １ is the same as equation (1).

[0040] [3] n is 0. [4] y / x is a real number that satisfies 20 / 80≦y / x≦65 / 35. [5] R ２ is a hydrogen atom and / or —CH ３ [6] Q is -COOH or -COOCH ３ It is the base.

[0041] The cyclic olefin polymer used in this embodiment is more preferably a polymer having one or more structures represented by the following formula (2).

[0042] In the above formula (2), R １ R is one or more divalent groups selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. ２ represents one or more monovalent groups selected from the group consisting of a hydrogen atom and hydrocarbon groups having 1 to 10 carbon atoms.

[0043] In the above formula (2), x and y represent copolymerization ratios and are real numbers satisfying 5 / 95≦y / x≦95 / 5, preferably 50 / 50≦y / x≦95 / 5, and more preferably 55 / 45≦y / x≦80 / 20. x and y are on a molar basis.

[0044] For each symbol in the above formula (2), the following preferable conditions can be mentioned, and these conditions can be used in combination as necessary. [1] R １ The group is a divalent group represented by the following formula (3):

[0045]

[0046] In the above formula (3), p is an integer of 0 to 2. Preferably, p is 1 in the above formula (3), which is a divalent group.

[0047] [2] R ２ is a hydrogen atom.

[0048] Examples of the ethylene or α-olefin include ethylene, propylene, butene-1, etc., with ethylene being preferred. Examples of the cyclic olefin include the cyclic olefin represented by the general formula [I] above, such as bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1]-2-heptene, and the like. ２，５ .1 ７，１０ ]-3-dodecene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, cyclopentadiene-benzyne adduct, and cyclopentadiene-acenaphthylene adduct are preferred, and bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 ２，５ .1 ７，１０ ]-3-dodecene is more preferred.

[0049] From the viewpoints of dimensional stability, moldability, and optical properties of the lens, as well as reducing the water absorption rate described below, the resin (A) is a copolymer of ethylene and tetracyclo[4.4.0.1]. ２，５ .1 ７，１０ It is preferable that the copolymer contains 1-methyl-3-dodecene.

[0050] The copolymer of ethylene or α-olefin and cyclic olefin according to this embodiment may contain repeating structural units derived from other copolymerizable monomers, as long as the excellent physical properties of the resin composition according to this embodiment and molded articles obtained from the resin composition are not impaired. The copolymerization ratio is not particularly limited, but the repeating structural units derived from monomers other than ethylene or α-olefin and cyclic olefin are preferably 20 mol % or less, and more preferably 10 mol % or less, when the cyclic olefin polymer is taken as 100 mol %. When the copolymerization ratio is equal to or less than the upper limit described above, the optical properties of the resulting resin composition and molded articles obtained from the resin composition are improved, and optical components with higher precision can be obtained.

[0051] Examples of other copolymerizable monomers include aromatic vinyl compounds. Aromatic vinyl compounds include styrene and its derivatives. Styrene derivatives are compounds in which another group is bonded to styrene, and examples include alkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, and p-ethylstyrene; substituted styrenes in which a hydroxyl group, alkoxy group, carboxyl group, acyloxy group, halogen, or the like is introduced into the benzene nucleus of styrene, such as hydroxystyrene, t-butoxystyrene, vinylbenzoic acid, vinylbenzyl acetate, o-chlorostyrene, and p-chlorostyrene; and vinylbiphenyl compounds such as 4-vinylbiphenyl and 4-hydroxy-4'-vinylbiphenyl. Among these, monomers having a benzene ring unit are preferred from the viewpoint of the optical properties of the resulting molded article, and for example, styrene and its derivatives are preferred.

[0052] The type of copolymer of ethylene or α-olefin and cyclic olefin according to the present embodiment is not particularly limited, and various known copolymer types can be applied, such as random copolymers, block copolymers, alternating copolymers, etc. Among them, random copolymers are preferred.

[0053] (Ring-Opening Polymer of Cyclic Olefin) As described above, the cyclic olefin polymer according to this embodiment includes at least one selected from a copolymer of ethylene or an α-olefin with a cyclic olefin, and a ring-opening polymer of a cyclic olefin. The ring-opening polymer of a cyclic olefin will be described below. Examples of the ring-opening polymer of a cyclic olefin include a ring-opening polymer of a norbornene monomer, a ring-opening polymer of a norbornene monomer and another monomer capable of ring-opening copolymerization with the norbornene monomer, and hydrogenated products thereof, and examples thereof include the norbornene polymers described in Japanese Patent No. 6,256,353.

[0054] Examples of the norbornene monomer include norbornene-based monomers, tetracyclododecene-based monomers, dicyclopentadiene-based monomers, and methanotetrahydrofluorene-based monomers.

[0055] <Dye (B)> The resin composition of the present embodiment contains the dye (B). Hereinafter, the dye (B) will be described.

[0056] The content of the dye (B) in the resin composition of this embodiment is ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ From the viewpoint of easily controlling the value of within a predetermined range, the content of the dye (B) is preferably 0.0003 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.0015 parts by mass or more, and even more preferably 0.002 parts by mass or more, relative to 100 parts by mass of the aforementioned resin (A), and is preferably 0.03 parts by mass or less, more preferably 0.015 parts by mass or less, even more preferably 0.01 parts by mass or less, even more preferably 0.008 parts by mass or less, and even more preferably 0.004 parts by mass or less. That is, the content of the dye (B) in the resin composition of this embodiment is preferably 0.0003 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.0015 parts by mass or less, even more preferably 0.0015 parts by mass or less, even more preferably 0.001 parts by mass or less, even more preferably 0.008 parts by mass or less, and even more preferably 0.004 parts by mass or less, relative to 100 parts by mass of the aforementioned resin (A). ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ From the viewpoint of easily controlling the value within a predetermined range, the amount is preferably 0.0003 parts by mass or more and 0.03 parts by mass or less, more preferably 0.0003 parts by mass or more and 0.015 parts by mass or less, even more preferably 0.001 parts by mass or more and 0.01 parts by mass or less, even more preferably 0.0015 parts by mass or more and 0.008 parts by mass or less, and even more preferably 0.002 parts by mass or more and 0.004 parts by mass or less, relative to 100 parts by mass of the resin (A).

[0057] The dye (B) is not particularly limited, and any known dye can be used. ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b＊ From the viewpoint of easily controlling the value of within a predetermined range, it is preferable to include a tetraazaporphyrin compound described in JP-A-2011-221456, and more preferably to include a compound represented by the following general formula (1):

[0058] (In the above general formula (1), R １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ Each of R represents a hydrogen atom or a linear, branched, or cyclic alkyl group. １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ Each of the groups cannot be the same. M represents Cu or VO.

[0059] The tetraazaporphyrin compound contains all of the R １ ~R ８ and any combination of M described in the publication. １ , R ３ , R ５ and R ７ is a linear, branched or cyclic alkyl group, and R ２ , R ４ , R ６ and R ８ is H and M is VO; １ , R ３ , R ５ and R ７ is a linear, branched or cyclic alkyl group, and R ２ , R ４ , R ６ and R ８ is H and M is Cu; １ , R ３ , R５ and R ７ is a linear, branched or cyclic alkyl group, and R ２ , R ４ , R ６ and R ８ is F and M is Cu; １ , R ３ , R ５ and R ７ is a linear, branched or cyclic alkyl group, and R ２ , R ４ , R ６ and R ８ Ga-OCH ２ CF ３ and M is Cu; １ , R ３ , R ５ and R ７ is a linear, branched or cyclic alkyl group, and R ２ , R ４ , R ６ and R ８ is —CN and M is Ni; and １ , R ３ , R ５ and R ７ is a phenyl group, and R ２ , R ４ , R ６ and R ８ is an n-butyl group, and M is VO; １ , R ３ , R ５ and R ７ is a tert-butyl group, and R ２ , R ４ , R ６ and R ８ More preferably, the compound includes a compound in which is a hydrogen atom and M is Cu.

[0060] The compound represented by general formula (1) can be produced, for example, by the method described in JP-A-2011-221456.

[0061] The dye (B) may contain a compound other than the compound represented by formula (1).

[0062] <Other Components> The resin composition of this embodiment may contain components other than the resin (A) and dye (B) as long as the effects of the present invention are not impaired. Examples of such components include phenolic stabilizers, higher fatty acid metal salts, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, hydrochloric acid absorbers, metal deactivators, antistatic agents, antifogging agents, lubricants, slip agents, nucleating agents, plasticizers, flame retardants, and phosphorus-based stabilizers, and these can be blended in appropriate amounts to the extent that the object of the present invention is not impaired.

[0063] <L ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ The resin composition of the present embodiment has a value of L ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ The values ​​of L are within the following ranges. ＊ :80 or more and 95 or less a ＊ : -5 or more and 5 or less b ＊ : -20 or more -5 or less

[0064] The above L ＊ The value of L is 80 or more and 95 or less, preferably 82 or more and 92 or less, and more preferably 85 or more and 90 or less. ＊ If the value of L is within the above range, the image will not be unnaturally dark or too bright. ＊ The value of can be controlled by the type and amount of the resin (A) and dye (B) used.

[0065] The above a ＊ The value of is -5 or more and 5 or less, preferably -3 or more and 3 or less, more preferably -2 or more and 2 or less, and further preferably -1 or more and 1.5 or less. ＊ When the value of is within the above range, the image does not appear unnaturally reddish or greenish, and color noise can be efficiently suppressed by suppressing excessive incidence of yellow light.＊ The value of can be controlled by the type and amount of the resin (A) and dye (B) used.

[0066] Above b ＊ The value of is -20 or more and -5 or less, preferably -16 or more and -7 or less, and more preferably -14 or more and -10 or less. ＊ When the value of b is within the above range, the image does not appear unnaturally bluish or yellowish, and color noise can be efficiently suppressed by suppressing excessive incidence of yellow light. ＊ The value of can be controlled by the type and amount of the resin (A) and dye (B) used.

[0067] <Water Absorption Rate> The resin composition of this embodiment has a water absorption rate of 0.15% or less, as measured by immersing a 1 mm-thick flat plate made of the resin composition in distilled water at 23°C for 24 hours in accordance with ASTM D570. A water absorption rate of 0.15% or less increases the stability of a molded article of the resin composition of the present invention and a lens containing the same under high-humidity conditions, which is preferable from the standpoint of reliability in high-humidity environments. The water absorption rate is preferably 0.10% or less, more preferably 0.05% or less. The lower limit of the water absorption rate is not particularly limited, but may be, for example, 0.000% or more, or 0.001% or more. That is, the water absorption rate of the resin composition of this embodiment is preferably 0.000% or more and 0.10% or less, more preferably 0.001% or more and 0.05% or less. The water absorption rate can be controlled by the type of resin (A) in the resin composition, or, when two or more resins are combined as resin (A), by the ratio of the resins. Specifically, for example, when the resin (A) contains at least one selected from a copolymer of an α-olefin and a cyclic olefin, and a ring-opening polymer of a cyclic olefin, the water absorption rate tends to decrease.

[0068] [Lens] The lens of this embodiment will be described below.

[0069] The lens of the present embodiment includes a molded article of the above-described resin composition.

[0070] The lens of this embodiment is preferably made of a molded article of the above-mentioned resin composition. That is, the lens of this embodiment is preferably obtained by molding the above-mentioned resin composition. From the viewpoint of suppressing color unevenness due to the angle of view, the lens of this embodiment has a thickness at its thickest part of preferably 0.1 mm or more and 5.0 mm or less, more preferably 0.5 mm or more and 2.0 mm or less.

[0071] The molding method is not particularly limited, and known methods such as injection molding and extrusion molding can be used.

[0072] Furthermore, the lens of the present invention can also employ various configurations other than the lens of the present embodiment described above. For example, the lens of the other embodiment can be the lens of the following other embodiment. The lens of the other embodiment is a lens including a molded article of a resin composition including a resin (A) and a dye (B), and the L ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ The values ​​of L are within the following ranges. ＊ :80 or more and 95 or less a ＊ : -5 or more and 5 or less b ＊ : -20 or more -5 or less

[0073] The resin composition in the lenses of other embodiments may be the same as the resin composition of this embodiment. Furthermore, the resin (A), the dye (B), and other components in the lenses of other embodiments may all be the same as the resin (A), the dye (B), and other components in the resin composition of this embodiment, and the contents of these components in the resin composition are also the same as those in the resin composition of this embodiment.

[0074] The method for molding the resin composition in the lens of the other embodiments is not particularly limited, and known methods such as injection molding and extrusion molding can be used.

[0075] [Light-Transmitting Filter] The light-transmitting filter of this embodiment will be described below.

[0076] The light-transmitting filter of this embodiment includes a molded article of the above-mentioned resin composition. The light-transmitting filter of this embodiment is preferably made of a molded article of the resin composition of the present invention. That is, the light-transmitting filter of this embodiment is preferably obtained by molding the above-mentioned resin composition. The molding method is not particularly limited, and known methods such as injection molding and extrusion molding can be used.

[0077] [Optical Member] The optical member of this embodiment will be described below.

[0078] The optical member of this embodiment includes the above-described lens or the above-described light-transmitting filter. Examples of such optical members include a lens module (lens unit) including multiple lenses and, if necessary, electronic components. When the optical member of this embodiment is a lens module (lens unit), the number of lenses in the lens module (lens unit) is not particularly limited, and may be two, four, six, ten, or more. Furthermore, the installation position of the lens of the present invention in a lens configuration consisting of multiple lenses is not particularly limited, and the number of lenses of the present invention in the lens configuration may be one, two, or more. Furthermore, when the optical member of this embodiment is a lens module (lens unit), a light-transmitting filter may be laminated on the lens in the lens module (lens unit).

[0079] [Imaging Camera] The imaging camera of this embodiment will be described below.

[0080] The imaging camera of this embodiment includes the optical member described above, and preferably includes a lens module (lens unit). The imaging camera is not particularly limited as long as it includes the optical member described above, and may be a digital camera or a film camera. It may also be a still camera, a video camera, an imaging camera mounted on a device such as a laptop computer, a tablet, or a smartphone, or an imaging camera used by being externally attached to such a device.

[0081] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0082] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0083] In the examples and comparative examples, the following raw materials were used.

[0084] <Resins> Resin 1: Ethylene and cyclic olefin (tetracyclo[4.4.0.1 ２，５ .1 ７，１０ ]-3-dodecene) (manufactured by Mitsui Chemicals, Inc., product name: APEL 5014CL: MFR: 36 g / 10 min (260°C, 2.16 kg load, in accordance with ASTM D1238), Tg: 135°C).

[0085] Resin 2: Polycarbonate (manufactured by Sumika Polycarbonate Co., Ltd., product name: SD2173M)

[0086] Resin 3: Ring-opening polymer of ethylene and cyclic olefin (manufactured by Zeon Corporation, product name: ZEONEX K26R)

[0087] Resin 4: Ethylene-TD-BNBD copolymer prepared by the following method. 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyl titanium dichloride (hereinafter referred to as transition metal compound (1)) was used as the polymerization catalyst, triisobutylaluminum (hereinafter referred to as TiBAL) was used as the organoaluminum compound catalyst, and triphenylcarbenium tetrakis(pentafluorophenyl)borate (hereinafter referred to as borate compound (1)) was used as the borate compound catalyst. A 2000 ml glass reaction vessel equipped with a stirrer was used to continuously copolymerize ethylene and the cyclic olefins benzonorbornadiene (hereinafter referred to as BNBD) and tetracyclododecene (hereinafter referred to as TD) in the same manner as described in JP 2022-78934 A. A mixture of cyclohexane and hexane was used as the reaction solvent, the reactor residence time was 30 minutes, and the polymerization temperature was 50°C. A continuous solution polymerization reaction was carried out by supplying transition metal compound (1) to the reactor at a ratio such that the polymer concentration in the reaction solution was 10% by mass, TiBAL at an atomic ratio of Al / Ti = 20, and the borate compound at an atomic ratio of B / Ti = 4. Methanol was added to the polymerization solution continuously withdrawn from the bottom of the reactor to terminate the polymerization reaction, yielding a polymer solution containing an ethylene-TD-BNBD copolymer. Aqueous sodium hydroxide solution and water were added to this polymer solution, and the catalyst residue remaining in the polymer was transferred to the aqueous layer and removed. The solvent and unreacted monomer were distilled off from the deashed solution, yielding pellets of Resin 4 (ethylene-TD-BNBD copolymer).

[0088] <Dye> Dye 1: In the following general formula (1), R １ and R ２ , R ３ and R ４ , R ５ and R ６ , R ７ and R ８ In each combination, one (R ２ , R ４ , R ６ , R ８ ) is a hydrogen atom, and the other (R １ , R ３ , R ５ , R７ ) is a tert-butyl group and M is Cu.

[0089]

[0090] Dye 2: (4Z)-4-[6-(2-ethylhexanoylamino)-2,3,3-trimethyl-1-octyl-2H-indol-1-ium-5-ylidene]-3-oxo-2-[6-(2-ethylhexanoylamino)-2,3,3-trimethyl-1-octyl-2H-indol-5-yl]cyclobuten-1-olate

[0091] Pigment 3: 2-(5-chlorobenzotriazol-2-yl)-5-(ethylamino)-4-methylphenol

[0092] Pigment 4: 2-tert-butyl-4-methyl-6-(5-octylsulfanylbenzotriazol-2-yl)phenol

[0093] [Example 1] 0.003 parts by mass of the dye 1 was added to 100 parts by mass of pellets made of the resin 1, and the mixture was melt-kneaded using a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.: TEX44) at a cylinder temperature of 260°C and a rotation speed of 150 rpm to obtain a resin composition 1. The obtained resin composition 1 was injection-molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.: model name: SE30DUZ) at a cylinder temperature of 260°C, an injection pressure of 600 bar, and a mold temperature of 130°C to produce a flat plate with a thickness of 1 mm and a lens with a thickness of 1.2 mm at its thickest point. The obtained lens was combined with five other lenses and a sensor to produce an imaging camera. The imaging camera was configured as follows, from the subject side: the obtained lens / five other lenses / sensor.

[0094] Example 2 A resin composition and a flat plate were prepared in the same manner as in Example 1, except that Resin 3 was used instead of Resin 1.

[0095] Example 3 A resin composition and a flat plate were prepared in the same manner as in Example 1, except that Resin 4 was used instead of Resin 1.

[0096] Comparative Example 1 A resin composition, a flat plate, a lens and an imaging camera were prepared in the same manner as in Example 1, except that dye 1 was not added.

[0097] Comparative Example 2 A resin composition, a flat plate, a lens and an imaging camera were produced in the same manner as in Example 1, except that 0.006 parts by mass of dye 2 was added instead of dye 1.

[0098] Comparative Example 3 A resin composition, a flat plate, a lens, and an imaging camera were prepared in the same manner as in Example 1, except that 0.024 parts by mass of dye 3 and 0.1 parts by mass of dye 4 were added instead of dye 1.

[0099] Comparative Example 4 A resin composition, a flat plate, a lens, and an imaging camera were prepared in the same manner as in Example 1, except that 0.006 parts by mass of dye 2, 0.024 parts by mass of dye 3, and 0.1 parts by mass of dye 4 were added instead of dye 1.

[0100] Comparative Example 5 A resin composition and a flat plate were prepared in the same manner as in Example 1, except that Resin 2 was used instead of Resin 1.

[0101] [Evaluation of Water Absorption] The obtained flat plate was immersed in distilled water at 23° C. for 24 hours in accordance with ASTM D570, and the water absorption was calculated from the rate of change in mass before and after the immersion.

[0102]

[0103] The water absorption rate was less than 0.05% in all of Examples 1 to 3 and Comparative Examples 1 to 4. On the other hand, Comparative Example 5 had a high water absorption rate and was judged to have poor reliability under high humidity conditions, so further evaluation was not carried out.

[0104] [Evaluation of Hue] The obtained flat plate was evaluated for hue using a spectroscopic haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z 8781-4:2013. ＊ , a ＊ and b ＊ The results of measuring the values ​​are shown below.

[0105]

[0106] [Evaluation of Color Noise] Using the obtained imaging camera, an exterior image was taken so that a building with a white exterior wall was captured. The subject, the exterior wall of the building, was trimmed so that nothing other than the exterior wall of the building was captured and the number of pixels was 630. Within the total of 630 pixels of the trimmed image of the exterior wall of the building, the portion with a hue angle in the range of 20 degrees to 60 degrees was defined as color noise, and the number of pixels corresponding to color noise was counted.

[0107]

[0108] In Example 1, the number of pixels corresponding to color noise was 0, but in all of Comparative Examples 1 to 4, the number of pixels corresponding to color noise exceeded 10. This shows that the resin composition according to this embodiment improves reliability under high humidity conditions and provides an imaging camera in which the generation of color noise is suppressed.

[0109] Here, the methods described in Patent Documents 1 and 2, etc., require the addition of a drive system or the like to correct color noise, which can result in an increase in the size of the imaging device, or in increased power consumption of the device due to complex image processing. On the other hand, this example demonstrates that the resin composition of this embodiment can provide an imaging camera in which the generation of color noise is suppressed. This demonstrates that the resin composition of this embodiment can address color noise without the use of an additional drive system or image processing technology.

[0110] This application claims priority based on Japanese Patent Application No. 2023-121906, filed on July 26, 2023, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. Resin (A), A dye (B), A resin composition comprising: A flat plate having a thickness of 1 mm made of the resin composition was measured in accordance with JIS Z 8781-4:2013. ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ The values ​​of are within the following ranges, L ＊ 80 and below a ＊ -5 or more, less than 5 b ＊ -20 or more -5 or less The resin composition has a water absorption of 0.15% or less as measured in accordance with ASTM D570 by immersing the flat plate in distilled water at 23°C for 24 hours.

2. The resin composition according to claim 1 , wherein the resin (A) comprises a thermoplastic resin.

3. The resin composition according to claim 1 or 2, wherein the resin (A) comprises at least one selected from the group consisting of a copolymer of an α-olefin and a cyclic olefin, and a ring-opening polymer of a cyclic olefin.

4. 3. The resin composition according to claim 1, wherein the resin (A) has a structural unit (a) derived from a cyclic olefin represented by the following general formula [I]: 【Chemistry 1】 (In the general formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R ａ and R ｂ are each independently the following atoms or hydrocarbon groups, and when q is 0, the respective bonds are bonded to form a 5-membered ring. １ ~R １８ and R ａ and R ｂ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom. Here, a halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

5. The resin (A) is a copolymer of ethylene and tetracyclo[4.4.0.1 ２，５ .1 ７，１０ 3. The resin composition according to claim 1, comprising a copolymer of 1-methyl-2-isopropyl-3-dodecene and 1-methyl-2-isopropyl-3-dodecene.

6. The resin composition according to claim 1 or 2, wherein the dye (B) comprises a compound represented by the following general formula (1): 【Chemistry 2】 (In the general formula (1), R １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ Each of R represents a hydrogen atom or a linear, branched, or cyclic alkyl group. １ and R ２ , R ３ and R ４ , R ５ and R ６ and R ７ and R ８ Each of the groups cannot be the same. M represents Cu or VO.

7. In the general formula (1), R １ , R ３ , R ５ and R ７ is a tert-butyl group, and R ２ , R ４ , R ６ and R ８ The resin composition according to claim 6, wherein is a hydrogen atom and M is Cu.

8. The resin composition according to claim 1 or 2, wherein the content of the dye (B) relative to 100 parts by mass of the resin (A) is 0.0003 parts by mass or more and 0.03 parts by mass or less.

9. A lens comprising a molded article of the resin composition according to claim 1.

10. A light-transmitting filter comprising a molded article of the resin composition according to claim 1.

11. An optical member comprising the lens according to claim 9 or the light-transmitting filter according to claim 10.

12. An imaging camera comprising the optical member according to claim 11.

Images