Composition, molded article and device

Abstract

This composition contains a phthalocyanine pigment, a black pigment, and a resin. The phthalocyanine pigment contains one or more compounds from a compound represented by general formula (Pc) and a dimer of the compound, and the black pigment contains one or more compounds selected from compounds represented by formulae (1)-(6).

Description

Composition, molded body and device

[0001] This application claims priority to Japanese Patent Application No. 2023-204091, filed December 1, 2023, the contents of which are incorporated herein by reference.

[0002] Conventionally, infrared cameras and infrared sensors are used to visualize infrared radiation emitted from an object as a change in the amount of infrared radiation caused by a change in the object's temperature, and are more stable in operation in dark places than detection using visible light, etc. Infrared cameras and infrared sensors are widely used in a variety of applications, including diagnosis in the medical field, non-destructive testing to detect deterioration in buildings and electrical equipment, night vision cameras in the security field, and personal authentication such as biometric authentication cameras in bank ATMs and airports.

[0003] LiDAR (Light Detection and Ranging) is a remote sensing method that irradiates an object with near-infrared, visible, or ultraviolet light and measures distance by detecting the reflected light with an optical sensor, and near-infrared (NIR) sensors are used in vehicles. LiDAR is currently used as a complement to adaptive cruise control and other systems installed in vehicles, but great demand is expected for advanced driving systems (ADAS) and future autonomous driving (AD), and advanced LiDAR is required to promote ADAS / AD.

[0004] Optical glass or optical resins are used as materials for optical components of the above-mentioned cameras, sensors, and the like. Among these, thermoplastic resin compositions containing high refractive index materials and optical lenses using such resin compositions are known as materials that block visible light and transmit infrared light. For example, Patent Document 1 proposes a thermoplastic resin composition containing a thermoplastic resin and a colorant, which has a refractive index of 1.60 or more at a wavelength of 894 nm and a thickness of 1 mm, and has a maximum transmittance of more than 0% and 1.00% or less at wavelengths of 380 nm to 630 nm and an average transmittance of 80% or more at wavelengths of 840 nm to 940 nm.

[0005] International Publication No. 2020 / 138050

[0006] In recent years, there has been a demand for highly black compositions that block visible light while transmitting infrared light. Perylene and other pigments are used as black pigments in these compositions. However, when these compositions are used to produce molded articles by injection molding, the molded articles can develop a reddish tinge due to factors such as the effects of heat during molding. It has been shown that adding a blue pigment to a composition containing a black pigment can improve blackness to a certain extent. However, since many blue pigments absorb infrared light, it is difficult to achieve both improved blackness and infrared transmission, limiting the improvement of sensing accuracy. While the above-mentioned prior art describes reducing noise caused by visible light by setting the maximum visible light transmittance and the average infrared transmittance within the above ranges, there is no mention of improving blackness, and there is still room for improvement.

[0007] The present invention aims to provide a composition, a molded article, and a device that can achieve both excellent blocking of visible light and excellent transmission of infrared light, as well as good heat resistance, and can achieve improved sensing accuracy and excellent sensing stability.

[0008] As a result of extensive research, the present inventors have found that, based on the knowledge that a specific phthalocyanine pigment has high infrared transmittance, adding the specific phthalocyanine pigment, which is a blue pigment, to a composition containing a specific black pigment and a resin, improves the degree of blackness, thereby effectively blocking visible light, and the above-mentioned properties of the specific phthalocyanine pigment allow for good infrared transmission, and in addition, good heat resistance can be achieved, resulting in improved sensing accuracy and enabling stable, excellent sensing.

[0009] That is, the present invention provides the following configuration: [1] A composition containing a phthalocyanine pigment, a black pigment, and a resin, wherein the phthalocyanine pigment is represented by the following general formula (Pc): (In the formula, M Ｐｃ is X Ｐｃ -Al (trivalent aluminum), X Ｐｃ- represents Co (trivalent cobalt), Sn (divalent tin), Fe (divalent iron) or Cu (divalent copper), Ｐｃ represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or —O—P(═O)R １ R ２ , -OC(=O)R ３ , -OSO ２ R ４ represents R １ , R ２ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent; R １ , R ２ may be bonded to each other to form a ring, R ３ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group; R ４ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent), and the black pigment contains one or more compounds represented by the following formulas (1) to (6) A composition comprising one or more compounds selected from the group consisting of compounds represented by the formula:

[0010] [2] The composition according to [1] above, wherein the average particle size of the phthalocyanine pigment is 1 nm or more and 500 nm or less.

[0011] [3] The composition according to the above [1], wherein the ratio of the number of moles of the phthalocyanine pigment to the number of moles of the total amount of the compounds represented by the formulas (1) to (6) contained in the black pigment is 5 / 95 to 99 / 1.

[0012] [4] The composition according to [1] above, wherein the resin is one or more selected from the group consisting of polyethylene terephthalate (PET) resin, polycarbonate (PC) resin, acrylonitrile styrene (AS) resin, polymethyl methacrylate (PMMA) resin, acrylonitrile / butadiene / styrene (ABS) copolymer resin, polyamide (PA) resin, and aminoalkyd resin.

[0013] [5] The composition according to any one of the above [1] to [4], which is a composition for a molded body or a composition for a coating material.

[0014] [6] A molded body obtained by molding the composition for molded bodies described in [5] above.

[0015] [7] The blackness (L ＊ ) is less than 34.

[0016] [8] The molded article according to [6] above, wherein the molded article has an infrared transmittance of 60% or more at a wavelength of 900 nm.

[0017] [9] A device comprising the molded article according to [6] above.

[0018] According to the present invention, it is possible to provide a composition, a molded article, and a device that can achieve both excellent blocking of visible light and excellent transmission of infrared light, as well as good heat resistance, and can achieve improved sensing accuracy and excellent sensing stability.

[0019] 1 is a schematic diagram showing an example of a device including a molded body obtained by molding the composition for a molded body of the present invention.

[0020] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0021] <Composition> The composition according to this embodiment is a composition containing a phthalocyanine pigment, a black pigment, and a resin.

[0022] (Phthalocyanine Pigment) The phthalocyanine pigment contains one or more compounds represented by the following general formula (Pc) or dimers of the compounds.

[0023] (In the formula, MＰｃ is X Ｐｃ -Al (trivalent aluminum), X Ｐｃ - represents Co (trivalent cobalt), Sn (divalent tin), Fe (divalent iron) or Cu (divalent copper), Ｐｃ represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or —O—P(═O)R １ R ２ , -OC(=O)R ３ , -OSO ２ R ４ represents R １ , R ２ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent; R １ , R ２ may be bonded to each other to form a ring, R ３ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group; R ４ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent.

[0024] Examples of the alkyl group which may have a substituent include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl groups, as well as alkyl groups having a substituent such as trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl groups. Of these, linear or branched alkyl groups are preferred, and linear or branched alkyl groups having 1 to 8 carbon atoms are more preferred.

[0025] Examples of the "aryl group" in the "aryl group which may have a substituent" include aryl groups such as a phenyl group, a p-tolyl group, a naphthyl group, a 6-methyl-2-naphthyl group, and an anthryl group, and aryl groups having a substituent such as a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group. Of these, an aryl group or an aryl group substituted with one chlorine atom, bromine atom, or nitro group is preferred, an aryl group is more preferred, a tolyl group or a phenyl group is even more preferred, and a phenyl group is particularly preferred.

[0026] Examples of alkoxyl groups which may have a substituent include linear or branched alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, as well as alkoxyl groups having a substituent such as trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy. Of these, linear or branched alkoxyl groups are preferred, and linear or branched alkoxyl groups having 1 to 8 carbon atoms are more preferred.

[0027] Examples of the aryloxy group which may have a substituent include aryloxy groups such as a phenoxy group, a p-methylphenoxy group, a naphthyloxy group, and an anthryloxy group, and aryloxy groups having a substituent such as a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group. Of these, an aryloxy group or an aryloxy group substituted with one chlorine atom, bromine atom, or nitro group is preferred, an aryloxy group is more preferred, a p-methylphenoxy group or a phenoxy group is even more preferred, and a phenoxy group is particularly preferred.

[0028] Examples of the cycloalkyl group which may have a substituent include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and an adamantyl group, and a cycloalkyl group which has a substituent such as a 2,5-dimethylcyclopentyl group or a 4-tert-butylcyclohexyl group.

[0029] Examples of the "heterocyclic group" in the "heterocyclic group which may have a substituent" include heterocyclic groups such as a pyridyl group, an N-oxopyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group, and heterocyclic groups having a substituent such as a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group. Of these, a pyridyl group or an N-oxopyridyl group is preferred.

[0030] The phthalocyanine pigment is not particularly limited as long as it is a compound represented by the above general formula (Pc) or a dimer of the compound. For example, Ｐｃ But, X Ｐｃ -Al (trivalent aluminum), X Ｐｃ-Co (trivalent cobalt), Cu (divalent copper), Sn (divalent tin), or Fe (divalent iron), the phthalocyanine pigment is represented by the following structural formula: (Al-Cl / Pc), (Al-F / Pc), (Al-Br / Pc), (Al-I / Pc), (Co-Cl / Pc), (Co-F / Pc), (Co-Br / Pc), (Co-I / Pc), (Cu / Pc), (Sn / Pc), (Fe / Pc), (Al-OH / Pc), (Pc / Al-O-Al / Pc), (Co-OH / Pc), or (Pc / Co-O-Co / Pc), respectively. The phthalocyanine pigment of this embodiment is typically contained in the composition as a blue pigment.

[0031]

[0032]

[0033] The average particle size of the phthalocyanine pigment is not particularly limited, but may be 1 nm or more, 3 nm or more, 5 nm or more, or 15 nm or more. The average particle size of the phthalocyanine pigment may be 500 nm or less, 100 nm or less, 75 nm or less, or 45 nm or less. By setting the average particle size of the phthalocyanine pigment to 1 nm or more and 500 nm or less, the dispersibility of the phthalocyanine pigment can be improved, and the blackness can be further improved with a small amount added. In this embodiment, the average particle size refers to the crystallite size calculated from the half-width measured by powder X-ray diffraction.

[0034] The content of the phthalocyanine pigment is not particularly limited, but is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 15 to 85% by mass, relative to 100% by mass of the total amount of pigments contained in the composition.

[0035] (Black Pigment) Examples of black pigments include perylene-based black pigments and lactone-based black pigments. Examples of perylene-based black pigments include compounds represented by the following formulas (1) to (5). Examples of lactone-based black pigments include a compound represented by the following formula (6). In this embodiment, the black pigment contains one or more compounds selected from the compounds represented by the following formulas (1) to (6).

[0036]

[0037] The black pigment may contain two specific isomers of the compounds represented by formulas (1) to (6), or may consist of the two specific isomers. In this case, for example, when the black pigment contains a compound represented by formula (2) and a compound represented by formula (3), the molar ratio of the compound represented by formula (2) to the compound represented by formula (3) is preferably 99 / 1 to 1 / 99, and more preferably 40 / 60 to 60 / 40. Furthermore, when the black pigment contains a compound represented by formula (4) and a compound represented by formula (5), the molar ratio of the compound represented by formula (4) to the compound represented by formula (5) is preferably 99 / 1 to 1 / 99, and more preferably 40 / 60 to 60 / 40.

[0038] In the composition of this embodiment, the ratio of the number of moles of the phthalocyanine pigment to the total number of moles of the compounds represented by Formulas (1) to (6) contained in the black pigment is not particularly limited, but is preferably 5 / 95 to 99 / 1, more preferably 5 / 95 to 95 / 5, even more preferably 45 / 55 to 95 / 5, and particularly preferably 70 / 30 to 90 / 10. By having the ratio be 5 / 95 to 99 / 1, the degree of blackness can be further improved, and by having the blending ratio of the phthalocyanine pigment to the black pigment be within an appropriate range, material efficiency can be improved.

[0039] (Resin) The resin is not particularly limited, but is preferably one or more selected from the group consisting of polyethylene terephthalate (PET) resin, polycarbonate (PC) resin, acrylonitrile styrene (AS) resin, polymethyl methacrylate (PMMA) resin, acrylonitrile / butadiene / styrene (ABS) copolymer resin, polyamide (PA) resin, and aminoalkyd resin. When the composition is used for a molded article, from the viewpoints of heat resistance and impact resistance, either or both of polyethylene terephthalate (PET) resin and polycarbonate (PC) resin are more preferred.

[0040] The melting point of the resin is preferably 150 to 350° C., and more preferably 200 to 300° C. In this embodiment, the melting point of the resin is measured by placing about 5 mg of resin in an AL (aluminum) pan, placing it on the sample stage of a thermogravimetric differential thermal analyzer (TG-DTA, manufactured by Hitachi High-Tech Science Corporation), and increasing the temperature stepwise from 30° C. to 400° C. The melting point is measured from the temperature at which the sample begins to melt until it is completely melted.

[0041] The use of the composition of this embodiment is not particularly limited, and examples thereof include a composition for molded bodies and a composition for coating. The resin content in the composition can be determined appropriately depending on the use of the composition. For example, in a composition for molded bodies, the resin content is preferably 5,000 to 50,000 parts by mass, more preferably 5,000 to 15,000 parts by mass, per 10 parts by mass of the total amount of the phthalocyanine pigment and the black pigment. For example, in a coating composition, the resin content is preferably 50 to 500 parts by mass, more preferably 50 to 100 parts by mass, per 10 parts by mass of the total amount of the phthalocyanine pigment and the black pigment. Note that the "total amount of the phthalocyanine pigment and the black pigment" refers to the mass of the pigment itself, even if the purity of the pigment is, for example, 90%, and does not take purity into consideration.

[0042] (Dispersing Aid) When dispersing the phthalocyanine pigment or black pigment in the composition, a dispersing aid such as a dye derivative or a surfactant can be used as appropriate. The use of a dispersing aid can further increase the blackness of the molded product. The dye derivative is not particularly limited, but examples thereof include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, an anthraquinone, an acridone, or a triazine. The surfactant is not particularly limited, but examples thereof include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl betaines such as alkyldimethylaminoacetic acid betaine; and amphoteric surfactants such as alkylimidazolines. These may be used alone or in combination of two or more.

[0043] (Other Components) The composition of the present embodiment may contain an antioxidant and a mold release agent as additives. Examples of antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane.

[0044] Preferably, the release agent is one that comprises 90% by mass or more of an ester of an alcohol and a fatty acid. Specific examples of the ester of an alcohol and a fatty acid include an ester of a monohydric alcohol and a fatty acid, and a partial or complete ester of a polyhydric alcohol and a fatty acid. The ester of a monohydric alcohol and a fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Furthermore, the partial or complete ester of a polyhydric alcohol and a fatty acid is preferably a partial or complete ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

[0045] Specific examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate.

[0046] Furthermore, other additives such as a processing stabilizer, an ultraviolet absorber, a flowability modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, a bluing agent, and an antibacterial agent may be added to the composition of the present embodiment.

[0047] <Method for Producing Composition> The method for producing a composition according to this embodiment involves mixing a phthalocyanine pigment containing a compound represented by general formula (Pc) or one or more dimers of the compound, a black pigment containing one or more compounds selected from the compounds represented by formulas (1) to (6), and a resin. The method for producing the composition is not limited to the above, and may include, for example, a step of mixing a phthalocyanine pigment containing a compound represented by general formula (Pc) or one or more dimers of the compound with a black pigment containing one or more compounds selected from the compounds represented by formulas (1) to (6) to obtain a pigment mixture, and a step of mixing the pigment mixture with a resin to obtain a composition. Furthermore, other steps may be included before the step of obtaining the pigment mixture, between the step of obtaining the pigment mixture and the step of obtaining the composition, and / or after the step of obtaining the composition, without departing from the spirit of the present invention.

[0048] <Molded Article> The molded article according to this embodiment is obtained by molding the above-described composition for molded articles. The molding method is not particularly limited, and injection molding, extrusion molding, blow molding, compression molding, vacuum molding, and the like can be used. For example, injection molding can be used to produce a three-dimensional product, and extrusion molding, as well as flat presses, can be used to produce a plate-shaped product. To produce a film-shaped product, melt extrusion and solution casting can be used. Examples of melt molding methods include inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. Furthermore, in the case of a resin that is cured with active energy rays, a cured product can be produced using various curing methods using active energy rays. In particular, when a thermosetting resin is used as the main component of the matrix resin, a molding method in which the molding material is made into a prepreg and then pressurized and heated using a press or an autoclave can be mentioned. Other examples include RTM (Resin Transfer Molding) molding, VaRTM (Vacuum Assist Resin Transfer Molding) molding, laminate molding, hand lay-up molding, and the like.

[0049] <Blackness> The blackness (L ＊ ) is not particularly limited, but is preferably less than 34, more preferably less than 32, and even more preferably less than 30. More specifically, it is preferably 25 to 33, and more preferably 25 to 30. ＊ ) is CIE-L ＊ a ＊ b ＊ It is determined using a color system. ＊ ) is less than 34, it is possible to block visible light better.

[0050] <Infrared transmittance> The infrared transmittance at a wavelength of 900 nm of the molded article according to this embodiment is not particularly limited, but is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. More specifically, it is preferably 60 to 90%, and preferably 80 to 90%. When the infrared transmittance at a wavelength of 900 nm of the molded article is 60% or more, infrared rays can be transmitted more effectively, and sensing accuracy can be further improved.

[0051] <Heat Resistance> In the molded article according to this embodiment, ＊ a ＊ b ＊ L in color system ＊ , a ＊ and b ＊ The color difference ΔE is calculated from the following formula (A) using ＊ The ab value is preferably less than 3, more preferably from 0.05 to 2.5, and even more preferably from 0.075 to 1.5. ＊ When the ab value is less than 3, the color change due to irradiation with light in the wavelength range from ultraviolet to infrared is small, the stability against heat is high, and good heat resistance can be realized. ＊ ab = [(ΔL ＊ ) ２ + (Δa ＊ ) ２ + (Δb ＊ ) ２ ] １／２ ...(A) [In formula (A), ΔL ＊ =L １ ＊ -L ０ ＊ , Δa ＊ = a １ ＊ -a ０ ＊ , Δb ＊ = b １ ＊ -b ０ ＊ represents L ０ ＊ , a ０ ＊ , and b ０ ＊represents the color coordinate of the molded body before irradiation with the xenon lamp, and L １ ＊ , a １ ＊ , and b １ ＊ represents the color coordinate of the molded body after irradiation with a xenon lamp.]

[0052] <Device> The device according to this embodiment is not particularly limited as long as it includes the molded article, but is typically a sensor. The use of the sensor is also not particularly limited, but for example, it is a remote sensing method such as LiDAR. An example of a remote sensing sensor is a near-infrared (NIR) sensor used in ADAS / AD of a vehicle.

[0053] FIG. 1 is a schematic diagram showing an example of a device including a molded body obtained by molding the composition for molded bodies of the present invention. This device typically employs a LiDAR. In FIG. 1, device 10 includes a reflector 11 composed of a molded body obtained by molding the composition for molded bodies, and an optical sensor 12. Reflector 11 transmits light of a specific wavelength among light rays L irradiated from a light source LS. For example, reflector 11 blocks visible light L1 and transmits infrared light L2 among light rays L irradiated from the light source LS. This improves the sensing accuracy and stability of optical sensor 12, thereby improving the reliability of device 10.

[0054] Examples of the present invention will be described below, but the present invention is not limited to the following examples.

[0055] Examples 1 to 14 Preparation of Composition for Molded Body A pigment mixture was prepared by mixing a phthalocyanine pigment and a black pigment to obtain the molar ratio shown in Table 1. Next, 10,000 parts by mass of resin was added to 10 parts by mass of the pigment mixture, and the mixture was mixed to obtain a composition for molded body. The phthalocyanine pigment, black pigment, and resin used in each example are shown below. The purity of the phthalocyanine pigment and resin was approximately 100%.

[0056] (Phthalocyanine pigment) Copper phthalocyanine pigment (Cu / Pc) Average particle size: 22 nm, M ＰＣ: Cu, Molecular weight: 576.08 Product name: FASTGEN BLUE PA5380 Manufacturer: DIC Corporation

[0057]

[0058] Tin phthalocyanine pigment (Sn / Pc) Average particle size: 30 nm, M Ｐｃ : Sn, Molecular weight: 631.25 Product name: Tin(II) Phthalocyanine Manufacturer: Tokyo Chemical Industry Co., Ltd.

[0059]

[0060] Aluminum phthalocyanine pigment (Al-Cl / Pc) Average particle size: 13 nm, M Ｐｃ : Al, X Ｐｃ :Cl, molecular weight: 574.97 Product name: PB79 Manufacturer: Joint Venture Meilida Pigment Industry Co. ,Ltd

[0061]

[0062] (Black Pigment) Black Pigment 1 (Perylene Black) Black Pigment 1 contains a compound represented by formula (1) (molecular weight: 630.66).

[0063]

[0064] Black Pigment 2 (Perylene Black) Black Pigment 2 contains a compound represented by formula (2) (molecular weight: 536.55) and a compound represented by formula (3) (molecular weight: 536.55) in a molar ratio of 50:50.

[0065]

[0066] Black Pigment 3 (Perylene Black) Black Pigment 3 contains a compound represented by formula (4) (molecular weight: 636.67) and a compound represented by formula (5) (molecular weight: 636.67) in a molar ratio of 50:50.

[0067]

[0068] Black Pigment 4 (Lactone Black) Black Pigment 4 contains a compound represented by formula (6) (molecular weight: 448.39).

[0069]

[0070] (Resin) Polycarbonate (PC) resin Product name: Panlite L-1225Z Manufacturer: Teijin Limited Melting point: 221-242°C In the structural formula, n represents an integer other than 0.

[0071]

[0072] Polyethylene terephthalate (PET) resin Product name: Mitsui Pet J125 Manufacturer: Mitsui Chemicals, Inc. Melting point: 251-262°C In the structural formula, n represents an integer other than 0.

[0073]

[0074] [Preparation of Molded Body] The composition for molded body obtained in each example was placed in an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., device name "PNX60III-5A") and injection molding was carried out under the following two conditions to obtain rectangular parallelepiped molded body 1 and molded body 2.

[0075] Molded body 1 Molding temperature: 280°C Residence time: 0 minutes Dimensions: length 5 cm, width 4 cm, height 2 mm

[0076] Molded body 2 Molding temperature: 280°C Residence time: 10 minutes Dimensions: length 5 cm, width 4 cm, height 2 mm

[0077] Comparative Example 1 A composition for a molded body and a molded body were obtained in the same manner as in Example 1, except that the black pigment was not used and the phthalocyanine pigment and resin were adjusted to the contents shown in Table 1.

[0078] Comparative Example 2 A composition for a molded body and a molded body were obtained in the same manner as in Example 1, except that the phthalocyanine pigment was not used and the black pigment and resin were adjusted to the contents shown in Table 1.

[0079] The molded articles obtained in the above Examples and Comparative Examples were measured and evaluated by the following methods. [Blackness] The blackness (L ＊ ) was measured. ＊ A value of less than 34 indicates good blackness, and L​＊ The lower the value, the higher the degree of blackness.

[0080] [Infrared transmittance] The infrared transmittance of the molded body 1 was measured using a spectrophotometer (manufactured by JASCO Corporation, device name "V-770"). An integrating sphere (manufactured by JASCO Corporation, device name "ISN-923") was used as an accessory device, and measurements were performed in 2 nm increments in the range of 300 nm to 2500 nm. An infrared transmittance of 60% or more indicates good infrared transmittance, and it can be determined that the higher the infrared transmittance value, the higher the infrared transmittance.

[0081] [Heat Resistance] The colorimetric values ​​of the molded body 1 and the molded body 2 were determined using a spectrophotometer (manufactured by Suncolor, device name "Datacolor 650"). Then, ΔE ＊ ab (=colorimetric value of molded body 2−colorimetric value of molded body 1) was determined. ＊ If the ab value is less than 3, it indicates good heat resistance, and ΔE ＊ The smaller the ab value, the smaller the color change and the higher the heat resistance. The results are shown in Table 1.

[0082]

[0083] From the results in Table 1, it can be seen that in all of Examples 1 to 14, the L ＊ value is less than 34, the infrared transmittance at a wavelength of 900 nm is 60% or more, and ΔE ＊ The ab value was less than 3, and it was found that the improved blackness provided excellent blocking of visible light and excellent transmission of infrared light, as well as good heat resistance.

[0084] On the other hand, in Comparative Example 1, the composition does not contain a black pigment, and L ＊ The blackness and infrared transmittance were poor. In Comparative Example 2, the composition did not contain a phthalocyanine pigment. ＊ The value was 34, which was poor in blackness.

[0085] 10 Device 11 Reflector 12 Optical sensor

Claims

1. A composition comprising a phthalocyanine pigment, a black pigment, and a resin, wherein the phthalocyanine pigment is represented by the following general formula (Pc): (In the formula, M Ｐｃ , X Ｐｃ -Al (trivalent aluminum), X Ｐｃ -Co (trivalent cobalt), Sn (divalent tin), Fe (divalent iron) or Cu (divalent copper), Ｐｃ represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -O-P(=O)R １ R ２ , -OC(=O)R ３ , -OSO ２ R ４ represents １ , R ２ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent; R １ , R ２ may be bonded to each other to form a ring, R ３ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group; R ４ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; and the black pigment contains one or more compounds represented by the following formulae (1) to (6) A composition comprising one or more compounds selected from the group consisting of compounds represented by the following formula:

2. The composition according to claim 1, wherein the average particle size of the phthalocyanine pigment is from 1 nm to 500 nm.

3. The composition according to claim 1, wherein a ratio of the number of moles of the phthalocyanine pigment to the number of moles of the total amount of the compounds represented by formulas (1) to (6) contained in the black pigment is 5 / 95 to 99 / 1.

4. The composition according to claim 1, wherein the resin is one or more selected from the group consisting of polyethylene terephthalate (PET) resin, polycarbonate (PC) resin, acrylonitrile styrene (AS) resin, polymethyl methacrylate (PMMA) resin, acrylonitrile / butadiene / styrene (ABS) copolymer resin, polyamide (PA) resin and aminoalkyd resin.

5. The composition according to any one of claims 1 to 4, which is a composition for molding or a composition for coating.

6. A molded body obtained by molding the composition for moldings according to claim 5.

7. The blackness (L ＊ 7. The molded article according to claim 6, wherein the molecular weight is less than 34.

8. The molded article according to claim 6, wherein the molded article has an infrared transmittance of 60% or more at a wavelength of 900 nm.

9. A device comprising the molded body according to claim 6.

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